CN111295406A - 环氧树脂组合物及其硬化物 - Google Patents
环氧树脂组合物及其硬化物 Download PDFInfo
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- CN111295406A CN111295406A CN201880070606.9A CN201880070606A CN111295406A CN 111295406 A CN111295406 A CN 111295406A CN 201880070606 A CN201880070606 A CN 201880070606A CN 111295406 A CN111295406 A CN 111295406A
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Abstract
本发明提供一种具有高耐热性、高机械强度且减振性优异的环氧树脂组合物和使用所述环氧树脂组合物的膜/成形材料。一种环氧树脂组合物,包含下述成分A~成分D。成分A:分子内具有噁唑烷酮环结构的环氧树脂,成分B:在30℃下为液态的环氧树脂,成分C:具有B‑M结构的二嵌段共聚物(此处,M是包含甲基丙烯酸甲酯的均聚物或含有至少50重量%甲基丙烯酸甲酯的共聚物的嵌段,B是对于环氧树脂和嵌段M不相容且其玻璃化转变温度Tg为20℃以下的嵌段,B及M所表示的各嵌段是直接键结或经由连结基而连结),成分D:作为双氰胺或其衍生物的胺系硬化剂。
Description
技术领域
本发明涉及一种环氧树脂组合物及使用所述环氧树脂组合物的膜、成形材料,所述环氧树脂组合物优选用于要求静音性的减振钢板、运动/休闲用途、一般产业用途中优选使用的粘着剂、接着剂或者成形材等。
背景技术
一直以来,在汽车和家电产品中,从强度和耐热性的观点出发,作为零件的一部分使用铁、铝等薄板,在汽车运行时、家电产品工作时,产生薄板的振动音。因此,为了防止所述振动音的产生,例如已知通过将具备树脂层(粘弹性体)的减振片贴附于薄板来提高薄板的减振性。
另外,配置在汽车的发动机室或家电产品的电动机附近的薄板容易变得高温,因此,期望即使在高温下也能够显现减振效果的减振片(减振材)。在这些构成材料中,使玻璃纤维或碳纤维等纤维与树脂复合而提升了强度的纤维增强树脂(纤维增强塑料(FiberReinforced Plastic,FRP))与金属同样地强度高,并且能够实现轻量化,因此近年来作为代替金属的材料而受到期待。
在这种状况下,提出了一种如下技术,其虽然不是与汽车用零件相关的技术,但通过在含有碳纤维或玻璃纤维等纤维填料的FRP层之间设置橡胶层或弹性体层之类的减振层来提升减振性(专利文献1、专利文献2)。但是,即使将这些技术直接转用于悬架臂(suspension arm)等汽车用零件上,也无法得到所期望的强度,因此要求在这一点上进行改善。另外,同样提出了通过使FRP层之间含有环氧粒子或低弹性橡胶粒子来提升FRP的tanδ的方案,但就减振性这一观点而言,未得到令人满意的tanδ值(专利文献3、专利文献5)。另外提出了一种使合成树脂制的减振层层叠于FRP层和FRP层之间的成型体,但仍然未得到令人满意的衰减系数,另外,认为对于汽车用途所需要的耐热性,也残留着课题(专利文献4)。
而且,几乎没有利用金属制或FRP制的零件本身来充分满足减振性的想法。
现有技术文献
专利文献
专利文献1:日本专利特开2011-183471号公报
专利文献2:日本专利特开2004-352024号公报
专利文献3:WO2012/147401
专利文献4:WO2016/132655
专利文献5:WO2016/104314
发明内容
