201132660 四、 指定代表圖： (一） 本案指定代表圖為：無。 (二） 本代表圖之元件符號簡單說明：無。 五、 本案若有化學式時，請揭示最能顯示發明特徵的 益。 予式： 六、 發明說明： 【發明所屬之技術領域】 本發明關於水系聚氨酯乳化液之製造方法及由此製1 方法所得之黏著劑。 【先前技術】 習知，從溶液中氨酯樹脂成分的微粒化的實現及分散 安定性等觀點，又，從其用途之黏著劑等的黏著性等特性 優良來看’氨酯樹脂溶液以含有多量有機溶液者為主體。 然而’因應近年的空氣污染防止、消防法的規範、勞 動衛生等的要求，在減少有機溶劑含量的狀態，更在不含 有機溶劑的狀態，使氨酯樹脂成分水分散的水系聚氨酯乳 化液（聚氨酯水分散液、水系氨酯樹脂）之使用正被繁盛地 研究。 例如’羧酸型聚酯系水系聚氨酯乳化液的情形，一般 才栗用 、 以相對於氨酯預聚物（prepolymer)的叛基1當量之未 滿 1 太 ' 當量的胺等鹼性化合物’中和氨酯預聚物而使水分散 201132660 的方法。 +然❿，如此所得的水系聚氨醋乳㈣已知I長時間儲 藏、保存時’例如黏著劑的黏著性能等各性能因吸收濕氣 水解而降低。 ^為了改善上述之缺點，在製造缓酸型聚醋系水系聚氨 乳化液之方法中，使用第3級單胺⑽mine)所形成的 申和d，以相對於氨酯預聚物的羧基i當量，使用m 當量的方法被提出（參見專利文獻j )。 根據此方法，被s忍為是顯著的水解性的原因之一的中 和劑’使用第3級單胺代替有機胺的使用，被認為可抑制 促進水解的游離羧基的生成，明顯改善耐水解性。 然而此方法由於過剩的第3級單胺，有水系聚氨醋乳 化液的臭氣變強的問題。 [先前技術文獻] [專利文獻] [專利文獻1]特開2000- 1 6970 1號公報 【發明内容】 【發明所欲解決之問題】 欲解決之問題點為’上述之先前技術為了改善水系聚 氨醋乳化液的耐水解性而使用過剩的第3級單胺所產生的 臭氣問題點。 【解決問題之技術手段】 本發明所涉之水系聚氨酯乳化液之製造方法，為氨醋 201132660 預t物以第一3級胺中和，再進行鏈延長及水分散而得水 系聚致酷乳化液之製造方法中，更具有水分散後的乳化液 中加入驗性較該第_ 3級胺弱的第二3級胺及之後加入鹼 金屬鹼之步驟為特徵。 又’本發明所涉之水系聚氨酯乳化液之製造方法，較 佳為上述氨酯預聚物為以多元醇及有機二異氰酸酯為主 成分所得者為特徵。201132660 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 5. If there is a chemical formula in this case, please disclose the benefits that best show the characteristics of the invention. PREFERENCE: VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing an aqueous polyurethane emulsion and an adhesive obtained by the method of the invention. [Prior Art] From the viewpoints of the realization of the atomization of the urethane resin component in the solution, the dispersion stability, and the like, the urethane resin solution is contained in view of excellent properties such as adhesion of the adhesive or the like. A large amount of organic solution is the main body. However, in response to the requirements of air pollution prevention, fire protection laws, and labor hygiene in recent years, water-based polyurethane emulsions in which the urethane resin component is water-dispersed in a state where the content of the organic solvent is reduced and the organic solvent-free state is contained ( The use of polyurethane aqueous dispersions and aqueous urethane resins is being studied vigorously. For example, in the case of a 'carboxylic acid type polyester-based water-based polyurethane emulsion, an alkaline compound such as an amine of less than 1 equivalent of less than 1 equivalent to the retort of the urethane prepolymer is used. A method of neutralizing a urethane prepolymer to disperse water in 201132660. + However, the water-based polyurethane milk (4) thus obtained is known to have a property such as adhesion and storage of the adhesive for a long period of time, for example, the adhesion property of the adhesive is lowered by absorption of moisture. In order to improve the above disadvantages, in the method for producing a slow acid type polylactic acid aqueous ammonia emulsion, the ratio d formed by the third stage monoamine (10)mine is used to be relative to the carboxyl group of the urethane prepolymer. Equivalent, a method using m equivalent is proposed (see Patent Document j). According to this method, the use of a third-stage monoamine instead of an organic amine, which is one of the causes of significant hydrolyzability, is considered to inhibit the formation of a free carboxyl group which promotes hydrolysis, and the hydrolysis resistance is remarkably improved. Sex. However, this method has a problem that the odor of the aqueous polyammonium emulsifiable liquid becomes strong due to the excess of the third-stage monoamine. [Prior Art Document] [Patent Document 1] [Patent Document 1] JP-A-2000-0656 1 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The problem to be solved is the above-mentioned prior art in order to improve water polymerization. The problem of odor caused by the use of excess third-stage monoamine in the hydrolysis resistance of the ammonia vinegar emulsion. [Technical means for solving the problem] The method for producing an aqueous polyurethane emulsion according to the present invention is that the ammonia vinegar 201132660 pre-taste is neutralized with the first tertiary amine, and then chain extension and water dispersion are carried out to obtain a water-based condensed emulsion. In the method for producing a liquid, a step of adding a second-stage amine which is weaker than the third-grade amine and then adding an alkali metal base is added to the emulsion having water-dispersed. Further, in the method for producing a water-based polyurethane emulsion according to the present invention, it is preferred that the urethane prepolymer is obtained by using a polyol and an organic diisocyanate as a main component.
