TWI374154B

TWI374154B - Two-liquid curing type aqueous resin composition and use thereof

Info

Publication number: TWI374154B
Application number: TW095110214A
Authority: TW
Inventors: Shinji Tachibana; Masakazu Masui; Shigeo Suzuki
Original assignee: Mitsui Takeda Chemicals Inc
Priority date: 2005-03-30
Filing date: 2006-03-24
Publication date: 2012-10-11
Also published as: CN101151293A; WO2006109432A1; TW200702350A; KR20070120173A; CN101151293B; KR100942404B1

Description

1374154 九、發明說明：【發明所屬之技術領域】本發明係關於由聚胺曱酸酯醇酸樹脂乳液，及可分散 •於該乳液之聚異氰酸酯硬化劑所構成，可提供水性塗布劑 (木工用塗料、汽車用塗料等水性塗料等）、水性底漆等有用之二液硬化型水性樹脂組成物（塗料用组成物等）以及其用途。【先前技術】 ® 聚胺曱酸酯樹脂具有優異之對於底材之密接性、耐磨損性、耐衝擊性及機械性強度，所以廣泛地使用在各種塗 •料、黏接劑或各種塗布劑等之用途等。該聚胺曱酸酯樹脂 -塗料已周知為溶解聚胺甲酸酯於有機溶劑而得之有機溶劑系聚胺曱酸酯樹脂塗料β然而，有機溶劑對於人體或環境不一疋有良好之影響，又，亦有引起火災之危險性。因此，近年來對於環境衛生的關心提高，替代有機溶劑系聚胺曱 _酸酯樹脂塗料，由分散聚胺甲酸酯樹脂於水中之聚胺甲酸酯樹脂水分散液所構成之水性聚胺曱酸酯樹脂塗料之開發快速進展。另一方面，醇酸樹脂為之塗膜表面之光澤性或耐水性良好，有重厚感覺且價格低，自古廣泛地使用在工業用途 •或汎用用途。例如為更擴大範圍地利用在各種塗料、黏接 •劑或各種塗布劑等用途，也檢討醇酸樹脂之乳化。特別是為賦予耐氣候性或耐溶劑性等附加價值，也開發將胺曱酸酯系樹脂複合化之胺曱酸酯醇酸樹脂乳液。 5 318059 1374154 例如曰本專利特開平6_299117號公報（專利文獻”揭示種以乾性，由或半乾性油及/或其脂肪酸作為必須成分而反應所得髮基彳貝為3〇至250之樹脂（A)、含氧缓酸（b)、 .其他之羥基化合物（C)以及有機異氰酸酯化合物（D)反應而 .得之包括水性樹脂、顏料及乾燥劑所構成之水性合成樹脂調配塗料用塗料組成物。該文獻中，具體使用以（半）乾性油及季戊四醇間之酯交換反應所得醇酸樹脂，加以胺甲酸酯化，再分散水中後，進行鏈增長。該等組成物在常溫下擊可進行交聯，具有良好之塗膜乾燥性、重厚感覺、塗刷性，同時無鄰接在羧基之酯鍵，所以其耐水解性也優異。但是， • A貝上其父聯反應需要長久時間，無法在短時間内獲得高 -硬度j塗膜，且耐水性、耐濕熱性、耐溶劑性之改進程度亦不南。又’日本專利特開平6_329892號公報（專利文獻2羯示一種由羥基價30至250之醇酸樹脂（A)、含氧羧酸（b)、籲有機異氰酸酯（C)和其他羥基化合物（D)反應而得之包括水性樹脂與硬化劑所構成之熱硬化型水性樹脂組成物。該文獻中記載明言使用胺基樹脂或嵌段異氰酸醋等硬化劑以硬化和上述專利文獻！同樣醇酸樹脂’可形成有高硬度或各種财久性之塗膜。然而，該組成物為將胺基樹脂或嵌段里 .氰酸酯當做硬化劑使用，因此，必須焙烤處理，在常溫; 並無法獲得高硬度之塗膜。又’以胺曱酸醋系塗膜材料為首之有機系頂漆塗料，塗布於石板、水泥、砂聚等無機材料被覆體時，為確保更 318059 6 ^74154 為強固之黏接性，當由丨但是以提升… 型聚胺甲酸酷樹脂等， θ ’土材之含浸性，甚至塗布作業性為目的，需雖L =里之有機溶劑。賴含有大量有機㈣之底漆，指出、塗布作業性、硬化後之塗膜性能，但亦被響，對之揮發對"作者造㈣康之不良影成物。.之不良影響等問題’故期待出現水性底漆組 —♦利文獻1:日本專利特開平6_29911?號公報（申請專利範圍，段落號碼[0011][0047]，實施例）卜專利文獻2·曰本專利特開平6 329892號公報（申請專 •利範圍，段落號碼[0028][〇〇34]，實施例） - 【發明内容】 (發明所欲解決之課題）因此，本發明之目的在提供可將聚胺曱酸酯樹脂及醇 -欠树月曰之又方的特性，在短時間内有效顯現之二液硬化型鲁水性樹脂組成物。本發明之另一目的在提供具有優異之硬度或耐磨損性等機械特性，同時耐水性、耐濕熱性、耐溶劑性皆高之二液硬化型水性樹脂組成物。本發明之又一目的在提供以聚胺曱酸酯醇酸樹脂乳液 •為主劑使用，主劑和硬化劑間之互溶性優異，同時形成塗 .膜之際，重厚感覺及塗布作業性皆優異之二液硬化型水性樹脂組成物。本發明之再一目的在提供胺甲酸酯成分中之醇酸樹脂 7 318059 1374154 t 成刀可》周整為任意比率，且可調控塗膜特性之二液硬水性樹脂組成物。 1 本發明之再另一目的在提供對於石板、水泥、砂漿等 …機材料被覆體之點接性、耐久性優異、跟頂漆材料間之 •黏接H、耐久性皆優異之二液硬化型水性樹脂組成物。本發明之其他目的在提供以木工用塗料、汽車用塗料、水性底漆等為主要用途之有用二液硬化型水性樹脂組成物（或塗料）^ •(解決課題之手段） —本發明人等為達成上述目的而精心研究結果發現，組 D刀子中具有活性氫原子之聚胺甲酸酯醇酸樹脂乳液及做 -為硬化劑之特定聚異氰酸酯時，可將聚胺甲酸酯樹脂及醇酸樹脂之雙方的特性在短時間内有效表現，並得具有優異之硬度或耐磨損性尊機械特性，同時耐水性、耐濕熱性、耐溶劑性皆高之二液硬化型水性樹脂組成物，而完成本發鲁明。亦即，本發明之水性樹脂組成物（二液硬化型水性樹脂組成物）包括分子中具有活性氫原子之聚胺甲酸酯醇酸樹脂乳液（A)及可分散於該乳液（A)之聚異氰酸酯所構成之硬化劑（B)。上述聚胺曱酸酯醇酸樹脂乳液（A)可為由羥基價 .3 0至2 5 0之醇酸樹脂和聚異氰酸酯間之反應所得之乳液。 •水私·曱酸醋醇酸樹脂乳液（A)之活性氫原子，例如可來源於輕基之氫原子。上述組成物尚可含有金屬乾燥劑（c)，且聚胺甲酸酯醇酸樹脂乳液（A)之醇酸樹脂成分可含有不飽和 318059 8 1374154 (發明之效果）本發明中’由於組合特定之聚胺甲酸醋醇酸樹脂乳液及特定之聚異氰酸醋所構成之硬化劑，因此，可將聚胺甲 .酸醋樹脂及醇酸樹脂雙方之特性在短時間内有效地顯現。 .又能具有優異之硬度或耐磨損性等機械特性，同時耐水性、耐濕熱性、耐溶劑性亦皆獲提升。再加上，即使使用聚胺甲酸醋醇酸樹脂乳液為主劑，主劑和硬化劑間之互溶性優異，同時形成塗膜之際其重厚感覺或塗布作業性亦優異。加之，胺甲酸酯成分中之醇酸樹脂成分可調整為任意比例，而可調控其塗膜特性。因此，本發明之二液硬化型 -水性樹脂組成物有用於做為木工用塗料、汽車用塗料、水 • 性底漆專水性塗料用途。【實施方式】本發明之二液硬化型水性樹脂組成物，包含分子中具有活性氫原子之聚胺甲酸酯醇酸樹脂乳液（A )，及可分散於鲁该乳液（A)之聚異氰酸酯所構成之硬化劑（B)，不僅對於基材具有優異之密接性，還具有優異之塗膜特性（特別是高硬度化特性）及耐水性。甲酸酯醇酴;fef腊乳液（A) ，聚胺曱酸酯醇酸樹脂乳液（A)係在分子中具有活性氫 .原子（例如羥基之氫原子等），至少是由聚異氰酸酯，與做為對於異氰酸基具有反應性活性氫原子之化合物（多元醇成分）的醇酸樹脂加以反應而得。本發明中之醇酸樹脂之羥 318059 1374154 基價在30至200左右，具有該等羥基價之醇酸樹脂用以倣為聚胺甲酸酯醇酸樹脂乳液之多元醇成分。再者，除醇酸樹脂之外，也可使用對於異氰酸基具有反應性活性氫原子之其他成分。上述活性氫原子來源於醇酸樹脂、具有活性氫原子之改質聚異氰酸酯、鏈增長劑及其他成分中之至少一個成分即可。 (U醇酸榭脂 .醇酸樹脂可為含有長鏈脂肪族多元羧酸之多元羧酸和多兀醇行縮合反應所得之聚酯（不含油之醇酸樹脂），但以使用油脂或脂肪酸所製成聚酯（油改質醇酸樹脂）為較佳。亦被稱為油改質聚酯之醇酸樹脂係含有由油脂及鸽和或不飽和高級脂肪酸中選擇至少一種之油成分和多元醇之反應所得聚酯’由油脂及飽和或不飽和高級脂肪酸中選擇至少一種之油成分和多元醇和多元羧酸之反應所得聚酯 _等。又’該等反應中，不僅包括酯化反應，也包括酯交換反應（例如油脂（三甘油酯等）和多元醇間之酯交換反應）。多元醇多元醇乃包括製造多元酯所使用之各種多元醇，例如 •脂肪族二醇[烷二醇（乙二醇、丙二醇、三亞甲基二醇、ι，2-.丁二醇、1，3-丁二醇、ι，4-丁二醇、1,5-戊二醇、3-曱基-1，5· 戍一醇、2,2-二甲基-ΐ，3-丙二醇、新戊二醇' 1，6-己二醇、 2,2-二乙基-1，3-丙二醇、3,3-二羥曱基庚烷、2-乙基-2-丁基 318059 1374154 _1，3-丙二醇、U2-十二烷二醇、U8_十八烷二醇等烧二醇)、稀二醇(2-丁稀_M_二醇、2,6•二甲基小辛稀J -酵等）、聚C2.4伸垸基二醇（二乙二醇、三乙二醇，平均分:量為15〇至4_左右之聚乙二醇、二丙二醇平均分 ::為15〇至4_左右之聚丙二醇，平均分子量為w 請〇〇左右之聚四亞刚二醇等)等]、脂環族二醇(a 壞己二醇、丨，4-環己烷二曱醇等環烷二醇類， ”化雙賴，或其C2.4環氧垸加成物等）、芳香族二醇本二紛等苯二醇類、二甲苯二醇等芳香脂肪族二醇、 -甲酸雙羥乙錯等聚醋二醇、雙酚A、雙酚s、雙酚雙齡類’或其（：2·4環氧燒加成物等）、三價以上之多 :族多元醇(甘油、山·己三醇、三羥甲基乙燒、曰 ==*2-經基甲基#丙二醇、2,4·二經基；基甲基）戊烧、2,2-雙（經基甲基）·3_ 丁醇等脂肪族A (: 醇、季戊四醇、二季戊四醇等季戊四醇類等)、糖醇二：梨糖酵、木糖醇、D·甘露糖醇等）等]。上述多元醇 :戈：：類以上組合使用。其中’以三價以上之多元醇 :甘=三經甲基丙烧、季戊四醇、二季戊四醇多7L醇為較佳。蛛油成分油成分包含油脂、植物油（棉籽油、亞麻仁花籽油、大豆油、米油飽和或不飽和脂肪酸。油脂之例如 ’由、蓖麻籽油、脫水蓖麻籽油、紅玉米油、胡麻油、向曰葵油、米 J2 318059 1374154 糠油、大麻籽油、油菜籽油、落花生油、椰子油、棕櫚油、木棉油、杏仁油、橄欖油、妥爾油、紫蘇軒油、桐油等）、動物油(牛油、豬油、羊油、山羊油、馬油、雞油、火雞 •油等）、魚油（緋魚油、解'魚油、鳕油、舌鳎魚油、比目魚 .油、經魚油、蹲魚油、，貼魚油等）、或其氮化油等。上^ 油月曰可早獨或2種以上組合使用。上述油脂中以植物 ’由特別疋亞麻仁油、紫蘇籽油、桐油、脫水蓖麻籽油等乾，油，大豆油、棉籽油、紅花轩油、玉来油、胡麻油、油莱籽油、米糠油等半乾性油，棕搁油、挪子油等不乾性油等為較佳。 - 飽和脂肪酸之例如辛酸、癸酸、壬酸、月桂酸、肉豆 -蔻酸、棕櫚酸、十七烷酸、硬脂酸、花生酸、山荼酸等直鏈或支鏈狀飽和C8·24脂肪酸等。不飽和脂肪酸之例如肉豆蔻油酸、棕櫚油酸、岩芹酸、油酸、反式_丨^十八烯酸、亞麻油酸、次亞麻油酸、桐酸、鳕油酸、花生油酸、芥酸籲等直鏈或支鏈狀不飽和C8 24脂肪酸等。該脂肪酸可具有羥基等取代基。具有羥基之脂肪酸，例如g麻籽油之主成分之蓖麻油酸、檜酸、二羥基硬脂酸等。脂肪酸也可為上述油脂經皂化等而得之脂肪酸，例如由脫水莲麻籽油所得之向二烯脂肪酸，或脫水蓖麻籽油、亞麻仁油、大豆油、紅 .花籽油、椰子油等所得脂肪酸（例如脫水萬麻籽油脂肪酸' -亞麻仁油脂肪酸、大豆油脂肪酸、紅花籽油脂肪酸、椰子油脂肪酸等）等。該飽和或不飽和脂肪酸可單獨或2種以上組合使用。該脂肪酸中’由乾性油或半乾性油所得脂肪酸 318059 1374154 (油酸、亞油酸、次亞麻油酸等），或高二烯脂肪酸等不飽 =脂肪酸為較佳。又’該脂肪酸中，由不乾性油所得脂肪酸（月桂酸、癸酸、辛酸、肉豆莲酸等），或含挪子油脂肪酸等餘和脂肪酸較多之脂肪酸，由能抑制樹脂之著色而言為較佳。特別是做為油成分而使用具有乾性油或半乾性油、不飽和脂肪酸等不飽和鍵之油成分時，這些油成分中所含不飽和鍵處和空氣中之氧作用發生氧化硬化反應而硬化，所 ’以能形成更優異之塗膜。該氧化硬化反應’通吊使用空氣中之氧而緩慢反應，但是為促進該反應亦可添加下述之金屬乾燥劑或乾燥劑 (C)。即，藉由組合具有以不飽和脂肪酸改質之醇酸樹脂成分之聚胺曱酸酯醇酸樹脂乳液（A)及金屬乾燥劑（c)，可在短時間内形成硬度等特性優異之塗膜。 • 元羧酸多元羧酸包括製造聚酯使用之各種多元羧酸，例如芳香族二羧酸或其酸酐（對苯二曱酸、間苯二甲酸、鄰苯二甲酸、鄰笨二曱酸酐等）、脂環族二羧酸或其酸酐（四氫鄰苯二曱酸、四氫鄰苯二甲酸酐、六氫鄰苯二曱酸、六氫鄰苯 .二甲酸酐、曱基四氫鄰苯二甲酸、氣橋酐（chlorenic anhydride)、5-降萡烯-2,3-二羧酸酐等）、脂肪族二羧酸或其酸酐（琥珀酸、琥珀酸酐、己二酸、壬二酸、癸二酸等 Com烧二缓酸、伊康酸、伊康酸酐、馬來酸、馬來酸酐、 14 318059 ^/4154 富馬酸、富馬料等不飽和二㈣等）、偏苯三酸、偏笨三 :文酐均苯：甲酸、均苯四曱酸肝、曱基環己烯三幾酸、，該羧馱之單至四烷酯等。這些多元羧酸可單獨或2種以上^· 口使用k些多凡幾酸中，常使用者為間苯二甲酸或對苯二甲酸等芳香族二羧酸等。 — 醇酸樹脂之調製，除上述脂肪酸或多元㈣之外，例如尚可使用苯甲酸、料笼—Γ «. ^ 文對弟二丁基本甲酸等芳香族單羧酸等做為羧酸成分。 ^ 丨述醇酸樹脂可利用慣用方法，例如以脂肪酸為原料之脂肪酸法，以油脂為原料之酉旨交換方法，實施單甘油醋法而製造之。脂肪酸法中，例如將脂肪酸、多元醇及多元緩酸做為原料，以22〇至25(rc左右，進行6至ι〇小時之 s曰化反應即可。酯化反應中’尚可添加極少量之例如單正丁基錫氧化物等醋化觸媒。該醋化觸媒劑之比例，相對於油成分1GG重量份，例如可使用G._(U s (U重量份， >以使用0.0001至〇.〇1重量份左里里物左右為較佳。又’酯化反應為除去反應巾所產生之縮合水’可使用和水共_之惰性溶劑（例如甲苯或二甲苯等芳香族烴等）^ 單甘油醋法中，例如在驗性觸媒存在下授祥油脂和多元醇，以23(^25(TC左右，進行2至3小時之醋交換反應，繼。之’加入多元醇，必要時再加入多元幾酸，在22〇至25(TC左右進行醋化反應即可。酯交換反應中，可添加極少量之例如氫氧仙、氫氧化鉀、氫氧化鐘、乙酸納、乙酸鋰等鹼性觸媒。 3)8059 15 1374154 醇酸樹脂t就各成分之比例而言，油成公刀’和多元醇成分及夕兀羧酸之合計量的比例（重量比）為前者/後 = 10/1至1/5’以5/1至1/3為較佳，以4/1至】/]太別以3/1至1.5/1為最佳）。 ‘”、（特多元醇成分之比例，相對於油成分1〇〇重量份例如為5至200重量份，以1〇至1〇〇重量份為較佳，以^至 70重量份為更佳（特別以20至5〇重量份為最佳）。至多元缓酸之比例，相對於油成分1〇〇重量份，例〇至謂重量份，以1至重量份為較佳，以5至3〇重量份為更佳（特別以10至4〇重量份為最佳）。醇酸樹脂可具有羥基及/或羧基，但是做為多元醇成分使用’-般至少具有經基。醇酸樹脂可在其支鏈上且仲基，也可在兩端具有該基。_ 工 ^ 如至）在兩末端具有羥基。醇酸樹脂之經基價「务备 1貝（乳氧化鉀mg/g) ’例如為3〇至 250，其中以40至230 A鲐〆土马較佳，以5〇至22〇為更佳（以60至200為最佳）。 £_2)聚異氰酸酯聚異氰酸酯只要分子φ 紅，± 干具有2個以上之異氰酸基就別無特別限制，通常使帛％ | t 更用於聚胺甲酸醋等製造中之聚異氰酸 S曰，例如脂肪族聚異氰酿 ^ ^ ^ _知、脂環族聚異氰酸酯、芳香脂酸防窃职从 a t異鼠酸酯等低分子量之聚異氰岐酯、預聚物、三聚里羞略 ”亂&崎體、二酮鈐以及該聚異氰酸醋之衍生物或改質物等。一an虹以及為κ八仇 16 318059 1374154 又’聚異氰酸酯」乃分子中具有複數之異氰酸基之化合物的總稱，包括二苯基甲烷二異氰酸酯、伸甲苯基二異氮酸酿、苯二甲基二異氰酸醋等低分子聚異氛酸^及該 •聚異氰酸酯所得衍生物、改質物、預聚物等。該「聚異氰 •酸醋衍纟物」75指低分子聚異氰酸酉旨所得化合物之總稱， ^括改質物、預聚物等。該「聚異氰酸酯改質物」：指低分子聚異氰酸酯或預聚物加以改質而成之反應物。上述脂肪族聚異氰酸酯，例如二異氰酸酯（例如三亞甲基二異氰酸酯、1，2-伸丙基二異氰酸酯、四亞甲基二異氰酸酿、1，2-伸丁基二異氰醋醋、2,3_伸丁基二異氛酸醋、伸丁基二異氰酸酯、六亞曱基二異氰酸酯、五亞甲基二異 •氰酸醋、2,4,4或2,2,4.三甲基六亞甲基二異氰酸醋等土^ 烷基二異氰酸酯、2,6_二異氰酸基甲基已酸酯等）、聚異氰酸酯（例如賴胺酸酯三異氰酸酯、M,8·三異氰酸基辛烷、 1，6，11-三異氰酸基十—烧、丨，8•二異氰酸基_4•異氰酸基甲鲁基辛烷、1，3,6·三異氰酸基己烷、2,5,7_三曱基u·二異氰酸基_5-異氰酸基甲基辛烷等烷基三異氰酸酯等）等。上述脂環族聚異氰酸酯之例如二異氰酸酯（例如1，3_ 環戊烧二異氰酸g旨、M.環己烧二異氛㈣n環己異进氰酸醋、3.異氰酸基甲基_3,5,5•三甲基環己基異氛酉= •(慣用名：異佛爾酮二異氰酸酯）、4,4，-亞甲基雙（環已美異 •氰酸酷）、曱基·2,4.環己烧二異氰酿I旨、曱基·2,6·環己烧二異氰酸酯、1，3-或Μ·雙(異氰酸基曱基)環已烷(慣用：：氫化伸二曱苯基二異氰酸酯）或其混合物、降冰片烷二異氰 318059 1374154 酸醋等）、聚異氰酸雖（例如i，3,5_三異氰酸基環己烧、】，3,5_ 三曱基異氰酸基環己:^、2_(3·異氰酸基丙基>2,5·二（異氰酸基曱基）-雙環[2·2.1]庚院、Μ·異氰酸基丙基）_2 6_二（異亂酸基甲基）-雙環（2.2.1)庚烷、3_(3·異氰酸基丙基）_2,5_二 .(異，酸基甲基）-雙環[2.2」]庚烧、5_(2•異氛酸基乙基）_2· 異氰酸基甲基-3-(3-異氰酸基丙基）·雙環[2 21]庚烧、6_(2· 異氰酸基乙基)-2-異氰酸基甲基_3♦異氰酸基丙基）_雙環 [2.2.1]庚烷、5-(2-異氰酸基乙基）_2_異氰酸基甲基_2_(3_異氛酸基丙基）-雙環[2.2.1]庚垸、6_(2_異氰酸基乙基）_2-異氛酸基曱基-2-(3-異氰酸基丙基）_雙環[2 21]庚烧等三異氛酸 - 酯等）。 ' 上述芳香脂肪族聚異氰酸酯之例如二異氰酸酯（例如 1，3-或1，4-苯二曱基二異氰酸酯或其混合物、ω，ω，·二異氰酸基-1，4-二乙基苯、153_或“ίο-異氰酸基“·甲基乙基)苯(慣用名：四曱基苯二曱基二異氰酸酯)或其混合物鲁等）、聚異氰酸酯（例如1，3,5-三異氰酸基甲基苯等三異氰酸酯等）。 ^ 上述方香族聚異氰酸酯之例如二異氰酸酯（例如間-伸苯基二異氰酸酯、對-伸苯基二異氰酸酯、4,4，-二苯基曱烷二異氰酸酯、1，5-萘二異氰酸酯、2,4，_或4,4，·二苯基曱烷 •二異氰酸酿或其混合物、2,4-或2,6-伸甲苯基二異氰酸醋 .或其混合物、4,4，·曱苯胺基二異氰酸酯、4,4、二苯基醚二異氰酸酯等）、聚異氰酸酯（例如三苯基甲烷-4,4, 4”_三異氰酸酯、1，3,5-三異氰酸酯苯、2,4,6·三異氰酸酯甲苯等三異 3J8059 18 1374154 氰酸酯，例如4,4，-二苯基曱烷_2 ?，ς s # μ 4 土 τ机ϋ，5,5 ·四異氰酸酯等四異氰酸酯等）。聚異氰酸酯之衍生物，例如上述聚異氰酸酯之二聚物、三聚物（含三聚異氰酸醋環之聚異氰酸醋）、縮二脲二，脲基甲酸酯（allophanate)、二氧化碳和上述聚異氰酸酯單體之反應所得具有2,4,6-氧基二啡基三酮環之聚異氰酸酯、碳化二醯亞胺、脲二酮、聚亞曱基聚苯基聚異氰酸酯（粗製 MDI、聚合MDI)以及粗製TDI等。、 ® 又，聚異氱酸酯之改質物，例如上述聚異氰酸酯或聚異氰酸酯衍生物和下述之低分子量多元醇或低分子量聚月女，係以聚異I酸酯之異氣酸基相較於低分子量多元醇之 -羥基或低分子量聚胺之胺基為過剩之當量比進行反應而得之多元醇改質體或聚胺改質體等。該聚異氰酸酯可單獨或 2種以上併用。 φ (13其他成分本舍明之乳液’除上述醇酸樹脂、聚異氰酸g旨之外，尚可含有對於異氰酸基，具有反應性之活性氫原子（例如經基、羧基、胺基等）之化合物做為其他成分。 -其他冬元_ • 具有經基之化合物，除上述醇酸樹脂之外，尚可含有其他多元醇。其他多元醇並無特別限制，可舉如聚胺甲酸酉旨之製造中所使用之各種多元醇’例如在上述醇酸樹脂項 318059 19 丄 J /Hi JH· 醇(聚醚多元醇、聚分子中至少且右%、聚醚醋多元醇等）和上述一氛酸基對#異氰酸基之含異氰酸基化合物，以異以下二當量比(異氰酸基/經基)為未達1(以09 以下為較佳，例如〇 HW 〇·9 酯多元醇等。 0.7左右）加以反應所得聚胺甲酸士述聚羥基烷’例如異丙《胺等共聚合而得液狀橡料。_ H細和其他之多元醇可覃元醇中，低分子旦J獨或2種以上組合使用。其他之多 ^ ^ ^ 里夕疋醇，例如新戊二醇或1，6-己二醇等烷一.，二乙二醇、二寸一乙一醇、聚乙二醇、二丙二醇、聚 ::;、：四亞甲基_二醇等聚伸C2亦醇、甘油、三 -矿土丙& $戊四醇等多元醇為較佳。這些低分子量多 :醇之分子量，其數平均分子量為62至5〇〇,其中以數平均/刀子量為62至200左右為較佳。又必要時’尚可併用曱醇、乙醇、丙醇類、丁醇類、 2乙基己醇、月桂醇、硬脂醇、2_氫硫基乙醇、聚氧化亞甲基二醇單曱醚等一元醇。、其他夕元醇之比率，例如相對於醇酸樹脂1〇〇重量伤例如為〇，丨至3〇〇重量份，其中，以1至200重量份為較佳’以3至150重量份為更佳（特別以5至1〇〇重量份為最佳）。是有陰缝^性基之仆厶物聚胺甲酸酯醇酸樹脂中，陰離子性基並非必要成分， 22 318059 1374154 但是藉導入陰離子性基，可提升聚胺甲酸酯醇酸樹脂之分政安定性。該陰離子性基，一般多數使用對於陰離子性基和對異氰酸基具有反應活性之氫原子的化合物而導入者。具有陰離子性基之含活性氫原子之化合物並無特別限制，例如含有羧基、續醯基、填酸基、續甜菜驗等含有甜菜鹼構造之基等陰離子性基，以及含有對於異氰酸基具有反應性之活性氫原子之基（例如羥基、胺基等）。上述具有陰離子性基之含活性氫原子化合物之種類並無特別限制，可列舉至少含有〗個陰離子性基及2個以上之活性氫原子之化合物。上述具有羧基之含活性氫原子之化合物，例如2,2 - -羥甲基乙酸、2,2-二羥甲基乳酸、2,2·二羥甲基丙酸、2，孓二羥甲基丁酸、2,2-二羥曱基酪酸、2 2_二經曱基戍經基㈣㈡甲基一酸或二㈣等），例如賴胺酸、精胺酸等二胺基羧酸等。上述具有磺醯基或磺酸基之含活性氫原子化合物之例如N，N-雙（2-羥乙基）-2-胺基乙磺酸、〗，3_伸苯二胺·4,6•二磺酸、二胺基丁磺酸、3,6·二胺基-2_甲苯磺酸、2,4-’二^ 基_5_甲苯石黃酸等。上述具有磷酸基之含活性氫原子化合物之例如2,3•二經基丙基苯基墙酸醋等。上述含有甜菜鹼構造基之含活性氫原子化合物之例如 N·甲基二乙醇胺等3級胺和丙烷磺内酯、^•丁烷磺内醋等反應所得含續基甜菜驗基化合物等。 318059 23 1374154 ，丨與二…陰離子性基之含活性氫原子化合物亦可列舉以環氧乙院或環氳丙,产虱内烷等核氧烷化合物加成而得氣化合物改質體。行疋壤、述’、有陰離子性基之含活性氫原子化合物可單獨或種以上組合使用。上述具有陰離子性基之化合物中，以具有鲮基之含活性氫原子化合物為較佳。 ’、有陰離子性基之化合物之比例，相對於醇酸樹脂 ⑽重量份’例如為1至刚重量份，以3至50重量份為較4土以5至30重里份為更佳。又，具有陰離子性基化合物和聚異氣酸醋之比例’相對於異氰酸酯1〇〇重量份，例如具有陰離子性基化合物為〇1至5〇重量份，以】至重$份為較佳，以3至30重量份左右為更佳。有聚合性某之化合物就提升塗膜物性之觀點，聚胺曱酸酯醇酸掛脂可和具 φ有聚合性基之化合物（例如聚合性不飽和化合物）反應，賦予來自聚合性不飽和化合物及其聚合物之特性。聚合性不飽和化合物可使用具活性氫原子之化合物，將具有聚合性基之（甲基）丙烯酸系成分導入至聚胺曱酸酯醇酸樹脂中。具有活性氫原子之聚合性不飽和化合物，例如含缓基 .化合物[(曱基）丙烯酸、馬來酸、伊康酸等]、含羥基化合物 .赵基乙基（甲基）丙烯酸酯、2-羥基丙基（甲基）丙稀酸酯、2-羥基丁基（甲基）丙烯酸酯等烷二醇單（（甲基）丙烯酸酯）；聚乙二醇單（甲基）丙烯酸酯、聚丙二醇單（甲基）丙稀 3】8059 24 1374154 酉夂酷等（聚）氧化伸C2_4烧二醇單”基）兩婦酸醋；三經甲兴丙烷早(f基)丙烯酸酯、三經甲基丙烷二(甲基)丙烯酸醋、甘油早(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇早（甲基）丙稀㈣、季戍四醇二（甲基）丙稀酸g|'季戍四醇二（甲基）丙稀酸酯、二季戊四醇四（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯等多元醇（甲基）丙烯酸酯；N•羥甲基 (甲基）丙稀醯胺等]、含亞胺基化合物[N_甲胺基乙基（甲基土）丙烯酸酯、第三丁胺基乙基（甲基）丙烯酸酯等]、環氧化合物和羧酸之反應所產生含羥基化合物[二環氧丙基醚型^ 氧樹脂和（甲基）丙歸酸之加成物、環氧丙基（甲基）丙稀酸酯，單緩酸及二㈣中選擇之飽和或不飽和賴之加成物等]。上述不飽和羧酸包括不飽和脂肪酸。這些聚合性不飽和化合物中，分子中含有丨至3個（例如1或2個）起基之化合物為較佳，例如2 ·經乙基（甲基）丙烯酸酯、2-羥丙基（甲基）丙烯酸酯、三羥曱基丙烷單（曱籲基）丙烯酸酯、三羥甲基丙烷二（曱基）丙烯酸酯、甘油單（甲基）丙烯酸酯、甘油二（曱基）丙烯酸酯、季戊四醇單（曱基）丙稀@夂酉曰、季戊四醇一（曱基）丙稀酸醋、季戊四醇三（甲基）丙烯酸酯' 二李戊四醇四（曱基）丙烯酸酯、二季戊四醇五 (甲基）丙烯酸酯等。特別是以分子中含有1個經基之聚合 .性不飽和化合物（例如2-羥乙基（甲基）丙烯酸酯、2_羥丙基 •(甲基）丙烯酸酯、三羥甲基丙烷二（曱基）丙烯酸酯、甘油二 (甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、二季戊四醇五（曱基）丙烯酸酯等）’分子中含有2個羥基之聚合性不飽 25 318059 1374154 礞 ==、二T:性基之含活性氫原子化合物、浔旛占=夕，k些成分僅以含有活性氬原子之反應成分而稱呼）之比例，相對 ” fot ί η夏比（異氰酸基/活性氫原子）為〇.4至 10為且，以0.6至5為較佳，以〇8至5(例為更佳。最佳上料以（即，錢縣/㈣氬料以上及3以下（例如⑽至2.7,以U至2.5為較佳，以1374154 IX. Description of the Invention: [Technical Field] The present invention relates to a polyamine phthalate alkyd resin emulsion and a polyisocyanate hardener which can be dispersed in the emulsion, and can provide an aqueous coating agent (carpentry) A two-liquid-curing aqueous resin composition (such as a coating composition) which is useful for use in water-based primers such as paints and automotive paints, and water-based primers, and uses thereof. [Prior Art] ® Polyamine phthalate resin has excellent adhesion to the substrate, abrasion resistance, impact resistance and mechanical strength, so it is widely used in various coating materials, adhesives or various coatings. The use of the agent, etc. The polyamine phthalate resin-coating is known as an organic solvent-based polyamine phthalate resin coating obtained by dissolving a polyurethane in an organic solvent. However, the organic solvent has a good influence on the human body or the environment. Also, there is a danger of fire. Therefore, in recent years, the concern for environmental sanitation has increased, replacing the organic solvent-based polyamine oxime resin coating, and the aqueous polyamine composed of the polyurethane resin aqueous dispersion of the polyurethane resin dispersed in water. The development of phthalate resin coatings has progressed rapidly. On the other hand, the alkyd resin has a good gloss or water resistance on the surface of the coating film, has a heavy feeling and is low in price, and has been widely used in industrial applications or in general applications since ancient times. For example, it is also used for various applications such as various coating materials, adhesives, or various coating agents, and the emulsification of alkyd resins is also reviewed. In particular, in order to impart added value such as weather resistance or solvent resistance, an amine phthalate alkyd resin emulsion in which an amine phthalate resin is composited has been developed. Japanese Laid-Open Patent Publication No. Hei 6-299117 (Patent Document) discloses a resin having a hairpin of 3 to 250 in a dry, semi-drying oil and/or a fatty acid thereof as an essential component (A). And an oxygen-containing acid (b), an other hydroxy compound (C), and an organic isocyanate compound (D), which are obtained by reacting an aqueous resin, a pigment, and a desiccant with a water-based synthetic resin composition coating composition. In this document, an alkyd resin obtained by a transesterification reaction between a (semi)drying oil and pentaerythritol is used, which is urethane-formed and redispersed in water to carry out chain growth. The compositions are capable of being attacked at normal temperature. Cross-linking, good film drying, heavy feeling, brushing, and no ester bond adjacent to the carboxyl group, so it is also excellent in hydrolysis resistance. However, it takes a long time for the parent to react on A shell. It is impossible to obtain a high-hardness j coating film in a short period of time, and the degree of improvement in water resistance, moist heat resistance, and solvent resistance is not too high. [Japanese Patent Laid-Open No. Hei 6_329892 (Special) Document 2 shows that an alkyd resin (A) having a hydroxyl group of 30 to 250, an oxycarboxylic acid (b), an organic isocyanate (C) and other hydroxy compound (D) are reacted to include an aqueous resin and a hardener. The composition of the thermosetting water-based resin composition is described in the literature. It is described in the literature that a curing agent such as an amine resin or a blocked isocyanuric acid is used to harden and the above-mentioned patent document! The same alkyd resin can be formed with high hardness or various kinds of wealth. A coating film of a long time. However, the composition is used as a hardener for an amine resin or a block of cyanate, and therefore, it must be baked at a normal temperature; and a coating film of high hardness cannot be obtained. Amino acid vinegar-based coating material is the first organic coating material. When applied to inorganic materials such as slate, cement, sand, etc., to ensure the adhesion of 318059 6 ^74154 is strong, Lifting... Polyurethane type resin, etc., θ 'Immersion of soil material, even coating workability, it is necessary to use L = organic solvent. Lay contains a large amount of organic (4) primer, indicating, coating workability, hardening Film after The performance, but also the sound, the volatilization of the "the author made (four) Kang's bad shadows.. The adverse effects and other issues', so look forward to the emergence of water-based primer group - ♦ Li literature 1: Japanese Patent Special Open 6_29911? (Patent Application Scope, Paragraph No. [0011] [0047], Example) Patent Document 2: Japanese Patent Laid-Open No. Hei No. Hei 6 329892 (Application No., paragraph number [0028] [〇〇 34], implementation EXAMPLES - SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) Accordingly, an object of the present invention is to provide a property in which a polyamine phthalate resin and an alcohol- eucalyptus can be effectively exhibited in a short period of time. The second liquid hardening type water-based resin composition. Another object of the present invention is to provide a two-liquid hardening type which has excellent mechanical properties such as hardness or wear resistance, and high water resistance, moist heat resistance and solvent resistance. Aqueous resin composition. Another object of the present invention is to provide a polyamine phthalate alkyd resin emulsion as a main agent, and the mutual solubility between the main agent and the hardener is excellent, and at the same time, when the film is formed, the thick feeling and the coating workability are both An excellent two-liquid hardening type aqueous resin composition. A further object of the present invention is to provide a two-part hard water-based resin composition which can be used to adjust the properties of the coating film by providing an alkyd resin 7 318059 1374154 t in the urethane component. 1 Still another object of the present invention is to provide a two-liquid hardening which is excellent in the joint property and durability of a machine material covering material such as slate, cement, mortar, etc., and the adhesion between the top lacquer material and the durability. Aqueous resin composition. Another object of the present invention is to provide a two-liquid-curable aqueous resin composition (or coating) which is mainly used for woodworking paints, automotive paints, water-based primers, and the like. In order to achieve the above objectives, it has been found that a polyurethane resin having an active hydrogen atom in the group D knife and a specific polyisocyanate as a hardener can be used. A two-liquid hardening type aqueous resin composition which is effective in a short period of time and which has excellent hardness or wear resistance and mechanical properties, and has high water resistance, moist heat resistance and solvent resistance. And complete this hair Lu Ming. That is, the aqueous resin composition (two-liquid-curing aqueous resin composition) of the present invention comprises a polyurethane urethane resin emulsion (A) having an active hydrogen atom in the molecule and is dispersible in the emulsion (A). A hardener (B) composed of a polyisocyanate. The above polyamine phthalate alkyd resin emulsion (A) may be an emulsion obtained by a reaction between an alkyd resin having a hydroxyl group of 30 to 250 and a polyisocyanate. • The active hydrogen atom of the water-free phthalic acid anhydride resin emulsion (A), for example, may be derived from a hydrogen atom of a light base. The above composition may further contain a metal desiccant (c), and the alkyd resin component of the polyurethane urethane resin emulsion (A) may contain unsaturated 318059 8 1374154 (Effect of the invention) In the present invention, The polyurethane foaming agent and the specific hardening agent made of polyisocyanuric acid can effectively exhibit the properties of both the polyurethane resin and the alkyd resin in a short period of time. It also has excellent mechanical properties such as hardness and wear resistance, as well as water resistance, damp heat resistance and solvent resistance. Further, even if a polyurethane urethane resin emulsion is used as a main component, the mutual solubility between the main component and the curing agent is excellent, and the feeling of heavyness or coating workability at the time of forming a coating film is also excellent. Further, the alkyd resin component in the urethane component can be adjusted to an arbitrary ratio to control the film properties. Therefore, the two-liquid hardening type-aqueous resin composition of the present invention is used as a water-based paint for woodworking paints, automotive paints, and water-based primers. [Embodiment] The two-liquid-curing aqueous resin composition of the present invention comprises a polyurethane urethane resin emulsion (A) having an active hydrogen atom in a molecule, and a polyisocyanate dispersible in the emulsion (A). The curing agent (B) is not only excellent in adhesion to the substrate, but also has excellent coating properties (especially high hardness properties) and water resistance. Carboxymate oxime; fef wax emulsion (A), polyamine phthalate alkyd resin emulsion (A) has active hydrogen in the molecule. Atom (such as hydrogen atom of hydroxyl group, etc.), at least polyisocyanate, and It is obtained by reacting an alkyd resin which is a compound (polyol component) having a reactive active hydrogen atom of an isocyanate group. The hydroxy acid 318059 1374154 of the alkyd resin of the present invention has a base price of about 30 to 200, and the alkyd resin having the hydroxyl value is used as a polyol component of a polyurethane urethane resin emulsion. Further, in addition to the alkyd resin, other components having a reactive active hydrogen atom to the isocyanate group may also be used. The active hydrogen atom may be derived from at least one of an alkyd resin, a modified polyisocyanate having an active hydrogen atom, a chain extender, and other components. (U alkyd rouge. The alkyd resin may be a polyester obtained from a condensation reaction of a polycarboxylic acid containing a long-chain aliphatic polycarboxylic acid and a polyterpene alcohol (an oil-free alkyd resin), but using a fat or a fatty acid. The polyester (oil-modified alkyd resin) is preferably produced. The alkyd resin, also known as the oil-modified polyester, contains at least one oil selected from the group consisting of fats and oils and pigeon or unsaturated fatty acids. The polyester obtained by the reaction of the polyol 'is selected from the oil component of at least one of the oil and the saturated or unsaturated higher fatty acid and the polyester obtained by the reaction of the polyol and the polycarboxylic acid. Further, in the reaction, the esterification reaction is included. Also includes transesterification reactions (such as transesterification between fats and oils (triglycerides, etc.) and polyols). Polyol polyols include various polyols used in the manufacture of polyesters, such as • aliphatic diols [alkane Alcohol (ethylene glycol, propylene glycol, trimethylene glycol, iota, 2-butanediol, 1,3-butanediol, iota, 4-butanediol, 1,5-pentanediol, 3-曱Base-1,5· sterol, 2,2-dimethyl-anthracene, 