本发明是鉴于此种情况而完成,目的在于提供一种具有高耐热性、高机械强度并且减振性优异的环氧树脂组合物、及使用所述环氧树脂组合物的成形材料。
为了达成所述目的,本发明人等人进行了努力研究,结果发现,通过使用特定的树脂组合物,能够解决所述课题,从而完成了本发明。即,本发明包含以下的构成。
本发明是一种环氧树脂组合物,包含下述成分A~成分D,
成分A:分子内具有噁唑烷酮环结构的环氧树脂,
成分B:在30℃下为液态的环氧树脂,
成分C:具有B-M结构的二嵌段共聚物,
(此处,M是包含甲基丙烯酸甲酯的均聚物或含有至少50重量%甲基丙烯酸甲酯的共聚物的嵌段,B是对于环氧树脂和嵌段M不相容且其玻璃化转变温度Tg为20℃以下的嵌段,B及M所表示的各嵌段是直接键结或经由连结基而连结)
成分D:作为双氰胺(dicyandiamide)或其衍生物的胺系硬化剂,且
所述环氧树脂组合物的特征在于,各成分的调配比例满足下述式:
A/(A+B)=0.05~0.25、
C/(A+B)=0.12~0.19、
D/(A+B)=1~10、
(此处,A~D分别是成分A~成分D的含量(质量))。
优选的是,成分(C)的嵌段M是包含甲基丙烯酸甲酯的均聚物的结构单元,嵌段B是选自1,4-聚丁二烯、聚丙烯酸丁酯以及聚(丙烯酸2-乙基己酯)的结构单元。
本发明的另一实施例是一种硬化物,所述硬化物是上述环氧树脂组合物的硬化物,其在0℃~10℃的温度区域中的tanδ为0.033以上,且Tg为120℃以上且160℃以下。
根据本发明,在硬化时可以获得减振性、衰减性优异的成形体,使用所述成形体的接着剂、成形材料等也可以获得同样的效果。即,根据本发明的树脂组合物,通过在环氧树脂组合物中适当地含有减振性高的丙烯酸系嵌段共聚物,而具有高耐热性,并且在广泛的温度区域具有高tanδ,因此减振性、衰减性优异,可以优选用于家电制品、汽车用零件等用途。
附图说明
图1是实施例1的硬化物的动态力学分析(Dynamic Mechanical Analysis,DMA)图表。
图2是实施例2的硬化物的DMA图表。
图3是实施例3的硬化物的DMA图表。
图4是比较例4的硬化物的DMA图表。
图5是比较例6的硬化物的DMA图表。
具体实施方式
本发明的环氧树脂组合物是包含下述成分(A)~成分(D)的环氧树脂组合物,成分(A)是分子内具有噁唑烷酮环结构的环氧树脂,成分(B)是在30℃下为液态的环氧树脂,成分(C)是包含B-M的嵌段共聚物,成分(D)是作为双氰胺或其衍生物的胺系硬化剂。以下,也简称为成分(A)、成分(B)、成分(C)、成分(D)。再者,成分(E)等其他成分也同样。再者,本发明的“环氧树脂组合物”是指硬化前的树脂组合物。
以下,对各成分进行说明。
成分(A)的分子内具有噁唑烷酮环结构的环氧树脂使包含含有此环氧树脂的环氧树脂组合物的预浸料在常温下的作业性良好,另外,提高所述环氧树脂组合物的硬化物的耐热性。本说明书中,所谓“常温”,是指10℃~30℃的温度范围。
作为成分(A),优选使异氰酸酯化合物(Y)与环氧树脂(X)反应而得到的分子内具有噁唑烷酮环结构的环氧树脂。
噁唑烷酮环结构是通过异氰酸酯基和环氧基的加成反应而生成。即,通过使过剩的环氧树脂(X)与异氰酸酯化合物(Y)反应,能够得到分子内具有噁唑烷酮环结构的环氧树脂(成分(A))。本发明中,能够将各种异氰酸酯化合物作为原料,但为了将噁唑烷酮环结构并入到环氧树脂的骨架中,优选为具有多个异氰酸酯基的异氰酸酯化合物。另外,为了使含有成分(A)的环氧树脂组合物的硬化物具有高耐热性,优选具有刚性结构的二异氰酸酯。
作为此种异氰酸酯化合物(Y),例如可列举:亚苯基二异氰酸酯(phenylenediisocyanate)、甲代亚苯基二异氰酸酯(toluylene diisocyanate)、双(异氰酸基甲基)苯、二苯基甲烷二异氰酸酯、双(异氰酸基甲基)环己烷、六亚甲基二异氰酸酯等二异氰酸酯。其中,优选通过使骨架具有苯环而成为刚性结构的亚苯基二异氰酸酯、甲代亚苯基二异氰酸酯、双(异氰酸基甲基)苯、及二苯基甲烷二异氰酸酯,其中,就经济上的获取容易性而言,尤其优选甲代亚苯基二异氰酸酯。
