CN110325596B - 热交联性组合物 - Google Patents

热交联性组合物 Download PDF

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Publication number
CN110325596B
CN110325596B CN201880013600.8A CN201880013600A CN110325596B CN 110325596 B CN110325596 B CN 110325596B CN 201880013600 A CN201880013600 A CN 201880013600A CN 110325596 B CN110325596 B CN 110325596B
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acid
crosslinkable composition
mass
thermally crosslinkable
modified polymer
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CN110325596A (zh
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张雁妹
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Sunstar Engineering Inc
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Sunstar Engineering Inc
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Abstract

本发明涉及一种热交联性组合物，该热交联性组合物含有熔点为110～150℃且结晶化温度为50～90℃的酸改性聚合物A、熔点为30～110℃且结晶化温度低于50℃的酸改性聚合物B、增粘树脂及固化剂，该热交联性组合物的结晶化温度为30～70℃。

Description

热交联性组合物
技术领域
本专利申请主张以日本专利申请第2017-135200号(2017年7月11日申请)为基础的巴黎公约的优先权，通过参照此处，将上述申请中记载的全部内容编入本说明书。
本发明涉及热交联性组合物、含有该热交联性组合物的热熔型粘合剂、膜状粘合剂及粘合性表皮材料用粘合剂、以及粘合性表皮材料及含有粘合性表皮材料的汽车内装部件及建筑内装材料。
背景技术
以往，在汽车内装部件中，为了将表皮材料与基材粘合而使用热交联性组合物。
专利文献1中提出了一种含有热塑性聚合物的单液型交联性组成物，所述热塑性聚合物含有羧酸基或其酸酐基。
专利文献2中提出了一种单液型交联性粘合剂，其包含聚烯烃与含苯乙烯热塑性弹性体的混合物，所述聚烯烃含有羧酸或其酸酐基且软化温度为80～140℃，所述含苯乙烯热塑性弹性体含有羧酸或其酸酐基且软化温度为80℃以上。
专利文献3中提出了一种粘合剂组成物，其含有软化点相差30℃以上的至少2种热塑性聚合物的混合物。
现有技术文献
专利文献
专利文献1日本特开2000-198940号公报
专利文献2日本特开2003-94524号公报
专利文献3日本特开2008-127450号公报
发明内容
发明所要解决的课题
但是，已知：在将涂有专利文献1、2所述的热交联性组合物的表皮材料加热到规定的温度后贴合到基材时，所配合的潜在性固化剂发挥作用，表现出汽车内装部件所要求的耐热性，但是涂布至表皮材料后直至使表皮材料与基材贴合为止的时间、即涂布后的保存期不充分。另外，关于专利文献3，存在如下课题：由于未配合潜在性固化剂，故而涂布后的保存期足够长，但是贴合后的耐热温度低，能适用的部位受限定。