3-propanediol, neopentyl '1,6-hexanediol, 2,2-diethyl-1,3-propanediol, 3,3-dihydroxydecylheptane, 2-ethyl-2-butyl 318059 1374154 1,3-1,3-propanediol , U2-dodecanediol, U8_octadecanediol, etc.), dilute diol (2-butane_M_diol, 2,6•dimethylisosapride J-fermented, etc.) ), poly C2.4 thiol diol (diethylene glycol, triethylene glycol, average: the amount of polyethylene glycol, dipropylene glycol average of 15 〇 to 4 _:: 15 〇 to 4 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Alkanediols, "Chemical bismuth, or its C2.4 epoxy oxime adduct, etc.", aromatic diols such as benzene glycols, aromatic diols such as xylene glycol, - formic acid Poly(ethylene glycol) and other polyglycol diols, bisphenol A, bisphenol s, bisphenol double ages or its (: 2·4 epoxy burnt adduct, etc.), more than three valences: family polyols ( Glycerin, sorbitol, trimethylol bromide, hydrazine ==*2-transmethylmethyl#propanediol, 2,4·diyl; methyl group), 2,2-dual base Base)·3_ aliphatic alcohols such as butanol (such as pentaerythritol such as alcohol, pentaerythritol or dipentaerythritol), sugar alcohols 2: pear glycoside, xylitol, D·mannitol, etc.). Ge:: Combinations of the above and above. Among them, 'polyols of more than three valences: glycerol = trimethyl ketone, pentaerythritol, dipentaerythritol and 7 liters of alcohol are preferred. The oil component of spider oil contains oil and vegetable oil (cotton oil) , linseed oil, soybean oil, rice oil saturated or unsaturated fatty acids. For example, 'yellow, castor seed oil, dehydrated castor seed oil, red corn oil, flax oil, hollyhock oil, rice J2 318059 1374154 Oyster sauce, hemp seed oil, rapeseed oil, groundnut oil, coconut oil, palm oil, kapok oil, almond oil, olive oil, tall oil, perilla oil, tung oil, etc.), animal oil (tallow, lard, sheep oil) , goat oil, horse oil, chicken oil, turkey oil, etc.), fish oil (salmon oil, solution 'fish oil, oyster sauce, tongue fish oil, flounder oil, fish oil, squid oil, fish oil, etc.), or Its nitriding oil, etc. The upper oily moon can be used alone or in combination of two or more. Among the above-mentioned fats and oils, the plants are made of special linseed oil, perilla seed oil, tung oil, dehydrated castor seed oil, oil, soybean oil, cottonseed oil, safflower oil, jade oil, sesame oil, oil seed oil, Semi-drying oil such as rice bran oil, palm oil, non-drying oil, etc. are preferred. - Straight or branched saturated C8 of saturated fatty acids such as caprylic acid, citric acid, citric acid, lauric acid, nutmeg-capric acid, palmitic acid, heptadecanoic acid, stearic acid, arachidic acid, behenic acid, etc. 24 fatty acids, etc. Examples of unsaturated fatty acids such as myristate oleic acid, palmitoleic acid, petroselinic acid, oleic acid, trans-p-octadecenoic acid, linoleic acid, linoleic acid, tungstic acid, oleic acid, peanut oleic acid, Erucic acid is called a linear or branched unsaturated C8 24 fatty acid or the like. The fatty acid may have a substituent such as a hydroxyl group. A fatty acid having a hydroxyl group such as ricinoleic acid, citric acid, dihydroxystearic acid or the like which is a main component of g-hemp seed oil. The fatty acid may also be a fatty acid obtained by saponification or the like, such as a diene fatty acid obtained from dehydrated lotus seed oil, or dehydrated castor seed oil, linseed oil, soybean oil, red flower seed oil, coconut oil. The obtained fatty acid (for example, dehydrated kenaf seed oil fatty acid - linseed oil fatty acid, soybean oil fatty acid, safflower oil fatty acid, coconut oil fatty acid, etc.). These saturated or unsaturated fatty acids may be used singly or in combination of two or more kinds. Among the fatty acids, fatty acids 318059 1374154 (oleic acid, linoleic acid, linoleic acid, etc.) derived from a dry oil or a semi-drying oil, or unsaturated fatty acids such as high diene fatty acids are preferred. In addition, in the fatty acid, fatty acids (lauric acid, citric acid, octanoic acid, myristic acid, etc.) obtained from non-drying oils, or fatty acids containing more fatty acids such as raspberry oil and fatty acids, can inhibit the coloration of the resin. It is better. In particular, when an oil component having an unsaturated bond such as a dry oil or a semi-drying oil or an unsaturated fatty acid is used as the oil component, the unsaturated bond contained in these oil components and the oxygen in the air undergo an oxidative hardening reaction to harden. , in order to form a more excellent coating film. The oxidative hardening reaction is slowly reacted by using oxygen in the air, but the following metal drier or desiccant (C) may be added to promote the reaction. In other words, by combining a polyamine phthalate alkyd resin emulsion (A) and a metal desiccant (c) having an alkyd resin component modified with an unsaturated fatty acid, it is possible to form a coating having excellent properties such as hardness in a short time. membrane. • The polycarboxylic acid polycarboxylic acid includes various polycarboxylic acids used in the production of polyesters, such as aromatic dicarboxylic acids or their anhydrides (terephthalic acid, isophthalic acid, phthalic acid, o-paraic acid anhydride, etc.) ), an alicyclic dicarboxylic acid or an anhydride thereof (tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic acid, dicarboxylic anhydride, mercapto tetrahydrogen Phthalic acid, chlorenic anhydride, 5-northene-2,3-dicarboxylic anhydride, etc., aliphatic dicarboxylic acid or its anhydride (succinic acid, succinic anhydride, adipic acid, azelaic acid) , sebacic acid, etc. Com, sulphuric acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, 14 318059 ^/4154 fumaric acid, fumarate, etc., unsaturated bis(tetra), etc. Acid, stupid three: phthalic anhydride benzene: formic acid, pyromellitic acid liver, mercaptocyclohexene triacid, carboxy oxime mono-tetraalkyl ester and the like. These polycarboxylic acids may be used singly or in combination of two or more kinds of acids, and the like is usually an aromatic dicarboxylic acid such as isophthalic acid or terephthalic acid. — Modification of alkyd resin, in addition to the above-mentioned fatty acid or polybasic (IV), for example, benzoic acid, a material cage-Γ«. ^ An aromatic monocarboxylic acid such as dibutyl benzoic acid is used as a carboxylic acid component. ^ The alkyd resin can be produced by a conventional method, for example, a fatty acid method using a fatty acid as a raw material, and a method of exchanging fats and oils as a raw material, and performing a monoglycerin method. In the fatty acid method, for example, a fatty acid, a polyhydric alcohol, and a polybasic acid are used as a raw material, and a sulfonation reaction is carried out at a temperature of from 22 to 25 (rc) for 6 to 10,000 hours. In the esterification reaction, a polar group may be added. A small amount of a vinegar catalyst such as mono-n-butyltin oxide. The proportion of the acetal catalyst may be, for example, G._(U s (U parts by weight, > to use 0.0001) with respect to 1 GG parts by weight of the oil component. 〇〇〇重量重量重量左为为为为为为为为。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 Etc.) ^ In the single glycerin method, for example, in the presence of an inert catalyst, the oil and the polyol are given at 23 (^25 (about TC, for 2 to 3 hours of vinegar exchange reaction, followed by 'addition of polyol) If necessary, add a plurality of polyacids, and carry out the acetation reaction at a temperature of 22 to 25 (TC). In the transesterification reaction, a very small amount such as oxyhydroxide, potassium hydroxide, hydrazine hydroxide, sodium acetate may be added. Alkaline catalyst such as lithium acetate. 3) 8059 15 1374154 Alkyd resin t is the ratio of each component The ratio of the ratio of the oil to the male knives and the polyol component and the cerium carboxylic acid (weight ratio) is preferably from 1/1 to 1/5' in the range of 5/1 to 1/3. 4/1 to 】/] too much from 3/1 to 1.5/1 is preferred. '", (the ratio of the specific polyol component is, for example, 5 to 200 parts by weight based on 1 part by weight of the oil component, It is preferably from 1 to 1 part by weight, more preferably from - to 70 parts by weight (particularly from 20 to 5 parts by weight), to the ratio of the polybasic acid to the oil component. The parts by weight to the parts by weight are preferably 1 part by weight, more preferably 5 to 3 parts by weight (particularly preferably 10 to 4 parts by weight). The alkyd resin may have a hydroxyl group and / or a carboxyl group, but as a polyol component, it has at least a radical. The alkyd resin may be on its branch and a secondary group, or may have such a group at both ends. Hydroxy. The base price of the alkyd resin is 1 lb (potassium lactate mg/g), for example, 3 to 250, of which 40 to 230 A is preferred, and 5 to 22 is Better (from 60 to 200) Good). £_2) Polyisocyanate polyisocyanate is not particularly limited as long as the molecule is φ red, and ± has more than two isocyanate groups. Usually, 帛% | t is more used in the manufacture of polyurethanes and the like. Isocyanate S曰, such as aliphatic polyisocyanurized ^ ^ ^ _ know, alicyclic polyisocyanate, aromatic acid anti-stolen from low molecular weight polyisocyanate, prepolymer , Sanjuli shy "chaos & Saskatchewan, diketone oxime and derivatives or modified substances of the polyisocyanuric acid. One an rainbow and κ 八仇16 318059 1374154 and 'polyisocyanate' is in the molecule A general term for a compound having a plurality of isocyanato groups, including diphenylmethane diisocyanate, tolyl diisoxanoic acid brewing, benzodimethylisocyanuric acid, and the like, and a low molecular polyisomeric acid Derivatives, modified materials, prepolymers and the like obtained from isocyanate. The "polyisocyanuric acid vinegar derivative" 75 refers to a general term for a compound obtained by low molecular weight polyisocyanate, including a modified substance, a prepolymer, and the like. The "polyisocyanate modified product" refers to a reactant obtained by modifying a low molecular polyisocyanate or a prepolymer. The above aliphatic polyisocyanate, such as diisocyanate (for example, trimethylene diisocyanate, 1,2-propyl diisocyanate, tetramethylene diisocyanate, 1,2-butyl butyl diisocyanate, 2,3_butyl butyl diiso-acid vinegar, butyl diisocyanate, hexamethylene diisocyanate, pentamethylene diiso Cyanate, 2,4,4 or 2,2,4. Methyl hexamethylene diisocyanate or the like, such as alkyl diisocyanate, 2,6-diisocyanatomethyl hexanoate, etc., polyisocyanate (for example, lysine triisocyanate, M, 8) · Triisocyanatooctane, 1,6,11-triisocyanatodec-decyl, oxime, 8 • diisocyanate _4 • isocyanatomethyl octyl octane, 1, 3, 6. An alkyltriisocyanate such as triisocyanatohexane or 2,5,7-tridecyl u-diisocyanate-5-isocyanatomethyloctane or the like). The above alicyclic polyisocyanate is, for example, a diisocyanate (for example, 1,3-cyclopentanyl diisocyanate, M. cyclohexane, diiso-octa(tetra) n-cyclohexamethylene cyanide, 3. isocyanatomethyl _3,5,5•Trimethylcyclohexyl isophthalide = • (common name: isophorone diisocyanate), 4,4,-methylene double (rings are beautiful • cyanate), 曱2·4. Cyclohexene diisocyanate, thiol 2,6·cyclohexene diisocyanate, 1,3- or Μ·bis(isocyanatononyl)cyclohexane (usually used) :: Hydrogenated diphenyl phenyl diisocyanate) or a mixture thereof, norbornane diisocyanide 318059 1374154 acid vinegar, etc., although polyisocyanate (for example, i,3,5-triisocyanate cyclohexane, 】 ,3,5_ tridecyl isocyanatocyclohexane: ^, 2_(3 · isocyanatopropyl) 2,5·di(isocyanatodecyl)-bicyclo[2·2.1] Gengyuan , Μ·isocyanatopropyl)_2 6_bis(isochalcylmethyl)-bicyclo(2.2.1)heptane, 3—(3·isocyanatopropyl)_2,5_二.( Iso, acid methyl)-bicyclo[2.2"]heptane, 5_(2•isoacylethyl)_2·isocyanatomethyl-3-(3-isocyanatopropyl)·bicyclic [2 21 ]Heptane, 6_(2·isocyanatoethyl)-2-isocyanatomethyl-3-3♦isocyanatopropyl)-bicyclo[2.2.1]heptane, 5-(2-iso Cyanate ethyl) 2 - isocyanatomethyl 2 - (3 - acetophenoxypropyl) - bicyclo [2.2.1] heptane, 6 - (2 - isocyanatoethyl) 2 - Oleic acid decyl-2-(3-isocyanatopropyl)-bicyclo[2 21]heptane and other triiso-acids - esters, etc.). 'The above aromatic aliphatic polyisocyanate such as diisocyanate (for example, 1,3- or 1,4-benzenedidecyl diisocyanate or a mixture thereof, ω, ω, diisocyanyl-1,4-diethyl) Benzene, 153_ or "ίο-isocyanato" methyl ethyl) benzene (common name: tetradecyl phenyldidecyl diisocyanate) or a mixture thereof, polyisocyanate (for example 1,3,5 - a triisocyanate such as triisocyanatomethylbenzene or the like). ^ such as a di-isocyanate of the above-mentioned aromatic polyisocyanate (for example, meta-phenylene diisocyanate, p-phenylene diisocyanate, 4,4,-diphenyldecane diisocyanate, 1,5-naphthalene diisocyanate, 2,4,_ or 4,4,-diphenylnonane•diisocyanate or a mixture thereof, 2,4- or 2,6-extended tolyldiisocyanate or a mixture thereof, 4, 4, · anthranilyl diisocyanate, 4, 4, diphenyl ether diisocyanate, etc.), polyisocyanate (for example, triphenylmethane-4,4,4"-triisocyanate, 1,3,5-triisocyanate benzene , 2,4,6·triisocyanate toluene, etc. Triiso 3J8059 18 1374154 Cyanate ester, such as 4,4,-diphenylnonane-2, ς s # μ 4 土τ机ϋ, 5,5 ·4 a tetraisocyanate such as an isocyanate, etc.) a derivative of a polyisocyanate such as a dimer of a polyisocyanate, a trimer (polyisocyanuric acid containing a trimeric isocyanate ring), a biuret II, a urea group A Polyisocyanate having 2,4,6-oxydimorphyltrione ring, carbodiimide obtained by reaction of allophanate, carbon dioxide and the above polyisocyanate monomer Ureadione, polyarylene polyphenyl polyisocyanate (crude MDI, polymeric MDI), and crude TDI, etc., ®, a modified product of polyisophthalic acid ester, such as the above polyisocyanate or polyisocyanate derivative, and the following The low molecular weight polyol or the low molecular weight polymoon female is reacted with an isocratic acid group of the polyisomeric acid ester in an excess equivalent ratio of the hydroxyl group of the low molecular weight polyol or the amine group of the low molecular weight polyamine. A polyol modified body, a polyamine modified body, etc. The polyisocyanate may be used singly or in combination of two or more kinds. φ (13 other components of the present invention) In addition to the above alkyd resin and polyisocyanate A compound having an active hydrogen atom (for example, a trans group, a carboxyl group, an amine group, etc.) which is reactive with an isocyanate group may be contained as another component. - Other winter elements _ • A compound having a trans group, in addition to the above alcohol Other than the acid resin, other polyols may be contained. Other polyols are not particularly limited, and various polyols used in the manufacture of polyurethanes are exemplified, for example, in the above alkyd resin item 318059 19 丄J / Hi JH· alcohol ( a polyether polyol, at least a right % of a polymolecular group, a polyether vinegar polyol, etc.) and an isocyanate group-containing isocyanate group-containing isocyanate group-containing compound having an equivalent ratio of two or less (isocyanate) The base/base group is less than 1 (preferably below 09, for example, 〇HW 〇·9 ester polyol, etc., about 0.7), and the resulting polyamine formic acid polyhydroxyalkane such as isopropyl "amine" Polymerized to obtain liquid rubber. _ H fine and other polyols can be used in the oxime alcohol, low molecular weight J alone or in combination of two or more. Others ^ ^ ^ sinyl alcohol, such as neopentyl glycol Or 1,6-hexanediol, etc., a diethylene glycol, a two-inch monoethyl alcohol, a polyethylene glycol, a dipropylene glycol, a poly::;, a tetramethylene-diol, etc. Polyols such as alcohol, glycerin, tri-mineral C & pentaerythritol are preferred. These low molecular weight poly-molecular weights have a number average molecular weight of 62 to 5 Å, and preferably a number average/knife amount of about 62 to 200. When necessary, 'can be used together with decyl alcohol, ethanol, propanol, butanol, 2-ethylhexanol, lauryl alcohol, stearyl alcohol, 2-hydrothioethyl alcohol, polyoxymethylene glycol monoterpene ether Wait for a monol. The ratio of other oxime alcohols, for example, 〇〇 to 〇〇, to 〇〇 to 3 parts by weight relative to the weight of the alkyd resin, wherein 1 to 200 parts by weight is preferably '3 to 150 parts by weight. More preferably (especially 5 to 1 part by weight is optimal). In the urethane resin having a scabbard base, the anionic group is not an essential component, 22 318059 1374154 However, by introducing an anionic group, the fraction of the polyurethane resin can be improved. Political stability. Most of the anionic group is introduced by using a compound having an anionic group and a hydrogen atom reactive toward an isocyanate group. The active hydrogen atom-containing compound having an anionic group is not particularly limited, and examples thereof include an anionic group such as a carboxyl group-containing group, a fluorenyl group, an acid group, a beet test, and the like, and an isocyanate group. a group having a reactive active hydrogen atom (e.g., a hydroxyl group, an amine group, etc.). The type of the active hydrogen atom-containing compound having an anionic group is not particularly limited, and examples thereof include a compound containing at least one anionic group and two or more active hydrogen atoms. The above-mentioned compound having an active hydrogen atom having a carboxyl group, for example, 2,2-hydroxymethylacetic acid, 2,2-dimethylollactic acid, 2,2·dimethylolpropionic acid, 2,nonyldimethylol Butyric acid, 2,2-dihydroxyindenyl butyric acid, 2 2 —di-fluorenyl hydrazino, phenyl (mono)methyl-acid or di(tetra), etc., such as diaminic acid, arginine, etc. The above-mentioned active hydrogen atom-containing compound having a sulfonyl group or a sulfonic acid group, for example, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid, ???, 3-phenylene diamine·4,6 • Disulfonic acid, diaminobutanesulfonic acid, 3,6·diamino-2-toluenesulfonic acid, 2,4-'diyl-5_tolueneic acid, and the like. The above-mentioned active hydrogen atom-containing compound having a phosphoric acid group, for example, 2,3•dipropyl phenyl phenolic acid vinegar or the like. The active-containing hydrogen atom-containing compound containing a betaine structural group, such as N-methyldiethanolamine, a tertiary amine such as N-methyldiethanolamine, a propane sultone, a butane sulfonate or the like, and a hydrazine-containing compound. 318059 23 1374154, an active hydrogen atom-containing compound of an anionic group, and a compound of a sulfonium compound such as a thiophene or a sulfonium alkane can be added to obtain a gas compound modified body. The active hydrogen atom-containing compound having an anionic group may be used singly or in combination of two or more kinds. Among the above compounds having an anionic group, a compound having an active hydrogen atom having a mercapto group is preferred. The ratio of the compound having an anionic group is preferably from 3 to 50 parts by weight, based on the weight of the alkyd resin (10) by weight, of from 3 to 50 parts by weight, more preferably from 5 to 30 parts by weight. Further, the ratio of the anionic group compound and the polyisocyanuric acid vinegar is preferably from 1 to 5 parts by weight, based on 1 part by weight of the isocyanate, of the anionic group. It is preferably from about 3 to 30 parts by weight. From the viewpoint of improving the physical properties of the coating film by a compound having a polymerizable property, the polyamine phthalate alkyd resin can be reacted with a compound having a polymerizable group (for example, a polymerizable unsaturated compound) to impart a polymerizable unsaturated compound. And the properties of its polymers. The polymerizable unsaturated compound can introduce a (meth)acrylic component having a polymerizable group into a polyamine phthalate alkyd resin by using a compound having an active hydrogen atom. A polymerizable unsaturated compound having an active hydrogen atom, for example, a suspending group, a compound [(indenyl)acrylic acid, maleic acid, itaconic acid, etc.], a hydroxyl group-containing compound, Zhaoki ethyl (meth) acrylate, 2-hydroxyl group Alkanediol mono((meth)acrylate) such as propyl (meth) acrylate or 2-hydroxybutyl (meth) acrylate; polyethylene glycol mono (meth) acrylate, polypropylene glycol Mono (methyl) propylene 3] 8059 24 1374154 酉夂 cool et al (poly) oxidized extension C2_4 glycerol mono" base) two women's vinegar; three by Jiaxing propane early (f-based) acrylate, three classics Propane di(meth)acrylic acid vinegar, glycerol early (meth) acrylate, glycerol di(meth) acrylate, pentaerythritol early (methyl) propylene (tetra), quaternary tetraol di(methyl) acrylate g|'polyol (meth) acrylate such as quaternary tetraol di(methyl) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate; N• hydroxymethyl Base (methyl) acrylamide, etc.], an imine-containing compound [N-methylaminoethyl (methyl) acrylate, The addition of tributylaminoethyl (meth) acrylate, etc.], the reaction of an epoxy compound and a carboxylic acid to produce a hydroxyl group-containing compound [diepoxypropyl ether type oxygen resin and (meth) acridine acid addition a substance, a glycidyl (meth) acrylate, a mono-salt acid, and a saturated or unsaturated-based adduct selected from the group consisting of the above-mentioned unsaturated carboxylic acids, including unsaturated fatty acids. Among the saturated compounds, a compound having 丨 to 3 (for example, 1 or 2) groups in the molecule is preferable, for example, 2 · ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate , trihydroxymercaptopropane mono(indolyl) acrylate, trimethylolpropane bis(indenyl) acrylate, glycerol mono(meth) acrylate, glycerol di(decyl) acrylate, pentaerythritol mono (曱) Base) propylene@夂酉曰, pentaerythritol-(mercapto)acrylic acid vinegar, pentaerythritol tris(meth)acrylate 'dipentaerythritol tetrakis(meth)acrylate, dipentaerythritol penta(meth)acrylate Ester, etc., especially in the molecule containing one base group. a compound (for example, 2-hydroxyethyl (meth) acrylate, 2- hydroxypropyl • (meth) acrylate, trimethylolpropane bis(indenyl) acrylate, glycerol di(meth) acrylate, Pentaerythritol tri(meth)acrylate, dipentaerythritol penta(indenyl) acrylate, etc. 'Polymeric unsaturated in the molecule containing two hydroxyl groups 25 318059 1374154 礞==, two T: group containing active hydrogen atom compound浔幡浔幡夕夕夕夕夕夕夕夕夕夕夕夕夕夕夕夕些些些 fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo fo Preferably, from 0.6 to 5, and from 8 to 5 (for example, better. The best loading is (ie, Qianxian/(iv) argon above and below 3 (eg (10) to 2.7, U to 2.5) Good

