TW201109357A

TW201109357A - Method for fabricating aqueous polyurethanes

Info

Publication number: TW201109357A
Application number: TW98129513A
Authority: TW
Inventors: Ruei-Shin Chen; Ya-Lin Cheng
Original assignee: Ind Tech Res Inst
Priority date: 2009-09-02
Filing date: 2009-09-02
Publication date: 2011-03-16
Also published as: TWI384002B

Abstract

Disclosed is a method for fabricating aqueous polyurethanes. First, diisocyanate, polyol, diol having hydrophilic group, and polyamine are reacted to form aqueous polyurethane, wherein the backbone of the polyurethane is free of ethylene glycol monomer to prevent swelling or dissolving in water. The aqueous polyurethane is further reacted with a PEO having NCO terminal groups to modify the aqueous polyurethane.

Description

201109357 六、發明說明：【發明所屬之技術領域】本發明係關於水性聚胺基甲酸醋，更特別關於其开^成方法。【先前技術】聚胺基甲酸酯（polyurethane ; PU)具有良好的舒適手感、耐摩擦性、反撥彈性、屈曲性、耐化學藥品性等優良 • 性質，因此經常應用於紡織品塗佈加工、皮革加工、接^ 劑、密封劑、塑膠成型等用途。業界產品型態以溶劑型ρζ 樹脂為主，由於在操作過程中大量使用有機溶劑稀釋，加熱硬化時溶劑就會釋出，造成加工處理過程易發生燃燒、 ***的問題。有鑑於此，加上世界環保意識抬頭，促使全球重視使用溶劑及後續處理的問題，舉例來說，歐盟宣佈在2007〜2010年將建築裝飾漆及亮光漆的VOCs (v〇iatile 〇aanic compounds)含量標準減半，最高只能達75 g/L，未來將陸續地實施在各種塗料應用上。在我國制訂V〇Cs相關管制法規後’我國合成皮產能快速滑落，2005年產量只剩7,000萬碼’產量落居中國大陸、南韓之後，排名全球 $三，合成皮公會會員廠家已從全盛時的27家剩下1〇多 2，今年起更嚴格管控v〇Cs的使用與排放，以上膠塗佈製程應用為例，若一條生產線的樹脂使用量為4,_ 年’即便廠房配置有集氣效率80%、設備效率90%的防制 =具，96〜98年每年也需繳交7〇〇萬的空污費，99年以後每年更需付出1，420萬元，pu樹脂的產品型態極待改變、 201109357 在pu樹脂的應用領域方面，賦予織物高機能性兼具手感的加工近年來備受重視，尤以透濕防水加工最廣為應用。目前透濕防水PU膜可分為吹膜及塗佈加工製得，吹膜的優點在於無溶劑製程、薄膜具厚實感、塑膠皮面質感、反撥性佳，但因機械設備投資大、生產速度慢、技術門檻南且產品樣式變化少，使得國内吹膜技術及PU膜等級參差不齊；而傳統的塗佈加工的優點在於生產速度快、設備便宜且式樣變化多，在加工及應用技術方面較為簡單，是目前業界最常使用的製程，但因原料及廢水溶劑含量多、製程VOCs排放多、集氣回收及排氣洗蘇效率要求高，使得業者競爭激烈卻成本墊高。為了因應全球實施V〇Cs降低趨勢’新原料的開發不僅需降低原料中V〇Cs的含量，更考量使用者都被動、想沿用原有設備製程進行生產，因此惟有將PU樹脂水性化使其環保性、安全性上的管制皆在標準範圍之内，同時具有工程合併之優點，也是樹脂開發者與加工業者避免陷入「環保錢坑」循環的作法。透濕防水PU樹脂水性化的研發方面，以親水性無孔塗層為例，透濕性是靠PU中含有親水基或分子主鏈]^含有親水成份來做調整，業界常用的主要成份為聚乙二醇 (polyethylene oxide，簡稱PE〇)。分子主鏈含高比例pE〇成分的水性PU ’在合成上不易反應製備外，因為的高親水性造成水性PU在水中有高度膨潤性而影定性’且會使得颜強度下降、牢度與耐賴差為^文善PEO在水中造成的高度膨雜問題，有研究結合離子官能基抑或是將PEO當鏈延長劑來進行親水膨潤性調整；另 201109357 * 外’也有以磺酸基取代羧酸基，大幅提高水性pu的親水性、減少溶劑的使用量，這一般常用於化妝品、洗髮等個人用品中。在複合配方方面，也有以水溶性PEO-水性PU 與一般水性PU二者互相調配使用，或是將PEO主鏈交錯連接高疏水性鏈段，側鏈適度導入親水膨潤性…等方法。 JP 2004300178-A揭示了利用PEO作為水性PU主鏈結構’配合導入陰離子官能基進行親水膨潤性調整的技術，由於陰離子官能基的帶電互斥力可以促使水性PU不易聚 • 集’限制了 PEO分子在水中的伸展範圍，故水性PU的親水膨潤性也受到控制而下降。 JP 2005060690-A使用末端具有胺基的PEO作為鏈延長劑’在水性PU合成的最後一個步驟加入、進行鏈延長反應’如此可避免PEO-水性PU在水中的膨潤問題，生成的PEO-水性PU並不單獨使用，需進一步配方調配後與一般水性PU混用，成為織物透濕防水加工用的塗佈液。 WO 2004069903-A1則為水溶性PU之專利，將PU分 • 子主鏈導入大量PEO結構，會造成PU分子完全溶解在水中，所以其吸水膨潤性相當嚴重，只能加入更多的水來解決其高黏度、無法加工問題，所以生成的水溶性PU固形份低；此水溶性PU需與一般自乳化水性pu混用，並配合微結構相分離塗膜技術進行透濕防水塗佈應用。 US 2003/0195293-A1揭示的水性PU組成配方中，混合使用了主鏈型與側鏈型PEO結構起始物，並限制主鏈的 PEO含量、將大比例的PE0移往側鏈，這樣的目的是使主鍵保持疏水性，防止水性PU在水中過度膨潤、並保有高「 201109357 物性；配合側鍵的PEO結構維持適度親水性，脂整體的透濕性可加強提升成膜後的防水性能。則不僅斟樹，主鏈的高強度也兼顧了塗佈 WO 200210248-A1以磺酸基取代常用的羧酸水性PU，磺酸基可以大幅提高水性PU的親水性土來合成低PEO的結構含量、卻仍保有高的親水性與強度’·進而降酸基的另一個好處是可以減少合成時的溶劑使^用磺類成品常用於化妝品、洗髮精等與人體有直接接觸=以這中，水性PU的吸水膨潤、含水保濕效果特別突出。、用品綜上所述，習知技藝中以PE〇作為水性pu合物的方式佔多數。而採用不含PE〇iPU樹脂、二進，始導入PEO結構以形成水性聚胺基甲酸酯的專利則 ^ 出。被提【發明内容】本發明提供一種水性聚胺基曱酸酯之形成方法，包括 (a)混合1.5至2.1莫耳份之二異氰酸酯與！莫耳份之聚乙二醇進行反應，使聚乙二醇之末端官能基由〇H改質為 NCO ; (b)混合1莫耳份之二異氰酸酯、〇丨至〇 9莫耳份: 多兀醇、及0.1至0.6莫耳份之含親水基之二元醇於有機溶劑中進行反應，形成PU預聚物，且PU預聚物之骨架中不含乙二醇單體；中和PU預聚物之親水基；將該PU預聚物分散於水中並與多元胺進行反應，使該pu預聚物之末端官能基NCO改質為NH2 ;以及（c)將(a)步驟中末端官能基201109357 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to aqueous polyurethane urethanes, and more particularly to methods for their formation. [Prior Art] Polyurethane (PU) has good properties such as comfortable hand, abrasion resistance, rebound elasticity, buckling, chemical resistance, etc., so it is often used in textile coating processing, leather. Processing, bonding agents, sealants, plastic molding and other purposes. The product type of the industry is mainly solvent-based ζ 树脂 resin. Due to the large amount of organic solvent dilution during the operation, the solvent will be released during heating and hardening, which causes the burning and explosion problems in the processing. In view of this, coupled with the rise of the world's environmental awareness, the global focus on the use of solvents and subsequent treatment issues, for example, the European Union announced that in 2007 ~ 2010 will be decorative paint and varnish VOCs (v〇iatile 〇 aanic compounds) The content standard is halved, up to 75 g/L, and will be implemented in various coating applications in the future. After the development of V〇Cs related regulations in China, 'China's synthetic leather production capacity has fallen rapidly. In 2005, the output was only 70 million yards'. After the production in mainland China and South Korea, it ranked third in the world. The synthetic leather guild members have been in full bloom. 27 households have more than 1 2 2, and this year, stricter control and use of v〇Cs is used. The above coating process is used as an example. If the resin usage of a production line is 4, _ year, even if the plant is equipped with gas. 80% efficiency, 90% equipment efficiency control, 96 to 98 years, also need to pay 70,000 yuan of air pollution fees, 99 years later, more than 14.2 million yuan per year, pu resin product type The state is extremely changing, 201109357 In the application field of pu resin, the processing that imparts high functionality and feel to the fabric has received much attention in recent years, especially in the application of moisture-permeable waterproof processing. At present, the moisture-permeable waterproof PU film can be divided into blown film and coating processing. The advantages of blown film are solvent-free process, thick film with real feeling, plastic leather texture and good backlash, but the investment in machinery and equipment is high. Slow, technical threshold and less change in product style, the domestic blown film technology and PU film grades are uneven; and the traditional coating processing has the advantages of fast production speed, cheap equipment and many changes in style, processing and application technology. The aspect is relatively simple, and it is the most commonly used process in the industry. However, due to the high content of raw materials and wastewater solvent, high emission of process VOCs, high gas recovery and exhaust gas washing efficiency, the competition is fierce but the cost is high. In order to reduce the trend of V〇Cs in response to global implementation, the development of new raw materials not only needs to reduce the content of V〇Cs in raw materials, but also considers that users are passive and want to use the original equipment process for production. Therefore, it is only possible to water-based PU resin. Environmental protection and safety control are within the scope of the standard, and at the same time have the advantages of engineering mergers, and it is also the practice of resin developers and processing industry to avoid falling into the "environmental money pit" cycle. In the research and development of water-permeable and waterproof PU resin, the hydrophilic non-porous coating is taken as an example. The moisture permeability is adjusted by the hydrophilic group or the molecular main chain in the PU. The main component commonly used in the industry is Polyethylene oxide (PE). The aqueous PU' with a high proportion of pE〇 in the main chain of the molecule is not easily synthesized in the synthesis, because the high hydrophilicity causes the aqueous PU to be highly swellable in water and is deterministic, and will cause the color strength to decrease, the fastness and the resistance. The difference is the high swelling problem caused by ^ Wenshan PEO in water. It is studied whether the ionic functional group is combined or the PEO is used as a chain extender for hydrophilic swelling adjustment. The other 201109357 * external 'also has a sulfonic acid group substituted carboxylic acid. Base, greatly improve the hydrophilicity of water-based pu, reduce the amount of solvent used, which is commonly used in cosmetics, shampoo and other personal products. In terms of the composite formulation, there are also methods in which a water-soluble PEO-aqueous PU and a general aqueous PU are mutually blended, or a PEO main chain is interlaced to a highly hydrophobic segment, and a side chain is appropriately introduced into a hydrophilic swelling property. JP 2004300178-A discloses a technique for utilizing PEO as an aqueous PU backbone structure to incorporate anionic functional groups for hydrophilic swellability adjustment, since the electrostatic repulsion of anionic functional groups can promote the hydrophilic PU to be difficult to aggregate. The extent of stretching in the water is such that the hydrophilic swellability of the aqueous PU is also controlled to decrease. JP 2005060690-A uses a PEO with an amine group at the end as a chain extender' to be added in the last step of aqueous PU synthesis, and undergoes a chain extension reaction. Thus, the problem of swelling of PEO-aqueous PU in water can be avoided, and the resulting PEO-aqueous PU It is not used alone. It needs to be further formulated and mixed with general water-based PU to become a coating liquid for fabric moisture-permeable waterproof processing. WO 2004069903-A1 is a patent of water-soluble PU. The introduction of PU sub-chain into a large number of PEO structures will cause the PU molecules to be completely dissolved in water, so the water swelling and swelling is quite serious, and only more water can be added to solve The high viscosity and the inability to process, so the resulting water-soluble PU solid content is low; the water-soluble PU needs to be mixed with the general self-emulsifying aqueous pu, and combined with the micro-structure phase separation coating technology for moisture-permeable waterproof coating application. In the aqueous PU composition formulation disclosed in US 2003/0195293-A1, a main chain type and a side chain type PEO structure starting material are mixed, and the PEO content of the main chain is restricted, and a large proportion of PE0 is moved to the side chain. The purpose is to keep the primary bond hydrophobic, prevent the excessive swelling of the aqueous PU in water, and maintain high "201109357 physical properties; the PEO structure with the side bond maintains moderate hydrophilicity, and the overall moisture permeability of the grease can enhance the waterproof performance after film formation. In addition to eucalyptus, the high strength of the main chain also takes into account the application of WO 200210248-A1 to replace the commonly used carboxylic acid aqueous PU with sulfonic acid groups. The sulfonic acid group can greatly improve the hydrophilic content of aqueous PU to synthesize the structure content of low PEO. However, it still retains high hydrophilicity and strength. · Another advantage of reducing the acid base is that it can reduce the solvent during the synthesis. The sulfonated products are often used in cosmetics, shampoos, etc., in direct contact with the human body. The water-absorbing PU has a water-absorbing swelling and water-containing moisturizing effect, and the product has been comprehensively described. In the conventional art, PE〇 is used as a water-based pu compound, and the use of PE〇iPU resin is not included. The invention provides a method for forming an aqueous polyurethane phthalate, comprising: (a) mixing 1.5 to 2.1 moles. The diisocyanate is reacted with the molybdenum polyethylene glycol to change the terminal functional group of the polyethylene glycol from 〇H to NCO; (b) mixing 1 mole of diisocyanate, 〇丨 to 〇9 Molens: Polydecyl alcohol, and 0.1 to 0.6 moles of hydrophilic group-containing glycol are reacted in an organic solvent to form a PU prepolymer, and the skeleton of the PU prepolymer does not contain ethylene glycol. Neutralizing the hydrophilic group of the PU prepolymer; dispersing the PU prepolymer in water and reacting with the polyamine to modify the terminal functional group NCO of the pu prepolymer to NH2; and (c) a) terminal functional group in the step