另外,作为环氧树脂(X),能够将各种环氧树脂作为具有噁唑烷酮环结构的环氧树脂的原料,但为了将噁唑烷酮环结构有效率地并入到环氧树脂的骨架中,优选在分子的两末端具有环氧基的环氧树脂。优选列举:双酚A型环氧树脂、双酚F型环氧树脂、联苯型环氧树脂等环氧树脂。其中,为了不使所得到的具有噁唑烷酮环结构的环氧树脂、即、成分(A)的粘度过高,尤其优选双酚A二缩水甘油醚、双酚F二缩水甘油醚、及联苯二缩水甘油醚。
作为具有噁唑烷酮环结构的环氧树脂,就生产性、耐热性、相容性等观点而言,优选软化点为60℃~100℃,环氧当量为300~400。
所述组合中,关于使作为异氰酸酯化合物(Y)的甲代亚苯基二异氰酸酯1分子与作为环氧树脂(X)的双酚A二缩水甘油醚2分子混合反应而得到的加成反应物,由于其使预浸料在常温下的作业性和环氧树脂组合物的硬化物的耐热性良好,因此尤其优选。
可作为市售品而获取的具有噁唑烷酮环结构的环氧树脂(成分(A))可列举:YD-952(商品名,新日铁住金化学股份有限公司制)或ACR1348(商品名、艾迪科(ADEKA)股份有限公司公司制)、DER852(商品名、陶氏(DOW)公司制造)等,任一者均优选用于本发明中,但尤其优选YD-952。
作为成分(A),也可以将如上所述的环氧树脂并用2种以上。
相对于本发明的环氧树脂组合物中所含的全部环氧树脂的合计量100质量份,成分(A)的含量优选为5质量份~25质量份。此处,全部环氧树脂含有成分(A)、成分(B)。如果成分(A)的量为5质量份以上,则含有所述成分(A)的环氧树脂组合物的硬化物的耐热性和机械物性提高,另外,从与成分(C)的相容性的观点出发也优选。另一方面,为了容易得到断裂韧性高且没有空隙(void)的成形品,优选为25质量份以下。成分(A)含量更优选为7质量份~22质量份,尤其优选为10质量份~20质量份。
为了调整成分(A)的粘度,本发明的环氧树脂组合物还含有成分(B)。根据分子量等,成分(A)也有可能成为液态,但成分(B)不会是成分(A)。成分(B)的30℃下的粘度优选为1000Pa·s以下。成分(B)的30℃下的粘度是通过使成分(B)以频率1Hz、2℃/min升温,并使用例如DSR-200(流变(Rheometrics)公司)等流变仪(旋转型动态粘弹性测定装置)测定30℃下的粘度而得到。
再者,成分(B)的分子量根据成分(B)的结构而不同,例如在双酚型二官能环氧树脂的情况下,优选200以上且不足600,更优选500以下。
作为此种环氧树脂的例子,例如可列举:双酚A型环氧树脂、双酚F型环氧树脂、联苯型环氧树脂、二环戊二烯型环氧树脂、苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、四缩水甘油基二胺型环氧树脂、缩水甘油基苯基醚型环氧树脂等。进而可列举:例如利用橡胶或氨基甲酸酯(urethane)等将这些环氧树脂改性而成的环氧树脂、将这些环氧树脂溴化而成的溴化环氧树脂等,但并不限定于此。另外,这些环氧树脂也可以并用2种以上。
环氧树脂组合物的硬化物具有高耐热性,即使在成形时被增温而达到硬化温度也不会发生急剧的粘度上升,就抑制所得到的成形品中的空隙产生的方面而言,成分(B)尤其优选双酚型的二官能环氧树脂。
成分(B)的含量只要以使成分(A)的含量成为所述范围的方式决定即可,但相对于环氧树脂组合物中含有的全部环氧树脂的合计量100质量份,优选为75质量份以上且95质量份以下。
本发明的环氧树脂组合物在不损害本发明的效果的范围内也可以含有成分(A)、成分(B)以外的环氧树脂(Z)。
