TW202112865A - Moisture-curable polyurethane hot-melt resin composition - Google Patents
Moisture-curable polyurethane hot-melt resin composition Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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Abstract
Description
本發明是有關於一種濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。The invention relates to a moisture-curing polyurethane hot-melt resin composition.
濕氣硬化型聚胺基甲酸酯熱熔接著劑由於是無溶劑,因此作為環境對應型接著劑,迄今仍進行以纖維接合/建材積層為中心的各式各樣的研究,於產業界亦被廣泛利用。Moisture-curing polyurethane hot-melt adhesives are solvent-free. Therefore, as environmentally compatible adhesives, various researches centered on fiber bonding and building materials lamination have been carried out, and they are also used in the industry. Is widely used.
所述濕氣硬化型聚胺基甲酸酯接著劑藉由作為其主劑的胺基甲酸酯預聚物所具有的異氰酸酯基的濕氣硬化而顯現最終的接著強度,但於各式各樣的基材的貼合中,即使是剛剛塗佈接著劑之後,亦要求高的初期接著強度。The moisture-curing polyurethane adhesive exhibits the final adhesive strength by moisture curing of the isocyanate group of the urethane prepolymer as its main agent, but it is in various types. In the bonding of such substrates, even immediately after application of the adhesive, high initial bonding strength is required.
為了獲得高的初期接著強度,通常大量使用結晶性聚酯多元醇(例如,參照專利文獻1)。然而,關於所述方法,有如下指摘:黏度高且塗佈困難,或所獲得的硬化皮膜亦變硬,因此,例如於纖維用途等要求柔軟性的領域中,手感降低。另外,若大量使用聚酯多元醇,則耐水解性亦變得不良,因此現狀是未推進利用。 [現有技術文獻] [專利文獻]In order to obtain high initial adhesive strength, crystalline polyester polyols are generally used in large amounts (for example, refer to Patent Document 1). However, regarding the above method, there are accusations that the viscosity is high and coating is difficult, or the obtained hardened film is also hard, so, for example, in fiber applications and other fields requiring flexibility, the hand feel is reduced. In addition, if a large amount of polyester polyol is used, the hydrolysis resistance also becomes poor, so the current situation is that the utilization is not promoted. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利特開2011-190309號公報[Patent Document 1] Japanese Patent Laid-Open No. 2011-190309
[發明所欲解決之課題] 本發明所欲解決的課題為提供一種低黏度性、初期接著強度、柔軟性、塗佈適應性及耐水解性優異的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。 [解決課題之手段][The problem to be solved by the invention] The problem to be solved by the present invention is to provide a moisture-curable polyurethane hot-melt resin composition with excellent low viscosity, initial adhesive strength, flexibility, coating adaptability, and hydrolysis resistance. [Means to solve the problem]
本發明提供一種濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物,含有以多元醇(A)及聚異氰酸酯(B)為原料的具有異氰酸酯基的胺基甲酸酯預聚物(i),且所述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物的特徵在於:所述多元醇(A)含有以己二酸為原料的聚酯多元醇(a1)、聚醚多元醇(a2)及芳香族聚酯多元醇(a3),所述聚酯多元醇(a1)及所述聚醚多元醇(a2)的合計使用量多於所述芳香族聚酯多元醇(a3)的使用量。 [發明的效果]The present invention provides a moisture-curing polyurethane hot-melt resin composition, which contains a polyurethane prepolymer (i ), and the moisture-curing polyurethane hot-melt resin composition is characterized in that: the polyol (A) contains adipic acid-based polyester polyol (a1), polyether polyol Alcohol (a2) and aromatic polyester polyol (a3), the total usage amount of the polyester polyol (a1) and the polyether polyol (a2) is greater than that of the aromatic polyester polyol (a3) ) Usage. [Effects of the invention]
本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物的低黏度性、初期接著強度、柔軟性、塗佈適應性及耐水解性優異。因此,本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物可特別適宜用於纖維用途。The moisture-curing polyurethane hot-melt resin composition of the present invention is excellent in low viscosity, initial adhesive strength, flexibility, coating suitability, and hydrolysis resistance. Therefore, the moisture-curing polyurethane hot-melt resin composition of the present invention can be particularly suitably used for fiber applications.
本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物包含以含有特定多元醇的多元醇(A)及聚異氰酸酯(B)為原料的具有異氰酸酯基的胺基甲酸酯預聚物(i)。The moisture-curing polyurethane hot-melt resin composition of the present invention comprises a polyol (A) containing a specific polyol and a polyisocyanate (B) as raw materials, and a urethane prepolymer having an isocyanate group物(i).
所述多元醇(A)含有以己二酸為原料的聚酯多元醇(a1)、聚醚多元醇(a2)及芳香族聚酯多元醇(a3)。The polyol (A) contains a polyester polyol (a1), a polyether polyol (a2), and an aromatic polyester polyol (a3) using adipic acid as a raw material.
於獲得優異的初期接著強度及柔軟性方面,所述聚酯多元醇(a1)是必需成分,例如可使用包含己二酸的多元酸與具有兩個以上的羥基的化合物的反應產物。The polyester polyol (a1) is an essential component in order to obtain excellent initial adhesive strength and flexibility. For example, a reaction product of a polybasic acid containing adipic acid and a compound having two or more hydroxyl groups can be used.
作為所述己二酸以外的多元酸,例如可使用琥珀酸、庚二酸、辛二酸、壬二酸、癸二酸(sebacic acid)、癸二酸(decanedioic acid)、十二烷二酸、二十烷二酸、檸康酸、衣康酸、檸康酸酐、衣康酸酐等脂肪族多元酸;1,4-環己烷二羧酸等脂環式多元酸等。該些多元酸可單獨使用,亦可併用兩種以上。作為所述己二酸的使用量,於所述多元酸中,較佳為50質量%以上,更佳為70質量%以上,進而佳為80質量%以上,特佳為90質量%以上。Examples of polybasic acids other than adipic acid include succinic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, and dodecanedioic acid. , Eicosandioic acid, citraconic acid, itaconic acid, citraconic anhydride, itaconic anhydride and other aliphatic polybasic acids; 1,4-cyclohexanedicarboxylic acid and other alicyclic polybasic acids, etc. These polybasic acids may be used alone, or two or more of them may be used in combination. The amount of the adipic acid used in the polybasic acid is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more.
作為所述具有兩個以上的羥基的化合物,例如可使用乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,12-十二烷二醇、二乙二醇、三乙二醇、四乙二醇、新戊二醇、1,2-丁二醇、1,3-丁二醇、2-甲基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、3-甲基-1,5-戊二醇、2-乙基-2-丁基-1,3-丙二醇、2-甲基-1,8-辛二醇、2,4-二乙基-1,5-戊二醇、三羥甲基乙烷、三羥甲基丙烷、季戊四醇等脂肪族化合物;環戊二醇、環己二醇、環己烷二甲醇、氫化雙酚A、該些的環氧烷加成物等脂環式化合物等。該些化合物可單獨使用,亦可併用兩種以上。該些中,就可獲得更進一步優異的初期接著強度及柔軟性的方面而言,較佳為使用脂肪族化合物及/或脂環式化合物,更佳為使用選自由乙二醇、1,4-丁二醇、二乙二醇、新戊二醇、1,2-丁二醇、1,3-丁二醇、2-甲基-1,3-丙二醇、3-甲基-1,5-戊二醇、2-乙基-2-丁基-1,3-丙二醇及2,4-二乙基-1,5-戊二醇所組成的群組中的一種以上的化合物。As the compound having two or more hydroxyl groups, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 ,7-Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol , Tetraethylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3- Propylene glycol, 3-methyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,4-diethyl Alpha-1,5-pentanediol, trimethylolethane, trimethylolpropane, pentaerythritol and other aliphatic compounds; cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, Alicyclic compounds such as these alkylene oxide adducts and the like. These compounds may be used alone, or two or more of them may be used in combination. Among these, it is preferable to use an aliphatic compound and/or an alicyclic compound, and more preferably to use an aliphatic compound and/or an alicyclic compound, in terms of obtaining further excellent initial bonding strength and flexibility, and more preferably to use selected from ethylene glycol, 1,4 -Butanediol, diethylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5 -One or more compounds in the group consisting of pentanediol, 2-ethyl-2-butyl-1,3-propanediol, and 2,4-diethyl-1,5-pentanediol.
