TWI697512B

TWI697512B - Polyester diol, thermoplastic polyurethane and article thereof

Info

Publication number: TWI697512B
Application number: TW108102088A
Authority: TW
Inventors: 鄒秋鵬; 陳震瑋; 鄭文瑋; 黃亭棣; 曾勝茂
Original assignee: 三晃股份有限公司
Priority date: 2019-01-18
Filing date: 2019-01-18
Publication date: 2020-07-01
Also published as: TW202028279A

Abstract

本發明提供一種玻璃轉移溫度(Tg)介於環境溫度與體溫之間的熱塑性聚胺基甲酸酯(TPU)，該熱塑性聚胺基甲酸酯之結構特徵是含有由下述式一表示之二羧基苯基聚酯結構或由下述式二表示之10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構的任一聚酯結構。 The present invention provides a thermoplastic polyurethane (TPU) with a glass transition temperature (Tg) between ambient temperature and body temperature. The structural feature of the thermoplastic polyurethane is expressed by the following formula 1. Dicarboxyphenyl polyester structure or 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide represented by the following formula two (DOPO-ITA) Any polyester structure of the polyester structure.

又，本發明提供一種含有由該式二表示之10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構之聚酯二醇，該聚酯結構相對於聚酯二醇整體的比例，以莫耳百分比計，為30%~70%。 In addition, the present invention provides a formula containing 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO -ITA) Polyester diol with a polyester structure, the ratio of the polyester structure to the whole polyester diol, calculated in mole percentage, is 30%~70%.

本發明並進一步提供一種使用該熱塑性聚胺基甲酸酯製得之成型品。 The present invention further provides a molded article prepared by using the thermoplastic polyurethane.

Description

聚酯二醇、熱塑性聚胺基甲酸酯及其成型品 Polyester diol, thermoplastic polyurethane and its molded products

本發明係關於一種玻璃轉移溫度介於環境溫度與體溫之間，含有二羧基苯基聚酯結構或10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物聚酯結構之任一聚酯結構的熱塑性聚胺基甲酸酯(以下有時簡稱為TPU)；並關於一種含有10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物聚酯結構之聚酯二醇，係用以製造上述熱塑性聚胺基甲酸酯；本發明亦關於一種使用該TPU製成的無溶劑熱熔膠、不織布與成型品。 The present invention relates to a glass transition temperature between ambient temperature and body temperature, containing dicarboxyphenyl polyester structure or 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa -10-phosphaphenanthrene-10-oxide polyester structure of any polyester structure of the thermoplastic polyurethane (hereinafter sometimes referred to as TPU); and about a kind of containing 10-(2,3-dicarboxyl (Propyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide polyester diol, which is used to manufacture the above-mentioned thermoplastic polyurethane; the present invention It also relates to a solvent-free hot melt adhesive, non-woven fabric and molded products made of the TPU.

熱塑性聚胺基甲酸酯被廣泛應用於家具業、鞋業、紡織業、生活用品、汽車工業、戶外休閒用品等的民生產業上。其結構為大分子主鏈上含有胺基甲酸酯基官能基(-NH-CO-O-)，是一種典型的多嵌段線性聚合物，通常係藉由二異氰酸酯(diisocyanate)、聚二醇(macroglycol)及二醇(diol，以下也稱為鏈延長劑)之加成反應而得。在聚胺基甲酸酯結構中的聚二醇鏈段，也習稱為軟段(Soft segment)，其捲曲柔軟的長鏈賦予TPU良好的伸長特性；而該二異氰酸酯與二醇加成形成之鏈段，則稱之為硬段(Hard segment)，硬段容易形成氫鍵作用，有利產生一種有序的結構(稱為結晶相)，而形成分子間的物理交聯。軟段與硬段相間組成的材料結構，在受熱環境下結晶相逐漸熔解，使得分子間物理交聯減少，聚合物會膠化變軟而具有可塑性，通常可以使用射出成型、押出成型、熔噴、壓延等方法加工，待其冷卻固化後得到成型品。 Thermoplastic polyurethane is widely used in civilian production industries such as furniture industry, footwear industry, textile industry, daily necessities, automobile industry, outdoor leisure products, etc. Its structure is that the main chain of the macromolecule contains a urethane functional group (-NH-CO-O-), which is a typical multi-block linear polymer, usually made of diisocyanate and polydiisocyanate. It is obtained by the addition reaction of alcohol (macroglycol) and diol (hereinafter also referred to as chain extender). The polyglycol segment in the polyurethane structure is also known as soft segment. Its long and soft curled chain gives TPU good elongation characteristics; and the diisocyanate and diol are added to form The chain segment is called the hard segment. The hard segment easily forms hydrogen bonds, which is beneficial to produce an ordered structure (called crystalline phase) and form physical crosslinks between molecules. The material structure composed of the soft segment and the hard segment gradually melts the crystalline phase in a heated environment, so that the physical cross-linking between molecules is reduced, and the polymer will gel and become soft and have plasticity. Usually, injection molding, extrusion molding, and melt blowing can be used. , Calendering and other methods, after cooling and solidification, the molded product is obtained.

在習知技藝中，TPU最常使用的軟段是脂肪族聚酯二醇或脂肪族聚醚二醇，軟段佔TPU的重量比例與選用之聚酯二醇或聚醚二醇的分子量大小會影響到該TPU的玻璃轉移溫度(以下有時簡稱為Tg)與結晶溫度(以下有時簡稱為Tc)，例如提高軟段比例或是提高聚酯二醇分子量，所得到TPU的玻璃轉移溫度趨向低溫，結晶度也會降低，使TPU的柔軟性表現越好；反之若硬段使用比例高，也就是用較多的鏈延長劑，則會提高聚合物的結晶度，從而提高材料的硬度與模量，玻璃轉移溫度也會提高一些。常見的TPU市售商品的玻璃轉移溫度，通常是在攝氏-10度以下，甚至在攝氏-40度以下。惟，若結晶溫度、玻璃轉移溫度低，則當其作為熱熔膠之情形時，於熔噴或是押出成膜加工後通常定型時間長，在捲取時容易互黏而必須借助離型紙或離型布收取，且工序複雜成本高。另，當直接應用作為不織布、膜材，或是作為熱熔膠貼合於織物時，也常會因定型時間慢，TPU內聚收縮而造成織物變皺。 In the prior art, the most commonly used soft segment of TPU is aliphatic polyester diol or aliphatic polyether diol, the weight ratio of the soft segment to TPU and the molecular weight of the selected polyester diol or polyether diol It will affect the glass transition temperature (hereinafter sometimes referred to as Tg) and crystallization temperature (hereinafter sometimes referred to as Tc) of the TPU, such as increasing the proportion of soft segments or increasing the molecular weight of polyester diol, and the glass transition temperature of the resulting TPU Towards low temperature, the crystallinity will also decrease, which will make the TPU softer performance better; on the contrary, if the proportion of hard segments is high, that is, more chain extenders are used, the crystallinity of the polymer will be increased, thereby increasing the hardness of the material With modulus, the glass transition temperature will also increase. The glass transition temperature of common TPU commercial products is usually below -10 degrees Celsius, or even below -40 degrees Celsius. However, if the crystallization temperature and glass transition temperature are low, when it is used as a hot-melt adhesive, it usually takes a long time to set after melt-blown or extruded film processing. It is easy to stick to each other during winding and must rely on release paper or The release cloth is collected, and the process is complicated and costly. In addition, when it is directly used as a non-woven fabric, film material, or as a hot-melt adhesive to be attached to the fabric, it often causes the fabric to wrinkle due to the slow setting time and the cohesive shrinkage of TPU.

本發明有興趣的課題是採用聚酯二元醇作為軟段原料之一來製成TPU，所形成之軟段至少含有二羧基苯基聚酯結構或10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(以下簡稱為含有DOPO-ITA結構)聚酯結構的任一聚酯結構，以下將探討相關之先前技術。 The subject of interest in the present invention is to use polyester glycol as one of the soft segment raw materials to make TPU, and the formed soft segment contains at least a dicarboxyphenyl polyester structure or 10-(2,3-dicarboxypropyl) )-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (herein referred to as containing DOPO-ITA structure) any polyester structure of the polyester structure, the following will discuss the related previous technology.

例如德國專利DE2816100C2公開一種阻燃劑是以DOPO或其衍生物和伊康酸加成後與多元醇縮合得到一分子量1000~20000克/莫耳、磷含量為5.3~8.5重量%的聚酯多元醇，其常溫下為玻璃態晶體，說明書提到可作為阻燃劑添加到熱塑性樹脂，例如苯乙烯(PS)、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)、聚氯乙烯(PVC)、丙烯腈-丁二烯-苯乙烯共聚物(ABS)等，以提高其難燃性能。說明書中提到使10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(以下簡稱為DOPO-ITA)與乙二醇之莫耳比為1比3，進行回流除水後，加熱減壓去除過量的乙二醇，充氮氣後，加入作為觸媒之氧化鍺 (GeO2)，升溫度到攝氏230度後得到一種含DOPO-ITA結構的聚酯二醇，化學登錄號碼68664-61-9，化學式為(C₁₇H₁₅O₆P.C₂H₆O₂)_x，玻璃轉移溫度約在攝氏60度，平均分子量(Mn)為4500。該含DOPO聚酯多元醇之軟化溫度高，黏度高，並不適合作為本發明TPU的軟段原料。 For example, German patent DE2816100C2 discloses a flame retardant which is a polyester polyol with a molecular weight of 1,000 to 20,000 g/mol and a phosphorus content of 5.3 to 8.5% by weight after the addition of DOPO or its derivatives and Iconic acid and condensation with polyols. Alcohol, which is a glassy crystal at room temperature. The specification mentions that it can be added as a flame retardant to thermoplastic resins, such as styrene (PS), polycarbonate (PC), polymethyl methacrylate (PMMA), and polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene copolymer (ABS), etc., to improve its flame resistance. The manual mentions that 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as DOPO-ITA) is combined with ethyl The molar ratio of glycol is 1:3. After refluxing to remove water, heating and reducing pressure to remove excess ethylene glycol, after filling with nitrogen, adding germanium oxide (GeO2) as a catalyst, raising the temperature to 230 degrees Celsius to obtain A kind of polyester diol with DOPO-ITA structure, chemical registration number 68664-61-9, chemical formula is (C ₁₇ H ₁₅ O ₆ PC ₂ H ₆ O ₂ ) _x , glass transition temperature is about 60 degrees Celsius, average molecular weight (Mn) is 4500. The DOPO-containing polyester polyol has high softening temperature and high viscosity, and is not suitable for the soft segment raw material of the TPU of the present invention.

例如美國專利第4529744號，公開一芳香族聚酯二醇，係指二羧基苯基聚酯二醇。其說明書也揭示組成、製造方法與可應用於PU發泡。目前此二羧基苯基聚酯二醇組成物已商品化，教示應用在溶劑型聚胺酯(以下有時簡稱為PU)有助於發泡定型。 For example, US Patent No. 4,529,744 discloses an aromatic polyester diol, which refers to a dicarboxyphenyl polyester diol. The specification also discloses the composition, manufacturing method and applicable PU foam. At present, this dicarboxyphenyl polyester diol composition has been commercialized, and the teaching is applied to solvent-based polyurethane (hereinafter sometimes referred to as PU) to help foaming and setting.