I 201109357 為NCO之聚乙二醇加入(b)步驟中末端官能基為NH2之PU 預聚物水溶液進行反應，即形成水性聚胺基甲酸酯。【實施方式】本發明提供一種水性聚胺基曱酸酯之形成方法，包括：混合1.5至2.1莫耳份之二異氰酸酯與1莫耳份之聚乙二醇進行反應，使聚乙二醇之末端官能基由OH改質為NCO。若二異氰酸酯之莫耳份低於上述範圍，則不易形成第1式 • 之末端改質產物，而是會形成大分子量的寡聚物 (oligomer)。另一方面，若二異氰酸酯之莫耳份高於上述範圍，則未反應的二異氰酸酯將會影響後續反應。上述反應式如第1式所示：I 201109357 The reaction of the polyethylene glycol of NCO to the aqueous solution of the PU prepolymer having a terminal functional group of NH2 in the step (b) is carried out to form an aqueous polyurethane. [Embodiment] The present invention provides a method for forming an aqueous polyamino phthalate, comprising: reacting 1.5 to 2.1 moles of diisocyanate with 1 mole of polyethylene glycol to form polyethylene glycol The terminal functional group is modified from OH to NCO. If the molar fraction of the diisocyanate is less than the above range, it is difficult to form the terminal modified product of the first formula, but a large molecular weight oligomer (oligomer) is formed. On the other hand, if the molar fraction of the diisocyanate is higher than the above range, the unreacted diisocyanate will affect the subsequent reaction. The above reaction formula is as shown in the first formula:

，n、R』、9,0卜。卜 0、9』'fTNC0 δ 0, n, R 』, 9, 0 Bu. Bu 0,9』'fTNC0 δ 0

OCN——R—NCO • (第1式）在本發明一實施例中，聚乙二醇之分子量約介於50至 20000之間，較佳約介於300至10000之間，且更佳約介於600至5000之間。若聚乙二醇之分子量小於上述範圍，則可能會使產物的透濕性不足。若聚乙二醇之分子量大於上述範圍，則可能會使產物吸水膨潤、失去安定性。第1式中的二異氰酸酯可為芳香族二異氰酸酯、脂肪族二異氰酸酯、或上述之組合。在本發明一實施例中，上 _ Γ · C ·« · 7 201109357 述二異氰酸酯包含二異氰酸甲苯酯（toluene diisocyanate， TDI)、對-二異氰酸笨酯（p-phenylene diisocyanate，PPDI)、二異氰酸 4,4' 二苯基甲烧醋（4,4r-diphenylmethane diisocyanate，MDI)、二異氰酸 ρ,ρ'-二苯基酯（p，p’-bisphenyl diisocyanate，BPDI)、異佛爾酮二異氰酸酯（isophorone diisocyanate ’ IPDI)、1,6-亞已基二異氰酸酯 (l，6-hexamethylene diisocynate，HDI)、二環己基甲烧-4， 4- 一異 II 酸 S旨 (hydrogenated diphenylmethane-4,4，-diisocyanate，H12MDI)、或上述之組合。此外，二異氰酸酯可進一步包括其他常見取代基如鹵素、硝基、氰基、烷基、烷氧基、_烷基、羥基、羧基、醯胺基、胺基、或上述之組合，只要不影響第i式中聚乙二醇的末端改質反應即可。接者此5 1莫耳份之二異氰酸酯、0.1至0.9莫耳份戈夕兀醇、及G.1至G.6莫耳份之含親水基之二元醇於有機淳劑中進行反應如第2式，形成一 pu預聚物，且pu預聚彩之骨架不含乙二醇單體。值得注意的是，上述多元醇或令親水基之二㈣不包含常見的乙二醇，這是因為乙二醇名使PU預聚物在後續水中分散的步驟中過度膨潤甚至^ 解。在這必需說明的是，第2式中含親水基之二元醇盆賴水基為減基，但可為其他親水基如亞硫酸基或銨基^ 第2式中的X取決於含親水基之二元醇第2式中的多元醇為丁二醇，_為其他多元醇如間吕之’第2式僅用以朗㈣偈限本發明。 201109357 OCN-R-NCO + (第2式）OCN - R - NCO • (Formula 1) In one embodiment of the invention, the molecular weight of the polyethylene glycol is between about 50 and 20,000, preferably between about 300 and 10,000, and more preferably about Between 600 and 5000. If the molecular weight of the polyethylene glycol is less than the above range, the moisture permeability of the product may be insufficient. If the molecular weight of the polyethylene glycol is larger than the above range, the product may be swollen and lose stability. The diisocyanate in the first formula may be an aromatic diisocyanate, an aliphatic diisocyanate, or a combination thereof. In an embodiment of the invention, the above-mentioned diisocyanate comprises toluene diisocyanate (TDI), p-phenylene diisocyanate (PPDI), and PP-phenylene diisocyanate (PPDI). ), 4,4'-diphenylmethane diisocyanate (MDI), bis, p--bisphenyl diisocyanate (BP, diisocyanato) ), isophorone diisocyanate 'IPDI, 1,6-hexamethylene diisocynate (HDI), dicyclohexylmethane-4, 4-isoisoic acid S (hydrogenated diphenylmethane-4, 4,-diisocyanate, H12MDI), or a combination thereof. Further, the diisocyanate may further include other common substituents such as a halogen, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkyl group, a hydroxyl group, a carboxyl group, a decylamino group, an amine group, or a combination thereof as long as it does not affect The terminal modification reaction of the polyethylene glycol in the i-th formula may be carried out. The 5 1 mole parts of diisocyanate, 0.1 to 0.9 moles of geranol, and G.1 to G.6 moles of the hydrophilic group-containing glycol are reacted in an organic tanning agent. In the second formula, a pu prepolymer is formed, and the skeleton of the pu prepolymer is free of ethylene glycol monomers. It is to be noted that the above polyol or the hydrophilic group (IV) does not contain a common ethylene glycol because the ethylene glycol name excessively swells or even dissolves the PU prepolymer in the subsequent step of dispersing in water. It should be noted that the glycol containing water group in the formula 2 is a subtractive group, but may be other hydrophilic groups such as a sulfite group or an ammonium group. The X in the formula 2 depends on the hydrophilic group-containing group. The polyol in the second formula of the diol is butane diol, and the _ is a polyol of the other formula, such as the second formula, which is only used in the present invention. 201109357 OCN-R-NCO + (Form 2)

OH + HCT 丫 'OH COOH (COOH)x 在使用定量二異氰酸酯的情況下，多元醇的比例越高則含親水基之二元醇的比例越低，反之亦然。如此一來，當多元醇的比例過低而含親水基之二元醇比例過高時，則會造成PU預聚物親水性太高而膨潤膠化(gel)。但若多元醇的比例過高而含親水基之二元醇比例過低時，則形成的 PU預聚物其親水基比例過低，將會無法在水中安定而凝集沈殿。上述二異氰酸酯的種類與前述相同，在此不贅述。上述多元醇之主要作用係與二異氰酸酯反應，形成一 PU聚合物。多元醇亦可作為物性調節劑，依照添加之多元醇分子量的不同，會決定合成產物之硬度，一般而言，低分子量之多元醇可使產物之硬度較高。上述之多元醇可為二醇類、多醇類、醚二醇類、或上述之組合。在本發明一實施例中，二醇類包含丙二醇、丁二醇、戊二醇、己二醇、環己二醇、環己基二甲醇(cyclohexyldimethanol，CHDM)、辛二醇、異戊二醇(neopentyl glycol，NPG)、三曱基戊二醇 (trimethylpentanediol，TMPD)、苯二曱醇、苯二齡、曱苯二紛或雙紛A (bisphenol-A) 、丁二醇己二酸共聚物 (poly(butanediol-co-adipate) glycol，簡稱 PBA)、聚丁二醇 (polytetramethylene glycol，簡稱 PTMEG)、己二醇-己二酸共聚物(poly(hexanediol-co-adipate) glycol，簡稱 PHA)、聚 201109357 丙二醇(polypropylene glycol，簡稱PPG)、或上述之組合。在本發明一實施例中，多醇類包含聚酯多元醇、聚多元醇、聚碳酸醋多元醇、聚己内醋多元醇、聚丙締酸I旨多元醇、或上述之組合，例如丙三醇、三甲基醇丙烧 (trimethylolpropane)、戊四醇（pentaerythritol)、笨三齡、或上述之組合。在本發明一實施例中，醚二醇類可為二丙二醇、三丙二醇、或上述之組合。上述含親水基之二元醇，其主要作用在於藉親水性官能基，使合成之聚合物能有效分散於水中，成為一種水性鲁 PU。上述親水性官能基包括叛酸根（COO _ )、亞硫酸根 (S032-)、或銨根（NR4 + )，如二羥甲基丙酸（dimethylol propionic acid ’ 簡稱 DMPA)、二經曱基丁酸（dimethylol butanoic acid，簡稱 DMBA)、雙（經乙基）胺 (bis(hydroxylethyl)amine)或3-雙（經乙基）胺基丙烧續酸納 (sodium 3-bis(hydroxyethyl)aminopropanesulfonate)。接著如第3式所示，加入驗類如三乙胺(triethylamine，簡稱TEA)以中和該PU預聚物之親水基。在其他實施例 · 中，鹼類可為氨水(NH4OH)、氫氧化鈉(NaOH)、三乙醇胺 [(HOCH2CH2)3N]等、或上述之組合。OH + HCT 丫 'OH COOH (COOH)x In the case of using a quantitative diisocyanate, the higher the proportion of the polyol, the lower the proportion of the glycol containing the hydrophilic group, and vice versa. As a result, when the proportion of the polyol is too low and the proportion of the glycol containing the hydrophilic group is too high, the hydrophilicity of the PU prepolymer is too high and the gel is gelled. However, if the proportion of the polyol is too high and the proportion of the hydrophilic group-containing glycol is too low, the formed PU prepolymer has a hydrophilic group ratio which is too low, and it will not settle in the water and agglomerate. The type of the above diisocyanate is the same as described above, and will not be described herein. The main function of the above polyol is to react with the diisocyanate to form a PU polymer. The polyol can also be used as a property modifier, and the hardness of the synthesized product is determined depending on the amount of the molecular weight of the added polyol. In general, the low molecular weight polyol can make the hardness of the product higher. The above polyol may be a glycol, a polyol, an ether glycol, or a combination thereof. In an embodiment of the invention, the diol comprises propylene glycol, butylene glycol, pentanediol, hexanediol, cyclohexanediol, cyclohexyldimethanol (CHDM), octanediol, isoprene glycol ( Neopentyl glycol (NPG), trimethylpentanediol (TMPD), benzophenanol, benzodiazepine, bisphenol-A, butanediol adipate copolymer ( Poly(butanediol-co-adipate) glycol, referred to as PBA), polytetramethylene glycol (PTMEG), hexanediol-co-adipate glycol (PHA), Poly 201109357 Polypropylene glycol (PPG), or a combination thereof. In an embodiment of the present invention, the polyol comprises a polyester polyol, a polyhydric alcohol, a polycarbonate polyol, a polycaprolactone polyol, a polypropionic acid I polyol, or a combination thereof, such as C3 Alcohol, trimethylolpropane, pentaerythritol, stupid three-year old, or a combination thereof. In one embodiment of the invention, the ether diols may be dipropylene glycol, tripropylene glycol, or a combination thereof. The above-mentioned hydrophilic group-containing glycol mainly functions by a hydrophilic functional group, so that the synthesized polymer can be effectively dispersed in water to become a water-based Lu PU. The above hydrophilic functional groups include tickose (COO _ ), sulfite (S032-), or ammonium (NR4 + ), such as dimethylol propionic acid (DMPA), diterpenoid Dimethylol butanoic acid (DMBA), bis(hydroxylethyl)amine or 3-bis(hydroxyethyl)aminopropanesulfonate . Next, as shown in the formula 3, a triethylamine (TEA) is added to neutralize the hydrophilic group of the PU prepolymer. In other embodiments, the base may be ammonia (NH4OH), sodium hydroxide (NaOH), triethanolamine [(HOCH2CH2)3N], or the like, or a combination thereof.