作為所述聚酯多元醇(a1)的數量平均分子量,就可獲得更進一步優異的初期接著強度及柔軟性的方面而言,較佳為小於2,800,更佳為300~2,500的範圍,進而佳為600~2,200的範圍。再者,所述聚酯多元醇(a1)的數量平均分子量表示藉由凝膠滲透層析(Gel Permeation Chromatography,GPC)法進行測定所得的值。The number average molecular weight of the polyester polyol (a1) is preferably less than 2,800, more preferably in the range of 300 to 2,500, and still more preferably, in terms of obtaining further excellent initial adhesive strength and flexibility. It is in the range of 600 to 2,200. In addition, the number average molecular weight of the polyester polyol (a1) represents a value measured by a gel permeation chromatography (Gel Permeation Chromatography, GPC) method.
作為所述聚酯多元醇(a1)的含有率,就可獲得更進一步優異的初期接著強度、塗佈適應性及柔軟性的方面而言,於多元醇(A)中,較佳為5質量%~80質量%的範圍,更佳為10質量%~75質量%的範圍,進而佳為15質量%~70質量%的範圍。The content of the polyester polyol (a1) is preferably 5 mass in the polyol (A) in terms of obtaining further excellent initial adhesive strength, coating suitability, and flexibility. The range of% to 80% by mass, more preferably the range of 10% to 75% by mass, and still more preferably the range of 15% to 70% by mass.
於獲得優異的低黏度性、柔軟性及耐水解性方面,所述聚醚多元醇(a2)是必需成分。作為所述聚醚多元醇(a2),例如可使用聚氧伸烷基多元醇;將具有兩個以上的活性氫原子的化合物的一種或兩種以上用作起始劑,使環氧烷等環狀醚開環聚合而成者等。In order to obtain excellent low viscosity, flexibility and hydrolysis resistance, the polyether polyol (a2) is an essential component. As the polyether polyol (a2), for example, polyoxyalkylene polyol can be used; one or two or more compounds having two or more active hydrogen atoms are used as the initiator, and alkylene oxide, etc. Ring-opening polymerization of cyclic ether, etc.
所述環狀醚的碳原子數較佳為2~10,更佳為2~6,進而佳為2~4。所述環狀醚中所含的氫原子可經鹵素原子取代。作為所述環狀醚,可使用一種或兩種以上,例如可使用環氧乙烷、環氧丙烷、1,2-環氧丁烷、2,3-環氧丁烷、氧化苯乙烯、表氯醇、四氫呋喃、烷基化四氫呋喃等。The number of carbon atoms of the cyclic ether is preferably 2-10, more preferably 2-6, and still more preferably 2-4. The hydrogen atom contained in the cyclic ether may be substituted with a halogen atom. As the cyclic ether, one kind or two or more kinds may be used. For example, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, and Chlorohydrin, tetrahydrofuran, alkylated tetrahydrofuran, etc.
作為所述起始劑,可使用一種或兩種以上,例如可使用乙二醇、二乙二醇、丙二醇、三亞甲基二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、水等具有兩個活性氫原子的化合物;甘油、二甘油、三羥甲基乙烷、三羥甲基丙烷、己三醇、單乙醇胺、二乙醇胺、三乙醇胺、乙二胺、季戊四醇、糖類等具有三個以上的活性氫原子的化合物等。As the initiator, one kind or two or more kinds can be used, for example, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol can be used , 1,6-hexanediol, neopentyl glycol, water and other compounds with two active hydrogen atoms; glycerol, diglycerol, trimethylolethane, trimethylolpropane, hexanetriol, monoethanolamine, Compounds having three or more active hydrogen atoms, such as diethanolamine, triethanolamine, ethylenediamine, pentaerythritol, sugars, and the like.
作為所述聚醚多元醇(a2),就可獲得更進一步優異的低黏度性、柔軟性、塗佈適應性及耐水解性的方面而言,較佳為使用聚氧丙烯二醇及/或聚四亞甲基二醇,更佳為聚氧丙烯二醇。As the polyether polyol (a2), it is preferable to use polyoxypropylene glycol and/or in terms of obtaining further excellent low viscosity, flexibility, coating adaptability, and hydrolysis resistance. Polytetramethylene glycol, more preferably polyoxypropylene glycol.
作為所述聚醚多元醇(a2)的數量平均分子量,就可獲得更進一步優異的低黏度性、柔軟性、塗佈適應性及耐水解性的方面而言,較佳為小於2,800,更佳為300~2,500的範圍,進而佳為600~2,200的範圍。再者,所述聚醚多元醇(a2)的數量平均分子量表示藉由凝膠滲透層析(GPC)法進行測定所得的值。The number average molecular weight of the polyether polyol (a2) is preferably less than 2,800 in terms of obtaining further excellent low viscosity, flexibility, coating adaptability, and hydrolysis resistance. It is the range of 300-2,500, More preferably, it is the range of 600-2,200. In addition, the number average molecular weight of the polyether polyol (a2) represents a value measured by a gel permeation chromatography (GPC) method.
作為所述聚醚多元醇(a2)的含有率,就可獲得更進一步優異的低黏度性、柔軟性及耐水解性的方面而言,於多元醇(A)中,較佳為5質量%~80質量%的範圍,更佳為10質量%~75質量%的範圍,進而佳為15質量%~70質量%的範圍。The content of the polyether polyol (a2) is preferably 5 mass% in the polyol (A) in terms of obtaining further excellent low viscosity, flexibility, and hydrolysis resistance. It is the range of -80 mass %, More preferably, it is the range of 10 mass%-75 mass %, More preferably, it is the range of 15 mass%-70 mass %.
於獲得優異的初期接著強度及柔軟性方面,所述芳香族聚酯多元醇(a3)是必需成分。作為所述芳香族聚酯多元醇(a3),例如可使用具有羥基的化合物與包含芳香族多元酸的多元酸的反應產物;具有兩個以上的羥基的芳香族化合物與多元酸的反應產物;具有兩個以上的羥基的芳香族化合物與包含芳香族多元酸的多元酸的反應產物等。The aromatic polyester polyol (a3) is an essential component in terms of obtaining excellent initial adhesive strength and flexibility. As the aromatic polyester polyol (a3), for example, a reaction product of a compound having a hydroxyl group and a polybasic acid containing an aromatic polybasic acid; a reaction product of an aromatic compound having two or more hydroxyl groups and a polybasic acid can be used; A reaction product of an aromatic compound having two or more hydroxyl groups and a polybasic acid containing an aromatic polybasic acid, and the like.
作為所述具有羥基的化合物,例如可使用乙二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,12-十二烷二醇、二乙二醇、三乙二醇、四乙二醇、新戊二醇、1,2-丁二醇、1,3-丁二醇、2-甲基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、3-甲基-1,5-戊二醇、2-乙基-2-丁基-1,3-丙二醇、2-甲基-1,8-辛二醇、2,4-二乙基-1,5-戊二醇、三羥甲基乙烷、三羥甲基丙烷、季戊四醇等脂肪族化合物;環戊二醇、環己二醇、環己烷二甲醇、氫化雙酚A、該些的環氧烷加成物等脂環式化合物等。該些化合物可單獨使用,亦可併用兩種以上。As the compound having a hydroxyl group, for example, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptane can be used. Glycol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol Alcohol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 3- Methyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-methyl-1,8-octanediol, 2,4-diethyl-1, Aliphatic compounds such as 5-pentanediol, trimethylolethane, trimethylolpropane, and pentaerythritol; cyclopentanediol, cyclohexanediol, cyclohexane dimethanol, hydrogenated bisphenol A, these Alicyclic compounds such as oxane adducts, etc. These compounds may be used alone, or two or more of them may be used in combination.