L2至2.3左右為更佳)範圍。在該範圍時，可藉遊離之里亂酸基，將聚胺T酸S旨預聚物在水分散後，增長其鍵長:、水分散後之聚胺甲酸醋醇酸樹脂成分之分子量，隨其目、的之用途而可任意調控。特別在需要高分子量之樹脂成分時，可加長鏈長而簡單地製成均勾之分散體而甚理想。 <製造聚胺甲酸酿醇酸樹脂之方法並無特別限制，例如可採用慣时法（大容量反m容液反應法等）反應而製成。大容量反應法’例如在無溶劑存在下，氮氣流中將聚異氰酸酯和上述含有活性氫原子之反應成分，在4〇至 85 C之反應溫度，反應i至24小時，以】至8小時左右為較佳。該反應通常多在攪拌聚異氰酸酯之同時，添加上述含有活性氫原子之反應成分而使其反應。 ^ 溶液反應法中，例如對於反應惰性之溶劑（有機溶劑及 -/或不具有活性氢原子之聚合性不飽和化合物）之存在下， .將聚異氰酸酯和含有活性氫原子之反應成分，在2〇至卯 C之反應溫度（4〇至80°C為較佳），反應1至24小時（1至 8小時為較佳）左右。又，含有醇酸樹脂成分之聚胺曱酸酯 27 318059 1^74154 預聚物之製’㈣容易調控反應性及黏度之溶液反應法為較佳。溶劑 —有機溶劑並無特別限制，可使用對於異氰酸基為惰性之溶劑，例如酮類（丙酮、曱基乙基酮、曱基異丁基酮、4_ 曱土 2戊鲷、環己酮等）、酯類（乙酸乙酯、乙酸丁酯、乙酸異丁醋、1·田条盆工# a , 如 T乳暴丙基·2·乙酸酯、3-曱氧基丁基乙酸酯等)/方香族烴類（苯、曱苯、二？苯等）、脂環族烴類（環己烷等）知肪族蛵類（己烷、異辛烷等）、醚類（二噁烷、四氫呋溶纖素類或卡必醇類（乙二醇單甲醚乙酸酯、乙一醇單乙醚乙酸酯、乙二醇單丁醚乙酸酯、乙二醇二曱醚、乙醇一乙驗、乙二醇二丁鍵、二乙二醇單甲驗乙酸醋、二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯、二乙二醇:曱喊、二乙二醇二乙峻、二乙二醇二丁_、丙二醇.單甲鱗乙酸醋、丙二醇單乙_乙酸醋、二丙二醇二甲驗、三 ^二醇丁基甲_'四乙二醇二甲越、聚乙二醇二甲醚、2,2,4_ :甲基-1’3·戊二醇二異丁酯、三乙二醇雙2·乙基己酸酯 )、含氮溶劑（例如Nm各㈣、Ν.乙基t各统酮、 N-甲基己内醯胺等。該溶劑可單獨或2種以上之混合溶劑使用。較佳之有機溶劑為容易去除之低沸A range of L2 to 2.3 is better). In this range, the polyamine T acid S prepolymer can be dispersed in water by the free acid group, and the bond length can be increased: the molecular weight of the polyurethane resin component after water dispersion, It can be arbitrarily regulated depending on its purpose. In particular, when a high molecular weight resin component is required, it is preferable to lengthen the chain length and simply form a uniform dispersion. < The method for producing the polyamic acid-brown alkyd resin is not particularly limited, and for example, it can be produced by a reaction using a conventional method (large-capacity inverse m-liquid reaction method, etc.). Large-capacity reaction method, for example, in the presence of a solvent, a polyisocyanate and the above-mentioned reactive component containing an active hydrogen atom in a nitrogen stream are reacted at a reaction temperature of 4 to 85 C for i to 24 hours, to about 8 hours. It is better. This reaction is usually carried out by adding the above-mentioned reaction component containing an active hydrogen atom while stirring the polyisocyanate. ^ In the solution reaction method, for example, in the presence of a solvent inert to the reaction (organic solvent and/or a polymerizable unsaturated compound having no active hydrogen atom), the polyisocyanate and the reactive component containing the active hydrogen atom are in 2 The reaction temperature of 〇C to 卯C (4 〇 to 80 ° C is preferred), and the reaction is about 1 to 24 hours (1 to 8 hours is preferred). Further, a polyamine phthalate containing an alkyd resin component is produced by a solution of a prepolymer which is easy to adjust the reactivity and viscosity. The solvent-organic solvent is not particularly limited, and a solvent inert to an isocyanate group such as a ketone (acetone, mercaptoethyl ketone, decyl isobutyl ketone, 4 曱 2 pentane, cyclohexanone) may be used. Etc.), esters (ethyl acetate, butyl acetate, isobutyl acetonate, 1 · field pots # a , such as T-lactyl propyl · 2 · acetate, 3-decyloxybutyl acetate Ester, etc.) / Fangxiang hydrocarbons (benzene, toluene, diphenyl, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aliphatic steroids (hexane, isooctane, etc.), ethers ( Dioxane, tetrahydrofurolysin or carbitol (ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol dioxime) Ether, ethanol, ethyl acetate, ethylene glycol dibutyl bond, diethylene glycol monoacetic acid acetate, glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol: shout , diethylene glycol diethylene sulphate, diethylene glycol dibutyl _, propylene glycol, monomethyl sulphate vinegar, propylene glycol monoethyl acetate vinegar, dipropylene glycol dimethyl sulphate, tri diol butyl _ _ tetraethylene glycol Jia Yue, polyethylene glycol dimethyl ether, 2, 2,4_: methyl-1'3·pentanediol diisobutyl ester, triethylene glycol di-2-ethylhexanoate), nitrogen-containing solvent (for example, Nm each (four), Ν.ethyl t decyl ketone , N-methyl caprolactam, etc. The solvent may be used singly or in combination of two or more. Preferred organic solvents are low boiling which are easy to remove.

