CN113166616B - 基材粘接性良好的聚氨酯树脂和使用该树脂的粘接剂组合物 - Google Patents

基材粘接性良好的聚氨酯树脂和使用该树脂的粘接剂组合物 Download PDF

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CN113166616B
CN113166616B CN201980077588.1A CN201980077588A CN113166616B CN 113166616 B CN113166616 B CN 113166616B CN 201980077588 A CN201980077588 A CN 201980077588A CN 113166616 B CN113166616 B CN 113166616B
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冈岛裕树
示野胜也
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Dongyang Textile Mc Co ltd
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Abstract

本发明提供耐热性优异且对各种基材的粘接性良好的聚氨酯树脂以及使用了该树脂的粘接剂组合物。一种聚氨酯树脂,其中作为共聚成分,含有聚碳酸酯多元醇(A)、有机二异氰酸酯(B)和扩链剂(C);在聚碳酸酯多元醇(A)中,含有60摩尔%以上的特定结构,玻璃化转变温度为50℃以上。

Description

基材粘接性良好的聚氨酯树脂和使用该树脂的粘接剂组合物
技术领域
本发明涉及使用了具有特定骨架的聚碳酸酯二醇和有机二异氰酸酯的、对各种基材的粘接性良好的聚氨酯树脂,以及使用了该树脂的粘接剂组合物。
背景技术
历来,聚氨酯树脂被广泛用作与例如,聚对苯二甲酸乙二醇酯膜、聚碳酸酯膜等基材的粘接剂。这是因为可以设计宽泛的物理特性、形态、固化图案,进一步地,耐化学品性等化学性质也优异(专利文献1)。
现有技术文献
专利文献
专利文献1:日本特开2013-245312号公报
发明内容
发明要解决的课题
但是,上述粘接剂的构成成分中,多含直链脂肪族骨架,从而使膜柔软或提高反应性,但该柔软性又会产生由热负荷、热水处理等导致的因流出、分解带来的密合性降低的课题。此外,发挥密合性受到基材的限制,基材选择性也成为课题。
为了解决上述以往技术课题从而完成本发明。即本发明涉及耐热性优异且对各种基材的粘接性良好的聚氨酯树脂和使用了该树脂的粘接剂组合物。
解决课题的手段
本发明人对上述主要因素进行各种研究,结果发现:使用了以具有特定骨架的聚碳酸酯二醇为主原料的聚氨酯树脂的粘接剂组合物,对各种基材的粘接性和耐热性优异,从而完成本发明。即,本发明具有以下构成。
一种聚氨酯树脂,其中作为共聚成分,含有聚碳酸酯多元醇(A)、有机二异氰酸酯(B)和扩链剂(C);聚碳酸酯多元醇(A)中,含有60摩尔%以上的下述通式(1)表示的结构;所述聚氨酯树脂的玻璃化转变温度为50℃以上。
[化1]
Figure BDA0003082791120000021
(在通式(1)中,n表示1~20的整数。)
上述有机二异氰酸酯(B)优选异佛尔酮二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯,上述扩链剂(C)优选碳原子数7以下的二醇化合物。
一种粘接剂组合物,其含有上述聚氨酯树脂和交联剂。
发明效果
本发明的聚氨酯树脂和该粘接剂组合物对各种基材的粘接性优异、耐热性和流出性也优异,因此,适宜为丝网油墨用的粘接剂、模内成型用的粘接剂等。
具体实施方式
本发明的聚氨酯树脂中,作为共聚成分,含有聚碳酸酯多元醇(A)、有机二异氰酸酯(B)和扩链剂(C)。