作為所述具有兩個以上的羥基的芳香族化合物,例如可使用雙酚A、雙酚F、該些的環氧烷(環氧乙烷、環氧丙烷、環氧丁烷等)加成物等。該些化合物可單獨使用,亦可併用兩種以上。該些中,就可獲得更進一步優異的初期接著強度及柔軟性的方面而言,較佳為使用雙酚A的環氧烷加成物,作為所述環氧烷的加成莫耳數,較佳為1莫耳~10莫耳的範圍。As the aromatic compound having two or more hydroxyl groups, for example, bisphenol A, bisphenol F, and these alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts can be used Wait. These compounds may be used alone, or two or more of them may be used in combination. Among these, it is preferable to use an alkylene oxide adduct of bisphenol A as the number of added moles of the alkylene oxide in terms of obtaining further excellent initial adhesive strength and flexibility. It is preferably in the range of 1 mol to 10 mol.
作為所述芳香族多元酸,例如可使用鄰苯二甲酸、間苯二甲酸、對苯二甲酸、鄰苯二甲酸酐等。作為此外的多元酸,例如可使用草酸、丙二酸、琥珀酸、己二酸、癸二酸、壬二酸、1,12-十二烷二羧酸等。該些多元酸可單獨使用,亦可併用兩種以上。作為所述芳香族多元酸,就可獲得更進一步優異的初期接著強度及柔軟性的方面而言,較佳為使用選自由鄰苯二甲酸、間苯二甲酸、對苯二甲酸及鄰苯二甲酸酐所組成的群組中的一種以上的化合物。As the aromatic polybasic acid, for example, phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, etc. can be used. As other polybasic acids, for example, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, 1,12-dodecane dicarboxylic acid, etc. can be used. These polybasic acids may be used alone, or two or more of them may be used in combination. As the aromatic polybasic acid, it is preferable to use one selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, and phthalic acid in terms of obtaining further excellent initial adhesion strength and flexibility. One or more compounds in the group consisting of formic anhydride.
作為其他多元酸,例如可使用琥珀酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸(sebacic acid)、癸二酸(decanedioic acid)、十二烷二酸、二十烷二酸、檸康酸、衣康酸、檸康酸酐、衣康酸酐等。As other polybasic acids, for example, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, two Decanedioic acid, citraconic acid, itaconic acid, citraconic anhydride, itaconic anhydride, etc.
作為所述芳香族聚酯多元醇(a3)的數量平均分子量,就可獲得更進一步優異的初期接著強度及柔軟性的方面而言,較佳為小於2,800,更佳為300~2,500的範圍,進而佳為600~2,200的範圍。再者,所述芳香族聚酯多元醇(a3)的數量平均分子量表示藉由凝膠滲透層析(GPC)法進行測定所得的值。The number average molecular weight of the aromatic polyester polyol (a3) is preferably less than 2,800, more preferably in the range of 300 to 2,500, in terms of obtaining further excellent initial bonding strength and flexibility. More preferably, it is the range of 600-2,200. In addition, the number average molecular weight of the aromatic polyester polyol (a3) represents a value measured by a gel permeation chromatography (GPC) method.
作為所述芳香族聚酯多元醇(a3)的含有率,就可獲得更進一步優異的初期接著強度、柔軟性及塗佈適應性的方面而言,於多元醇(A)中,較佳為1質量%~49質量%的範圍,更佳為4質量%~47質量%的範圍,進而佳為8質量%~45質量%的範圍。As the content rate of the aromatic polyester polyol (a3), in terms of obtaining further excellent initial adhesive strength, flexibility, and coating suitability, among the polyol (A), it is preferably The range of 1% by mass to 49% by mass, more preferably the range of 4% by mass to 47% by mass, and still more preferably the range of 8% by mass to 45% by mass.
再者,於本發明中,於全部滿足本申請案發明所欲解決的課題方面,必須是所述聚酯多元醇(a1)及所述聚醚多元醇(a2)的合計使用量多於所述芳香族聚酯多元醇(a3)的使用量。作為所述聚酯多元醇(a1)及所述聚醚多元醇(a2)的合計使用量與所述芳香族聚酯多元醇(a3)的使用量的比率[((a1)+(a2))/(a3)],較佳為99/1~51/49的範圍,更佳為95/5~53/47的範圍,進而佳為90/10~55/45的範圍。Furthermore, in the present invention, in order to satisfy all the problems to be solved by the invention of this application, the total amount of the polyester polyol (a1) and the polyether polyol (a2) must be more than the total amount used. The amount of aromatic polyester polyol (a3) used is described. As the ratio of the total usage amount of the polyester polyol (a1) and the polyether polyol (a2) to the usage amount of the aromatic polyester polyol (a3) [((a1)+(a2) )/(A3)], preferably in the range of 99/1 to 51/49, more preferably in the range of 95/5 to 53/47, and still more preferably in the range of 90/10 to 55/45.
另外,作為所述聚酯多元醇(a1)與所述聚醚多元醇(a2)的質量比[(a1)/(a2)],較佳為90/10~10/90的範圍,更佳為85/15~15/85的範圍,進而佳為80/20~20/80的範圍。In addition, the mass ratio [(a1)/(a2)] of the polyester polyol (a1) to the polyether polyol (a2) is preferably in the range of 90/10 to 10/90, more preferably It is the range of 85/15-15/85, More preferably, it is the range of 80/20-20/80.
作為所述多元醇(A),除使用所述多元醇(a1)~多元醇(a3)以外,視需要亦可使用其他多元醇。As the polyol (A), in addition to the polyol (a1) to the polyol (a3), other polyols may be used as needed.
作為所述其他多元醇,例如可使用所述(a1)及(a3)以外的聚酯多元醇、聚碳酸酯多元醇、聚丙烯酸多元醇、聚丁二烯多元醇、氫化聚丁二烯多元醇等。該些多元醇可單獨使用,亦可併用兩種以上。As the other polyols, for example, polyester polyols, polycarbonate polyols, polyacrylic polyols, polybutadiene polyols, and hydrogenated polybutadiene polyols other than (a1) and (a3) can be used. Alcohol etc. These polyols may be used singly, or two or more of them may be used in combination.
作為所述聚酯多元醇(a1)、所述聚醚多元醇(a2)及所述芳香族聚酯多元醇(a3)的合計量,於所述多元醇(A)中,較佳為50質量%以上,更佳為70質量%以上,進而佳為80質量%以上,特佳為90質量%以上。As the total amount of the polyester polyol (a1), the polyether polyol (a2), and the aromatic polyester polyol (a3), in the polyol (A), it is preferably 50 Mass% or more, more preferably 70 mass% or more, still more preferably 80 mass% or more, particularly preferably 90 mass% or more.
作為所述聚異氰酸酯(B),例如可使用聚亞甲基聚苯基聚異氰酸酯、二苯基甲烷二異氰酸酯、碳二醯亞胺改質二苯基甲烷二異氰酸酯異氰酸酯、伸苯基二異氰酸酯、甲苯二異氰酸酯、萘二異氰酸酯等芳香族聚異氰酸酯;六亞甲基二異氰酸酯、離胺酸二異氰酸酯、環己烷二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷二異氰酸酯、伸二甲苯基二異氰酸酯、四甲基伸二甲苯基二異氰酸酯等脂肪族聚異氰酸酯或脂環族聚異氰酸酯等。該些中,就可獲得更進一步優異的反應性及最終接著強度的方面而言,較佳為使用芳香族聚異氰酸酯,更佳為二苯基甲烷二異氰酸酯。As the polyisocyanate (B), for example, polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate isocyanate, phenylene diisocyanate, Aromatic polyisocyanates such as toluene diisocyanate and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate Aliphatic polyisocyanates such as isocyanate and tetramethylxylylene diisocyanate, or alicyclic polyisocyanates, etc. Among these, in terms of obtaining further excellent reactivity and final bonding strength, it is preferable to use an aromatic polyisocyanate, and more preferably diphenylmethane diisocyanate.