如酮類（丙酮、甲基乙其帕田# w ^ J 7…缺乙基酮、甲基異丁基酮等）、醋類(乙酸乙酉曰、乙—酸丁醋等）、_(二健、四氣。夫。南等）、芳香族烴類(甲本專)寺。有機溶劑以使用丙酮、甲基乙基酮、甲 318059 28 1374154 基）丙烯酸酯等。這些化合物可單獨或2種以上併用。較佳化合物之例如芳香族乙烯（苯乙烯、二乙烯苯等）、丙烯腈^ (甲基）丙烯酸CK10烷基酯（甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等）、乙二醇二（甲基）丙烯酸酯、丁二醇二（甲基）丙烯酸酯、三羥曱基丙烷三（甲基） =烯酸酯、季戊四醇四（甲基）丙烯酸酯、（甲基）丙烯酸稀^ 酯等。形成硬質皮膜時，惰性化合物以使用苯乙烯、二乙烯苯、曱基丙烯酸甲酯、乙二醇二甲基丙烯酸酯、丁二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、甲基丙烯酸烯丙酉旨為較多。反應中’隨必要亦可使用例如胺系觸媒（三級胺等）、錫系觸媒（有機錫化合物等）、鉛系觸媒等常用之胺曱酸酯化觸媒、醌系、氫醌系、酚系等自由基聚合抑制劑。又，也可利用例如蒸餾或萃取等周知方法，從反應生成物中去除聚異氰酸酯等未反應成分。又，於具有陰離子性基之聚胺甲酸酯酸醇預聚物之製造中，在適當階段（反應前’反應後或下述之水分散過程）中’亦可添加胺類（例如三曱胺、三乙胺、三正丙胺、三丁胺、二異丙基乙胺、三苯胺、2-二曱胺基乙醇、三乙醇胺、一曱基丙醇胺、：N-曱基六氫吡啶等）、無機鹼（例如氫氧化鉀、氫氧化鈉等鹼金屬氫氧化物、氨等）等中和劑，中和陰離子性基而形成鹽。該中和劑之添加量，相對於陰離子性 30 318059 1374154 基1當量，例如為0.6至1.2當量，07至M當量為較佳以0.8至1當量左右為更佳。 • 鏈增長劑然後，為獲得聚胺曱酸酯醇酸樹脂乳液（A)，必要時將聚胺甲酸酯酸醇預聚物和溶劑（惰性不飽和化合物及/或有機溶诏）一起分散在水中而得水分散物。又，具有陰離子性基之聚胺曱酸酯酸醇預聚物可使用上述中和劑調製水分散物。又，當聚胺甲酸醋酸醇預聚物含有異氰酸基時，可在水中與鏈增長劑（多胺及/或水）反應。藉該反應，末端具有異氰酸基之聚胺甲酸㈣醇預聚物可因鏈增長劑而形成鍵 ^ ^之聚胺曱酸酯醇酸樹脂，而可得聚胺曱酸酯醇酸樹脂刀放在水中狀態之聚胺曱酸酯醇酸樹脂乳液（A)。做為鏈增長劑之多胺，祇要具有2個以上之胺基之化合物，別無特別限制，可舉例如伸烷二胺(伸乙二胺、13_ =二胺、M·丁二胺、〗，6_六亞曱基二胺）、脂環族二胺（1，’4_ %己：胺、3_胺甲基_3,5,5_二f基環己胺(慣用名為異氟爾胺）、M’·二環己基甲炫二胺、以，胺甲基)環己烧、 /欠烷二胺)、芳香族二胺(伸二甲苯二胺等)、雜環二胺(六虱:啡、2,5·二甲基六氫謂等）、聯胺、二缓酸二酿醜肼等）、聚伸烧基多胺（二伸乙三胺、三伸乙四胺夕胺類，例如羥基C^o烷基肼（羥乙基肼等）、羥基 “燒基聚C2.4伸烧基多胺（經乙基二伸乙三胺等）、叫胺土 2-1〇燒基）經基C2.l〇烧基胺（Ν·(2_胺乙基）乙醇胺等）、 318059 31 1374154 胺基CVw烷二醇（3·胺基丙烷二醇等）等胺基醇類。上述多胺可單獨或以2種以上之混合物使用。這些多胺中，用含羥基之多胺（上述胺基醇類）時，可將活性氫原子導入於聚 .胺甲酸酷醇酸樹脂。又，該等多胺也可以於一部分或全部 .被掩遮之形態下，例如以酮亞胺、酮連氮或胺鹽等之方式。醇酸樹脂成分和末端具有異氰酸基之聚胺甲酸酯預聚物2胺在水令之反應方法，並無特別限制，可採用周知之分散方》，例如將前述聚胺甲酸酉旨醇酸預H 一邊使用=散機(均質分散機或均質機等)攪拌，一邊添加水而使其分散於水中之方法，或水中添加上述聚胺甲酸酿醇酸預物：分散之方法等皆可採用。所產生分散物中添加多 -胺，藉多胺將醇酸樹脂成分和末端具有異氛酸基之聚胺甲酸酯預聚物進行鏈增長反應即可。 &^分散聚胺▼酸酯醇酸預聚物用途之水之使用量，祇要能調製成聚胺甲酸醋醇趨預聚物之水分散液，別無特別限籲制，例如相對於聚胺曱酸酯醇酸預聚物〗〇〇重量份，〇至1000重量份左右。 '' "又，多胺之使用量，相對於聚胺甲酸酯醇酸預聚物之異氛酉文基多胺之胺基的當量比（胺基/異氛酸基），例如0.2 至1·5為且’以〇 5至丨3為較佳，以〇 7至Μ左右為更 •佳。多胺通常滴加在攪拌中之聚胺甲酸醋醇酸預聚物之水 .刀政液中。多胺之滴加宜在呢以下溫度進行，滴加完後，再於搜拌令，例如在常溫下完成反應即可。藉此鏈增長反應’聚胺甲酸㈣酸預聚物藉多胺及/或水增長鍵長， 318059 32 1374154 ;二去5合所產生之乳液包含有機溶劑時，必要時可藉洛餾荨去除有機溶劑。町j秸又，聚胺？酸醋醇酸樹脂乳液（A)中，聚胺甲酸酯醇酸樹脂乳液之安定性要捋為㈣圍’可調配有界面活性劑。不阻礙耐水性範該界面活性劑並無特別限制，例如陰離子性界面活性 ?(:列如脂肪酸鹽、烷基硫酸酯鹽、烷基笨磺酸鹽、烷基萘 %酸鹽、烷基磺基琥珀酸鹽、土不笙、也你，/ κ1曱乙基炫基硫酸酯鹽 =其Λ 面活性劑（例如聚氧伸乙基烧基趟等聚氧 =基炫絲、聚氧伸乙基衍生物、去水山梨醇脂肪酸酉旨、水乳伸乙基去水山梨醇脂肪酸醋、聚氧伸乙基山梨醇脂肪酸醋、甘油脂肪酸醋、聚氧伸乙基燒胺、垸基烧醇醯胺等）、 %雔子糸及兩性離子系界面活性劑(例如烷基胺鹽、第々級敍鹽、院基甜菜驗、胺氧化物等）、水溶性高分子或保護膠體（例如明膠、H纖維素、經乙基纖維素、經丙基纖維素〔竣甲基纖維素'聚乙二醇、聚氧伸乙基.聚氧伸丙基嵌段共聚物、聚丙烯醯胺、聚丙烯酸、聚丙烯酸鹽、藻酸鈉、聚乙烯醇部分皂化物等)。本發明中，上述高分子分散劑：外，尚可使用例如磷酸三鈣、氧化鈦、碳酸鈣、二氧化矽等無機物做為界面活性劑用途。該界面活性劑可單獨或2 種以上併用。又，添加界面活性劑時，由於具有離子性官能基之界面活性劑，和聚胺甲酸酯醇酸樹脂之陰離子性基之相互作用，有時水性分散物之安定性會有下降之情形。因此’多數為使用非離子系界面活性劑。 318059 37 1274154Such as ketones (acetone, methyl ethyl kepaita # w ^ J 7 ... lack of ethyl ketone, methyl isobutyl ketone, etc.), vinegar (acetic acid acetate, ethyl butyl vinegar, etc.), _ (two Jian, Siqi. Fu. South, etc.), aromatic hydrocarbons (A special) temple. The organic solvent is acetone, methyl ethyl ketone, methyl 318059 28 1374154 acrylate or the like. These compounds may be used alone or in combination of two or more. Preferred compounds are, for example, aromatic ethylene (styrene, divinylbenzene, etc.), acrylonitrile ketoalkyl (meth)acrylate (methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethyl acrylate) Hexyl ester, etc.), ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, trihydroxymercaptopropane tri(methyl)=enoate, pentaerythritol tetra(meth)acrylate , (meth)acrylic acid dilute ester, and the like. When forming a hard film, the inert compound is styrene, divinylbenzene, methyl methacrylate, ethylene glycol dimethacrylate, butanediol diacrylate, trimethylolpropane triacrylate, methacrylic acid. Allyl is intended to be more. In the reaction, if necessary, an amine-based catalyst such as an amine-based catalyst (such as a tertiary amine), a tin-based catalyst (such as an organotin compound), or a lead-based catalyst can be used. Radical polymerization inhibitors such as lanthanides and phenols. Further, an unreacted component such as polyisocyanate may be removed from the reaction product by a known method such as distillation or extraction. Further, in the production of a polyurethane-based prepolymer having an anionic group, an amine (for example, triterpenoid) may be added at an appropriate stage (before the reaction or after the water dispersion process described below). Amine, triethylamine, tri-n-propylamine, tributylamine, diisopropylethylamine, triphenylamine, 2-diguanylaminoethanol, triethanolamine, monodecylpropanolamine, N-mercaptohexahydropyridine A neutralizing agent such as an inorganic base (for example, an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide or ammonia) neutralizes an anionic group to form a salt. The amount of the neutralizing agent to be added is preferably from 0.6 to 1.2 equivalents per equivalent of the anionic 30 318 059 1374154 bases, and more preferably from about 0.8 to 1 equivalents per equivalent of from 07 to 1 equivalent. • Chain extender Then, in order to obtain the polyamine phthalate alkyd resin emulsion (A), if necessary, the polyurethane acid alcohol prepolymer and the solvent (inert unsaturated compound and/or organic solvent) are dispersed together. A water dispersion is obtained in water. Further, the polyamine phthalate acid prepolymer having an anionic group can prepare an aqueous dispersion using the above neutralizing agent. Further, when the polyacetate acetate prepolymer contains an isocyanate group, it can be reacted with a chain extender (polyamine and/or water) in water. By this reaction, the poly(tetra)carboxylic acid prepolymer having an isocyanate group at the end may form a polyamine phthalate alkyd resin which is a bond of a chain extender, and a polyamine phthalate alkyd resin can be obtained. A polyamine phthalate alkyd emulsion (A) in which the knife is placed in a water state. The polyamine which is a chain extender is not particularly limited as long as it has a compound having two or more amine groups, and examples thereof include alkanediamine (ethylenediamine, 13_=diamine, M·butylamine). , 6_hexamethylenediamine), alicyclic diamine (1, '4_% hexyl: amine, 3-aminomethyl-3,5,5-di-f-cyclohexylamine (commonly known as isofluoride) Amine, M'. dicyclohexylmethyl diamine, amine methyl) cyclohexane, / underalkylenediamine, aromatic diamine (xylenediamine, etc.), heterocyclic diamine (six虱: morphine, 2,5· dimethyl hexahydro, etc.), hydrazine, bis-acidic acid, ugly sputum, etc.), poly-stranded polyamine (diethylenediamine, succinylamine) Classes, for example, hydroxy C^oalkyl hydrazine (hydroxyethyl hydrazine, etc.), hydroxy "alkylated poly C2.4 extended alkyl polyamine (ethyl ethyl diethylenetriamine, etc.), called amine 2-1 〇 Alkyl alcohols such as a base group of a C2.l sulfonylamine (Ν·(2-aminoethyl)ethanolamine, etc.), 318059 31 1374154, an amine-based CVw alkanediol (3·aminopropanediol, etc.) The above polyamines may be used singly or in combination of two or more. Among these polyamines, a hydroxyl group-containing polyamine (the above amine) may be used. In the case of alcohols, an active hydrogen atom can be introduced into the poly(amino)carboxylic acid alkyd resin. Further, the polyamines can also be partially or completely masked, for example, ketimine or ketazine. Or a method of an amine salt, etc. The alkyd resin component and the polyurethane prepolymer 2 amine having an isocyanate group at the end are not particularly limited, and a known dispersion method can be used, for example, The above-mentioned polyurethane is used in the form of a polyacrylic acid pre-alcoholic acid pre-H, which is stirred by using a machine (a homogenizer or a homogenizer), and is added with water to disperse it in water. A method of dispersing or the like can be used, and a poly-amine is added to the resulting dispersion, and the polyalcohol component of the alkyd resin component and the terminal urethane prepolymer having an octa-acid group can be subjected to a chain growth reaction. &^ Dispersing the amount of water used in the use of the polyamine-acidic acid prepolymer, as long as it can be prepared into an aqueous dispersion of the polyurethane foam prepolymer, there is no particular limitation, for example, Polyamine phthalate alkyd prepolymer 〇〇 by weight, up to 1000 The weight ratio is about . '' " Again, the amount of polyamine used, relative to the amine group of the polyamidoformic acid prepolymer, the amine group / aryl group ), for example, from 0.2 to 1.5, and that 'preferably from 〇5 to 丨3, and more preferably from about Μ7 to about 。. Polyamines are usually added dropwise to the stirred polyurethane urethane prepolymer. The water. Knife in the liquid. Polyamine drop should be carried out at the following temperature, after the addition is completed, and then in the search order, for example, the reaction can be completed at room temperature. By this chain growth reaction 'polyaminecarboxylic acid (four) The acid prepolymer is extended by polyamine and/or water, 318059 32 1374154; when the emulsion produced by the second decoupling 5 contains an organic solvent, the organic solvent can be removed by using a hydrazine. Machi j straw, polyamine? In the acid anhydride alkyd resin emulsion (A), the stability of the polyurethane foaming alkyd resin emulsion is (4) surrounded by a surfactant. The surfactant is not particularly limited, and is not particularly limited, for example, anionic interfacial activity ((e.g., fatty acid salt, alkyl sulfate salt, alkyl sulfonate, alkyl naphthalene acid salt, alkyl sulfonate) Succinate, soil, and you, / κ1 曱 ethyl thiosulfate salt = its 面 surfactant (such as polyoxy-extension ethyl ruthenium and other polyoxygen = basal silk, polyoxygen Base derivative, sorbitan fatty acid hydrazine, water emulsion, ethyl sorbitan fatty acid vinegar, polyoxyethylene sorbitol fatty acid vinegar, glycerin fatty acid vinegar, polyoxyalkylene amine, decyl ketone Indoleamine, etc., % scorpion scorpion and zwitterionic surfactants (eg alkylamine salts, sulphate salts, laboratory beet tests, amine oxides, etc.), water soluble polymers or protective colloids (eg gelatin) , H cellulose, ethyl cellulose, propyl cellulose [竣 methyl cellulose 'polyethylene glycol, polyoxyethylene ethyl. polyoxypropyl propyl block copolymer, polypropylene decylamine, poly Acrylic acid, polyacrylic acid salt, sodium alginate, polyvinyl alcohol partial saponified product, etc.). In the present invention, the above polymer component Powder: In addition, inorganic substances such as tricalcium phosphate, titanium oxide, calcium carbonate, and cerium oxide may be used as a surfactant. The surfactant may be used alone or in combination of two or more. When a surfactant is added, Due to the interaction between the surfactant having an ionic functional group and the anionic group of the polyurethane urethane resin, the stability of the aqueous dispersion may be lowered. Therefore, most of the nonionic systems are used. Surfactant. 318059 37 1274154

::界面活性劑或分散劑藉授拌(包括用均質機等 :)、混合能分散於聚胺甲酸酯醇酸樹脂乳液⑷中之聚】氰酸醋。这些聚異氰酸酉旨中，以聚異氛酸酷衍生物為佳， .使用聚氰酸醋改質物為更佳，以分散性聚異氰酸醋為最佳。性聚異氰酸酯分散性聚異氰酸函旨，例如由聚異氰酸醋和對於異氛酸 •基具有反應性之活性氫原子之界面活性或分散性成分(且有界面活性能力或分散性能力之成分）反應而製得。〃 ^上述聚異氰酸酯通常可列舉如脂肪族聚異氰酸酯、脂壤族聚異氣酸醋、芳香脂肪族聚異氰酸醋、芳香族聚里氰 -酸酿及該等聚異氰酸酿為基礎之衍生物或改質物，或含有該等何生物或改質物之聚異氰酸酯等。該聚異氰酸酯可單獨或2種以上組合使用。脂肪族聚異氰酸酯，例如上述脂肪族聚異氰酸酯等，鲁較佳之t異氰酸酯例如四亞曱基二異氰酸醋、五亞曱基二異氰酸酯、六亞曱基二異氰酸酯等。脂％族聚異氰酸酯之例如上述脂環族聚異氰酸酯等，車又佳之聚異氰酸酯例如異氟爾酮二異氰酸酯、1，3-或1,4-雙（異氰酸甲酯）環己烷、降冰片烷二異氰酸酯等。 • 芳香脂肪族聚異氰酸酯之例如上述芳香脂肪族聚異氰 •酸醋等’較佳之聚異氰酸酯為1，3-或1，4·雙（1-異氰酸基-1-甲基乙基）笨等。芳香族聚異氰酸酯之例如上述芳香族聚異氰酸酯等。 39 318059 1374154 或分散性#公界面活性或分散性成分，祇要具有活性氫原子， ::=ΓΓ性能力或分散性能力之成分即可。界面活性或刀…成为’雖然也可以為陰離子性界面活性劑，一 =:ΓϊΓΓ劑和至少具有環氧乙炫鏈之化合物所二成：中選擇一種而構成。非離子性界面活性劑，例如且毯：、鲢基等含活性氫原子之反應性基，以具有羥基： ,面活性劑為佳。非離子性界面活性劑，可以二酸酉旨、蔗糖脂肪酸醋等多元醇脂肪酸醋，有4 Τ者為較佳。亦即，非離子性界面活性劑以二 2伸乙基單元之聚氧伸烷基系界面活性；基之聚氧伸乙基系界面活性劑為最佳。 k、有經聚氧伸烧基系界面活性劑中，氧伸燒基單元伸乙基、氧伸丙基、氧伸乳氧伸烷Auk 2·5伸絲單元，該等 =„兀至少含有氧伸乙基單元即可，由氧伸乙基單，院Γ元之無規或嵌段共聚物亦可。聚氧: ，基早位中之乳伸乙基單元的含量，通常為心_ /〇，以80至100莫耳％左右為較佳。、耳非離子性界面活性劑，祇要具有活性氫原子可為如聚氧伸乙基炫基_(例如聚氧伸㈣1 乳伸乙基單月桂醚、聚氧伸承 _、聚氧其„:氧伸乙基早癸驗、聚氧伸乙基單錄氣i乳伸乙基早硬_、聚氧伸乙基單油醚乙基€8-24烷基醚等）、聚氧 X乳伸伸乙基單辛基苯絲、聚氧伸乙=基=(例如聚氧早壬基本基醚'聚氧伸 318059 41 I基St苯，等聚氧伸乙基C"2燒基％芳基趟聚氧伸絲絲趟⑽如聚㈣其聚氧伸乙基聚氧伸丙基單_、聚氧二醚、取氧袖^早癸越、聚氧伸乙基聚氧伸丙基單錄壤也乳伸乙基聚氧伸丙基單硬脂醚、聚氧伸乙丙基單油醚等聚氧伸乙基聚氧伸丙美C 申對應於聚氧伸乙基聚氧伸 i 8λ24Λ^Μ’或其相聚氧伸丁美C ” 醚之聚氧伸乙基 "8·24烷基醚等）、聚氧伸乙基去水山梨醇高級 :=醋(例如聚氧伸乙基去水山梨醇單繼、聚= ==ΓΤ:、聚氧伸乙基去水山梨醇單油酿、 ^ ^水山梨醇二硬脂酯、聚氧伸乙基去水山梨醇 -月曰酉曰等聚氧伸乙基去水山梨醇肋月桂舻"S Μ南級脂肪酸酯(例如聚氧伸乙基單月桂酉文酉曰、聚氧伸乙基單硬脂酸醋等之聚早脂肪酸醋等)等。該等非離子早c:24 ^使用。較佳之非離子性界面活性= HC8、聚氧伸乙基C812 聚伸乙基聚氧伸Cw伸烷基〇824醚 t t虱在酸醋醇酸樹脂乳液(A)中，非離子性界 7刀子中之氧伸乙基單元之平均含量通常在10 右，以〗2至30個左右為較佳。個左具環氧乙烧鏈(特別是聚環氧乙具有：性氯原子就行，例如可例舉甲醇、乙醇、丙醇= -酵、己醇、2_乙基己醇等單貌醇心。燒醇等低級醇 318059 42 1374154 類)作為起始劑，至少含有環氧乙烷之伸烷基氧化物藉開環聚合而加成之烷氧基聚伸烷基醚二醇。又，為對於聚胺甲酸酯醇酸樹脂乳液（A)能安定分散而言，具有活性氫原子和 •環氧乙烷鏈之化合物之平均分子量，通常為1〇〇至4〇〇〇 • 左右，以200至2000左右為較佳。具有環氧乙烷鏈（特別是聚環氧乙烷鏈）之化合物還包括聚異氰酸酯以烷氧基聚伸烷基醚二醇和二烷醇胺反應之化合物，二览醇胺和烧氧基聚氧伸乙基乙二醇單稀丙= 或烷氧基聚氧伸乙基（曱基）丙烯酸酯間之麥克爾加成物等。烧氧基聚伸烷基醚乙二醇，例如可例舉甲氧基聚伸乙醚乙二醇、乙氡基聚伸乙醚乙二醇、甲氧基聚伸丁二二醇、乙氧基聚伸"乙二醇等Cl.4院氧基聚‘伸燒基喊乙二醇0:: Interfacial active agent or dispersing agent by mixing (including using a homogenizer or the like:), mixing the polyglycolic acid vinegar dispersed in the polyurethane (5). Among these polyisocyanates, polyisocyanuric acid derivatives are preferred, and polycyanate modified materials are more preferably used, and dispersible polyisocyanuric acid is preferred. Polyisocyanate dispersible polyisocyanate, for example, an interfacially active or dispersible component of polyisocyanuric acid and an active hydrogen atom reactive with an isomeric acid group (and having interfacial activity or dispersibility) The component is obtained by reaction. 〃 ^The above polyisocyanate is generally exemplified by aliphatic polyisocyanate, lipopoly polyisophthalic acid vinegar, aromatic aliphatic polyisocyanuric acid, aromatic polycyanic acid-acid brewing and the like. Derivatives or modifications, or polyisocyanates containing such organisms or modifications. These polyisocyanates may be used singly or in combination of two or more kinds. An aliphatic polyisocyanate such as the above aliphatic polyisocyanate or the like is preferably a t isocyanate such as tetradecyl diisocyanate, pentadecyl diisocyanate or hexamethylene diisocyanate. The aliphatic % polyisocyanate is, for example, the above alicyclic polyisocyanate, etc., and the polyisocyanate such as isophorone diisocyanate, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, Borneane diisocyanate and the like. • Aromatic aliphatic polyisocyanate such as the above-mentioned aromatic aliphatic polyisocyanuric acid vinegar, etc. The preferred polyisocyanate is 1,3- or 1,4-bis(1-isocyanato-1-methylethyl) Stupid and so on. Examples of the aromatic polyisocyanate include the above aromatic polyisocyanate. 39 318059 1374154 Or dispersibility # 公 interface active or dispersible ingredients, as long as it has an active hydrogen atom, ::= inertia or dispersibility. The interfacial activity or the knives may be formed as an anionic surfactant, a compound selected from the group consisting of a bismuth agent and a compound having at least an epoxy chain. The nonionic surfactant, for example, a reactive group containing an active hydrogen atom such as a carpet or a mercapto group, preferably has a hydroxyl group: a surfactant. The nonionic surfactant may be a polyhydric alcohol fatty acid vinegar such as a diacid or a sucrose fatty acid vinegar, and 4 or more is preferred. That is, the nonionic surfactant is preferably a polyoxyalkylene-based interfacial activity of a diethylidene unit; and a polyoxyethylene surfactant is preferred. k. In the polyoxyalkylene-based surfactant, the oxygen-expanding base unit is extended with an ethyl group, an oxygen-extended propyl group, and an oxygen-extended oxetane Auk 2·5 wire-extension unit, and the The oxygen-extended ethyl unit can be, and the oxygen-extended ethyl group can be used as a random or block copolymer. The polyoxygen: the content of the ethyl group in the early position of the base is usually the heart _ /〇, preferably about 80 to 100 mol%. The ear nonionic surfactant, as long as it has an active hydrogen atom, may be, for example, a polyoxyethylidene group (for example, polyoxy-extension (tetra) 1 milk-extended ethyl group Monolauryl ether, polyoxygen extension _, polyoxygen „: oxygen extension ethyl early test, polyoxygen extension ethyl single recording gas i milk extension ethyl early hard _, polyoxygen extension ethyl monoether ether ethyl €8-24 alkyl ether, etc., polyoxyxyl milk extended ethyl monooctylbenzene, polyoxyethylene = base = (for example, polyoxygen early basic ethers 'polyoxy extension 318059 41 I based St benzene , et al., polyoxy-extension ethyl C" 2 alkyl-based aryl hydrazine polyoxy-extension silk silk 趟 (10) such as poly (four) its polyoxy-extension ethyl polyoxy-extension propyl single _, polyoxydiether, oxygen sleeves ^ early癸越, polyoxy-extension ethyl polyoxy-propion propyl mono-recording Ethyl polyoxyalkylidene monostearyl ether, polyoxyethylene ethyl propyl ether monoether ether, etc. Polyoxyethylene extended polyethyl phenyl acetoxime C 申对应对应对应对应对应对应对应对应对应对应对应对应对应对应对应对应对应对应对应对应Or its polyoxygen butyl butyl C ′ ether polyoxy-extension ethyl " 8 · 24 alkyl ether, etc., polyoxy-extension ethyl sorbitan high: = vinegar (such as polyoxy-extension ethyl dehydrated sorbus Alcohol single, poly = == ΓΤ:, polyoxyethylene ethyl sorbitan mono-oil, ^ ^ sorbitan distearyl ester, polyoxy-extended ethyl sorbitan - moon 曰酉曰Oxygen-extended ethyl sorbitan rib laurel "S ΜSouth-grade fatty acid ester (for example, polyoxy-extension ethyl laurel, scorpion scorpion, polyoxy-extension ethyl monostearic acid vinegar, etc. Etc. etc. These nonionics are used early c: 24 ^. Preferred nonionic interfacial activity = HC8, polyoxyethylene ethyl C812 polyethylidene polyoxyethylene extension Cw alkyl 〇 824 ether tt虱 in sour vinegar In the alkyd resin emulsion (A), the average content of the oxygen-extended ethyl unit in the non-ionic boundary 7 knives is usually 10 right, preferably about 2 to 30. In particular, polyethylene oxide has: The chlorine atom may, for example, be a monohydric alcohol such as methanol, ethanol, propanol = - yeast, hexanol or 2-ethylhexanol. The lower alcohol such as aryl alcohol (318059 42 1374154) is used as a starter and contains at least An alkoxy-polymerized alkyl ether diol which is added by ring-opening polymerization of an alkylene oxide of an ethylene oxide. Further, in terms of stable dispersion of the polyurethane (alk) resin emulsion (A) The average molecular weight of a compound having an active hydrogen atom and an ethylene oxide chain is usually from about 1 to about 4 Å, preferably from about 200 to about 2,000. It has an ethylene oxide chain (especially poly The compound of the ethylene oxide chain also includes a compound in which a polyisocyanate is reacted with an alkoxy polyalkylene glycol and a dialkanolamine, a di-alcoholamine and an alkoxy polyoxyethylene ethylene glycol mono-propyl = or Michael addition between alkoxy polyoxyethylene ethyl (decyl) acrylate, and the like. The alkoxy-polyalkylene glycol glycol may, for example, be methoxy-polyethyl ether glycol, ethoxylated polyethylene glycol, methoxy-polybutylene glycol, ethoxylated. Stretch " ethylene glycol and other Cl.4 hospital oxygen poly' extension base shouting ethylene glycol 0

二烷醇胺’可例舉二乙醇胺、二丙醇胺、二乙醇苯胺等二羥基C2-6烷胺。二異丙醇胺聚異氰酸酯和烷氧基聚伸烷基醚乙二醇及二烷醇胺之反應，乃將聚異氰酸酯及烷氧基聚伸烷基醚乙二醇，以異氰酸基/經基之當量比為3至30,較佳為10至25左右二以反應後，除去未反應之聚異氰酸酯，繼之，將二烷醇胺 •以異氰酸基/胺基之當量比為0.5至2，較佳為0.8至i 2 .左右進行反應。聚異氰酸酯和烷氧基聚伸烷基醚乙二醇之反應，可在40至100°C左右下進行2至24小時左右。反應在氮環境中進行為理想，也可使用下述之惰性有機溶 318059 43 1374154 劑。未反應之聚異氰酸酯之去除，可使用蒸餾法、萃取法等周知方法。蒸餾法可採用連續蒸餾法、分批蒸餾法、薄膜蒸餾法等。其中，以使用薄膜蒸餾法為較佳。萃取法可採用連續萃取法、分批萃取法等液_液萃取法等，萃取用溶劑可使用己烷、乙酸乙酯等比較低極性之有機溶劑。和: 院醇胺之反應，可在室溫至12(rc左右，氮環境中進行為理想。又’該反應也和上述同樣可使用惰性有機溶劑而進行0The dialkanolamine' may, for example, be a dihydroxy C2-6 alkylamine such as diethanolamine, dipropanolamine or diethanolaniline. The reaction of diisopropanolamine polyisocyanate and alkoxy polyalkylene glycol ethylene glycol and dialkanolamine is carried out by polyisocyanate and alkoxy polyalkylene glycol, and isocyanate/ The equivalence ratio of the radical is from 3 to 30, preferably from about 10 to about 25, after the reaction, the unreacted polyisocyanate is removed, and then the equivalent ratio of the dialkanolamine to the isocyanato group/amine group is The reaction is carried out at about 0.5 to 2, preferably 0.8 to i 2 . The reaction of the polyisocyanate with the alkoxy polyalkylene glycol can be carried out at about 40 to 100 ° C for about 2 to 24 hours. The reaction is preferably carried out in a nitrogen atmosphere, and the following inert organic solvent 318059 43 1374154 may also be used. As the removal of the unreacted polyisocyanate, a known method such as a distillation method or an extraction method can be used. The distillation method may employ a continuous distillation method, a batch distillation method, a thin film distillation method, or the like. Among them, a thin film distillation method is preferred. The extraction method may be a liquid-liquid extraction method such as a continuous extraction method or a batch extraction method, and a solvent having a relatively low polarity such as hexane or ethyl acetate may be used as the extraction solvent. And: the reaction of the hospital alcohol amine can be carried out at room temperature to about 12 (rc, in a nitrogen atmosphere. Further, the reaction can also be carried out using an inert organic solvent as described above.

