201221531 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種水系聚胺基甲酸g旨樹脂組成物，特 別是有關耐水性及财酸性、耐驗性等之对藥品性及塗料安 定性優異的水系聚胺基甲酸酯樹脂組成物、含有該水系聚 胺基曱酸酯樹脂組成物之塗料、及在板狀材料表面上塗布 該水系聚胺基甲酸s旨樹脂組成物所成的塗裝品。 【先前技術】 聚胺基曱酸i旨樹脂由於具有财摩擦性、接著性、非黏 接性及橡膠彈性’故廣泛地被使用做為塗料、接著劑、黏 接劑及塗布劑等。而且，近年來就對環境污染或勞動衛生 等之安全性而言，有很多水系聚胺基甲酸酯樹脂組成物之 報告。 然而，水系聚胺基f酸酯樹脂組成物與溶劑系或無溶 劑系者相比時，會有耐水性、耐藥品性、耐熱性及拉伸特 性等之物性差的問題。 例如，使用於塗裝表面處理鋼板時之塗料，特別是以 具有=水性及耐酸性、耐鹼性等之耐藥品性為必要條件， 准目如之水ϋ胺基曱酸醋樹脂組成物中仍未有可滿足此 等物性者。 此外’提高纖維基材之防水性及防油性者，已提案有 使夕吕月匕異氰酸自曰與氟化醇之反應生成物與含聚氧化烯基 之物質反應而成的說化聚合物(專利文獻1}。然而，由於該 乱化聚合物與鋼板之密接性差，故做為鋼板用塗料使用是 不適當的。 另外，已揭不有在側鏈上含有長鍵烧基之水系聚胺基 4/33 ⑧ 201221531 曱酸醋樹脂做為耐水性、耐藥品性、耐熱性等經改善的水 系聚胺基甲酸s旨樹脂。^而，該水系聚胺基甲酸醋樹脂， 使用短的支鏈二醇做為續予⑽基f酸§旨化時(專利文獻 2〜4)，由於凝聚能f高的胺基曱㈣鍵互相接近，且所生 成的胺基曱酸S旨預聚物凝聚、黏度上昇，而導致不易進行 水分散。 此外’已揭示有由具有長鏈烷基之異氰酸酯化合物與 多7L醇及水所成的水分散型聚胺基曱酸酯樹脂組成物(專利 文獻5及6) °此時’可改善耐水性、对藥品性及对熱性， 惟會有塗料之安全性的問題。 [習知技術文獻] [專利文獻] [專利文獻丨]日本特表平11-511814號公報 [專利文獻2]日本特開2000-007909號公報 [專利文獻3]日本特表2005-510600號公報 [專利文獻4]日本特開2005-068228號公報 [專利文獻5] WO06/038466號公報 [專利文獻6]日本特開2009-20331(5號公報 【發明内容】 [發明所欲解決之課題] 本發明人荨為解決前述習知的缺點，再三深入研究檢 討的結果’發現藉由使在胺基曱酸酯樹脂骨架中排入一定 量之長鏈垸二醇化合物的胺基甲酸酯預聚物予以水伸長， "T衣付具有優異的对水性、财酸性、对驗性等之财藥品性、 及與基材之密接性等，且具有優異的塗料安定性之水系胺 基曱酸酯樹脂組成物，遂而達成本發明。 5/33 201221531 因此本發明之目的係提供一種具有優異的耐水性' 耐藥品性(耐酸性、耐鹼性)及與基材之密接性等且具有優異 的塗料安定性之可適合使用於表面處理鋼板塗料用途之水 系胺基曱酸酿樹脂組成物、含有該水系聚胺基甲酸酯樹脂 之塗料、及塗布該塗料而成的板狀塗裝品。 [用以解決課題之手段] 換言之’本發明係關於一種水系聚胺基甲酸酯樹脂組 成物、含有該水系聚胺基甲酸酯樹脂組成物之塗料、及在 板狀材料上塗布該塗料而成的塗裝品，其特徵係將多元醇 (A)、異氰酸§旨出）、及含有羧基及/或磺酸基之導入陰離子 性基的多7C醇(C)反應所得的在末端具有異氰酸酯基之胺基 甲酸S旨預聚物’使料有陰離子性基之巾和劑(D)分散於水 中’予以水伸長而成的水系聚胺基曱酸酯樹脂組成物，其 特徵為前述(A)成分以碳原子數10〜32之長鏈烷二醇化合 物(a)為必要成分’並且前述(a)成分之摻合量為(A)、(B)及(C) 成分之總量的1〜2〇質量％，前述出)成分之異氰酸酯基 (NC0)與前述(A)成分及前述(C)成分之全部羥基(OH)的當 量比(NCO/OH)為 1.3 〜1.9。 釗述(a)化合物以碳原子數12〜18之長鏈烧二醇化合物 為車义佳。如述導入陰離子性基的多元醇(c)之摻合量較佳為 前述(A)、（B)及(〇成分之總量的〇.1〜3〇質量0/〇。 而且，本發明之塗料，適合塗布於表面處理鋼板。 [發明之效果] 藉由本發明之水系聚胺基曱酸酯樹脂組成物，可得具 有優異安定性的塗料。而且，藉由將本發明之塗料塗布於 經表面處理的鋼板上，可製得具有具優異耐水性及耐藥品 201221531 性等的塗膜之塗裝品。 [實施發明之形態] 本發明之水系聚胺基甲酸酯樹脂組成物係將多元醇 (A)、異氰酸酯(B)、及含有選自羧基與磺酸基之陰離子性基 的導入陰離子性基的多元醇(〇反應所得的在末端含有異氰 酸酷基之胺基曱酸酯預聚物，使用具有陰離子性基之中和 劑成分(D)分散於水中，予以水伸長而成的水系聚胺基甲酸 酯樹脂組成物。 前述(A)成分以碳原子數10〜32之長鏈烷二醇化合物 (a)為必要成分。此時，該(a)成分之摻合量為(a)、（b)及(匸) 成分之總量的1〜2〇質量％，較佳為15〜15質量％，更佳 為2〜10質量％。 、 則达⑻成分之按合量低於i質量％時，水系聚胺基甲 酸醋樹脂組成物之料性及_品鱗低，岐過 %時，胺基曱_預聚物對水之分散赌低，料易刹 造水系聚胺基曱酸酯樹脂，涂料 —· 于不易农 求。 土卄之文疋性降低，故不為企 碳原子數為1G〜32之長鏈垸二醇化 八一 醇、十四烧二醇 醇、十八烧二醇、- 醇、十一烷二醇、十二烷二醇、十三烷0 彳如六一201221531 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a water-based polyglycolic acid g-resin composition, particularly relating to chemical resistance and paint stability in terms of water resistance, acidity, and durability. An excellent aqueous polyurethane resin composition, a coating material containing the aqueous polyamino phthalate resin composition, and a resin composition coated with the aqueous polyaminocarboxylic acid on the surface of the plate material Painting products. [Prior Art] The polyamino phthalic acid-based resin is widely used as a coating material, an adhesive, an adhesive, a coating agent, and the like because of its friction, adhesion, non-adhesiveness, and rubber elasticity. Moreover, in recent years, there have been many reports of water-based polyurethane resin compositions for the safety of environmental pollution or labor hygiene. However, when the aqueous polyamino-based acid ester resin composition is compared with a solvent-based or solvent-free one, the physical properties such as water resistance, chemical resistance, heat resistance, and tensile properties are inferior. For example, a coating material used for coating a surface-treated steel sheet is particularly required to have a chemical property such as water resistance, acid resistance, alkali resistance, etc., and is required to be in the form of a hydrazine-based phthalic acid vinegar resin composition. There are still no ones that can satisfy these physical properties. In addition, in order to improve the water repellency and oil repellency of the fiber substrate, a polymerized polymer obtained by reacting a reaction product of isocyanic acid with fluorinated alcohol and a substance containing a polyoxyalkylene group has been proposed ( Patent Document 1} However, since the miscible polymer and the steel sheet have poor adhesion, it is not suitable for use as a coating material for steel sheets. Further, it has been revealed that an aqueous polyamine having a long bond group in a side chain has been disclosed. Base 4/33 8 201221531 The vinegar vinegar resin is an improved water-based polyurethane resin which is improved in water resistance, chemical resistance, heat resistance, etc., and the water-based polyurethane resin, using a short branch When the chain diol is used for the continuation of the (10)-based f acid (Patent Documents 2 to 4), the amine ruthenium (tetra) bond having a high cohesive energy f is close to each other, and the resulting amino phthalic acid S is a prepolymer. Condensation and viscosity increase, resulting in difficulty in water dispersion. Further, a water-dispersed polyamine phthalate resin composition composed of an isocyanate compound having a long-chain alkyl group and 7L of an alcohol and water has been disclosed (Patent Document 5 and 6) ° At this time, it can improve water resistance and chemical properties. In the case of the heat, there is a problem of the safety of the paint. [Purpose of the technical documents] [Patent Document] [Patent Document] Japanese Patent Publication No. Hei 11-511814 (Patent Document 2) JP-A-2000-007909 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2005-510228 (Patent Document 5) Japanese Laid-Open Patent Publication No. 2005-068228 (Patent Document 5) WO06/038466 (Patent Document 6) JP-A-2009-20331 (Publication No. 5) SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The present inventors have solved the above-mentioned conventional drawbacks, and have repeatedly studied the results of the review and found that by discharging a certain amount in the skeleton of the amino phthalate resin The urethane prepolymer of the chain decanediol compound is water-stretched, and the T-coating has excellent properties such as water resistance, acidity, compatibility, and adhesion to a substrate. The present invention is achieved by an aqueous amine phthalate resin composition having excellent coating stability. 5/33 201221531 Therefore, the object of the present invention is to provide an excellent water resistance 'chemical resistance (acid resistance, resistance) Alkaline) and adhesion to the substrate, etc. An aqueous amine-based phthalic acid-based resin composition which is excellent for coating stability and suitable for use in surface-treated steel sheet coating applications, a coating containing the aqueous polyurethane resin, and a plate coating coated with the coating material [Means for Solving the Problem] In other words, the present invention relates to an aqueous polyurethane resin composition, a coating containing the aqueous polyurethane resin composition, and a sheet material. A coated article obtained by applying the coating material is characterized in that a polyol (A), an isocyanate is used, and a poly 7C alcohol (C) having an anionic group containing a carboxyl group and/or a sulfonic acid group is reacted. The obtained amino acid-based amino acid phthalate resin composition having an isocyanate group at the terminal is a prepolymer of a prepolymer which has an anionic group and an agent (D) dispersed in water. It is characterized in that the (A) component has a long-chain alkylene glycol compound (a) having a carbon number of 10 to 32 as an essential component' and the blending amount of the above component (a) is (A), (B) and C) 1 to 2% by mass of the total amount of the components, and the isocyanate group of the above-mentioned component (NC) 0) The ratio (NCO/OH) to the total hydroxyl group (OH) of the component (A) and the component (C) is 1.3 to 1.9. The compound (a) is described as a long-chain diol compound having 12 to 18 carbon atoms. The blending amount of the polyol (c) into which the anionic group is introduced is preferably the above-mentioned (A), (B) and (the total amount of the quinone component is 11 to 3 〇 mass 0 / 〇. Moreover, the present invention The coating material is suitable for application to a surface-treated steel sheet. [Effects of the Invention] By using the aqueous polyamine phthalate resin composition of the present invention, a coating having excellent stability can be obtained. Further, by coating the coating of the present invention with On the surface-treated steel sheet, a coated product having a coating film having excellent water resistance and resistance to chemicals 201221531 can be obtained. [Mode for Carrying Out the Invention] The aqueous polyurethane resin composition of the present invention will be a polyol (A), an isocyanate (B), and an anion group-containing polyol containing an anion group selected from a carboxyl group and a sulfonic acid group (an aminoguanidine acid having an isocyanate group at the terminal obtained by the reaction of hydrazine) The ester prepolymer is a water-based polyurethane resin composition obtained by dispersing an anionic base neutralizer component (D) in water and elongating water. The component (A) has a carbon number of 10 〜 The long-chain alkanediol compound (a) of 32 is an essential component. At this time, the (a) The blending amount of the components is 1 to 2% by mass, preferably 15 to 15% by mass, more preferably 2 to 10% by mass, based on the total amount of the components (a), (b) and (匸). (8) When the combined amount of the components is less than i% by mass, the materiality of the aqueous polyurethane resin composition and the _ scale are low, and when the 5% is exceeded, the amine 曱 _ prepolymer has a low gambling on the water. It is easy to make water-based polyamine phthalate resin, and the coating is difficult to grow. The soil of the earthworm is reduced, so it is not a long-chain diol octadecyl alcohol with a carbon number of 1G~32. Tetrahydrogenated diol, octadecyl diol, - alcohol, undecanediol, dodecanediol, tridecane 0 such as six one