作为此种环氧树脂,是分子内不具有恶唑烷酮环结构,并且在30℃下为固体的环氧树脂。例如,二官能环氧树脂中可以举出双酚A型环氧树脂、双酚F型环氧树脂、联苯型环氧树脂、二环戊二烯型环氧树脂、以及对这些进行了改性而成的环氧树脂等的固体物质。作为三官能以上的多官能环氧树脂,可以列举例如苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、四缩水甘油基二氨基二苯基甲烷之类的缩水甘油基胺型环氧树脂、四(缩水甘油氧基苯基)乙烷和三(缩水甘油氧基苯基)甲烷之类的缩水甘油基苯基醚型环氧树脂、三缩水甘油基氨基苯酚之类的缩水甘油基胺型且缩水甘油基苯基醚型环氧树脂。此外,还可以举出将这些环氧树脂改性而成的环氧树脂、将这些环氧树脂溴化而成的溴化环氧树脂等,但只要是30℃下为固体的环氧树脂,则不限定于这些。
另外,也可以将这些环氧树脂的两种以上组合而作为其他环氧树脂(Z)使用。
成分(C)即包含B-M的嵌段共聚物(以下,有时简称为二嵌段共聚物)是用于维持环氧树脂组合物的优异耐热性、同时提高韧性和减振性而必须的成分。
此处,B及M所表示的各嵌段直接连结或者经由中间分子而连结。
作为成分(C)使用的二嵌段共聚物中,嵌段M是包含聚甲基丙烯酸甲酯的均聚物或至少含有50质量%甲基丙烯酸甲酯的共聚物的嵌段。另外,嵌段B是与嵌段M不相容,其玻璃化转变温度Tg(以下有时仅记载为Tg)为20℃以下的嵌段。
作为成分(C),具体来说,可列举:聚(甲基丙烯酸甲酯)/聚(丙烯酸丁酯)的二嵌段共聚物等。
通过将与环氧树脂不相容的聚合物选择为软嵌段(嵌段B),选择容易与环氧树脂相容的聚合物作为硬嵌段(嵌段M),并与成分(A)组合,从而二嵌段共聚物在环氧树脂中良好地微分散。通过使所述结构的二嵌段共聚物微分散在环氧树脂中,能够抑制环氧树脂组合物的硬化物的机械物性降低,同时提高tanδ。
具有作为容易与环氧树脂相容的聚合物的硬嵌段的聚(甲基丙烯酸甲酯)/聚(丙烯酸丁酯)的二嵌段共聚物由于在环氧树脂中的分散良好,且能够抑制环氧树脂组合物的硬化物的机械物性降低,因此更优选。可作为市售品而获取的聚(甲基丙烯酸甲酯)/聚(丙烯酸丁酯)的二嵌段共聚物例如可列举:阿科玛(ARKEMA)公司的纳米增强(Nanostrength)D51N等。
成分(C)的含量相对于环氧树脂组合物中含有的全部环氧树脂的合计100质量份,若为12质量份以上,则环氧树脂组合物的硬化物在0℃以上的tanδ变高,从而优选,若为19质量份以下,则环氧树脂组合物的硬化物的弯曲强度变高,从而优选。尤其优选为13~17质量份。
本发明的环氧树脂组合物的硬化物通过设为上述那样的组成,在环氧树脂中丙烯酸系共聚物具有海岛结构而相分离,从而以相互连结的紧密的状态存在。因此,认为起因于环氧树脂的tanδ和起因于丙烯酸成分的tanδ没有明确的峰分离,起因于丙烯酸成分的tanδ扩散,从而可以在0℃以上的宽温度区域得到高的tanδ。
成分(D)用作硬化剂。作为用作成分(D)的硬化剂,只要具有本发明的效果,则没有特别限定,例如可使用胺系硬化剂、咪唑类、酸酐、氯化硼胺络合物等。
其中,作为胺系硬化剂,可以举出例如双氰胺、二氨基二苯基砜等。
另外,作为咪唑类,可列举:2-苯基-4,5-二羟甲基咪唑、2-苯基-4-甲基-5-羟甲基咪唑等。
另外,作为酸酐,可列举:氢化甲基纳迪克酸酐、甲基六氢邻苯二甲酸酐等。
其中,通过使用双氰胺,环氧树脂组合物不会因空气中的湿气而性能发生变化,能够长期稳定地保持环氧树脂组合物的品质,并且能够在比较低的温度下完成硬化,因此优选。此处,所谓比较低的温度,是指100℃~130℃左右。
成分(D)的含量根据种类而不同,例如为双氰胺时,相对于环氧树脂组合物中所含的环氧树脂(A+B)或(A+B+Z)100质量份,通常为1质量份~25质量份。