例如美國專利第5128197號，提到一種形狀記憶聚合物的織物，其中纖維是由具有成形記憶功能的聚胺酯彈性體製成。說明書提到彈性體在高於約攝氏40度的玻璃移轉點附近經歷彈性模數變化的性質，其在高於產物的玻璃轉移點的溫度下變成橡膠狀，在低於玻璃轉移點的溫度下則變成玻璃狀，並且通過在使彈性體記憶成基本形狀之後再將織物變形至低於玻璃轉移溫度以下的溫度，可以在織物中設定變形形狀，通過將織物加熱至特定溫度來恢復基本形狀，此說明書中提示使用芳香族二醇，例如雙(2-羥乙基)氫醌，來作為鏈延長劑，對於提高Tg效果明顯，另，也提示使用芳香族聚二醇，例如雙酚A與環氧丙烷共聚物，來作為軟段，但說明書也提到高Tg的織物接觸皮膚觸感硬並不被喜愛。 For example, US Patent No. 5,128,197 mentions a shape memory polymer fabric, in which the fibers are made of polyurethane elastomer with a shape memory function. The specification mentions the property that elastomers undergo a change in elastic modulus near the glass transition point higher than about 40 degrees Celsius. It becomes rubbery at a temperature higher than the glass transition point of the product, and at a temperature lower than the glass transition point. The bottom becomes glassy, and by deforming the fabric to a temperature below the glass transition temperature after the elastomer is memorized into the basic shape, the deformed shape can be set in the fabric, and the basic shape can be restored by heating the fabric to a specific temperature In this specification, it is suggested to use aromatic diols, such as bis(2-hydroxyethyl)hydroquinone, as a chain extender, which has a significant effect on increasing Tg. In addition, it also suggests the use of aromatic polyglycols, such as bisphenol A. Copolymer with propylene oxide is used as the soft segment, but the specification also mentions that the fabric with high Tg touches the skin and feels hard and is not liked.

例如臺灣專利第200413459號，提供一種製造水可稀釋性含磷聚合物前驅物之方法，用作為聚丙烯酸-胺基甲酸酯預聚合物的原料，已製造一種水可稀釋性含磷聚合物前驅物的方法及應用在水性防腐蝕阻燃之塗料配方。說明書提到一種含有10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)結構的聚酯二醇，包含其化學登錄號碼455333-14-9，化學式為(C₁₇H₁₅O₆P.C₆H₁₄O₂)x，及化學登錄號碼455333-15-0，化學式為 (C₁₇H₁₅O₆P.C₆H₁₀O₄.C₆H₁₄O₂)x。該說明書所提供之製法，係以不同比例的2-次甲基-1,4-丁二酸(以下也稱為伊康酸)、1,6-己二酸、DOPO、抗氧化劑1,4-二羥基苯)及錫觸媒，氮氣下在110℃下攪拌加熱4小時，然後加熱至攝氏180度直到不再有水被蒸餾出來，減壓真空下加熱為期8小時以移除殘留水，並以³¹P-NMR(核磁共振)追蹤至DOPO加成到伊康酸之不飽和鍵完成為止，由其實施例得知其酸價(Acid value)都大於5毫克氫氧化鉀/克(mg KOH/g)。此法所得之含有DOPO-ITA結構的聚酯二醇的酸價太高，並不適合作為本發明TPU的軟段原料。 For example, Taiwan Patent No. 200413459 provides a method for producing a water-dilutable phosphorous polymer precursor, which is used as a raw material for polyacrylic acid-urethane prepolymer, and has produced a water-dilutable phosphorous polymer The precursor method and its application in the formulation of water-based anti-corrosion and flame-retardant coatings. The instruction mentions a polyester containing 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) structure Alcohol, including its chemical registration number 455333-14-9, the chemical formula is (C ₁₇ H ₁₅ O ₆ PC ₆ H ₁₄ O ₂ )x, and the chemical registration number 455333-15-0, the chemical formula is (C ₁₇ H ₁₅ O ₆ PC ₆ H ₁₀ O ₄ .C ₆ H ₁₄ O ₂ )x. The preparation method provided in this manual is based on different ratios of 2-methine-1,4-succinic acid (hereinafter also referred to as itaconic acid), 1,6-adipic acid, DOPO, antioxidant 1,4 -Dihydroxybenzene) and tin catalyst, stir and heat at 110°C under nitrogen for 4 hours, then heat to 180°C until no more water is distilled out, heat under reduced pressure and vacuum for 8 hours to remove residual water, And with ³¹ P-NMR (nuclear magnetic resonance) tracking until the addition of DOPO to the completion of the unsaturated bond of itaconic acid, the example shows that its acid value is greater than 5 milligrams potassium hydroxide/gram (mg KOH/g). The acid value of the polyester diol containing the DOPO-ITA structure obtained by this method is too high and is not suitable for the soft segment raw material of the TPU of the present invention.

例如中國專利CN101743266A提出一種以DOPO為原料的聚酯多元醇，平均分子量大於20000，常溫下為玻璃態聚合物，可運用到熔融紡絲的聚醯胺纖維(例如PA6、PA12和PA66)和聚酯纖維(PET)，有很好的溶解性，可以提高材料阻燃效果，但提到無法在聚胺酯材料(PU)中使用。其說明書中提到以DOPO-ITA與過量的乙二醇回流除水後，加熱減壓去除過量的乙二醇後，充氮氣之後，加入微量以單乙二醇溶解的氧化鍺(GeO2)與三羥甲基丙烷，溫度提高到攝氏260度後得到一種含DOPO-ITA結構的聚酯二醇，其軟化點約在攝氏100度至130之間，Tg高於攝氏60度，也顯然不適用於作為本發明TPU的軟段原料。 For example, Chinese patent CN101743266A proposes a polyester polyol with DOPO as raw material, with an average molecular weight greater than 20,000, and a glassy polymer at room temperature, which can be used in melt-spun polyamide fibers (such as PA6, PA12 and PA66) and poly Ester fiber (PET) has good solubility and can improve the flame retardant effect of the material, but it is mentioned that it cannot be used in polyurethane material (PU). The manual mentions that after refluxing DOPO-ITA and excess ethylene glycol to remove water, heating and decompressing to remove excess ethylene glycol, after filling with nitrogen, a trace amount of germanium oxide (GeO2) dissolved in monoethylene glycol and Trimethylolpropane, when the temperature is increased to 260 degrees Celsius, a polyester diol containing DOPO-ITA structure is obtained. Its softening point is between 100 degrees Celsius and 130 degrees Celsius, and Tg is higher than 60 degrees Celsius, which is obviously not applicable. Used as the soft segment raw material of the TPU of the present invention.

又例如中國專利CN101914854提出一種溶劑型防水透濕聚胺酯(PU)，由脂肪族聚酯多元醇18.5%~19.5%與聚醚多元醇34.0%~35%，丁二醇7.0%~8.0%，4,4-二異氰酸二苯甲烷26.5%~29.0%與多種助劑混合製成，提到環境溫度高於此胺酯的玻璃轉化溫度其透氣性會提高，有助於穿著者排汗感到舒適，當寒冷的環境溫度低於此胺酯的玻璃轉化溫度時，有低溫保暖功能。 Another example is the Chinese patent CN101914854 proposed a solvent-based waterproof and moisture-permeable polyurethane (PU), composed of aliphatic polyester polyol 18.5%~19.5%, polyether polyol 34.0%~35%, butylene glycol 7.0%~8.0%, 4 ,4-Diisocyanate diphenylmethane 26.5%~29.0% is mixed with a variety of additives. It is mentioned that the ambient temperature is higher than the glass transition temperature of this urethane. The air permeability will be improved, which will help the wearer to perspiration. Comfortable, when the cold environment temperature is lower than the glass transition temperature of this urethane, it has the function of low temperature keeping warm.

例如日本公開專利JPS53118497A提出一種溶劑型聚胺酯，在說明書的實施例中提示一種含有DOPO-ITA結構的聚酯二醇製法，係以DOPO、伊康酸、乙二醇為原料，從攝氏120度加熱至攝氏180度(每小時升溫攝氏20度)，然後在攝氏200度真空蒸餾去水，再回加過量之乙二醇調整羥值(OH value)至106.7mgKOH/g、酸價(Acid value)2.5mgKOH/g，再與二苯基甲烷異氰酸甲酯(也可以簡稱為MDI)的二甲基甲醯胺(DMF)聚合，得到一難燃的聚胺酯，化學登錄號碼69068-45-7。此法以過量的乙二醇調整羥值所得到的聚酯二醇，不易控制聚胺酯的軟硬鏈段比例 For example, Japanese published patent JPS53118497A proposes a solvent-based polyurethane. In the examples of the specification, a method for preparing polyester diol containing DOPO-ITA structure is suggested, which uses DOPO, Iconic acid, and ethylene glycol as raw materials, and heats at 120 degrees Celsius. To 180 degrees Celsius (20 degrees Celsius per hour), then Then the water was distilled in vacuum at 200 degrees Celsius, and excess ethylene glycol was added back to adjust the OH value to 106.7mgKOH/g and the acid value 2.5mgKOH/g, and then diphenylmethane isocyanide The dimethylformamide (DMF) of methyl acid methyl ester (also referred to as MDI) is polymerized to obtain a flame-retardant polyurethane, chemical registration number 69068-45-7. This method uses excess ethylene glycol to adjust the hydroxyl value of the polyester diol, which is not easy to control the ratio of the soft and hard segments of the polyurethane

例如臺灣專利第I614306B號，揭示一種溶劑型聚胺酯與環氧樹酯混合成的接著劑組成物，係應用於印刷電路板產業，此說明書中提到以DOPO-ITA、含苯二甲酸等兩種以上多元羧酸及兩種以上低分子量二醇製備數目平均分子量(Mn)8000~16000且玻璃轉化溫度高於室溫的聚酯二醇組成物，再藉由一種以上的溶劑溶解並與鏈延長劑、異氰酸酯反應，生成特定高酸價範圍的聚胺酯，其玻璃轉化溫度在-20℃~100℃，文中並進一步揭示該玻璃轉化溫度之下限較佳為-10℃，更佳為0℃，另揭示該玻璃轉化溫度之上限較佳為80℃，更佳為60℃。其所提到的含有DOPO-ITA結構的聚酯二醇的分子量、黏度高、酸價高，亦不適合作為本發明TPU的軟段原料。 For example, Taiwan Patent No. I614306B discloses an adhesive composition composed of a solvent-based polyurethane and epoxy resin, which is used in the printed circuit board industry. This specification mentions two types of DOPO-ITA and phthalic acid. The above polycarboxylic acid and two or more low-molecular-weight diols are used to prepare a polyester diol composition with a number average molecular weight (Mn) of 8000~16000 and a glass transition temperature higher than room temperature, and then dissolve and extend the chain with more than one solvent The glass transition temperature is between -20°C and 100°C. The text further reveals that the lower limit of the glass transition temperature is preferably -10°C, and more preferably 0°C. It is revealed that the upper limit of the glass transition temperature is preferably 80°C, more preferably 60°C. The mentioned polyester diol containing DOPO-ITA structure has high molecular weight, high viscosity and high acid value, and it is not suitable for the soft segment raw material of the TPU of the present invention.