另外,作為所述聚異氰酸酯(B)的使用量,就可獲得更進一步優異的接著強度的方面而言,於胺基甲酸酯預聚物(i)的原料中,較佳為5質量%~60質量%的範圍,更佳為15質量%~50質量%的範圍。In addition, the amount of the polyisocyanate (B) used is preferably 5% by mass in the raw material of the urethane prepolymer (i) in terms of obtaining more excellent adhesive strength. It is in the range of -60% by mass, more preferably in the range of 15% by mass to 50% by mass.
所述胺基甲酸酯預聚物(i)是使所述多元醇(A)與所述聚異氰酸酯(B)反應而獲得者,且為於聚合物末端或分子內具有可與存在於空氣中或供胺基甲酸酯預聚物塗佈的框體或被黏著體中的水分反應而形成交聯結構的異氰酸酯基者。The urethane prepolymer (i) is obtained by reacting the polyol (A) with the polyisocyanate (B), and has a polymer end or molecule capable of interacting with the air Neutralizes or forms a cross-linked isocyanate group by reacting with moisture in the frame or adherend to which the urethane prepolymer is applied.
作為所述胺基甲酸酯預聚物(i)的製造方法,例如可藉由如下方式來製造:於放入有所述聚異氰酸酯(B)的反應容器中滴加所述多元醇(A),然後進行加熱,並於所述聚異氰酸酯(B)所具有的異氰酸酯基相對於所述多元醇(A)所具有的羥基而過剩的條件下進行反應。As a method of producing the urethane prepolymer (i), for example, it can be produced by dropping the polyol (A) into a reaction vessel containing the polyisocyanate (B). ), and then heating and reacting under the condition that the isocyanate group of the polyisocyanate (B) is excessive with respect to the hydroxyl group of the polyol (A).
作為所述胺基甲酸酯預聚物(i)的胺基甲酸酯鍵量,就可獲得更進一步優異的初期接著強度、柔軟性及低黏度性的方面而言,較佳為0.5 mol/kg~3 mol/kg的範圍,更佳為0.9 mol/kg~2.7 mol/kg的範圍,進而佳為1.1 mol/kg~2.4 mol/kg的範圍。The amount of urethane bonds of the urethane prepolymer (i) is preferably 0.5 mol in terms of obtaining further excellent initial adhesion strength, flexibility, and low viscosity. /kg to 3 mol/kg, more preferably 0.9 mol/kg to 2.7 mol/kg, still more preferably 1.1 mol/kg to 2.4 mol/kg.
作為製造所述胺基甲酸酯預聚物(i)時的、所述聚異氰酸酯(B)所具有的異氰酸酯基與所述多元醇(A)所具有的羥基的當量比([異氰酸酯基/羥基]),就可獲得更進一步優異的初期接著強度、柔軟性及低黏度性的方面而言,較佳為1.1~1.5的範圍,更佳為1.15~1.45的範圍。As the equivalent ratio of the isocyanate group of the polyisocyanate (B) to the hydroxyl group of the polyol (A) when the urethane prepolymer (i) is produced ([isocyanate group/ Hydroxy]), in terms of obtaining further excellent initial adhesive strength, flexibility, and low viscosity, the range is preferably 1.1 to 1.5, and more preferably 1.15 to 1.45.
作為所述胺基甲酸酯預聚物(i)的異氰酸酯基含有率(以下,簡記為「NCO%」),就可獲得更進一步優異的初期接著強度、柔軟性及低黏度性的方面而言,較佳為1質量%~4質量%的範圍,更佳為1.2質量%~3.5質量%的範圍。再者,所述胺基甲酸酯預聚物(i)的NCO%表示依據日本工業標準(Japanese Industrial Standards,JIS)K1603-1:2007,並藉由電位差滴定法進行測定所得的值。As the isocyanate group content of the urethane prepolymer (i) (hereinafter, abbreviated as "NCO%"), further excellent initial adhesive strength, flexibility, and low viscosity can be obtained. In other words, it is preferably in the range of 1% by mass to 4% by mass, and more preferably in the range of 1.2% by mass to 3.5% by mass. Furthermore, the NCO% of the urethane prepolymer (i) represents a value obtained by measuring according to Japanese Industrial Standards (JIS) K1603-1:2007 and by potentiometric titration.
本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物除含有所述胺基甲酸酯預聚物(i)以外,視需要亦可含有其他添加劑。The moisture-curable polyurethane hot-melt resin composition of the present invention may contain other additives as needed in addition to the urethane prepolymer (i).
作為所述其他添加劑,例如可使用抗氧化劑、黏著賦予劑、塑化劑、穩定劑、填充材、染料、顏料、螢光增白劑、矽烷偶合劑、蠟等。該些添加劑可單獨使用,亦可併用兩種以上。As the other additives, for example, antioxidants, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent whitening agents, silane coupling agents, waxes, etc. can be used. These additives may be used alone, or two or more of them may be used in combination.
作為獲得所述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物的硬化皮膜的方法,例如可列舉如下方法:將所述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物於50℃~130℃下熔融,然後塗敷於基材上,並進行濕氣硬化。As a method of obtaining a cured film of the moisture-curing polyurethane hot-melt resin composition, for example, the following method can be cited: the moisture-curing polyurethane hot-melt resin composition is applied to It is melted at 50℃~130℃, then coated on the base material and cured by moisture.
作為所述基材,例如可使用丙烯酸系樹脂、胺基甲酸酯系樹脂、矽系樹脂、環氧系樹脂、氟系樹脂、聚苯乙烯系樹脂、聚酯系樹脂、聚碸系樹脂、聚芳酯系樹脂、聚氯乙烯樹脂、聚偏二氯乙烯、環烯烴樹脂、聚烯烴系樹脂、聚醯亞胺系樹脂、脂環式聚醯亞胺系樹脂、纖維素系樹脂、聚碳酸酯(Polycarbonate,PC)、聚對苯二甲酸丁二酯(Polybutylene Terephthalate,PBT)、改質聚苯醚(Polyphenyl Ether,PPE)、聚萘二甲酸乙二酯(Polyethylene Naphthalate,PEN)、聚對苯二甲酸乙二酯(Polyethylene Terephthalate,PET)、乳酸聚合物、丙烯腈-丁二烯-苯乙烯(Acrylonitrile Butadiene Styrene,ABS)樹脂、丙烯腈-苯乙烯(Acrylonitrile Styrene,AS)樹脂等樹脂膜;中密度纖維板(Medium Density Fiberboard,MDF)、膠合板、塑合板(particle board)等木質基材;不織布、織布、編織物等纖維基材等。所述基材視需要亦可實施電暈處理、電漿處理、底漆處理等。As the substrate, for example, acrylic resins, urethane resins, silicon resins, epoxy resins, fluorine resins, polystyrene resins, polyester resins, polycure resins, etc. can be used. Polyarylate resin, polyvinyl chloride resin, polyvinylidene chloride, cycloolefin resin, polyolefin resin, polyimide resin, alicyclic polyimide resin, cellulose resin, polycarbonate Polycarbonate (PC), Polybutylene Terephthalate (PBT), Modified Polyphenyl Ether (PPE), Polyethylene Naphthalate (PEN), Poly Polyethylene Terephthalate (PET), lactic acid polymer, Acrylonitrile Butadiene Styrene (ABS) resin, Acrylonitrile Styrene (AS) resin and other resin films ; Medium Density Fiberboard (MDF), plywood, plastic plywood (particle board) and other wooden substrates; non-woven fabrics, woven fabrics, woven fabrics and other fiber substrates. The substrate may also be subjected to corona treatment, plasma treatment, primer treatment, etc. as needed.
