CN109071918B - 固化树脂用组合物及其固化物 - Google Patents
固化树脂用组合物及其固化物 Download PDFInfo
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- CN109071918B CN109071918B CN201780026301.3A CN201780026301A CN109071918B CN 109071918 B CN109071918 B CN 109071918B CN 201780026301 A CN201780026301 A CN 201780026301A CN 109071918 B CN109071918 B CN 109071918B
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- benzoxazine
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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Abstract
Description
技术领域
本发明涉及含有特定的多官能苯并噁嗪化合物和特定的多官能环氧化合物的固化树脂用组合物及作为其加聚物的固化物。
背景技术
苯并噁嗪化合物指具有含有苯骨架和噁嗪骨架的苯并噁嗪环的化合物,作为其固化物(聚合物)的苯并噁嗪树脂的耐热性、机械强度等物性优异,在多方面的领域中用作各种用途用的高性能材料。
专利文献1公开了特定结构的新颖的苯并噁嗪化合物及其制备方法,记载了该苯并噁嗪化合物具有高导热率,并且可用该苯并噁嗪化合物制备具有高导热率的苯并噁嗪树脂固化物。
专利文献2公开了主链中具有特定的苯并噁嗪环结构的聚苯并噁嗪树脂的反应性末端的一部分或全部已封端的热固性树脂,记载了该热固性树脂在溶解于溶剂中时的保存稳定性优异。
现有技术文献
专利文献
专利文献1:日本特开2013-60407号公报
专利文献2:日本特开2012-36318号公报。
发明内容
发明所要解决的课题
但是,在粘接剂、密封材料、涂料、复合材料用基质树脂等领域,为了能够适合于更苛刻的使用条件,需要在维持强度的同时,更加高耐热性、高耐变形性的固化树脂。但是,在以往的苯并噁嗪树脂固化物中,尚未得到这些性能方面令人满意的产品。
因此,本发明的课题在于,提供可得到高耐热性且高耐变形性的固化物的、含有苯并噁嗪化合物的固化树脂用组合物,和该固化物。
解决课题的手段
为了解决上述课题,本发明人进行了深入研究,结果开发了含有特定的多官能苯并噁嗪化合物和特定的多官能环氧化合物的新颖的固化树脂用组合物,并发现其固化物在强度、耐热性优异的同时,弹性模量高,耐变形性也优异,从而完成本发明。
即,根据本发明,提供固化树脂用组合物,其含有(A) 具有至少2个苯并噁嗪环的多官能苯并噁嗪化合物和(B) 具有至少1个降莰烷结构和至少2个环氧基的多官能环氧化合物。多官能苯并噁嗪化合物(A)为第一苯并噁嗪化合物或第二苯并噁嗪化合物。第一苯并噁嗪化合物具有至少2个用下述式(1)表示的苯并噁嗪环结构,2个苯并噁嗪环结构中的苯环彼此连接。第二苯并噁嗪化合物用下述式(2)表示。
[化1]
在式(1)中,R表示碳原子数为1~12的链状烷基、碳原子数为3~8的环状烷基或碳原子数为6~14的芳基,该芳基可具有卤素或碳原子数为1~12的链状烷基作为取代基。
[化2]
在式(2)中,L是含有1~5个芳环的二价有机基团或碳原子数为2~10的亚烷基。
另外,根据另一观点的本发明,提供将含有多官能苯并噁嗪化合物(A)和多官能环氧化合物(B)的固化树脂用组合物固化得到的固化物。
发明效果
本发明的固化树脂用组合物为含有多官能苯并噁嗪化合物(A)和多官能环氧化合物(B)的新颖的组合物,该组合物的固化物具有耐热性良好、且难以热分解、玻璃化转变温度高的特征。另外,固化物的机械强度也优异。因此,本发明的固化树脂用组合物可用于面向需要高耐热性、高耐冲击性的场景的粘接剂、密封材料、涂料、复合材料用基质树脂等用途。另外,本发明的固化物在高温下和/或施加高冲击时发挥优异的坚固性。