例如中國專利CN104927038A提出一種無溶劑一鍋法，在反應器中放入DOPO、小分子多元醇，先以氮氣去除空氣後升溫至攝氏90度使DOPO全溶，降溫至攝氏70度至攝氏80度並加入不飽和二元酸(例如伊康酸)或酸酐，再反應4至6小時，然後加入二元酸和抗氧劑(三苯磷)，在攝氏100度至攝氏140度反應3至12小時，再漸進升溫至攝氏180度下除水2至6小時，繼續升溫至200℃除水3至4小時，最後加入有機金屬催化劑(例如鈦酸酯類)，經真空除水3至4小時，得到一含有酸價低於5mgKOH/g的DOPO-ITA的聚酯二醇，惟此酸價高，亦不適合用於作為本發明TPU的軟段原料。 For example, Chinese patent CN104927038A proposes a solvent-free one-pot method, in which DOPO and small molecule polyols are put into the reactor, the air is removed with nitrogen first, and the temperature is raised to 90 degrees Celsius to fully dissolve DOPO, and the temperature is reduced to 70 degrees Celsius to 80 degrees Celsius. And add unsaturated dibasic acid (such as itaconic acid) or acid anhydride, and react for 4 to 6 hours, then add dibasic acid and antioxidant (triphenylphosphine), react at 100°C to 140°C for 3-12 Then gradually increase the temperature to 180 degrees Celsius to remove water for 2 to 6 hours, continue to increase the temperature to 200°C to remove water for 3 to 4 hours, and finally add organometallic catalysts (such as titanates), and vacuum for 3 to 4 hours , A polyester diol containing DOPO-ITA with an acid value of less than 5 mgKOH/g is obtained. However, this high acid value is not suitable for use as the soft segment raw material of the TPU of the present invention.

查目前公開文獻與市售商品，惟尚未看到其玻璃轉移溫度(Tg)介於環境溫度與體溫之間的TPU及成型品，這吸引我們努力開發使其實現，作為織物、鞋材、飾物、玩具、運動用品與生活用品的新素材。 Check the current public literature and commercial products, but we have not yet seen TPU and molded products whose glass transition temperature (Tg) is between ambient temperature and body temperature. It is now used as a new material for fabrics, shoe materials, accessories, toys, sports goods and daily necessities.

因此，本發明之目的在於提供一種熱塑性聚胺基甲酸酯(TPU)及使用該熱塑性聚胺基甲酸酯(TPU)製造之成型品，該成型品具有在環境溫度下會展現剛性與挺性，接觸體溫則會變得柔軟有彈性的特點，當應用於與人體接觸之紡織品(例如衣褲、帽子、標籤布、窗簾等)、鞋材、裝飾品(例如錶帶、腕帶等)、玩具、運動用品及生活用品等時，可賦予一新奇的觸感、趣味與新功能。 Therefore, the object of the present invention is to provide a thermoplastic polyurethane (TPU) and a molded product manufactured using the thermoplastic polyurethane (TPU), which exhibits rigidity and stiffness at ambient temperature. Sex, the characteristics of being soft and elastic when exposed to body temperature, when applied to textiles (such as clothes, hats, label cloth, curtains, etc.), shoe materials, and decorations (such as watch bands, wristbands, etc.) in contact with the human body , Toys, sports goods and daily necessities, etc., can give a novel touch, interest and new functions.

本發明人等為達到上述目的而經潛心研究後，提出一種玻璃轉移溫度(Tg)介於環境溫度與體溫之間的熱塑性聚胺基甲酸酯(TPU)，其特徵在於含有二羧基苯基聚酯結構(如式一所示)或10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構(如式二所示)的任一聚酯結構，該聚酯結構的平均分子量(Mn)為700至2500g/mole之範圍，較佳在1000至2000g/mole之範圍。 After intensive research in order to achieve the above objective, the inventors proposed a thermoplastic polyurethane (TPU) with a glass transition temperature (Tg) between ambient temperature and body temperature, which is characterized by containing a dicarboxyl phenyl group. Polyester structure (as shown in formula one) or 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA ) Any polyester structure of the polyester structure (as shown in Formula 2), the average molecular weight (Mn) of the polyester structure is in the range of 700 to 2500 g/mole, preferably in the range of 1000 to 2000 g/mole.

本發明之熱塑性聚胺基甲酸酯(TPU)，其所含之二羧基苯基聚酯結構相對於熱塑性聚胺基甲酸酯(TPU)整體的比例，以莫耳百分比計，為6%~25%。 In the thermoplastic polyurethane (TPU) of the present invention, the proportion of the dicarboxyphenyl polyester structure contained in the thermoplastic polyurethane (TPU) relative to the whole thermoplastic polyurethane (TPU) is 6% in molar percentage. ~25%.

本發明之熱塑性聚胺基甲酸酯(TPU)，其所含之10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構相對於熱塑性聚胺基甲酸酯(TPU)整體的比例，以莫耳百分比計，為5%~20%。 The thermoplastic polyurethane (TPU) of the present invention contains 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -The ratio of the oxide (DOPO-ITA) polyester structure to the entire thermoplastic polyurethane (TPU) is 5%-20% in terms of mole percentage.

又，本發明之熱塑性聚胺基甲酸酯(TPU)，其軟段的重量百分比為60%至80%。 In addition, in the thermoplastic polyurethane (TPU) of the present invention, the weight percentage of the soft segment is 60% to 80%.

於本發明中，環境溫度是指最適宜人類生活的溫度，在此為介於攝氏10度至攝氏30度之間；而所述之體溫係指人與高等哺乳動物之表層溫度與深部體溫，在此為介於攝氏30度至攝氏40度之間。 In the present invention, the ambient temperature refers to the temperature most suitable for human life, and here is between 10 degrees Celsius and 30 degrees Celsius; and the body temperature refers to the surface temperature and deep body temperature of humans and higher mammals, Here it is between 30 degrees Celsius and 40 degrees Celsius.

又，本發明之熱塑性聚胺基甲酸酯(TPU)的玻璃轉移溫度(Tg)介於環境溫度與體溫之間，係指介於攝氏10度至攝氏40度之間，較佳介於攝氏15度至攝氏28度之間。 In addition, the glass transition temperature (Tg) of the thermoplastic polyurethane (TPU) of the present invention is between ambient temperature and body temperature, which means between 10°C and 40°C, preferably between 15°C Between degrees and 28 degrees Celsius.

又，本發明之熱塑性聚胺基甲酸酯(TPU)具有熱熔膠功能，係指TPU軟化點介於攝氏50度至攝氏100度之間，較佳介於攝氏60度至攝氏85度之間。 In addition, the thermoplastic polyurethane (TPU) of the present invention has a hot melt adhesive function, which means that the softening point of TPU is between 50°C and 100°C, preferably between 60°C and 85°C .

本發明進一步提供一種使用上述熱塑性聚胺基甲酸酯(TPU)製造之無溶劑熱熔膠。 The present invention further provides a solvent-free hot melt adhesive manufactured using the above-mentioned thermoplastic polyurethane (TPU).

又，本發明進一步提供一種使用上述熱塑性聚胺基甲酸酯(TPU)製造之不織布。 In addition, the present invention further provides a non-woven fabric manufactured using the above-mentioned thermoplastic polyurethane (TPU).

又，本發明進一步提供一種使用上述熱塑性聚胺基甲酸酯(TPU)製造之成型品。該成型品為紡織品、鞋材、裝飾品、玩具、運動用品及生活用品。 In addition, the present invention further provides a molded article manufactured using the above-mentioned thermoplastic polyurethane (TPU). The molded products are textiles, shoe materials, decorations, toys, sports goods and daily necessities.

另，本發明提出一種聚酯二醇，係用以製造上述含有由式二表示之10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構的熱塑性聚胺基甲酸酯(TPU)，該聚酯二醇所含有之由式二表示之10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構相對於聚酯二醇整體的比例，以莫耳百分比計，為30%~70%，該聚酯結構的平均分子量(Mn)為700至2500g/mole之範圍，

In addition, the present invention proposes a polyester diol, which is used to produce the above-mentioned 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphorus represented by formula two. Polyphenanthrene-10-oxide (DOPO-ITA) polyester structure thermoplastic polyurethane (TPU), the polyester diol contains 10-(2,3-dicarboxypropane represented by formula two) (Base)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) The ratio of the polyester structure relative to the entire polyester diol, in mole percentage, is 30%~70%, the average molecular weight (Mn) of the polyester structure is in the range of 700 to 2500g/mole,

本發明之含有由該式二表示之10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構的聚酯二醇，其羥基值介於160.3至44.8毫克氫氧化鉀/克(以下以mgKOH/g表示)。 The present invention contains 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) represented by the formula two The polyester diol with a polyester structure has a hydroxyl value of 160.3 to 44.8 mg potassium hydroxide/g (hereinafter expressed as mgKOH/g).

上述10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構中的二羧酸為伊康酸與9,10-二氫-9-氧雜-10-磷雜菲-10- 氧化物(DOPO)的加成物，或者為伊康酸、選自琥珀酸或1,6-己二酸之任一者及9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO)的加成物。 The dicarboxylic acid in the above 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) polyester structure is Iconic acid and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- The adduct of oxide (DOPO), or itaconic acid, any one selected from succinic acid or 1,6-adipic acid and 9,10-dihydro-9-oxa-10-phosphaphenanthrene -10-Oxide (DOPO) adduct.

上述含有10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構之聚酯二醇的二醇單體選自C2~C8的脂肪族二醇。 The above-mentioned polyester diols containing 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) polyester structure The diol monomer is selected from C2~C8 aliphatic diols.

上述C2~C8的脂肪族二醇為乙二醇、1,2-丙二醇或1,3-丙二醇之丙二醇、丁二醇、2-甲基-1,3-丙二醇、二乙二醇、戊二醇、新戊二醇、己二醇、1,4-環己二醇、2-乙基己二醇、辛二醇或此等之組合。 The above C2~C8 aliphatic diols are propylene glycol, butanediol, 2-methyl-1,3-propanediol, diethylene glycol, pentane diethylene glycol, 1,2-propanediol or 1,3-propanediol Alcohol, neopentyl glycol, hexanediol, 1,4-cyclohexanediol, 2-ethylhexanediol, octanediol or a combination of these.

上述含有10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構之聚酯二醇，更佳選自下述式三所示之DOPO/伊康酸/1,6-己二醇之聚酯二醇(分子式為(C₁₇H₁₅O₆P.C₆H₁₄O₂)_x)、DOPO/伊康酸/二乙二醇的聚酯二醇(分子式為(C₁₇H₁₅O₆P.C₄H₁₀O₃)_x)、DOPO/伊康酸/己二酸/己二醇的聚酯二醇(分子式為(C₁₇H₁₅O₆P.C₆H₁₀O₄.C₆H₁₄O₂)_x)、DOPO/伊康酸/琥珀酸/二乙二醇的聚酯二醇(分子式為(C₁₇H₁₅O₆P.C₄H₆O₄.C₄H₁₀O₃)_x)中之任一者或其等之組合，式三

式中，n為1~10，x為1~10，b為1~6。 The above-mentioned polyester diols containing 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) polyester structure , More preferably selected from the DOPO/itaconic acid/1,6-hexanediol polyester diol shown in the following formula 3 (the molecular formula is (C ₁₇ H ₁₅ O ₆ PC ₆ H ₁₄ O ₂ ) _x ), Polyester diol of DOPO/itaconic acid/diethylene glycol (the molecular formula is (C ₁₇ H ₁₅ O ₆ PC ₄ H ₁₀ O ₃ ) _x ), the polyol of DOPO/itaconic acid/adipic acid/hexanediol Ester diol (molecular formula (C ₁₇ H ₁₅ O ₆ PC ₆ H ₁₀ O ₄ .C ₆ H ₁₄ O ₂ ) _x ), DOPO/itaconic acid/succinic acid/diethylene glycol polyester diol (molecular formula Is any one of (C ₁₇ H ₁₅ O ₆ PC ₄ H ₆ O ₄ .C ₄ H ₁₀ O ₃ ) _x ) or a combination thereof, formula three

In the formula, n is 1~10, x is 1~10, and b is 1~6.