OCNvwwv^w^nco NEt3 OCN^^v^p^NCO -- (C〇〇H)x (COO· +HNEt3)x (第3式）接著將第3式中的PU預聚物分散於水中並與多元胺 10 201109357 進行反應，使該PU預聚物之末端官能基NCO改質為NH2, 如第4式所示。在式4中，多元胺為乙二胺，但多元胺可為其他含有2-4個胺基之多元胺如二乙三胺、三乙四胺、 2-曱基-1，5-戊二胺、結構式為H2N-(CH2)m —NH2之化合物’其中m為0〜12之整數、或上述之組合。OCNvwwv^w^nco NEt3 OCN^^v^p^NCO -- (C〇〇H)x (COO· +HNEt3)x (Formula 3) Next, the PU prepolymer in Formula 3 is dispersed in water and The reaction with the polyamine 10 201109357 is carried out to modify the terminal functional group NCO of the PU prepolymer to NH2, as shown in the fourth formula. In Formula 4, the polyamine is ethylenediamine, but the polyamine may be other polyamines having 2 to 4 amine groups such as diethylenetriamine, triethylenetetramine, 2-mercapto-1,5-pentane An amine, a compound of the formula H2N-(CH2)m-NH2, wherein m is an integer from 0 to 12, or a combination thereof.

(COO- +HNEt3)x H20(COO- +HNEt3)x H20

Et3NH+ OOC OCN 、 OCNEt3NH+ OOC OCN, OCN

Et3NH+ OOC·Et3NH+ OOC·

OCNOCN

COO·十HNEt3 NCO H2N' .NH,COO·Ten HNEt3 NCO H2N' .NH,

(第4式) 將PU預聚物分散於水中後，複數個PU預聚物將會彼此纏繞(tangled)形成第4式所示之球狀物，其粒徑約介於數十至數百奈米（nm)。上述纏繞現象可參考論文 Polyurethane Anionomers. II. Phase Inversion and Its Effect on Physical properties, Pofymer, Vol. 34, 2776 (1992)。上述球狀物之表面含有親水基及PU預聚物末端之NCO基。雖然水亦會與PU預聚物末端之NCO基反應，但其反應速率遠低於多元胺與NCO官能基之反應速率。PU預聚物末端 201109357 之NCO基與多元胺的莫耳比介於1 : 0.2至1 : 0.9之間。若多元胺之比例過低，則無法將PU預聚物之末端完全改質為NH2。若多元胺之比例過高，則未反應之多元胺將影響後續反應。最後將第1式的產物加入第4式的水溶液中進行反應，即形成一水性聚胺基曱酸酯如第5式。(Form 4) After dispersing the PU prepolymer in water, a plurality of PU prepolymers will be tangled to each other to form a sphere of the formula 4 having a particle diameter of about several tens to several hundreds. Nano (nm). The above-mentioned entanglement phenomenon can be referred to the paper Polyurethane Anionomers. II. Phase Inversion and Its Effect on Physical properties, Pofymer, Vol. 34, 2776 (1992). The surface of the above spherical material contains a hydrophilic group and an NCO group at the end of the PU prepolymer. Although the water also reacts with the NCO group at the end of the PU prepolymer, the reaction rate is much lower than the reaction rate of the polyamine and the NCO functional group. The prepolymer end of the PU prepolymer 201109357 has a molar ratio of NCO groups to polyamines ranging from 1: 0.2 to 1: 0.9. If the proportion of the polyamine is too low, the end of the PU prepolymer cannot be completely modified to NH2. If the proportion of polyamine is too high, the unreacted polyamine will affect the subsequent reaction. Finally, the product of the formula 1 is added to the aqueous solution of the formula 4 to carry out a reaction to form an aqueous polyamino phthalate such as the formula 5.

(第5式）(Type 5)