作為塗敷所述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物的方法,例如可列舉使用輥式塗佈機、噴霧塗佈機、T模塗佈機、刀式塗佈機、缺角輪塗佈機等的方法。As a method of applying the moisture-curable polyurethane hot-melt resin composition, for example, the use of a roll coater, spray coater, T-die coater, knife coater, Methods such as missing corner wheel coater.
於所述塗敷後,例如於溫度20℃~80℃、相對濕度50%~90%下老化0.5天~3天,可獲得最終接著強度。After the coating, the final bonding strength can be obtained by aging at a temperature of 20°C to 80°C and a relative humidity of 50% to 90% for 0.5 to 3 days.
作為本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物,就可獲得更進一步優異的初期接著強度的方面而言,硬化前的20℃下的熔融黏彈性的所述儲存彈性係數(G')較佳為0.1 MPa以上,較佳為0.2 MPa~1,000 MPa的範圍,更佳為0.3 MPa~500 MPa的範圍。As the moisture-curing polyurethane hot-melt resin composition of the present invention, in terms of obtaining further excellent initial adhesive strength, the storage elasticity is the melt viscoelasticity at 20°C before curing The coefficient (G') is preferably 0.1 MPa or more, preferably in the range of 0.2 MPa to 1,000 MPa, more preferably in the range of 0.3 MPa to 500 MPa.
再者,所述儲存彈性係數(G')表示如下儲存彈性係數(G'):將濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物於110℃下熔融1小時,然後取樣10 ml,放置於熔融黏彈性測定裝置(安東帕(Anton Paar)公司製造的「MCR-302」)的平行板上,自110℃至10℃以降溫速度1℃/min、頻率1 Hz進行熔融黏彈性測定時的20℃下的儲存彈性係數(G')。Furthermore, the storage elastic coefficient (G') represents the following storage elastic coefficient (G'): the moisture-curable polyurethane hot-melt resin composition is melted at 110°C for 1 hour, and then 10 ml is sampled , Placed on the parallel plate of the melt viscoelasticity measuring device (Anton Paar (Anton Paar) "MCR-302") parallel plate, from 110 ℃ to 10 ℃ with a cooling rate of 1 ℃/min, frequency 1 Hz for melt viscoelasticity The storage elastic coefficient (G') at 20°C during the measurement.
另外,作為本發明的硬化皮膜的楊氏係數,就可獲得更進一步優異的柔軟性的方面而言,較佳為20 MPa以下,更佳為0.5 MPa~15 MPa的範圍,進而佳為1 MPa~10 MPa的範圍。In addition, the Young's coefficient of the cured film of the present invention is preferably 20 MPa or less, more preferably in the range of 0.5 MPa to 15 MPa, and still more preferably 1 MPa in terms of obtaining more excellent flexibility. ~10 MPa range.
再者,所述楊氏係數表示如下值:將濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物於110℃下熔融1小時後,於經脫模處理的聚對苯二甲酸乙二酯基材上,以使硬化後的膜厚成為100 μm的方式使用刀式塗佈機進行塗敷,並放置3天,藉此獲得硬化皮膜,自脫模PET剝離硬化皮膜,利用2號啞鈴進行衝壓加工,並將所得者作為試驗片,針對該試驗片,使用滕喜龍(Tensilon)拉伸試驗機(艾安德(Orientec)股份有限公司製造的「RTM-100」),於25℃的環境下,以十字頭速度:200 mm/min進行拉伸試驗,根據此時的圖表的原點與伸長率為2.5%時的應力進行測定而得的值。In addition, the Young’s coefficient represents the following value: after the moisture-curing polyurethane hot-melt resin composition is melted at 110°C for 1 hour, the mold release-treated polyethylene terephthalate On the ester substrate, apply it with a knife coater so that the cured film thickness becomes 100 μm, and leave it for 3 days to obtain a cured film. The cured film is peeled from the mold release PET, and a No. 2 dumbbell is used. Press processing and use the resultant as a test piece. For this test piece, a Tensilon tensile testing machine ("RTM-100" manufactured by Orientec Co., Ltd.) was used at 25°C. Under the environment, the tensile test is performed at a crosshead speed: 200 mm/min, and the value is measured based on the origin of the graph at this time and the stress at an elongation of 2.5%.
以上,本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物的低黏度性、初期接著強度、柔軟性、塗佈適應性及耐水解性優異。因此,本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物可特別適宜用於纖維用途。 [實施例]As described above, the moisture-curable polyurethane hot-melt resin composition of the present invention is excellent in low viscosity, initial adhesive strength, flexibility, coating suitability, and hydrolysis resistance. Therefore, the moisture-curing polyurethane hot-melt resin composition of the present invention can be particularly suitably used for fiber applications. [Example]
以下,藉由實施例而對本發明進一步進行詳細說明。Hereinafter, the present invention will be further described in detail through examples.
[實施例1] 於包括溫度計、攪拌機、惰性氣體導入口及回流冷卻器的四口燒瓶中投入35質量份的脂肪族聚酯多元醇(使丁二醇及己二酸反應而得者,數量平均分子量:1,000,以下簡記為「BG/AA」)、35質量份的聚氧丙烯二醇(數量平均分子量:1,000,以下簡記為「PPG」)、30質量份的芳香族聚酯多元醇(使新戊二醇及鄰苯二甲酸(o-phthalic acid)反應而得者,數量平均分子量:1,000,以下簡記為「NPG/PA1000」),於90℃下進行減壓加熱,藉此脫水至水分含有率成為0.05質量%以下。 繼而,將容器內溫度冷卻至60℃,然後添加33質量份的4,4'-二苯基甲烷二異氰酸酯(以下簡記為「MDI」),升溫至110℃,反應約3小時,直至異氰酸酯基含有率成為一定,獲得具有異氰酸酯基的胺基甲酸酯預聚物(i-1),從而獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。所述胺基甲酸酯預聚物(i-1)的NCO%為1.7質量%,胺基甲酸酯鍵量為1.50 mol/kg,合成時的[NCO/OH]為1.32。[Example 1] Put 35 parts by mass of aliphatic polyester polyol (derived from the reaction of butanediol and adipic acid into a four-necked flask including a thermometer, agitator, inert gas inlet and reflux cooler, number average molecular weight: 1,000, Hereinafter referred to as "BG/AA"), 35 parts by mass of polyoxypropylene glycol (number average molecular weight: 1,000, hereafter referred to as "PPG"), 30 parts by mass of aromatic polyester polyol (using neopentyl glycol It is obtained by reacting with o-phthalic acid, number average molecular weight: 1,000, hereinafter abbreviated as "NPG/PA1000"), heated at 90°C under reduced pressure, and dehydrated until the moisture content becomes 0.05 Less than mass%. Then, the temperature in the container was cooled to 60°C, and 33 parts by mass of 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") was added, the temperature was raised to 110°C, and the reaction was carried out for about 3 hours until the isocyanate group The content rate becomes constant, the urethane prepolymer (i-1) having an isocyanate group is obtained, and a moisture-curable polyurethane hot-melt resin composition is obtained. The NCO% of the urethane prepolymer (i-1) was 1.7% by mass, the amount of urethane bonds was 1.50 mol/kg, and the [NCO/OH] during synthesis was 1.32.