上述選自該式三所示之任一者或其等之組合的聚酯二醇其酸價<1.8mgKOH/g。 The acid value of the polyester diol selected from any one of the formula 3 or a combination thereof is less than 1.8 mgKOH/g.

根據本發明，本發明所述的熱塑性聚胺基甲酸酯(以下簡稱為TPU)可由下述方法取得：將含有二羧基苯基聚酯結構或含有10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構的聚二醇組成物(下文簡稱聚二醇組成物)、鏈延長劑及有機二異氰酸酯，依莫耳數比值為0.95

有機二異氰酸酯/(聚二醇組成物+鏈延長劑)

1.10的比例，混合加熱而成。 According to the present invention, the thermoplastic polyurethane (hereinafter referred to as TPU) of the present invention can be obtained by the following method: a polyester structure containing a dicarboxyphenyl group or a 10-(2,3-dicarboxypropyl group) )-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) polyester structure polyglycol composition (hereinafter referred to as polyglycol composition), chain extension Agent and organic diisocyanate, the ratio of Yimole number is 0.95

Organic diisocyanate/(polyglycol composition + chain extender)

1.10 ratio, mixed and heated.

根據本發明，本發明所述的具有熱熔膠功能的TPU可由下述方法取得：使含有二羧基苯基聚酯結構或含有10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構的聚二醇組成物(下文簡稱為聚二醇組成物)、鏈延長劑以及有機二異氰酸酯為較佳的比例，亦即聚二醇組成物的重量比值為60%

聚二醇組成物/(聚二醇組成物+鏈延長劑+有機二異氰酸酯)

80%，其莫耳數比值為0.98

有機二異氰酸酯/(聚二醇組成物+鏈延長劑)

1.05的比例。 According to the present invention, the TPU with hot-melt adhesive function described in the present invention can be obtained by the following method: containing dicarboxyphenyl polyester structure or containing 10-(2,3-dicarboxypropyl)-9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) polyester structure polyglycol composition (hereinafter referred to as polyglycol composition), chain extender and organic diisocyanate Is a preferred ratio, that is, the weight ratio of the polyglycol composition is 60%

Polyglycol composition/(polyglycol composition + chain extender + organic diisocyanate)

80%, its molar ratio is 0.98

Organic diisocyanate/(polyglycol composition + chain extender)

1.05 ratio.

根據本發明，本發明所述之聚二醇組成物除了具有含二羧基苯基聚酯結構的聚酯二醇或是具有含10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構的聚酯二醇外，另外亦可選擇性組合脂肪族聚二醇。 According to the present invention, the polyglycol composition of the present invention has a polyester diol containing a dicarboxyphenyl polyester structure or a polyester diol containing 10-(2,3-dicarboxypropyl)-9,10- In addition to the polyester diol of the dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) polyester structure, aliphatic polyglycols can also be optionally combined.

本發明之含二羧基苯基聚酯結構的聚酯二醇，其中二羧酸苯基單體較佳選自1,2-苯二甲酸、1,3-苯二甲酸、1,4-苯二甲酸、苯二甲酸酐，或其等與己二酸等之組合，其二醇單體則較佳選自C2~C8的脂肪族二醇，包括乙二醇、丙二醇如1,2-丙二醇和1,3-丙二醇、丁二醇、2-甲基-1,3-丙二醇、二乙二醇、戊二醇和新戊二醇、己二醇、1,4-環己二醇、2-乙基己二醇、辛二醇或此等之組合。 In the polyester diol containing a dicarboxyphenyl polyester structure of the present invention, the dicarboxylic phenyl monomer is preferably selected from 1,2-phthalic acid, 1,3-phthalic acid, and 1,4-benzene Dicarboxylic acid, phthalic anhydride, or a combination thereof with adipic acid, etc. The diol monomer is preferably selected from C2-C8 aliphatic diols, including ethylene glycol, propylene glycol such as 1,2-propylene glycol And 1,3-propanediol, butanediol, 2-methyl-1,3-propanediol, diethylene glycol, pentanediol and neopentyl glycol, hexanediol, 1,4-cyclohexanediol, 2- Ethyl hexanediol, octanediol or a combination of these.

本發明之含二羧基苯基聚酯結構的聚酯二醇，更佳為1,2-苯二甲酸/二乙二醇的聚酯二醇(化學登錄號碼為CAS 25916-41-0，化學式為(C₈H₆O₄.C₄H₁₀O₃)_x))、1,2-苯二甲酸/己二醇的聚酯二醇(化學登錄號碼為CAS 27516-71-8，化學式為(C₈H₆O₄.C₆H₁₄O₂)_x))、1,4-苯二甲酸/1,6-己二酸/二乙二醇的聚酯二醇(化學式為(C₈H₆O₄.C₆H₁₀O₄.C₆H₁₄O₂)_x))。更佳為其羥基值介於160.3至56.1mg KOH/g，莫耳平均分子量介於700克/莫耳至2000克/莫耳，酸價<1mg KOH/g。 The polyester diol containing a dicarboxyphenyl polyester structure of the present invention is more preferably a 1,2-phthalic acid/diethylene glycol polyester diol (chemical registration number is CAS 25916-41-0, chemical formula (C ₈ H ₆ O ₄ .C ₄ H ₁₀ O ₃ ) _x )), 1,2-phthalic acid/hexanediol polyester diol (chemical registration number is CAS 27516-71-8, chemical formula is (C ₈ H ₆ O ₄ .C ₆ H ₁₄ O ₂ ) _x )), 1,4-phthalic acid/1,6-adipic acid/diethylene glycol polyester diol (chemical formula is (C ₈ H ₆ O ₄ .C ₆ H ₁₀ O ₄ .C ₆ H ₁₄ O ₂ ) _x )). More preferably, the hydroxyl value is between 160.3 and 56.1 mg KOH/g, the molar average molecular weight is between 700 g/mole and 2000 g/mole, and the acid value is less than 1 mg KOH/g.

又，本發明之含有10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構的聚酯二醇，較佳為其二羧酸係指伊康酸與9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO)的加成物及其與琥珀酸或1,6-己二酸等之組合，其中DOPO-ITA聚酯結構相對於聚酯二醇組成物整體之比例，以莫耳百分比計，在30%以上70%以下，其中二醇單體選自C2~C8的脂肪族二醇，包括乙二醇、丙二醇如1,2-丙二醇和1,3-丙二醇、丁二醇、2-甲基-1,3-丙二醇、二乙二醇、戊二醇和新戊二醇、己二醇、1,4-環己二醇、2-乙基己二醇、辛二醇或此等之組合。 In addition, the polyester structure of the present invention containing 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) Polyester diol, preferably its dicarboxylic acid refers to the adduct of itaconic acid and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and its combination with A combination of succinic acid or 1,6-adipic acid, etc., in which the ratio of the DOPO-ITA polyester structure to the overall polyester diol composition For example, in terms of mole percentage, it is above 30% and below 70%, where the diol monomer is selected from C2~C8 aliphatic diols, including ethylene glycol, propylene glycol such as 1,2-propanediol and 1,3-propanediol , Butanediol, 2-methyl-1,3-propanediol, diethylene glycol, pentanediol and neopentyl glycol, hexanediol, 1,4-cyclohexanediol, 2-ethylhexanediol, Octanediol or a combination of these.

於本發明中，所述的脂肪族聚二醇包括但不限於聚乙二醇、經改質之聚乙二醇、聚丙二醇、聚三亞甲基醚二醇、聚四亞甲基醚二醇、聚琥珀酸-1,6-己二醇酯二醇、聚己二酸-1,4-丁二醇酯二醇(在下文中，簡稱為PBA)、聚己二酸乙二醇-1,4-丁二醇酯二醇、聚己二酸-1,4-丁二醇-1,6-己二醇酯二醇、聚己內酯二醇及其等之組合。 In the present invention, the aliphatic polyglycol includes but is not limited to polyethylene glycol, modified polyethylene glycol, polypropylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol , Polysuccinic acid-1,6-hexanediol ester diol, polyadipate-1,4-butanediol ester diol (hereinafter referred to as PBA), polyethylene adipate-1, 4-butanediol ester diol, polyadipate-1,4-butanediol-1,6-hexanediol ester diol, polycaprolactone diol, and combinations thereof.

其中，較佳為PBA，其羥基值介於160.3至56.1mg KOH/g，分子量(Mn)介於700克/莫耳至2000克/莫耳、酸價<0.5mg KOH/g。 Among them, PBA is preferred, the hydroxyl value of which is between 160.3 and 56.1 mg KOH/g, the molecular weight (Mn) is between 700 g/mole and 2000 g/mole, and the acid value is <0.5 mg KOH/g.

於本發明中，所述的有機二異氰酸酯包括但不限於二苯甲基烷-4,4-二異氰酸酯(在下文中，簡稱為MDI)、二環己基甲烷二異氰酸酯、二環己基甲烷二異氰酸酯、二環己基甲烷二異氰酸酯及其等之組合。其中，較佳為MDI。 In the present invention, the organic diisocyanate includes, but is not limited to, benzhydryl-4,4-diisocyanate (hereinafter referred to as MDI), dicyclohexylmethane diisocyanate, dicyclohexylmethane diisocyanate, Dicyclohexylmethane diisocyanate and combinations thereof. Among them, MDI is preferred.

於本發明中，所使用的鏈延長劑係指脂肪族二醇，包括但不限於其二醇單體係選自C2~C8的脂肪族二醇，包括乙二醇、丙二醇如1,2-丙二醇和1,3-丙二醇、丁二醇、2-甲基-1,3-丙二醇、二乙二醇、戊二醇和新戊二醇、己二醇、1,4-環己二醇、2-乙基己二醇、辛二醇及其等之組合。其中，較佳為1,4-丁二醇。 In the present invention, the chain extender used refers to aliphatic diols, including but not limited to aliphatic diols whose diol system is selected from C2~C8, including ethylene glycol, propylene glycol such as 1,2- Propylene glycol and 1,3-propanediol, butanediol, 2-methyl-1,3-propanediol, diethylene glycol, pentanediol and neopentyl glycol, hexanediol, 1,4-cyclohexanediol, 2 -Ethyl hexanediol, octanediol and combinations thereof. Among them, 1,4-butanediol is preferred.

於本發明中，可於製造TPU時添加助劑，該助劑包括但不限於抗氧化劑、抗UV劑、耐熱劑、滑劑、觸媒、色料及其等之組合。 In the present invention, auxiliary agents can be added during the manufacture of TPU. The auxiliary agents include but are not limited to antioxidants, anti-UV agents, heat-resistant agents, lubricants, catalysts, colorants, and combinations thereof.

本發明所提出之含有二羧基苯基聚酯結構的TPU，可作為無溶劑熱熔膠，其與聚酯織物的接著性佳，更特別的是，具有非常優秀的耐水解性，可適用於開發長期使用且經常水洗的用品。 The TPU containing the dicarboxyphenyl polyester structure proposed by the present invention can be used as a solvent-free hot melt adhesive. It has good adhesion to polyester fabrics, and more particularly, has excellent hydrolysis resistance. It can be applied to the development of long-term use and frequently washed products.

另，本發明之含有10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)的TPU亦可作為無溶劑熱熔膠，其結構中之DOPO所含有的磷原子使其具有本質型的難燃性且不會遷移，其容易水分解的特性，可使其適用於開發難燃紡織品或是容易處理的拋棄式用品。 In addition, the TPU of the present invention containing 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) can also be As a solvent-free hot melt adhesive, the phosphorous atoms contained in the DOPO in its structure make it inherently flame-retardant and non-migrating. Its easy water-decomposability makes it suitable for the development of flame-retardant textiles or easy Disposable supplies for disposal.