在第5式中，末端為NCO之聚乙二醇傾向於與單一球狀物之表面上的兩個胺基進行反應，而不傾向於與兩球狀物上的胺基分別進行反應，使兩球狀物交聯。這是因為微 12 201109357 觀來看，兩球狀物之間的距離遠大於單一球狀物上兩個胺基的距離。在這必需說明的是，本發明在形成第3式的中間物後，先以多元胺使球狀物表面的NC〇改質為NH2，未與多元胺反應的NCO亦會被水轉化為NH2，接著再以末端為 NCO之聚乙二醇(NCO-PEO-NCO)將聚乙二醇接枝於球狀物表面，由於NCO與球狀物表面的Ntj2反應性比水高1〇〇倍以上，所以可以確保接枝反應的完整性。本發明並不建 • 議取第3式的中間物（表面為NCO之球狀物）直接與末端為 NH2之聚乙一醇（NH2-PEO-NH2)進行反應，如jp 2005060690-A所教示之技術，因為球狀物是在水中形成，在末端為NH2之聚乙二醇加入前，球狀物表面的Nc〇會與水反應成為NH2，而後續接枝反應的化學計量受影響、不完整。雖然本發明在形成式3之中間物後，需要兩步才能完成所謂的水性PU產物，比JP 2005060690-A的步驟多出一步。但本發明之產品不論是在黏度、抗張強度、及透 • 濕度等性質上均優於JP 2005060690-A之步驟所完成的產品。經上述步驟後，利用減壓蒸餾法或蒸氣蒸餾法（steam distillation)將部分有機溶劑與水去除，而得有機溶劑 < 丨5〇/〇之水性PU分散液，且該水性pu之固形份介於1 〇〜&重量 %。為了讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉數實施例配合所附圖示，作詳細說明如下： 201109357 【實施例】實施例1 在反應槽 A 中，將 209.68 g 之 PEO (polyethylene oxide) (Mn=2000)、26.1 g丙酮與46.55 g之異佛爾酮二異氰酸酯 (isophorone diisocyanate，簡稱 IPDI)於 60°C 下反應 4 小時後，降溫備用。在反應槽B中，將42.63 g之二羥曱基丁酸（dimethylol butionic acid，簡稱 DMBA)、424.12 g 之聚丁二醇(polytetramethylene glycol，簡稱 PTMEG) (Mn=2000) 及52.17 g之丙酮於通有氮氣保護的反應槽中攪拌均勻，待上述原料呈均一相時，將179.80 g之IPDI加入反應槽中， 60°C下反應4小時後，將反應槽的溫度降至50°C並添加 29.0 g之三乙胺(triethylamine ; TEA)進行中和反應20分鐘；將已中和並具親水基之預聚物迅速加入攪拌速率為500 rpm的2217 g去離子水中進行水分散，接著加入經水稀釋的乙二胺（ethylene diamine，簡稱EDA) 12.95 g以進行鏈延長反應。在EDA加入、攪拌30分鐘後，接著將反應槽A 内預先準備好的混合物加入，於50°C下持續攪拌4小時，獲得一固形份為30 wt%的水性PU分散液。將水性PU以培養皿鑄造(casting)烘乾可得到一完整薄膜，以JIS L1099 A-2方法測試薄膜的透濕度為1365 g/m2*day。實施例2 在反應槽 A 中，將 27.21 g 之 PEO (Mn=2000)、3.55 g 201109357 丙酮與6.04 g之異佛爾_二異級醋,狀紙下反應 4小時後，降溫備用。在反應槽B中，將9 47 g之二羥甲基丁酸(DMBA)、108.68 g 之聚丁二醇(pTMEG) (Mn=2〇〇〇) 及14·19β丙酮於通有氮氣保護的反應槽中攪拌均勾，待上述原料主均-相時，將48.69 §之1]?〇1加入反應槽中， 60C下反應4小k後’將反應槽的溫度降至赃並添加 6.51 g之三乙胺(TEA)進行中和反應2()分鐘；將已中和並具親水基之預聚物迅速加入擾拌速率為5〇〇 rpm的im 2 • g去離子水中進行水分散，接著加入經水稀釋的乙二胺 (EDA) 2.67 g以進行鏈延長反應。在eDa加入、攪拌30 分鐘後’接著將反應槽A内預先準備好的混合物加入，於 50°C下持續攪拌4小時，獲得一固形份為15 wt%的水性pu 分散液’利用減壓蒸餾除去部分有機溶劑與水後，固形份提升為21 wt%。將水性pu以培養皿鎊造(casting)供乾可得到一完整薄膜’以JISL1099 A-2方法測試薄膜的透濕度為 2164 g/m2.day 〇 • 實施例3 在反應槽 A 中，將 17.49 g 之 PEO (Mn=600)、2.44 g 丙酮與12.94g之異佛爾酮二異氰酸酯（ipdI)於60°C下反應 4小時後，降溫備用。在反應槽B中，將9.48 g之二羥曱基丁酸(DMBA)、116.18 g 之聚丁二醇(PTMEG) (Mn=2000) 及14.98 g之丙酮於通有氮氣保護的反應槽中攪拌均勻，待上述原料呈均一相時，將44.01 g之IPDI加入反應槽中， 60°C下反應4小時後，將反應槽的溫度降至5(TC並添加^ 15 201109357 6.49 g之三乙胺（TEA)進行中和反應2〇分鐘；將已中和並具親水基之預聚物迅速加入攪拌速率為5〇〇 rpm的1138.9 g去離子水中進行水分散，接著加入經水稀釋的乙二胺 (EDA) 2.69 g以進行鏈延長反應。在EDA加入、攪拌3〇分鐘後，接著將反應槽A内預先準備好的混合物加入，於 50°C下持續攪拌4小時’獲得一固形份為15 wt%的水性pu 分散液’利用減壓蒸餾除去部分有機溶劑與水後，固形份提升為24 wt%。將水性PU以培養皿鑄造(casting)烘乾可得到一完整薄膜，以JIS L1099 A-2方法測試薄膜的透濕度為 Π93 g/m2· day。實施例4 在反應槽 A 中’將 27.67 g 之 PEO (Mn=1000)、3.04 g 丙醐與12.29 g之異佛爾酮二異氰酸酯(IPDI)於60°C下反應 4小時後，降溫備用。在反應槽b中，將9.49 g之二經甲基丁酸(DMBA)、93.22 g 之聚丙二醇(ρρο) (Mn=1000)及 14.43 g之丙酮於通有氮氣保護的反應槽中攪拌均勻，待上述原料呈均一相時，將57.53 g之IPDI加入反應槽中，60 t：下反應4小時後，將反應槽的溫度降至50°C並添加6.49 g之三乙胺(TEA)進行中和反應20分鐘；將已中和並具親水基之預聚物迅速加入攪拌速率為500 rpm的542.5 g去離子水中進行水分散，接著加入經水稀釋的乙二胺（EDA) 3.44 g以進行鏈延長反應。在EDA加入、攪拌30分鐘後，接著將反應槽A内預先準備好的混合物加入，於50。(：下持續攪拌4小時，獲得一固形份為25 wt%的水性PU分散液。 5 201109357 將水性PU以培養皿鑄造(casting)烘乾可得到一完整薄膜以JISL1099 A-2方法測試薄膜的透濕度為1127g/m2.day。實施例5 在反應槽 A 中，將 65.63 g 之 PEO (Mn=1000)、8.55 g N-曱基〇比洛酮（N-methyl pyrrolidone，簡稱 NMP)與 29.14 g 之異佛爾酮二異氰酸酯（IPDI)於80°C下反應4小時後，降溫備用。在反應槽B中，將8.30 g之二羥曱基丁酸 φ (DMBA)、67.17 g 之丁二醇-己二酸共聚物 (poly(butanediol-co-adipate) glycol，簡稱 PBA) (Mn=2000) 及8.95 g之NMP於通有氮氣保護的反應槽中攪拌均勻，待上述原料呈均一相時，將31.85 g之IPDI加入反應槽中， 80°C下反應4小時後，將反應槽的溫度降至50°C並添加 5.76 g之三乙胺（TEA)進行中和反應20分鐘；將已中和並具親水基之預聚物迅速加入攪拌速率為500 rpm的1500 g 去離子水中進行水分散，接著加入經水稀釋的乙二胺(EDA) • 1.66 g以進行鏈延長反應。在EDA加入、攪拌30分鐘後，接著將反應槽A内預先準備好的混合物加入，於50°C下持續攪拌4小時，獲得一固形份為12 wt%的水性PU分散液，利用減壓蒸餾除去部分有機溶劑與水後，固形份提升為20 wt%。將水性pu以培養皿鑄造(casting)烘乾可得到一完整薄膜，以JISL1099 A-2方法測試薄膜的透濕度為2594 g/m2 •day ° 實施例6 17 201109357 在反應槽 A 中，將 22.06 g 之 PEO (Mn=2000)、2.49 g N-曱基吡咯酮(NMP)與4.90 g之異佛爾酮二異氰酸酯（IPDI) 於80°C下反應4小時後，降溫備用。在反應槽B中，將8.29 g之二羥曱基丁酸（DMBA)、119.27 g之聚丁二醇 (PTMEG，Mn=2000)及14.96 g之NMP於通有氮氣保護的反應槽中攪拌均勻，待上述原料呈均一相時，將47.95 g之 IPDI加入反應槽中，80°C下反應4小時後，將反應槽的溫度降至50°C並添加5.64 g之三乙胺（TEA)進行中和反應20 分鐘；將已中和並具親水基之預聚物迅速加入攪拌速率為 500 rpm的440 g去離子水中進行水分散，接著加入經水稀釋的乙二胺(EDA) 1.72 g以進行鏈延長反應。在EDA加入、攪拌30分鐘後，接著將反應槽A内預先準備好的混合物加入，於50°C下持續攪拌4小時，獲得一固形份為30 wt%的水性PU分散液。將水性PU以培養皿鑄造(casting) 烘乾可得到一完整薄膜，以JISL1099A-2方法測試薄膜的透濕度為835 g/m2«day。實施例7 在反應槽 A 中，將 15.35 g 之 PEO (Mn=1000)、1.76 g 丙酮與6.82 g之異佛爾酮二異氰酸酯（IPDI)於60°C下反應 4小時後，降溫備用。在反應槽B中，將9.48 g之二羥甲基丁酸(DMBA)、122.34 g 之聚丁二醇(PTMEG，Mn=2000) 及15.8 lg之丙酮於通有氮氣保護的反應槽中攪拌均勻，待上述原料呈均一相時，將46.15 g之IPDI加入反應槽中， 60°C下反應4小時後，將反應槽的溫度降至50°C並添加 18 201109357 6.48 g之三乙胺（TEA)進行中和反應2〇分鐘；將已中和並具親水基之預聚物迅速加入攪拌速率為500 rpm的437.7 g 去離子水中進行水分散，接著加入經水稀釋的乙二胺(EDA) 2.69 g以進行鏈延長反應。在EDA加入、攪拌30分鐘後，接著將反應槽A内預先準備好的混合物加入，於50。(：下持續攪拌4小時，獲得一固形份為30 wt%的水性pu分散液。將水性PU以培養皿鑄造(casting)烘乾可得到一完整薄膜，以JIS L1099 A-2方法測試薄膜的透濕度為1440 g/m2.day。實施例8 在反應槽 A 中，將 40.61 g 之 PEO (Mn=1000)、15.0 g 丙酮與18.03 g之異佛爾酮二異氰酸醋（IPDI)於60°c下反應 4小時後，降溫備用。在反應槽b中，將9.48 g之二羥甲基丁酸(DMBA)、90.18 g 之聚丁二醇(pTMEG，Mn=2000) 及35.0 g之丙酮於通有氮氣保護的反應槽中擾拌均勻，待上述原料呈均一相時，將42.37 g之IPDI加入反應槽中， 60°C下反應4小時後，將反應槽的溫度降至50〇c並添加 6.46 g之三乙胺（TEA)進行中和反應2〇分鐘；將已中和並具親水基之預聚物迅速加入攪拌速率為5〇〇 rpm的1156.9 g去離子水中進行水分散，接著加入經水稀釋的乙二胺 (EDA) 2.78 g以進行鏈延長反應。在eda力口入、攪拌30 分鐘後，接著將反應槽A内預先準備好的混合物加入，於 5〇°C下持續攪拌4小時，獲得一固形份為15 wt%的水性pu 分散液，利用減壓蒸餾除去部分有機溶劑與水後，固形份提升為23 wt%。將水性PU以培養皿鑄造（casting)烘乾可得。 19 201109357 到一完整薄膜，以JISL1099 A-2方法測試薄膜的透濕度為 3025 g/m2· day ° 實施例9 在反應槽 A 中’將 73.65 g 之 JEFFAMINE® EO-2003、 73.64 g丙酮與18.89 g之異佛爾酮二異氰酸醋（IPDI)於80 。(：下反應4小時後’其末端之胺基改質為NCO如第6式。 h2nIn the formula 5, the polyethylene glycol having an NCO end tends to react with the two amine groups on the surface of the single sphere, and does not tend to react with the amine groups on the two spheres, respectively. The two spheres are crosslinked. This is because micro 12 201109357, the distance between the two spheres is much larger than the distance between the two amine groups on a single sphere. It should be noted that, after forming the intermediate of the third formula, the NC 〇 on the surface of the spheroid is modified to NH 2 by a polyamine, and the NCO which is not reacted with the polyamine is also converted into NH 2 by water. Then, polyethylene glycol is grafted onto the surface of the sphere with polyethylene glycol (NCO-PEO-NCO) with NCO at the end, because the Ntj2 reactivity of the NCO with the surface of the sphere is 1 times higher than that of water. Above, the integrity of the grafting reaction can be ensured. The present invention does not construct the intermediate of the third formula (the spherical surface of the NCO) and reacts directly with the ethylene glycol (NH2-PEO-NH2) having a terminal of NH2, as taught by jp 2005060690-A. Technology, because the sphere is formed in water, Nc〇 on the surface of the sphere will react with water to become NH2 before the addition of polyethylene glycol with NH2 at the end, and the stoichiometry of the subsequent grafting reaction is affected and incomplete. . Although the present invention requires two steps to form the so-called aqueous PU product after forming the intermediate of Formula 3, it is one step further than the step of JP 2005060690-A. However, the product of the present invention is superior to the product of the steps of JP 2005060690-A in terms of viscosity, tensile strength, and moisture permeability. After the above steps, a part of the organic solvent and water are removed by vacuum distillation or steam distillation to obtain an aqueous PU dispersion of an organic solvent < 5丨/〇, and the solid content of the aqueous pu Between 1 〇 ~ & weight %. The above and other objects, features, and advantages of the present invention will become more apparent and understood. 209.68 g of PEO (polyethylene oxide) (Mn=2000), 26.1 g of acetone and 46.55 g of isophorone diisocyanate (IPDI) were reacted at 60 ° C for 4 hours, and then cooled to stand. In the reaction tank B, 42.63 g of dimethylol butionic acid (DMBA), 424.12 g of polytetramethylene glycol (PTMEG) (Mn=2000) and 52.17 g of acetone were used. Stir well in a nitrogen-protected reaction tank. When the above raw materials are in a uniform phase, add 179.80 g of IPDI to the reaction tank. After reacting at 60 ° C for 4 hours, the temperature of the reaction tank is lowered to 50 ° C and added. 29.0 g of triethylamine (TEA) was subjected to a neutralization reaction for 20 minutes; the neutralized and hydrophilic group prepolymer was rapidly added to 2217 g of deionized water at a stirring rate of 500 rpm for water dispersion, followed by addition. Water-diluted ethylene diamine (EDA) 12.95 g for chain extension reaction. After the EDA was added and stirred for 30 minutes, the previously prepared mixture in the reaction tank A was further added, and stirring was continued at 50 ° C for 4 hours to obtain an aqueous PU dispersion having a solid content of 30 wt%. The aqueous PU was cast by a petri dish to obtain a complete film, and the film was tested for moisture permeability of 1365 g/m2*day by the JIS L1099 A-2 method. Example 2 In the reaction tank A, 27.21 g of PEO (Mn = 2000) and 3.55 g of 201109357 acetone were reacted with 6.04 g of isophor-diiso- vinegar under a paper for 4 hours, and then cooled to stand. In reaction tank B, 9 47 g of dimethylolbutanoic acid (DMBA), 108.68 g of polytetramethylene glycol (pTMEG) (Mn=2〇〇〇) and 14·19β acetone were protected by nitrogen. Stir in the reaction tank. When the main raw phase of the above raw materials is used, add 48.69 §1]?