又，本發明所涉之水系聚氨酯乳化液之製造方法，較 佳為’上述多元醇為聚酯多元醇為特徵。 本發明所涉之水系聚氨酯乳化液之製造方法，較 佳為，上诚笸— 本旦 3級胺，相對於上述氨酯預聚物的羧基i 萬里加入1. 〇〜1.1當量為特徵。 月所涉之水系聚氨酯乳化液之製造方法， 為上述第—3級胺，相對於中逢口針沾ν、+, γ s匕 一 對於中和别的上述氨酯預潔 土 * ϊ，加入卜3當量為特徵。Further, in the method for producing an aqueous polyurethane emulsion according to the present invention, it is preferred that the polyol is a polyester polyol. Preferably, the method for producing an aqueous polyurethane emulsion according to the present invention is characterized in that, the above-mentioned sulfonate-based amine is added to the carboxyl group of the urethane prepolymer by 1. 〇 to 1.1 equivalent. The manufacturing method of the water-based polyurethane emulsion involved in the month is the above-mentioned third-grade amine, which is added to the neutralization of the above-mentioned urethane pre-cleaned soil* 相对 with respect to the Zhongfeng mouth and needle ν, +, γ s匕Bu 3 equivalents are characteristic.
又本發明所涉之水系聚氨酯乳化液之製造方法， ，.，，，上述鹼金屬鹼，相對於中 羧基 T、中和則的上述氨酯預聚物 1田篁’加入0.2〜0.4當量為特徵。 又，本發明所涉及之黏著 系聚氨醋乳化液之製造方法广、特徵在於’由上述 成分者。 ★ 斤侍的水系聚氨酯乳化液為 又，本發明所涉及之黏 著劑為特徵。 著劑，較佳為 鞋用聚氨S旨點 【發明之功效】 4 201132660 本發明所涉之水李平_ < 、&乱礼化液之製造方法，氨酯預 聚物以第一3級胺中和，再谁耔 ^ 丹進仃鏈延長及水分散而得水系 聚氣西旨乳化液之製造方法中，头击 $中因為更具有在水分散後的乳 化液中’加入驗性較該第一 3級胺弱的第…胺、之後 力驗金屬驗的步驟，因此不產生使用過剩中和劑所產生 的臭氣_，可得到耐水解性良好的水系聚氨醋乳化液。 由本毛月所涉之水系聚氨醋乳化液之製造方法所 得的水系聚氨醋乳化液為主成分的黏著劑，可適宜得到上 述水系聚氨酯乳化液之製造方法的效果。 【實施方式】 本發明之實施型態如下說明。 本實施型態所涉及之大备耳，g — A1 卜 < 求系聚虱酯乳化液之製造方法， 氣西旨預聚物以第一 3級脸由4 s. U. 吸胺中和，再進行鏈延長及水分散而 得水系聚氨酯乳化液之萝裨古、土 Λ ^ 、Further, in the method for producing a water-based polyurethane emulsion according to the present invention, the above-mentioned alkali metal base is characterized in that 0.2 to 0.4 equivalent of the above-mentioned urethane prepolymer 1 is added to the intermediate carboxyl group T and neutralized. . Further, the method for producing an adhesive polyurethane emulsion according to the present invention is broad and characterized by the above-mentioned components. ★ The water-based polyurethane emulsion of the jinji is also characterized by the adhesive according to the present invention. The agent, preferably the polyamine S for shoe use [effect of the invention] 4 201132660 The water Li Ping _ < , & manufacturing method of the chaos liquid, the urethane prepolymer is the first Neutralization of the third-grade amine, and whoever 耔^ Danjin 仃 chain extension and water dispersion, the water-based gas-gathering emulsion manufacturing method, the head shot is more in the emulsion after the water dispersion The amine which is weaker than the first tertiary amine, and then the metal test step, so that the odor generated by using the excess neutralizing agent is not generated, and the aqueous polyurethane foam having good hydrolysis resistance can be obtained. . The aqueous polyurethane emulsion obtained by the method for producing a water-based polyurethane foam according to the method of the present invention can preferably obtain the effect of the above-described method for producing a water-based polyurethane emulsion. [Embodiment] The embodiment of the present invention will be described below. In the present embodiment, the large preparation ear, g - A1 卜 < is a method for producing a poly phthalate emulsion, and the gas-based prepolymer is neutralized by a first 3 stage face by 4 s. U. , and then carry out chain extension and water dispersion to obtain a water-based polyurethane emulsion of radix, earthworm ^,
Ik方法中，更具有水分散後的乳 化液中加入驗性較該第_ 3 d級胺弱的第二3級胺，之後加 入鹼金屬鹼之步驟。 氨醋預聚物較佳為以多元醇及有機二異氰酸醋作為主 原料使用，經氨酯化反應所得到。 多元醇可使用聚酯多元醇、聚醚多元醇、或聚碳酸酯 夕元醇等的適田物。在此之中，《酯多元醇在對於多種基 材的黏著性及價格面上為適宜者。 聚酯多元醇，例如，酞酸、異酞酸、對酞酸、萘二羧 酸、琥珀酸、丙二酸、己_缺 ,,“ 巳一酸、1，4-環己基二羧酸 '順丁 201132660 烯二酸、反丁烯二酸、其他的二質子酸等，及乙二醇、丨，2_ 丙二醇、1，3-丙二醇、1 1 Λ i’2-丁一％、1，4-丁二醇、15_戊 -一醇、1，6 -己二醇、 曱基庚院、二乙二醇 二醇。 又例如經由低分 1，8-辛二醇、丨，9_壬二醇' 3 3二羥 、二丙二醇、新戊二醇、環己烷—^一 醇及二羧酸縮合所得的縮合系聚 酯多元醇。