更优选为相对于环氧树脂组合物中含有的环氧树脂所具有的环氧基的总摩尔数,双氰胺的活性氢的摩尔数优选成为0.6倍~1.0倍的量。通过设为0.6倍以上,而得到耐热性良好、机械物性良好(即强度高)的硬化物。另外,通过设为1.0倍以下,而得到机械物性良好的硬化物。更优选为0.6倍~0.8倍。
再者,环氧树脂组合物中所含的环氧树脂所具有的环氧基的总摩尔数根据投入量来计算即可。
本发明的环氧树脂组合物也可以含有成分(E)作为硬化促进剂。作为硬化促进剂,可列举:脲化合物、叔胺类及其盐类、咪唑及其盐类、路易斯酸(Lewis acid)类或布朗斯特酸( acid)类及其盐类等。其中,就保存稳定性和促进能力的平衡而言,适宜地使用脲化合物。
作为脲化合物,例如可使用N,N-二甲基-N'-(3,4-二氯苯基)脲、甲苯双(二甲基脲)、4,4'-亚甲基双(苯基二甲基脲)、3-苯基-1,1-二甲基脲等。作为脲化合物的市售品,可列举:DCMU99(保土谷化学(股)制造)、欧米固(Omicure)24、欧米固(Omicure)52、欧米固(Omicure)94(以上为艾默罗德性能有限责任公司(Emerald performance,LLC)制造)等。
相对于全部环氧树脂成分100质量份,成分(E)的调配量优选1质量份~7质量份,更优选3质量份~5质量份。在不满1质量份的情况下,反应未充分进行,硬化物的弹性模量和耐热性有时会降低。另外,在超过7质量份的情况下,环氧树脂的自聚合反应会阻碍环氧树脂与硬化剂的反应,因此,有时硬化物的韧性降低、或者弹性模量降低。
在本发明的环氧树脂组合物中,作为任意成分,也可以含有热塑性树脂、热塑性弹性体、弹性体、及消泡剂、流平剂(leveling agent)等各种添加剂(成分(F))。
作为成分(F),例如在含有热塑性树脂、热塑性弹性体或弹性体的情况下,不仅具有改变本发明的环氧树脂组合物的粘弹性而使粘度、储存弹性模量以及触变性(thixotropy)变得合理的作用,而且提升环氧树脂组合物的硬化物的断裂韧性。热塑性树脂、热塑性弹性体以及弹性体可以单独使用,也可以并用两种以上。相对于树脂组合物整体100质量份,这些添加剂可调配1质量份~15质量份,优选1质量份~10质量份。
热塑性树脂等可以溶解于环氧树脂成分中,也可以以微粒子、长纤维、短纤维、织物、无纺布、网眼(mesh)、纸浆(pulp)等形状包含在环氧树脂组合物中。
作为热塑性树脂,优选使用在主链上具有选自由碳-碳键、酰胺键、酰亚胺键、酯键、醚键、碳酸酯键、氨基甲酸酯键、脲键、硫醚键、砜键、咪唑键及羰基键所组成的群组中的至少一个键的热塑性树脂。更具体来说,例如可列举:聚丙烯酸酯、聚酰胺、聚芳族聚酰胺、聚酯、聚碳酸酯、聚苯硫醚、聚苯并咪唑、聚酰亚胺、聚醚酰亚胺、聚砜、以及聚醚砜之类的属于工程塑料的热塑性树脂。
其中,就耐热性优异而言,尤其优选使用聚酰亚胺、聚醚酰亚胺、聚砜以及聚醚砜等。另外,就提升本发明的环氧树脂组合物的硬化物的断裂韧性以及维持耐环境性的观点而言,优选为这些热塑性树脂具有与环氧树脂的反应性官能基。作为具有与环氧树脂的优选反应性的官能基,可列举:羧基、氨基以及羟基等。
作为成分(F),可添加消泡剂、流平剂以提升表面平滑性。相对于树脂组合物整体100质量份,这些添加剂可调配0.01质量份~3质量份、优选0.01质量份~1质量份。若调配量不足0.01质量份,则无法显现使表面平滑的效果,若超过3质量份,则添加剂会在表面引起渗出(bleed-out),反而成为损害平滑性的主要原因,因此不优选。另外,视需要还可调配颜料及其他添加剂。
但是,为了整体上保持为液态,本发明的环氧树脂组合物宜将成分(A)~(D)成分的调配量设为组合物整体的50质量%以上、优选80质量%以上。再者,溶剂不作为添加剂处理。