上述硬化劑（B)用之聚異氰酸酯和具有活性氫原子之非離子性化合物（即包含具有活性氫原子之非離子性界面活性劑及/或具有聚環氧乙烧鏈之化合物）間之比例，相對於聚異，酸S旨（包括聚異氰酸g旨衍生物）之可反應之異氮酸基1當量’非離子性化合物之活性氫原子可由GG1至W f量’較佳由（UH2至〇·15當量，更佳由〇〇15至〇丨當量左右的範圍加以選擇。當非離子性化合物之比例過：時，對於聚胺曱酸醋醇酸樹脂乳液(A)之分散性有下降之情形，相反地’比例過高時，親水性過高即耐水性等 ^加上’為提高塗膜之耐水性，上述聚異氰酸醋（以聚 ^古酉夂S旨衍生物為較佳）和偶合劑反應為較有利。該偶合劑 -’ί於&異氰g旨之異氰酸基有反應性之活性氫原子， =基、胺基、嶋官能基。偶合劑具有交聯或聚合 7解^合性基等），該水解縮合性基之例如貌氧基（甲乳土、乙氧基、丙氧基、丁氧基、第三丁氧基…烧氧 318059 44 1374154 1至3 個左右之該等水解典型者為矽烷偶合基）等。偶合劑在—分子+可具有縮合性基。這種偶合劑可為鈦偶合劑，劑。夕：偶合劑之例如含魏基之錢偶合劑㈣基乙基 .:乳基錢、w基丙基三甲氧基錢等疏基c2 4烧基二C,4院氧基石夕燒等），含有胺基之石夕燒偶合劑胺乙基 :甲氧基石夕燒、r胺乙基三乙氧基石夕燒、厂胺丙基三甲 _氧矽烷、r-胺丙基三乙氧基石夕烷等胺基c24炫基三c“4 烷軋基矽烷等）’含有羧基之矽烷偶合劑（万·羧乙基三甲氧基=烷、τ-羧丙基三曱氧基矽烷、7_羧丙基三乙氧基矽 '元等叛基C2_4烷基二c]·4烧氧基>5夕院等）等。該等矽炫偶合 '劑可單獨或2種以上組合使用。較佳之偶合劑為含疏基之石夕烷偶合劑’例如7 -巯基丙基三甲氧基矽烧等。上述聚異氰酸酯和偶合劑間之比例，相對於聚異氛酸醋之異氰酸基1當量，偶合劑之活性氫原子可由〇〇丨至 • 0.3舊里’車父佳由〇.〇2至〇,25當！’更佳由〇.〇5至〇2當量左右的範圍加以選擇。做為硬化劑（B)之聚異氰酸酯，例如由上述聚異氮酸酉旨 (以聚異氰酸酯衍生物為較佳），和具有活性氫原子之非離子性界面活性劑及/或具有聚氧伸乙基鏈之化合物，必要 *時’再加以偶合劍於攪拌下反應而製成。反應溫度可選擇 •適當溫度，一般在50至90°C左右。反應時間也無特別限制’例如1至24小時，其中’以1至8小時左右為較佳。反應可在觸媒（胺系觸媒、錫系觸媒等）之存在下進行。又， 318059 45 1374154 該，應也可㈣性有機㈣（非反隸有機溶劑）之存在下進仃為防止—液硬化型水性樹脂組成物受有機溶劑之污染，且提高操作方便性，以有機溶劑之不存在下反應生產在室溫下具有流動性之液狀之聚異氛酸醋為較佳。下文中，硬化劑使用聚異氰酸酉旨之際，以硬化劑（聚異氛酸而記載之。上述U I1生有機溶劑之例如酮類（丙酮、甲基乙美酮、甲基異丁基酮、4·甲基_2-戊酮、環己酮等）、醋類酸乙醋、乙酸丁醋、乙酸異丁酯、1-甲氧基丙基-2-乙酸醋、甲乳基丁基乙酸g旨等）、芳香族烴類（苯、甲苯、二甲苯 J)、脂環族烴類(環己烧等)、脂肪族煙類(己烧、異辛烧外醚類（二。惡烧、四氫十南等）、溶纖素類或卡必醇類（乙 -醇單甲峻乙酸[乙二醇單乙_乙酸醋、乙二醇單丁鍵乙酸醋、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚、 ::二醇單甲醚乙酸酯、二乙二醇單乙醚乙酸酯、二乙二醇早：醚乙酸醋、二乙二醇二甲基醚、二乙二醇二乙醚、 :乙二醇二丁醚、丙二醇單甲喊乙酸醋、丙二醇單乙鱗乙酉“旨、二丙二醇二甲驗、三乙二醇丁基甲基鍵、四乙二醇 =^聚乙二醇二甲酸、2,2,4_三T基·1>3•戊二醇二異丁 ^ —乙一醇雙乙基己酸酯等），含氮溶劑（Ν-甲基吡、ν·乙基㈣烧酮、Ν_甲基己内酿胺等卜上述溶劑早獨或2種以上做為混合溶劑使用。 Λ ，做為硬化劑（聚異氰酸酯）(B)用之具有界面活性能，刀放施力之聚異氰酸酯衍生物，可利用周知合成方法 318059 46 1374154 調製’各成分之反應順序可根據反應成分之種類而選擇之。例如聚異氰酸酯衍生物（低分子聚異氰酸醋之三聚物等）’以非離子性界面活性劑及/或具有聚氧伸乙基鏈之化合物’及必要時之偶合劑，加以反應而可製得硬化劑（聚異氰酸酯）(B) ’特別是可製得分散性聚異氰酸酯。又，使用聚異氰酸酯和對於異氰酸基具有反應性之活性氫原子之複數個反應成分時，可使用複數個聚異氰酸酯，各反應成分可依照適當順序投入反應。例如以聚異氰酸酯（低分子聚異氰酸酯或聚異氰酸酯衍生物）和具有聚環氧乙烷鏈之化合物（烷氧基聚伸乙基伸烷基醚二醇等）反應而合成具有末端異氰酸基和聚環氧乙烷鏈之化合物，必要時，去除殘留之聚異氰酸酯後，戶斤合成之化合物和二烷醇胺反應而製成含有2個羥基和聚環氧乙烷鏈之化合物，再以此化合物和聚異氰酸酯（以三聚物等之聚異氰酸酯衍生物為較佳）反應亦可。按照這樣方法，反應性成分（含對異氰酸基具有反應性之活性氫原子之非離子性界面活性劑及/或具有聚環氧乙院鏈之化合物’以及必要時，再加以偶合劑），例如可預先和聚異氰酸喊應，也可以在合成聚異氰酸㈣生物之中間階段反應。更可以將反應生成物和聚異氰酸§旨衍生物反應而製造。尚可以將聚異氰_和反應性成分反應之後，進行最後的三聚物化、脲基旨化、縮二脲化反庫等。例如亦可使低分子聚異氰㈣和具有聚氧伸乙基鏈之二醇 ^乙二_)及·物反應，進行三聚物化化反應等。藉上述各種反應可得目的之硬化劑（聚異㈣ 3J8059 47 1374154 酯）（B)。Ratio between the polyisocyanate used for the above hardener (B) and the nonionic compound having an active hydrogen atom (that is, a compound containing a nonionic surfactant having an active hydrogen atom and/or a compound having a polyepoxy chain) With respect to the polyiso isomer, the acid S (including the polyisocyanate g derivative) can react with the isobornic acid group. 1 equivalent of the active hydrogen atom of the nonionic compound can be preferably from GG1 to Wf. UH2 to 〇15 equivalent, more preferably selected from the range of 〇〇15 to 〇丨 equivalent. When the proportion of the nonionic compound exceeds:, the dispersibility of the polyamine phthalic acid resin emulsion (A) In the case of a decrease, when the ratio is too high, the hydrophilicity is too high, that is, the water resistance, etc. plus 'to improve the water resistance of the coating film, the above-mentioned polyisocyanuric acid vinegar Preferably, it is more advantageous to react with a coupling agent. The coupling agent is an active hydrogen atom which is reactive with an isocyanate group, a group, an amine group, a hydrazine functional group. Having cross-linking or polymerizing 7-resolving groups, etc.), such as the appearance of the hydrolyzable condensable group Group (A milk soil, ethoxy, propoxy, butoxy, tert-butoxy ... 3,180,594,413,741,541 burning oxygen of up to about 3 such as those typically hydrolyzed silane-coupling group). The coupling agent may have a condensable group at the molecule. This coupling agent can be a titanium coupling agent.夕: The coupling agent is, for example, a Weiji-containing money coupling agent (tetra)ylethyl.: a milk-based money, a w-propyl propyl trimethoxy group, a sulfhydryl group, a c2 4 alkyl group, a C, a 4-yard oxygen stone, etc.) Amine-containing coupling agent amine group containing amine group: methoxy sulphur, r-amine ethyl triethoxy sulphur, plant amine propyl trimethyl oxane, r-aminopropyl triethoxy oxalate Equivalent group c24 succinyl c c "4 alkane-rolled decane, etc." carboxy-containing decane coupling agent (wan·carboxyethyltrimethoxy=alkane, τ-carboxypropyltrimethoxy decane, 7-carboxypropyl a triethoxy hydrazine ′′, such as a thiol C 2 —4 alkyl di c]·4 alkoxy group, etc., etc. These oxime coupling agents may be used alone or in combination of two or more. The mixture is a sulfhydryl-containing alkane coupling agent, such as 7-mercaptopropyltrimethoxysulfonium, etc. The ratio between the above polyisocyanate and the coupling agent is 1 equivalent to the isocyanate group of the polyisocyanate. The active hydrogen atom of the coupling agent can be selected from the range of 〇〇丨 to 0.3 old ' 'Chef Jia 〇〇〇 2 to 〇, 25 when! 'Better from 〇. 〇 5 to 〇 2 equivalents. Hardener (B) The polyisocyanate is, for example, the above polyisocyanate (preferably a polyisocyanate derivative), and a nonionic surfactant having an active hydrogen atom and/or a compound having a polyoxyethylene chain, necessary* When the 'synthesis sword is reacted under stirring, the reaction temperature can be selected to be appropriate temperature, generally about 50 to 90 ° C. The reaction time is also not particularly limited 'for example, 1 to 24 hours, where 'to 1 to 8 The reaction time can be carried out in the presence of a catalyst (amine-based catalyst, tin-based catalyst, etc.). Further, 318059 45 1374154 It should also be possible to use (iv) organic (four) (non-reverse organic solvent). The presence of the lower enthalpy is to prevent the liquid-hardening type aqueous resin composition from being contaminated by the organic solvent, and to improve the handling convenience, and reacting in the absence of an organic solvent to produce a liquid polyisomeric acid having fluidity at room temperature. Vinegar is preferred. Hereinafter, when the hardening agent is used as the polyisocyanate, it is described by a hardening agent (polyisocyanuric acid). For example, the above-mentioned U I1 raw organic solvent such as a ketone (acetone, methyl methacrylate) Methyl isobutyl ketone, 4·methyl-2-pentanone, cyclohexanone, etc.), vinegar acid vinegar, butyl acetate, isobutyl acetate, 1-methoxypropyl-2-acetic acid vinegar, methyl lactyl butyl acetate g), aromatic hydrocarbons (benzene, toluene, xylene J), alicyclic hydrocarbons (such as cyclohexane), aliphatic cigarettes (hexilated, isooctyl ether) (two. , tetrahydrothene, etc.), cellosolve or carbitol (ethyl alcohol monomethyl acetonitrile [ethylene glycol monoethyl acetate, ethylene glycol monobutyl acetate, ethylene glycol dimethyl ether , ethylene glycol diethyl ether, ethylene glycol dibutyl ether, :: glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol early: ether acetate, diethylene glycol Methyl ether, diethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol monomethyl acetate, propylene glycol monoethyl acetonide, dipropylene glycol dimethyl test, triethylene glycol butyl methyl bond, tetraethyl Glycol = ^ polyethylene glycol dicarboxylic acid, 2, 2, 4 - tri-T-group · 1 > 3 • pentanediol diisobutyl ^ - ethyl alcohol diethyl hexanoate, etc.), nitrogen-containing solvent (Ν- Methyl pyridyl, ν·ethyl (tetra) ketone, Ν_methyl caprolactam, etc. Early alone or as a mixture of two or more solvents. Λ As a hardener (polyisocyanate) (B), it has an interfacial activity, and a polyisocyanate derivative which can be applied by a knife can be prepared by a known synthesis method 318059 46 1374154. The reaction sequence of each component can be determined according to the reaction component. Choose from the category. For example, a polyisocyanate derivative (a low molecular polyisocyanate terpolymer, etc.) is reacted with a nonionic surfactant and/or a compound having a polyoxyethylene chain and, if necessary, a coupling agent. A hardener (polyisocyanate) (B) can be produced. In particular, a dispersible polyisocyanate can be obtained. Further, when a plurality of reaction components of a polyisocyanate and an active hydrogen atom reactive with an isocyanate group are used, a plurality of polyisocyanates may be used, and each reaction component may be introduced into the reaction in an appropriate order. For example, a polyisocyanate (low molecular polyisocyanate or polyisocyanate derivative) and a compound having a polyethylene oxide chain (alkoxy polyethylene alkyl ether glycol, etc.) are reacted to synthesize a terminal isocyanate group and a compound of a polyethylene oxide chain, if necessary, after removing the residual polyisocyanate, the compound synthesized by the compound and the dialkanolamine are reacted to form a compound containing two hydroxyl groups and a polyethylene oxide chain, and then The compound and the polyisocyanate (preferably, a polyisocyanate derivative such as a trimer) may be reacted. According to such a method, a reactive component (a nonionic surfactant containing an active hydrogen atom reactive toward an isocyanate group and/or a compound having a polyepoxy chain) and, if necessary, a coupling agent) For example, it may be pre-treated with polyisocyanate or may be reacted in the intermediate stage of the synthesis of polyisocyanate (IV) organisms. Further, the reaction product can be produced by reacting with a polyisocyanate derivative. It is also possible to carry out the final trimerization, the urea group, the biuretization, and the like after reacting the polyisocyanate with the reactive component. For example, a low molecular polyisocyanate (tetra) and a diol having a polyoxyethylene chain may be reacted to carry out a trimerization reaction or the like. By the above various reactions, the desired hardener (polyiso(4) 3J8059 47 1374154 ester) (B) can be obtained.

硬化劑（聚異氰酸酯）(B)之平均官处 2·5至4為較佳。又，異氛酸基含量：二5=5,以 5至30重量％左右為較佳。當硬化篁。，以均官能基數未達2時，耐水性會變；，又、亂酸醋)(，平化劑(聚異氰酸_)對於具有活性二:: 醇酸樹脂乳液㈨之分散性有降低之情形。又，里未達3重心時，由於交聯密度不足而耐水性 !:相=，超過50重量％時，對具活性氨原子之聚胺甲酸酉曰醇酸樹脂乳液（A)之分散性有降低之問題。The average of the hardener (polyisocyanate) (B) is preferably from 2.5 to 4. Further, the content of the odor acid group is preferably 2 5 = 5, preferably about 5 to 30% by weight. When hardened. When the number of functional groups is less than 2, the water resistance will change; and, again, the acid vinegar) (the flattening agent (polyisocyanate) has a lower dispersibility for the active two:: alkyd resin emulsion (9) In other cases, when the center of gravity is not reached, the water resistance is insufficient due to insufficient crosslink density!: phase =, when it exceeds 50% by weight, the polyurethane (A) having a reactive ammonia atom is used. There is a problem of reduced dispersion.

又奴付所期待之異氰酸基含量之硬化劑用聚異氛酸在反應過程㈣輕定之異㈣基含量時终止反應即可。較佳方法為所產生之硬化劑（聚異氰㈣）(b)中之異氰酸基含量，上述範圍之比例，事先混合聚異氰酸醋（較佳為包括聚異氰酸料生物）'具有活性氫原子之非離子性界面活性劑及/或具有聚環氧乙烧鏈之化合物，以及必要時包括偶合劑，進行各成分之反應到反應完成。上述硬化劑（聚異氰酸酯）(B)可單獨或2種以上併用。該等硬化劑（聚異氰酸酯）(B)中，較佳之聚異氰酸酯可例舉係由聚異氰酸酯（較佳為聚異氰酸酯衍生物），和對異氰酸基具有反應性之活性氫原子之非離子性界面活性劑之反應所產生分散性聚異氰酸酯，或由聚異氰酸酯（較佳為低分手眾異氰酸或裝異氰酸酯衍生物）和對異氰酸基具反應性之活性氫原子之具有聚環氧乙烷鏈之化合物（烷氧基聚伸 48 318059 qv4154 產？二醇)及二烷醇胺’以上述同樣方法反應而將此:右令原子之化合物（例如末端經基化合物），再等聚i - /二風原子化合物和聚異氛酸醋（較佳為三聚物 :亂g曰何生物)反應所產生之分散性聚異氰酸酯聚氣伸=硬化劑（聚異氰醆sgt)(B)為分散性聚異氰酸醋之聚乳伸乙基改質聚異氰酸酯。岸佳異亂酸sl)⑻中，也可含有對異氰酸基非反合劑（特別是料偶合劑）。财基或環氧丙基之錢偶合劑（例如r•環氧丙減乙乳基料、卜環氧丙氧基丙基三甲氧基石夕氧基環己基)乙基三甲氧基卿)、含乙烯二、>5二其^(乙稀基二乙氧基石夕燒、乙婦基三甲氧基石夕氧義丙其▲婦丙氧基乙基三甲氧基㈣、Η甲基）稀丙氧基丙基三甲氧基矽烷等）等。昱氯2 ’使用聚異酸酿等做為硬化’）時，也可含有對叫3基非反應性之溶劑。該溶劑可使用各種惰性 It例如酮類（丙酮、甲基乙基_、甲基異丁基_、心甲基啊、琢己酮等）、酿類（乙酸乙酯 '乙酸丁醋、乙酸異芳二甲氧基丙基·2·乙酸酯' 3_甲氧基丁基乙酸酯等)、月，肪二垣類（本、曱苯、二甲笨等）、脂環族烴類（環己燒等）、 ^ (己院、異辛院等）、驗類（二°惡烧、四氫D夫喃等）、 / 今纖素類或卡必醇類f (乙一知早甲醚乙酸酯、乙二醇單乙醚The sclerosant of the isocyanate content which is expected to be used is also used to terminate the reaction when the reaction (4) is lightly determined. Preferably, the content of the isocyanate group in the hardener (polyisocyanate (IV)) (b) produced, the ratio of the above range, is premixed with polyisocyanuric acid (preferably including polyisocyanate biomass) A nonionic surfactant having an active hydrogen atom and/or a compound having a polyethylene oxide chain, and a coupling agent if necessary, and reacting the components until the reaction is completed. The above-mentioned curing agent (polyisocyanate) (B) may be used singly or in combination of two or more kinds. Among the hardeners (polyisocyanate) (B), preferred polyisocyanates are exemplified by polyisocyanates (preferably polyisocyanate derivatives) and nonionics of active hydrogen atoms reactive toward isocyanato groups. The reaction of a surfactant produces a dispersible polyisocyanate, or a polycyclic ring of a polyisocyanate (preferably a low-particulate isocyanate or an isocyanate derivative) and an active hydrogen atom reactive toward isocyanate The compound of the oxyethylene chain (alkoxy-glycolic 48 318059 qv4154-produced diol) and the dialkanolamine' are reacted in the same manner as above: a compound of a right-hand atom (for example, a terminal-based compound), and the like. a dispersible polyisocyanate polygas extension = hardener (polyisocyanuric acid sgt) produced by the reaction of a poly-i-/dipholine atomic compound and a polyiso-acid vinegar (preferably a terpolymer: a chaotic organism) B) is a polycondensed polyisocyanate of polyisocyanuric acid. In the case of the acid (s), it is also possible to contain a non-trans isocyanate (especially a coupling agent). A hydroxyl-based or epoxy-propylated money coupling agent (for example, r•epoxy-propyl-ethyl emulsion base, butyl glycoxypropyltrimethoxy-oxocyclohexyl)ethyltrimethoxy), Ethylene II, >5二其^(Ethyl diethoxy sulphur, Evolyl trimethoxy, Oxygen, propylene, phenoxyethyl trimethoxy (tetra), fluorenylmethyl) Propyl trimethoxy decane, etc.). When ruthenium chloride 2' is used as the hardening by polyisophthalic acid or the like, a solvent which is not reactive with the 3-group may be contained. The solvent can use various inert It such as ketones (acetone, methyl ethyl _, methyl isobutyl _, methyl ketone, ketohexanone, etc.), brewing (ethyl acetate ' acetic acid butyl vinegar, acetic acid isofang Dimethoxypropyl·2·acetate '3_methoxybutyl acetate, etc.), month, fat diterpenoids (benzo, toluene, dimethyl strepene, etc.), alicyclic hydrocarbons ( Cyclohexene, etc.), ^ (Xinyuan, Yixinyuan, etc.), test (two-degree burnt, tetrahydro D-fu, etc.), / present fibrin or carbitol f (yiyizhi early methyl ether) Acetate, ethylene glycol monoethyl ether