[實施例2] 於包括溫度計、攪拌機、惰性氣體導入口及回流冷卻器的四口燒瓶中投入25質量份的BG/AA、50質量份的PPG、25質量份的NPG/PA1000,於90℃下進行減壓加熱,藉此脫水至水分含有率成為0.05質量%以下。 繼而,添加33質量份的MDI,升溫至110℃,反應約3小時,直至異氰酸酯基含有率成為一定,獲得具有異氰酸酯基的胺基甲酸酯預聚物(i-2),從而獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。所述胺基甲酸酯預聚物(i-2)的NCO%為1.7質量%,胺基甲酸酯鍵量為1.50 mol/kg,合成時的[NCO/OH]為1.32。[Example 2] Put 25 parts by mass of BG/AA, 50 parts by mass of PPG, and 25 parts by mass of NPG/PA1000 into a four-necked flask including thermometer, stirrer, inert gas inlet and reflux cooler, and heat under reduced pressure at 90°C By this, it is dehydrated until the moisture content becomes 0.05% by mass or less. Then, 33 parts by mass of MDI was added, the temperature was raised to 110°C, and the reaction was carried out for about 3 hours until the isocyanate group content became constant to obtain a urethane prepolymer (i-2) having an isocyanate group, thereby obtaining moisture Hardening polyurethane hot-melt resin composition. The NCO% of the urethane prepolymer (i-2) was 1.7% by mass, the amount of urethane bonds was 1.50 mol/kg, and the [NCO/OH] during synthesis was 1.32.
[實施例3] 於包括溫度計、攪拌機、惰性氣體導入口及回流冷卻器的四口燒瓶中投入35質量份的脂肪族聚酯多元醇(使新戊二醇及己二酸反應而得者,數量平均分子量:1,000,以下簡記為「NPG/AA」)、35質量份的PPG、30質量份的芳香族聚酯多元醇(使雙酚A的環氧丙烷6莫耳加成物及癸二酸反應而得者,數量平均分子量:1,000,以下簡記為「BISA6PO/SEBA」),於90℃下進行減壓加熱,藉此脫水至水分含有率成為0.05質量%以下。 繼而,將容器內溫度冷卻至60℃,然後添加33質量份的MDI,升溫至110℃,反應約3小時,直至異氰酸酯基含有率成為一定,獲得具有異氰酸酯基的胺基甲酸酯預聚物(i-3),從而獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。所述胺基甲酸酯預聚物(i-3)的NCO%為1.7質量%,胺基甲酸酯鍵量為1.50 mol/kg,合成時的[NCO/OH]為1.32。[Example 3] Put 35 parts by mass of aliphatic polyester polyol (obtained by the reaction of neopentyl glycol and adipic acid in a four-necked flask including a thermometer, agitator, inert gas inlet and reflux cooler, number average molecular weight: 1,000 , Hereinafter abbreviated as "NPG/AA"), 35 parts by mass of PPG, 30 parts by mass of aromatic polyester polyol (resulting from the reaction of 6 mol adduct of bisphenol A with propylene oxide and sebacic acid , Number average molecular weight: 1,000, hereinafter abbreviated as "BISA6PO/SEBA"), heat under reduced pressure at 90°C, thereby dehydrating until the moisture content becomes 0.05% by mass or less. Then, the temperature in the container was cooled to 60°C, 33 parts by mass of MDI was added, the temperature was raised to 110°C, and the reaction was carried out for about 3 hours until the isocyanate group content became constant, and a urethane prepolymer having isocyanate groups was obtained. (I-3), thereby obtaining a moisture-curing polyurethane hot-melt resin composition. The NCO% of the urethane prepolymer (i-3) was 1.7% by mass, the amount of urethane bonds was 1.50 mol/kg, and the [NCO/OH] during synthesis was 1.32.
[實施例4] 於包括溫度計、攪拌機、惰性氣體導入口及回流冷卻器的四口燒瓶中投入20質量份的NPG/AA、40質量份的PPG、40質量份的BISA6PO/SEBA,於90℃下進行減壓加熱,藉此脫水至水分含有率成為0.05質量%以下。 繼而,將容器內溫度冷卻至60℃,然後添加33質量份的MDI,升溫至110℃,反應約3小時,直至異氰酸酯基含有率成為一定,獲得具有異氰酸酯基的胺基甲酸酯預聚物(i-4),從而獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。所述胺基甲酸酯預聚物(i-4)的NCO%為1.7質量%,胺基甲酸酯鍵量為1.50 mol/kg,合成時的[NCO/OH]為1.32。[Example 4] Put 20 parts by mass of NPG/AA, 40 parts by mass of PPG, and 40 parts by mass of BISA6PO/SEBA into a four-necked flask including a thermometer, stirrer, inert gas inlet and reflux cooler, and heat under reduced pressure at 90°C By this, it is dehydrated until the moisture content becomes 0.05% by mass or less. Then, the temperature in the container was cooled to 60°C, 33 parts by mass of MDI was added, the temperature was raised to 110°C, and the reaction was carried out for about 3 hours until the isocyanate group content became constant, and a urethane prepolymer having isocyanate groups was obtained. (I-4), thereby obtaining a moisture-curing polyurethane hot-melt resin composition. The NCO% of the urethane prepolymer (i-4) was 1.7% by mass, the amount of urethane bonds was 1.50 mol/kg, and the [NCO/OH] during synthesis was 1.32.
[實施例5] 於包括溫度計、攪拌機、惰性氣體導入口及回流冷卻器的四口燒瓶中投入55質量份的NPG/AA、30質量份的PPG、15質量份的NPG/PA1000,於90℃下進行減壓加熱,藉此脫水至水分含有率成為0.05質量%以下。 繼而,將容器內溫度冷卻至60℃,然後添加33質量份的MDI,升溫至110℃,反應約3小時,直至異氰酸酯基含有率成為一定,獲得具有異氰酸酯基的胺基甲酸酯預聚物(i-5),從而獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。所述胺基甲酸酯預聚物(i-5)的NCO%為1.7質量%,胺基甲酸酯鍵量為1.50 mol/kg,合成時的[NCO/OH]為1.32。[Example 5] Put 55 parts by mass of NPG/AA, 30 parts by mass of PPG, and 15 parts by mass of NPG/PA1000 into a four-necked flask including thermometer, stirrer, inert gas inlet and reflux cooler, and heat under reduced pressure at 90°C By this, it is dehydrated until the moisture content becomes 0.05% by mass or less. Then, the temperature in the container was cooled to 60°C, 33 parts by mass of MDI was added, the temperature was raised to 110°C, and the reaction was carried out for about 3 hours until the isocyanate group content became constant, and a urethane prepolymer having isocyanate groups was obtained. (I-5), thereby obtaining a moisture-curing polyurethane hot-melt resin composition. The NCO% of the urethane prepolymer (i-5) was 1.7% by mass, the amount of urethane bonds was 1.50 mol/kg, and the [NCO/OH] during synthesis was 1.32.
[實施例6] 於包括溫度計、攪拌機、惰性氣體導入口及回流冷卻器的四口燒瓶中投入30質量份的脂肪族聚酯多元醇(使二乙二醇及己二酸反應而得者,數量平均分子量:1000,以下簡記為「DEG/AA」)、30質量份的PPG、40質量份的芳香族聚酯多元醇(使新戊二醇及鄰苯二甲酸(o-phthalic acid)反應而得者,數量平均分子量:2,000,以下簡記為「NPG/PA2000」),於90℃下進行減壓加熱,藉此脫水至水分含有率成為0.05質量%以下。 繼而,將容器內溫度冷卻至60℃,然後添加28質量份的MDI,升溫至110℃,反應約3小時,直至異氰酸酯基含有率成為一定,獲得具有異氰酸酯基的胺基甲酸酯預聚物(i-6),從而獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。所述胺基甲酸酯預聚物(i-6)的NCO%為1.8質量%,胺基甲酸酯鍵量為1.25 mol/kg,合成時的[NCO/OH]為1.40。[Example 6] Put 30 parts by mass of aliphatic polyester polyol (derived from the reaction of diethylene glycol and adipic acid in a four-necked flask including a thermometer, agitator, inert gas inlet and reflux cooler, number average molecular weight: 1000 , Hereinafter abbreviated as "DEG/AA"), 30 parts by mass of PPG, 40 parts by mass of aromatic polyester polyol (resulting from the reaction of neopentyl glycol and o-phthalic acid, the quantity Average molecular weight: 2,000, hereinafter abbreviated as "NPG/PA2000"), and heat under reduced pressure at 90°C to dehydrate until the moisture content becomes 0.05% by mass or less. Then, the temperature in the container was cooled to 60°C, 28 parts by mass of MDI were added, the temperature was raised to 110°C, and the reaction was carried out for about 3 hours until the isocyanate group content became constant, and a urethane prepolymer having isocyanate groups was obtained. (I-6), thereby obtaining a moisture-curing polyurethane hot-melt resin composition. The NCO% of the urethane prepolymer (i-6) was 1.8% by mass, the amount of urethane bonds was 1.25 mol/kg, and the [NCO/OH] during synthesis was 1.40.