十五烷二醇、十六烷二醇、十七燒一7L 九焼* ^一醇、一十炫* ^一醇、二+ —— .十三烧二醇、二十四燒， 醇、二十五烷 二醇、二十七烷二醇、二十八燒 十烷二醇、三十一烷二醇、三十 二醇。 十烷二醇、二十二烷二醇、 醇、二十六烷 醇、二十九烷二醇、三 境二醇等之直鏈或支鏈 及耐藥品性優異的水系 於此等之中，就可製得耐水性 7/33 201221531 聚胺基曱酸酯樹脂組成物而言，（a)成分係較佳為碳原子數 為12〜18之長鏈烷二醇，更佳為1,12-十二烷二醇或1，12-十八烧二醇。 前述(a)成分以外之多元醇(A)沒有特別的限制，例如可 使用聚醚多元醇類、聚酯多元醇類、聚酯聚碳酸酯多元醇 類、結晶性或非結晶性聚碳酸酯多元醇類、數量平均分子 量低於200之低分子多元醇類等。 前述聚醚多元醇類係除了 1,2-丙二醇、1，3-丙二醇；三 羥甲基丙烷、丙三醇、聚丙三醇、季戊四醇等之前述低分 子多元醇以外，可舉例如雙酚A、乙二胺等之胺化合物等 的氧化乙烯及/或氧化丙烯加成物；聚四亞曱基醚乙二醇等。 前述聚酯多元醇類係可舉例如藉由與前述的低分子多 元醇等之多元醇、與較其化學論量更為少量的多元竣酸或 其酯、酸酐、羧酸鹵化物等之酯形成性衍生物進行直接酯 化反應或酯交換反應而得的聚酯多元醇；及藉由前述多元 醇、與内酯類或其水解開環反應所得的羥基羧酸之直接酯 化反應而得的聚酯多元醇。 上述多元叛酸可舉例如草酸、丙二酸、號50酸、戊二 酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十二院 二酸、2-曱基琥珀酸、2-曱基己二酸、3-曱基己二酸、3-曱 基戊二酸、2-曱基辛二酸、3,8-二曱基癸二酸、3,7-二曱基 癸二酸、氫化二聚酸、二聚酸等之脂肪族二羧酸類；苯二 曱酸、對苯二甲酸、異苯二甲酸、萘二羧酸等之芳香族二 羧酸類；環己烷二羧酸等之脂環式二羧酸等之脂環式二羧 酸類；偏苯三酸、均苯三曱酸、蓖麻油脂肪酸之三聚物等 之三羧酸類；均苯四曱酸等之4元以上之羧酸。 201221531 元：===，生物係可舉例如上述之多 多元麟之甲酿、乙阶、=化物寻^竣酸4化物；上述 戊醋等之低級脂肪族_等/日、異丙§日、丁_、異丁酉旨、 时前述$類係可舉—己内以_己_、£-己 ㈣二切旨，趣^ 醇等Ιίίίδ1聚碳酸®旨多71醇類係可舉例如聚己内醋多元 妒：,二醇與碳酸烷二醋之反應生成物、碳酸乙二 轉之反應生錢及有機二紐反麵得的反應生 可二f ; f述結晶性或非結晶性之聚碳酸酯多元醇類係 丙二醇、M_ 丁二醇，己二醇、二乙二醇、 =-醇、及/或聚四甲二醇等之二醇與膦、二芳基碳酸酉旨 生 本基碳酸醋)或環式碳酸酯(例如碳酸丙二⑹之反應 生成物等。 〜 醚夕疋醇類、聚S旨多元醇類、聚®旨聚碳酸醋多 -mm或非結晶性之聚碳酸·多元翻的數量 句分子量係較佳為300〜5000，更佳為5〇〇〜3〇〇〇。 前述數量平均好4低於之齡衫元醇類係可 r如乙一醇、1，2-丙二醇、u_丙二醇、2_甲基分丙二 、一乙二醇、三乙二醇、2_丁基_2•乙基·】，3-丙二醇、 丁-醇、新戊醇、3·甲基_2,4_戊二醇、2,4_ —，：戊—醇、;1，6_己二醇、卩庚二醇、3,5-庚二醇、 〜醇、2-甲基-辛二醇、！，9-壬二醇等之脂肪族二醇’、環 97 33 201221531 己烷二曱醇、環己烷二醇等脂環式二醇；三羥甲基乙烷、 三羥曱基丙烷、己糖醇類、戊糖醇類、丙三醇、聚丙三醇、 季戊四醇、二季戊四醇、四經甲基丙烧等之3價以上的多 元醇。 異氰酸酯(B)沒有特別的限制，可使用二異氰酸酯及在 1分子中具有3個以上異氰酸酯基之聚異氰酸酯等。 二異氰酸酯係可舉例如二異氰酸曱苯二酯、二苯基曱 烷_4,4’_二異氰酸酯、p-二異氰酸苯二酯、二異氰酸二甲苯 二酯、二異氰酸！.,5-萘二酯、3,3’-二曱基二笨基-4,4'-二異 氰酸酯、二異氰酸二茴香胺酯、異氰酸四曱基二甲笨二酯 等之芳香族二異氰酸酯類；異佛酮二異氰酸酯、二環己基 曱烷_4,4'_二異氰酸酯、反式及/或順式-1,4-環己烷二異氰酸 酯、二異氰酸原菠烯酯等之脂環式二異氰酸酯類；1,6-六亞 曱基二異氰酸酯、2,2,4-及/或(2,4,4)-三曱基六亞甲基二異氰 酸酯、賴胺酸二異氰酸酯等之脂肪族二異氰酸酯類；及此 等之混合物。 前述聚異氰酸酯係可舉例如三苯基曱烷三異氰酸酯、 1-曱基苯-2,4,6-三異氰酸酯、二甲基三苯基甲烷四異氰酸 酯、此等之混合物等的3官能以上之異氰酸酯、此等3官 能以上之異氰酸酯的羰二醯亞胺改性、異氰酸酯改性、縮 二脲改性等之改性物、將此等以各種嵌段化劑予以嵌段化 的嵌段異氰酸酯、前述二異氰酸酯之異氰酸酯（三聚物)及縮 二脲三聚物等。 於此等之中，就容易取得、可製得耐候性及強度等優 異的水系聚胺基曱酸酯樹脂組成物而言，較佳係使用脂肪 族二異氰酸酯或脂環式二異氰酸酯較佳，更佳係使用1，6- 201221531 二環己基曱烷-4,4'-二異氰酸酯、異 乂)，人陰離子性基之多元醇為含㈣基及/或磺酸基 之夕兀醇類’可舉出例如二羥曱基丙酸、二羥曱基丁酸、 二經甲基戊酸、二經甲基己酸等之含羧基的多元醇類、1,4-丁烧-=_魏等之含俩基的多元醇類。 —於此等之巾’就容易取得而言較佳係使用含叛酸基的 多兀醇類，特佳係使用二羥曱基丙酸。 二此外’（C)導入陰離子性基的多元醇的摻合量，相對於 刖述(A)、（B)及(〇成分之總量而言，較佳為〇1〜3〇質量％ 之範圍的1，更佳為〇5〜2〇質量％之量，最佳為〇1〜1〇 質之量。（C)成分之摻合量低於01質量％時，由於聚胺 基甲酸鞋之水分散性差，會有水系聚胺基曱酸酯樹脂之保 存安定性、或塗料之安定性降低的情形，而超過3〇質量％ 時’會有伴隨胺基曱酸酯鍵之凝聚能量增加而導致胺基甲 酸酯預聚物之黏度上昇’且變得不易進行水分散等之問題。 另外’前述多元醇(A)、聚異氰酸酯(B)及(c)導入陰離 子性基之多元醇的摻合量，在使此等反應的階段中前述多 元醇(A)及導入陰離子性基之多元醇(c)相對於全部羥基1 當量而言，異氰酸酯（B)之異氰酸酯基(NCO)的當量比 (NCO/OH)為1.3〜1.9之量，較佳為1.4〜1.8之量，更佳為 1.5〜1.7之量。Pentadecanediol, hexadecanediol, seventeen-burning one 7L nine-inch*^-ol, one-tenth*, one-alcohol, two----tridecene diol, twenty-four burning, alcohol, Tefocane diol, heptacosane diol, octadecane decane diol, tridecane diol, and triacon diol. a linear or branched chain such as decacodiol, behenic acid glycol, alcohol, hexadecanol, octadecanediol or tri-dimensional diol, and a water-based product excellent in chemical resistance. The water-resistant 7/33 201221531 polyamino phthalate resin composition, the component (a) is preferably a long-chain alkyl diol having 12 to 18 carbon atoms, more preferably 1, 12-dodecanediol or 1,12-octadecanthene diol. The polyol (A) other than the above component (a) is not particularly limited, and for example, polyether polyols, polyester polyols, polyester polycarbonate polyols, crystalline or amorphous polycarbonates can be used. Polyols, low molecular weight polyols having a number average molecular weight of less than 200, and the like. The polyether polyols include, in addition to the above-mentioned low molecular polyols such as 1,2-propanediol, 1,3-propanediol, trimethylolpropane, glycerin, polyglycerol, and pentaerythritol, for example, bisphenol A. An ethylene oxide and/or propylene oxide adduct such as an amine compound such as ethylenediamine; polytetramethylene ether glycol or the like. The polyester polyols may, for example, be esters with a polyhydric alcohol such as the above-described low molecular polyol or a smaller amount of a polybasic citric acid or an ester thereof, an acid anhydride, a carboxylic acid halide or the like. a polyester polyol obtained by direct esterification or transesterification of a forming derivative; and a direct esterification reaction of the above-mentioned polyol, a hydroxycarboxylic acid obtained by reacting a lactone with a lactone or its hydrolysis ring-opening reaction Polyester polyol. The above polyvalent tickic acid may, for example, be oxalic acid, malonic acid, 50 acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, diterpene diacid, 2-indole Succinic acid, 2-mercaptoadipate, 3-mercaptoadipate, 3-mercaptoglutaric acid, 2-mercaptooctanedioic acid, 3,8-dimercapto azelaic acid, 3,7 An aliphatic dicarboxylic acid such as dimercaptosuccinic acid, hydrogenated dimer acid or dimer acid; aromatic dicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid or naphthalene dicarboxylic acid An alicyclic dicarboxylic acid such as an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid; a tricarboxylic acid such as a trimer of trimellitic acid, trimesic acid or a castor oil fatty acid; A carboxylic acid of 4 or more yuan such as tetradecanoic acid. 201221531 yuan: ===, the biological system can be, for example, the above-mentioned multi-component arbor, the second-order, the sulphate, and the lower-grade aliphatic _etc/day, isopropyl § , Ding _, 异丁酉,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Internal vinegar multi-component hydrazine: the reaction product of diol and alkyl carbonate diacetate, the reaction of ethylene carbonate and the reaction of organic dinuclear reaction can produce two f; f the crystalline or amorphous aggregate Carbonate polyols are diols such as propylene glycol, M-butanediol, hexanediol, diethylene glycol, =-alcohol, and/or polytetramethylene glycol, and phosphine, diaryl carbonate Carbonic acid vinegar) or a cyclic carbonate (for example, a reaction product of propylene carbonate (6), etc.. ~ Ether oxime alcohol, poly S-polyol, poly-polycarbonate poly-mm or amorphous polycarbonate The molecular weight of the multivariate scalar is preferably from 300 to 5,000, more preferably from 5 to 3 〇〇〇. The above number is preferably 4, less than the age of the phenolic alcohol, such as ethyl alcohol. 1,2-propanediol, u-propylene glycol, 2-methylperpropylene di, monoethylene glycol, triethylene glycol, 2-butyl-2-ethyl}, 3-propanediol, butanol, neopentyl Alcohol, 3·methyl 2,4-pentylene glycol, 2,4_,: pentanol, 1,6-hexanediol, helium heptanediol, 3,5-heptanediol, ~alcohol, Aliphatic diols such as 2-methyl-octanediol, !, 9-nonanediol, ring 97 33 201221531 alicyclic diol such as hexanediethanol or cyclohexanediol; trimethylol A trivalent or higher polyhydric alcohol such as ethane, trihydroxydecylpropane, hexitol, pentitol, glycerol, polyglycerol, pentaerythritol, dipentaerythritol or tetrapropylidene. Isocyanate (B) There is no particular limitation, and a diisocyanate and a polyisocyanate having three or more isocyanate groups in one molecule can be used. Examples of the diisocyanate include nonylphenyl diisocyanate and diphenyl decane _4,4. '_Diisocyanate, p-diphenylocyanate, xylene diisocyanate, diisocyanate!, 5-naphthalened diester, 3,3'-dimercapto-diphenyl-4 , 4'-diisocyanate, diisyl diisocyanate, isocyanate Aromatic diisocyanates such as dimethyl diester; isophorone diisocyanate, dicyclohexyldecane _4,4'-diisocyanate, trans and/or cis-1,4-cyclohexane An alicyclic diisocyanate such as isocyanate or diisocyanatosine; 1,6-hexamethylene diisocyanate, 2,2,4- and/or (2,4,4)-trimethyl An aliphatic diisocyanate such as hexamethylene