因此，本发明的目的在于提供一种热交联性组合物，涂布在表皮材料上的热交联性组合物对基材的初期密合性及耐热性优异，涂布后的保存期充分。
用于解决课题的技术手段
本发明人针对热交联性组合物的初期密合性和耐热性进行了深入研究，结果发现，作为原料聚合物(base polymer)将熔点和结晶化温度比较高的热塑性聚合物与熔点和结晶化温度比较低的热塑性聚合物组合使用，并且发现通过两者的配合，热交联性组合物的结晶化温度变得比较低，维持优异的耐热性，同时在比较低的温度下也表现出粘合性，对基材的润湿性提高，从而能够确保涂布在表皮材料上的热交联性组合物对基材的初期密合性。
另外，本发明人发现，通过使用上述熔点及结晶化温度比较低的热塑性聚合物，熔点及结晶化温度比以往使用的热塑性聚合物高的热塑性聚合物的使用变得可能。其结果，即使在热交联性组合物中的固化剂的量比较少的情况下，也能够得到优异的耐热性，通过减少固化剂的量，也能够使涂布后保存期提高。
本发明中，包含以下内容。
[1]一种热交联性组合物，含有熔点为110～150℃且结晶化温度为50～90℃的酸改性聚合物A、熔点为30～110℃且结晶化温度低于50℃的酸改性聚合物B、增粘树脂及固化剂，且所述热交联性组合物的结晶化温度为30～70℃。
[2]根据[1]所述的热交联性组合物，其中，相对于100质量份的酸改性聚合物A，含有30～200质量份酸改性聚合物B，且相对于总量100质量份的酸改性聚合物A及B，含有20～200质量份增粘树脂及0.2～3质量份固化剂。
[3]根据[1]或[2]所述的热交联性组合物，其中，在100质量％的全部增粘树脂中，酸值为5以下的增粘树脂为20～100质量％。
[4]根据[3]所述的热交联性组合物，其中，酸值在5以下的增粘树脂选自松香类、萜烯类及石油树脂类。
[5]根据[1]～[4]中任一项所述的热交联性组合物，其中，固化剂是熔点为150℃以上的固态多胺化合物。
[6]根据[5]所述的热交联性组合物，其中，熔点为150℃以上的固态多胺化合物是酰肼类多胺。
[7]根据[1]～[6]中任一项所述的热交联性组合物，其中，进一步含有酸未改性热塑性树脂。
[8]根据[7]所述的热交联性组合物，其中，酸未改性热塑性树脂是酸未改性的含有苯乙烯的热塑性弹性体。
[9]根据[1]～[8]中任一项所述的热交联性组合物，进一步含有溶剂。
[10]一种热熔型粘合剂，含有[1]～[9]中任一项所述的热交联性组合物。
[11]一种膜状粘合剂，含有[1]～[9]中任一项所述的热交联性组合物。
[12]一种粘合性表皮材料用粘合剂，含有[1]～[9]中任一项所述的热交联性组合物。
[13]一种粘合性表皮材料，含有[12]所述的粘合剂。
[14]一种汽车内装部件，含有[13]所述的粘合性表皮材料和聚烯烃基材。
[15]一种建筑用内装材料，含有[13]所述的粘合性表皮材料和聚烯烃基材。
发明效果
根据本发明，能够得到对基材的优异的初期密合性、耐热性及充分长的涂布后保存期，故而粘合性和耐热性优异的热熔型、膜型、预涂布型粘合剂适合用于要求耐热性的建筑用内装材料、汽车内装部件的粘合。
具体实施方式
本发明的热交联性组合物含有：熔点为110～150℃且结晶化温度为50～90℃的酸改性聚合物A(以下、也称为酸改性聚合物A)及熔点为30～110℃且结晶化温度低于50℃的酸改性聚合物B(以下、也称为酸改性聚合物B)。
作为酸改性聚合物A及酸改性聚合物B，能够使用含有羧酸基或其酸酐基的热塑性聚合物。
作为含有羧酸基或其酸酐基的热塑性聚合物，可以举出例如含有羧酸基或其酸酐基的烯烃类聚合物、丁二烯类聚合物、酯类聚合物、碳酸酯类聚合物、聚氨酯类聚合物及酰胺类聚合物等。其中，优选含有羧酸基或其酸酐基的烯烃类聚合物。