<聚碳酸酯多元醇(A)>
本发明使用的聚碳酸酯多元醇(A)需要含有下述通式(1)表示的结构。以聚碳酸酯多元醇(A)整体为100摩尔%时,通式(1)表示的结构含量需要为60摩尔%以上,优选70摩尔%以上,更优选75摩尔%以上,进一步地优选80摩尔%以上,,更进一步地优选90摩尔%以上,特别优选95摩尔%以上,即使是100摩尔%也没有问题。。通过含有通式(1)表示的结构,从而可以赋予聚氨酯树脂柔软性,体现优异的粘接性和耐热性。
[化1]
Figure BDA0003082791120000031
在通式(1)中,n表示1~20的整数。优选地,n为2以上,更优选3以上,进一步地优选5以上。此外,优选18以下,更优选15以下,进一步地优选10以下。如果在上述范围内,那么可以提高得到的聚氨酯树脂的内聚力,体现优异的粘接性和耐热性。
作为具有通式(1)表示的结构的聚碳酸酯多元醇以外的聚碳酸酯多元醇(A),可以使用脂肪族聚碳酸酯多元醇、脂环族聚碳酸酯或芳香族聚碳酸酯多元醇。以聚碳酸酯多元醇(A)整体为100摩尔%时,这些聚碳酸酯多元醇优选40摩尔%以下,更优选30摩尔%以下,进一步地优选20摩尔%以下,更进一步地优选10摩尔%以下,特别优选5摩尔%以下,即使是0摩尔%也没有问题。
作为脂肪族聚碳酸酯多元醇,无特别限定,可以使用丁二醇、戊二醇、己二醇、聚己内醇、聚丁二醇、丙二醇、新戊二醇等直链或支链的脂肪族二醇与碳酸二酯等通过反应得到的聚碳酸酯二醇。作为脂环族聚碳酸酯多元醇,无特别限定,可以使用通过使异山梨醇等脂环族二醇和碳酸二酯等反应得到的聚碳酸酯二醇。作为芳香族聚碳酸酯二醇,无特别限定,可以使用通过使苯二甲醇、萘二甲醇等芳香族二醇与碳酸二酯等反应得到的聚碳酸酯二醇。可以使用上述二醇中由组合1种或2种以上的原料形成的聚碳酸酯二醇。
聚碳酸酯多元醇(A)的数均分子量优选300~2,500,更优选500~1,500。通过使数均分子量在上述下限值以上,从而可以提高得到的聚氨酯树脂的内聚力,,显现优异的粘接性、耐热性。此外,通过使数均分子量在上述上限值以下,从而可以适当地确保氨酯键数目,可以显现优异的粘接性、耐热性。
聚碳酸酯二醇(A)的数均分子量通过下述算式计算。
数均分子量=(56.1×1000×价数)/羟值[mgKOH/g]
在上述式中,价数是1分子中的羟基数量,[mgKOH/g]是羟值的单位。
<有机二异氰酸酯(B)>
本发明中使用的有机二异氰酸酯(B),可列举四亚甲基二异氰酸酯、六亚甲基二异氰酸酯(HDI)、2-甲基-1,5-戊烷二异氰酸酯、十亚甲基二异氰酸酯、3-甲基-1,5-戊烷二异氰酸酯、赖氨酸二异氰酸酯等脂肪族二异氰酸酯;异佛尔酮二异氰酸酯(IPDI)、氢化甲苯二异氰酸酯、氢化二苯基甲烷二异氰酸酯、氢化苯二甲基二异氰酸酯、氢化四甲基苯二甲基二异氰酸酯、环己基二异氰酸酯等脂环族二异氰酸酯;2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯(MDI)、2,4’-二苯基甲烷二异氰酸酯、2,2’-二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯、1,4-萘二异氰酸酯、邻苯二异氰酸酯、对苯二异氰酸酯、间苯二异氰酸酯、邻苯二甲基二异氰酸酯、间苯二甲基二异氰酸酯、对苯二甲基二异氰酸酯、四甲基苯二甲基二异氰酸酯、4,4’-二苯基醚二异氰酸酯、2-硝基二苯基-4,4’-二异氰酸酯、2,2’-二苯基丙烷-4,4’-二异氰酸酯、3,3’-二甲基二苯基甲烷-4,4’-二异氰酸酯、4,4’-二苯基丙烷二异氰酸酯、3,3’-二甲氧基二苯基-4,4’-二异氰酸酯等芳香族二异氰酸酯。此外,还可列举含有2种以上上述有机二异氰酸酯的混合物、这些有机二异氰酸酯的氨基甲酸酯改性体、脲基甲酸酯改性体、脲改性体、缩二脲改性体、脲二酮改性体、脲亚胺改性体、异氰脲酸酯改性体、碳二亚胺改性体等。本发明中,优选有机二异氰酸酯为六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或4,4’-二苯基甲烷二异氰酸酯,进一步地,特别优选得到的聚氨酯树脂的溶剂溶解性良好,此外,制造时的凝胶化可能性小、耐候性和树脂的机械强度优异的异佛尔酮二异氰酸酯。