附图说明
图1是表示实施例6的DSC测定结果和通过该测定求得的玻璃化转变温度(Tg)的曲线图。
具体实施方式
本发明的固化树脂用组合物含有(A) 具有至少2个苯并噁嗪环的多官能苯并噁嗪化合物和(B) 具有至少1个降莰烷结构和至少2个环氧基的多官能环氧化合物。以下将固化树脂用组合物简称为组合物,将这些多官能苯并噁嗪化合物和多官能环氧化合物分别称为成分(A)和成分(B)。需说明的是,在本发明中,成分(A)和(B)可分别为以单体形式使用的化合物,或该化合物的分子的一部分或全部聚合形成低聚物。即,在本发明的组合物中,成分(A)和(B)可分别为形成固化树脂前的预聚物的状态。
上述成分(A)为第一苯并噁嗪化合物或第二苯并噁嗪化合物。作为成分(A),本发明的组合物可含有多种第一苯并噁嗪化合物,或含有多种第二苯并噁嗪化合物,或含有第一苯并噁嗪化合物和第二苯并噁嗪化合物。另外,可含有第一和第二苯并噁嗪化合物以外的苯并噁嗪化合物。
上述第一苯并噁嗪化合物为具有至少2个用下述式(1)表示的苯并噁嗪环结构的化合物。
[化3]
在式(1)中,R表示碳原子数为1~12的链状烷基、碳原子数为3~8的环状烷基或碳原子数为6~14的芳基,该芳基可具有卤素或碳原子数为1~12的链状烷基作为取代基。在第一苯并噁嗪化合物中,用式(1)表示的2个苯并噁嗪环结构中的苯环彼此连接。这些苯环可经由连接基连接,或不经由连接基而直接连接。另外,用式(1)表示的苯并噁嗪环结构可在苯环上具有取代基。
第一苯并噁嗪化合物具有多个用式(1)表示的苯并噁嗪环结构,这些多个苯并噁嗪环结构中的多个R可相同或不同。另外,第一苯并噁嗪化合物可含有用式(1)表示的苯并噁嗪环结构以外的苯并噁嗪环结构。
第一苯并噁嗪化合物优选为用下述式(1a)表示的化合物。
[化4]
在式(1a)中,R表示碳原子数为1~12的链状烷基、碳原子数为3~8的环状烷基或碳原子数为6~14的芳基,该芳基可具有卤素或碳原子数为1~12的链状烷基作为取代基。式(1a)中的多个R可相同或不同。X是氢或碳原子数为1~6的烃基。式(1a)中的多个X可相同或不同。Y是碳原子数为1~6的亚烷基、氧、硫、SO2基或羰基。m为0或1,n为1~10的整数。m为0指苯环彼此不经由连接基而直接连接。
在上述式(1)和(1a)中的R是碳原子数为1~12的链状烷基的情况下,作为其具体例,可列举出甲基、乙基、丙基、异丙基、正丁基、异丁基、叔丁基等。在R是碳原子数为3~8的环状烷基的情况下,作为其具体例,可列举出环戊基、环己基等。在R是碳原子数为6~14的芳基的情况下,作为其具体例,可列举出苯基、1-萘基、2-萘基、菲基、联苯基等。在R是具有卤素或碳原子数为1~12的链状烷基作为取代基的碳原子数为6~14的芳基的情况下,作为其具体例,可列举出邻甲苯基、间甲苯基、对甲苯基、二甲苯基、邻乙基苯基、间乙基苯基、对乙基苯基、邻叔丁基苯基、间叔丁基苯基、对叔丁基苯基、邻氯苯基、邻溴苯基等。以处理性良好的观点,R优选选自甲基、乙基、丙基、苯基和邻甲基苯基。
作为第一苯并噁嗪化合物的具体例,可列举出下述式(1X)所示的化合物和该化合物聚合得到的低聚物。
[化5]
上述第二苯并噁嗪化合物为用下述式(2)表示的化合物。
[化6]
在式(2)中,L为含有1~5个芳环的二价有机基团或碳原子数为2~10的亚烷基。本发明的组合物可含有用式(2)表示、但L不同的多种第二苯并噁嗪化合物。
在式(2)中的L为含有1~5个芳环的二价有机基团的情况下,可具有单环结构、多环结构、稠环结构等。另外,该有机基团可含有氧和/或硫。作为该有机基团的具体例,可列举出下述式(3)所示的基团。
[化7]
作为第二苯并噁嗪化合物的具体例,可列举出下述式(2X)所示的化合物和该化合物聚合得到的低聚物。
[化8]
成分(A)的制备方法无特殊限制。另外,作为成分(A),也可使用市售品。作为市售品的实例,可列举出四国化成株式会社制的双酚F-苯胺型(F-a型)苯并噁嗪化合物和苯酚-二氨基二苯基甲烷型(P-d型)苯并噁嗪化合物等。