作为含有羧酸基或其酸酐基的烯烃类聚合物的例子，可以举出不饱和二元酸，例如马来酸、富马酸、柠康酸、中康酸(Mesaconic acid)、(甲基)丙烯酸等或导入其酸酐而改性的烯烃类聚合物。(甲基)丙烯酸是丙烯酸和甲基丙烯酸的总称。
作为烯烃类聚合物，可以举出选自苯乙烯、丙烯、丁烯中至少1种单体的均聚物或共聚物、以及与其他可共聚单体形成的共聚物。
作为其他可共聚的单体，可以举出乙酸乙烯酯、丙烯酸酯、苯乙烯、丁二烯、异戊二烯等。作为丙烯酸酯，可以举出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯等。(甲基)丙烯酸酯是丙烯酸酯和甲基丙烯酸酯的总称。
作为烯烃类聚合物的具体例子，可以举出聚丙烯、丙烯-1-丁烯-乙烯共聚物、丙烯-1-丁烯共聚物、苯乙烯-乙烯/1-丁烯-苯乙烯共聚物、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸酯共聚物、丙烯-丙烯酸酯共聚物、丙烯-丙烯酸酯-乙烯共聚物、丙烯-1-丁烯-乙烯-丙烯酸酯共聚物等。
当酸改性聚合物A是酸改性烯烃类聚合物时，对于烯烃类聚合物而言，以烯烃类聚合物为基准，优选含有20～90质量％来自丙烯的结构单元、1～60质量％来自1-丁烯的结构单元、0.1～10质量％来自乙烯的结构单元，更有选含有60～80质量％来自丙烯的结构单元、10～25质量％来自1-丁烯的结构单元、1～5质量％来自乙烯的结构单元。
当酸改性聚合物B是酸改性烯烃类聚合物时，对于烯烃类聚合物而言，以烯烃类聚合物为基准，优选含有55～95质量％来自丙烯的结构单元、5～40质量％来自丙烯酸酯和/或1-丁烯的结构单元、0～5质量％来自乙烯的结构单元。当来自乙烯的结构单元多时粘合性降低，并且当来自1-丁烯的结构单元少时不能得到初期密合性，因此，当酸改性聚合物B是酸变性烯烃类聚合物时，烯烃类聚合物更优选含有70～90质量％来自丙烯的结构单元、10～30质量％来自丙烯酸酯和/或1-丁烯的结构单元，并且不含来自乙烯的结构单元。
酸改性聚合物A及酸改性聚合物B中的酸含量分别以酸改性聚合物的质量为基准，优选0.1～10质量％、更有选0.5～5质量％、进一步优选1～4质量％。酸改性聚合物A及B中的酸含量在上述范围内时，存在能够容易得到充分交联性的倾向。
酸改性聚合物A的熔点为110～150℃，优选115～140℃、更优选120～135℃。酸改性聚合物A的熔点低于110℃时，存在难以得到充足的耐热性的倾向。酸改性聚合物A的熔点超过150℃时，存在难以得到交联性组成物的涂布性及低温下的粘合性、难以得到与基材的初期密合性的倾向。另外，酸改性聚合物A的熔点超过150℃时，存在如下倾向：涂布时的加热温度过高，因此作业性降低，当使用溶剂的情况下针对其种类、含量的选择性降低。
酸改性聚合物A的结晶化温度为50～90℃，优选55～85℃，更优选60～80℃，进一步优选60～70℃。酸改性聚合物A的结晶化温度低于50℃时，存在难以得到充足的耐热性的倾向。酸改性聚合物A的结晶化温度超过90℃时，存在难以得到与基材的初期密合性的倾向。
酸改性聚合物B的熔点为30～110℃，优选40～100℃，更优选50～95℃，进一步优选60～90℃。酸改性聚合物B的熔点低于30℃时，存在难以得到充足的耐热性、粘连性(blocking)容易降低的倾向。酸改性聚合物B的熔点超过110℃时，存在难以得到与基材的初期密合性的倾向。
酸改性聚合物B的结晶化温度低于50℃，优选0以上且低于50℃，更优选5以上且低于50℃，进一步优选8以上且低于50℃。酸改性聚合物B的结晶化温度为50℃以上时，存在难以得到与基材的初期密合性的倾向。
对于熔点而言，通过差示扫描热量计(DSC)将试料以10℃/分钟升温到200℃，将观测到的吸热峰中的峰顶的温度作为熔点。对于结晶化温度而言，通过差示扫描热量计(DSC)将试料升温到200℃，将以10℃/分钟降温时所观测到的发热峰中的峰顶的温度作为结晶化温度。