相对于聚碳酸酯多元醇(A)100质量份,有机二异氰酸酯(B)的共聚量优选1质量份以上,更优选2质量份以上,进一步地优选5质量份以上,特别优选10质量份以上。此外,优选60质量份以下,更优选50质量份以下,进一步地优选45质量份以下,特别优选40质量份以下。通过该含量在上述范围内,从而可以得到粘接性和耐热性优异聚氨酯树脂。
<扩链剂(C)>
本发明中使用的扩链剂(C)只要是延长聚氨酯树脂的分子链的化合物,就无特别限定,优选具有与有机二异氰酸酯(B)反应的基团。作为扩链剂(C),无特别限定,基于制造时的凝胶化、反应性的观点,优选多元醇化合物,更优选二醇化合物。作为二醇化合物,可以为脂肪族二醇化合物、芳香族二醇化合物或脂环族二醇化合物中的任一种,优选脂肪族二醇化合物。其中,优选碳原子数为10以下的直链或支链的脂肪族二醇化合物,更优选碳原子数为7以下的直链或支链的脂肪族二醇化合物。其下限无特别限定,优选碳原子数为2以上的直链或支链的脂肪族二醇化合物,更优选碳原子数为3以上的直链或支链的脂肪族二醇化合物。具体而言,可列举乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、3-甲基-1,5-戊二醇、新戊二醇、2-乙基-4-丁基-1,3-丙二醇、二乙二醇、二丙二醇、新戊二醇等。本发明中,基于反应性、耐热性的观点,优选新戊二醇或1,6-己二醇。
相对于聚碳酸酯多元醇(A)100质量份,扩链剂(C)的共聚量优选1质量份以上,更优选2质量份以上,进一步地优选3质量份以上,特别优选4质量份以上。此外,优选20质量份以下,更优选15质量份以下,进一步地优选10质量份以下,特别优选8质量份以下。通过使该含量在上述范围内,可以得到粘接性和耐热性优异聚氨酯树脂。
<聚氨酯树脂>
本发明的聚氨酯树脂的玻璃化转变温度需要为50℃以上。优选55℃以上,更优选60℃以上。通过使该温度在上述下限值以上,可以抑制热负荷带来的与基材的粘接性的降低,抑制流出的发生。此外,优选120℃以下。更优选110℃以下,进一步地优选100℃以下,特别优选95℃以下。通过使该温度在上述上限值以下,可以抑制对基材的粘接性的降低。
本发明的聚氨酯树脂的数均分子量优选5,000~50,000,更优选8,000~30,000,进一步地优选12,000~22,000。通过使数均分子量在上述下限值以上,可以抑制因聚氨酯树脂内聚力的降低引起的粘接性降低;热负荷引起的与基材的粘接性降低。此外,通过使数均分子量在上述上限值以下,可抑制聚氨酯树脂的溶液(清漆)粘度的上升,操作变容易。
以聚氨酯树脂为100质量%时,聚碳酸酯多元醇(A)、有机二异氰酸酯(B)和扩链剂(C)的总量优选80质量%以上,更优选90质量%以上,进一步地优选95质量%,特别优选99质量%以上,即使是100质量%也没有问题。通过使该总量在上述范围内,可以显现优异的粘接性和耐热性。
作为本发明使用的聚氨酯树脂的合成方法,可以将具有特定骨架的聚碳酸酯二醇(A)和有机二异氰酸酯(B)、扩链剂(C)一起加入反应容器,也可以分别加入。对于体系内的聚碳酸酯二醇(A)和扩链剂(C)的羟值的总合,与有机二异氰酸酯(B)的异氰酸酯基的总合,优选异氰酸酯基/羟基的官能团的比例在1以下使反应进行。更优选0.99以下,进一步地优选0.98以下。此外,该比例优选0.90以上,更优选0.94以上,进一步地优选0.96以上。此外,该反应,可以在存在或不存在相对于异氰酸酯基为惰性溶剂的条件下使反应进行,从而可以稳定地制造。作为该溶剂,无特别限定,可列举酯系溶剂(乙酸乙酯、乙酸丁酯、丁酸乙酯等);醚系溶剂(二恶烷、四氢呋喃、二乙醚等);酮系溶剂(环己酮、甲基乙基酮、甲基异丁酮等);芳香族烃系溶剂(苯、甲苯、二甲苯等)和它们的混合溶剂。作为反应装置,不仅有具备搅拌装置的反应容器(反应罐),也可以使用捏合机、双轴挤压机之类的混合混炼装置。