diisocyanate or lysine diisocyanate; and a mixture thereof. The polyisocyanate may, for example, be triphenyldecane triisocyanate or 1-mercaptobenzene-2,4. , a trifunctional or higher isocyanate such as a mixture of 6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, or the like, a carbodiimide modification of the trifunctional or higher isocyanate, an isocyanate modification, or a condensation A modified product such as urea modification, a blocked isocyanate which is blocked with various blocking agents, an isocyanate (trimer) of the above diisocyanate, a biuret trimer, and the like. Among these, it is preferable to use an aliphatic diisocyanate or an alicyclic diisocyanate in an aqueous polyamine phthalate resin composition which is easily obtained and which is excellent in weather resistance and strength. More preferably, 1,6-201221531 dicyclohexyldecane-4,4'-diisocyanate, isoindole is used, and the human anionic group polyol is a sulfonium group containing a (tetra) group and/or a sulfonic acid group. For example, a carboxyl group-containing polyol such as dihydroxymethyl propionic acid, dihydroxymethyl butyl acid, di-methyl valeric acid or di-methyl hexanoic acid, and 1,4-butane-=_wei may be mentioned. And other two-group polyols. It is preferable to use a polysterol containing a tickic acid group, and it is preferable to use a dihydroxymethyl propionic acid. Further, the blending amount of the (C)-introduced polyol is preferably 〇1 to 3〇% by mass based on the total amount of the components (A), (B) and (〇). The range of 1, more preferably 〇 5 to 2 〇 mass%, the best is 〇1~1 〇 quality. When the blending amount of the component (C) is less than 01% by mass, due to the polyamino formate shoe The water dispersibility is poor, and the storage stability of the aqueous polyamine phthalate resin or the stability of the coating is lowered, and when it exceeds 3% by mass, the aggregation energy accompanying the amino phthalate bond increases. However, the viscosity of the urethane prepolymer is increased, and it becomes difficult to carry out water dispersion, etc. Further, the aforementioned polyol (A), polyisocyanate (B), and (c) are introduced into an anionic group-containing polyol. The amount of the isocyanate group (NCO) of the isocyanate (B) in the stage of the reaction, in which the polyol (A) and the polyol (c) introduced into the anionic group are equivalent to 1 equivalent of all the hydroxyl groups. The equivalent ratio (NCO/OH) is an amount of from 1.3 to 1.9, preferably from 1.4 to 1.8, more preferably from 1.5 to 1.7.
六亞甲基二異氰酸酯 佛酮二異氰酸酯。 NCO/OH比低於1.3時，由於胺基曱酸酯預聚物為較高 分子量化，故有胺基曱酸酯預聚物之水分散性降低的傾 向，有水系聚胺基曱酸酯樹脂之保存安定性或塗料之安定 性惡化的情形。此外，NCO/OH比超過1.9時，於預聚物進 11/33 201221531 行水分散時，由於藉由異氰酸酯基與水反應所生成的二氧 化碳激烈發泡，於製造樹脂組成物時會產生障礙，且樹脂 之耐水性、耐酸性等之效果降低。 曰 於製造本發明之水系聚胺基甲酸酯樹脂組成物時，首 先可按照需要使用於反應中為惰性且與水之親和性大的溶 劑，使多元醇(A)、異氰酸酯(B)及導入陰離子性基之多元醇 (C)反應，合成末端異氰酸酯胺基曱酸酯預聚物。 於前述反應中為惰性且與水之親和性大的溶劑，較佳 者例如丙酌、甲基乙m、四氫料、ν·曱基〜比 錢綱等。此等之溶劑，通常相對於製造預聚物時使用的 前述原料之合計量100質量份而言使用3〜100質量份。此 等溶劑使㈣點⑽t：以下之溶劑時，以於合成水系聚胺基 甲酸酯樹脂後，藉甴減壓餾去等除去其溶劑較佳。 &使末端異氰酸賴基甲酸賤物進行水分散的方法 =可舉出例如有⑴於水中加入預聚物予以分散的預聚物混 :法’⑺在縣财加人水㈣分散轉相法[水分散 ^使用的陰離子性基中和_)為使存在於分散系中的陰 每丁性之基中和者，可添加預聚物及水中之任何一種。 如此使末端異鎌自旨胺基甲酸g旨預聚物予以水分散Hexamethylene diisocyanate Fosone diisocyanate. When the NCO/OH ratio is less than 1.3, since the amino phthalate prepolymer has a higher molecular weight, the water dispersibility of the amino phthalate prepolymer tends to decrease, and the aqueous polyamino phthalate has a tendency. The preservation stability of the resin or the deterioration of the stability of the paint. Further, when the NCO/OH ratio exceeds 1.9, when the prepolymer is dispersed in water at 11/33 201221531, the carbon dioxide generated by the reaction of the isocyanate group with water is strongly foamed, which causes an obstacle in the production of the resin composition. Further, the effect of water resistance, acid resistance, and the like of the resin is lowered. When producing the aqueous polyurethane resin composition of the present invention, first, a solvent which is inert in the reaction and has a high affinity with water can be used, and the polyol (A) and the isocyanate (B) can be used. The terminal isocyanate amino phthalate prepolymer is synthesized by introducing an anionic group-containing polyol (C). The solvent which is inert in the above reaction and has a high affinity with water is preferably, for example, a solvent, a methyl ethyl group, a tetrahydrogen material, a ν·decyl group or a hydroxy group. The solvent is usually used in an amount of from 3 to 100 parts by mass based on 100 parts by mass of the total amount of the above-mentioned raw materials used in the production of the prepolymer. When the solvent is at least (10) t: the following solvent, it is preferred to remove the solvent by distillation under reduced pressure after synthesizing the aqueous polyurethane resin. & a method of dispersing a terminal isocyanate ruthenium phthalate in water =, for example, (1) prepolymer mixed with a prepolymer dispersed in water to be mixed: the method '(7) is dispersed in a county-funded water (four) The phase method [anionic group neutralization _ used for water dispersion] is any one of a prepolymer and water added to neutralize the base of the cation per butyl group present in the dispersion. So that the terminal isomerized from the urethane prepolymer is water-dispersed
由在水巾予财伸長，合縣剌之 酸酯樹脂組成物.。 T 前述陰離子性基中和劑⑼係可舉出例如三甲胺、三乙 、:丁胺等之三㈣安類、ν,ν•二甲基乙醇胺 、Ν,Ν-二甲 Ν’Ν_二丙基乙醇胺、^二曱基胺基_2_甲基_2·丙 #自寺^—烧基鍵燒鮮胺類、N•炫基-即-二鏈烧醇胺 <、三乙醇胺等之三鏈燒醇胺類的3級胺化合物；錢、氫 12/33 201221531By the extension of the water towel, the acid resin composition of Hexian. T The above-mentioned anionic base neutralizing agent (9) may, for example, be a tris(tetra)anthracene such as trimethylamine, triethyl or butylamine, ν, ν dimethylethanolamine, hydrazine, hydrazine-dimethyl hydrazine Ν 二Propylethanolamine, dimethylamino-based 2-methyl-2-propanol #自寺^-burning bond-burning fresh amines, N•shyl----di-chain-alcoholamines<, triethanolamine, etc. a tertiary amine compound of a tri-chain alcoholic amine; money, hydrogen 12/33 201221531
氧化—曱胺、氩氧化鈉、氫氧化鉀、氫氧化鋰等之驗 合物。 G 離子:的使用量，相對於前述(C)成分中具有的陰 離子[生基1當置而言’較佳為0.5〜2.0當量之量，更佳為 〇.8叫.5當量之量。中和劑之使用量過於不足時，恐會有由 水系聚胺基甲酸I旨樹脂所得的塗料之㈤水性 伸率等之物性降低的情形。 進行前述水伸長時，以溫度為30〜75°C進行撥拄日不 以水伸長較佳，溫度更佳為4〇〜65t。 U予 …溫度低於3〇t：時，由於需要長時間進行反應時，生產 效f降低，超過75t時，伴隨因水伸長反應激烈產生二氧 化石反而導致發泡現象，含有低沸點溶劑時等時會產生制造 上的問題。 衣。 觀察前述水伸長時之反應終點的方法，由於使用IR(紅 外線分光光度計)確認異氰酸酯基消失的方法簡單，故較佳。 於製造本發明之水系聚胺基曱酸酯樹脂組成物時，於 聚胺基曱酸I旨進行水分散時亦可使用乳化劑。乳化劑例如 一般的陰離子性界面活性劑及非離子性界面活性劑、以及 級胺鹽、二級胺鹽、三級胺鹽、四級胺鹽及吡錠鏽鹽等 之陽離子性界面活性劑，以及甜菜鹼型、硫酸酯型及磺酸 型等之兩性界面活性劑等之習知者。 刚述陰離子性界面活性劑係可舉出例如十二炫基硫酸 鈉、十二烷基硫酸鉀、十二烷基硫酸銨等之烷基硫酸鹽類； 十一烷基聚乙二醇醚硫酸鈉、聚氧化乙烯烷醚硫酸銨等之 聚氧化乙烯醚硫酸鹽類；磺基蓖麻酸鈉；砜化鏈烷烴之鹼 金屬鹽、砜化鏈烷烴之銨鹽等之烷基磺酸鹽；月桂酸納、 13/33 201221531 三乙醇胺油酸鹽、三乙醇胺松香酸鹽等之脂肪酸鹽；苯福 酸納、驗苯贿基乙烯之驗金屬硫酸鹽等之錄芳基石黃酸 ^高烧基萘績酸鹽；萘項酸甲_合物；二烧基谱基號 拍酸鹽；聚氧化乙稀絲麵鹽；料化乙触基芳基^ 酸鹽；聚氧化乙烯_酸鹽；聚氧化乙稀㈣醋酸鹽；ν_ 醯基胺基酸鹽；Ν-醯基甲基牛續酸鹽等。 前述非離子性界面活性劑係可舉出例如山梨糖醇針單 月^酸^山梨糖醇針單油酸_等之多元醇的脂肪酸部分 :員，“紅的;聚㊉ 二：數^，醇的氧化乙稀及/或氣化丙稀加成物；燒 基本紛之軋化乙細及/或氧化丙埽加成物；燒二醇及二 氧化乙烯及/或氧化丙晞加成物等。構成此等之非:; 生界面活性劑的碳數卜18之醇，例如甲醇、乙醇 、戊醇、異戊醇、第3· 戊醇、己醇、辛醇、癸醇、月桂醇、 硬脂醇等. # 醇' 前=基苯_可舉出例如麵、f基絲、2,4-二· 弟3-丁基笨酚、2,5_二_苐3_丁基苯 — 酉分、4.(1，3_四甲基丁基_分、4_ ‘一/ ^丁基笨 4楚。☆ β ^ ，、节暴本酚、4-壬基苯酚、 -苐3-辛基祕、4_十二烧基笨紛 齡、4-(3,5_二甲基庚基胸、萃J，一甲基庚基)本 $酚、雙酚A、雙酚F等。 則述可舉祕乙二醇、u•丙二醇、^-丙 ;'2_甲基-U-丙二醇、2_丁基乙基#丙二醇 土 ，_、一酉子、1，6-己二醇等，烷二胺例如此之产二 之醇性縣被取代成胺基者等。而且，氧化乙烯及^丙子 14/33 201221531 烯加成物可為無規加成物’亦可為嵌段加成物。 前述陽離子性界面活性劑係可舉出例如月桂基三曱基 氣化銨、硬脂基三曱基氯化銨、二硬脂基二曱基氣化銨、 二癸基二甲基氣化銨、月桂基笨曱基二曱基氯化銨、二癸 基二曱基氣化敍、烧基溴化°比錠鹽及月桂酸咪。坐鏽鹽等。 前述兩性界面活性劑係可舉出例如椰子油脂肪酸醯胺 丙基二曱基醋酸甜菜鹼、月桂基二甲基胺基酸甜菜鹼、2_ 烷基_N-羧基曱基羥基曱基咪唑鑷鹽甜菜鹼、月桂基羥基 磺基甜菜鹼、月桂醯基醯胺乙基羥基乙基羧基曱基甜菜 鹼、羥基丙基破酸之金屬鹽等之甜菜驗型、月桂基胺基 丙酸之金屬鹽等之胺基酸型、硫酸酯型及磺酸型等。 前述乳化劑之使用量係沒有特別的限制，就塗布水系 聚胺基曱酸_脂組成物所彳獨_之耐水性、強产、拉 :率等之物性而言，相對於前述㈧〜(c)成分之總量二質 里份而言較佳為1〜30質量份，更佳為5〜2〇質量份 =質量份時，無法得到提高分散性之效果，超過3〇質量 ，恐會有前述塗膜之物性降低的情形。 、 可：上’於本發明之水系聚胺基甲二旨組成物中， 17 U賦予聚胺基甲酸@旨分子巾 另外配合-般於胺基曱㈣财物巾㈣較 前述交聯難可舉出例如蜜胺、單— 曱基蜜胺、三經甲基蜜胺、吨f -經 六羥甲基蜜胺、甲基化羥甲基蜜胺V丁::經甲，胺、 蜜胺樹脂等。於本發明中’以使用由==蜜胺、 胺基甲酸酯之分散性優異的低價蜜胺較佳.、田、擇對聚 使用本發明之水系聚胺基甲：二： 脂組成物做為塗料 15/33 201221531 等時，可適當稀釋使用。稀釋時之固體 別的限制’就分散性或為製得塗膜、成形體;二= 而言，相對於前述⑷〜—衫總量”=性專 佳為1〜65質量份，更佳為5〜50質量份。里伤而吕，幸父 亦可=需水系聚胺基曱酸酿樹脂組成物中， 顏料；染料；造膜助劑；石更化劑.！ 、加劍例如 劑；整平劑：消泡劑；防止〜―；黏度調整 劑；苯盼系化合物、磷,/二二匕二’受阻胺等之光安定 劑；由=唪李化人& Γ〜5為荒糸化合物等之抗氧化 d由一㈣化合物、笨甲酸㈣化 苯并三唾系化合物所成的紫外線吸收劑；自 賴予劑;無機或有機填充劑;可塑劑.；4 r 靜電劑；補強劑；觸媒^ /，千^，抗 敍劑；及防錄劑等。丄抗囷劑；防黴劑；防腐 另外，於塗料或塗布劑中 酸曝組成物時，亦可使:=:明之水系聚胺基甲 密接性之石夕貌偶 土而Μ寺別是賦予堅固 縮聚物二聲合劑及環氧化合物乳切、四燒氧基魏及其 於前述各種添加劑中，將本 樹脂組成物使用於暴露在屋外之塗胺基f酸酯 =先錢劑、紫外線吸_及抗氧化劑較佳。 刖述受阻胺系光安定劑係可舉 领咬基硬編論、U,2,6,6·五=料2,2,6,6-四Μ 啶基)癸醆酯、雙2 2 6 6五尹其a又（，2,6,6·四甲基-4-哌 辛氧A 22以雙（’:， 基底11 定基)癸酸醋、雙(1. 辛軋基·2,2，Μ，W•。㈣_s|、似6,6_五尹基 16/33 201221531 冰口底咬基甲基甲基丙烯酸醋、2,2,6,6_四甲基冰娘咬基甲基 甲基丙烯酸g旨、肆(2,2,6,6·四甲基·4«基)mi丁烧四 羧酉文自曰、肆（1，2,2,6,6-五曱基·4_哌啶基)_丨，2,3,4_丁烷四羧酸 酉曰、雙(2,2,6,6-四曱基-4-哌啶基）·雙(十二烷基卜^冬丁 烷四羧酸酯、雙（1，2,2,6,6-五甲基_4_哌啶基）.