〇1 to the reaction tank, and react at 60C for 4 hours, then reduce the temperature of the reaction tank to 赃 and add 6.51 g. The triethylamine (TEA) was subjected to a neutralization reaction for 2 () minutes; the neutralized and hydrophilic group prepolymer was rapidly added to the water dispersion in im 2 • g deionized water at a disruption rate of 5 rpm. Next, water-diluted ethylenediamine (EDA) 2.67 g was added for chain extension reaction. After the eDa was added and stirred for 30 minutes, 'the mixture prepared in the reaction tank A was then added, and stirring was continued at 50 ° C for 4 hours to obtain a solid pu dispersion having a solid content of 15 wt%. After removing part of the organic solvent and water, the solid content was increased to 21 wt%. The aqueous pu was cast in a petri dish for drying to obtain a complete film. The moisture permeability of the film was measured by the JIS L1099 A-2 method to be 2164 g/m2.day. Example 3 In the reaction tank A, 17.49 The PEO (Mn = 600), 2.44 g of acetone and 12.94 g of isophorone diisocyanate (ipdI) of g were reacted at 60 ° C for 4 hours, and then cooled to stand. In reaction tank B, 9.48 g of dihydroxymercaptobutyric acid (DMBA), 116.18 g of polytetramethylene glycol (PTMEG) (Mn=2000) and 14.98 g of acetone were stirred in a nitrogen-protected reaction tank. Evenly, when the above raw materials are in a uniform phase, 44.01 g of IPDI is added to the reaction tank, and after reacting at 60 ° C for 4 hours, the temperature of the reaction tank is lowered to 5 (TC and added ^ 15 201109357 6.49 g of triethylamine The (TEA) was subjected to a neutralization reaction for 2 minutes; the neutralized and hydrophilic group prepolymer was rapidly added to 1138.9 g of deionized water at a stirring rate of 5 rpm for water dispersion, followed by the addition of water-diluted ethylene. Amine (EDA) 2.69 g for chain extension reaction. After EDA was added and stirred for 3 minutes, the previously prepared mixture in reaction tank A was added, and stirring was continued at 50 ° C for 4 hours to obtain a solid fraction. After 15 wt% of the aqueous pu dispersion was removed by vacuum distillation to remove part of the organic solvent and water, the solid content was increased to 24 wt%. The aqueous PU was cast by a petri dish to obtain a complete film to JIS L1099. The moisture permeability of the film was Π93 g/m2·day by the A-2 method. Example 4 In tank A, '27.67 g of PEO (Mn=1000), 3.04 g of propylene fluorene and 12.29 g of isophorone diisocyanate (IPDI) were reacted at 60 ° C for 4 hours, then cooled down for use. In reaction tank b Medium, 9.49 g of methylbutyric acid (DMBA), 93.22 g of polypropylene glycol (ρρο) (Mn=1000) and 14.43 g of acetone are uniformly stirred in a nitrogen-protected reaction tank until the above raw materials are present. In the homogeneous phase, 57.53 g of IPDI was added to the reaction tank, and after reacting for 4 hours at 60 t:, the temperature of the reaction vessel was lowered to 50 ° C and 6.49 g of triethylamine (TEA) was added for neutralization reaction for 20 minutes. The neutralized and hydrophilic group prepolymer was rapidly added to 542.5 g of deionized water at a stirring rate of 500 rpm for water dispersion, followed by the addition of water-diluted ethylenediamine (EDA) 3.44 g for chain extension reaction. After the EDA was added and stirred for 30 minutes, the previously prepared mixture in the reaction tank A was further added, and the mixture was stirred at 50° for 4 hours to obtain a solid PU dispersion having a solid content of 25 wt%. 5 201109357 The water-based PU is casted in a petri dish to obtain a complete film by the JIS L1099 A-2 method. The moisture permeability of the test film was 1127 g/m2.day. Example 5 In the reaction tank A, 65.63 g of PEO (Mn = 1000) and 8.55 g of N-methyl pyrrolidone (NMP) were used. After reacting with 29.14 g of isophorone diisocyanate (IPDI) at 80 ° C for 4 hours, the temperature was lowered for use. In the reaction tank B, 8.30 g of dihydroxymercaptobutyric acid φ (DMBA) and 67.17 g of poly(butanediol-co-adipate) glycol (abbreviated as PBA) (Mn= 2000) and 8.95 g of NMP were uniformly stirred in a nitrogen-protected reaction tank. When the above raw materials were in a homogeneous phase, 31.85 g of IPDI was added to the reaction tank, and after reacting at 80 ° C for 4 hours, the reaction tank was The temperature was lowered to 50 ° C and 5.76 g of triethylamine (TEA) was added for neutralization for 20 minutes; the neutralized and hydrophilic group prepolymer was quickly added to 1500 g of deionized water at a stirring rate of 500 rpm. The water was dispersed, followed by the addition of water-diluted ethylenediamine (EDA) • 1.66 g for chain extension reaction. After the EDA was added and stirred for 30 minutes, the previously prepared mixture in the reaction tank A was further added, and stirring was continued at 50 ° C for 4 hours to obtain a solid PU dispersion having a solid content of 12 wt%, which was distilled under reduced pressure. After removing part of the organic solvent and water, the solid content was increased to 20 wt%. The aqueous pu was cast by a petri dish to obtain a complete film, and the moisture permeability of the film was measured by the JIS L1099 A-2 method to be 2594 g/m 2 •day ° Example 6 17 201109357 In the reaction tank A, 22.06 The PEO of g (Mn = 2000), 2.49 g of N-mercaptopyrrolidone (NMP) and 4.90 g of isophorone diisocyanate (IPDI) were reacted at 80 ° C for 4 hours, and then cooled to stand. In reaction tank B, 8.29 g of dihydroxyindolebutyric acid (DMBA), 119.27 g of polytetramethylene glycol (PTMEG, Mn=2000) and 14.96 g of NMP were uniformly stirred in a nitrogen-protected reaction tank. When the above raw materials are in a uniform phase, 47.95 g of IPDI is added to the reaction tank, and after reacting at 80 ° C for 4 hours, the temperature of the reaction tank is lowered to 50 ° C and 5.64 g of triethylamine (TEA) is added. The reaction was neutralized for 20 minutes; the neutralized and hydrophilic group prepolymer was quickly added to 440 g of deionized water at a stirring rate of 500 rpm for water dispersion, followed by the addition of water-diluted ethylenediamine (EDA) 1.72 g. Perform a chain extension reaction. After the EDA was added and stirred for 30 minutes, the previously prepared mixture in the reaction tank A was further added, and stirring was continued at 50 ° C for 4 hours to obtain an aqueous PU dispersion having a solid content of 30 wt%. The aqueous PU was cast by a petri dish to obtain a complete film, and the moisture permeability of the film was measured by the JIS L1099A-2 method to be 835 g/m2 «day. Example 7 In Reaction tank A, 15.35 g of PEO (Mn = 1000), 1.76 g of acetone and 6.82 g of isophorone diisocyanate (IPDI) were reacted at 60 ° C for 4 hours, and then cooled to stand. In the reaction tank B, 9.48 g of dimethylolbutanoic acid (DMBA), 122.34 g of polytetramethylene glycol (PTMEG, Mn=2000) and 15.8 g of acetone were uniformly stirred in a nitrogen-protected reaction vessel. When the above raw materials are in a uniform phase, 46.15 g of IPDI is added to the reaction tank, and after reacting at 60 ° C for 4 hours, the temperature of the reaction tank is lowered to 50 ° C and 18 201109357 6.48 g of triethylamine (TEA) is added. The neutralization reaction was carried out for 2 minutes; the neutralized and hydrophilic group prepolymer was rapidly added to 437.7 g of deionized water at a stirring rate of 500 rpm for water dispersion, followed by the addition of water-diluted ethylenediamine (EDA). 2.69 g for chain extension reaction. After the EDA was added and stirred for 30 minutes, the previously prepared mixture in the reaction tank A was then added at 50. (: stirring was continued for 4 hours to obtain a solid pu dispersion having a solid content of 30 wt%. The aqueous PU was cast by a petri dish to obtain a complete film, and the film was tested by the JIS L1099 A-2 method. The moisture permeability was 1440 g/m2.day. Example 8 In reaction tank A, 40.61 g of PEO (Mn = 1000), 15.0 g of acetone and 18.03 g of isophorone diisocyanate (IPDI) were used. After reacting for 4 hours at 60 ° C, the temperature was set aside. In reaction tank b, 9.48 g of dimethylolbutanoic acid (DMBA), 90.18 g of polytetramethylene glycol (pTMEG, Mn=2000) and 35.0 g were used. The acetone was uniformly mixed in a nitrogen-protected reaction tank. When the above raw materials were in a uniform phase, 42.37 g of IPDI was added to the reaction tank, and after reacting at 60 ° C for 4 hours, the temperature of the reaction tank was lowered to 50 Torr. c and adding 6.46 g of triethylamine (TEA) for neutralization reaction for 2 minutes; the neutralized and hydrophilic group prepolymer was quickly added to 1156.9 g of deionized water at a stirring rate of 5 rpm for water dispersion. Then, 2.78 g of ethylene diamine (EDA) diluted with water was added for chain extension reaction. After eda force, stirring for 30 minutes, The mixture prepared in the reaction tank A was added in advance, and stirring was continued at 5 ° C for 4 hours to obtain an aqueous pu dispersion having a solid content of 15 wt%, and a part of the organic solvent and water were removed by distillation under reduced pressure. The amount is increased to 23 wt%. The aqueous PU is obtained by casting and drying. 19 201109357 To a complete film, the moisture permeability of the film is measured by the JIS L1099 A-2 method to be 3025 g/m2·day °. 9 In reaction tank A, '73.65 g of JEFFAMINE® EO-2003, 73.64 g of acetone and 18.89 g of isophorone diisocyanate (IPDI) at 80. (: 4 hours after the reaction) The amine group is modified to NCO such as the formula 6. h2n