为了促进上述这样的氨基甲酸酯化反应,可以使用在通常的氨基甲酸酯化反应中使用的催化剂。作为催化剂,可以使用例如锡系催化剂(月桂酸三甲基锡、二月桂酸二甲基锡、三甲基氢氧化锡、二甲基二氢氧化锡、辛酸锡等);铋系催化剂;铅系催化剂(油酸铅、2-乙基己二酸铅等);胺系催化剂(三乙胺、三丁胺、吗啉、二氮杂双环辛烷等)等。这些催化剂,可以单独使用,也可以并用2种以上。
<交联剂>
本发明中使用的交联剂,只要是与上述聚氨酯树脂反应而交联的物质,就无特别限定。优选1分子中具有2个以上的官能团的化合物,作为官能团,可列举异氰酸酯基、环氧基、氨基、羟甲基、烷氧基甲基、亚氨基、金属螯合基团、吖丙啶基等。作为具体的化合物,可列举多官能异氰酸酯化合物、多官能环氧化合物、多官能三聚氰胺化合物、金属交联剂、多官能氮丙啶化合物等。
多官能异氰酸酯化合物是每1分子具有2个以上异氰酸酯基的化合物。作为具体例,可列举甲苯二异氰酸酯(TDI)、4,4’-二苯基甲烷二异氰酸酯(MDI)、六亚甲基二异氰酸酯、邻苯二甲基二异氰酸酯、间苯二甲基二异氰酸酯、对苯二甲基二异氰酸酯、1,5-萘二异氰酸酯、1,4-萘二异氰酸酯、1,8-萘二异氰酸酯、氢化二苯基甲烷二异氰酸酯、氢化甲苯二异氰酸酯、氢化苯二甲基二异氰酸酯、异佛尔酮二异氰酸酯等二异氰酸酯化合物、由它们形成的聚异氰酸酯化合物,可列举有机二异氰酸酯的氨基甲酸酯改性体、脲基甲酸酯改性体、脲改性体、缩二脲改性体、脲二酮改性体、脲亚胺改性体、异氰脲酸酯改性体、碳二亚胺改性体等。它们可以单独使用,也可以并用2种以上。
多官能环氧化合物是每1分子具有2个以上环氧基的化合物。作为具体例,可列举1,6-己二醇、新戊二醇、聚亚烷基二醇之类的脂肪族二醇的二缩水甘油醚;山梨糖醇、脱水山梨糖醇、聚甘油、季戊四醇、二甘油、甘油、三羟甲基丙烷等脂肪族多元醇的聚缩水甘油醚;环己烷二甲醇等脂环族多元醇的聚缩水甘油醚;对苯二甲酸、间苯二甲酸、萘二羧酸、偏苯三酸、己二酸、癸二酸等脂肪族或芳香族多元羧酸的二缩水甘油酯或聚缩水甘油酯。此外,可列举间苯二酚、双(对羟基苯基)甲烷、2,2-双(对羟基苯基)丙烷、三(对羟基苯基)甲烷、1,1,2,2-四(对羟基苯基)乙烷等多元苯酚的二缩水甘油醚或者聚缩水甘油醚、N,N-二缩水甘油苯胺、N,N-二缩水甘油基甲苯胺、N,N,N’,N’-四缩水甘油-双(对氨基苯基)甲烷之类的胺的N-缩水甘油衍生物、氨基酚的三缩水甘油衍生物、三缩水甘油三(2-羟基乙基)异氰脲酸酯、三缩水甘油异氰脲酸酯、邻甲酚型环氧、苯酚酚醛清漆型环氧、双苯酚型多官能环氧化合物。它们可以单独使用,也可以并用2种以上。
作为金属交联剂,可列举在铝、锌、镉、镍、钴、铜、钙、钡、钛、锰、铁、铅、锆、铬、锡等金属上配位了乙酰丙酮、乙酰乙酸甲酯、乙酰乙酸乙酯、乳酸乙酯、水杨酸甲酯等的金属螯合物等。它们可以单独使用,也可以并用2种以上。
多官能氮丙啶化合物是每1分子具有2个以上吖丙啶基的化合物。作为具体例,可列举N,N’-六亚甲基-1,6-双(1-吖丙啶甲酰胺)、三羟甲基丙烷-三-β-吖丙啶基丙酸酯、双间苯二甲酰基-1-(2-甲基吖丙啶)、三-1-吖丙啶基氧化膦、N,N’-二苯基乙烷-4,4’-双(1-吖丙啶甲酰胺)等。它们可以单独使用,也可以并用2种以上。
作为上述交联剂,优选多官能异氰酸酯化合物。更优选苯二甲基二异氰酸酯或其改性体。