酸改性聚合物A的重均分子量(Mw)优选1万～100万，更优选3万～50万，进一步优选5万～10万。酸改性聚合物A的重均分子量(Mw)在上述范围内时，存在容易得到适度的熔点及结晶化温度的倾向。
酸改性聚合物B的重均分子量(Mw)优选1万～100万，更优选3万～50万，进一步优选5万～20万。酸改性聚合物B的重均分子量(Mw)在上述范围内时，存在容易得到适度的熔点及结晶化温度的倾向。
重均分子量Mw使用凝胶渗透色谱法进行测定，通过聚苯乙烯换算从而算出。
热交联性组合物中，相对于100质量份的酸改性聚合物A，酸改性聚合物B优选含有30～200质量份、更优选40～190质量份、进一步优选50～180质量份、特别优选60～170质量份。酸改性聚合物B的含量在上述范围内时，存在与基材的初期密合性及耐热性均能充分地获得的倾向。
对于热交联性组合物中的酸改性聚合物A及酸改性聚合物B的总含量，以热交联性组合物的固态成分为基准，优选为10～80质量份，更优选为20～70质量份，进一步优选为25～65质量份，特别优选为30～60质量份。酸改性聚合物A及B的含量在上述范围内时，存在容易得到与基材的初期密合性和耐热性的倾向。
热交联性组合物进一步含有增粘树脂。
增粘树脂的酸值优选为5以下，更优选为4以下，进一步优选为3以下。酸值为5以下时，存在交联性粘合剂的涂布后的保存期易于延长的倾向。
增粘树脂可以在常温下为液态，或者也可以在常温下为固态。增粘树脂在常温为固态时，增粘树脂的软化点优选为90～130℃，更优选为95～125℃，进一步优选为95～110℃。
作为酸值为5以下的增粘树脂，可以举出松香树脂、松香酸酯、石油树脂、古马隆-茚树脂(Coumarone indene resins)、酚醛树脂、萜烯酚醛树脂(Terpene phenolicResin)、二甲苯树脂、以及它们的氢化物、歧化物、部分氢化改性物等。其中，优选松香类、萜烯类及石油树脂类，更优选歧化松香树脂。使用歧化松香树脂时，存在容易同时得到优异的与基材和/或表皮材料的初期密合性以及充分的耐热性的倾向。
热交联性组合物中，相对于总量100质量份的酸改性聚合物A及B，增粘树脂优选含有20～200质量份，更优选含有30～150质量份，进一步优选含有40～100质量份。
在热交联性组合物含有酸值为5以下的增粘树脂的情况下，热交联性组合物中的酸值为5以下的增粘树脂在全部增粘树脂100质量％中优选为20～100质量％，更优选30～90质量％，进一步优选40～80质量％。
热交联性组合物进一步含有固化剂。
固化剂优选潜在性固化剂。作为潜在性固化剂的例子，可以举出固态多胺化合物。
固态多胺化合物的熔点优选为80℃以上、更优选为100℃以上、进一步优选为120℃以上、特别优选为150℃以上。固态多胺化合物的熔点优选为230℃以下、更优选为200℃以下。
作为熔点为80～230℃的固态多胺化合物，例如可以举出：
4,4’-二氨基二苯基甲烷、2,4’-二氨基二苯基甲烷、3,3’-二氨基二苯基甲烷、3,4’-二氨基二苯基甲烷、2,2’-二氨基联苯、3,3’二氨基联苯、邻苯二胺、2,3-甲苯二胺、2,4-甲苯二胺、2,6-甲苯二胺、3,4-甲苯二胺、1,5-萘二胺、1,3-双(3-氨基苯氧基)苯、4,4’-二氨基二苯基砜、3,3’-二氨基二苯基砜、2,4-二氨基-6-苯基-1,3,5-三嗪等熔点为80～230℃的芳香族多胺；
1,14-十四烷二胺、1,16-六癸烷二胺等熔点为80～230℃的脂肪族多胺；
下述式(1)所示的1，3-双(肼基羰基乙基)-5-异丙基乙内酰脲、
[化学式1]
Figure BDA0002177044020000071
下述式(2)所示的化合物、
[化学式2]
Figure BDA0002177044020000072
下述式(3)所示的化合物、