(ED-2003)(ED-2003)

y〜39,（x+y)~6 (第6式）在反應槽B中，將9.50 g之二羥甲基丁酸(DMBA)、 138.39 g 之聚丁二醇（PTMEG，Mn=2000)及 50.26 g 之丙酮於通有氮氣保護的反應槽中攪拌均勻，待上述原料呈均一相時，將53.08 g之IPDI加入反應槽中，60°C下反應4小 _ 時後，將反應槽的溫度降至50°C並添加6.48 g之三乙胺 (TEA)進行中和反應20分鐘；將已中和並具親水基之170 g 預聚物迅速加入攪拌速率為500 rpm的1155.9 g去離子水中進行水分散’接著加入經水稀釋的乙二胺(EDA) 3.4 g以進行鏈延長反應。在EOA加入、攪拌30分鐘後，接著將反應槽A内預先準備好的混合物加入，於50°C下持續攪拌 4小時’獲得一固形份為15 wt%的水性pu分散液，其pH 值為7.96 ’黏度為43.5 CpS，溶液中固成份之平均粒徑為 20 201109357 162nm。將水性PU以培養皿鑄造(casting)烘乾可得到一完整薄膜，厚度為0.060mm。以JIS L1099 A-2方法測試薄膜的透濕度為2727 g/m2.day，抗張強度為143 kg/cm2，伸長率為 691% ’ 100%模數為 19 kg/cm2。比較例1 在反應槽中，將9.48 g之二羥甲基丁酸(DMBA)、 137.52 g 之聚丁二醇(ptmEG，Mn=2000)及 50 g 之丙酮於 • 通有氮氣保護的反應槽中攪拌均勻，待上述原料呈均一相時’將53.13 g之IPDI加入反應槽中，60°C下反應4小時後，將反應槽的溫度降至5〇。(：並添加6.49 g之三乙胺（TEA) 進行中和反應20分鐘；將已中和並具親水基之21112 g預聚物迅速加入攪拌速率為5〇〇 rprn的1163.7 g去離子水中進行水分散’接著加入72.35 g之JEFFAMINE® ED-2003，於5〇°C下持續攪拌4小時，獲得一固形份為16 wt%的水性 PU分散液’其pH值為7.62，黏度為20.5 cps，溶液中固 • 成份之平均粒徑為149nm。將水性pu以培養皿鑄造(casting) 烘乾可得到一完整薄膜，厚度為0 061mm。以JISL1099 A-2 方法測試薄膜的透濕度為2058 g/m2 · day，抗張強度為85 kg/cm2，伸長率為 916%，1〇〇%模數為 u kg/cm2。如前所述’本發明先改質再接枝的兩步製程產物（實施例9)的物性優於直接改質及接枝的一步製程產物（比較例 1)。雖然本發明已以數個較佳實施例揭露如上’然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之『 201109357 精神和範圍内，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。y~39, (x+y)~6 (Formula 6) In reaction tank B, 9.50 g of dimethylolbutanoic acid (DMBA) and 138.39 g of polytetramethylene glycol (PTMEG, Mn=2000) And 50.26 g of acetone is uniformly stirred in a nitrogen-protected reaction tank. When the above raw materials are in a uniform phase, 53.08 g of IPDI is added to the reaction tank, and after reacting at 60 ° C for 4 hours, the reaction tank is The temperature was lowered to 50 ° C and 6.48 g of triethylamine (TEA) was added for neutralization for 20 minutes; the neutralized and hydrophilic group of 170 g of the prepolymer was quickly added to 1155.9 g of deionized at a stirring rate of 500 rpm. Water dispersion was carried out in water' followed by the addition of water-diluted ethylenediamine (EDA) 3.4 g for chain extension reaction. After the EOA was added and stirred for 30 minutes, the previously prepared mixture in the reaction tank A was further added, and stirring was continued at 50 ° C for 4 hours to obtain a solid pu dispersion having a solid content of 15 wt%, and the pH was 7.96 'The viscosity is 43.5 CpS, and the average particle size of the solid component in the solution is 20 201109357 162 nm. The aqueous PU was cast by a petri dish to obtain a complete film having a thickness of 0.060 mm. The film was tested for moisture permeability of 2727 g/m2.day by the JIS L1099 A-2 method, tensile strength of 143 kg/cm2, elongation of 691% ‘100% modulus of 19 kg/cm2. Comparative Example 1 In a reaction tank, 9.48 g of dimethylolbutanoic acid (DMBA), 137.52 g of polytetramethylene glycol (ptmEG, Mn=2000) and 50 g of acetone were used in a nitrogen-protected reaction tank. Stir well, and when the above raw materials were in a uniform phase, add 53.13 g of IPDI to the reaction tank, and after reacting at 60 ° C for 4 hours, the temperature of the reaction tank was lowered to 5 Torr. (: and adding 6.49 g of triethylamine (TEA) for neutralization reaction for 20 minutes; the neutralized and hydrophilic group of 21112 g of prepolymer was quickly added to 1163.7 g of deionized water at a stirring rate of 5 〇〇rprn. Water dispersion' was then added to 72.35 g of JEFFAMINE® ED-2003 and stirring was continued for 5 hours at 5 ° C to obtain a solid PU dispersion of 16 wt% with a pH of 7.62 and a viscosity of 20.5 cps. The average particle size of the solid component in the solution was 149 nm. The aqueous pu was cast in a petri dish to obtain a complete film having a thickness of 0 061 mm. The moisture permeability of the film was measured by the JIS L1099 A-2 method to be 2058 g/ M2 · day, the tensile strength is 85 kg/cm2, the elongation is 916%, and the 1% modulus is u kg/cm2. As described above, the two-step process product of the invention is first modified and then grafted ( The physical properties of Example 9) are superior to those of the one-step process of direct modification and grafting (Comparative Example 1). Although the invention has been disclosed in several preferred embodiments as above, it is not intended to limit the invention, The artist can be employed without departing from the spirit and scope of the "201109357" of the present invention. The modifications and alterations, and therefore the scope of the invention as defined depending on the scope of the appended patent and their equivalents.