根據本發明，可提供一種玻璃轉化溫度(Tg)介於環境溫度與體溫之間的熱塑性聚胺基甲酸酯及其成型品，由於其玻璃轉化溫度高於環境溫度，因此具有容易定型、不易產生皺折、於展示或是放置時可產生挺拔有型之視覺感等優點，另一方面，因其玻璃轉化溫度低於人體體溫，故當與人體接觸時卻反而會覺得柔軟舒適。藉由以上特點，若應用於紡織品(例如衣褲、帽子、標籤布、窗簾等)、鞋材、裝飾品(例如錶帶、腕帶等)、玩具、運動用品及生活用品等，則將為消費者提供一新的觸感、趣味與功能。 According to the present invention, a thermoplastic polyurethane with a glass transition temperature (Tg) between ambient temperature and body temperature and its molded products can be provided. Because the glass transition temperature is higher than the ambient temperature, it is easy to set and difficult to set. It has the advantages of wrinkles and a straight and stylish visual sense when displayed or placed. On the other hand, because its glass transition temperature is lower than the body temperature of the human body, it will feel soft and comfortable when in contact with the human body. With the above characteristics, if it is applied to textiles (such as clothes, hats, label cloth, curtains, etc.), shoe materials, decorations (such as watch bands, wristbands, etc.), toys, sports goods and daily necessities, it will be Consumers provide a new touch, fun and function.

另，根據本發明，亦可提供一種用以製造上述熱塑性聚胺基甲酸酯(TPU)之聚酯二醇。 In addition, according to the present invention, it is also possible to provide a polyester diol for producing the above-mentioned thermoplastic polyurethane (TPU).

圖1係實施例7含有二羧基苯基聚酯結構之TPU的紅外光譜圖。 Figure 1 is the infrared spectrum of the TPU containing the dicarboxyphenyl polyester structure in Example 7.

圖2係實施例8含有二羧基苯基聚酯結構之TPU的紅外光譜圖。 Figure 2 is the infrared spectrum of the TPU containing the dicarboxyphenyl polyester structure in Example 8.

圖3係實施例9含有二羧基苯基聚酯結構之TPU的紅外光譜圖。 Figure 3 is the infrared spectrum of the TPU containing the dicarboxyphenyl polyester structure in Example 9.

圖4係實施例10含有二羧基苯基聚酯結構之TPU的紅外光譜圖。 Figure 4 is the infrared spectrum of the TPU of Example 10 containing the dicarboxyphenyl polyester structure.

圖5係實施例11含有二羧基苯基聚酯結構之TPU的紅外光譜圖。 Figure 5 is the infrared spectrum of the TPU containing the dicarboxyphenyl polyester structure in Example 11.

圖6係實施例12含有二羧基苯基聚酯結構之TPU的紅外光譜圖。 Figure 6 is the infrared spectrum of the TPU containing the dicarboxyphenyl polyester structure in Example 12.

圖7係比較例1含有二羧基苯基聚酯結構之TPU的紅外光譜圖。 Figure 7 is the infrared spectrum of the TPU containing the dicarboxyphenyl polyester structure of Comparative Example 1.

圖8係實施例13含有DOPO-ITA聚酯結構之TPU的紅外光譜圖。 Figure 8 is the infrared spectrum of Example 13 TPU containing the DOPO-ITA polyester structure.

圖9係實施例14含有DOPO-ITA聚酯結構之TPU的紅外光譜圖。 Figure 9 is the infrared spectrum of the TPU containing the DOPO-ITA polyester structure in Example 14.

圖10係實施例15含有DOPO-ITA聚酯結構之TPU的紅外光譜圖。 Figure 10 is the infrared spectrum of Example 15 TPU containing the DOPO-ITA polyester structure.

圖11係實施例16含有DOPO-ITA聚酯結構之TPU的紅外光譜圖。 Figure 11 is the infrared spectrum of Example 16 TPU containing the DOPO-ITA polyester structure.

圖12係實施例17含有DOPO-ITA聚酯結構之TPU的紅外光譜圖。 Figure 12 is the infrared spectrum of the TPU containing the DOPO-ITA polyester structure in Example 17.

圖13係實施例18含有DOPO-ITA聚酯結構之TPU的紅外光譜圖。 Figure 13 is the infrared spectrum of Example 18 TPU containing DOPO-ITA polyester structure.

圖14係比較例2含有DOPO-ITA聚酯結構之TPU的紅外光譜圖。 Figure 14 is the infrared spectrum of Comparative Example 2 TPU containing DOPO-ITA polyester structure.

圖15係實施例19含有二羧基苯基聚酯結構之TPU的紅外光譜圖。 Figure 15 is the infrared spectrum of the TPU containing the dicarboxyphenyl polyester structure in Example 19.

圖16係實施例20含有二羧基苯基聚酯結構之TPU的紅外光譜圖。 Figure 16 is the infrared spectrum of the TPU containing the dicarboxyphenyl polyester structure in Example 20.

圖17係實施例21含有二羧基苯基聚酯結構之TPU的紅外光譜圖。 Figure 17 is the infrared spectrum of the TPU containing the dicarboxyphenyl polyester structure in Example 21.

圖18係比較例3之TPU的紅外光譜圖。 Figure 18 is the infrared spectrum of the TPU of Comparative Example 3.

以下藉由特定具體實施例說明本發明，惟此等實施例僅是用以說明及理解本發明，本發明並不限於此等實施例。又，本發明亦可藉由其它不同方式加以施行或應用，故在不悖離本發明所揭示之精神下加以修飾與變更而成者皆屬於本發明之範圍。另，本說明書的所有數值範圍皆包含其上下限值，且其中之任何整數皆可作為最小值或最大值而形成下位範圍等。 The present invention will be described below with specific specific embodiments, but these embodiments are only used to illustrate and understand the present invention, and the present invention is not limited to these embodiments. In addition, the present invention can also be implemented or applied in other different ways, so modifications and changes made without departing from the spirit of the present invention fall within the scope of the present invention. In addition, all numerical ranges in this specification include the upper and lower limits, and any integers therein can be used as the minimum or maximum value to form a lower range, etc.

於本發明中，運用下列之測量方法： In the present invention, the following measurement methods are used:

傅立葉轉換紅外線光譜儀：選用儀器機型為Thermo Nicolet 330FT-IR，進行表面分析，具體而言，係藉由衰減全反射(ATR)測試，掃描範圍從4000cm^-1到650cm^-1，以了解待測物之結構特徵。 Fourier transform infrared spectrometer: Thermo Nicolet 330FT-IR is selected for surface analysis. Specifically, the attenuated total reflectance (ATR) test is used. The scanning range is from 4000cm ^-1 to 650cm ^-1 to understand the test The structural characteristics of things.

差示掃描熱量分析儀(differential scanning calorimetry，DSC)選用Mettler Toledo^®公司儀器DSC821e差示掃描熱量分析儀，利用能秤量至 ±0.01毫克的微量天平精秤樣品，約在5至10毫克，放入鋁DSC坩鍋內，然後將蓋子牢牢固定。使用前將DSC腔室內溫度設定在攝氏25度。將樣品坩鍋和對照坩鍋(空白)置入DSC槽腔室內。氮氣流速為每分鐘80毫升，以每分鐘攝氏10度之降溫速率，將溫度降低至攝氏-80度並維持3分鐘，然後以每分鐘攝氏10度之加熱速度升高至220度至250度後維持3分鐘，以每分鐘降溫攝氏10度之冷卻速率，降溫至攝氏-80度後維持3分鐘，這過程出現之峰值為其結晶溫度(Tc)；再以每分鐘攝氏5~10度之升溫速率，第二次升至220度至250度；從過程中得到之反折點為其玻璃轉移溫度(Tg)，得到之峰值為其熔點(Tm)。 Differential scanning calorimetry (differential scanning calorimetry, DSC) uses Mettler Toledo ^® instrument DSC821e differential scanning calorimetry, using a microbalance that can weigh to ±0.01 mg to accurately weigh the sample, about 5 to 10 mg, and put it in Inside the aluminum DSC crucible, then secure the lid firmly. Set the temperature in the DSC chamber at 25 degrees Celsius before use. Place the sample crucible and the control crucible (blank) into the DSC tank chamber. Nitrogen flow rate is 80 ml per minute. At a cooling rate of 10 degrees Celsius per minute, the temperature is reduced to -80 degrees Celsius and maintained for 3 minutes, and then heated at a heating rate of 10 degrees Celsius per minute to 220 degrees to 250 degrees. Maintain for 3 minutes, at a cooling rate of 10 degrees Celsius per minute, cool to -80 degrees Celsius and maintain for 3 minutes. The peak of this process is the crystallization temperature (Tc); then the temperature rises at 5-10 degrees Celsius per minute The rate is increased to 220 degrees to 250 degrees for the second time; the reflex point obtained from the process is the glass transition temperature (Tg), and the peak value obtained is the melting point (Tm).

軟化點測試方法係參考美國標準方法(ASTM)D1525來進行：準備2mm厚度熱壓試片兩片相疊，將有針頭且重量1公斤的砝碼放於試片之上，放入可控溫循環的烘箱中25分鐘後，紀錄針頭可針入試片的溫度。 The softening point test method refers to the American Standard Method (ASTM) D1525: prepare two hot-pressed test pieces of 2mm thickness on top of each other, put a weight with a needle and a weight of 1 kg on the test piece, and put it in a controlled temperature After 25 minutes in the circulating oven, record the temperature at which the needle can penetrate the test piece.

羥值分析係參考美國標準方法(ASTM)D4274-99來進行。 The hydroxyl value analysis was performed with reference to American Standard Method (ASTM) D4274-99.

酸價分析係參考美國標準(ASTM)D4662來進行。 The acid value analysis is performed with reference to American Standard (ASTM) D4662.

聚二醇分子量(Mn)計算公式=(56100×2)/(羥值+酸價) Polyglycol molecular weight (Mn) calculation formula = (56100×2)/(hydroxyl value + acid value)

黏度分析則是使用Brookfield型號：椎板式LVDV-I來進行。 Viscosity analysis is carried out using Brookfield model: laminar LVDV-I.

聚酯二醇含磷量的計算值(P wt%)=[(DOPO為原料的莫耳數×30.97)/聚酯二醇成品總重]×100% Calculated value of phosphorus content of polyester diol (P wt%)=[(Mole number of DOPO as raw material×30.97)/total weight of finished polyester diol]×100%

TPU含磷量的計算值(P wt%)=[(聚酯二醇的重量×聚酯二醇含磷量的計算值)/TPU的總重量]×100% Calculated value of phosphorus content in TPU (P wt%)=[(weight of polyester diol×calculated value of phosphorus content in polyester diol)/total weight of TPU]×100%

凝膠層析儀(Gel Permeation Chromatography，GPC) Gel Permeation Chromatography (GPC)

選用Waters 2487，管柱型號為HR1/HR3/HR4。移動相為四氫呋喃(THF)，流速為每分鐘1毫升，用於測定樣品之數目平均分子量(Mn)、重量平均分子量(Mw)及峰位分子量(Mp)，係基於以聚苯乙烯標準液所進行之外部校準。 Choose Waters 2487, the column model is HR1/HR3/HR4. The mobile phase is tetrahydrofuran (THF), and the flow rate is 1 ml per minute. It is used to determine the number average molecular weight (Mn), weight average molecular weight (Mw) and peak molecular weight (Mp) of the sample, based on the polystyrene standard solution. External calibration performed.