[化学式3]
Figure BDA0002177044020000073
己二酸二酰肼、癸二酸二酰肼、十二烷酸酰肼、十二烷二酸二酰肼、间苯二甲酸二酰肼、水杨酸酰肼等的酰肼类多胺等。其中，优选1,5-萘二胺、4,4’-二氨基二苯基砜、3,3’-二氨基二苯基砜、2，4-二氨基-6-苯基-1，3，5-三嗪、式(2)所示的化合物、式(3)所示的化合物、己二酸二酰肼、癸二酸二酰肼、十二烷酸酰肼、十二烷二酸二酰肼、间苯二甲酸二酰肼、水杨酸酰肼等熔点为150℃以上的固态多胺化合物，更优选熔点为150℃以上的酰肼类多胺。
另外，也能够使用熔点低于80℃的固态多胺化合物。作为其例，可以举出间苯二胺、2,5-甲苯二胺、2,4’-二氨基联苯、1,12-十二烷二胺、1,10-癸二胺、1,8-辛二胺等。
另外，作为固化剂，能够使用通过1个分子中含有2个氨基或亚氨基的二胺与羰基化合物(醛或铜)的反应从而得到的水解性的反应产物、改性胺(例如使环氧树脂与过剩的多胺反应从而得到的胺加成物)等。
热交联性组合物中，相对于总量100质量份的酸改性聚合物A及B，固化剂优选含有0.2～3质量份、更优选含有0.4～2.5质量份、进一步优选含有0.6～2质量份、特别优选含有0.8～1.5质量份。
热交联性组合物根据需要能够含有热塑性树脂。
作为热塑性树脂，可以举出例如丙烯酸树脂、乙烯基树脂、聚酰胺树脂、聚酯树脂、聚烯烃、聚氨酯、苯乙烯共聚物、非晶质聚α-烯烃、乙烯-乙酸乙烯酯共聚物。
作为苯乙烯共聚物的例子，可以举出苯乙烯-丁二烯共聚物、苯乙烯-丙烯腈-丁二烯共聚物、苯乙烯-丁二烯-丁烯-苯乙烯共聚物、苯乙烯-乙烯-丁烯-苯乙烯共聚物、苯乙烯-丁二烯-苯乙烯共聚物、苯乙烯-异戊二烯共聚物、苯乙烯-异戊二烯-苯乙烯共聚物、苯乙烯-乙烯-丙烯-苯乙烯共聚物、苯乙烯-乙烯-丁烯-苯乙烯共聚物、苯乙烯-乙烯-乙烯-丙烯-苯乙烯共聚物、及它们的酸改性物及氢化物等。对于苯乙烯共聚物而言，苯乙烯共聚物中的由苯乙烯构成的单元结构的比例优选为10～60％，更优选为15～50％，进一步优选为20～40％。
热塑性树脂优选酸未改性热塑性树脂。所谓的酸未改性热塑性树脂是指酸值为0的热塑性树脂。作为酸未改性热塑性树脂，优选上述的苯乙烯共聚物的酸未改性物，更优选酸未改性的含有苯乙烯的热塑性弹性体。
热塑性树脂在200℃、5kg负荷下的熔体流动速率(MFR)优选为0.1～30g/10分钟，更优选为1～20g/10分钟，进一步优选为5～15g/10分钟。
热塑性树脂的软化点优选为60℃以上，更优选为65℃以上，进一步优选为70℃以上。
相对于总量100质量份的酸改性聚合物A及B，热交联性组合物中的热塑性树脂的含量优选为1～100质量份，更优选为5～50质量份，进一步优选为10～30质量份。热交联性组合物在上述范围内含有热塑性树脂时，存在容易使热交联性组合物中的成分相溶化的倾向、以及容易得到成膜性的倾向。
热交联性组合物中根据需要为了提高涂布性可以含有溶剂。作为溶剂的例子，可以举出甲苯、二甲苯、苯、1,1,1-三氯乙烷、二氯甲烷、环己烷、烷基环己烷等有机溶剂。
当热交联性组合物含有溶剂的情况下，热交联性组合物中的有机溶剂的含量只要是不妨碍本发明的效果的范围内的量即可，没有特别限制，以热交联性组合物为基准，例如为50～90质量％等。
热交联性组合物中，根据需要能够以不妨碍本发明的效果的范围的量含有各种添加剂，例如着色剂、稳定剂、粘度调节剂、消泡剂等。
本发明的热交联性组合物的结晶化温度为30～70℃。结晶化温度低于30℃时，存在难以得到充分的涂布后粘连性的倾向。结晶化温度超过70℃时，存在与基材或表皮材料的初期密合性易于降低的倾向。本发明的热交联性组合物的结晶化温度优选为30～65℃、更优选为40～60℃。
本发明的热交联性组合物可以如下获得：将酸改性聚合物A、酸改性聚合物B、增粘剂及固化剂，根据需要与热塑性树脂、溶剂和/或添加剂等任意成分一起，优选一边加热一边搅拌混合从而得到。