^ ®义SI、乙二醇單丁 M 醚乙酉夂酯、乙二醇二甲醚、乙二醇二 -、、乙二醇二丁醚、二乙二醇單甲醚乙酸酯、二乙二醇 318059 49 1374154 單乙趟乙酸酯、二乙二醇單丁越乙酸酯、二乙二醇二T醚、二乙二醇二乙醚、二乙二醇二丁醚、丙二醇單甲醚乙酸酯、内二醇單乙醚乙酸酯、二丙二醇二曱醚、三乙二醇丁基曱 • 基醚、四乙二醇二曱醚、聚乙二醇二曱醚、2,2,4-三曱基-ΐ，3- 戊二醇二異丁酸酯、三乙二醇雙2-乙基己酸酯等）、含氮溶劑（Ν-甲基吡咯烷酮、Ν-乙基吡咯烷酮、Ν-甲基己内醯胺）等。該溶劑可單獨或2種以上做為混合溶劑使用。本發明之二液硬化型水性樹脂組成物中，對於聚胺甲 •酸酯醇酸樹脂乳液（Α)之硬化劑（Β)之使用量，祇要能發揮本發明之效果，別無限制，例如，以固形物換算，相對於戎胺曱酸酯醇睃樹脂乳液（Α)ι 〇〇重量份，硬化劑（β)為j 至15〇重量份，以〇.5至60重量份為較佳，以！至4〇重量份左右為更佳（例如2至35重量份，最佳為3至3〇重量份）。對於聚胺甲酸酯醇酸樹脂乳液（Α)之硬化劑（Β)之使用量，以固形物換算，例如硬化劑⑻中之反應性基（例如聚異氮酸西旨中之異氰酸基）和聚胺甲酸醋醇酸樹脂乳液(Α)中之聚胺曱酸S旨醇酸樹脂中之活性氫原子之當量比（例如異氰酸基/活性氫原子）而言，為〇3至4，以〇4至3為較佳、， Q.5至2左右為更佳。當異氰酸基和活性氣原子之當量比超過該範圍時，過多之異氰酸基和水反應而產生二氧化碳’會嚴重損害塗膜之外觀’又’上述當量比未達上述範圍時，由於交聯密度不^及塗膜中之殘存活性氫原子而使耐水性有顯者劣變之問題存在。χ，聚胺甲酸_酸樹脂 318059 50 1374154 乳液（A)中之聚胺甲酸酯醇酸樹脂中所占活性氫原子乃指具有末端異氰酸基之聚胺曱酸酿醇酸預聚物在鏈增長時所用多胺中之羥基，或聚胺曱酸酯醇酸預聚物（不含異氰酸基） .中之羥基，和聚胺甲酸酯醇酸預聚物合成時所用具有陰離 .子性之含活性氫原子之化合物中之羧基，和自由基聚合時所用含活性氫原子之不飽和化合物中之經基及/或叛基之合計。 •金屬乾燥劑或紇操备UC、本發明之水性樹脂組成物（二液硬化型水性樹脂組成物#)，可含有金屬乾燥劑（C)。金屬乾燥劑（c)可使用慣用之金屬乾燥劑（塗料用乾燥劑）之脂肪酸金屬鹽。該脂肪酸金屬鹽之例如環烷（naphthene)酸金屬鹽（環烷酸鈷、環烷酸鉛、％烷酸鍅、環烷酸錳、環烷酸鋅等環烷酸之多價金屬 •鹽荨）、辛酸金屬鹽（辛酸始、辛酸猛、辛酸斜、辛酸錯、 #辛酸鋅等辛酸之多價金屬鹽等）等。這些金屬乾燥劑可單獨或2種以上組合使用。一般，組合2種以上之該脂肪酸金屬鹽時，已知可得高效果，例如環烷酸鈷和其他之環烷酸金屬鹽（例如環烷酸鉛 '環烷酸锆、環烷酸錳、環烷酸鋅等）之併用系為廣況使用。再者，上述脂肪酸金屬鹽可由金屬 •和胺形成配位化合物。特別是含有不同種金屬之脂肪酸金 •屬鹽或金屬和胺之複合物做為無鉛乾燥劑，而可調製成高活性之乾燥劑，對於環保也有益。該等金屬乾燥劑有市售之胺配位化合物之金屬乾燥劑，例#大日本油墨化學工業 318059 1374154 (產業上之利用可行性）本發明之二液硬化型水性樹脂組成物，有用於作為黏接劑、塗布劑（塗料、印刷油墨等）、底漆，可使用在各種底材（金屬、塑膠或高分子材料'石板、水泥、砂漿等無機 .材料、紙、木材等）之表面被覆用途。特別是本發明之二液硬化型水性塗料了在常溫硬化及加熱硬化，例如常溫^化系可提供木工用塗料或水性底漆之用途，加熱硬化系可提供八車用塗料而使用。本發明藉實施例詳細說明如下，惟本發明不受該實施例之侷限。又，實施例及比較例所示之份量及❶皆代表重 • 量份及重量％。醇酸樹脂（PEsn：^蜩芈j 備有攪拌機'氮氣導入管、精餾塔及溫度計之五頸燒瓶中，加入高二烯脂肪酸（K.F.產業公司製品，高二埽化 φ物）3308.3份、季戊四醇821.2份及異苯二曱酸487.3份，導入氮氣下再加入酯化觸媒之單正丁基錫氧化物〇·2份，混合液升溫至230°C ’攪拌8小時，於去除縮合水之同時使羧基和羥基反應。確認反應液到達既定之羥基含量後，降溫到30°C ’而得羥基價為75.3之醇酸樹脂（PES1)。醇酸樹1旨（PES2、PES3、PES4、PES5)之調贺按照醇酸樹脂（PES1)相同操作，以表1所示配方調製得醇酸樹脂（PES2、PES3、PES4、PES5)。 53 318059 1374154 表1 醇酸樹脂 PES1 PES2 PES3 PES4 PES5 油成分 (份）高二缔月旨肪酸 3308.3 — — — 一脫水乾麻籽油脂肪酸 — 3385.2 — — 一大豆油脂肪酸 _ 一 3249.0 一一椰子油脂肪酸 _ — 2941.3 2761.1 多價多元醇(份）季戊四醇 821.2 840.3 861.1 1176.5 1288.5 多價多元羧酸(份）異苯二曱酸 487.3 498.6 511 698.1 764.6 觸媒(份）單正丁基錫氧化物 0.2 0.2 0.2 0.2 0.2 經基價(氫氧化鉀mg/g) 75.3 74.2 85.8 136.3 184.5 含有活性氫原子之聚胺曱酸酯醇酸樹脂乳液（al)之調製備有攪拌機、戴式冷凝器、氮氣導入管、矽膠乾燥管及溫度計之五頸燒瓶中，投入曱苯二異氰酸酯（三井武田化學公司製品、COSMONATE T-80)174.2份、甲基乙基酮 207.1份，在氮氣流中攪拌至完全均勻，然後添加羥基價為75.3之醇酸樹脂（PES1)272.9份、新戊基二醇38.1份以 •及二羥曱基丁酸32.6份，在70至80°C下攪拌2小時，確認反應液已到達既定之異氰酸酯含量後，一面添加甲基乙基酮138.1份一面降溫，獲得含有聚胺曱酸酯醇酸預聚物之反應混合液（含醇酸成分之末端異氰酸酯聚胺曱酸酯預聚物之曱基乙基酮溶液）。 ' 所得含有聚胺曱酸酯醇酸預聚物之反應混合液863份 •藉均質分散機攪拌下，添加2-二曱胺基乙醇之1 5%水溶液 117.5份，再添加去離子水1268.2份，而得乳淡粉紅色之 54 318059 1374154 水分散液。該分散液中，在30°C以下滴加192.3份之ι〇% 之N-(2-胺乙基）乙醇胺而進行鏈增長化反應，減壓下於5〇 °C除去曱基乙基酮及水’添加無鉛乾燥劑⑴s B日本公司製品，ADDITOL VXW 6206)4.4 份，而得固形物 36 8〇/〇，黏度（25°C)46mPa· s，PH7.6，平均粒徑84nm之含有活性氫原子之聚胺甲酸酯醇酸樹脂乳液（al)。活性氧n之聚胺甲酸酯醇酸樹脂、夕，f 備有攪拌機、戴式冷凝器、氮氣導入管、矽膠乾燥管及溫度計之五頸燒瓶中，投入甲苯二異氰酸酯（三井武田化學公司製品，COSMONATE τ-80)174.2份及曱基乙基酮 208.7伤在氮氟流中攪拌至完全均勻，再加入經基價為 Μ.2之醇酸樹脂（PES2)276 9份、新戊二醇％丨份及二羥甲基丁酸32.6份，在70至80t溫度下擾拌2小時，確認反應液到達既定之異氰酸酯含量後，一面添加曱基乙基酮 139.1伤一面降溫，而得含有聚胺曱酸酯醇酸預聚物之反應混合液（含有醇酸成分之末端異氰酸醋聚胺甲酸酯預聚物之甲基乙基酮溶液）。所得含有聚胺甲酸酯醇酸預聚物之反應混合液中，加 2㈣錄（銘含量為6重量％)，溶液3 7份、環烧酸錯（錯 3量為6重量％)溶液5 6份及三乙胺2〇份攪拌均勻。繼 =用均貝分散機攪拌之去離子水1377.1份中，以少量徐 ^ 述έ有t胺曱酸醋醇酸預聚物之反應混合液 898.9 f刀’而得乳淡粉紅色之水分散液。該分散液中，於 318059 55 1374154 3〇°C以下溫度滴加N-(2-胺乙基）乙醇胺之10%水溶液 192·3份而進行鏈増長化反應，減壓下於5G°C去除曱基乙基酮及水，而得固形物為36 7〇/〇，黏度（25t>c)37mh · s， PH7.6,平均粒徑為59nm之含有活性氫原子之聚胺甲酸西旨醇酸樹脂乳液（a2)。^®SI, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol di-, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethyl Glycol 318059 49 1374154 monoacetic acid acetate, diethylene glycol monobutyl acetate, diethylene glycol di T ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether Acetate, lactone monoethyl ether acetate, dipropylene glycol dioxime ether, triethylene glycol butyl hydrazine ether, tetraethylene glycol dioxime ether, polyethylene glycol dioxime ether, 2, 2, 4-trimethyl-anthracene, 3-pentanediol diisobutyrate, triethylene glycol bis 2-ethylhexanoate, etc.), nitrogen-containing solvent (Ν-methylpyrrolidone, Ν-ethylpyrrolidone, Ν-methyl caprolactam) and the like. The solvent may be used singly or in combination of two or more. In the two-liquid-curing aqueous resin composition of the present invention, the amount of the curing agent (polyamide) of the polyamine methyl ester resin emulsion (Α) is not limited as long as the effect of the present invention can be exerted, for example, In terms of solid content, the hardener (β) is from j to 15 parts by weight, preferably from 5 to 60 parts by weight, based on the weight of the amidoxime oxime oxime resin emulsion (Α). To! It is more preferably about 4 parts by weight (e.g., 2 to 35 parts by weight, most preferably 3 to 3 parts by weight). The amount of the hardener (Β) used in the polyurethane resin emulsion (Α) is, in terms of solid content, for example, a reactive group in the hardener (8) (for example, isocyanic acid in the polyisophthalic acid And the ratio of the active hydrogen atom in the alkyd resin of the polyamine phthalic acid resin emulsion (Α) to the active hydrogen atom in the alkyd resin (for example, isocyanate group / active hydrogen atom), 〇3 To 4, 〇4 to 3 is preferred, and Q.5 to 2 is more preferred. When the equivalent ratio of the isocyanato group to the active gas atom exceeds the range, excessive reaction of the isocyanate group with water to produce carbon dioxide 'will seriously impair the appearance of the coating film' and the above equivalent ratio does not reach the above range, There is a problem in that the crosslink density is not as good as the residual hydrogen atom in the coating film, and the water resistance is remarkably deteriorated. χ, polyaminecarboxylic acid _ acid resin 318059 50 1374154 The active hydrogen atom in the polyurethane resin in the emulsion (A) refers to the polyamine phthalic acid prealky acid prepolymer having a terminal isocyanate group. The hydroxyl group in the polyamine used in the chain growth, or the polyamine phthalate alkyd prepolymer (containing no isocyanate group). The hydroxyl group in the polyamine, and the polycarbamate alkyd prepolymer are used in the synthesis. The carboxyl group in the compound containing an active hydrogen atom, and the total of the radical and/or the ruthenium in the unsaturated compound containing an active hydrogen atom used in the radical polymerization. • A metal desiccant or an anthraquinone UC, an aqueous resin composition of the present invention (two-liquid-curing aqueous resin composition #), may contain a metal desiccant (C). As the metal desiccant (c), a fatty acid metal salt of a conventional metal desiccant (drying agent for coating) can be used. The fatty acid metal salt is, for example, a naphthene acid metal salt (cobalt of naphthene, lead naphthenate, bismuth naphthenate, manganese naphthenate, naphthenic acid, etc. ), octanoic acid metal salt (octanoic acid, octanoic acid, octanoic acid, octanoic acid, #octanoic acid and other polyvalent metal salts such as octanoic acid). These metal desiccants may be used alone or in combination of two or more. In general, when two or more kinds of the fatty acid metal salt are combined, high effects such as cobalt naphthenate and other naphthenic acid metal salts (for example, lead naphthenate 'zirconium naphthenate, manganese naphthenate, and the like) are known. The combination of zinc naphthenate and the like is used in a wide range of applications. Further, the above fatty acid metal salt may form a coordination compound from a metal and an amine. In particular, fatty acid gold salts or metal and amine complexes containing different kinds of metals are used as lead-free desiccants, and can be made into a highly active desiccant, which is also environmentally friendly. The metal desiccant is a metal desiccant of a commercially available amine complex compound. Example #大日本墨化学工业318059 1374154 (Industrial Applicability) The two-liquid hardening type aqueous resin composition of the present invention is useful as Adhesives, coating agents (coatings, printing inks, etc.), primers, can be used on the surface of various substrates (metal, plastic or polymer materials 'slate, cement, mortar and other inorganic materials, paper, wood, etc.) use. In particular, the two-liquid-curable water-based paint of the present invention is used for room temperature hardening and heat hardening, for example, it can be used for woodworking paints or water-based primers at room temperature, and can be used for eight-vehicle paints by heat curing. The invention is described in detail by way of examples, but the invention is not limited by the examples. Further, the parts and amounts shown in the examples and comparative examples represent the parts by weight and % by weight. Alkyd resin (PEsn: ^蜩芈j equipped with a stirrer' nitrogen inlet tube, distillation column and thermometer in a five-necked flask, adding high-diene fatty acid (KF Industry Co., Ltd., high-definition φ) 3308.3 parts, pentaerythritol 821.2 487.3 parts of isophthalic acid and 2 parts of mono-n-butyltin oxide 酯·2 parts of the esterification catalyst were introduced under nitrogen, and the mixture was heated to 230 ° C. Stirring for 8 hours to remove the condensation water Reacts with the hydroxyl group. After confirming that the reaction solution reaches a predetermined hydroxyl group content, it is cooled to 30 ° C' to obtain an alkyd resin (PES1) having a hydroxyl group value of 75.3. Alkyd tree 1 (PES2, PES3, PES4, PES5) According to the same operation of alkyd resin (PES1), the alkyd resin (PES2, PES3, PES4, PES5) was prepared according to the formula shown in Table 1. 53 318059 1374154 Table 1 Alkyd resin PES1 PES2 PES3 PES4 PES5 Oil composition (parts) High Grade II Fatty Acid 3308.3 — — — A Dehydrated Dry Hemp Seed Oil Fatty Acid — 3385.2 — — A Soybean Oil Fatty Acid _ 3249.0 One Coconut Oil Fatty Acid _ — 2941.3 2761.1 Multivalent Polyol (Parts) Pentaerythritol 8 21.2 840.3 861.1 1176.5 1288.5 Polyvalent polycarboxylic acid (parts) Isophthalic acid 487.3 498.6 511 698.1 764.6 Catalyst (parts) Mono-n-butyltin oxide 0.2 0.2 0.2 0.2 0.2 Base price (potassium hydroxide mg/g) 75.3 74.2 85.8 136.3 184.5 Preparation of polyamine phthalate alkyd resin emulsion (al) containing active hydrogen atom Prepared in a five-necked flask equipped with a stirrer, a wearing condenser, a nitrogen inlet tube, a silicone drying tube and a thermometer, and injecting benzene. 174.2 parts of diisocyanate (product of Mitsui Takeda Chemical Co., Ltd., COSMONATE T-80), 207.1 parts of methyl ethyl ketone, stirred to complete homogeneity in a nitrogen stream, and then added 272.9 parts of alkyd resin (PES1) having a hydroxyl group price of 75.3. 38.1 parts of neopentyl glycol and 32.6 parts of dihydroxymercaptobutyric acid were stirred at 70 to 80 ° C for 2 hours. After confirming that the reaction solution had reached a predetermined isocyanate content, 138.1 parts of methyl ethyl ketone was added thereto. While lowering the temperature, a reaction mixture containing a polyamine phthalate alkyd prepolymer (a mercapto ethyl ketone solution containing a terminal isocyanate polyamine phthalate prepolymer of an alkyd component) was obtained. Acid ester 863 parts of the reaction mixture of the alkyd prepolymer. • Stirring with a homodisperser, adding 117.5 parts of a 1 5% aqueous solution of 2-diamine-ethanol, and adding 1268.2 parts of deionized water to obtain a pale pink color. 54 318059 1374154 Aqueous dispersion. In the dispersion, 192.3 parts by mass of N-(2-aminoethyl)ethanolamine was added dropwise at 30 ° C or lower to carry out a chain extension reaction, and the mercapto ethyl ketone was removed at 5 ° C under reduced pressure. And water 'added lead-free desiccant (1) s B Japanese company product, ADDITOL VXW 6206) 4.4 parts, and obtained solid matter 36 8 〇 / 〇, viscosity (25 ° C) 46 mPa · s, pH 7.6, average particle size of 84 nm Polyurethane alkyd resin emulsion (al) of active hydrogen atom. A polyamine formate resin of the active oxygen n, a f-type flask equipped with a stirrer, a wearable condenser, a nitrogen inlet tube, a silicone drying tube and a thermometer, and a toluene diisocyanate (product of Mitsui Takeda Chemical Co., Ltd.) , COSMONATE τ-80) 174.2 parts and mercapto ethyl ketone 208.7 wounds were stirred until completely uniform in the nitrogen fluoride stream, and then added 276 9 parts of alkyd resin (PES2) with a base price of Μ.2, neopentyl glycol 3 parts of aliquots and 32.6 parts of dimethylolbutanoic acid were scrambled for 2 hours at a temperature of 70 to 80 t. After confirming that the reaction solution reached a predetermined isocyanate content, it was cooled by adding thiol ketone 139.1 while containing a polyglycol. A reaction mixture of an amine phthalate alkyd prepolymer (a methyl ethyl ketone solution of a terminal isocyanate urethane prepolymer containing an alkyd component). In the obtained reaction mixture containing the polyurethane urethane prepolymer, 2 (four) is recorded (the content is 6 wt%), the solution is 37 parts, and the solution of the ring-burning acid (the amount of the wrong 3 is 6% by weight) 5 6 parts and 2 parts of triethylamine were stirred well. Following the =1377.1 parts of deionized water stirred with a homodisperser, a small amount of the reaction mixture 898.9 f knife of the t-amine phthalic acid prepolymer was used to disperse the milky pink water. liquid. In the dispersion, 192. 3 parts of a 10% aqueous solution of N-(2-aminoethyl)ethanolamine was added dropwise at a temperature of 318059 55 1374154 3 ° C or lower to carry out a chain lengthening reaction, and the pressure was removed at 5 G ° C under reduced pressure. Mercaptoethyl ketone and water, the solid content is 36 7 〇 / 〇, viscosity (25t > c) 37mh · s, pH 7.6, average particle size of 59nm containing active hydrogen atom of polyamine formic acid Acid resin emulsion (a2).

按照表2所示配方，藉由含有活性氯原子之聚胺甲酸酯醇酸樹脂乳液（a2)相同操作，製得含有活性氫原子之聚胺曱酸酯醇酸樹脂乳液（a3、a4)。According to the formulation shown in Table 2, a polyamine phthalate alkyd resin emulsion containing active hydrogen atoms (a3, a4) was prepared by the same operation of the polyurethane resin alkyd resin emulsion (a2) containing an active chlorine atom. .