雙（十二烷 基)-1，2,3,4-丁烧四羧酸g旨、雙〇,2,2,6,6_五甲基_4_〇底啶基)_2_ 丁基·2-(3,5-二-3-丁基-4-羥基笨甲基）丙二酸酯、】_(2_羥基乙 基)-2,2,6,6-四甲基-4-哌啶醇/琥珀酸二乙酯聚縮物、丨，6_雙 (2,2,6,6-四曱基-4-哌啶基胺基）己烷/二溴乙烷聚縮物、〗,6_ 雙(2,2,6,6-四甲基-4-哌啶基胺基）己烷/2.4_二氯_6_嗎啉基_5_ 二嗪聚縮物、1，6-雙(2,2,6,6-四甲基_4_哌啶基胺基）己烷/2,4-二氣-6-第3-辛基胺基-s-三嗪聚縮物、丨，^]•肆[2,4_雙(义 丁基-Ν-(2,2,6,6-四曱基冰哌啶基）胺基）_s•三嗪_6_ 基]-1,5,8,12-四氮雜十二烷、肆[2,4_雙(仏丁基 以-(1，2,2,6,6-五甲基冰旅啶基)胺基)_s_三嗪 四氮雜十二烷、1,6,11-參[2,4-雙(N-丁基-N-(2,2,6,6-四曱基 冬旅α疋基)胺基)-5-二°秦_6-基胺基]—院、1，6,11-參[2,4_雙 (N-丁基->1-(1，2,2,6,6-五甲基_4-〇底咬基)胺基)_§_三嗪_6_基胺 基]十一烷、3,9-雙[1,1·二甲基-2-[參(2,2,6,6-四甲基_4_哌啶 基氧化Ik氧基)丁基.氧基]乙基]-2,4,8,10-四氧雜螺旋[5,5] 十一烷、3,9-雙[1，1·二曱基-2-[參(1,2,2,6,6-五曱基_4—略啶基 乳化Ik氧基)丁基幾氧基]乙基]-2,4,8，10-四氧雜螺旋[5 5]十 一烷等。 ’ 前述紫外線吸收劑係可舉出例如2，4 -二經基二笨甲 嗣、2-技基-4-甲氧基一本曱、2-經基-4-辛氧基二笨曱酮、 5,5’-亞甲基雙(2-羥基_4_曱氧基二苯甲酮）等之厶經基二苯 〆 » 17/33 201221531 膝5·?基苯基)苯并三唾、2仰基_5.第 辛土本基）本开二唑、2_(2_羥基_3,5_二_第3_ 氯化笨并三唾、2„(2_經基_3•第 f本基)_5_ 苯并三唾、2 η、ι Γ 本基氯化 C-經基，3,5-二枯烯基苯基)苯并三唑、22 苯并三唾細)、2必羥基_3·第3_ 土-羧基不基）苯并三唑之聚乙二醇酯、2 ，醯氧基乙基糾基苯基]苯并三唾、冲铺；^甲 基丙稀醯氧基乙基)七第3_丁基苯基]笨并三。坐、〒声其 叫甲基丙_氧基乙基)_5•第3_辛基笨基]笨共三^ J ::基f (2_曱基丙烯醯氧基乙基)-5_第3_ 丁基苯基]-5-，化笨并—坐、2_[2令基·5·(2_甲基丙烯酸氧基乙基)苯基] 第上丁基-5·(2_甲基丙烯酿氧基乙基) 美r其殘基"3-第3_戊基-5_(2-甲基两稀酿氧 土 土）本基J本开二唑、2H>羥基-3-第3-丁基-5-(3_甲美丙 刺氧基丙基)笨基R氣化苯并三外叫經基_4 =稀酿氧基曱基)苯基]苯并三。坐、叫經基邻-甲基丙ς ^氧基_2·經基丙基)笨基]笨并三唾、2私經基邻-甲 烯^氧基丙麟基胸^铸之冲絲苯基)笨并三唾 類’· 2-㈣基_4_T A基苯基)_4,6_二苯基#5.三唪 =基本基)_4,6_雙(2,4_二甲基笨基)_u，5_三唤、2_經基㈣ 14似12〜⑶混合料基韻基丙氧辦基]从雙 一甲基苯基h，3,5_三嗓、2_[玲基冬(2_丙稀酿氧基^ 乳基〉苯基Μ，6_雙(4·曱墓笨基H，3,5-I。秦、2-(2,4-二祕3 烯丙基苯基)·4.6雙(2,4_二？基苯基 經基-3·甲基-4-己氧基苯基Η,3,5_三嗪等之2_(2_經基笨 18/33 201221531 基(3,5-一弟3-丁基_4,基)苯曱酸醋、十一 3·丁基·4__笨甲酸_、十六烧基(3,5_ 1 ’二 :=:5= =④’-乙氧基草:替 早替本胺寺之取代草轉苯胺類；土 ,苯基丙稀酸酯、甲基_2_氛基·3_甲基_3|甲氧&^_ :希酸”氰基丙烯酸酯類；各種之金屬鹽或;屬;)合 物、特別是鎳或路之鹽或螯合物類等。 〃虫C» 化劑前述抗氧化劑係可舉出例如⑽、笨嶋硫系抗氧 〃磷系抗氧化劑係可舉出例如三苯基碟酸醋 第3-丁基苯基)磷酸酯、參(25_二_ / ”一 參(壬基笨基)鱗酸醋、參(二壬基苯基)魏;旨本3酸^ Γ第基3本丁=i、二苯基酸性鱗酸，、2,2'亞甲她 土本基)辛基磷酸酯、二苯基癸基磷酸酯、二 辛基磷酸酯、二(壬基苯基)季戊四醇二魏、苯 f,、三丁基磷酸醋、參(2_乙基己基)磷酸醋：；:二 基械酯、三賴基填義、二了基酸性彻㈣旨、_ ^A test compound of oxidized guanamine, sodium argon oxide, potassium hydroxide, lithium hydroxide or the like. The amount of G ion used is preferably 0.5 to 2.0 equivalents, more preferably 〇.8 Å. 5 equivalents, based on the anion (sogenic group 1) present in the component (C). When the amount of the neutralizing agent used is too small, there is a fear that the physical properties such as the water-extension ratio of the coating material obtained from the aqueous polyaminocarboxylic acid I resin may be lowered. When the water is stretched as described above, it is preferred that the temperature is not changed with water at a temperature of 30 to 75 ° C, and the temperature is more preferably from 4 to 65 t. When the temperature is lower than 3〇t:, the production efficiency f is lowered when the reaction is required to be carried out for a long period of time. When the temperature exceeds 75 t, the precipitation of the carbon dioxide is caused by the intense reaction of the water, and the foaming phenomenon is caused by the low boiling point solvent. Isochronization creates manufacturing problems. clothes. The method of observing the end point of the reaction at the time of water elongation is preferable because the method of confirming the disappearance of the isocyanate group by IR (infrared spectrophotometer) is simple. When the aqueous polyamine phthalate resin composition of the present invention is produced, an emulsifier may be used in the case where the polyamino phthalic acid I is subjected to water dispersion. An emulsifier such as a general anionic surfactant and a nonionic surfactant, and a cationic surfactant such as a graded amine salt, a secondary amine salt, a tertiary amine salt, a quaternary amine salt, and a pyridinium salt. And a conventional surfactant such as a betaine type, a sulfate type, or a sulfonic acid type. Examples of the anionic surfactants include alkyl sulfates such as sodium dodecyl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate; and undecyl polyglycol ether sulfuric acid; a polyoxyethylene ether sulfate such as sodium, polyoxyethylene alkyl ether sulfate or the like; sodium sulfo ricinoleate; an alkali metal salt of a sulfonated alkane; an alkylsulfonate of an sulfonated alkane ammonium salt; Sodium laurate, 13/33 201221531 triethanolamine oleate, triethanolamine rosinate, etc.; fatty acid salts such as sodium benzoate, phenyl bromide, metal sulphate, etc. Acid salt; naphthyl acid methylate; dicalcinyl sulfonate; polyethylene oxide silk salt; carbaryl aryl acid salt; polyoxyethylene _ acid salt; polyoxidation Ethyl (tetra) acetate; ν_ mercaptoamine; Ν-mercaptomethyl borate; The nonionic surfactant may, for example, be a fatty acid moiety of a polyhydric alcohol such as sorbitol needle monoxide, sorbitol needle monooleate or the like: member, "red; poly 12: number ^, Oxidized ethylene oxide and/or vaporized propylene adduct of alcohol; burnt acetylated and/or propylene oxide adducts; diol and ethylene oxide and/or propylene oxide adduct Etc.. constitutes the non-:: the alcohol of the surfactant, such as methanol, ethanol, pentanol, isoamyl alcohol, 3, pentanol, hexanol, octanol, decyl alcohol, lauryl alcohol , stearyl alcohol, etc. #醇'前前基苯_ can be exemplified by, for example, face, f-based wire, 2,4-di-tert 3-butyl phenol, 2,5-di-苐3_butylbenzene — 酉, 4. (1,3_tetramethylbutyl _, 4_ '- / butyl butyl 4 Chu. ☆ β ^ ,, violent phenol, 4-nonyl phenol, - 苐 3-辛基秘, 4_12 burning base, 4-(3,5-dimethylheptyl chest, extraction J, monomethylheptyl), phenol, bisphenol A, bisphenol F, etc. The description may be as follows: ethylene glycol, u. propylene glycol, ^-propyl; '2_methyl-U-propylene glycol, 2_butylethyl #propylene glycol soil, _, a scorpion, 1 6-hexanediol or the like, an alkanediamine such as an alcoholic county in which the second is substituted with an amine group, etc. Moreover, the ethylene oxide and the ethyl propylene 14/33 201221531 olefin adduct may be a random adduct. 'The block addition product may also be mentioned. The above-mentioned cationic surfactant may, for example, be lauryl tridecyl ammonium hydride, stearyl tridecyl ammonium chloride, distearyl di decyl ammonium hydride. , dimercapto dimethyl ammonium hydride, lauryl adenyl dimercapto ammonium chloride, dimercapto fluorenyl sulfonate, bromine bromide ratio ingot salt and lauric acid mic. The amphoteric surfactants may, for example, be coconut oil fatty acid guanamine propyl dimercaptoacetate betaine, lauryl dimethyl amino acid betaine, 2-alkyl-N-carboxyl hydroxy hydroxy hydrazinium oxime Beet test of salt betaine, lauryl hydroxy sulfobetaine, lauryl decylamine ethyl hydroxyethyl carboxy decyl betaine, hydroxypropyl cleavage metal salt, etc., metal of lauryl alanine propionate An amino acid type, a sulfate type, a sulfonic acid type, etc., such as a salt, etc. The amount of the emulsifier used is not particularly limited, and coating is carried out. The physical properties of the polyamine-based citric acid-fat composition are preferably relative to the total amount of the above-mentioned components (8) to (c). When it is 1 to 30 parts by mass, more preferably 5 to 2 parts by mass = part by mass, the effect of improving the dispersibility cannot be obtained, and if it exceeds 3 Å, the physical properties of the coating film may be lowered. In the aqueous polyamine-based composition of the present invention, 17 U is imparted to the polyaminocarbamic acid, and the molecular towel is additionally blended with the amine-based ruthenium (tetrazide), and the cross-linking is difficult to exemplify, for example, melamine. , mono-mercapto melamine, trimethyl melamine, ton f - hexamethylol melamine, methylated methylol melamine V butyl:: via a, amine, melamine resin. In the present invention, it is preferred to use a low-cost melamine which is excellent in dispersibility of == melamine or urethane, and to use the water-based polyamine A of the present invention: When the material is used as paint 15/33 201221531, it can be diluted appropriately. The other limitation of the solid at the time of dilution is to disperse or to obtain a coating film or a molded body; in the case of the second, the total amount of the above (4) to the total amount of the shirt is preferably 1 to 65 parts by mass, more preferably 5~50 parts by mass. Injury and Lv, the father can also be = water-based polyamine phthalic acid resin composition, pigment; dye; filming aid; stone modifier. Leveling agent: antifoaming agent; prevention of ~-; viscosity modifier; benzene expectant compound, phosphorus, / dioxin II hindered amine and other light stabilizer; by = 唪 Lihua people & Γ ~ 5 for the waste An anti-oxidation d of a ruthenium compound or the like, an ultraviolet absorber composed of a compound (IV), a benzoic acid (tetra) benzotrisate compound, a self-reinforcing agent, an inorganic or organic filler, a plasticizer, a 4 r electrostatic agent, and a reinforcing agent. Catalyst ^ /, thousand ^, anti-narrative agent; and anti-recording agent, etc.. Anti-caries agent; anti-fungal agent; anti-corrosion In addition, in the coating or coating agent acid exposure composition, can also make: =: The water-based polyamine-based adhesion of the Ming Dynasty is the same as that of the earth. The temple is given a strong polycondensate two-voice mixture and epoxy compound milk cutting, four-burning oxygen Wei and its Among the various additives mentioned above, it is preferred to use the resin composition for exposure to an amine-based f-ester which is exposed to the outside, a precursor, an ultraviolet absorber, and an antioxidant. The hindered amine-based light stabilizer can be used as a bite. Hard programming, U, 2,6,6·5=material 2,2,6,6-tetradecylpyridyl) decyl ester, double 2 2 6 6 five Yin its a again (, 2, 6, 6 ·Tetramethyl-4-pipeoctin A 22 is a double (':, base 11 base) citric acid vinegar, double (1. 