本发明的热交联性组合物不含溶剂时，热交联性组合物能够作为热熔型粘合剂使用。另外，通过将本发明的热交联性组合物涂布在薄膜上，从而能够制成含有本发明的热交联性组合物的膜状粘合剂。
对于含有本发明的热交联性组合物的粘合性表皮材料用粘合剂，例如可以使用喷枪、模涂布机、辊涂机等，优选一边加热一边涂布至基材及表皮材料的表面。例如，将本发明的粘合性表皮材料用粘合剂喷涂至表皮材料的粘合面，或者使用辊涂机、逗号涂布机等以5～500μm厚度涂布后，在常温下或使用热风等加热干燥装置使溶剂干燥，从而能够在表皮材料上形成粘合剂的被膜。如此得到的粘合性表皮材料可以直接供于接下来的成型工序，或者也可以在室温～60℃以下的温度下保存几个月后供于成型工序。
作为基材的例子，可以举出聚烯烃，例如聚丙烯、聚乙烯、乙烯-丙烯共聚物等，由木、纸、金属、尼龙、聚酯、聚碳酸酯、聚氨酯、丙烯酸、ABS等形成的膜或片、板、成型体等。这些基材可以是例如汽车内装用的内装部件。
作为表皮材料的例子，可以举出聚氯乙烯发泡体、聚烯烃发泡体、例如聚乙烯及聚丙烯发泡体等。
对于本发明的粘合性表皮材料，在成型工序中，例如能够将表面温度维持在25～90℃的基材、与使表面温度上升至165～220℃的粘合性表皮材料，以贴合时的基材和粘合性表皮材料的表面温度为50～150℃的方式进行贴合。贴合时，通过采用在基材侧设细孔从背面抽吸从而使表皮材料贴合的真空成型法，能够有效地进行粘合。
为了防止在叠合保管时的熔接，本发明的粘合性表皮材料中的溶剂含量优选为2重量％以下。
本发明的粘合性表皮材料能够与上述基材贴合进而成为层叠体。本发明的粘合性表皮材料能够适用于建筑用内装材料例如隔板、地板材料、柜体外装、层叠钢板等，汽车内装材料例如天花板、车门装饰件、仪表盘、仪表盘消音器、中央控制台、立柱、装饰品、后隔板、座椅等。
汽车内装材料也可以是包含本发明的粘合性表皮材料和聚烯烃基材的汽车内装材料。
以下，举出实施例及比较例更具体地说明本发明，但本发明并不限于此。
实施例
[熔点]
对于熔点，通过差示扫描热量计(DSC)，将试料以10℃/分钟升温到200℃，将观测到的吸热峰中的峰顶的温度作为熔点。
[结晶化温度]
对于结晶化温度，通过差示扫描热量计(DSC)，将试料升温到200℃，将以10℃/分钟降温时所观测到的发热峰中的峰顶的温度作为结晶化温度。
[酸值]
基于JIS K 0070决定酸值。
[热交联性组合物]
将下述表1所示的份数的酸改性聚合物、增粘树脂、固化剂、热塑性树脂加入溶剂中，在80℃使其搅拌分散2小时，得到粘合剂。
[粘合测试用试料]
在聚乙烯发泡体表皮材料上涂布上述粘合剂使其干燥后达到50μm的厚度，在60℃下进行了5分钟的干燥。接下来，在粘合剂涂布后1天以内，一边用远红外线加热器将该表皮材料加热至150℃以上，一边叠合至已经于80℃加热2分钟的PP板，在0.5kg/cm2、20秒的条件下压接，得到层叠体(条件1)。另外，除了使用粘合剂涂布后保管6个月后(保管温度5～35℃)的表皮材料以外，与条件1同样地得到层叠体(条件2)。
[初期蠕变]
得到层叠体后，立即在60℃的氛围中向90度角方向施加200g/25mm的负荷，测定5分钟后的剥离长度(mm)。
[初期剥离强度]
得到层叠体5分钟后，测定180度剥离时的剥离强度(N/25mm)。
[耐热蠕变]
在20℃×24小时后，在90℃的氛围中向90度方向施加200g/25mm的负荷，测定24小时后的剥离长度(mm)。
[表1]
Figure BDA0002177044020000111
单位：g
[表2]
Figure BDA0002177044020000121
BA：基材侧的界面破坏
FB：表皮材料的材料破坏
CF：粘合剂的凝聚破坏
[酸改性聚合物1]