此類的縮合系聚酯多元醇具體地例如，使乙二 醇，3丙醇1，4 丁二醇等的低分子多元醇與破珀酸、 戊一酉文、己一酸、庚二酸、軟木酸acid)、壬二In the Ik method, a step of adding an alkali metal base which is weaker than the amine of the third grade d amine is added to the emulsified liquid having a water dispersion. The ammonia vinegar prepolymer is preferably obtained by using a polyol and an organic diisocyanate as a main raw material by a urethanization reaction. As the polyol, an appropriate material such as a polyester polyol, a polyether polyol, or a polycarbonate oxime can be used. Among them, "ester polyols are suitable for adhesion to a variety of substrates and in terms of price." Polyester polyols, for example, citric acid, isophthalic acid, p-nonanoic acid, naphthalene dicarboxylic acid, succinic acid, malonic acid, hexamole, "monic acid, 1,4-cyclohexyl dicarboxylic acid"顺丁201132660 enedic acid, fumaric acid, other diprotonic acids, etc., and ethylene glycol, hydrazine, 2_ propylene glycol, 1,3-propanediol, 1 1 Λ i'2-butyl-%, 1,4 -butanediol, 15-pentane-monool, 1,6-hexanediol, thioglycol, diethylene glycol diol. Further, for example, via low-part 1,8-octanediol, hydrazine, 9_壬a condensed polyester polyol obtained by condensing a diol ' 3 3 dihydroxy, dipropylene glycol, neopentyl glycol, cyclohexane-alcohol, and a dicarboxylic acid. Such a condensed polyester polyol is specifically, for example, a low molecular polyol such as ethylene glycol, 3 propanol 1,4 butanediol, and the like, as described below, with aspartic acid, penicillin, hexanoic acid, pimelic acid, acid acid)
Kazelaic acid)、癸二酸（sebacic acid)、癸烷二羧酸、 環己烷二羧酸等的脂肪族二羧酸縮合所得的縮合系聚酯多 元醇。 再者，也可使用ε -己内酯等的環狀酯、二醇的一部 刀變更為六亞甲基二胺或異佛爾酮二胺㈠s〇ph〇r〇ne diamine)等胺類的聚酯醯胺多元醇等。 上述各多元醇皆可單獨使用，也可混合複數個使用， 再者’也可使用上述的共聚合物。 有機二異氰酸酿沒有特別限定，但考慮覆膜的強度及 耐候性等，較佳為脂肪族或脂環族二異氰酸酯。 脂肪族二異氰酸酯可使用四亞甲基二異氰酸酯、六亞 甲基一異氰酸S曰、十亞甲基二異氰酸酯（decamethyiene diisocyanate)、賴胺酸二異氰酸醋（iySine diisocyanate) 等。其中，以六亞曱基二異氰酸酯為適宜。 脂環族二異氰酸酯可使用異佛爾酮二異氰酸酯 201132660 (isophorone di isocyanate)、氫化甲笨二異氰酸酯 '氣化 二甲苯二異氰酸酯、氫化二苯曱烷二異氰酸酯、四曱基二 曱笨二異氰酸醋（tetramethylxylene diisocyanate)等。 其中’以異佛爾酮二異氰酸酯為適宜。 又可進一步使用上述脂肪族二異氰酸酯或脂環族二異 氰酸酯的氨酯改質體、碳二亞胺改質體、脲基甲醋 (allophanate)改質體、尿素改質體、二縮脲（biuret)改質 體、異氰酸二元基（uretod ion)改質體、腺酮亞胺基 (uretonimine)改質體、異氰脲酸酯（is〇cyanurate)改質體 等的異氰酸酯改質體。 上述脂肪族二異氰酸酯或脂環族二異氰酸酯或其改質 體可單獨使用，也可混合2種以上使用。 然而，也可使用2, 4-甲笨二異氰酸酯、2,6_甲苯二異 氰酸酯、二甲苯-1，4-二異氰酸酯、二曱笨-—二異氰酸 酯、4, 4’ -二苯甲烷二異氰酸酯、2,4，_二苯曱烷二異氰 酸酯、4,4’ -二苯醚二異氰酸酯、2_硝基二苯基_4,4，_ 二異氰酸酯、2,2’ -二笨丙烷_4,4，_二異氰酸酯、3,3，— 二甲基二苯基甲烷-4,4，-二異氰酸酯、4,4，_二苯丙烷二 異氰酸酯、間苯二異氰酸酯、對苯二異氰酸酯、萘_丨，4_ 二異氰酸醋、萘-1，5-二異氰酸醋、3, 3, _二甲氧基二苯基 -4,4,-二異氰酸酿等的芳香族二異氰酸醋、聚苯聚亞甲基 聚異氮酉义西曰（p〇lyphenylene㈣岸让 P〇lyiS〇Cyanate)、未精製的曱笨二異氰酸醋（crude tolylene cHisocyanate)等的芳香族聚異氰酸醋。 201132660 以多元醇與有機二異氰酸酯為主原料使用而進行氨酿 化反應之時，可適當使用低分子多元醇或親水化劑。 低刀子多元醇例如乙—醇、1,3-丙二醇、ι，2_丙二醇、 1,2-丁 二醇、1，3_丁二醇、1,4-丁二醇、1>5_戊二醇、i 6_ 从一岬、新戍二醇、1,8 -辛 己二醇、3-甲基 壬二醇、3, 3-二羥曱基庚烷、二乙二醇、l 4_環己烷二醇、 1,4-環己烷二曱醇、2 -乙基- i，3_丙二醇、2_正丙基n 丙二醇、2-異丙基-1,3-丙二醇、2_正丁基^―丙二醇、 2_異丁基-1，3-丙二醇、2-第三丁基—丙二醇、2〜曱基 -2-乙基-1,3-丙二醇、2,2-二乙基_1，3_丙二醇、2_乙基_2_ 正丙基-1,3-丙二醇、2-乙基_2 —正丁基^―丙二醇、2_ 乙基-3-乙基-1,4-丁二醇、2_甲基_3_乙基_14 丁二醇、 2, 3-二乙基-1，5-戊二醇、2, 4_二乙基 <，5_戊二醇、2, 3，^ 三乙基_1，5-戊二醇、三羥甲基丙烷、二羥曱基丙酸、二羥 甲基丁酸、二元酸二醇、甘、，占 未丄、^ 畔甘/由、季戊四醇、雙酚Λ的烯烴 氧化物加成物等。 親水化劑可適宜使用陰 性者。其中’具有2個以上 羧酸的陰離子性親水化劑， 適宜。 離子性、陽離子性、或非離子 異氰酸酯反應性基且具有丨個 在獲得本發明之效果上，特別 具有2個以上異氰酸g旨反庫性其曰昆女 久應性基且具有丨個羧酸 離子性親水化劑例如，2,2_二經甲基丙酸、. 丁酸、2, 2-二羥甲基戊酸等。 里甲4 又以多元醇與有機二異氰酸 日芍王原枓使用而進行凑 201132660 i旨化反應的過程，藉由加入丙酮，可提高水分散性。添加 的丙酮在水分散後被除去（脫溶劑）。 氨酯化反應較佳以預聚物的NC0理論當量比（NC〇基 /0H基）為1.2/1〜1.8/1進行。 氨酯預聚物的羧基以3級胺（第一 3級胺）中和。 第—3級胺可使用脂肪族、芳香族、雜環等適宜物， 但其中以脂肪族3級單胺特別適宜。 月旨肪族3級單胺可列舉三甲胺、三乙胺、三乙醇胺、 N-甲基二乙醇胺等，其中以三乙胺為佳。 第一 3級胺宜以相對於氨酯預聚物的羧基丨當量加入 1. 0 1 ’ 1田里。此時，第一 3級胺過量使用時，恐使所得 的水糸t *11醋乳化液的臭氣變強。 然而，使用下述詳細的鹼性較第—3級胺弱的第二3 級胺代替第-3級胺時，例如即使加入與叛基相同當量也 無法進行充分的中和，無法獲得良好的水分散性。 Φ 另方面，使用下述詳細的驗金屬驗及水代替第一 3 級胺時，因為氨酯預聚物中的陰離子性基少，不能得到良 好的水分散性。 氨酯預聚物在水分散的過程進—步使乳化物鏈延長。 鏈延長劑，除了水以外’可使用例如乙二胺、六亞曱基二 胺、二甲笨二胺、異佛爾酮二胺、二乙稀三胺、N-胺基乙 基一 N-乙醇胺等的(數平均)分子量未滿5〇〇的低分子聚胺 等。 使氨醋預聚物水分散，得到水系聚氨醋乳化液 9 201132660 (emulsion) ° 可使用鏈延長劑及反應停止劑。反應停止劑可使用例 如乙胺、丙胺、丁胺等1級胺；二乙胺、二丁胺等2級胺 等之單胺類。 本實施型態所涉及之水系聚氨酯乳化液之製造方法， 進一步具有’水分散而得的上述水系聚氨酯乳化液中加入 驗性較第一3級胺弱的第二3級胺、之後加入鹼金屬鹼的 步驟。 第二3級胺可使用從第一 3級胺所例示者中比選擇作 為第—3級胺者的鹼性弱者。使用的第二3級胺較第一 3 級胺的臭氣弱。 例如’使用pKa(解離常數，在水中，25〇c)為3.28的 二乙胺作為第一 3級胺的情形，可適宜使用pKa(解離常數） 為6· 24的三乙醇胺作為第二3級胺。A condensed polyester polyol obtained by condensation of an aliphatic dicarboxylic acid such as Kazelaic acid, sebacic acid, decanedicarboxylic acid or cyclohexanedicarboxylic acid. Further, a cyclic ester such as ε-caprolactone or a sulfonate may be changed to an amine such as hexamethylenediamine or isophoronediamine (one) s〇ph〇r〇ne diamine). Polyester phthalamide polyol and the like. Each of the above polyols may be used singly or in combination of plural kinds. Further, the above-mentioned copolymer may be used. The organic diisocyanate is not particularly limited, and is preferably an aliphatic or alicyclic diisocyanate in view of the strength and weather resistance of the film. As the aliphatic diisocyanate, tetramethylene diisocyanate, hexamethylene monoisocyanate S曰, decamethyiene diisocyanate, lysine diisocyanate or the like can be used. Among them, hexamethylene diisocyanate