[實施例7] 於包括溫度計、攪拌機、惰性氣體導入口及回流冷卻器的四口燒瓶中投入20質量份的DEG/AA、50質量份的PPG、30質量份的芳香族聚酯多元醇(使乙二醇及鄰苯二甲酸(o-phthalic acid)反應而得者,數量平均分子量:600,以下簡記為「EG/PA600」),於90℃下進行減壓加熱,藉此脫水至水分含有率成為0.05質量%以下。 繼而,將容器內溫度冷卻至60℃,然後添加38質量份的MDI,升溫至110℃,反應約3小時,直至異氰酸酯基含有率成為一定,獲得具有異氰酸酯基的胺基甲酸酯預聚物(i-7),從而獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。所述胺基甲酸酯預聚物(i-7)的NCO%為1.6質量%,胺基甲酸酯鍵量為1.74 mol/kg,合成時的[NCO/OH]為1.27。[Example 7] Put 20 parts by mass of DEG/AA, 50 parts by mass of PPG, and 30 parts by mass of aromatic polyester polyol (making ethylene glycol and O-phthalic acid (o-phthalic acid) reaction, number average molecular weight: 600, hereinafter abbreviated as "EG/PA600"), heated at 90°C under reduced pressure, thereby dehydrating until the moisture content becomes 0.05 mass %the following. Then, the temperature in the container was cooled to 60°C, 38 parts by mass of MDI were added, the temperature was raised to 110°C, and the reaction was carried out for about 3 hours until the isocyanate group content became constant, and a urethane prepolymer having isocyanate groups was obtained. (I-7), thereby obtaining a moisture-curing polyurethane hot-melt resin composition. The NCO% of the urethane prepolymer (i-7) was 1.6% by mass, the amount of urethane bonds was 1.74 mol/kg, and the [NCO/OH] during synthesis was 1.27.
[比較例1] 於包括溫度計、攪拌機、惰性氣體導入口及回流冷卻器的四口燒瓶中投入15質量份的BG/AA、15質量份的PPG、70質量份的NPG/PA,於90℃下進行減壓加熱,藉此脫水至水分含有率成為0.05質量%以下。 繼而,將容器內溫度冷卻至60℃,然後添加35質量份的MDI,升溫至110℃,反應約3小時,直至異氰酸酯基含有率成為一定,獲得具有異氰酸酯基的胺基甲酸酯預聚物(i-R1),從而獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。所述胺基甲酸酯預聚物(i-R1)的NCO%為2.2質量%,胺基甲酸酯鍵量為1.48 mol/kg,合成時的[NCO/OH]為1.40。[Comparative Example 1] Put 15 parts by mass of BG/AA, 15 parts by mass of PPG, and 70 parts by mass of NPG/PA into a four-necked flask including thermometer, stirrer, inert gas inlet and reflux cooler, and heat under reduced pressure at 90°C By this, it is dehydrated until the moisture content becomes 0.05% by mass or less. Then, the temperature in the container was cooled to 60°C, 35 parts by mass of MDI was added, the temperature was raised to 110°C, and the reaction was carried out for about 3 hours until the isocyanate group content became constant, and a urethane prepolymer having isocyanate groups was obtained. (I-R1), thereby obtaining a moisture-curing polyurethane hot-melt resin composition. The NCO% of the urethane prepolymer (i-R1) is 2.2% by mass, the amount of urethane bonds is 1.48 mol/kg, and the [NCO/OH] during synthesis is 1.40.
[比較例2] 於包括溫度計、攪拌機、惰性氣體導入口及回流冷卻器的四口燒瓶中投入70質量份的PPG、30質量份的NPG/PA1000,於90℃下進行減壓加熱,藉此脫水至水分含有率成為0.05質量%以下。 繼而,將容器內溫度冷卻至60℃,然後添加33質量份的MDI,升溫至110℃,反應約3小時,直至異氰酸酯基含有率成為一定,獲得具有異氰酸酯基的胺基甲酸酯預聚物(i-R2),從而獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。所述胺基甲酸酯預聚物(i-R2)的NCO%為1.7質量%,胺基甲酸酯鍵量為1.50 mol/kg,合成時的[NCO/OH]為1.32。[Comparative Example 2] Put 70 parts by mass of PPG and 30 parts by mass of NPG/PA1000 into a four-necked flask including a thermometer, agitator, an inert gas inlet, and a reflux cooler, and heat it under reduced pressure at 90°C to achieve dehydration to moisture content. Be 0.05% by mass or less. Then, the temperature in the container was cooled to 60°C, 33 parts by mass of MDI was added, the temperature was raised to 110°C, and the reaction was carried out for about 3 hours until the isocyanate group content became constant, and a urethane prepolymer having isocyanate groups was obtained. (I-R2), thereby obtaining a moisture-curing polyurethane hot-melt resin composition. The NCO% of the urethane prepolymer (i-R2) is 1.7% by mass, the amount of urethane bonds is 1.50 mol/kg, and the [NCO/OH] during synthesis is 1.32.
[比較例3] 於包括溫度計、攪拌機、惰性氣體導入口及回流冷卻器的四口燒瓶中投入70質量份的BG/AA、30質量份的NPG/PA1000,於90℃下進行減壓加熱,藉此脫水至水分含有率成為0.05質量%以下。 繼而,將容器內溫度冷卻至60℃,然後添加33質量份的MDI,升溫至110℃,反應約3小時,直至異氰酸酯基含有率成為一定,獲得具有異氰酸酯基的胺基甲酸酯預聚物(i-R3),從而獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。所述胺基甲酸酯預聚物(i-R3)的NCO%為1.7質量%,胺基甲酸酯鍵量為1.50 mol/kg,合成時的[NCO/OH]為1.32。[Comparative Example 3] Put 70 parts by mass of BG/AA and 30 parts by mass of NPG/PA1000 into a four-necked flask including a thermometer, agitator, an inert gas inlet and a reflux cooler, and heat under reduced pressure at 90°C, thereby dehydrating to moisture The content rate is 0.05% by mass or less. Then, the temperature in the container was cooled to 60°C, 33 parts by mass of MDI was added, the temperature was raised to 110°C, and the reaction was carried out for about 3 hours until the isocyanate group content became constant, and a urethane prepolymer having isocyanate groups was obtained. (I-R3), thereby obtaining a moisture-curing polyurethane hot-melt resin composition. The NCO% of the urethane prepolymer (i-R3) was 1.7% by mass, the amount of urethane bonds was 1.50 mol/kg, and the [NCO/OH] during synthesis was 1.32.
[數量平均分子量的測定方法] 於實施例及比較例中,多元醇等的數量平均分子量表示藉由凝膠滲透層析(GPC)法於下述條件下測定所得的值。[Measurement method of number average molecular weight] In the examples and comparative examples, the number average molecular weight of polyols and the like represents a value measured by a gel permeation chromatography (GPC) method under the following conditions.