辛 rolling base 2, 2, Μ, W•. (4) _s|, like 6,6 _五尹基16/33 201221531 Bottom bite methyl methacrylate, 2,2,6,6_tetramethyl glacial bite methyl methacrylate g, 肆 (2, 2, 6 ,6·tetramethyl·4«yl)mi-butylate tetracarboxylic hydrazine from hydrazine, hydrazine (1,2,2,6,6-pentamethylene-4-ylpiperidinyl)_丨, 2,3, 4_Butane tetracarboxylate, bis(2,2,6,6-tetradecyl-4-piperidinyl)·bis(dodecylbu-butanetetracarboxylate, double (1) , 2,2,6,6-pentamethyl_4_piperidinyl). bis(dodecyl)-1,2,3,4-butanetetracarboxylic acid g, biguanide, 2,2 ,6,6-pentamethyl_4_decridinyl)_2_butyl-2-(3,5-di-3-butyl-4-hydroxymethyl)malonate,]_(2 _hydroxyethyl)-2,2,6,6- Methyl-4-piperidinol/diethyl succinate polycondensate, hydrazine, 6-bis(2,2,6,6-tetradecyl-4-piperidylamino)hexane/dibromoethane Alkane polycondensate, 〗 6_bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane/2.4_dichloro-6-morpholinyl-5-diazine polycondensate 1,6-bis(2,2,6,6-tetramethyl_4-piperidinyl)hexane/2,4-dioxa-6-3-octylamino-s-three Pyrazine polycondensate, hydrazine, ^]•肆[2,4_bis(yibutyl-indole-(2,2,6,6-tetradecyl)piperidinyl)amino)_s•triazine_6_ 1,1,5,8,12-tetraazadodecane, 肆[2,4_bis(p-butyl-(1,2,2,6,6-pentamethyl) Amino)_s_triazinetetraazadodecane, 1,6,11-gin[2,4-bis(N-butyl-N-(2,2,6,6-tetradecyl) Indenyl)amino)-5-di-Qin-6-ylamino]-hospital, 1,6,11-paran [2,4_bis(N-butyl->1-(1,2, 2,6,6-pentamethyl_4-indenyl)Amino)_§_Triazine_6-ylamino]undecane, 3,9-bis[1,1·dimethyl- 2-[Ref. (2,2,6,6-tetramethyl-4-piperidinyloxylated Ikoxy)butyl.oxy]ethyl]-2,4,8,10-tetraoxahelix [ 5,5] undecane, 3,9-bis[1,1·didecyl-2-[paratide (1,2,2,6,6-pentamethyl-4--azulidine) emulsification Ik oxy)butyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5 5]decane and the like. The ultraviolet ray absorbing agent may, for example, be 2,4-di-diyldibenzopyrene, 2-technyl-4-methoxy-indenyl, 2-pyridyl-4-octyloxydoprene , 5,5'-methylenebis(2-hydroxy-4-indolyl benzophenone), etc. 厶 二 二 〆 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 2, 仰基_5. 辛土土基)本开二唑, 2_(2_hydroxy_3,5_二_3_ chlorinated stupid and saliva, 2„(2_经基_3•第f))_5_ benzotrisene, 2 η, ι Γ base chlorinated C-carbyl group, 3,5-dicumenylphenyl)benzotriazole, 22 benzotrisole), 2 must Hydroxy_3·3__-carboxy-carboxy-free) Polyethylene glycol ester of benzotriazole, 2, decyloxyethyl phenyl phenyl] benzotrisole, scouring; ^methyl propylene oxime Ethyl ethyl) succinyl 3 - butyl phenyl] stupid three. sitting, snoring called methyl propyl oxyethyl) _ 5 • 3 _ octyl stupid] stupid three ^ J :: base f (2_Mercaptopropenyloxyethyl)-5_3rd butylphenyl]-5-, stupid and sitting, 2_[2 yl ·5·(2_methacrylic acid oxyethyl Phenyl] phenyl] butyl butyl-5·(2-methyl propylene oxyethyl) mer r its residue "3- 3rd_e Base-5_(2-methyl dilute oxy-oxygen soil) base J-opened oxadiazole, 2H> hydroxy-3-3-3-butyl-5-(3-methylpyranyloxypropyl) The radical R is a gasified benzotriene, which is called a phenyl group, a benzoic acid group, a phenyl group, a benzotrienyl group, a phenyl group, a benzoic acid group, a phenyl group Stupid base] stupid and three saliva, 2 vaginal-ne-methoxyl-propyl propyl-based chest ^ cast lining phenyl) stupid and three-salt '· 2- (tetra) _4_T A phenyl)_4 ,6_diphenyl#5.三唪=basic group)_4,6_bis(2,4-dimethylphenyl)_u,5_three call, 2_base (four) 14 like 12~(3) mixture韵基基丙氧基基] From bis-methylphenyl h,3,5_三嗓, 2_[玲基冬(2_丙丙氧氧^乳基)phenyl Μ,6_双(4 ·The tomb base H,3,5-I. Qin, 2-(2,4-di-sec3,allylphenyl)·4.6 bis (2,4-di-phenylphenyl)--3 2-yl-2-hexyloxyphenyl hydrazine, 3,5-triazine, etc. 2_(2_ via base stupid 18/33 201221531 base (3,5-mono-3-butyl-4,yl)benzoic acid Vinegar, eleven 3 · butyl · 4__ stupin formic acid _, hexadecyl group (3,5_ 1 'two:=:5==4'-ethoxy grass: for the replacement of the grass Aniline; soil, phenyl acrylate, methyl_2_ Aromatic group 3_methyl_3|methoxy&^_: citric acid "cyanoacrylate"; various metal salts or genus;), especially nickel or road salt or chelate The aphid C» chemical agent is, for example, (10), and the abbreviated sulfur-based anti-phosphorus-phosphorus-based antioxidant is, for example, triphenyl oleate or 3-butylphenyl phosphate. , ginseng (25_二_ / ” ginseng (壬基笨基) squash vinegar, ginseng (didecyl phenyl) Wei; the purpose of this 3 acid ^ Γ 3 3 = = = i, diphenyl acid scale Acid, 2,2' methylene, her soil base) octyl phosphate, diphenylphosphonium phosphate, dioctyl phosphate, bis(nonylphenyl) pentaerythritol diwei, benzene f, and tributyl Phosphoric acid vinegar, ginseng (2_ethylhexyl) phosphate vinegar:;: dibasic ester, trilynyl-filled, di-based acid (4), _ ^
酸醋、三月桂基三硫化碟酸醋、雙(新戍‘ J —幻，5第3_ 丁基本基)季戍四醇二鱗醆醋、雔 (，弟3-丁基-4-甲基苯基)季戊四醇二磷酸酿、雙(2 = 19/33 201221531 二枯烯基苯基)李戊四醇二碟酸酯、二硬脂基季戊四醇二礙 酸酯、四(C12-C15混合烷基)-4,4，-二異亞丙基二笨基磷酸 Sg、雙[2,2 -亞曱基雙(4,6-;戊基苯基)]·異亞丙基二苯基 磷酸酯、四-十三烷基· 4,4’ -亞丁基雙(2-第3_丁基_5_曱基 苯酚)二磷酸酯、六（十三烷基）· ^，孓參(2_曱基_5_第3_丁基 -4-羥基苯基)丁烷•三磷酸酯、肆(2,4_二_第3_丁基苯基)聯 笨二鱗酸酯、參(2-[[2,4,7,9-肆-第 3-丁基二笨并 二氧雜磷(phosphepin)-6-基)氧化]乙基]胺、9，ι〇_二氫冬氧雜 -10-磷菲-10-氧化物、參4,8,10-肆-第3-丁基二苯并 [d，f][l，3,2]二氧雜磷-6-基）氧化]乙基)胺、2-(1,〗_二甲基乙 基)-6-曱基·4-[3-[[2,4,8，10-反式（ι，ι_二曱基乙基）二笨并 [明[1，3,2]二氧雜碟-6-基]氧化]丙基]笨盼_2-丁基_2_乙基丙 一醇· 2,4,6-三-第3-丁基笨盼單鱗酸g旨等。 本酉分糸抗氧化劑係可舉出例如2,6-二-第3·丁基-ρ-曱 酚' 2,6-二苯基-4-十八烷氧基苯酚、硬脂基(3,5_二第>丁 基-4-羥基笨基)丙酸酯、二硬脂基(3,5_二_第3_丁基_4_羥基 笨曱基)磷酸酯、十三烷基· 3,5-二-第3-丁基-4-羥基苯甲基 硫化乙酸酯、硫化二乙烯雙[(3,5_二-第3_丁基羥基苯 丙酸酯]、4,4，-硫化雙(6_第3_丁基_111_甲酚）、2_辛基硫^_4^6_ 一(3,5-二-第3-丁基-4-經基苯氧基)-s_三嗪、2,2，_亞甲基雙 (4-曱基-6-第3-丁基苯酚）、雙[3,3-雙(4-羥基-3-第3-丁基笨 基)丁酸]乙二醇酯、4,4，-亞丁基雙(2,6-二-第3-丁基苯酚）、 4,4 -亞丁基雙(6-第3-丁基-3-甲基笨盼）、2,2’-亞乙基雙(4 6· 二-第3-丁基苯酚)、ι，〗,^參(2-甲基-4·羥基-5-第3-丁基苯基） 丁烷、雙[2-第3-丁基-6-(2-羥基-3-第3-丁基-5-甲基苯甲基） 苯基]對苯二甲酸酯、u，5_參(2,6_二甲基_3_羥基·4_第3_^_ 20/33 201221531 基笨甲基)異氰酸酯、1,3,5-參(3,5-二第3-丁基-4-羥基笨曱 基)異氮駿酯、1，3,5_參(3,5_二第3_丁基_4_羥基苯曱基；)_2,4,6_ 二甲基笨、1,3,5-參[(3,5-二-第3-丁基-4-羥基笨基)丙氧基乙 基]異氮酸酯、肆[亞曱基-3-(3，，5’-二-第3 丁基-4，-經基苯基) 丙酸酉旨]甲燒、2-第3-丁基-4-曱基-6-(2-丙稀感氧基-3-第3- 丁基5_曱基笨甲基)苯酚、3,9-雙[2-(3-第3-丁基-4-羥基-5- :基殘基肉桂醯氧基)-U_二曱基乙基]-2,4,8，10-四氧雜螺 j[j·5]十〜烷、三乙二醇雙[泠-(3-第3_丁基-4-羥基-5-曱基 本基)丙酸酯]、生育酚等。 - 0 杬氧化劑係可舉出例如硫化二丙酸之二桂月酯、 其二§3、肉丑急§旨、硬脂酸醋、二硬脂酸醋等之二搞 酸S旨類及季細醇四（/3_十二烧基·丙酸醋 、夕70醇的/5 -烧基疏基丙酸酉旨類。 各使胺系光安定劑、㈣線吸《丨及抗氧化劑之 0.001質旦彳八_ A、、伤，将佳為0.01〜5質量份。小於 *量份時對大於 化劑丨、紫二。、抗氧 中之方法、於水分散時Μ料的方法、添加於預聚物 添加的方法中之任何方^於水相中的方法、於水分散後 醇中之方奸添加於卿物加於多元 本發明之水系聚胺美 法較佳。 出例如塗料、黏著劍、^面，樹脂组成物之用途係可舉 黏著劑、成形體等。 文貝別、有機及/或無機粉體之 21 /33 201221531 ’可舉Hi齡麵纖轉相、感 ㈣、噴墨紙塗布劑、印刷油墨之黏著劑、鋼板用涂: 農業用薄膜用塗布劑、玻璃、石板、 土布片！、 讨用涂袓+ ^ 反此欢土寺無機系構造 材用主枓、木工塗料、纖維處理劑、海綿 保險套等。於此等之中’以使用作為塗料： 維' _、電子材料零件及鋼板之塗布材料㈣;特= 使用作為表面處理鋼板用之塗特更佳。 ’疋 使用本發明之水线胺基曱_咖旨組成物料塗料時， 例如可稭由刷子塗布、滾筒”、噴霧塗布、照相 布、可逆輥塗布、刀塗布、棒塗布、簾幕觀塗布 '浸^ 布、棍塗布、刮刀塗布等之適當選擇的方法塗布於。土 【實施方式】 、土竹上。 /以下，藉由實施例更詳細地說明本發明，惟本發 受此等所限制。 x [實施例] [實施例1] 在反應燒瓶中加入做為多元醇(A)中之長鏈烷二醇化 合物(a)之1,12-十八烷二醇0.0g(〇.〇2〇9莫耳）、做為其它的 (A)成分之由1，6-己二醇與己二酸及異對苯二曱酸（己二酸/ 異對笨二曱酸之質量比為50/50)所得的聚酯多元醇(數量平 均分子量1750)65.7g(0.0375莫耳）、做為異氰酸酷(B)之二 環己基曱烧-4,4’·二異氰酸酯（以下記載為氫化 MDI)42.5g(0.1620莫耳）、做為導入陰離子性基之多元醇(c) 之二羥曱基丙酸5_74g(0.0428莫耳）。 此時之(A)〜(C)成分的總量中之⑻成分的比例為5質 量。/〇 ’（C)成分之比例為4.8質量％，NCO/OH之當量比為 22/33 201221531 1.6。 另外，加入溶劑之N-曱基-2-。比略炫j同25.7g，在氮氣 氣流、100〜110°C下進行反應2〜3小時，確認nc〇之含 率為3.4%以下。然後，加入做為陰離子性基中和劑(D)之三 乙胺4.33g(0.0428莫耳）’使中和率變為1.〇，製得固體含 量為80質量％之胺基曱酸酯預聚物。 在水110g中加入消泡劑(ADEKA(股)製、B1016)0.1g、 及為了使前述胺基甲酸酯預聚物之中和率變為0.2的三乙 胺1.18g(0.0117莫耳)且進行攪拌而得的水溶液中，加入前 述胺基曱酸酯預聚物109g，在20〜40°C下進行攪拌15分 鐘予以分散。將所得的胺基曱酸酯預聚物之分散液，在30 〜40°C下進行水伸長反應12小時，進而在50〜55°C下以藉 由IR(紅外線分光光度計)測定確認直至NCO基消失之時間 來進行水伸長反應，以製得固體含量為40%之水系聚胺基 甲酸酯樹脂組成物。 [實施例2] 在反應燒瓶中加入做為多元醇(A)中之長鏈烷二醇化 合物⑻之1,12-十八烧二醇12.0g(0.0593莫耳）、做為其它 的(A)成分之由1,6-己二醇與己二酸之聚碳酸酯二醇(數量 平均分子量2000)49.0g(0.0245莫耳）、做為異氰酸酯(B)之 異佛酮二異氰酸酯（以下記載為IPDl)51.9g(0.234莫耳)及做 為導入陰離子性基之多元醇（C)之二羥曱基丙酸 7.17g(0.0535 莫耳）。 此時之(A)〜(C)成分的總量中之⑻成分的比例為1〇質 量％ ’（C)成分之比例為6.0質量％，NCO/OH之當量比為 1.7。 23/33 201221531 另外，加入做為·溶劑之N-曱基_2_π比哈炫_ 24.6g，在 亂氣氣流、100〜110°C下進行反應2〜3小時，碟5忍NC〇% 為5.4%以下。然後，加入做為陰離子性基中和齊'1(D)之二乙 胺5.41g(0.0535莫耳），使中和率變為1〇，製得固體含量 為80質量％之胺基曱酸酯預聚物。 在水110g中加入消泡劑(ΑΜκα(股)製、Bl〇l6)〇.lg’ 及在與前述胺基曱酸酯預聚物之中和率變為0.2下加入三 乙胺1.47g(0.0145莫耳)進行攪拌所得的水溶浪中’加入前 述胺基甲酸酯預聚物108g，在20〜4(TC下進行攪拌15分 鐘予以分散。將所得的胺基曱酸酯預聚物之分散液’在30 〜40°C下進行水伸長反應12小時，進而在C下以藉 由IR(紅外線分光光度計_)測定確認直至NCO基消失之時間 來進行水伸長反應，以製得固體含量為40%之水系聚胺基 曱酸S旨樹脂組成物。 [實施例3] 在反應燒瓶中加入做為多元醇(A)中之長鏈烧二醇化 合物⑻之1，12-十八烷二醇2.4g(0.0084莫耳）、做為其它的 (A)成分之聚四四亞甲基醚乙二醇（數量平均分子量 2000)81.4g(0.0407莫耳）、做為異氰酸酯(B)之氫化MDI 31.9g(0.1216莫耳)及做為導入陰離子性基之多元醇(C)之二 羥曱基丙酸4.30g(0.0321莫耳）。 此時之(A)〜(C)成分的總量中之⑻成分的比例為2質 量％，（C)成分之比例為3.6質量％ ’ NCO/OH之當量比為 1.5。 