上述成分(B)为具有至少1个降莰烷结构和至少2个环氧基的多官能环氧化合物。本发明的组合物可含有多种多官能环氧化合物作为成分(B)。成分(B)优选为脂环式环氧化合物,更优选为具有下述式(4)所示的具有环氧基的5元环结构、6元环结构或降莰烷环结构的化合物。
[化9]
作为成分(B)的具体例,可列举出下述式(5)所示的化合物。
[化10]
以下说明成分(B)的制备例。例如,如下述式(6)所示,通过使化合物(a)与间氯过苯甲酸反应,可制备化合物(5-1)。化合物(a)可通过丁二烯与二环戊二烯的Diels-Alder反应来合成。
[化11]
如下述式(7)所示,通过使化合物(b) (三环戊二烯)与间氯过苯甲酸反应,可制备化合物(5-2)。化合物(b)可通过环戊二烯与二环戊二烯的Diels-Alder反应来合成。
[化12]
如下述式(8)所示,通过使化合物(c)与间氯过苯甲酸反应,可制备化合物(5-3)。化合物(c)可通过丁二烯与环戊二烯的Diels-Alder反应来合成。
[化13]
通过使二环戊二烯与过一硫酸氢钾(OXONE,过硫酸氢钾复合盐)反应,可制备下述化合物(5-4)。化合物(5-4)为二环戊二烯二环氧化物,由SHANDONG QIHUAN BIOCHEMICALCO., LTD.等市售,在本发明中也可使用这样的市售品。
[化14]
相对于100质量份的成分(A),成分(B)的含有比例优选为5质量份以上且100质量份以下,更优选为10质量份以上且50质量份以下。若将含有比例调整至该范围内,则得到良好的耐热性。需说明的是,在本发明的组合物含有多种多官能苯并噁嗪化合物作为成分(A)的情况下,将这些化合物的总计视为100质量份。在本发明的组合物含有多种多官能环氧化合物作为成分(B)的情况下,上述“成分(B)的含有比例”指这些化合物的总计的比例。
本发明的组合物可进一步含有(C) 至少1种固化剂作为任意成分。以下将该固化剂称为成分(C)。
作为成分(C)的实例,可列举出芳族胺类(二乙基甲苯二胺、间苯二胺、二氨基二苯基甲烷、二氨基二苯基砜、间苯二甲胺、它们的衍生物等)、脂族胺(三亚乙基四胺、异佛尔酮二胺等)、咪唑类(咪唑、咪唑衍生物等)、双氰胺、四甲基胍、羧酸酐(甲基六氢邻苯二甲酸酐等)、羧酸酰肼(己二酸酰肼等)、羧酸酰胺、单官能苯酚、多官能苯酚类(双酚A、双酚硫醚(bisphenol sulphide)、多酚化合物等)、聚硫醇、羧酸盐、路易斯酸络合物(三氟化硼乙基胺络合物等)等。它们可单独使用,或以2种以上的混合物形式使用。本发明的组合物优选含有选自咪唑类、芳族胺类和多官能酚类的至少1种固化剂作为成分(C)。
相对于100质量份的成分(A),成分(C)的含有比例优选超过0质量份且为40质量份以下,更优选超过0质量份且为30质量份以下。虽然本发明的组合物即使不掺混成分(C)也可通过热来固化,但若以该范围的比例含有成分(C),则可更有效地进行固化反应。需说明的是,在本发明的组合物含有多种固化剂作为成分(C)的情况下,上述“成分(C)的含有比例”指这些多种固化剂的总计的比例。
本发明的组合物可在不损害本发明的效果的范围内含有成分(A)以外的苯并噁嗪化合物和/或成分(B)以外的环氧化合物。在希望降低组合物的粘度的情况下,可在组合物中添加苯并噁嗪环为1个的单官能苯并噁嗪化合物。
另外,本发明的组合物可在不损害其物性的范围内含有纳米碳、阻燃剂、脱模剂等。
作为纳米碳,例如可列举出碳纳米管、富勒烯、它们的衍生物等。
作为阻燃剂,例如可列举出红磷、磷酸三苯基酯、磷酸三甲苯基酯、磷酸三(二甲苯基)酯、磷酸甲苯基二苯基酯、磷酸二甲苯基二苯基酯、间苯二酚双(苯基磷酸酯)、双酚A双(二苯基磷酸酯)等磷酸酯或硼酸酯等。
作为脱模剂,例如可列举出硅油、硬脂酸酯、巴西棕榈蜡等。
在将本发明的组合物制成固化的固化物来制备膜状成型物的情况下,可掺混溶剂来将该组合物的粘度调整至适合于形成薄膜的范围。作为溶剂,只要可溶解各成分则无特殊限制,例如可列举出烃类、醚类、酯类、含卤素溶剂类等。在组合物含有溶剂的情况下,可通过在基材等上涂布溶液状的组合物,挥发溶剂,并进行热固化,来得到固化物。