於本發明實施例所使用之聚酯二醇原料來源說明如下。 The source of the polyester diol raw materials used in the examples of the present invention is described as follows.

本發明之含有二羧基苯基聚酯結構之聚酯二醇，其中1,2-苯二甲酸/二乙二醇的聚酯二醇(化學登錄號碼為CAS 25916-41-0，化學式為(C₈H₆O₄.C₄H₁₀O₃)_x))來自Stepan公司，商品名PD-56；1,2-苯二甲酸/己二醇的聚酯二醇(化學登錄號碼為CAS 27516-71-8，化學式為(C₈H₆O₄.C₆H₁₄O₂)_x))來自Stepan公司，商品名PH-56；1,4-苯二甲酸/1,6-己二酸/二乙二醇的聚酯二醇(化學式為(C₈H₆O₄.C₆H₁₀O₄.C₆H₁₄O₂)_x))來自臺灣久峰興業，商品名JF-022P。 The polyester diol containing the dicarboxyphenyl polyester structure of the present invention, wherein the polyester diol of 1,2-phthalic acid/diethylene glycol (chemical registration number is CAS 25916-41-0, and the chemical formula is ( C ₈ H ₆ O ₄ .C ₄ H ₁₀ O ₃ ) _x )) from Stepan Company, trade name PD-56; 1,2-phthalic acid/hexanediol polyester diol (chemical registration number is CAS 27516 -71-8, the chemical formula is (C ₈ H ₆ O ₄ .C ₆ H ₁₄ O ₂ ) _x )) from Stepan Company, trade name PH-56; 1,4-phthalic acid/1,6-adipic acid /Diethylene glycol polyester diol (chemical formula (C ₈ H ₆ O ₄ .C ₆ H ₁₀ O ₄ .C ₆ H ₁₄ O ₂ ) _x )) comes from Taiwan Jiufeng Industrial, trade name JF-022P.

本發明使用之聚己二酸-1,4-丁二醇的聚酯二醇PBA700(商品名P-700)、PBA1000(商品名PE-14)及PBA2000(商品名PE-24)，以及聚己二酸乙二醇-1,4-丁二醇酯二醇PEBA2000(商品名PE-224)均來自三晃公司。 The polyester diols PBA700 (trade name P-700), PBA1000 (trade name PE-14) and PBA2000 (trade name PE-24) of polyadipate-1,4-butanediol used in the present invention, and poly Ethylene glycol-1,4-butanediol adipate glycol PEBA2000 (trade name PE-224) is from Sanko Corporation.

本發明使用之聚四亞甲基醚二醇PTMEG1000來自日本三菱公司。 The polytetramethylene ether glycol PTMEG1000 used in the present invention comes from Mitsubishi Corporation of Japan.

本發明使用之含有10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構的聚酯二醇，在此提出其合成方法如實施例1至實施例6： The present invention contains 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) polyester structure poly Ester diol, its synthesis method is proposed here as in Example 1 to Example 6:

[實施例1] [Example 1]

本發明之含有10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構的聚酯二醇，係自行研究以一鍋法在攝氏140~220度，進行加成，縮合與除水後製備而成，實施方式說明如下：準備可進行機械攪拌之3L圓底4頸瓶及長度30cm、內徑1.5cm、外徑4cm的分餾管(內填充玻璃珠)、蒸餾收集瓶、溫度計，以表一所示之用料數據，加入二醇加熱攪拌均勻後，依序加入伊康酸及DOPO，將內溫升溫到攝氏140~180度，調整油溫以控制分餾管餾出之水溫維持在攝氏97~100度，並收集蒸出之水至其理論產生重量的95%以上(歷時3~4小時)，進行減壓加熱到內溫達攝氏210~215度，維持10小時後，加入作為觸媒的二氯化錫，追蹤酸價至低於1.8mgKOH/g，停止加熱並以氮氣降溫收集成品，秤重計算收率與含磷量，並記錄外觀並檢測羥基值、酸價、黏度。其結果示於表一。 The polyester of the present invention containing 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) polyester structure Glycol, prepared by self-study by one-pot method at 140-220 degrees Celsius, adding, condensing and dewatering. The implementation mode is as follows: Prepare a 3L round-bottomed 4-neck bottle that can be mechanically stirred and a length of 30cm , Fractionation tube with inner diameter of 1.5cm and outer diameter of 4cm (filled with glass beads), distillation collection flask, thermometer, according to the material data shown in Table 1, add glycol, heat and stir evenly, add itaconic acid and DOPO, raise the internal temperature to 140~180 degrees Celsius, adjust the oil temperature to control the temperature of the water distilled from the fractionation tube to maintain 97~100 degrees Celsius, and collect the steamed water to 95% of its theoretical production weight (3~4 hours), heat under reduced pressure until the internal temperature reaches 210~215 degrees Celsius. After maintaining for 10 hours, add tin dichloride as a catalyst, track the acid value to less than 1.8mgKOH/g, stop Heat and cool with nitrogen to collect the finished product, weigh to calculate the yield and phosphorus content, record the appearance and detect the hydroxyl value, acid value, and viscosity. The results are shown in Table 1.

[實施例2~6] [Examples 2~6]

除了使用表一、表二所示之用料數據外，其餘皆以與實施例1相同製法及檢測方式進行。其結果如表一、表二所示。 Except for using the material data shown in Table 1 and Table 2, the rest are all carried out with the same preparation method and detection method as in Example 1. The results are shown in Table 1 and Table 2.

本發明之含有二羧基苯基聚酯結構之TPU的實驗室小量製法，實施方式說明如下(實施例7~實施例12及比較例1)：在將含有二羧基苯基聚酯結構之聚酯二醇與選擇性組合的脂肪族聚二醇之組合物、二醇以及助劑(1公克的抗氧化劑1010、1公克的蒙旦蠟及25毫克的觸媒T9)的混合物放入1升的金屬桶中，進行機械攪拌，以加熱板使內溫控制在攝氏110度，於攪拌下將已預熱到攝氏110度的MDI液體一次加入，持續攪拌3分鐘，紀錄第2分鐘之料溫，至第3分鐘時，將反應內容物倒入盛盤並取樣在攝氏190度，荷重2160克的條件下分析熔融流動指數(以MI(190℃，2160g，10min)表示)，同時也將該盛盤放至預熱在攝氏70度的循環烘箱中熟成24小時後取出。紀錄TPU成品外觀，接觸手心溫度感覺其柔軟度之變化，測試TPU軟化點，玻璃轉移溫度(Tg)並進行耐水解測試，將實施例7~實施例10之相關數據及結果示於表三，將實施例11、實施例12及比較例1之相關數據及結果示於表四。又，使用傅立葉轉換紅外線光譜儀(儀器機型：Thermo Nicolet 330FT-IR)，對實施例7~實施例12所得到之TPU成品(含有二羧基苯基聚酯結構者)進行衰減全反射(ATR)測試，得到之紅外光譜圖如圖1~6所示，確認為本案發明所欲完成之熱塑性聚胺基甲酸酯(TPU)，另，對比較例1之TPU成品所測得之紅外光譜圖則如圖7所示。 The method for preparing a small amount of TPU containing dicarboxyphenyl polyester structure in the present invention is described as follows (Example 7~Example 12 and Comparative Example 1): The method for preparing a TPU containing dicarboxyphenyl polyester structure is as follows: A mixture of ester diol and optionally combined aliphatic polyglycol, diol and additives (1 gram of antioxidant 1010, 1 gram of Montan wax and 25 mg of catalyst T9) are placed in 1 liter In the metal bucket, mechanically stir, use the heating plate to control the internal temperature at 110 degrees Celsius, and preheat the Add the MDI liquid at 110 degrees Celsius at one time, keep stirring for 3 minutes, record the material temperature at the second minute, and at the third minute, pour the reaction contents into the tray and sample at 190 degrees Celsius and load 2160 grams for analysis Melt flow index (expressed in MI (190°C, 2160g, 10min)), and at the same time, put the tray to preheat in a circulating oven at 70°C for 24 hours and then take it out. Record the appearance of the TPU finished product, feel the change in softness at the temperature of the palm of the hand, test the TPU softening point, glass transition temperature (Tg) and conduct a hydrolysis resistance test. The relevant data and results of Examples 7 to 10 are shown in Table 3. The relevant data and results of Example 11, Example 12 and Comparative Example 1 are shown in Table 4. In addition, a Fourier transform infrared spectrometer (instrument model: Thermo Nicolet 330FT-IR) was used to perform attenuated total reflectance (ATR) on the TPU products obtained in Examples 7 to 12 (containing dicarboxyphenyl polyester structure) In the test, the infrared spectra obtained are shown in Figures 1 to 6, which are confirmed to be the thermoplastic polyurethane (TPU) that the present invention intends to complete. In addition, the infrared spectra measured on the TPU product of Comparative Example 1 It is shown in Figure 7.

本發明含10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構之TPU的實驗室小量製法，實施方式說明如下(實施例13~實施例18及比較例2)：在將實施例1~實施例6得到的含10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構之聚酯二醇與選擇性組合的脂肪族聚二醇之組合物、二醇及助劑(1公克的抗氧化劑1010、1公克的蒙旦蠟、0.75公克的紫外線吸收劑UV-329及25毫克的觸媒T9)的混合物放入1升的金屬桶中，進行機械攪拌，以加熱板使內溫控制在攝氏110 度，攪拌下將已預熱到攝氏110度的MDI液體一次加入，持續攪拌3分鐘，紀錄第2分鐘之料溫，至第3分鐘時，將反應內容物倒入盛盤並取樣取樣在攝氏190度，荷重2160克的條件下分析熔融流動指數(以MI(190℃，2160g，10min)表示)，同時也將該盛盤放至預熱在攝氏70度的循環烘箱中熟成24小時後取出。紀錄TPU成品外觀，接觸手心溫度感覺其柔軟度之變化，測試TPU軟化點，玻璃轉移溫度(Tg)並進行耐水解測試，將實施例13~實施例16之相關數據及結果示於表五，將實施例17、實施例18及比較例2之相關數據及結果示於表六。又，使用傅立葉轉換紅外線光譜儀(儀器機型：Thermo Nicolet 330FT-IR)，對實施例13~實施例18所得到之TPU成品(含有DOPO-ITA聚酯結構者)進行衰減全反射(ATR)測試，得到之紅外光譜圖如圖8~13所示，確認為本案發明所欲完成之熱塑性聚胺基甲酸酯(TPU)，另，對比較例2之TPU成品所測得之紅外光譜圖則如圖14所示。 Experiment of the present invention containing 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) polyester structure TPU The method of small-volume production is described as follows (Example 13~Example 18 and Comparative Example 2): In Example 1~Example 6 containing 10-(2,3-dicarboxypropyl)-9, Combination of 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) polyester structure polyester diol and selective combination of aliphatic polyglycol, diol and The mixture of additives (1 gram of antioxidant 1010, 1 gram of Montan wax, 0.75 grams of ultraviolet absorber UV-329 and 25 mg of catalyst T9) was put into a 1 liter metal bucket and mechanically stirred to The heating plate keeps the internal temperature controlled at 110 Celsius Add the MDI liquid preheated to 110 degrees Celsius under stirring. Continue stirring for 3 minutes. Record the temperature of the material at the second minute. At the third minute, pour the reaction contents into the tray and sample at Celsius. Analyze the melt flow index (expressed in MI (190°C, 2160g, 10min)) under the condition of 190°C and a load of 2160g. At the same time, put the pan to preheat and mature in a circulating oven at 70°C for 24 hours and then take it out . Record the appearance of the TPU finished product, feel the change in softness at the temperature of the palm of the hand, test the TPU softening point, the glass transition temperature (Tg) and perform the hydrolysis resistance test. The relevant data and results of Examples 13 to 16 are shown in Table 5. The relevant data and results of Example 17, Example 18 and Comparative Example 2 are shown in Table 6. In addition, a Fourier transform infrared spectrometer (instrument model: Thermo Nicolet 330FT-IR) was used to perform attenuated total reflectance (ATR) tests on the TPU products obtained in Examples 13 to 18 (containing DOPO-ITA polyester structure) , The obtained infrared spectrograms are shown in Figures 8-13, which are confirmed to be the thermoplastic polyurethane (TPU) that the present invention intends to complete. In addition, the infrared spectrograms measured for the TPU product of Comparative Example 2 As shown in Figure 14.