酸改性PBE120、马来酸改性丙烯/1-丁烯/乙烯共聚物、熔点120℃、结晶化温度80℃、重均分子量75000、1-丁烯含量约17质量％、酸含量3质量％
[酸改性聚合物2]
酸改性PB70、马来酸改性丙烯/1-丁烯共聚物、熔点70℃、结晶化温度20℃、重均分子量65000、1-丁烯含量约26质量％、马来酸含量2质量％
[酸未改性聚合物1]
酸未改性PBE120、丙烯/1-丁烯/乙烯共聚物、熔点120℃、结晶化温度80℃、重均分子量70000、1-丁烯含量约18质量％、酸含量0质量％
[酸未改性聚合物2]
酸未改性PB70、丙烯/1-丁烯共聚物、熔点70℃、结晶化温度25℃、重均分子量68000、1-丁烯含量约26质量％、马来酸含量0质量％
[酸未改性聚合物3]
Vestoplast(注册商标)520、软化点87℃、富含1-丁烯的无定形聚α-烯烃、重均分子量63000
[酸未改性聚合物4]
Vestoplast(注册商标)750、软化点107℃、富含聚丙烯的无定形聚α-烯烃、重均分子量92000
[增粘树脂1]
Neopolymer 140、石油树脂类增粘剂、软化点145℃、酸值0mgOH/g、重均分子量2100、无官能团
[增粘树脂2]
FK100、歧化松香类、酸值5以下、软化点96～102℃
[增粘树脂3]
HARITACK 4821、松香改性马来酸、酸值15～30、软化点100～115℃
[固化剂]
十二烷二酸二酰肼(DDH)、熔点190℃
[热塑性树脂]
ASAHIKASEI公司制Tufprene A、酸未改性的含苯乙烯热塑性弹性体(苯乙烯含量约40％、丁二烯含量约60％)。

Claims (15)

1.一种热交联性组合物，所述热交联性组合物含有：
熔点为110～150℃且结晶化温度为50～90℃的酸改性聚合物A、
熔点为30～110℃且结晶化温度低于50℃的酸改性聚合物B、
增粘树脂、以及
固化剂，
所述热交联性组合物的结晶化温度为30～70℃，
在所述热交联性组合物中，相对于100质量份的酸改性聚合物A，含有50～180质量份酸改性聚合物B，
所述酸改性聚合物A和所述酸改性聚合物B为酸改性烯烃类聚合物。
2.根据权利要求1所述的热交联性组合物，其中，
相对于100质量份的酸改性聚合物A，含有50～180质量份酸改性聚合物B，
并且，相对于总量100质量份的酸改性聚合物A及B，含有20～200质量份增粘树脂及0.2～3质量份固化剂。
3.根据权利要求1或2所述的热交联性组合物，其中，在100质量％的全部增粘树脂中，酸值为5以下的增粘树脂为20～100质量％。
4.根据权利要求3所述的热交联性组合物，其中，酸值为5以下的增粘树脂选自松香类、萜烯类及石油树脂类。
5.根据权利要求1或2所述的热交联性组合物，其中，固化剂是熔点为150℃以上的固态多胺化合物。
6.根据权利要求5所述的热交联性组合物，其中，熔点为150℃以上的固态多胺化合物是酰肼类多胺。
7.根据权利要求1或2所述的热交联性组合物，其中，进一步含有酸未改性热塑性树脂。
8.根据权利要求7所述的热交联性组合物，其中，酸未改性热塑性树脂是酸未改性的含有苯乙烯的热塑性弹性体。
9.根据权利要求1或2所述的热交联性组合物，其中，进一步含有溶剂。
10.一种热熔型粘合剂，含有权利要求1～8中任一项所述的热交联性组合物。
11.一种膜状粘合剂，含有权利要求1～9中任一项所述的热交联性组合物。
12.一种粘合性表皮材料用粘合剂，含有权利要求1～9中任一项所述的热交联性组合物。
13.一种粘合性表皮材料，含有权利要求12所述的粘合剂。
14.一种汽车内装部件，含有权利要求13所述的粘合性表皮材料和聚烯烃基材。
15.一种建筑用内装材料，含有权利要求13所述的粘合性表皮材料和聚烯烃基材。
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