在本发明的组合物中,从成型性、固化性和操作性等观点出发,相对于溶剂以外的所有成分的总质量,成分(A)的质量比优选10质量%以上且95质量%以下,更优选20质量%以上且92质量%以下,进一步优选30质量%以上且90质量%以下。通常,由于在将该组合物固化得到固化物时溶剂被除去,所以组合物中的溶剂的质量比不会对固化物的特性造成大的影响。
本发明的组合物可通过用捏合或混合装置将成分(A)和(B),以及根据需要适宜添加的成分(C)、其它的添加剂和溶剂混合来制备。
捏合或混合的方法无特殊限制,例如可列举出使用捏合机、行星式混合机、双螺杆挤出机等的方法。另外,在成分(A)和(B)在室温下是高粘度的液状的情况等中,可根据需要加热而捏合,也可在加压或减压条件下捏合。从保存稳定性的观点出发,优选在捏合后立即在冷藏库、冷冻库中保管。
在制备FRP用预浸料的情况下,本发明的组合物的粘度在50℃下优选为10~3000Pa·s,更优选为10~2500Pa·s,最优选为100~2000Pa·s。在用于密封材料或涂布用途的情况下,只要不妨碍密封、涂布等的操作,组合物的粘度无特殊限制。
本发明的组合物可通过在与公知的苯并噁嗪化合物或环氧化合物同样的条件下进行成分(A)和(B)的开环聚合,由此固化。例如,可通过于180℃~300℃将本发明的组合物加热30分钟~10小时,来得到本发明的固化物。
本发明的组合物可形成在维持强度的同时,高耐热性、高耐变形性的固化物。认为本发明的组合物形成这样的优异固化物的原因如下。在苯并噁嗪化合物的均聚中,通过聚合生成酚羟基。认为该酚羟基在高温、例如200℃以上经由酮-烯醇互变异构而使高分子链断裂,因此耐热性低,玻璃化转变温度也降低。认为本发明的成分(B)难以均聚,并与来源于上述苯并噁嗪的酚羟基反应,因此防止高分子链的断裂。此外认为,由于是多官能的,所以交联密度提高,另外由于降莰烷结构为刚性,所以得到的固化物在也具有良好的刚性的同时,显示高弹性模量。据推断,通过将以上多种主要因素组合,本发明的组合物可形成在维持强度的同时,高耐热性、高耐变形性的固化物。
从密封材料用途的耐热性的观点出发,固化物的玻璃化转变温度优选为200℃以上。根据本发明优选方案的固化物显示220℃以上的玻璃化转变温度,根据特别优选方案的固化物可显示240℃以上的玻璃化转变温度。
实施例
以下列举实施例和比较例来具体地说明本发明,但本发明并不限定于这些实施例。
<成分(A):多官能苯并噁嗪化合物(在表1和2中,简写为苯并噁嗪)>
(A1):下述式(1-1)的双酚F-苯胺型(F-a型)苯并噁嗪化合物(四国化成株式会社制)
[化15]
(A2):下述式(2-1)的苯酚-二氨基二苯基甲烷型(P-d型)苯并噁嗪化合物(四国化成株式会社制)
[化16]
<成分(B)或(B’):多官能环氧化合物(在表1和2中,简写为环氧)>
(B1):化合物(5-1)
依据《土田诏一等,“丁二烯与环戊二烯的Diels-Alder反应-三聚体的确定-”,石油学会志,1972年,第15卷,3期,p189-192》所记载的方法合成上述式(6)所示的化合物(a)。向反应容器中投入15.9L的氯仿和1.6kg的化合物(a),边于0℃搅拌边滴加4.5kg的间氯过苯甲酸。将得到的混合物升温至室温,进行12小时的上述式(6)的反应。通过过滤除去副产物间氯苯甲酸,用1N氢氧化钠水溶液清洗3次滤液,进而用饱和食盐水清洗。用硫酸镁干燥有机层,通过过滤除去硫酸镁,浓缩滤液得到粗品。向粗品中加入2kg的甲苯而在室温下溶解。向其中滴加6kg的庚烷进行结晶,于5℃熟化1小时。滤取结晶物并用己烷清洗,于35℃减压干燥24小时,作为白色固体得到1.4kg的下述化合物(5-1)。
[化17]
(B2):化合物(5-2) (三环戊二烯二环氧化物)