is suitable. As the alicyclic diisocyanate, isophorone diisocyanate 201132660 (isophorone di isocyanate), hydrogenated methyl diisocyanate 'vaporized xylene diisocyanate, hydrogenated diphenyl decane diisocyanate, tetradecyl diphenyl diisocyanate can be used. Tetraacetate (tetramethylxylene diisocyanate) and the like. Wherein 'isophorone diisocyanate is suitable. Further, the urethane modified body of the above aliphatic diisocyanate or alicyclic diisocyanate, carbodiimide modified body, allophanate modified body, urea modified body, biuret ( Biuret) isocyanate modification of modified body, uretod ion modified substance, uretonimine modified substance, isocyanurate modified substance, etc. body. The above aliphatic diisocyanate or alicyclic diisocyanate or a modified form thereof may be used singly or in combination of two or more kinds. However, it is also possible to use 2,4-methyl diisocyanate, 2,6-toluene diisocyanate, xylene-1,4-diisocyanate, diterpene-diisocyanate, 4,4'-diphenylmethane diisocyanate. , 2,4,-diphenylnonane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4,-diisocyanate, 2,2'-diphenylpropane_4 , 4,_Diisocyanate, 3,3,-Dimethyldiphenylmethane-4,4,-diisocyanate, 4,4,-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthalene _丨, 4_ diisocyanate, naphthalene-1,5-diisocyanate, 3,3, _dimethoxydiphenyl-4,4,-diisocyanate, etc. Aromatic isocyanic acid, polyphenylene polymethylene polyisocyanine (P〇lyphenylene (4) shore P让lyiS〇Cyanate), unrefined aromatic tocylene bismuth acetonide (crude tolylene cHisocyanate) Polyisocyanuric acid. 201132660 When a polyol and an organic diisocyanate are used as a main raw material to carry out an ammonia brewing reaction, a low molecular weight polyol or a hydrophilizing agent can be suitably used. Low knife polyol such as ethyl alcohol, 1,3-propanediol, iota, 2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1> Glycol, i 6_ from monoterpene, neodecanediol, 1,8-octanediol, 3-methylnonanediol, 3,3-dihydroxydecylheptane, diethylene glycol, l 4_ Cyclohexanediol, 1,4-cyclohexanedimethanol, 2-ethyl-i, 3-propylene glycol, 2-n-propyl n-propylene glycol, 2-isopropyl-1,3-propanediol, 2_ n-Butyl-propanediol, 2-isobutyl-1,3-propanediol, 2-tert-butyl-propanediol, 2~mercapto-2-ethyl-1,3-propanediol, 2,2-diethyl Base_1,3_propylene glycol, 2_ethyl_2-n-propyl-1,3-propanediol, 2-ethyl-2-n-butyl-propanediol, 2-ethyl-3-ethyl-1,4 -butanediol, 2-methyl_3_ethyl_14 butanediol, 2,3-diethyl-1,5-pentanediol, 2,4-diethyl<,5-pentane Alcohol, 2, 3, ^ triethyl-1,5-pentanediol, trimethylolpropane, dihydroxymethyl propionic acid, dimethylolbutanoic acid, dibasic acid diol, gan,丄, ^ 甘 / /, pentaerythritol, bisphenol oxime olefin oxide adducts and the like. A hydrophilizing agent can be suitably used. Among them, an anionic hydrophilizing agent having two or more carboxylic acids is suitable. An ionic, cationic or nonionic isocyanate-reactive group having one or more of the effects of the present invention, in particular having two or more isocyanic acid groups, and having a long-lasting basis The carboxylic acid ionic hydrophilizing agent is, for example, 2,2-di-methylpropionic acid, butyric acid, 2,2-dihydroxymethylvaleric acid or the like. Lijia 4 is also used in the process of the reaction of the polyol and the organic diisocyanate, and the water dispersibility is improved by adding acetone. The added acetone was removed after water dispersion (desolvation). The urethanization reaction is preferably carried out at a theoretical equivalent ratio of NC0 (NC thiol / 0H group) of the prepolymer of from 1.2/1 to 1.8/1. The carboxyl group of the urethane prepolymer is neutralized with a tertiary amine (first tertiary amine). As the third-grade amine, an aliphatic, aromatic, heterocyclic or the like can be used, but among them, an aliphatic tertiary monoamine is particularly suitable. Examples of the mono-aliphatic monoamines include trimethylamine, triethylamine, triethanolamine, N-methyldiethanolamine, etc., of which triethylamine is preferred. The first tertiary amine is preferably added to the field of 1. 