相对于聚氨酯树脂100质量份,交联剂的含量优选1质量份以上,更优选2质量份以上,进一步地优选3质量份以上。此外,该含量优选30质量份以下,更优选25质量份以下,进一步地优选20质量份以下。通过使该含量在上述范围内,可以显现优异的粘接性和耐热性。
<粘接剂组合物>
本发明的粘接剂组合物为含有上述聚氨酯树脂和上述交联剂的组合物。粘接剂组合物的固体成分中,聚氨酯树脂的含量优选60质量%以上,更优选70质量%以上,进一步地优选80质量%以上。此外,该含量优选98质量%以下,更优选95质量%以下,进一步地优选93质量%以下。通过在上述范围内含有该树脂,可以显现优异的粘接性和耐热性。
本发明的粘接剂组合物可以用有机溶剂稀释成为清漆。作为有机溶剂,无特别限定,可列举酯系溶剂(乙酸乙酯、乙酸丁酯、丁酸乙酯等)、醚系溶剂(二恶烷、四氢呋喃、二乙醚等);酮系溶剂(环己酮、甲基乙基酮、甲基异丁酮等);芳香族烃系溶剂(苯、甲苯、二甲苯等)和它们的混合溶剂。相对于聚氨酯树脂100质量份,有机溶剂优选50质量份以上,更优选100质量份以上,进一步地优选200质量份以上。此外,该含量优选2000质量份以下,更优选1000质量份以下,进一步地优选500质量份以下。该含量在上述范围内时,粘接剂组合物的保存稳定性良好,对基材的涂布性提高。此外,在成本方面也有利。
在不损害本发明的效果的范围内,粘接剂组合物中可以含有紫外线吸收剂,抗氧化剂,阻燃剂,填料等公知的添加剂。
实施例
以下,使用实施例对本发明进行说明,但是本发明并不受实施例所限定。除非另有说明,实施例中,份表示质量份,%表示质量%。此外,各测定项目a按照以下的方法进行。
<数均分子量(Mn)>
在4ml的四氢呋喃(添加5mM氯化四丁铵)中溶解4mg试料(聚碳酸酯多元醇(A)或聚氨酯树脂)后,使用0.2μm的膜过滤器过滤,作为试料溶液。用凝胶渗透色谱对试料溶液进行分析。作为装置,使用TOSOH HLC-8220,作为检测器,使用示差折光率检测器,在流速1mL/分钟,色谱柱温度40℃下,进行测定。分子量标准中使用单分散聚苯乙烯,数均分子量作为标准聚苯乙烯换算值,省略与分子量小于1000相当的部分进行计算。
<玻璃化转变温度(Tg)>
玻璃化转变温度是根据动态粘弹性的温度依存性测定结果,以储能弹性模量(E')的拐点处的温度为玻璃化转变温度。在聚丙烯膜(东洋纺株式会社制造P2161,厚度50μm)上,以湿膜厚(干燥前的厚度)200μm涂布得到的聚氨酯树脂溶液,在120℃下进行1小时加热,使溶剂挥发(干燥)。接着,从聚丙烯膜剥离聚氨酯树脂溶液干燥后的膜,作为聚氨酯树脂的试料膜。测定该试料膜的玻璃化转变温度。装置使用IT计测制御株式会社制造的动态粘弹性测定装置DVA-220,测定0℃~150℃(4℃/min,10Hz)的温度依存性。
聚氨酯树脂(U1)的制造例
向具备温度计、搅拌机、回流式冷却管和蒸馏管的反应容器中,加入100份UC-100(宇部兴产制聚碳酸酯二醇)、5份新戊二醇,204份甲基乙基酮(MEK),溶解后,投入31份异佛尔酮二异氰酸酯,搅拌,形成均匀的溶液。之后,加入0.5份的BiCAT8210(The ShepherdChemical Company制)作为催化剂,在75℃下反应5小时。使其充分反应,投入113份甲基乙基酮(MEK)搅拌后,得到作为目标的固体成分浓度(NV)30质量%的聚氨酯树脂(U1)的溶液。由此得到的聚氨酯树脂(U1)的特性如表1所示。
聚氨酯树脂(U2)~(U10)的制造例
除了变更原料的种类和混合比例,与聚氨酯树脂(U1)的制造例同样地得到聚氨酯树脂(U2)~(U10)。它们的特性如表1所示。
[表1]
Figure BDA0003082791120000091
实施例1~8、比较例1~3