与化合物(a)同样地依据上述文献所记载的方法合成上述式(7)所示的化合物(b)。向反应容器中投入59.2kg的氯仿和4.0kg的化合物(b),边于-10℃搅拌边滴加10.6kg的间氯过苯甲酸。将得到的混合物升温至室温,进行12小时的上述式(7)的反应。通过过滤除去副产物间氯苯甲酸,用42.0kg的5%亚硫酸钠水溶液清洗滤液。用41.6kg的1N氢氧化钠水溶液清洗4次有机层,进而用48.0kg的饱和食盐水清洗。用硫酸镁干燥有机层,通过过滤除去硫酸镁,浓缩滤液得到5.1kg的粗品。向粗品中加入3.5kg的甲苯而在室温下溶解。向其中滴加13.7kg的庚烷进行结晶,于5℃熟化1小时。滤取结晶物并用庚烷清洗,于35℃减压干燥12小时,作为白色固体得到2.8kg的下述化合物(5-2)。
[化18]
(B3):化合物(5-3) (联降莰烷二环氧化物)
与化合物(a)同样地依据上述文献所记载的方法合成上述式(8)所示的化合物(c)。向反应容器中投入600g的氯仿和40.0g的化合物(c),边于-10℃搅拌边滴加100g的间氯过苯甲酸。将得到的混合物升温至室温,进行12小时的上述式(8)的反应。通过过滤除去副产物间氯苯甲酸,用400g的5%亚硫酸钠水溶液清洗滤液。用400g的1N氢氧化钠水溶液清洗4次有机层,进而用400g的饱和食盐水清洗。用硫酸镁干燥有机层,通过过滤除去硫酸镁,浓缩滤液得到46.2g的粗品。向粗品中加入30g的甲苯而在室温下溶解。向其中滴加130g的庚烷进行结晶,于5℃熟化1小时。滤取结晶物并用庚烷清洗,于35℃减压干燥12小时,作为白色固体得到30.2g的下述化合物(5-3)。
[化19]
(B4):化合物(5-4) (二环戊二烯二环氧化物)
在反应容器中装入10kg的二环戊二烯、68kg的碳酸氢钠、100L的丙酮和130L的离子交换水,冷却至10℃以下。控制冷却使得将反应液的温度维持在30℃以下,缓慢地添加84kg的OXONE,边搅拌边进行10小时反应。进行2次使用100L的醋酸乙酯的萃取,将得到的有机层分开取得并合并。接着,用100L的混合水溶液(含有20重量%的食盐和20重量%的硫代硫酸钠)清洗该有机层,进而用100L的离子交换水清洗2次。用硫酸镁干燥清洗后的有机层,通过过滤除去硫酸镁,从滤液蒸馏除去有机溶剂,作为白色固体得到11kg的下述化合物(5-4)。
[化20]
作为比较例用的环氧化合物,使用不具有降莰烷结构的成分(B’)。
(B’):下述式(9)的CELLOXIDE (注册商标) 2021P (DAICEL CHEMICALINDUSTRIES, LTD.制)
[化21]
<成分(C):固化剂>
(C1):下述式(10)的双(4-羟基苯基)硫醚(TDP,东京化成株式会社制)
[化22]
(C2):SAN-AID SI-150 (阳离子聚合引发剂,三新化学工业株式会社制)
<固化物的性能评价>
向厚度为3mm的模具中注入固化树脂用组合物,加热使其固化。对于得到的固化物,测定以下性能。固化物制备条件如后所述。
(玻璃化转变温度Tg)
玻璃化转变温度Tg使用X-DSC-7000 (HITACHI HIGH-TECH SCIENCE CORPORATION制),通过N2流量为20mL/分钟、升温速度为20℃/分钟的条件下的差示扫描热量测定DSC来求得。
(弯曲试验1)
依据JIS K 7171,制备固化物的70mm×25mm×3mm的长条状试验片,在以下条件下进行3点弯曲试验,测定弯曲强度、弯曲弹性模量和弯曲变形。
试验装置:5582万能材料试验仪(INSTRON公司制)
试验速度:1.5mm/分钟
支点间距离:48mm
试验片的前处理:无
试验温度:23℃。
(弯曲试验2)
除了将试验温度设为120℃以外,与弯曲试验1同样地进行测定。
(弯曲试验3)
在进行将固化物的试验片在90℃热水中浸渍72小时的前处理后,与弯曲试验1同样地进行测定。
(实施例1)
以表1所示的质量比将上述成分(A1)、(B1)和(C1)投入至行星式混合机中,在50℃、真空下捏合1小时,制备组合物1。需说明的是,在本实施例中“真空下”指的是用真空泵减压,使真空度为-0.8MPa (表压)以下的气氛。
将50g的组合物1加热至100℃,放入加热至100℃的厚度为3mm的金属模具中,在Mini-jet烘箱(Mini-jet oven,MO-921型,富山产业株式会社制)内固化,得到固化物1。固化在以2℃/分钟的升温速度从120℃升温至240℃,并于240℃保持8小时的条件下进行。对于得到的固化物1,评价上述性能。将固化条件和性能评价结果示出于表1中。