另外，加入做為溶劑之N-曱基吡咯烷酮26_8g，在 氮氣氣流、100〜1HTC下進行反應2〜3小時’確認NCO% 24 / 33 ⑧ 201221531 變為2.3%以下後，加入做為陰離子性基中和劑(D)之三乙胺 3.24g(0.0320莫耳)使得中和率變為丨.〇，以製得固體含量為 80質量％之胺基曱酸醋預聚物。 在水110g中加入消泡劑(ADEKA(股)製、B1016)0,1 g， 及使得前述胺基曱酸酯預聚物之中和率變為〇.2的三乙胺 • 0.88S(0.0087莫耳）。然後，在進行攪拌所得的水溶液中加 入前述胺基曱酸酯預聚物l〇9g，在20〜40°C下進行攪拌 15分鐘予以分散。將所得的胺基曱酸酯預聚物之分散液， 在30〜40°C下進行水伸長反應12小時，進而在〜65°C 下以藉由IR(紅外線分光光度計)測定確認直至NCO基消失 之時間來進行水伸長反應，以製得固體含量為40%之水系 聚胺基曱酸酯樹脂組成物。 [比較例1] 除使用做為（A)成分之實施例1使用的聚酯多元醇 77.7g(0.0444莫耳)及做為(B)成分之氫化MDI 36.6g(0.14〇 莫耳），且沒有使用（a)成分外，藉由與實施例1相同的方法， 使(A)〜(C)成分進行反應。確認NCO%為2.9%以下。然後， 加入做為陰離子性基中和劑(D)之三乙胺4.33g(0.0428莫 耳)使得中和率變為1.0，以製得固體含量為80質量％之胺 基甲酸酯預聚物。 進料時之(A)〜(C)成分的總量中(c)成分之比例為4.8 質量％，NCO/OH之當量比為1.6。 藉由與實施例1相同的方法將所得的胺基曱酸酯預聚 物進行水分散及水伸長反應’以製得固體含置為40%之水 系聚胺基甲酸酯樹脂組成物。 [比較例2] 25/33 201221531 除使用做為(a)成分之1，12-十八烷二醇30.0g(0.]〇5莫 耳）、做為其他(A)成分之實施例1使用的聚酯多元醇 18.0g(0.0103莫耳)及做為(B)成分之氫化MDI 66.2g(0.252 莫耳)外’藉由與實施例1相同的方法，使(A)〜(C)成分進 行反應。確認NCO之含率％為5.3%以下後，加入做為陰離 子性基中和劑(D)之三乙胺4.33g(0.0428莫耳)使得中和率 髮為1.0 ’以製得固體含量為8〇質量％之胺基曱酸酯預聚 物。 加入時之(A)〜(〇成分之總量中⑻成分之比例為25質 置％ ’（C)成分之比例為4.8質量。/〇，NC〇/〇H之當量比為 1.6。 使用所得的胺基甲酸酯預聚物，藉由與實施例丨相同 的方法，試行製造水系聚胺基曱醆酯樹脂組成物時，胺基 曱酸醋預聚物之水分散差’無法製得分散性良好的水系聚 胺基甲酸酯樹脂组成物。 [比較例3] 除使用（a)成分外之做為(A)成分之實施例】使用的聚酯 多το醇77.ig(0.G441莫耳）及做為成分之氫化MDi 3l.lg(0.119莫耳)外，藉由與實施例！相同的方法，使 〜(C)成分進行反應.。確認NCO之含率％為〇 6%以下後， 加入做為陰離子性基中和劑(D)之三乙胺4 33g(〇 〇428莫 耳)使得中和率變為1.0，以製得固體含量為8〇質量％之胺 基甲酸酯預聚物。 進料時之(A)〜(C)成分的總量中，（a)成分之比例為5 質Ϊ%，（C)成分之比例為4‘8質量〇/〇，NC〇/〇H之當量比為 U。 26/33 201221531 將所得的胺基曱酸酯預聚物藉由與實施例】相同的方 法，試行製造水系聚胺基曱酸酯樹脂組成物時，胺基曱酸 酯預聚物無法分散於水中，無法製得水系聚胺基甲酸酯樹 脂組成物。 [比較例4] 除使用（a)成分外之做為(a)成分之實施例〗使用的聚酯 多兀醇53.8g(0.0307莫耳）及做為成分之氫化MDI 54.5g(0.208莫耳)外，藉由與實施例】相同的方法，使(A) 〜(c)成分進行反應。確認NC0之含率％為6 3%以下後， 加入做為陰離子性基中和劑(D)之三乙胺4 33g(〇 〇428莫 耳)使得中和率變為1.0，以製得固體含量為80質量％之胺 基曱酸醋預聚物。 進料時之(A)〜(C)成分的總量中，（a)成分之比例為5 質置％ ’（C)成分之比例為4.8質量％ , NC〇/〇H之當量比為 2.2。 使用所得的胺基甲酸酯預聚物’藉由與實施例1相同 的方法，試行製造水系聚胺基甲酸酯樹脂組成物時，於胺 基甲酸酯預聚物進行水分散時，伴隨產生二氧化碳而導致 顯著發泡，無法製得水系聚胺基甲酸酯樹脂組成物。 [比較例5] 除使用1，8-辛二醇6.〇g(〇.〇41莫耳)取代⑻長鏈烷二醇 化合物、做為其他之(A)成分的實施例丨使用的聚酯多元醇 58.9g(0.0337莫耳)及做為(B)成分之氫化MDI 49.3g(0.188 莫耳)外，藉由與實施例1相同的方法，使(A)〜(c)成分進 行反應。確認NCO之含率％為4·0%以下後，加入做為陰離 子性基中和劑(D)之三乙胺4 33g(0.0428莫耳)使得中和率 27/33 201221531 為1.0 ’以製得固體含量為80質量％之胺基甲酸酯預聚物。 進料時之(A)〜(C)成分的總量中，]，8-辛二醇之為5質 量％ ’（C)成分之比例為4.8質量％，NCO/OH之當量比為 1.6。 使用所得的胺基曱酸酯預聚物，藉由與實施例1相同 的方法，進行水分散及水伸長反應，製得固體含量為40% 之水系聚胺基曱酸酯樹脂組成物。 [比較例6] 將與前述實施例1使罔者相同的胺基甲酸酯預聚物於 相同條件下進行水分散後，使用鏈伸長劑之乙二胺 3.57g(0.119莫耳)予以高分子量化，且製得水系聚胺基甲酸 酯樹脂組成物。 [比較例7] 除了相對於前述(A)、（B)及(C)成分之總量100質量份 而言’於水中添加10質量份的使前述比較例6使用之乳化 劑(ADEKA(股)製、製品名 AdekaPluronicF-108):聚丙二醇 的氧化乙烯加成物、平均分子量15500、氧化乙烯含量80 質量％)且進行水分散外，NCO/OH之當量比、中和率及固 體含量等設定與比較例6相同，以與比較例6相同的製造 條件，製得水系聚胺基甲酸酯樹脂組成物。 <性能評估> 如下述進行評估前述實施例1〜3及比較例1、5〜7所 得的水系聚胺基曱酸酯樹脂組成物之塗料安定性、塗膜之 耐水性、耐酸性、耐鹼沒及密接性。 此等之結果如表1所示。 [塗料安定性] 28/33 201221531 相對於藉由前述實施例及比較例所得的水系聚胺基曱 酸酉曰樹脂組成物100質量份而言，使CYMEL 325(曰本 Cytec Industries公司製、曱基化蜜胺樹脂、固體含量8〇%)15 質量份進行混合攪拌，再加入二甲基乙醇胺，將pH值調整 為8.5 ’製得試驗液。測定所得的試驗液在4〇它下放置 日前後之黏度，藉由上昇的黏度評估塗料之安定性。 〇：沒有黏度上昇情形，安定性良好 △:觀察到黏度上昇情形 X:觀察到顯著的黏度上昇情形 [試驗體製作] 使用電性鍍敷鋅之鋼板做為基材，且使用pH值為η 〜13之脫脂劑，在6(rc下進行脫脂處理5分鐘。在經脫脂 處理的電性織辞之鋼板上，以厚度塗布藉由前述^ 施例1〜5及比較例丨〜4所得的水系聚胺基曱酸酯樹脂二 成物。在300°C之環境下4秒鐘以使鋼板之板溫加熱乾. 75°C，而製作試驗體。 ” [耐水性試驗] 有關所得的試驗體，在65°c、95%之相對濕度下，進 行24小時之耐水斑試驗，以下述基準藉由目視評ς 之塗膜狀態。 便 5:塗膜沒有異常情形 4:塗膜之浮出情形為全面積之5%以下 3.塗膜之浮出情形為全面積之6〜2〇% 2.塗膜之浮出情形為全面積之21%以卜 1:塗膜完全被剝落 [耐酸性試驗] 29/33 201221531 將試驗體於1質量％之h2S〇4水溶液(25ΐ)中浸潰24 小時’且以下述基準藉由目視評估浸潰後之塗膜狀雖。 5··塗膜沒有異常情形 “ 4.塗膜之浮出情形為全面積之以下 3:塗膜之浮出情形為全面積之6〜2〇〇/〇 2:塗膜之浮出情形為全面積之21%以上 1:塗膜完全被剝落 [财驗性試驗] 使用前述試驗體於1 fi%tNa0H水溶液中浸 潰1小時，以下述基準藉由目視評估。 5:塗膜沒有異常情形 4:塗膜之浮出情形為全面積之5%以下 3:塗膜之浮出情形為全面積之6〜20〇/〇 2:塗膜之浮出情形為全面積之2ΐ〇/〇以上 1:塗膜完全被剝落 [密接性] 在未處理的電性鍍敷鋅之鋼板上，以厚度塗布水 系聚胺基曱酸酯樹脂組成物後，在300°c之環境、鋼板之溫 度為150°C下進行加熱乾燥15秒，製得試驗體。 藉由JIS Κ5600_5·6(交叉切斷法），以下述基準評估該試 驗片之塗膜剝落情形。 5:塗膜沒有異常情形 4:塗膜上稱許有浮出情形(5%以下之面積） 3:塗膜上很少有浮出情形(超過5%、20%以下之面積) 2:塗膜上有很多浮出情形(超過20%之面積） 1:塗膜完全被剝落 30/33 201221531 [表i] 實施 例1 實施 例2 實施 例3 比較 例1 比較 例5 比較例 6 比較 例7 ⑻成 分 種類 C18*i C12*2 C18 - C8 C18 C18 摻合 量*3 5 10 2 0 5 5 5 NCO/OH 當 量比 1.6 1.7 1.5 1.6 1.6 1.6 1.6 鏈伸長 水伸 長 水伸 長 水伸 長 水伸 長 水伸 長 EDA*4 EDA 乳化劑η 一 - - 10 塗料安定性 〇 〇 〇 〇 〇 X X 耐水性 5 4 5 1 2 5 3 耐酸性 4 4 4 3 3 4 4 耐驗性 4 3 4 1 2 4 4 密接性 5 5 5 5 5 5 3 *1: C18: 1,12-十八烷二醇 *2: C12: 1,12-十二烷二醇 *3:摻合量:相對於(A)、（B)及(C)成分之總量而言的質 量％ *4:乙二胺 *5: Adeka Pluronic F-108:相對於(a)、(B)及(C)成分之總 量100質量份而言之乳化劑的質量份數 由前述實施例及比較例之結果可知，確認僅本發明之 水系聚胺基曱酸酯組成物，可得塗料安定性、耐水性、耐 藥品性及密接性全部皆佳的結果。 [產業上之利用價值] 本發明之水系聚胺基曱酸酯樹脂組成物’由於為水 31/33 201221531 系，不僅不會對環境造成破壞且作業性佳，可形成具有優 異的塗料安定性、耐水性、耐酸性及耐鹼性等之耐藥品性 的塗膜，藉由塗布於木材、紙、纖維、玻璃、電子材料零 件及鋼板等之表面上，適合於製造耐水性、耐藥品性優異 的材料或成形品。 【圖式簡單說明】 無。 【主要元件符號說明】 無。Sour vinegar, trilauryl trisulfide dish vinegar, double (Xinyi 'J-illusion, 5 3rd_but basic base) quaternary tetraol di-flavonoid vinegar, 雔 (, 3- 3--4--4-methyl Phenyl) pentaerythritol diphosphate, bis (2 = 19/33 201221531 dicumenyl phenyl) pentaerythritol dimonate, distearyl pentaerythritol dicaprate, tetra (C12-C15 mixed alkyl) -4,4,-diisopropylidene dipyridyl phosphate Sg, bis[2,2-indenyl bis(4,6-;pentylphenyl)]-isopropylidene diphenyl phosphate , tetra-tridecyl· 4,4′-butylidene bis(2-tert-butyl-5-nonylphenol) diphosphate, hexakis(tridecyl)·^, ginseng (2_ Mercapto-5_3_butyl-4-hydroxyphenyl)butane•triphosphate, bismuth (2,4_di_3_butylphenyl) bismuth dicarboxylate, ginseng (2 -[[2,4,7,9-肆-3rd-butyldi-phosphonium-6-yl) oxidized]ethyl]amine, 9, ι〇_ dihydrooxo -10-phosphaphenanthrene-10-oxide, ginseng 4,8,10-fluorene-tert 3-butyldibenzo[d,f][l,3,2]dioxaphosphon-6-yl) oxidation Ethyl)amine, 2-(1, _dimethylethyl)-6-fluorenyl 4-[3-[[2,4,8,10-trans (ι,ι_二曱) Ethyl) [明[1,3,2] Dioxaxo-6-yl]Oxidation]propyl] 笨盼_2-butyl-2-ethylpropanol·2,4,6-tri-3- Butyl phenyl is expected to be monosqualic. The present herbicidal antioxidant may, for example, be 2,6-di-butyl butyl-p-nonylphenol 2,6-diphenyl-4-octadecyloxyphenol or stearyl group (3) , 5_二第> butyl-4-hydroxyphenyl)propionate, distearyl (3,5-di-3-3-butyl-4-hydroxyl) phosphate, tridecane 3,5-di-tert 3-butyl-4-hydroxybenzylsulfuric acid acetate, divinyl sulfide bis[(3,5-di- 3rd-butylhydroxypropionate), 4 , 4,-sulfurized bis(6_3_butyl_111_cresol), 2_octylsulfide^_4^6_ one (3,5-di-tert 3-butyl-4-phenylphenoxy -s_triazine, 2,2,_methylenebis(4-mercapto-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-第3- Butyl phenyl) butyrate] ethylene glycol ester, 4,4,-butylene bis(2,6-di-3-butylphenol), 4,4-butylene bis (6-3-but Benzyl-3-methyl phenyl), 2,2'-ethylenebis(4 6 · bis-tert-butylphenol), ι, 〗, ^ gin (2-methyl-4 hydroxy-5 -3-butylphenyl)butane, bis[2-tert 3-butyl-6-(2-hydroxy-3-3-3-butyl-5-methylbenzyl)phenyl]p-benzene Diformate, u, 5_ gin (2,6-dimethyl_3_hydroxy·4_3_^_ 20/33 201221531 base methyl) Acid ester, 1,3,5-gin (3,5-di-3-butyl-4-hydroxy adenyl)iso-n-benzoate, 1,3,5-parameter (3,5_2, 3_) Butyl-4-hydroxyphenylhydrazine;)_2,4,6-dimethyl phenyl, 1,3,5-para[(3,5-di-3-butyl-4-hydroxyphenyl)propoxy Ethylethyl]isoxanoate, hydrazine [indolyl-3-(3,,5'-di-butyl butyl-4,-p-phenyl) propionate] 3-butyl-4-mercapto-6-(2-propanoloxy-3-tert-butyl-5-fluorenylmethyl)phenol, 3,9-bis[2-(3- 3-butyl-4-hydroxy-5-:yl residue cinnamyloxy)-U-didecylethyl]-2,4,8,10-tetraoxaspiro j[j·5] ten~ Alkane, triethylene glycol bis[泠-(3- 3 -butyl-4-hydroxy-5-fluorenyl) propionate], tocopherol, etc. - 0 杬 oxidizing agent is exemplified by dipropyl sulfide Acidic lauric acid ester, its second §3, meat ugly §, stearic acid vinegar, stearic acid vinegar, etc., two kinds of acid S and quaternary alcohol 4 (/3_12 base) Propionate vinegar, eve 70 alcohol, /5-alkyl ketone propionate, each of the amine-based light stabilizers, (4) line suction "丨 and antioxidants 0.001 quality 彳 eight _ A, injury, will Preferably, it is 0.01 to 5 parts by mass. The method for the preparation of bismuth, bismuth, anti-oxidation, the method of dip in water dispersion, the method of adding to the prepolymer, or the method in the aqueous phase, in the alcohol after water dispersion It is preferred that the genus is added to the water-based polyamine method of the present invention. For example, the coating material, the adhesive sword, and the surface of the resin composition are used as an adhesive or a molded article. Wenbeibe, organic and/or inorganic powder 21 /33 201221531 'Can be used for Hi-grade facial fiber phase change, sensation (four), inkjet paper coating agent, printing ink adhesive, steel plate coating: coating for agricultural film Agent, glass, slate, earth cloth!讨 袓 袓 + ^ 反 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢 欢Among these, 'use as a coating: Dimensions _, electronic material parts and steel plate coating materials (4); special = use as a surface treated steel plate is better. 'When using the water-based amine hydrazine of the present invention, for example, the coating material can be coated with a brush, a roller, a spray coating, a photographic cloth, a reversible roll coating, a knife coating, a bar coating, a curtain coating coating' A method of appropriately selecting a dip cloth, a stick coating, a knife coating, or the like is applied to the soil [embodiment] and the soil bamboo. / Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is limited thereto. x [Examples] [Example 1] 1,12-octadecanediol 0.0g (〇.