備有授摔機、戴式冷凝器、氮氣導入管、♦膠乾燥管及溫度計之五頸燒瓶中，投入甲苯二異氰酸酯（三井武田化 •學公司製品，COSMONATE Τ·80)174·2份及甲基乙基酉同 16 0.2伤，在氣氣流中，擾拌至完全均勻，加入經基價為 85.8之醇酸樹脂（peS3)251.6份、新戊二醇36.4份及二經曱基丁酸33.7份，在70至80°C下授拌2小時，確認反應液到達既定之異氰酸g旨含量後’ 一面加入甲基乙基酮1 $ •伤一面降溫’而得含有聚胺甲酸酯醇酸預聚物之反應混合 •液（含有醇酸成分之末端異氰酸酯聚胺甲酸酯預聚物之甲基乙基酮溶液）。所得含有聚胺曱酸酯醇酸預聚物之反應混合液762 9 56 318059 1374154 份用均質分散機攪拌中’添加2•二甲胺基乙醇之15〇/〇水溶液121.6份’再添加去離子水1355 5份，而得乳淡粉紅色之水分散液。該分散液在儿它以下溫度，滴加N-(2-胺乙基）乙醇胺之10%水溶液192.3份而進行鏈增長化反應，而得含有活性氫原子之聚胺曱酸酯醇酸樹脂乳液。備有攪拌機、戴式冷凝器、氮氣導入管及溫度計之五頸燒瓶中’所得含有活性氫原子之聚胺曱酸酯醇酸樹脂乳液2437.6份’授拌中，加入不飽和化合物之苯乙烯124 〇份，自由基聚合起始劑之2,2’_偶氮雙異丁腈79份，升溫到80°C ’反應4小時’減壓下在5(rc去除甲基乙基酮及水，加入無錯乾燥劑（ADDITOL VXW 6206)5.3份，而得固形物為 37.7% ’ 黏度（25。(：）131mPa · s ’ pH8.0，平均粒徑為 74nm 之含有活性氫原子之聚胺甲酸酯醇酸樹脂乳液（a5)。舍省活性氧！子之聚胺甲酸酯醇酸榭脂齓液（a6>i之調劁備有攪拌機、戴式冷凝器、氮氣導入管、矽膠乾燥管及溫度計之五頸燒瓶中’投入曱苯二異氰酸酯（三井武田化學公司製品’ COSMONATE Τ-80)174.2份及曱基乙基酮 202.9份’在氮氣流中攪拌至完全均勻，加入經基價為74 2 之醇酸樹脂（PES2)258.9份，甘油單甲基丙烯酸酯8份，新戍二醇35.6份及二經甲基丁酸30.4份，在70至80 °C下授拌2小時’確認反應液到達既定之異氰酸酯含量，一面添加曱基乙基酮135.2份一面降溫至301，而得含有聚胺曱酸S旨醇酸預聚物之反應混合液（含有醇酸成分之末端異氰 318059 57 1374154 酸酯聚胺甲酸酯預聚物之甲基乙基酮溶液）。所得含有聚胺甲酸酯醇酸預聚物之反應混合液845.2 份’加入環烷酸鈷（鈷含量為6重量％)溶液4乃份及環烷酸錯（錯含量為6重量％)溶液6.7份，使用均質分散機攪拌中，添加2-二曱胺基乙醇之丨5〇/0水溶液109.9份，再加入去離子水1694.7份’而得乳淡粉紅色之水分散液。該分散液在30°C以下的溫度’滴加n-(2-胺乙基）乙醇胺之10%水溶液192.3份而進行鏈增長化反應，而得含有活性氫原子之聚胺甲酸酯醇酸樹脂乳液。備有攪拌機、戴式冷凝器、氮氣導入管及溫度計之燒瓶内’所得含有活性氫原子之聚胺曱酸酯醇酸樹脂乳液 2853.3份在授拌中加入不飽和化合物之甲基丙烯酸甲酯 120.4份及乙二醇二曱基丙烯酸酯6·3份，自由基聚合起始劑之2,2、偶氮雙異丁腈8份，升溫至8〇°c，反應4小時，在減壓下於50。(：除去甲基乙.基酮及水，而得固形物為 37.3% ’ 黏度（25°C)100mPa · s，pH7.6，平均粒徑為 82nm 之含有活性氫原子之聚胺曱酸酯醇酸樹脂乳液（a6)。盒有活性虱原子之眾胺甲酸酯醇酸樹脂乳液(a7 $ 之镅色按照表3所示配方，藉由含有活性氫原子之聚胺曱酸酯醇酸樹脂乳液（a2)相同操作，而調製得含有活性氫原子之聚胺甲酸酯醇酸樹脂乳液（a7至39)。全有活性氧胺曱酸酯榭脂乳液⑴夕”j 318059 58 1374154 備有攪拌機、戴式冷凝器、氮氣導入管、矽膠乾燥管及溫度計之五頸燒瓶中，投入4,4，·二苯基甲烷二異氰酸= 250.2份及曱基乙基酮3〇3 〇份，在氮環境中，升溫至^ C，攪拌至4,4 -二笨基甲烧二異氰酸酯完全溶解。然後， .升溫至50°C，加入曱基丙烯酸2-羥乙基酯26份，攪拌3〇分鐘使異氰酸基和羥基反應。反應後，依順序添加分子量為1000之聚丙二醇（三井武田化學公司製品，ACTocot Ρ-22)94·〇份’二丙二醇25 2份，二乙二醇2〇份二經甲基丁酸39份，調整溫度在5〇至6(rc之同時攪拌4小時，確認反應液到達既定之異氰酸酯含量，降溫至3〇它，而得 •含有聚胺曱酸酯聚合物之反應混合液（末端異氰酸酯聚胺曱酸酯預聚物之曱基乙基酮溶液）。所得含有聚胺曱酸酯聚合物之反應混合液757 4份用均質分散機授拌下，加入2·二曱胺基乙醇之15%水溶液 156.4份，再加入去離子水983 4份，而得乳青白色之水分 •散液。該分散液中’於3(rc以下的溫度滴加N(2胺乙乙醇胺，！0〇/〇水溶液138.9份而進行鍵增長化反應、減土壓下於50 C除去曱基乙基酮及水’而得固形物為34 9%，黏度(^t)3400mPa· s，pH8.3,平均粒徑為3inm之含有活性氫原子之聚胺曱酸酯樹脂乳淚（al〇)。全直鱼^原子之聚麼!之言固必備有攪拌機、戴式冷凝器、^ t # " 、、7机〇〇虱軋ν入官 '矽膠乾燥管及溫度計之五頸燒瓶中，投入4 4，_ -键其田ρ 田k ，4 —本基曱烷二異氰酸酯 318059 59 1374154 250.2份及不飽和化合物之苯乙烯U61份，在氮環境中，升溫至4(TC，攪拌至4,4，-二笨基曱烷二異氰酸醋^全溶解。然後，升温混合液至50°C，依順序加入分子量為1〇〇〇之聚丙二醇（三井武田化學公司製品，沉 • Ρ·22)128.6份，二乙二醇27.3份，三羥甲基丙烷12 4份，二羥甲基丁酸45·7份及調整黏度用之曱基乙基酮1934 份，調整溫度在50至60°C之同時攪拌4小時，確認反應液到達既定之異氰酸酯含量，降溫至30°C，而得含有聚胺甲酸酯聚合物之反應混合液（末端異氰酸酯聚胺甲酸酯預聚物之不飽和單體（苯乙稀）·曱基乙基酮溶液）。 • 所得含有聚胺曱酸酯預聚物之反應混合液773.7份中’投入不飽和化合物之三羥甲基丙烷三丙烯酸酯17 4 份，用均質分散機攪拌中，添加2_二曱胺基乙醇之15%水溶液183.4份，再加入去離子水1333份，而得乳青白色之水分散液。該水分散液在3(TC以下的溫度，滴加n-(2-胺 φ乙基）乙醇胺之1〇〇/0水溶液丨38 9份而進行鏈增長化反應，而得含有不飽和化合物（苯乙烯_三羥甲基丙烷三丙烯酸酯）之聚胺甲酸酯樹脂乳液。備有授拌機、戴式冷凝器、氮氣導入管及溫度計之燒瓶中’所得含有不飽和化合物（苯乙烯_三羥曱基丙烷三丙 •稀酸醋）之聚胺曱酸酯樹脂乳液2446.4份中，授拌下加入 •自由基聚合起始劑之2,2，-偶氮雙異丁腈3.8份，升溫至80 C ’反應2小時，減壓下於5〇〇c去除甲基乙基酮及水，而得固形物為35.0%，黏度（25°C)42mPa . s ’ pH8.6，平均粒 60 3)8059In a five-necked flask equipped with a shattering machine, a wearing condenser, a nitrogen inlet tube, a ♦ gel drying tube and a thermometer, 174·2 parts of toluene diisocyanate (product of Mitsui Takeda Chemical Co., Ltd., COSMONATE Τ80) were introduced. Methyl ethyl hydrazine with 16 0.2 injury, in the gas stream, disturbed to complete uniformity, adding 251.6 parts of alkyd resin (peS3) with a base price of 85.8, 36.4 parts of neopentyl glycol and dimercaptobutyric acid 33.7 parts, mixed at 70 to 80 ° C for 2 hours, confirming that the reaction solution reached a predetermined content of isocyanate g, 'one side added methyl ethyl ketone 1 $ • one side of the wound is cooled' and contains urethane A reaction mixture solution of a prepolymeric acid prepolymer (a methyl ethyl ketone solution containing a terminal isocyanate polyurethane prepolymer of an alkyd component). The obtained reaction mixture containing the polyamine phthalate alkyd prepolymer 762 9 56 318059 1374154 parts was stirred with a homodisperser to add 121.6 parts of a 15 〇 / 〇 aqueous solution of 2 dimethylaminoethanol. Water 1355 5 parts, and a milky pink water dispersion. The dispersion was subjected to a chain extension reaction at a temperature below the temperature of 192.3 parts of a 10% aqueous solution of N-(2-aminoethyl)ethanolamine to obtain a polyamine phthalate alkyd resin emulsion containing an active hydrogen atom. . 2437.6 parts of a polyamine phthalate alkyd resin emulsion containing active hydrogen atoms obtained in a five-necked flask equipped with a stirrer, a wearer condenser, a nitrogen inlet tube and a thermometer. Styrene 124 with an unsaturated compound added thereto 〇, 79 parts of 2,2'-azobisisobutyronitrile of free radical polymerization initiator, warmed to 80 ° C 'reaction 4 hours' under reduced pressure at 5 (rc removal of methyl ethyl ketone and water, 5.3 parts of the error-free desiccant (ADDITOL VXW 6206) was added to obtain a solid content of 37.7% 'viscosity (25. (:) 131 mPa · s 'pH 8.0, average particle size of 74 nm of polyamine containing active hydrogen atoms). Acidic Alkyd Resin Emulsion (a5). Sodium Reactive Oxygen! Polyurethane Alkyd Ester Sputum (a6> 之之劁劁劁劁劁劁劁劁劁劁劁劁劁劁劁劁劁劁劁劁劁劁劁劁劁劁劁 a a a a a a a In a five-necked flask of a tube and a thermometer, 'input benzene diisocyanate (product of Mitsui Takeda Chemical Co., Ltd. 'COSMONATE Τ-80) 174.2 parts and 202.9 parts of decyl ethyl ketone were stirred until completely uniform in a nitrogen stream, and the base price was added. 258.9 parts of alkyd resin (PES2) of 74 2, glycerol monomethacrylic acid 8 parts of ester, 35.6 parts of neodecanediol and 30.4 parts of dimethylbutyric acid, and mixed at 70 to 80 °C for 2 hours, confirming that the reaction solution reached a predetermined isocyanate content, and adding 135.2 parts of mercaptoethyl ketone. The temperature is lowered to 301, and the reaction mixture containing the polyamine phthalic acid S-alkyd prepolymer (the methyl ethyl group of the terminal isocyanide 318059 57 1374154 acid ester polyurethane prepolymer containing the alkyd component) is obtained. Ketone solution). The resulting reaction mixture containing polyurethane prepolymer prepolymer 845.2 parts 'addition of cobalt naphthenate (cobalt content of 6 wt%) solution 4 parts by weight and naphthenic acid error (error content is 6 6.7 parts by weight of the solution, stirred with a homodisperser, adding 109.9 parts of 丨5〇/0 aqueous solution of 2-diamylaminoethanol, and then adding 1694.7 parts of deionized water to obtain a milky pink water dispersion The dispersion was subjected to a chain extension reaction by dropwise addition of 192.3 parts of a 10% aqueous solution of n-(2-aminoethyl)ethanolamine at a temperature of 30 ° C or lower to obtain a polyurethane having an active hydrogen atom. Acid resin emulsion. Flask with mixer, wearing condenser, nitrogen inlet tube and thermometer 'After obtaining 2853.3 parts of polyamine phthalate alkyd resin emulsion containing active hydrogen atom, 120.4 parts of methyl methacrylate and 6·3 parts of ethylene glycol dimercapto acrylate were added to the unsaturated compound. Polymerization initiator 2, 2, azobisisobutyronitrile 8 parts, the temperature was raised to 8 ° C, the reaction was carried out for 4 hours, under reduced pressure at 50. (: removal of methyl ethyl ketone and water, The solid matter was 37.3% 'viscosity (25 ° C) 100 mPa · s, pH 7.6, and an active hydrogen atom-containing polyamine phthalate alkyd resin emulsion (a6) having an average particle diameter of 82 nm. A carbamate alkyd resin emulsion having an active ruthenium atom (the color of a7 $ is the same as that shown in Table 3, and the same operation is carried out by a polyamine phthalate alkyd resin emulsion (a2) containing an active hydrogen atom. The polyurethane urethane resin emulsion (a7 to 39) containing active hydrogen atoms is prepared. All of the active oxyamine phthalate oxime emulsions (1) 夕"j 318059 58 1374154 are equipped with a mixer, a wearer, In a five-necked flask of a nitrogen gas introduction tube, a silicone drying tube and a thermometer, 4,4, diphenylmethane diisocyanate = 250.2 parts and decyl ethyl ketone 3 〇 3 parts were added, and the temperature was raised in a nitrogen atmosphere. To ^ C, stir until 4,4 - di-p-methoxylated diisocyanate is completely dissolved. Then, heat up to 50 ° C, add 26 parts of 2-hydroxyethyl methacrylate, stir for 3 minutes to make isocyanic acid The reaction with a hydroxyl group. After the reaction, a polypropylene glycol having a molecular weight of 1000 (product of Mitsui Takeda Chemical Co., Ltd., ACtocot Ρ-22) 94·2 parts of dipropylene glycol, 2 parts of dipropylene glycol, and 2 parts of diethylene glycol are added in this order. 39 parts of butyric acid, the temperature was adjusted at 5 〇 to 6 (rc while stirring for 4 hours, confirming the arrival of the reaction solution The isocyanate content is lowered to 3 Torr, and a reaction mixture containing a polyamine phthalate polymer (a thioglycol ethyl ketone solution of a terminal isocyanate polyamine phthalate prepolymer) is obtained. 4 parts of the reaction mixture of the acid ester polymer were mixed with a homodisperser, 156.4 parts of a 15% aqueous solution of 2,2,2,5-aminoethanol, and 983 4 parts of deionized water were added to obtain a milky white water. • Dispersion. In the dispersion, N (2 amine ethyl alcoholamine, 13 份 / 〇 aqueous solution 138.9 parts was added to the temperature below rc to carry out the bond growth reaction, and the soil reduction was carried out at 50 C to remove the sulfhydryl group. Ethyl ketone and water 'have a solid content of 34 9%, a viscosity (^t) of 3400 mPa·s, a pH of 8.3, an average particle size of 3 inm of polyamine phthalate resin containing active hydrogen atoms (al〇) ). All the straight fish ^ atomic gathering! The words must have a blender, wearing a condenser, ^ t # ",, 7 machine rolling ν into the official 'silicone drying tube and thermometer in the five-necked flask , input 4 4, _ - bond Qitian ρ field k, 4 - decyl decane diisocyanate 318059 59 1374154 250.2 parts and unsaturated The styrene U61 part of the compound is heated to 4 (TC, stirred to 4,4,-di-p-decyl diisocyanate vinegar in a nitrogen atmosphere. Then, the mixture is heated to 50 ° C, 128.6 parts of polypropylene glycol (product of Mitsui Takeda Chemical Co., Ltd., Shen • Ρ·22), 128.6 parts of diethylene glycol, 12 parts of trimethylolpropane, and dimethylolbutyric acid were added in this order. 4,7 parts and 1934 parts of thiol ethyl ketone used for adjusting the viscosity, and the temperature was adjusted at 50 to 60 ° C for 4 hours, and it was confirmed that the reaction liquid reached a predetermined isocyanate content, and the temperature was lowered to 30 ° C to obtain a poly A reaction mixture of a urethane polymer (unsaturated monomer (styrene) thioglycol ethyl ketone solution of a terminal isocyanate polyurethane prepolymer). • In 773.7 parts of the obtained reaction mixture containing the polyamine phthalate prepolymer, 17 parts of trimethylolpropane triacrylate which was charged with an unsaturated compound, and stirred with a homodisperser, and added with 2-diamine. 183.4 parts of a 15% aqueous solution of ethanol, and then added 1333 parts of deionized water to obtain a milky white aqueous dispersion. The aqueous dispersion is subjected to a chain extension reaction at a temperature of 3 (TC or less, dropwise addition of 38 parts of n-(2-amine φethyl)ethanolamine 1 〇〇 /0 aqueous solution to obtain an unsaturated compound ( Polyurethane resin emulsion of styrene_trimethylolpropane triacrylate) In the flask equipped with a mixer, a condenser, a nitrogen inlet tube and a thermometer, the resulting unsaturated compound (styrene) 2446.4 parts of a polyamine phthalate resin emulsion of trishydroxypropylpropane tripropylene dilute acid vinegar, and 3.8 parts of 2,2,-azobisisobutyronitrile added with a radical polymerization initiator. The temperature was raised to 80 C 'reaction for 2 hours, and methyl ethyl ketone and water were removed at 5 〇〇c under reduced pressure to obtain a solid content of 35.0%, and a viscosity (25 ° C) of 42 mPa. s 'pH 8.6, average granules 60 3) 8059

1374154 V 徑為88nm之含有活性氫原子之聚胺曱酸酯丙烯酸樹脂乳液（all)。表2 聚胺甲酸薛醇酸樹脂乳液（A)份 a 1 a 2 a 3 a 4 a 5 a 6 聚異氰酸ϋ MDI 一一一一一一 TDI 174. 2 174. 2 174. 2 174. 2 174. 2 ί74. 2 聚醇 PPG — 一一 — 一一 PTG 一一一 44. 3 一一 PES1 272. 9 一一一 — 一醇酸樹脂 PES2 一 276. 9 一一一 258. 9 FES3 — 一 251. 6 一 251. 6 一 PES4 一一一 113. 9 一一 DPG 一一一一 — 一低分子量多元醇 DEG 一 ~ 一一一一 NPG 38. 1 38. 1 36. 4 46 36. 4 35. 6 TMP 一一一 — 一一含陰離子性基化合物 DMBA 32.6 32. 6 33. 7 24. 6 33. 7 30. 4 含活性氩原子不袍和 HEMA 一一一一一一也合物 CLM 一一一一一 8 有機溶劑 MEK 207, 1 208. 7 160. 2 161. 2 160. 2 202. 9 不飽和有機溶蒯 SM 一一一一一一有機溶倒（追加部分） MEK 138. 1 139. 1 106. 8 107. 5 106. 8 135. 2 中和劑 15XDMEtA 117. 5 一一一 121. 6 109. 9 TEA 一 20. 0 1B. A 15. 1 一 - 多胺 10XA-EA 192. 3 192. 3 192. 3 192. 3 192. 3 192. 3 去離子水 1268. 2 1377. 1 1086. 8 1232. 1 1355. 5 1694. 7 su — — 一一 124 一不飽和化合物 MUA 一一 — — 120. 4 (追加部分） THP-A 一一一一一一 EGMA 一 — 一一一 6. 3 自由基聚合起始劑 AIBN 一一 — 一 7. 9 8 混合乾嫖劑 4. 4 一一一 5. 3 — 金屬乾燥劑（C)(份） NaPhCo 一 3. 7 3. 6 一 — 4. 5 NaPhZr 一 5. 6 5. 3 一一 1 7 固形物（％) 36. 8 36. 7 37. 7 33. 6 37. 7 37. 3 2 5*C黏度（mP a • s) 46 37 88 256 131 100 Ρ Η 7. 6 7. 6 7. 4 7. 8 8 7. 6 平均粒徑（η m) 84 59 49 78 74 82 61 318059 1374154 表聚胺甲酸酯醇酸樹脂乳液(A)(份） a 7 a 8 a 9 a 10 all 聚異氮酸酯 UDI 一一一 250. 2 250.2 TOI 174. 2 174. 2 174. 2 — 一多元醇 PPG 一一一 94 128.6 PTG 一 44. 3 39. 1 — 一醇酸樹脂 PES1 一一一 — 一 PES2 254. 8 — 一一一 PES3 一一 — 一一 PES4 一 113. 9 一 — 一 PES5 一一 89. 3 — — 低分子量多元醇 DPG 一一一 25.2 一 DEG 一 '— 一 20 27. 3 NPG 38. 1 46 40. 7 一 — TMP 一 — — — 12.4 含陰離子性基化合物 DUBA 一一 23. 2 39 45. 7 DMPA 29. 6 22. 2 — 一一含活性氫原子不飽和化合物 HEHA — 一一 26 — GLM 一一一一一有機溶劑 UEK 165.6 160. 3 118.4 303 193. 4 不飽和有機溶劑 SM 一一一一 116.] 有機溶劑（追加部分） UEK 165.6 106. 8 78. 9 一一中和劑 ISXDMEtA 一一一 156. 4 183. 4 TEA 20 15. 1 14. 3 一一聚胺 10XA-EA 192. 3 192. 3 23B. 1 138. 9 138. 9 去離子水 1109. 5 1224. 2 9S8 983. 4 1333 不餘和化合物 (追;jo部分） SM 一一一 _ — MUA 一一 — 一一 THP-A 一 — 一一 17. 4 EGMA 一一一一一自由基聚合起始劑 AtBN 一 — 一 — 3. 8 金屬乾燥劑(C)(份）混合乾燥劑 — 一一一一 NaPhMn 3. 6 一 — — 一固形物（％) 38 32.4 41. 6 34.9 35 2 51〇黏度（^^3-5) 300 5340 660 3400 42 pH 7. 4 7. 8 7. 6 8. 3 8.6 平均粒徑（n m) 79 60 71 31 881374154 V polyamine phthalate acrylic resin emulsion (all) containing active hydrogen atoms at a diameter of 88 nm. Table 2 Polyammonium sulphate resin emulsion (A) parts a 1 a 2 a 3 a 4 a 5 a 6 cesium polyisocyanate MDI 1111 1 TDI 174. 2 174. 2 174. 2 174. 2 174. 2 ί74. 2 Polyol PPG - one by one - one by one PTG one by one 44. 3 one one PES1 272. 9 one one - one alkyd resin PES2 a 276. 9 one one one 258. 9 FES3 — 1251. 6 251. 6 A PES 4 117. 9 -11 DPG -11 - a low molecular weight polyol DEG 1-1 to 117 NPG 38. 1 38. 1 36. 4 46 36. 4 35. 6 TMP 1-1—one anionic group-containing compound DMBA 32.6 32. 6 33. 7 24. 6 33. 7 30. 4 Containing active argon atoms without robes and HEMA 1-1 one-to-one conjugate CLM 1111 1 8 Organic solvents MEK 207, 1 208. 7 160. 2 161. 2 160. 2 202. 9 Unsaturated organic solvent SM One-to-one organic solution (additional part) MEK 138. 1 139. 1 106. 8 107. 5 106. 8 135. 2 Neutralizing agent 15XDMEtA 117. 5 One one one 121. 6 109. 9 TEA a 20. 0 1B. A 15. 1 mono-polyamine 10XA-EA 192 . 3 192. 3 19 2. 3 192. 3 192. 3 192. 3 Deionized water 1268. 2 1377. 1 1086. 8 1232. 1 1355. 5 1694. 7 su — — One 124 One unsaturated compound MUA One-120. 4 (additional part) THP-A 1111 - EGMA 1-1 - 6.1 6. Free radical polymerization initiator AIBN one - one 7. 9 8 mixed cognac 4. 4 one one one 5. 3 — Metal desiccant (C) (parts) NaPhCo - 3. 7 3. 6 - 4. 5 NaPhZr - 5. 6 5. 3 -1 7 Solids (%) 36. 8 36. 7 37. 7 33. 6 37. 7 37. 3 2 5*C Viscosity (mP a • s) 46 37 88 256 131 100 Ρ Η 7. 6 7. 6 7. 4 7. 8 8 7. 6 Average particle size (η m 84 59 49 78 74 82 61 318059 1374154 Polyurethane alkyd resin emulsion (A) (parts) a 7 a 8 a 9 a 10 all Polyisophthalate UDI One to one 250. 2 250.2 TOI 174 2 174. 2 174. 2 — A polyol PPG 1-94 948.6 PTG a 44. 3 39. 1 — an alkyd resin PES1 one to one — one PES2 254. 8 — one one one PES3 one one — One PES4 one 113. 9 one - one PES5 one one 89. 3 - Low molecular weight polyol DPG 1 - 25.2 A DEG a - 20 20 27. 3 NPG 38. 1 46 40. 7 A - TMP a - 12. Aliene compound DUBA one 23. 2 39 45. 7 DMPA 29. 6 22. 2 — One-to-one unsaturated compound containing active hydrogen atom HEHA — 1-2 — GLM One-to-one organic solvent UEK 165.6 160. 3 118.4 303 193. 4 Unsaturated organic solvent SM One by one 116.] Organic solvent (additional part) UEK 165.6 106. 8 78. 9 One-and-one neutralizer ISXDMEtA One-to-one 156. 4 183. 4 TEA 20 15. 1 14. 3 One-polyamine 10XA-EA 192. 3 192. 3 23B. 1 138. 9 138. 9 Deionized water 1109. 5 1224. 2 9S8 983. 4 1333 Residual compound (chasing; jo part) SM one by one _ — MUA one by one — one THP- A one - one one 17.4 EGMA one-to-one radical polymerization initiator AtBN one - one - 3. 8 metal desiccant (C) (parts) mixed desiccant - one by one NaPhMn 3. 6 one — — A solid (%) 38 32.4 41. 6 34.9 35 2 51〇 Viscosity (^^3-5) 300 5340 660 3400 42 pH 7. 4 7. 8 7. 6 8. 3 8.6 Average particle size (n m) 79 60 71 31 88

又，表2及表3中之成分及其代號之意義如下： 62 318059 1374154 聚異氰酸酯 MDI : 4,4’-二苯基曱烷二異氰酸酯 TDI :曱苯二異氰酸酯（三井武田化學公司製品， • COSMONATE T-80) . 多元醇 PPG :分子量為1000之聚丙二醇（三井武田化學公司製品，ACTOCOL P-22) PTG :分子量為2000之聚四亞甲基醚乙二醇（保土谷籲化學工業公司製品，PTG-2000SN) 低< 分子量多元醇 DPG ：二丙二醇 DEG ：二乙二醇 NPG ：新戊二醇 TMP ：三羥曱基丙烷含陰離子性基化合物 DMBA :二羥甲基丁酸 DMPA :二羥曱基丙酸含活·十生氫原子之不飽矛口 4匕合物 HEMA :曱基丙烯酸2-羥基乙基酯 GLM :甘油單甲基丙烯酸酯（日本油脂公司製品，混合物 GLM) 有機溶劑 MEK :曱基乙基酮不含活性氫原子不飽和化合物（不飽和有機溶劑） 63 318059 1374154 SM :苯乙烯 MMA :曱基丙烯酸曱酯 TMP-A :三羥曱基丙烷三丙烯酸酯 EGMA:乙二醇二曱基丙稀酸酯中和劑 15%〇]\^1八：15%2-二曱胺基乙醇水溶液 TEA :三乙基胺聚胺 10%A-EA: 10%N-(2-胺乙基）乙醇胺水溶液自由基聚合起始劑 AIBN : 2,2’-偶氮雙異丁腈金屬乾燥劑混合乾燥劑：無鉛乾燥劑，鈷含量5重量％，鋰含量 0.2重量％，鍅含量7.5重量％(U.C.B.日本公司製品， ADDITOL VXW 6206)Further, the meanings of the components and their symbols in Tables 2 and 3 are as follows: 62 318059 1374154 Polyisocyanate MDI: 4,4'-diphenyldecane diisocyanate TDI: terpene diisocyanate (product of Mitsui Takeda Chemical Co., Ltd., COSMONATE T-80) . Polyol PPG: Polypropylene glycol with a molecular weight of 1000 (product of Mitsui Takeda Chemical Co., Ltd., ACTOCOL P-22) PTG: Polytetramethylene ether glycol with a molecular weight of 2000 (Bao Tu Gu Yu Chemical Industry Co., Ltd. Product, PTG-2000SN) Low < Molecular Weight Polyol DPG : Dipropylene Glycol DEG : Diethylene Glycol NPG : Neopentyl Glycol TPP : Trihydroxymethylpropane Propane Containing Anionic Compound DMBA : Dimethylol Butyric Acid DMPA : Dihydromercaptopropionic acid contains a live ten-hydrogen atom of insufficient spear 4 condensate HEMA: 2-hydroxyethyl methacrylate GLM: glycerol monomethacrylate (product of Japan Oil Company, mixture GLM) Organic solvent MEK: mercaptoethyl ketone contains no active hydrogen atom unsaturated compound (unsaturated organic solvent) 63 318059 1374154 SM : styrene MMA : decyl methacrylate TMP-A : trihydroxy decyl propane triacrylate EGMA :B Glycol dimercapto acrylate neutralizer 15% 〇] \^1 8: 15% 2-diammonium ethanol aqueous solution TEA: triethylamine polyamine 10% A-EA: 10% N-( 2-Aminoethyl)ethanolamine aqueous solution free radical polymerization initiator AIBN : 2,2'-azobisisobutyronitrile metal desiccant mixed desiccant: lead-free desiccant, cobalt content 5% by weight, lithium content 0.2% by weight,鍅 content 7.5 wt% (UCB Japan product, ADDITOL VXW 6206)

NaPhCo :環统酸鈷（钻含量6重量％)NaPhCo: cobalt cyclate (drilling content 6% by weight)

NaPhZr :環烷酸鍅（鍅含量6重量％)NaPhZr: bismuth naphthenate (鍅 content 6 wt%)