本發明也放大製備含有二羧基苯基聚酯結構之熱塑性聚胺基甲酸酯(TPU)，應用於不織布製造，也評估作為熱熔膠之效果，實施方式說明如下。 The present invention also scales up the preparation of thermoplastic polyurethane (TPU) containing a dicarboxyphenyl polyester structure, which is applied to the manufacture of non-woven fabrics, and is also evaluated as a hot melt adhesive. The embodiments are described below.

實施例19：將100公斤含有二羧基苯基聚酯結構之聚酯二醇PD-56添加抗氧化劑1010(0.436公斤)及觸媒T9(15克)，預熱至攝氏105度/流速345kg/hr，1,4-丁二醇預熱至攝氏50度且設定流速31.48kg，二苯基甲烷二異氰酸酯(也簡稱為MDI)預熱至攝氏70度且設定流速125.2kg/hr，其MDI/(聚酯二醇+二醇)的流量表所示之莫耳比值為0.955，打入合成灌注機高速混合後，以每分鐘8.5公斤的灌注速度，連續灌注入塗有離型劑的盛盤中，藉由傳動皮帶輸送經過攝氏100度烘箱，確定成形後環境溫度下靜置24小時，取下膠塊解碎並造粒。成品分析熔融流動指數與玻璃轉移溫度(Tg)。 Example 19: Add antioxidant 1010 (0.436 kg) and catalyst T9 (15 g) to 100 kg of polyester diol PD-56 containing dicarboxyphenyl polyester structure, and preheat to 105°C/flow rate 345kg/ hr, 1,4-butanediol is preheated to 50 degrees Celsius and set flow rate 31.48kg, diphenylmethane diisocyanate (also referred to as MDI) is preheated to 70 degrees Celsius and set flow rate 125.2kg/hr, its MDI/ The molar ratio shown in the flow table of (polyester diol + diol) is 0.955. After being injected into a synthetic infusion machine for high-speed mixing, the injection rate is 8.5 kg per minute and continuously poured into the tray coated with release agent. In the process, the belt is conveyed through an oven at 100 degrees Celsius, and after forming, it is allowed to stand for 24 hours at an ambient temperature, and the rubber block is removed to disintegrate and granulate. Finished product analysis melt flow index and glass transition temperature (Tg).

實施例20及實施例21及改變MDI/(聚酯二醇+二醇)的流量表所示之莫耳比值至0.974及0.993，其餘操作皆同實施例19。 In Example 20 and Example 21, the molar ratio shown in the flow meter of MDI/(polyester diol + diol) was changed to 0.974 and 0.993, and the other operations were the same as in Example 19.

比較例3則是選用脂肪族聚酯二醇組成物，其MDI/(聚酯二醇+二醇)的流量表所示之莫耳比值至0.980，其餘操作同實施例19。 In Comparative Example 3, an aliphatic polyester diol composition was selected, and the molar ratio shown in the flow meter of MDI/(polyester diol + diol) was 0.980. The other operations were the same as in Example 19.

將實施例19~實施例21及比較例3之相關數據及結果示於表七。 The relevant data and results of Example 19 to Example 21 and Comparative Example 3 are shown in Table 7.

表七所述硬度、拉伸強度、斷裂伸長率、耐水解試驗、軟化點之測試是使用射出片進行測試，將實施例19、實施例20、實施例21及比較例3製得之TPU膠粒，使用之射出機型為義展YC V-90型，射出溫度為攝氏170~205度，模具溫度為攝氏25~30度。 The hardness, tensile strength, elongation at break, hydrolysis resistance test, and softening point test described in Table 7 are tested by using an injection sheet. The TPU glue prepared in Example 19, Example 20, Example 21 and Comparative Example 3 The injection model used is Yizhan YC V-90, the injection temperature is 170~205°C, and the mold temperature is 25~30°C.

硬度測試係參考美國標準方法(ASTM)D1238來進行。 The hardness test is carried out with reference to American Standard Method (ASTM) D1238.

拉伸強度及斷裂伸長率測試係參考日本標準方法(JIS)K7311來進行。 The tensile strength and elongation at break are tested with reference to Japanese Standard Method (JIS) K7311.

又，使用傅立葉轉換紅外線光譜儀(儀器機型：Thermo Nicolet 330FT-IR)，對實施例19~實施例21所得到之含有二羧基苯基聚酯結構的TPU成品進行衰減全反射(ATR)測試而得到的紅外光譜圖如圖15~17所示，確認為本案發明所欲完成之熱塑性聚胺基甲酸酯(TPU)，另，對比較例3之TPU成品所測得之紅外光譜圖則如圖18所示。 In addition, a Fourier transform infrared spectrometer (instrument model: Thermo Nicolet 330FT-IR) was used to perform attenuated total reflectance (ATR) tests on the TPU products containing dicarboxyphenyl polyester structure obtained in Examples 19 to 21. The obtained infrared spectrograms are shown in Figures 15 to 17, which are confirmed to be the thermoplastic polyurethane (TPU) that the present invention intends to complete. In addition, the infrared spectrograms measured for the TPU product of Comparative Example 3 are as follows Shown in Figure 18.

根據表七，含有本發明之熱塑性聚胺基甲酸酯的熱熔接著劑其在攝氏90度的熱水中至發生水解的天數皆至少在40天以上，相對於此，由比較例3之熱塑性聚胺基甲酸酯製成的熱熔接著劑8天即發生水解，故可知由本發明之含有二羧基苯基聚酯結構之熱塑性聚胺基甲酸酯製成的熱熔接著劑具有優異之耐高溫水解性。 According to Table 7, the hot melt adhesive containing the thermoplastic polyurethane of the present invention has at least 40 days or more of hydrolysis in hot water at 90 degrees Celsius. In contrast to this, from the comparison of Comparative Example 3 The hot melt adhesive made of thermoplastic polyurethane is hydrolyzed in 8 days, so it can be known that the hot melt adhesive made of the thermoplastic polyurethane containing dicarboxyphenyl polyester structure of the present invention has excellent properties The high temperature hydrolysis resistance.

又，使用實施例19、實施例20、實施例21及比較例3製得之TPU膠粒進行熔噴試驗，以入料溫度攝氏110度至120度，噴嘴溫度攝氏225至235度，紡壓2500至3000psi之條件進行熔噴，室溫下以滾輪收取0.5mm的不織布。 In addition, the TPU pellets prepared in Example 19, Example 20, Example 21, and Comparative Example 3 were used for melt-blowing tests. The feed temperature was 110°C to 120°C, the nozzle temperature was 225°C to 235°C, and the spinning pressure Melt blown under the conditions of 2500 to 3000 psi, and take up 0.5mm non-woven fabric with rollers at room temperature.

試驗結果，實施例19、實施例20及實施例21之TPU膠粒都能順利成絲，且在室溫下就能順利收取，得到表面平順且有挺性的TPU不織布。而比較例3之TPU膠粒雖可成絲，但冷卻固化速度慢，使得不織布表面會有結球粒狀物，在室溫下收取時不織布自身互黏不易分開。 As a result of the test, the TPU rubber particles of Example 19, Example 20, and Example 21 can be smoothly formed into filaments, and can be smoothly collected at room temperature, and TPU non-woven fabrics with a smooth and stiff surface are obtained. Although the TPU rubber particles of Comparative Example 3 can be filamentous, the cooling and solidification speed is slow, so that the surface of the non-woven fabric will have nodular pellets, and the non-woven fabric will stick to each other and not easy to separate when taken at room temperature.

另一方面，參考中國國家標準GBT 2791測試方法，將實施例19、實施例20及實施例21熔噴得到的TPU不織布夾在兩片聚酯梭織布中進行貼合測試，使用熱壓機進行貼合測試，溫度設定在攝氏130℃，時間為25秒，壓力設定為5kg/cm²；另將比較例3熔噴得到的TPU不織布也同上操作，其熱壓機溫度設定在攝氏100℃，時間為10秒，壓力設定為5kg/cm²；再將以上得到之貼合織物試片放置16小時後，裁切成2.5cm×12cm長條，使用高鐵科技萬能試驗機，型號為AI-7000S，進行剝離強度測試，拉伸速度100mm/min，根據表七，結果都能在1.6kgf/cm以上，都具備熱熔膠的功能。特別的是，含有本發明之熱塑性聚胺基甲酸酯作為熱熔膠的織布外觀較挺，接觸到手心或是皮膚，會變得柔軟，而使用比較例3之熱塑性聚胺基甲酸酯作為熱熔膠的織布，比較容易收縮產生皺摺。 On the other hand, referring to the Chinese national standard GBT 2791 test method, the TPU non-woven fabric obtained by meltblowning in Example 19, Example 20 and Example 21 was sandwiched between two pieces of polyester woven fabric for bonding test, using a hot press The bonding test was carried out, the temperature was set at 130°C, the time was 25 seconds, and the pressure was set at 5kg/cm ² ; the TPU non-woven fabric obtained by meltblown in Comparative Example 3 was also operated as above, and the temperature of the hot press was set at 100°C , The time is 10 seconds, and the pressure is set to 5kg/cm ² ; and after placing the fabric test piece obtained above for 16 hours, it is cut into 2.5cm×12cm strips, using the high-speed rail technology universal testing machine, model AI- 7000S, the peel strength test, the tensile speed is 100mm/min, according to Table 7, the results can be above 1.6kgf/cm, all have the function of hot melt adhesive. In particular, the woven fabric containing the thermoplastic polyurethane of the present invention as a hot melt adhesive has a stiffer appearance and becomes softer when it touches the palm of the hand or the skin. The thermoplastic polyurethane of Comparative Example 3 is used As the woven fabric of hot melt adhesive, ester is easier to shrink and produce wrinkles.

又，放大製備含有10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構之TPU的方法與上述放大製備含有二羧基苯基聚酯結構之熱塑性聚胺基甲酸酯(TPU)的方法相同，故在此不再敘述。 In addition, scale-up preparation of TPU containing 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) polyester structure The method is the same as the above-mentioned method for amplifying the preparation of thermoplastic polyurethane (TPU) containing dicarboxyphenyl polyester structure, so it will not be described here.