0 1 '1 relative to the carboxyl equivalent of the urethane prepolymer. At this time, when the first 3-stage amine is used in excess, the odor of the obtained hydrazine t*11 vinegar emulsion may become strong. However, when the following third-order amine having a lower basicity than the third-order amine is used in place of the third-grade amine, for example, even if the same equivalent amount as the rebel is added, sufficient neutralization cannot be performed, and good results cannot be obtained. Water dispersibility. Φ On the other hand, when the following detailed metal test and water were used instead of the first-order amine, since the anionic group in the urethane prepolymer was small, good water dispersibility could not be obtained. The urethane prepolymer is further extended in the process of water dispersion to extend the emulsion chain. Chain extenders, other than water, may be used, for example, ethylenediamine, hexamethylenediamine, dimethyldiamine, isophoronediamine, diethylenetriamine, N-aminoethyl-N- A low molecular polyamine having a (number average) molecular weight of less than 5 Å such as ethanolamine. Dispersing the ammonia acetal prepolymer in water to obtain an aqueous polyurethane emulsion 9 201132660 (emulsion) ° A chain extender and a reaction stopper can be used. As the reaction stopper, a monoamine such as a first-grade amine such as ethylamine, propylamine or butylamine; or a tertiary amine such as a diethylamine or dibutylamine can be used. In the method for producing a water-based polyurethane emulsion according to the present embodiment, a water-based polyurethane emulsion obtained by dispersing water is further added with a second third-order amine which is less sensitive than the first-order amine, and then an alkali metal is added. The step of the base. As the second tertiary amine, an alkaline weaker which is selected from the first-order amines as the third-order amine can be used. The second grade 3 amine used is weaker than the first grade 3 amine. For example, in the case of using diethylamine having a pKa (dissociation constant in water, 25 〇c) of 3.28 as the first tertiary amine, triethanolamine having a pKa (dissociation constant) of 6.4 can be suitably used as the second tertiary stage. amine.
又第二3級胺也可使用三異丙醇胺、高級烷基變性嗎 啉等。 第二3級胺，相對於氨酯預聚物的羧基丨當量，較佳 添加卜3當量。加入第=3級胺的量’相對於氨酯預聚物 的叛基1當量，未滿i當料，所得水系聚氨酷乳化液的 对水解性的效果恐怕不能充分獲得，另一方面，超過3當 量時，所得水系聚氨酯乳化液的臭氣恐怕變強。 " ^然而，使用第-3級胺代替第二3級胺時，所得水系 聚氣酯乳化液的臭氣恐怕增強。 另一方面，使用下述詳細 驗代替 級胺 10 201132660 時，pH值急據上升及鹼金屬鹼鱼 q ,R _ ^ w兴第一3級胺離子交換反應 同時發生，恐產生聚氨酯樹脂的 J硬票物。又此時，鹼金屬 驗過剩量使用時’與鹼金屬進行 仃離子交換的第一3級胺多 重形成游離狀態’所得水系聚氨酷聋丨务杰沾自〆 机目日礼化液的臭氣恐會增強。 藉由進一步加入鹼金屬鹼，盥 q ^ 興第一 3級胺部分進行離 子交換。 鹼金屬鹼沒有特別限定，例如鹼金屬 '鹼土金屬、或 鲁 上述之化合物、氨、及有機鹼。 鹼金屬可例如鋰' 鈉及鉀，鹼土金屬例如鎂、鈣及鋇。 又上述之化合物例如氧化物、氫氧化物、碳酸鹽、碳酸氫 鹽、罐酸鹽、醋酸等有機酸鹽。 上述之中，以氫氧化鈉、氫氧化鉀、氫氧化鈣、氧化 鈣、氫氧化鎂、氧化鎂等鹼金屬或鹼土金屬的氫氧化物、 氧化物，便宜而容易獲取。 鹼金屬鹼，相對於上述氨酯預聚物的羧基丨當量，較 _ 佳加入4當量。加入驗金屬驗的量，相對於上述氨 酯預聚物的羧基1當量，未滿〇. 2當量時，所得水系聚教 δ旨乳化液的pH未充分上升，恐無法充分獲得耐水解性的效 果，另一方面’超過〇· 4當量時，所得水系聚氨酯乳化液 的臭氣恐會增強。 然而，省略加入驗金屬驗的步驟，以加入第二3級胺 的步驟代替，第二3級胺添加超過3當量而大幅過剩時， 上述所得的水系聚氨酯乳化液的臭氣恐會增強，而且，所 得水系聚氨酯乳化液恐會經時膠化。 11 201132660 根據上述說明之本實施型 之製造方法，不會產生接… 水系聚氣醋乳化液 个會產生使用過剩中和劑所產 題，可得耐水解性良好的水系聚氨醋乳化液。 問 本實施型態所涉之水系 者，即使進行i 曰礼化夜為耐水解性優良 耐濕熱性、耐：：優Γ维持柔軟性、初 丁熟，具有優良的儲藏安定性。 水夺：實！型態所涉之黏著劑，以上述本實施型態所涉之 尺系聚虱酉曰乳化液之製造方法 主成分。因此，可系^醋乳化液為 化液之… 貫施型態所涉之水系聚_ 化及之效果的黏著劑。 除了 態之黏著劑，只要是可得到本發明效果者， 法本實施型態所涉之水系聚氨酯乳化液之 聚氨酯乳化液為主成分以外，也可包含由其 、方法所得的水系聚氨酯乳化液。 本發明所涉之黏著劑宜為鞋用聚氨酯黏著劑。 醋乳:二膠、皮革、橡膠或纖維等的鞋材’使用水系聚| 下I占合^ ϋ種生產步驟或下降溫度等的不同條件 之σ月形’於鞋材各部材塗佈黏著劑至進行壓接加工 又二：損害點著性，可尋求長黏合時間(可貼合時間)。 ° 可維持鞋的高度黏著強度之耐熱性。 =明所涉之黏著劑作為鞋用聚氨酯黏著劑使用時， 貫現長黏合時間及良好耐熱性。 [實施例] 列舉實施例及比較例，進一步說明本發明。然而，本 12 201132660 發明非限定於下列說明之實施例者° (實施例） 在乾燥氣體下置換具備回流冷卻管、滴下漏斗、氣體 導入管、攪拌裝置及溫度計的2L容量的燒瓶後，分別加入 414. 8(數值為原單位，包含以下各成份的使用總量為 1 000.0)的WT-404C聚酯多元醇）之高分子多元醇、4·5的 1，6-HG(1，6-己二醇）、1.9 的 NPG (新戊二醇）、及 的 DMPA(2,2-二經曱基丙酸）之低分子多元醇’在90°C加熱20 • 分鐘後，溫度調節至約75°C。 之後，分別加入33. 5的I抑I (異佛爾酮二異氰酸酯） 及33. 8的HDI(六亞曱基二異氰酸酯）之有機二異氰酸酯、 〇. 05的DOTDL(二月桂酸二辛基錫）之氨酯化觸媒，在901 反應2小時後，冷卻至6 0 °C以下。所得的氨酯預聚物的致 酸基含量為1.12mmol/g。其次，加入452.4的丙酮作為稀 釋劑’在5 5 °C再反應1小時。之後，加入中和劑6. 〇 (對竣 • 基1當量為1當量）的TEA(三乙胺），攪拌20分鐘，混合 後冷卻至50°C。 所知含叛酸鹽的異氰酸酯基末端的氨酯預聚物溶液中 加入550. 4的水，使之乳化。此氨酯預聚物分散液中加入 胺延長劑3.6的EDA(乙二胺），進行鏈延長反應。在脫溶 劑操作下除去丙酮及水後，為調整固形分追加水得到聚 氨酯乳化液。 所得聚氨醋乳化液中加入20_0(對中和前的羧酸基ι 當量為2.25當量）的TELA(三乙醇胺），攪拌2〇分鐘思 13 201132660 °再加入14. i(對中和前的羧酸基1當量為0.25當量） 的Κ0Η水溶液（1„〇1/1)，攪拌2〇分鐘’混合、過渡’得到 水性聚氨酯乳化液。評估此水性聚氨酯乳化液的特性。 (比較例）Further, as the second tertiary amine, triisopropanolamine, a higher alkyl-denatured morpholine or the like can be used. The second tertiary amine is preferably added in an amount of 3 equivalents based on the carboxyl equivalent of the urethane prepolymer. When the amount of the amine of the third stage is added to the equivalent amount of the urethane prepolymer, the amount of the amine of the urethane prepolymer is less than 1 equivalent, and the effect of the hydrolyzability of the obtained aqueous polyurethane emulsion may not be sufficiently obtained. When it exceeds 3 equivalents, the odor of the obtained aqueous polyurethane emulsion may become strong. " ^ However, when a third-grade amine is used instead of the second-order amine, the odor of the resulting aqueous poly-ester emulsion may be enhanced. On the other hand, when the following detailed test was used instead of the amine 10 201132660, the pH value increased sharply and the alkali metal alkali fish q, R _ ^ w X the first 3 amine ion exchange reaction occurred simultaneously, which may cause the polyurethane resin J Hard ticket. At this time, when the alkali metal is used in excess, the first-stage amine of the first-order amine exchanged with the alkali metal is formed into a free state, and the water-based polyamine is used to smear the smell of the celestial liquid. Gas fear will increase. The ion exchange is carried out by further adding an alkali metal base to the first 3-stage amine moiety. The alkali metal base is not particularly limited, and examples thereof include an alkali metal 'alkaline earth metal, or a compound of the above, ammonia, and an organic base. The alkali metals may be, for example, lithium 'sodium and potassium, alkaline earth metals such as magnesium, calcium and barium. Further, the above compounds are, for example, an organic acid salt such as an oxide, a hydroxide, a carbonate, a hydrogencarbonate, a pot acid or an acetic acid. Among the above, alkali metal or alkaline earth metal hydroxides and oxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, magnesium hydroxide, and magnesium oxide are easily and inexpensively obtained. The alkali metal base is preferably added in an amount of 4 equivalents based on the carboxyl group equivalent of the above urethane prepolymer. When the amount of the metal test is added, the amount of the carboxyl group of the urethane prepolymer is less than 当量. 2 equivalents, the pH of the obtained water system is not sufficiently increased, and the hydrolysis resistance may not be sufficiently obtained. On the other hand, when the amount exceeds 〇·4 equivalent, the odor of the obtained aqueous polyurethane emulsion may be enhanced. However, the step of adding the metal test is omitted, and the step of adding the second tertiary amine is replaced. When the second tertiary amine is added in excess of 3 equivalents and is excessively large, the odor of the aqueous polyurethane emulsion obtained above may be enhanced, and The resulting aqueous polyurethane emulsion may gel over time. 11 201132660 According to the manufacturing method of the present embodiment described above, the water-based polyacetal emulsion is produced by using an excessive neutralizing agent, and a water-based polyurethane emulsion having excellent hydrolysis resistance can be obtained. In the water system of this embodiment, it is excellent in hydrolysis resistance, heat resistance, and resistance: it is excellent in maintaining softness and ripening, and has excellent storage stability. Water wins: Real! The adhesive to which the type relates is the main component of the method for producing a polystyrene emulsion according to the above embodiment. Therefore, the vinegar emulsion can be used as a hydrating agent for the hydration of the water system. In addition to the adhesive of the present invention, the polyurethane emulsion of the aqueous polyurethane emulsion according to the embodiment of the present invention may contain, in addition to the main component, a water-based polyurethane emulsion obtained by the method. The adhesive to which the present invention relates is preferably a polyurethane adhesive for shoes. Vinegar: A shoe material such as a rubber, a rubber, a rubber or a fiber. 'Using a water-based polymer|The lower I occupies the 生产 形 形 形 形 形 形 形 形 形 形 形 形 形 形 形 形 形To the crimping process and the second: damage the punctuation, you can seek long bonding time (adaptable time). ° Maintains the heat resistance of the shoe's high adhesion strength. = When the adhesive involved is used as a polyurethane adhesive for shoes, it has a long bonding time and good heat resistance. [Examples] The present invention will be further described by way of examples and comparative examples. However, the invention of the present invention is not limited to the examples described below. (Example) A 2 L-capacity flask equipped with a reflux cooling tube, a dropping funnel, a gas introduction tube, a stirring device, and a thermometer was replaced under a dry gas, and then added separately. 