測定裝置:高速GPC裝置(東曹(Tosoh)股份有限公司製造的「HLC-8220GPC」) 管柱:將東曹股份有限公司製造的下述管柱串聯連接來使用。 「TSKgel G5000」(7.8 mmI.D.×30 cm)×1根 「TSKgel G4000」(7.8 mmI.D.×30 cm)×1根 「TSKgel G3000」(7.8 mmI.D.×30 cm)×1根 「TSKgel G2000」(7.8 mmI.D.×30 cm)×1根 檢測器:RI(示差折射計) 管柱溫度:40℃ 溶離液:四氫呋喃(Tetrahydrofuran,THF) 流速:1.0 mL/min 注入量:100 μL(試樣濃度0.4質量%的四氫呋喃溶液) 標準試樣:使用下述標準聚苯乙烯來製成標準曲線。Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Co., Ltd.) String: The following pipe strings manufactured by Tosoh Co., Ltd. are connected in series and used. "TSKgel G5000" (7.8 mmI.D.×30 cm)×1 "TSKgel G4000" (7.8 mmI.D.×30 cm)×1 "TSKgel G3000" (7.8 mmI.D.×30 cm)×1 "TSKgel G2000" (7.8 mmI.D.×30 cm)×1 Detector: RI (differential refractometer) Column temperature: 40℃ Eluent: Tetrahydrofuran (Tetrahydrofuran, THF) Flow rate: 1.0 mL/min Injection volume: 100 μL (a tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard sample: Use the following standard polystyrene to make a standard curve.
(標準聚苯乙烯) 東曹股份有限公司製造的「TSKgel標準聚苯乙烯A-500」 東曹股份有限公司製造的「TSKgel標準聚苯乙烯A-1000」 東曹股份有限公司製造的「TSKgel標準聚苯乙烯A-2500」 東曹股份有限公司製造的「TSKgel標準聚苯乙烯A-5000」 東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-1」 東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-2」 東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-4」 東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-10」 東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-20」 東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-40」 東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-80」 東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-128」 東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-288」 東曹股份有限公司製造的「TSKgel標準聚苯乙烯F-550」(Standard polystyrene) "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Co., Ltd. "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Co., Ltd.
[黏度的測定方法] 將實施例及比較例中所獲得的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物於120℃下熔融1小時,然後取樣1 ml,利用錐板(cone-plate)黏度計(40P錐體,轉子轉速:50 rpm)來測定熔融黏度,並如以下般評價低黏度性。 「○」:小於30,000 mPa·s 「×」:30,000 mPa·s以上[Method of Measuring Viscosity] The moisture-curing polyurethane hot-melt resin composition obtained in the examples and comparative examples was melted at 120°C for 1 hour, and then 1 ml was sampled, and the cone-plate viscometer (40P) Cone, rotor speed: 50 rpm) to measure the melt viscosity, and evaluate the low viscosity as follows. "○": Less than 30,000 mPa·s "×": 30,000 mPa·s or more
[初期接著強度的測定方法] 使實施例及比較例中所獲得的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物分別於120℃的溫度下熔融1小時。使用敷料器(applicator),將該接著劑以使厚度成為100 μm的方式塗佈於聚對苯二甲酸乙二酯片材上。於該塗佈層上貼合聚對苯二甲酸乙二酯片材,利用壓接輥進行壓接。於壓接後5分鐘後,使用島津製作所股份有限公司製造的精密萬能試驗機「AG-10NX」來測定接著強度(N/25 mm),並如以下般評價初期接著強度。 「○」:接著強度為15(N/25 mm)以上。 「×」:接著強度小於15(N/25 mm)。[Measuring method of initial adhesive strength] The moisture-curable polyurethane hot-melt resin compositions obtained in the Examples and Comparative Examples were melted at a temperature of 120°C for 1 hour, respectively. Using an applicator, the adhesive was applied to the polyethylene terephthalate sheet so that the thickness would be 100 μm. A polyethylene terephthalate sheet was stuck on the coating layer, and pressure-bonded with a pressure-bonding roller. Five minutes after crimping, the adhesion strength (N/25 mm) was measured using the precision universal testing machine "AG-10NX" manufactured by Shimadzu Corporation, and the initial adhesion strength was evaluated as follows. "○": Adhesive strength is 15 (N/25 mm) or more. "×": Adhesion strength is less than 15 (N/25 mm).
[柔軟性的評價方法] 將實施例及比較例中所獲得的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物於110℃下熔融1小時,然後,於聚酯不織布上,使用刀式塗佈機以使硬化後的膜厚成為100 μm的方式進行塗敷,並放置3天,藉此獲得硬化皮膜。根據對其的觸感而如以下般評價柔軟性。 「○」:富有柔軟性。 「×」:給人硬的印象。[Method of evaluating flexibility] The moisture-curing polyurethane hot-melt resin composition obtained in the examples and comparative examples was melted at 110°C for 1 hour, and then, on the polyester non-woven fabric, a knife coater was used to harden The latter was applied so that the film thickness became 100 μm, and it was left for 3 days to obtain a hardened film. Based on the touch, the softness was evaluated as follows. "○": Rich in flexibility. "×": Gives a hard impression.
[塗佈適應性的評價方法] 將實施例及比較例中所獲得的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物於110℃下熔融1小時,然後,於聚對苯二甲酸乙二酯片材上,使用敷料器以使厚度成為100 μm的方式進行塗佈,並如以下般評價塗佈適應性。 「○」:塗佈不均勻,塗佈條紋少。 「×」:塗佈不均勻,塗佈條紋多。[Evaluation method of coating suitability] The moisture-curing polyurethane hot-melt resin composition obtained in the examples and comparative examples was melted at 110°C for 1 hour, and then a dressing was applied on a polyethylene terephthalate sheet The device was coated so that the thickness was 100 μm, and the coating suitability was evaluated as follows. "○": The coating is uneven and there are few coating streaks. "×": The coating is uneven and there are many coating streaks.
[耐水解性的評價方法] 將實施例及比較例中所獲得的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物於110℃下熔融1小時,然後,於脫模紙上,使用敷料器以使厚度成為100 μm的方式進行塗佈,並放置3天,藉此獲得硬化皮膜。將所獲得的硬化皮膜於70℃、濕度95%的條件下固化3週。依據JIS-K7312(1996),使用島津製作所股份有限公司製造的「自動繪圖儀(autograph)AG-I」,於固化前後測定皮膜的抗張力,將以固化前的值為100時的固化後的相對值為50以上的情況評價為「○」、將小於50的情況評價為「×」。[Evaluation method of hydrolysis resistance] The moisture-curing polyurethane hot-melt resin composition obtained in the Examples and Comparative Examples was melted at 110°C for 1 hour, and then, on a release paper, an applicator was used to make the thickness 100 μm. The method is applied and left for 3 days to obtain a hardened film. The obtained cured film was cured for 3 weeks under the conditions of 70°C and 95% humidity. According to JIS-K7312 (1996), using the "autograph AG-I" manufactured by Shimadzu Corporation, the tensile strength of the film is measured before and after curing, and the relative value after curing when the value before curing is 100 When the value is 50 or more, it is evaluated as "○", and when it is less than 50, it is evaluated as "×".
[表1]
[表2]
[表3]
可知:本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物的低黏度性、初期接著強度、柔軟性、塗佈適應性及耐水解性優異。It can be seen that the moisture-curing polyurethane hot-melt resin composition of the present invention is excellent in low viscosity, initial adhesive strength, flexibility, coating suitability, and hydrolysis resistance.
另一方面,比較例1是芳香族聚酯多元醇的使用量多於本發明中所規定的範圍的態樣,低黏度性、柔軟性及塗佈適應性不良。On the other hand, in Comparative Example 1, the amount of the aromatic polyester polyol used was more than the range specified in the present invention, and the low viscosity, flexibility, and coating adaptability were poor.
比較例2是不使用聚酯多元醇(a1)的態樣,塗佈適應性不良。In Comparative Example 2, the polyester polyol (a1) was not used, and the coating adaptability was poor.
比較例3是不使用聚醚多元醇(a2)的態樣,耐水解性不良。In Comparative Example 3, the polyether polyol (a2) was not used, and the hydrolysis resistance was poor.
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