另外，如表八所示，將實施例19、實施例20及實施例21得到之TPU膠粒以及熔噴得到之TPU不織布，分別以差示掃描熱量分析儀(DSC)分析其結晶溫度(Tc)、玻璃轉移溫度(Tg)及熔點(Tm)，也以凝膠層析儀(GPC)分析其數目平均分子量(Mn)、重量平均分子量(Mw)及峰位分子量(Mp)，發現了使用實施例19~21之TPU粒子製作成的熔噴布，該熔噴布的分子量會大於該所使用的TPU粒子，其詳細的機制雖然尚未清楚明白，但由該熔噴布製成的成型品因分子量大而具有強固不易損壞的優點。 In addition, as shown in Table 8, the TPU rubber particles obtained in Example 19, Example 20, and Example 21 and the TPU non-woven fabric obtained by meltblown were analyzed by differential scanning calorimetry (DSC) to analyze their crystallization temperature (Tc). ), glass transition temperature (Tg) and melting point (Tm). The number average molecular weight (Mn), weight average molecular weight (Mw) and peak molecular weight (Mp) were also analyzed by gel chromatography (GPC). The melt blown cloth made of TPU particles in Examples 19-21 has a molecular weight greater than that of the TPU particles used. Although the detailed mechanism is not yet clear, the molded article made of the melt blown cloth is due to The molecular weight is large and it has the advantage of being strong and not easily damaged.

上述各實施形態只要技術上允許，則能適當加以組合來實施。又，本發明所屬技術領域中具有通常知識者基於上述各實施形態加以修正或變更而成者，只要具備有本發明之精神，則亦包含於本發明之範圍內。 Each of the above-mentioned embodiments can be implemented in appropriate combination as long as it is technically permitted. In addition, those having ordinary knowledge in the technical field to which the present invention pertains are modified or changed based on the above-mentioned embodiments, as long as they possess the spirit of the present invention, they are also included in the scope of the present invention.

本發明之熱塑性聚胺基甲酸酯，由於其玻璃轉化溫度介於環境溫度與人體體溫之間，故使用該熱塑性聚胺基甲酸酯所製成之成型品具有容易定型、不易產生皺折、於展示或是放置時可產生挺拔有型之視覺感等優點，而當與人體接觸時則會覺得柔軟舒適，因此特別適用於紡織品(例如衣褲、帽子、標籤布、窗簾等)、鞋材、裝飾品(例如錶帶、腕帶等)、玩具、運動用品及生活用品等，具有產業利用性。 The thermoplastic polyurethane of the present invention has a glass transition temperature between the ambient temperature and the body temperature of the human body, so molded articles made of the thermoplastic polyurethane are easy to shape and not easy to produce wrinkles , It can produce a straight and stylish visual sense when displayed or placed, and it will feel soft and comfortable when in contact with the human body, so it is especially suitable for textiles (such as underwear, hats, label cloth, curtains, etc.), shoes Materials, decorations (such as watchbands, wristbands, etc.), toys, sports goods and daily necessities, etc., have industrial applications.

又，若使用本發明之含有由該式二表示之10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構的聚酯二醇，則可製造上述之熱塑性聚胺基甲酸酯，故本發明之聚酯二醇亦具有產業利用性。 Moreover, if the present invention contains 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide represented by the formula II ( DOPO-ITA) polyester diol with a polyester structure can produce the above-mentioned thermoplastic polyurethane, so the polyester diol of the present invention also has industrial applicability.

Claims

一種玻璃轉移溫度(Tg)介於環境溫度與體溫之間的熱塑性聚胺基甲酸酯(TPU)，含有由式一表示之二羧基苯基聚酯結構或由式二表示之10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構的任一聚酯結構，該聚酯結構的平均分子量(Mn)為700至2500g/mole之範圍，

其中，該二羧基苯基聚酯結構相對於熱塑性聚胺基甲酸酯(TPU)整體的比例，以莫耳百分比計，為6%~25%；其中，該熱塑性聚胺基甲酸酯(TPU)的軟段的重量百分比為60%至80%。 A thermoplastic polyurethane (TPU) with a glass transition temperature (Tg) between ambient temperature and body temperature, containing a dicarboxyphenyl polyester structure represented by formula one or 10-(2) represented by formula two ,3-Dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) any polyester structure of the polyester structure, the polyester structure The average molecular weight (Mn) is in the range of 700 to 2500g/mole,

Wherein, the ratio of the dicarboxyphenyl polyester structure to the whole thermoplastic polyurethane (TPU) is 6% to 25% in mole percentage; wherein, the thermoplastic polyurethane ( The weight percentage of the soft segment of TPU) is 60% to 80%.

如請求項1所述之熱塑性聚胺基甲酸酯(TPU)，其所含之10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構相對於熱塑性聚胺基甲酸酯(TPU)整體的比例，以莫耳百分比計，為5%~20%。 The thermoplastic polyurethane (TPU) as described in claim 1, which contains 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphorus The ratio of the phenanthrene-10-oxide (DOPO-ITA) polyester structure to the entire thermoplastic polyurethane (TPU) is 5%-20% in molar percentage.

如請求項1至2中任一項所述之熱塑性聚胺基甲酸酯(TPU)，其玻璃轉移溫度(Tg)係介於攝氏10度至攝氏40度之間。 The thermoplastic polyurethane (TPU) according to any one of claims 1 to 2, its glass transition temperature (Tg) is between 10 degrees Celsius and 40 degrees Celsius.

如請求項1至2中任一項所述之熱塑性聚胺基甲酸酯(TPU)，其玻璃轉移溫度(Tg)係介於攝氏15度至攝氏28度之間。 The thermoplastic polyurethane (TPU) according to any one of claims 1 to 2, its glass transition temperature (Tg) is between 15 degrees Celsius and 28 degrees Celsius.

如請求項1至2中任一項所述之熱塑性聚胺基甲酸酯(TPU)，其軟化點係介於攝氏50度至攝氏100度之間。 The thermoplastic polyurethane (TPU) according to any one of claims 1 to 2 has a softening point between 50°C and 100°C.

如請求項1至2中任一項所述之熱塑性聚胺基甲酸酯(TPU)，其軟化點係介於攝氏60度至攝氏85度之間。 The thermoplastic polyurethane (TPU) according to any one of claims 1 to 2 has a softening point between 60°C and 85°C.

如請求項1至2中任一項所述之熱塑性聚胺基甲酸酯(TPU)，其具有熱熔膠功能。 The thermoplastic polyurethane (TPU) according to any one of claims 1 to 2, which has a hot melt adhesive function.

一種無溶劑熱熔膠，係使用請求項1至7中任一項所述之熱塑性聚胺基甲酸酯(TPU)製成。 A solvent-free hot melt adhesive, which is made of the thermoplastic polyurethane (TPU) described in any one of claims 1 to 7.

一種不織布，係使用請求項1至7中任一項所述之熱塑性聚胺基甲酸酯(TPU)製成。 A non-woven fabric made of the thermoplastic polyurethane (TPU) described in any one of claims 1 to 7.

一種成型品，係使用請求項1至7中任一項所述之熱塑性聚胺基甲酸酯(TPU)製成。 A molded product made using the thermoplastic polyurethane (TPU) described in any one of claims 1 to 7.

如請求項10所述之成型品，其為紡織品、鞋材、裝飾品、玩具、運動用品及生活用品。 The molded article described in claim 10, which is textiles, shoe materials, decorations, toys, sports goods, and daily necessities.

一種聚酯二醇，係用以製造請求項1所述之含有由式二表示之10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構的熱塑性聚胺基甲酸酯(TPU)，該聚酯二醇所含有之由式二表示之10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構相對於聚酯二醇整體的比例，以莫耳百分比計，為30%~70%，該聚酯結構的平均分子量(Mn)為700至2500g/mole之範圍，

A polyester diol, which is used to manufacture the 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphorus represented by formula 2 described in claim 1 Polyphenanthrene-10-oxide (DOPO-ITA) polyester structure thermoplastic polyurethane (TPU), the polyester diol contains 10-(2,3-dicarboxypropane represented by formula two) (Base)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-ITA) The ratio of the polyester structure relative to the entire polyester diol, in mole percentage, is 30%~70%, the average molecular weight (Mn) of the polyester structure is in the range of 700 to 2500 g/mole,

如請求項12所述之聚酯二醇，其羥基值介於160.3至44.8毫克氫氧化鉀/克(以下以mgKOH/g表示)。 The polyester diol according to claim 12 has a hydroxyl value of 160.3 to 44.8 mg potassium hydroxide/g (hereinafter expressed as mgKOH/g).

如請求項12或13所述之聚酯二醇，其中，該10-(2,3-二羧基丙基)-9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO-ITA)聚酯結構中的二羧酸為伊康酸與9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO)的加成物，或者為伊康酸、選自琥珀酸或1,6-己二酸之任一者及9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物(DOPO)的加成物。 The polyester diol according to claim 12 or 13, wherein the 10-(2,3-dicarboxypropyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- The dicarboxylic acid in the oxide (DOPO-ITA) polyester structure is an adduct of itaconic acid and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), Or it is the addition of itaconic acid, any one selected from succinic acid or 1,6-adipic acid and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) Into things.

如請求項12或13所述之聚酯二醇，其二醇單體選自C2~C8的脂肪族二醇。 The polyester diol according to claim 12 or 13, wherein the diol monomer is selected from C2-C8 aliphatic diols.

如請求項15所述之聚酯二醇，其中，該C2~C8的脂肪族二醇為乙二醇、1,2-丙二醇或1,3-丙二醇之丙二醇、丁二醇、2-甲基-1,3-丙二醇、二乙二醇、戊二醇、新戊二醇、己二醇、1,4-環己二醇、2-乙基己二醇、辛二醇或此等之組合。 The polyester diol according to claim 15, wherein the C2-C8 aliphatic diol is propylene glycol, butylene glycol, 2-methyl ethylene glycol, 1,2-propanediol or 1,3-propanediol -1,3-propanediol, diethylene glycol, pentanediol, neopentyl glycol, hexanediol, 1,4-cyclohexanediol, 2-ethylhexanediol, octanediol or a combination of these .

如請求項12或13所述之聚酯二醇，其為選自下述式三所示之DOPO/伊康酸/1,6-己二醇之聚酯二醇(分子式為(C₁₇H₁₅O₆P.C₆H₁₄O₂)_x)、DOPO/伊康酸/二乙二醇的聚酯二醇(分子式為(C₁₇H₁₅O₆P.C₄H₁₀O₃)_x)、 DOPO/伊康酸/己二酸/己二醇的聚酯二醇(分子式為(C₁₇H₁₅O₆P.C₆H₁₀O₄.C₆H₁₄O₂)_x)、DOPO/伊康酸/琥珀酸/二乙二醇的聚酯二醇(分子式為(C₁₇H₁₅O₆P.C₄H₆O₄.C₄H₁₀O₃)_x)中之任一者或其等之組合，

式中，n為1~10，x為1~10，b為1~6。 The polyester diol according to claim 12 or 13, which is a polyester diol selected from DOPO/iconic acid/1,6-hexanediol shown in the following formula 3 (the molecular formula is (C ₁₇ H ₁₅ O ₆ PC ₆ H ₁₄ O ₂ ) _x ), DOPO/Iconic acid/diethylene glycol polyester diol (molecular formula (C ₁₇ H ₁₅ O ₆ PC ₄ H ₁₀ O ₃ ) _x ), DOPO/ Polyester diol of itaconic acid/adipic acid/hexanediol (molecular formula is (C ₁₇ H ₁₅ O ₆ PC ₆ H ₁₀ O ₄ .C ₆ H ₁₄ O ₂ ) _x ), DOPO/itaconic acid/succinate Acid/diethylene glycol polyester diol (the molecular formula is (C ₁₇ H ₁₅ O ₆ PC ₄ H ₆ O ₄ .C ₄ H ₁₀ O ₃ ) _x ) any one or a combination thereof,

In the formula, n is 1~10, x is 1~10, and b is 1~6.

如請求項17所述之聚酯二醇，其酸價<1.8mgKOH/g。 The polyester diol described in claim 17 has an acid value of <1.8 mgKOH/g.