使用上述聚氨酯树脂(U1)~(U10)制作层叠体,进行初期粘接力(粘接性)和耐热性的评价。另外,对于实施例8,相对于聚氨酯树脂溶液100质量份(固体成分换算30质量份),作为交联剂,添加4质量份(固体成分换算3质量份)的D-110N(三井化学制,固体成分浓度75质量%)进行评价。
层叠体的制作
在聚碳酸酯膜上(住友电木株式会社制造,EC105,0.5mm)用刮棒涂布机涂布聚氨酯树脂(P1)的溶液使干膜厚(干燥后的膜厚)为5μm,在120℃下进行3分钟加热,使溶剂挥发(干燥)。接着,在上述膜的聚氨酯树脂面上,用干式层压机压合(干式层压)聚碳酸酯膜(住友电木株式会社制造,EC105,0.5mm)。在辊温度120℃、辊荷重3kg/cm、被压合物速度1m/分钟下进行干式层压。接着,在80℃下、进行1小时的老化,得到层叠体。
初期粘接力(粘接性)试验
从上述层叠体切取宽度15mm的短条状,进行使用TENSILON(注册商标)(东洋测器(株)制,UTM-IV)的剥离(T型剥离,拉伸速度100mm/分钟),观察剥离的状态,评价粘接性。评价结果如表2所示。
(评价)
○:粘接剂内聚破裂或材料破裂。
△:界面剥离,且粘接强度为10N/15mm。
×:粘接强度小于10N/15mm。
耐热性试验
将上述层叠体在105℃下进行300小时处理(静置),与初期粘接力试验同样地评价粘接性。
(评价)
◎:不发生浮起,粘接剂内聚破裂或材料破裂。
○:不发生浮起,主要为内聚剥离,一部分界面剥离。
△:不发生浮起,界面剥离。
×:发生浮起。
[表2]
Figure BDA0003082791120000111
表1、表2使用的化合物如以下所示。
UC-100:基于1,4-环己烷二甲醇的宇部兴产制造的聚碳酸酯二醇,数均分子量=1000,聚碳酸酯多元醇(A)中的通式(1)所示结构的含有比例100摩尔%
UH-100:基于1,6-己二醇的宇部兴产制造的聚碳酸酯二醇,数均分子量=1000,聚碳酸酯多元醇(A)中的通式(1)所示的结构的含有比例0摩尔%
PH-100:基于1,6-己二醇和1,5-戊二醇的宇部兴产制造的聚碳酸酯二醇,数均分子量=1000,聚碳酸酯多元醇(A)中的通式(1)所示的结构的含有比例0摩尔%
UM-90(3/1):基于1,4-环己烷二甲醇和1,6-己二醇的宇部兴产制造的聚碳酸酯二醇,数均分子量=900,聚碳酸酯多元醇(A)中的通式(1)所示的结构的含有比例75摩尔%
UM-90(1/1):基于1,4-环己烷二甲醇和1,6-己二醇的宇部兴产制造的聚碳酸酯二醇,数均分子量=900,聚碳酸酯多元醇(A)中的通式(1)所示的结构的含有比例50摩尔%
D-110N:三井化学制造,间苯二甲基二异氰酸酯的三羟甲基丙烷加成物,固体成分比例75质量%
IPDI:异佛尔酮二异氰酸酯
MDI:二苯基甲烷二异氰酸酯
HDI:六亚甲基二异氰酸酯
NPG:新戊二醇
HD:1,6-己二醇

Claims (4)

1.一种聚氨酯树脂,其中作为共聚成分,含有聚碳酸酯多元醇(A)、有机二异氰酸酯(B)和扩链剂(C);聚碳酸酯多元醇(A)中,含有60摩尔%以上的下述通式(1)表示的结构;相对于聚碳酸酯多元醇(A)100质量份,所述有机二异氰酸酯(B)的共聚量为1质量份以上,60质量份以下;
[化1]
Figure FDA0003921003840000011
在通式(1)中,n表示1~20的整数,
所述聚氨酯树脂的玻璃化转变温度为50℃以上。
2.根据权利要求1所述的聚氨酯树脂,所述有机二异氰酸酯(B)为异佛尔酮二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯或六亚甲基二异氰酸酯。
3.根据权利要求1或2所述的聚氨酯树脂,所述扩链剂(C)为碳原子数10以下的二醇化合物。
4.一种粘接剂组合物,其含有权利要求1~3中任一项所述的聚氨酯树脂和交联剂。
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