(实施例2~10、比较例1~5)
除了各成分的种类和质量比、以及固化条件如表1和2所示以外,与实施例1同样地分别制备实施例2~10和比较例1~5的组合物和固化物,并评价性能。将结果示出于表1和2中。另外,将实施例6的DSC测定结果和通过DSC测定求得的Tg示出于图1中。
在实施例2中使用与实施例1相同的组合物1,变更固化条件。在其它的实施例和比较例中,选择固化条件使得各固化物显示更高的性能。另外,在比较例3和4中不使用成分(B),在比较例5中不使用成分(A)。
[表1]
[表2]
实施例的固化物与比较例的固化物相比,玻璃化转变温度(Tg)显著地高,可知耐热性优异。需说明的是,虽然在实施例1和2中是在不同的条件下固化组合物1,但得到的固化物显示几乎相同的性能,可知在该范围内不受固化条件的影响。另外,实施例1、2、5和6的固化物与比较例1的固化物相比,通过弯曲试验得到的强度为同等,并且弹性模量和变形优异,可知在维持强度的同时,良好地实现高耐热性、高耐变形性。
产业上的可利用性
本发明的组合物可用于要求粘附性、固化时的低收缩性、高耐热性等物性的领域。例如,可用于复合材料用的基质树脂、电子领域的密封材料、层合板等、涂料、粘接剂等。
Claims (3)
1.固化树脂用组合物,其含有(A) 具有至少2个苯并噁嗪环的多官能苯并噁嗪化合物和(B) 具有至少1个降莰烷结构和至少2个环氧基的多官能环氧化合物,
所述多官能苯并噁嗪化合物(A)为第一苯并噁嗪化合物或第二苯并噁嗪化合物,
所述第一苯并噁嗪化合物具有至少2个用下述式(1)表示的苯并噁嗪环结构,2个所述苯并噁嗪环结构中的苯环彼此连接,
在式(1)中,R表示碳原子数为1~12的链状烷基、碳原子数为3~8的环状烷基或碳原子数为6~14的芳基,所述芳基可具有卤素或碳原子数为1~12的链状烷基作为取代基,
所述第二苯并噁嗪化合物是用下述式(2)表示的化合物,
在式(2)中,L是含有1~5个芳环的二价有机基团或碳原子数为2~10的亚烷基,
所述多官能环氧化合物(B) 包含下述化合物中的任意至少一种,
2.权利要求1所述的固化树脂用组合物,其进一步含有(C) 选自咪唑类、芳族胺类和多官能苯酚类的至少1种固化剂,
相对于100质量份的所述多官能苯并噁嗪化合物(A),所述固化剂(C)的含有比例超过0质量份且为40质量份以下。
3.固化物,其是将权利要求1或2所述的固化树脂用组合物固化而得。
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Publication number | Publication date |
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PT3450499T (pt) | 2024-01-12 |
EP3450499B1 (en) | 2023-11-01 |
US20190119447A1 (en) | 2019-04-25 |
TW201803859A (zh) | 2018-02-01 |
CN109071918A (zh) | 2018-12-21 |
TWI762483B (zh) | 2022-05-01 |
WO2017188448A1 (ja) | 2017-11-02 |
JP6952684B2 (ja) | 2021-10-20 |
KR102324393B1 (ko) | 2021-11-10 |
EP3450499A1 (en) | 2019-03-06 |
KR20190003590A (ko) | 2019-01-09 |
EP3450499A4 (en) | 2019-10-09 |
JPWO2017188448A1 (ja) | 2019-03-07 |
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