〇) as a long-chain alkylene glycol compound (a) in the polyol (A) was added to the reaction flask. 2〇9mol), as the other component (A), the mass ratio of 1,6-hexanediol to adipic acid and isophthalic acid (adipic acid/isoparaxamic acid) is 50/50) The obtained polyester polyol (quantitative average molecular weight: 1750) 65.7 g (0.0375 mol), as diisocyanate (B) dicyclohexyl oxime-4,4'-diisocyanate (described below) 42.5 g (0.1620 mol) of hydrogenated MDI), 5_74 g (0.0428 mol) of dihydroxymethyl propionic acid as the polyol (c) introduced into the anionic group. At this time, the components (A) to (C) The ratio of the component (8) in the total amount is 5 mass. The ratio of the component (〇) is 4.8% by mass, and the equivalent ratio of NCO/OH is 22/33 201221531 1.6. In addition, N-mercapto-2 is added to the solvent. - The ratio of 25.7g is slightly more than 25.7g, and the reaction is carried out for 2 to 3 hours under a nitrogen gas stream at 100 to 110 ° C to confirm that the content of nc〇 is 3.4% or less. Then, it is added as an anionic base neutralizer ( D) Triethylamine 4.33 g (0.0428 mol)' The neutralization ratio was changed to 1. 〇, and an amino phthalate prepolymer having a solid content of 80% by mass was obtained. An antifoaming agent was added to 110 g of water. 0.1 g (made by ADEKA Co., Ltd., B1016), and an aqueous solution obtained by stirring 1.18 g (0.0117 mol) of triethylamine having a neutralization ratio of the urethane prepolymer of 0.2. 109 g of the aforementioned amino phthalate prepolymer was added, and the mixture was stirred at 20 to 40 ° C for 15 minutes to disperse. The obtained dispersion of the amino phthalate prepolymer was carried out at 30 to 40 ° C. The water was subjected to a reaction for 12 hours, and further, at 50 to 55 ° C, a water elongation reaction was carried out by an IR (infrared spectrophotometer) measurement until the disappearance of the NCO group to obtain a solid content. The amount of the aqueous polyurethane resin composition was 40%. [Example 2] 1,12-octadecane was added as a long-chain alkanediol compound (8) in the polyol (A) in a reaction flask. 12.0 g (0.0593 mol) of diol, as other (A) component, polycarbonate diol (number average molecular weight 2000) of 1,6-hexanediol and adipic acid (49.0 g (0.0245 m)) 51.9 g (0.234 mol) of isophorone diisocyanate (hereinafter referred to as IPD1) of isocyanate (B) and 7.17 g (0.0535) of dihydroxymethyl propionic acid as polyol (C) introduced with anionic group. Moore). In this case, the ratio of the component (8) in the total amount of the components (A) to (C) is 1% by mass. The ratio of the component (C) is 6.0% by mass, and the equivalent ratio of NCO/OH is 1.7. 23/33 201221531 In addition, as a solvent, N-mercapto-2_π is more than 24.6g, and the reaction is carried out in a gas stream at 100~110 °C for 2 to 3 hours. The dish 5 is NC〇%. 5.4% or less. Then, 5.41 g (0.0535 mol) of diethylamine which is an anionic group neutralized with a '1 (D) was added, and the neutralization ratio was changed to 1 Torr to prepare an amino decanoic acid having a solid content of 80% by mass. Ester prepolymer. An antifoaming agent (manufactured by ΑΜκα, Bl〇l6) 〇.lg' was added to 110 g of water, and 1.47 g of triethylamine was added under the above-mentioned neutralization ratio of the amino phthalate prepolymer to 0.2 ( 0.0145 moles] 108 g of the aforementioned urethane prepolymer was added to the water-soluble wave obtained by stirring, and the mixture was stirred at 20 to 4 (TC for 15 minutes to disperse. The obtained amino phthalate prepolymer was used. The dispersion liquid was subjected to a water elongation reaction at 30 to 40 ° C for 12 hours, and further, a water elongation reaction was carried out under C at a time until the disappearance of the NCO group by IR (infrared spectrophotometer) measurement to obtain a solid. A water-based polyamino decanoic acid S composition having a content of 40%. [Example 3] 1,12-eighteen as a long-chain glycerol compound (8) in a polyol (A) was added to a reaction flask. Alkanediol 2.4g (0.0084 mol), as other (A) component polytetramethylene ether glycol (number average molecular weight 2000) 81.4g (0.0407 mol), as isocyanate (B) Hydrogenated MDI 31.9 g (0.1216 mol) and 4.30 g (0.0321 mol) of dihydroxymethyl propionic acid as the polyol (C) introduced into the anionic group. At this time (A) to (C) The ratio of the component (8) in the total amount of the components is 2% by mass, and the ratio of the component (C) is 3.6% by mass. The equivalent ratio of NCO/OH is 1.5. Further, N-mercaptopyrrolidone 26_8g as a solvent is added. The reaction was carried out under a nitrogen gas stream at 100 to 1 HTC for 2 to 3 hours. After confirming that NCO% 24 / 33 8 201221531 was changed to 2.3% or less, 3.24 g (0.0320) of triethylamine as an anionic base neutralizer (D) was added. Mohr) The neutralization rate was changed to 丨.〇 to prepare an amino phthalic acid vinegar prepolymer having a solid content of 80% by mass. An antifoaming agent (ADEKA (manufactured by ADEKA), B1016) was added to 110 g of water. , 1 g, and triethylamine 0.88S (0.0087 mol) which causes the neutralization ratio of the aforementioned amino phthalate prepolymer to become 0.2. Then, the aforementioned amine group is added to the aqueous solution obtained by stirring. The phthalate prepolymer l〇9g was dispersed by stirring at 20 to 40 ° C for 15 minutes. The obtained dispersion of the amino phthalate prepolymer was subjected to water elongation reaction at 30 to 40 ° C. After 12 hours, the water elongation reaction was confirmed by IR (infrared spectrophotometer) measurement until the disappearance of the NCO group at ~65 ° C. An aqueous polyamine phthalate resin composition having a solid content of 40% was obtained. [Comparative Example 1] 77.7 g (0.0444 m) of the polyester polyol used in Example 1 as the component (A) was used. The components (A) to (C) were reacted in the same manner as in Example 1 except that the hydrogenated MDI of the component (B) was 36.6 g (0.14 mmol), and the component (a) was not used. It was confirmed that the NCO% was 2.9% or less. Then, 4.33 g (0.0428 mol) of triethylamine as an anionic radical neutralizing agent (D) was added so that the neutralization ratio became 1.0 to obtain a urethane prepolymer having a solid content of 80% by mass. Things. The ratio of the component (c) in the total amount of the components (A) to (C) at the time of the feed was 4.8% by mass, and the equivalent ratio of NCO/OH was 1.6. The obtained amino phthalate prepolymer was subjected to water dispersion and water elongation reaction by the same method as in Example 1 to obtain a water-based polyurethane resin composition having a solid content of 40%. [Comparative Example 2] 25/33 201221531 Example 1 was used as the (a) component of 1,12-octadecanediol (30.0 g (0.] 〇 5 mol) as the other (A) component. (A) to (C) by the same method as in Example 1 using 18.0 g (0.0103 mol) of the polyester polyol and 66.2 g (0.252 mol) of hydrogenated MDI as the component (B) The ingredients are reacted. After confirming that the content ratio of NCO was 5.3% or less, 4.33 g (0.0428 mol) of triethylamine as an anionic base neutralizer (D) was added so that the neutralization rate was 1.0 ' to obtain a solid content of 8 〇% by mass of amino phthalate prepolymer. At the time of the addition (A) to (the total amount of the component (8) in the total amount of the component of the component is 25, the ratio of the component (C) is 4.8 mass. /〇, the equivalent ratio of NC〇/〇H is 1.6. The urethane prepolymer, when the aqueous polyamine oxime resin composition was tried to be produced in the same manner as in Example ,, the water dispersion of the amino phthalic acid vinegar prepolymer was poor. A water-based polyurethane resin composition having good dispersibility. [Comparative Example 3] Example of the component (A) excluding the component (a)] Polyester oxime alcohol used in 77.ig (0) In addition to the hydrogenated MDi 3l.lg (0.119 mole) as a component, the ~(C) component was reacted in the same manner as in Example!. It was confirmed that the % content of NCO was 〇. After 6% or less, 43.3 g (〇〇428 mol) of triethylamine as an anionic group neutralizing agent (D) was added so that the neutralization ratio became 1.0 to obtain an amine having a solid content of 8% by mass. The urethane prepolymer. In the total amount of the components (A) to (C) at the time of feeding, the ratio of the component (a) is 5% by mass, and the ratio of the component (C) is 4'8 mass 〇 / 〇, the equivalent of NC〇/〇H The ratio is U. 26/33 201221531 The obtained amino phthalate prepolymer is preliminarily polymerized by the same method as in the example, when the aqueous