NaPhMn :環烧酸锰（猛含量6重量％) 實施例1 二液硬化型水性塗料（cl)之調製上述含有活性氫原子之聚胺曱酸酯醇酸樹脂乳液 (al)178.4份中，加入成膜助劑之N-曱基吡咯烷酮（NMP)9.4 份，使用聚氧伸乙基改質六亞曱基二異氰酸酯三聚物（三井 64 318059 1374154 武田化學公司製品，TAKENATE WD_24〇)i2 2份為硬化劑 (B)，經混合而調製得二液硬化型水性塗料（Η)。赶估用塗腔之镧寧j .。所得二液硬化型水性塗料（cl)使用100以m之塗布器’塗布於玻璃板及鋼板上。又，上述水性塗料塗布於玻璃板之後’在室溫下乾燥硬化〗星期做為評估用塗膜。又， φ上述水性塗料塗布於鋼板之後，於12(rc下燒烤30分鐘，做為評估用塗膜。又，使用240號之砂紙研磨未經加工之山面，進行毛刷塗布在室溫下乾燥硬化至翌日，再用4⑼號 .之砂紙研磨塗膜表面，再度用毛刷塗布，重複塗布2次穿: 成合計4層之塗膜，最後一次塗布後，在室溫下乾燥硬= 1星期’做為評估用塗膜。鲁實施例2至9 乂表4所示配方，按照貫施例相同操作，調製二液硬化型水性塗料（c2至c9)，再按照實施们相同操作，形成比較例1至4 以表3所示配方，按照實施例1相同摔液硬化型水性塗料_^13)，再按照實施例^關作’形成評估用塗膜。又’比較例3及4由於未混合有硬 318059 65 1374154 又，表4中之成分及其代號之意義如下：成膜助劑 NMP : N-甲基吡咯烷酮硬化劑（B) . B1 :聚氧伸乙基改質六亞曱基二異氰酸酯三聚物，三井武田化學公司製品，TAKENATE WD-240，異氰酸酯含量16.9重量％ Β2 :聚氧伸乙基聚氧化伸烷基改質六亞曱基二異氰酸 • 酯三聚物，三井武田化學公司製品，TAKENATE WD-248，異氰酸酯含量15.4重量％。評估 Π)聚胺甲酸酯醇酸樹脂乳液（Α)及硬化劑（Β)之互溶性含有活性氫原子聚胺甲酸酯醇酸樹脂乳液（al至all) 之調製例舉所得聚胺甲酸酯醇酸樹脂乳液（A)和硬化劑（B) 放入容量為300ml之樣品瓶中約1分鐘，用肉眼觀察按照表4所示比率混合時之互溶性，並依據下述基準評估之。 ◎:輕輕地搖動樣品瓶就能完全混合〇：用力搖動樣品瓶就能完全混合 △:用力搖動樣品瓶尚可混合（但隨時間經過會發生相分離） :用力搖動試料瓶也無法混合而發生相分離。 (2)塗膜之成膜性 67 318059 1374154 各貫施例及各比較例所得二液硬化型水性塗料塗布於玻璃板’用肉眼觀察塗膜之膜形成性，按照下述基準評估之。 ◎:塗膜不會發生裂羊:（容易獲得塗膜）〇：塗膜之一部分發生裂紋 · △:塗膜整體發生裂紋 X :無法形成臈 (3)塗膜外鏰各貫施例及各比較例所得二液硬化型水性塗料塗布4 層方、山毛櫸材B卞，用肉眼觀察塗膜外觀，按照下述基準評估之。NaPhMn: manganese sulphonate (6% by weight) Example 1 Preparation of a two-liquid-curing aqueous coating (cl) The above-mentioned active hydrogen atom-containing polyamine phthalate alkyd emulsion (al) was added to 178.4 parts. 9.4 parts of N-mercaptopyrrolidone (NMP), a film-forming auxiliary, using polyoxyethylene ethyl modified hexamethylene diisocyanate trimer (Mitsui 64 318059 1374154 Takeda Chemical Co., Ltd., TAKENATE WD_24〇) i2 2 parts A two-liquid hardening type water-based paint (Η) is prepared by mixing the hardener (B). Evaluate the use of the coating chamber. The obtained two-liquid-curable aqueous coating material (cl) was applied onto a glass plate and a steel plate using a coater of 100 m. Further, after the aqueous coating material was applied to a glass plate, it was dried and hardened at room temperature for a week as a coating film for evaluation. Further, φ of the above water-based paint was applied to a steel sheet, and then baked at 12 (rc for 30 minutes) as a coating film for evaluation. Further, the unprocessed mountain surface was polished using a No. 240 sandpaper, and brush coating was performed at room temperature. Dry and harden until the next day, and then grind the surface of the coating with 4(9). sandpaper, apply again with a brush, repeat the coating 2 times: into a total of 4 layers of coating film, after the last coating, dry at room temperature = 1 "Week" as the coating film for evaluation. The examples shown in Tables 2 to 9 are the same as those in the same example, and the two-liquid hardening type water-based paints (c2 to c9) are prepared, and then formed according to the same operation of the implementers. Comparative Examples 1 to 4 In the formulation shown in Table 3, the same liquid-repellent-type aqueous coating material as in Example 1 was used, and the coating film for evaluation was formed in accordance with the Example. Further, 'Comparative Examples 3 and 4 are unmixed with hard 318059 65 1374154. The meanings of the components in Table 4 and their codes are as follows: Film-forming auxiliary NMP: N-methylpyrrolidone hardener (B) . B1 : Polyoxygen Ethyl modified hexamethylene diisocyanate trimer, manufactured by Mitsui Takeda Chemical Co., Ltd., TAKENATE WD-240, isocyanate content 16.9 wt% Β2: polyoxy-extension ethyl polyoxyalkylene alkyl modified hexamethylene Isocyanate • ester trimer, product of Mitsui Takeda Chemical Co., Ltd., TAKENATE WD-248, isocyanate content 15.4% by weight. Evaluation of Π) Polycarbamate alkyd resin emulsion (Α) and hardener (Β) miscibility with active hydrogen atom polyurethane urethane resin emulsion (al to all) modulation exemplified by the obtained polyamine The acid ester alkyd resin emulsion (A) and the hardener (B) were placed in a sample bottle having a capacity of 300 ml for about 1 minute, and the mutual solubility at the ratios shown in Table 4 was visually observed and evaluated according to the following criteria. . ◎: Mix the sample bottle gently by shaking it gently: shake the sample bottle to mix completely. △: Shake the sample bottle carefully, but mix it (but phase separation occurs with time): shaking the sample bottle hard can not be mixed. Phase separation occurs. (2) Film-forming property of the coating film 67 318059 1374154 The two-liquid-curing aqueous coating material obtained in each of the examples and the comparative examples was applied to a glass plate. The film formability of the coating film was visually observed and evaluated according to the following criteria. ◎: The coating film does not crack the sheep: (Easy to obtain the coating film) 〇: Cracks occur in one part of the coating film. △: Cracks occur in the entire coating film. X: 臈 (3) coating film is not formed. The two-liquid-curable water-based paint obtained in the comparative example was coated with a four-layered and beech material B卞, and the appearance of the coating film was observed with the naked eye, and evaluated according to the following criteria.

◎ 〇 △ X 塗膜整體呈現高光澤而有重厚感覺塗膜整體有光澤塗膜整體呈退光狀態或白濁狀態塗膜整體發生裂紋 (4)耐水枓各貫施例及各比較例所得二液硬化型水性塗料塗布於鋼板及山毛櫸材（4層）時之㈣表面上垂滴水，不觀窣而上：加以覆盍，保持24小時後之塗膜狀態，用肉眼硗察而按照以下基準評估之。 ◎:塗膜整體無任何變化〇：塗膜有局部膨潤（發生鼓泡） 318059 68 1374154 △:塗膜整體膨潤或白化 X:塗膜整體溶解 XX ··水浸入裂紋中無法評估 (5)对濕執性各貝施例及各比較例所得二液硬化型水性塗料塗布於玻璃板、鋼板及山毛櫸材（4層）時之㈣表面上垂滴彿騰水’立即將裝有沸水之破璃瓶（槪底部分留有若干空隙之直徑為約5cm之瓶)放置於其上，防止水蒸汽揮發下覆蓋而保持20分鐘後，用肉眼觀察塗膜狀態，按照下述基準評估之。 ◎:塗膜整體無任何變化〇：塗膜有局部膨潤 △:塗膜整體膨潤或白化 X:塗膜整體溶解 XX:沸水浸入裂紋中無法評估 (6)封溶査I丨枓各實施例及各比較例所得二液硬化型水性塗料塗布於 f璃板及鋼板時之塗膜’使用甲基乙基酮進行摩擦試驗（免洗：筷先端夾以二布’浸潰甲基乙基嗣後擦拭塗媒）時加以測疋直至塗膜剥落為止之擦拭次數（來回一次計為 A，限為100次），按照下述基準評估之。 * ◎ : 100次以上也不會剝落，塗膜整體無任何變化 318059 69 1374154 〇.100次以上雖不會剝落，但塗膜整體有若干膨潤 △ : 5 0次以下塗膜整體剝落 X : 10次以下塗膜整體剝落鉛筆碩唐各實施例及各比較例所得二液硬化型水性塗料塗布於玻璃板、鋼板及山毛櫸材（4層）時之塗膜，依據JIS K5600-5-4方法測定鉛筆硬度。 (8)耐簽字筆油黑沄+μ 各實施例及各比較例所得二液硬化型水性塗料塗布4 次在山毛櫸材上所形成塗膜上，使m及紅色之ς二甲本，字筆劃線’保持3小時後，用乙醇擦拭乾淨，以肉眼觀察塗膜狀態，按照下述基準評估之。 ◎ •紅、黑色之簽字筆油墨可完全擦栻乾淨：紅、黑色之簽字筆油墨可局部或其中一色可擦拭乾淨 △:紅起溶解 X :紅乾淨色之簽子筆油墨可擦拭乾淨，但連塗膜一黑色之簽字筆油墨染入塗膜中完全無法擦拭各貝她例及各比較例之評估結果示於表5中 318059 70 1374154 Ο 耐溶劑性等。又，硬度之表現需要長久時間。實施例10 23°C，50% RH之條件下，以上述含有活性氫原子之 . 聚胺曱酸酯醇酸樹脂乳液（a4) 88.2份，添加成膜助劑之N-甲基吡咯烷酮（NMP) 6.8份而成之聚胺曱酸酯醇酸樹脂乳液（A)及硬化劑（B)之聚氧伸乙基聚氧化伸烷基改質六亞曱基二異氰酸酯三聚物（三井武田化學公司製品，ΤΑΚΕΝΑΤΕ 籲 WD-248，異氰酸基含量15.4%)及自來水，以聚胺曱酸酯醇酸樹脂乳液(Α)/硬化劑（Β)/自來水=95/5/95之比例（重量 - 比率）混合，調製而成二液硬化型水性底漆。事先用吹風機 . 處理表面之石板表面，在23°C、50% RH之條件下，將調製後之上述二液硬化型水性底漆立刻使用毛刷以塗布量為 150g/m2均句塗布後放置3小時。該塗膜表面上，以主劑及硬化劑之重量比率為1: 1的比例混合後之二液型胺甲酸馨酯系樹脂（地板用塗膜材料，三井武田化學公司製品，主劑：TAKENATE F-135，硬化劑：TAKELAC PC-5300)即刻使用鏝刀以塗布量為2000g/m2均勻塗布，在23°C，50% RH 下熟成7曰而製成石板塗布樣本。 • 實施例11 . 上述含有活性氫原子之聚胺曱酸酯醇酸樹脂乳液（a4) 88.2份，加以成膜助劑之N-甲基吡咯烷酮（NMP) 6.8份而成之聚胺曱酸酯醇酸樹脂乳液（A)、以80%濃度含有上述改 72 318059 1374154 .•i 質六亞甲基二異氰酸酯三聚物（ΤΑΚΕΝΑΤΕ WD-248)之丙二醇單曱醚乙酸酯（PMA)溶液作為硬化劑（B)以及自來水，以聚胺曱酸酯醇酸樹脂乳液（A)/硬化劑（B)/自來水 =95/6.3/95之比例（重量比）混合而調製成二液硬化型水性底漆，除上述之外，皆按照實施例10相同方法製成石板塗布試料。實施例12 • 上述含有活性氫原子之聚胺曱酸酯醇酸樹脂乳液（a4) 88,2份，加入成膜助劑之N-曱基吡咯烷酮（NMP) 6.8份而 - 成之聚胺曱酸酯醇酸樹脂乳液（A)、以80%濃度含有上述改 . 質六亞曱基二異氰酸酯三聚物（TAKENATE WD-248)之丙酮溶液作為硬化劑（Β)以及自來水，以聚胺甲酸酯醇酸樹脂乳液（Α)/硬化劑（Β)/自來水=95/6.3/95之比例（重量比）混合而成為二液硬化型水性底漆，除上述之外，皆按照實施例鲁10相同方法製成石板塗布試料。實施例13 上述含有活性氫原子之聚胺曱酸酯醇酸樹脂乳液（a9) 86.8份，加入成膜助劑之N-甲基吡咯烷酮（NMP) 8.2份而 - 成之聚胺曱酸酯醇酸樹脂乳液（A)、以80%濃度含有上述改質六亞甲基二異氰酸酯三聚物（TAKENATE WD-248)之丙二醇單曱醚乙酸酯（PMA)溶液作為硬化劑（B)以及自來水，以聚胺曱酸酯醇酸樹脂乳液（A)/硬化劑（B)/自來水 73 318059 1374154 =95/6.3/95之比例（重量比）混合而成二液硬化型水性底漆，除上述之外，皆按照實施例10相同方法製成石板塗布試料。比較例5 替代二液硬化型水性底漆’改用加系i液濕氣硬化型溶劑系底漆组成物（三井武田化學公司製品，Takenate M-402P)之外，皆按照實施例10相同方法製成石板塗布試料。比較例6◎ 〇 △ X The overall appearance of the coating film is high-gloss and has a thick feeling. The overall glossy film of the coating film is in a state of fading or white turbidity. The entire coating film is cracked. (4) Water-resistant sputum and the two liquids obtained in each comparative example. When the hardened water-based paint is applied to the steel plate and the beech (4 layers), the surface of the (4) dripping water is dripping on the surface, and the film is covered. The film state is maintained after 24 hours, and it is evaluated by the naked eye and evaluated according to the following criteria. It. ◎: There is no change in the whole film. 〇: The film is partially swollen (bubble occurs) 318059 68 1374154 △: The whole film is swollen or whitened X: The film is dissolved in the whole XX ·· Water immersion in the crack cannot be evaluated (5) The application of the two-liquid hardening type water-based paint obtained by the wet-resistance method and each comparative example on the glass plate, the steel plate and the beech (four layers) (4) on the surface of the dripping water, the water will be filled with boiling water. A bottle (a bottle having a diameter of about 5 cm with a plurality of voids left in the bottom portion) was placed thereon to prevent the water vapor from being volatilized and covered for 20 minutes, and the state of the coating film was observed with the naked eye, and evaluated according to the following criteria. ◎: There is no change in the whole coating film 〇: The coating film has partial swelling △: The whole film is swollen or whitened X: The whole film is dissolved XX: The boiling water is immersed in the crack and cannot be evaluated (6) Sealing solution I The coating film of the two-liquid-curing water-based paint obtained in each comparative example was applied to the glass plate and the steel plate. The rubbing test was carried out using methyl ethyl ketone (no-wash: the chopsticks were clamped with two cloths) and the methyl ethyl hydrazine was dipped. When the medium is applied, the number of wipings until the coating film is peeled off (returned to A once, limited to 100 times) is evaluated according to the following criteria. * ◎ : It will not peel off even if it is more than 100 times. There is no change in the whole film. 318059 69 1374154 〇. Although it will not peel off after 100 times or more, the whole film has some swelling △: 50 times or less of the film is peeled off completely X : 10 The coating film of the glass film, the steel plate, and the beech (4 layers) was applied to the glass film, the steel plate, and the beech (four layers), and the coating film was measured according to JIS K5600-5-4. Pencil hardness. (8) Resistant signature pen oil black 沄+μ The two-liquid-curing water-based paint obtained in each of the examples and the comparative examples was applied four times on the coating film formed on the beech wood to make m and red bismuth, and the strokes were drawn. After the line was kept for 3 hours, it was wiped clean with ethanol, and the state of the film was observed with the naked eye, and it was evaluated according to the following criteria. ◎ • Red and black signature pen ink can be completely wiped clean: red, black signature pen ink can be partially or one of the colors can be wiped clean △: red to dissolve X: red clean color of the signature pen ink can be wiped clean, but Even the film-black pen ink was dyed into the film and could not be wiped. The evaluation results of each case and each comparative example are shown in Table 5, 318059 70 1374154 耐 Solvent resistance. Also, the performance of hardness takes a long time. Example 10 Under the conditions of 23 ° C and 50% RH, 88.2 parts of the polyamine phthalate alkyd resin emulsion (a4) containing the above active hydrogen atom was added, and a film-forming auxiliary N-methylpyrrolidone (NMP) was added. ) 6.8 parts of polyamine phthalate alkyd resin emulsion (A) and hardener (B) polyoxyalkylene ethyl polyoxyalkylene alkyl modified hexamethylene diisocyanate trimer (Mitsui Takeda Chemical Co., Ltd. Company products, 吁 WD-248, isocyanate content 15.4%) and tap water, with a ratio of polyamine phthalate alkyd resin emulsion (Α) / hardener (Β) / tap water = 95/5/95 ( The weight-ratio is mixed to prepare a two-liquid hardening water-based primer. The surface of the slate is treated in advance, and the prepared two-liquid-curing aqueous primer is immediately coated with a coating amount of 150 g/m 2 at 23 ° C and 50% RH. 3 hours. On the surface of the coating film, a two-component type urethane-based resin which is mixed at a weight ratio of a main component and a curing agent of 1:1 (a coating material for flooring, a product of Mitsui Takeda Chemical Co., Ltd., main agent: TAKENATE) F-135, hardener: TAKELAC PC-5300) Immediately coated with a trowel at a coating weight of 2000 g/m2, and cooked at 23 ° C, 50% RH to form a slate coated sample. • Example 11. 88.2 parts of the above-mentioned polyamine phthalate alkyd resin emulsion (a4) containing an active hydrogen atom, and a polyamine phthalate obtained by adding 6.8 parts of N-methylpyrrolidone (NMP) as a film-forming auxiliary. Alkyd resin emulsion (A), containing propylene glycol monoterpene ether acetate (PMA) solution of the above modified 72 318059 1374154.•i hexamethylene diisocyanate trimer (ΤΑΚΕΝΑΤΕ WD-248) at 80% concentration The hardener (B) and the tap water are mixed with a polyamine phthalate alkyd resin emulsion (A)/hardener (B)/tap water=95/6.3/95 ratio (weight ratio) to prepare a two-liquid hardening type water. A primer coating sample was prepared in the same manner as in Example 10 except for the above. Example 12: The above-mentioned active hydrogen atom-containing polyamine phthalate alkyd resin emulsion (a4) 88, 2 parts, N-mercaptopyrrolidone (NMP) 6.8 parts of a film-forming auxiliary was added to form a polyamine oxime An acid ester alkyd resin emulsion (A) containing an acetone solution of the above-mentioned modified hexamethylene diisocyanate trimer (TAKENATE WD-248) at 80% concentration as a hardener (Β) and tap water to a polyamine Acidic alkyd resin emulsion (Α) / hardener (Β) / tap water = 95 / 6.3 / 95 ratio (weight ratio) mixed to become a two-liquid hardening type water-based primer, in addition to the above, in accordance with the examples 10 The same method was used to prepare a slate coating sample. Example 13 86.8 parts of the above-mentioned polyamine phthalate alkyd resin emulsion (a9) containing an active hydrogen atom, and 8.2 parts of N-methylpyrrolidone (NMP) which is added to a film-forming auxiliary agent to form a polyamine phthalate alcohol Acid resin emulsion (A), a propylene glycol monoterpene ether acetate (PMA) solution containing the above modified hexamethylene diisocyanate trimer (TAKENATE WD-248) at 80% concentration as a hardener (B) and tap water a two-liquid hardening aqueous primer mixed with a polyamine phthalate alkyd resin emulsion (A) / hardener (B) / tap water 73 318059 1374154 = 95 / 6.3 / 95 ratio (weight ratio), in addition to the above A slate coating sample was prepared in the same manner as in Example 10 except for the same procedure. Comparative Example 5 The same method as in Example 10 was carried out except that the two-liquid-curing aqueous primer was replaced with a liquid-based solvent-based primer composition (product of Mitsui Takeda Chemical Co., Takenate M-402P). Made of slate coated samples. Comparative Example 6

替代二液硬化型水性底漆’改用MDI系1液濕氣硬化型溶劑系底漆組成物（三井武田化學公司製品，m_PRENE AX-616)之外，皆按照實施例10相同方法製成石板塗布試料。 • 使用上述實施例1〇至14及比較例5、6之評估用石板塗布試料，提供下述評試驗用途。评估試驗 Π)耐水德之外觀變化有蓋塑膠容器中裝入自來水，將樣本(形成有塗膜之石板）以整體浸水狀態浸潰水中，纟^、挪仙條件下放置7曰。然後，自水中取出，用肉目p兹目由& — 山用岡眼硯察聚胺曱酸酯塗膜之表面狀態’無剝落、膨潤之試料以n主_ + 了寸M 〇表不，確認剝落、 318059 74 1374154 v 膨潤等之變化之試料評估為X。 α)常熊點接性樣本之聚胺甲酸醋塗膜表面，u 25mm寬度加以刻痕’藉90度剝離試驗測定其轉強度（N/mm)。 (3)耐水黏棬柹使料水後之外觀評估用樣本，按照常態黏接性相同方法測定黏接強度（N/mm)。 (4)乾燥黏桩枓耐水後之外觀評估用樣本，在23t、5〇% RH條件下放置1曰後，按照常態點接性相同方法測定黏接強度 (N/mm)。各實施例及各比較例之試驗結果示於表6中。 • 表6 1 η 實 1 1 施例比較例外觀變化 I \J 〇一 11 ΤΓ" 12 〇 13 〇 14 5 ~〇~ 6 常態黏接性(N/mm) 2.02 1 ·7 1 ς〇〇耐水黏接性（N/mm) 0.94 [ΓΓΪ4 1.59 1.17— 1.73 Τα2 1Τ2Γ 1.98— jjT 1.59 1.23 2.3 乾燥黏接性（N/mn〇 · 1.〆 0.74 0.76 卜1.4 1.41 由表6之結果顯示實施例之水性底漆對於各種料被覆物、頂漆材料’可獲得與溶㈣底漆相同黏接性、耐久性皆優異之二液硬化型水性底漆。 318059 75A slate was prepared in the same manner as in Example 10 except that the two-liquid-curing aqueous primer was replaced with an MDI-based one-component moisture-curing solvent-based primer composition (product of Mitsui Takeda Chemical Co., Ltd., m_PRENE AX-616). Coating the sample. • The evaluation slate coating samples of the above Examples 1A to 14 and Comparative Examples 5 and 6 were used to provide the following evaluation test uses. Evaluation test Π) Change in appearance of water resistance The tap water is placed in a covered plastic container, and the sample (the slab formed with the coating film) is immersed in the water in a state of overall immersion, and placed under the conditions of 纟^ and 仙仙. Then, it is taken out from the water, and the surface state of the polyamine phthalate coating film is examined by the eye & the eye. The sample without the peeling and swelling is n main _ + inch M 〇 The sample which confirmed the change of peeling, 318059 74 1374154 v swelling, etc. was evaluated as X. α) Chang Xiong spotting The surface of the polyurethane coating film of the sample, u 25 mm width and scratches were measured by a 90 degree peel test (N/mm). (3) Water-resistant adhesive The adhesion evaluation (N/mm) was measured in the same manner as in the normal state. (4) Dry-adhesive pile 枓 After the water-resistant appearance evaluation sample was placed under conditions of 23t and 5〇% RH, the adhesion strength (N/mm) was measured in the same manner as the normal point contact property. The test results of the respective examples and comparative examples are shown in Table 6. • Table 6 1 η Real 1 1 Example Comparative Example Appearance Change I \J 〇11 ΤΓ" 12 〇13 〇14 5 ~〇~ 6 Normal Adhesion (N/mm) 2.02 1 ·7 1 ς〇〇 Water resistance Adhesiveness (N/mm) 0.94 [ΓΓΪ4 1.59 1.17— 1.73 Τα2 1Τ2Γ 1.98— jjT 1.59 1.23 2.3 Dry adhesion (N/mn〇· 1.〆0.74 0.76 卜 1.4 1.41 The results of Table 6 show the examples Water-based primer is a two-liquid-curing water-based primer that is excellent in adhesion and durability to various coating materials and top coat materials. 318059 75

Claims

1374154

X. The scope of application for patents:

A two-liquid hardening type aqueous resin composition comprising a polyurethane urethane resin emulsion (A) having an active hydrogen atom in a molecule and a hardener (B) dispersible in the emulsion (A), wherein , the ratio of the hardener (B) to the polyurethane (1) relative to the polyurethane (A) is '3' to 4 (equivalent ratio) of the isocyanate group/active hydrogen atom in terms of solid content, and a hardener ( B) A dispersible polyisocyanate obtained by a reaction of a polyisocyanate and an interfacial activity or a dispersible component containing an active hydrogen atom reactive with an isocyanate group. 2. The liquid-hardening type aqueous resin composition of claim 1, wherein the polyamine phthalate alkyd resin emulsion (A) is via an alkyd resin having a hydroxyl group value of 30 to 250 and a polyisocyanate. The resulting emulsion is reacted. 3. The liquid-hardening type aqueous resin composition according to claim 1, wherein the polyurethane resin emulsion (A) contains an active hydrogen atom derived from a hydroxyl group. 4. The liquid-hardening type aqueous resin composition according to the first aspect of the patent application, wherein 'the metal-containing desiccant (C) is further contained, and the alkyd resin component of the polyurethane-alkyd resin emulsion (A) is contained Unsaturated fatty acids are used as constituent units. 5. The liquid-hardening type aqueous resin composition according to the first aspect of the invention, wherein the polyurethane alkyd resin emulsion (A) further comprises a (meth)acrylic component having a polymerizable group. 6. For example, in the scope of patent application, item 2 bis liquid hardening type water-based resin composition, 318059 amendment 76 1374154 name 9$j 1021.4 poor nose; application: ... L01 year) month 12 曰碜 main replacement page ··

• b- Θ 01-3⁄4, with the order that the interface active or dispersible component is at least one selected from the group consisting of compounds having an ethylene oxide chain. 7. If the liquid-solidified water-based resin composition of the patent application scope item 〉 is cured at room temperature. 8. A two-liquid-curing aqueous coating comprising a polyurethane urethane resin emulsion having an active hydrogen atom in a molecule and a hardener (Β) dispersible in the emulsion (Α), The isocyanate group/active hydrogen atom is from 0.3 to 4 (equivalent ratio) based on the solid content of the hardener (Β) ratio of the polyurethane urethane resin emulsion (Α), and the hardener (Β) A dispersible polyisocyanate obtained by a reaction of a polyisocyanate and an interfacial activity or a dispersible component containing an active hydrogen atom reactive with an isocyanate group. 9. A two-liquid-curing aqueous primer comprising a polyurethane urethane resin emulsion having an active hydrogen atom in a molecule and a hardener (Β) dispersible in the emulsion (Α), wherein The hardener (Β) ratio of the polyamine phthalate alkyd resin emulsion (Α) is from 0.3 to 4 (equivalent ratio) of the isocyanato group/active ruthenium atom in terms of solid content, and the hardener (Β) system A dispersible polyisocyanate obtained by a reaction of a polyisocyanate and an interfacial activity or a dispersible component containing an active hydrogen atom reactive toward an isocyanate group. . 〇〇如申请申请申请如如如如如如如如如如如如如如如如如液液液液液液液液液液液液液液液液液液液液液液液液液Surfactant. 11. For example, the second paragraph of the patent scope of the liquid-hardening type of water-based resin composition, 318059 amendment 77 1374154 ....%μ〇2. The application of the case in July, 101, i, the name f replacement Page · Among them, the interface active or dispersible components are composed of polyoxyalkylene-based C8_24 alkyl ether, polyoxy-extended ethyl C8.12 alkylphenyl ether, polyoxy-extension ethyl polyoxy-extension C3_6 alkylene C8. The at least one selected from the group consisting of 24 ethers. 318059 Amendment 78