414. 8 (value is the original unit, including the following components used in total amount of 000.0) WT-404C polyester polyol) polymer polyol, 4·5 1,6-HG (1,6- Hexanediol), 1.9 NPG (neopentyl glycol), and DMPA (2,2-dipyridylpropionic acid) low molecular polyol 'heated at 90 ° C for 20 minutes, the temperature was adjusted to about 75 ° C. Thereafter, 31.5 I of I (isophorone diisocyanate) and 33. 8 of HDI (hexamethylene diisocyanate) of organic diisocyanate, 〇. 05 of DOTDL (dioctyl dilaurate) The urethane-catalyzed catalyst of tin) was reacted at 901 for 2 hours and then cooled to 60 ° C or lower. The resulting urethane prepolymer had an acid group content of 1.12 mmol/g. Next, 452.4 of acetone was added as a diluent, and the reaction was further carried out at 55 ° C for 1 hour. Thereafter, TEA (triethylamine), which was neutralized by a neutralizing agent of 6. 〇 (p. 基 1 eq.), was stirred for 20 minutes, and then cooled to 50 ° C after mixing. The solution of the urethane prepolymer containing the isocyanate group containing the tartrate salt was added to 50.4% of water to emulsify it. To the urethane prepolymer dispersion, EDA (ethylenediamine) of an amine extender of 3.6 was added to carry out a chain extension reaction. After removing acetone and water under the action of the desolvent, water was added to adjust the solid content to obtain a polyurethane emulsion. To the obtained polyurethane foam, 20% (the carboxylic acid group equivalent of 2.25 equivalents before the neutralization) was added to TELA (triethanolamine), and the mixture was stirred for 2 minutes. 13 201132660 ° and then added 14. i (before neutralization) A carboxylic acid group (1 equivalent of 0.25 equivalent) of an aqueous solution of Κ0 ( (1 〇 1 / 1) was stirred for 2 ' minutes to "mix and transition" to obtain an aqueous polyurethane emulsion. The properties of the aqueous polyurethane emulsion were evaluated. (Comparative Example)
與實施例相同步驟所得的聚氨醋乳化液，不加入TEU 及Κ0Η水洛液，直接作為評估用的水性聚氨酯乳化液。 (參考例1) 與實施例相同步驟所得的聚氨酯乳化液，加入6.0(對 中和前的幾酸基1當量為1當量）的TEA，授拌2。分鐘，镰 混合（未加入·水溶液），作為評估用的水性聚氨醋乳化 液。所得水性聚氨酉旨乳化液與其他例（實施例、比較例、及 參考例2 - 4)不同，臭味強。 (參考例2) 與實施例相同步驟所得的聚氨醋乳化液，加入2〇 〇(對 中和前的羧酸基1當量為2.25當量）的TELA，攪拌2〇分 鐘’是合（未加入KOH水溶液）’作為評估用的水性聚氨醋籲 乳化液。 (參考例3) 與實施例相同步驟所得的聚氨酯乳化液，加入40.0(對 中和前的羧酸基1當量為4.5〇當量）的TELA，攪拌2〇分 鐘，混合（未加入臟水溶液），作為評估用的水性聚氨醋 乳化液。 (參考例4) 與實施例相同步驟所得的聚氨酿乳化液，加入2〇.〇(對 14 201132660 中和前的敌酸基1當量為2.00當量）的Dabc〇 NCM(高級烷 基變性嗎啉），攪拌20分鐘，混合（未加入K〇H水溶液）， 作為評估用的水性聚氨酯乳化液。 水性聚氣S旨乳化液的初期耐熱性，以下列條件進行試 驗，對於黏合的寬20mm基材（笨乙烯丁二烯橡膠（Styrene Butadiene Rubber))的長度原尺寸3〇mm的試驗片，從原尺 寸的伸長量（單位 • mm) ° 試驗方法，首先，裁切寬2〇nim、長100mm尺寸的基材。 之後，切下的基材一面的長度方向由中心向兩側各2〇mm(共 40賴）的範圍覆蓋保養帶，同時在基材覆蓋保養帶的位置以 外的長度方向的兩端（各30mm)塗佈底漆塗料（2. 5%三氣異 氰酸（Trich〇l〇r〇iSOCyanuric acid)的丙酮溶液）後，在 60°C 150秒的條件下以乾燥爐乾燥。再將水系聚氨酯乳化 液（黏著劑）及水系異氰酸酯硬化劑的調配液（黏著劑/硬化 劑-95/5)以均質混合器在2〇〇〇rpmx3〇秒的條件下攪拌、混 合，在塗佈底漆塗料的位置再一次塗佈後，在6〇它、 心條件下在乾燥爐乾燥。之後，從乾燥爐取出基材，剝除 保養帶後，以塗佈面為内側，從基材的長度方向中心對折， 以50kg/cm2加壓力壓接基材1〇秒。之後，壓接的基材在 25C、5分鐘保養的試驗片，在7〇〇c溫度下維持分鐘。 測定此試驗片在黏著面重疊的位置的長度尺寸，從的 原尺寸伸長多少。 水性聚氨酯乳化液的黏合時間（Tack TUe)，以下列條 件進行試驗，對於兩件黏合的1〇mm正方基材（苯乙烯丁二 15 201132660 烯橡膠）疊合的試驗片’目視確認乾燥後時間經過的黏合狀 態的變化’至被確認為黏合不良所經過的時間（單位：⑴“）。 試驗方法，首先’準備數個適當長度的寬1〇咖的基材 (苯乙烯丁二稀橡膠）。各基材—面全部，在與初期耐执性 情況相同的溫度等條件下，再一次塗佈與初期耐熱性使用 相同之底漆塗料及水系聚氨s旨乳化液（黏著劑）及水系異氛 酸醋硬化劑的調配液（黏著劑/硬化劑=95/5)。其次，將塗 佈調配液而乾燥的基材從乾燥爐中取出。從乾燥爐二 時間作為起始時間(0min)，起始時及經過imin，分別製造 裁切長度lGmm的l〇mm正方形2片’使此2片的水系聚氣 醋乳化液（黏著劑）調配液的黏合面彼此 片。試驗片以手指強壓後，目視確認基材彼此是否^驗 對於被確認為黏著不自& 4 & μ , •者不艮的4驗片，從乾燥爐取出至試驗片 調製所經過的時間為黏合時間（Tack 了丨^^)。 實施例t匕較例及參考例卜4的初期对熱性及黏合時 斤不。表1為製造的水性聚氨酯乳化 液（黏著劑）在6 0。(：儲存者。 [表1]The polyurethane emulsion obtained in the same manner as in the examples was directly used as an aqueous polyurethane emulsion for evaluation without adding TEU and Κ0Η水洛液. (Reference Example 1) A polyurethane emulsion obtained in the same manner as in the Example was added with 6.0 (1 equivalent of a few acid groups before neutralization) of TEA, and 2 was mixed. Minutes, 镰 mixed (not added to the aqueous solution) as an aqueous polyurethane emulsion for evaluation. The obtained aqueous polyurethane-based emulsion was different from the other examples (Example, Comparative Example, and Reference Example 2-4) in that the odor was strong. (Reference Example 2) The polyurethane emulsion