22 20110935722 201109357

【圖式簡單說明】無。【主要元件符號說明】無。 23[Simple description of the diagram] None. [Main component symbol description] None. twenty three

Claims

201109357 七、申請專利範圍： 1. 一種水性聚胺基甲酸酯之形成方法，包括： (a) 混合1.5至2.1莫耳份之二異氰酸酯與1莫耳份之聚乙二醇進行反應，使聚乙二醇之末端官能基由OH改質為 NCO ; (b) 混合1莫耳份之二異氰酸酯、0.1至0.9莫耳份之多元醇、及0.1至0.6莫耳份之含親水基之二元醇於有機溶劑中進行反應，形成一 PU預聚物，且該PU預聚物之骨架中不含乙二醇單體； _ 中和該PU預聚物之親水基；將該PU預聚物分散於水中並與一多元胺進行反應，使該PU預聚物之末端官能基NCO改質為NH2 ;以及 (c) 將（a)步驟中末端官能基為NCO之聚乙二醇加入(b) 步驟中末端官能基為NH2之PU預聚物水溶液進行反應，即形成一水性聚胺基曱酸酯。 2. 如申請專利範圍第1項所述之水性聚胺基甲酸酯之形成方法，其中該二異氰酸S旨包括芳香族二異氰酸醋、脂鲁肪族二異氰酸酯、或上述之組合。 3. 如申請專利範圍第2項所述之水性聚胺基曱酸酯之形成方法，其中該二異氰酸酯包括二異氰酸曱苯酯、對-二異氰酸苯酯、二異氰酸-4,4’-二苯基曱酯、二異氰酸-ρ,ρ’-聯苯酯、1，6-六亞曱基二異氰酸酯、二環已基甲烷-4,4’-二異氰酸S旨、或上述之組合。 4. 如申請專利範圍第1項所述之水性聚胺基曱酸酯之形成方法，其中該多元醇包括二醇類、多醇類、醚二醇類、 24 201109357 或上述之組合。如申叫專利範圍第4項所述之水性聚胺基甲酸酯之 / 一'方法，其中該二醇類包括丙二醇、丁二醇、戊二醇、 ::::¾已二醇、環己基二甲醇、辛二醇、異戊二醇、二一:戊二醇、笨二曱醇、苯二酚、曱苯二酚或雙酚A、 Ιι醇·己二酸共聚物、聚丁二醇、己二醇·己二酸共聚物、聚丙一醇、或上述之組合。201109357 VII. Patent application scope: 1. A method for forming an aqueous polyurethane, comprising: (a) mixing 1.5 to 2.1 moles of diisocyanate with 1 mole of polyethylene glycol to cause reaction The terminal functional group of polyethylene glycol is modified from OH to NCO; (b) mixing 1 mole of diisocyanate, 0.1 to 0.9 moles of polyol, and 0.1 to 0.6 moles of hydrophilic group The alcohol is reacted in an organic solvent to form a PU prepolymer, and the backbone of the PU prepolymer contains no ethylene glycol monomer; _ neutralizing the hydrophilic group of the PU prepolymer; prepolymerizing the PU Dispersing in water and reacting with a polyamine to modify the terminal functional group NCO of the PU prepolymer to NH2; and (c) adding the polyethylene glycol having a terminal functional group of NCO in the step (a) (b) The step of reacting an aqueous solution of a PU prepolymer having a terminal functional group of NH2 to form an aqueous polyamino phthalate. 2. The method for forming an aqueous polyurethane according to claim 1, wherein the diisocyanate S comprises an aromatic diisocyanate, a alicyclic diisocyanate, or the above combination. 3. The method for forming an aqueous polyamino phthalate according to claim 2, wherein the diisocyanate comprises phenylphenyl diisocyanate, phenyl p-diisocyanate, diisocyanate- 4,4'-diphenyldecyl ester, diisocyanate-ρ,ρ'-biphenyl ester, 1,6-hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate Acid S, or a combination of the above. 4. The method of forming an aqueous polyamino phthalate according to claim 1, wherein the polyol comprises a glycol, a polyol, an ether glycol, 24 201109357 or a combination thereof. The method of claim 2, wherein the diol comprises propylene glycol, butanediol, pentanediol, ::::3⁄4 hexanediol, a ring Hexyldimethanol, octanediol, isoprenediol, diamyl: pentanediol, stannitol, benzenediol, hydroquinone or bisphenol A, oxime adipic acid copolymer, polybutane Alcohol, hexanediol/adipate copolymer, polypropanol, or a combination thereof.

>、6·如中請專利範圍第4項所述之水性聚胺基甲酸醋之开^方法’其中該多醇類包括聚醋多it醇、聚ϋ多元醇、聚厌酉夂酉曰多兀醇、聚己内酯多元醇、聚丙烯酸酯多元醇、或上述之組合。 / 7·如申請專利範圍f 4項所述之水性聚胺基曱酸醋之形成方法’其中該多醇類包括丙三醇 '三T基醇丙烧、戊四醇、笨三酚、或上述之組合。 …8.如巾請專利範圍第4項所述之水性聚胺基曱酸醋之形成方法’其中該醚二醇類包括二丙二醇、三丙二醇上述之组合。 9·如申明專利範圍第丨項所述之水性聚胺基曱酸醋之形成方法’其中該含親水基之二㈣其親水基包括幾酸根 (co〇 )、亞硫酸根（s〇3·2)或銨根(nr4+)。 10. 如申明專利範圍第1項所述之水性聚胺基甲酸酯之 $成方法’其中該含親水基之二元醇包括二經甲基丙酸、 -I甲基τι'雙（輕乙基)胺、3_雙（經乙基)胺基丙烧石黃酸納、或上述之組合。 11. 如申1專彳!II請第〗項所述之水性聚胺基甲酸醋之「 25 _ 201109357 $成^法’其中該多元胺含有2·4健基，包括乙二胺、 _乙—胺、二乙四胺、2_曱基-1,5-戊二胺、結構式為Η2Ν (CH2)m〜NH2之化合物，其中m為0〜12之整數、或上述之組合。、12·如申请專利範圍第1項所述之水性聚胺基甲酸酯之，成方法，其中該末端改質為NCO的聚乙二醇之重量分子量約介於50至20000之間。 ,13.如申請專利範圍第1項所述之水性聚胺基甲酸酯之>, 6 · The method for opening an aqueous polyurethane based on the fourth aspect of the patent scope, wherein the polyol comprises polyacetal polyhydric alcohol, polyhydric polyhydric alcohol, polylysine Polynonol, polycaprolactone polyol, polyacrylate polyol, or a combination thereof. / 7. The method for forming an aqueous polyamine phthalic acid vinegar as described in claim 4, wherein the polyol comprises glycerol 'tri-T-propanol, pentaerythritol, styrotriol, or Combination of the above. 8. The method for forming an aqueous polyamine phthalic acid vinegar according to the fourth aspect of the invention, wherein the ether diol comprises a combination of dipropylene glycol and tripropylene glycol. 9. The method for forming an aqueous polyamine phthalic acid vinegar according to the invention of claim </ RTI> wherein the hydrophilic group comprises a hydroxyl group (co〇) and a sulfite group (s〇3· 2) or ammonium (nr4+). 10. The method for forming an aqueous polyurethane according to claim 1, wherein the hydrophilic group-containing diol comprises di-methylpropionic acid, -I methyl τι' double (light) Ethyl)amine, 3_bis(ethyl)aminopropionate, or a combination thereof. 11. For the application of the special 1! II, please refer to the "25 _ 201109357 $ method" of the aqueous polyurethane according to the item, wherein the polyamine contains 2-4, including ethylenediamine, _B. An amine, diethylenetetramine, 2_mercapto-1,5-pentanediamine, a compound of the formula Η2Ν (CH2)m~NH2, wherein m is an integer from 0 to 12, or a combination thereof. The method for producing an aqueous polyurethane according to claim 1, wherein the polyethylene glycol having the terminal modified to NCO has a weight molecular weight of between about 50 and 20,000. The aqueous polyurethane as described in claim 1

^成方法’其中該末端改質為NCO的聚乙二醇之重量分子里約介於300至loooo之間。 1項所述之水性聚胺基曱酸酯之為NCO的聚乙二醇之重量分子 K如申請專利範圍第形成方法，其中該末端改質量約介於600至5000之間^成方法' The weight of the polyethylene glycol in which the end is modified to NCO is between about 300 and loooo. The aqueous polyamine phthalate described in the above item is a weighting molecule of polyethylene glycol of NCO. K is as in the method of forming the patent range, wherein the terminal modification amount is between 600 and 5000.

26 201109357 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化學式：26 201109357 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 chemical formula that best shows the characteristics of the invention:

22