polyamine phthalate resin composition is experimentally produced. The material could not be dispersed in water, and the aqueous polyurethane resin composition could not be obtained. [Comparative Example 4] Polyester sterol used in the example of the component (a) except the component (a) The components (A) to (c) were reacted in the same manner as in the Example except that 53.8 g (0.0307 mol) and the hydrogenated MDI as a component were 54.5 g (0.208 mol), and the content of NC0 was confirmed. After the % is 6 3% or less, the triethylamine 4 33 g (〇〇428 mol) as an anionic radical neutralizer (D) is added so that the neutralization ratio becomes 1.0 to obtain a solid content of 80% by mass. Amino citrate prepolymer. In the total amount of components (A) to (C) at the time of feeding, the ratio of the component (a) is 5, and the ratio of the component (C) is 4.8% by mass. The equivalent ratio of NC〇/〇H was 2.2. Using the obtained urethane prepolymer', a water-based polyurethane resin composition was experimentally produced by the same method as in Example 1. When the urethane prepolymer was subjected to water dispersion, significant foaming was caused accompanying the generation of carbon dioxide, and the aqueous polyurethane resin composition could not be obtained. [Comparative Example 5] Except that 1,8-octane was used. Diol 6. 〇g (〇.〇41 mole) substituted (8) long-chain alkanediol compound, as an example of the other (A) component 丨 used polyester polyol 58.9g (0.0337 mol) and made The components (A) to (c) were reacted in the same manner as in Example 1 except that the hydrogenated MDI of the component (B) was 49.3 g (0.188 mol). After confirming that the content ratio of NCO is 4% or less, triethylamine 4 33 g (0.0428 mol) as an anionic radical neutralizing agent (D) is added so that the neutralization ratio is 27/33 201221531 is 1.0'. A urethane prepolymer having a solid content of 80% by mass was obtained. In the total amount of the components (A) to (C) at the time of the feed,], the ratio of the 8-octanediol was 5% by mass. The ratio of the component (C) was 4.8% by mass, and the equivalent ratio of NCO/OH was 1.6. Using the obtained amino phthalate prepolymer, water dispersion and water elongation reaction were carried out in the same manner as in Example 1 to obtain an aqueous polyamine phthalate resin composition having a solid content of 40%. [Comparative Example 6] The same urethane prepolymer as the above Example 1 was subjected to water dispersion under the same conditions, and then subjected to a chain extender of ethylenediamine 3.57 g (0.119 mol). The molecular weight was changed, and an aqueous polyurethane resin composition was obtained. [Comparative Example 7] In addition to 10 parts by mass of water, the emulsifier used in the above Comparative Example 6 was added to 100 parts by mass of the total amount of the components (A), (B) and (C) (ADEKA) ), product name: AdekaPluronic F-108): ethylene oxide adduct of polypropylene glycol, average molecular weight 15500, ethylene oxide content 80% by mass), water dispersion, NCO/OH equivalent ratio, neutralization ratio, solid content, etc. In the same manner as in Comparative Example 6, the aqueous polyurethane resin composition was obtained under the same production conditions as in Comparative Example 6. <Performance Evaluation> The coating stability of the aqueous polyamine phthalate resin composition obtained in the above Examples 1 to 3 and Comparative Examples 1 and 5 to 7 was evaluated as follows, and the water resistance and acid resistance of the coating film were evaluated. Alkali resistance is not as good as adhesion. The results of these are shown in Table 1. [Coating property stability] 28/33 201221531 CYMEL 325 (manufactured by C本 Cytec Industries Co., Ltd.) was used for 100 parts by mass of the aqueous polyamine bismuth ruthenate resin composition obtained by the above Examples and Comparative Examples. The base melamine resin and the solid content of 8% by mass of 15 parts by mass were mixed and stirred, and then dimethylethanolamine was added thereto to adjust the pH to 8.5 ' to prepare a test liquid. The viscosity of the test liquid obtained before and after the test was placed at 4 Torr, and the stability of the paint was evaluated by the increased viscosity. 〇: No increase in viscosity, good stability △: Observed viscosity increase X: Significant viscosity increase observed [Preparation of test piece] Using an electroplated zinc plate as a substrate and using a pH of η The degreaser of ～13 was degreased at 6 (rc for 5 minutes). On the steel sheet of the degreased electrical sculpt, the thicknesses were coated with the above-mentioned Examples 1 to 5 and Comparative Examples 丨 to 4. Water-based polyamine phthalate resin dimer. The test piece was prepared by heating the plate of the steel plate at 300 ° C for 4 seconds in an environment of 300 ° C. "Water resistance test" The film was subjected to a water spot test for 24 hours at 65 ° C and 95% relative humidity, and the film state was visually evaluated by the following criteria. 5: No abnormality of the coating film 4: floating of the coating film The case is 5% or less of the total area. 3. The floating condition of the coating film is 6 to 2% of the total area. 2. The floating film of the coating film is 21% of the total area. The coating film is completely peeled off [acid resistance] Test] 29/33 201221531 The test body was immersed in 1% by mass of h2S〇4 aqueous solution (25 ΐ) for 24 hours' and It is possible to visually evaluate the film shape after the impregnation. 5··There is no abnormality in the coating film. 4. The floating film of the coating film is below the full area. 3: The floating film of the coating film is the full area of 6~ 2〇〇/〇2: The film is floated out at 21% or more of the entire area. 1: The film is completely peeled off. [Experimental test] The test body was immersed in 1 fi% tNa0H aqueous solution for 1 hour, below. The reference is evaluated by visual inspection. 5: There is no abnormality in the coating film. 4: The floating film of the coating film is 5% or less of the total area. 3: The floating film of the coating film is 6 to 20 〇/〇2 of the whole area: coating The film floats out at a total area of 2 ΐ〇/〇 or more. 1: The coating film is completely peeled off [Adhesiveness] On an untreated electroplated zinc-plated steel sheet, a water-based polyamine phthalate resin is applied in a thickness. After the object, the test piece was prepared by heating and drying at a temperature of 300 ° C and a temperature of the steel plate at 150 ° C for 15 seconds. The test piece was evaluated by the following criteria by JIS Κ 5600_5·6 (cross cutting method). Peeling of the coating film. 5: There is no abnormality in the coating film. 4: The coating film is said to have a floating condition (area of 5% or less). 3: There is little floating on the coating film. Shape (more than 5%, 20% or less area) 2: There are many floating conditions on the coating film (more than 20% of the area) 1: The coating film is completely peeled off 30/33 201221531 [Table i] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 5 Comparative Example 6 Comparative Example 7 (8) Component type C18*i C12*2 C18 - C8 C18 C18 Blending amount *3 5 10 2 0 5 5 5 NCO/OH equivalent ratio 1.6 1.7 1.5 1.6 1.6 1.6 1.6 Chain Elongation Water Elongation Water Elongation Water Elongation Water Elongation Water Elongation EDA*4 EDA Emulsifier η I - 10 Coating Stability XX Water Resistance 5 4 5 1 2 5 3 Acid Resistance 4 4 4 3 3 4 4 Testability 4 3 4 1 2 4 4 Adhesion 5 5 5 5 5 5 3 *1: C18: 1,12-octadecanediol*2: C12: 1,12-dodecanediol *3: blending amount: mass % relative to the total amount of the components (A), (B), and (C) *4: ethylenediamine*5: Adeka Pluronic F-108: relative to (a), The mass fraction of the emulsifier in terms of 100 parts by mass of the total of the components (B) and (C) is known from the results of the above examples and comparative examples, and it is confirmed that only the aqueous polyamine phthalate composition of the present invention can be used. Paint stability, water resistance, resistance Resistance and adhesion are all good results. [Industrial use value] The water-based polyamine phthalate resin composition of the present invention is water 31/33 201221531, which not only does not cause damage to the environment, but also has excellent workability, and can form excellent paint stability. A coating film that is resistant to chemicals such as water resistance, acid resistance, and alkali resistance, and is applied to the surface of wood, paper, fiber, glass, electronic parts, and steel sheets, and is suitable for producing water resistance and chemical resistance. Excellent material or molded product. [Simple description of the diagram] None. [Main component symbol description] None.