obtained in the same procedure as in the Example was added to TENA (2 equivalents to 2.25 equivalents of the carboxylic acid group before neutralization), and stirred for 2 minutes. KOH aqueous solution) 'As an aqueous polyurethane foam emulsion for evaluation. (Reference Example 3) The polyurethane emulsion obtained in the same procedure as in the Example was added to a TEA of 40.0 (1 equivalent of 4.5 eq equivalent of the carboxylic acid group before neutralization), stirred for 2 minutes, and mixed (without adding a dirty aqueous solution). As an aqueous polyurethane emulsion for evaluation. (Reference Example 4) The urethane-branched emulsion obtained in the same procedure as in the Example was added with Dabc〇NCM (higher alkyl denaturation) of 2〇.〇 (1 equivalent of the base acid group before the neutralization of 14 201132660). The porphyrin) was stirred for 20 minutes and mixed (without addition of K〇H aqueous solution) as an aqueous polyurethane emulsion for evaluation. The initial heat resistance of the emulsion was measured under the following conditions, and the test piece having a length of 3 mm in the length of the bonded 20 mm wide substrate (Styrene Butadiene Rubber) was Elongation of the original size (unit • mm) ° Test method, first, cut the substrate with a width of 2〇nim and a length of 100mm. After that, the length direction of one side of the cut substrate is covered by the maintenance tape from the center to the range of 2 mm (40 Å) on both sides, and at the both ends of the length direction except the position where the substrate covers the maintenance tape (30 mm each) After applying a primer coating (2. 5% tri-gas isocyanic acid (Trich® 〇r〇i SOCyanuric acid) in acetone), it was dried in a drying oven at 60 ° C for 150 seconds. Then, the aqueous polyurethane emulsion (adhesive) and the aqueous isocyanate curing agent (adhesive/hardener-95/5) are stirred and mixed in a homomixer at 2 rpm x 3 sec. After the position of the primer coating is applied again, it is dried in a drying oven under 6 、 and heart conditions. Thereafter, the substrate was taken out from the drying oven, and after the maintenance tape was peeled off, the coated surface was placed inside, and the center of the substrate was folded in half, and the substrate was pressure-bonded at 50 kg/cm 2 for 1 second. Thereafter, the test piece in which the pressure-bonded substrate was maintained at 25 C for 5 minutes was maintained at a temperature of 7 ° C for a minute. The length dimension of the test piece at the position where the adhesive faces overlap was measured, and how much the original size was elongated. The bonding time of the aqueous polyurethane emulsion (Tack TUe) was tested under the following conditions. The test piece of the two-bonded 1 〇mm square substrate (styrene butyl 2 201132660 olefin rubber) was visually confirmed. The change of the pasted state of the bond to the time it has been confirmed to be poorly bonded (unit: (1) "). Test method, first, 'prepare several substrates of appropriate length of 1 〇 coffee (styrene butyl rubber) Each substrate-surface is coated with the same primer paint and water-based polyurethane emulsifier (adhesive) and water system under the same conditions as the initial resistance. The formulation of the sulphuric acid sulphuric acid hardener (adhesive/hardener=95/5). Secondly, the substrate dried by the coating solution is taken out from the drying oven. The drying time is taken as the starting time (0 min). ), at the beginning and after imin, respectively, to make 2 pieces of l〇mm squares with a cutting length of lGmm', so that the bonding surfaces of the two water-based polyglycolic emulsified emulsions (adhesives) are combined with each other. After strong pressure, the eye It is confirmed whether or not the substrates are inspected for each other. For the 4 specimens that are confirmed to be adhesively self-adhesive, the time taken from the drying oven to the test piece is the bonding time (Tack 丨) ^^). The initial examples of the examples t匕 and the reference examples are not related to heat and adhesion. Table 1 shows the manufactured aqueous polyurethane emulsion (adhesive) at 60. (: stock. [Table 1 ]
【圖式簡單說明】 間的試驗結果如表]所_ + ± , 16 201132660 無。 【主要元件符號說明 無0[Simple description of the diagram] The test results between the tables are as follows: _ + ± , 16 201132660 None. [Main component symbol description No 0