关于本发明的环氧树脂组合物的制造方法,没有特别限制,利用公知的方法制造即可。例如,可以同时混合构成环氧树脂组合物的全部成分,或者也可以预先混合组合物中含有的环氧树脂的一部分和成分(D)(硬化剂)等来调制母料(master batch),使用所述母料来调制组合物。混合操作可以使用三辊磨机、行星式混合机、捏合机、万能搅拌机、均化器、均质分配器(homo dispenser)等混合机。
例如,环氧树脂组合物可利用以下的工序来制造。
工序(1):使成分(D)均匀地分散在环氧树脂一部分中而制备树脂组合物的工序;
工序(2):将环氧树脂(成分(A)及成分(B)、或在包含环氧树脂(Z)等的情况下,为成分(A)、(B)和(Z)全部)、成分(C)和添加剂等加入溶解容器中,在140℃~170℃下加热混合1~6小时,得到二嵌段共聚物溶解基质的母料的工序;以及
工序(3):将工序(2)中得到的母料冷却至50℃~70℃后,添加工序(1)中得到的树脂组合物,在50℃~70℃下混合0.5~2小时,得到环氧树脂组合物的工序。
再者,还可以在工序(2)和工序(3)之间包括以下工序(3')。此时,在工序(2)中加入一部分环氧树脂,在工序(3)中加入剩余的环氧树脂。
工序(3'):将热塑性树脂溶解基质和成分(A)、成分(B)、成分(C)、成分(Z)的剩余部分加入溶解容器中,在70℃~140℃下加热混合1~3小时而得到母料的工序。
通过将本发明的环氧树脂组合物溶解于脱模纸等中并进行涂布,可以得到环氧树脂组合物的膜。本发明的膜通过贴附在基材上,而作为表面保护膜、接着膜是有用的。
另外,其使用方法优选将本发明的环氧树脂组合物涂布于脱模纸等基材的表面。得到的涂布层可以在未硬化的状态下粘贴在其他基材上进行硬化,也可以使涂布层自身硬化而作为膜使用。
实施例
以下,通过实施例对本发明进行具体说明,但本发明不受这些实施例任何限定。再者,表1中的成分(A)~成分(F)的含量均为质量份。
<原材料>
·具有噁唑烷酮环的二官能环氧树脂(商品名:YD-952、新日铁住金化学(股)制)
·双酚A型二官能环氧树脂(商品名:YD-128,新日铁住金化学(股)制,粘度(25℃)13000mPa·s、常温液体)
·双酚A型二官能固体环氧树脂(商品名:YD-011,新日铁住金化学(股)制,常温固体)
·苯酚酚醛清漆型二官能环氧树脂(商品名:KDPN-1020,新日铁住金化学(股)制,常温液体)
·丙烯酸系嵌段共聚物(聚(甲基丙烯酸甲酯)/聚(丙烯酸丁酯)的二嵌段共聚物)(商品名:纳米增强(Nanostrength)D51N、阿科玛(ARKEMA)(股)制)
·丙烯酸系嵌段共聚物(聚(甲基丙烯酸甲酯)/聚(丙烯酸丁酯)/聚(甲基丙烯酸甲酯)的三嵌段共聚物,进而二甲基丙烯酰胺共聚而成)(商品名:纳米增强(Nanostrength)M52N、阿科玛(ARKEMA)(股)制)
·双氰胺(商品名:迪西(DICY)15,三菱化学(股)制)
·3-(3,4-二氯苯基)-1,1-二甲基脲(商品名:DCMU99,保土谷化学(股)制)
实施例1~3、比较例1~6
在表1所示的各实施例和比较例的环氧树脂组合物的组成中、用三辊磨机使成分(B-1)(商品名:YD-128)的一部分,成分(D-1)(商品名:DICY15)、成分(E-1)(商品名:DCMU)均匀分散,制备树脂组合物1。
将从表1所示的各成分中去除了用于制备树脂组合物的成分后的全部成分计量到玻璃烧瓶中,并在150℃下加热混合,由此得到均匀的母料。接着,将所得到的母料冷却到60℃以下后,计量并添加树脂组合物1,并在60℃~70℃下加热混合,由此均匀地分散,得到环氧树脂组合物。所得到的环氧树脂组合物的组成分别如表1所记载。
将所得到的环氧树脂组合物与厚度1mm的聚四氟乙烯制的隔片(spacer)一起用金属板夹住,并在150℃、1MPa下压制保持60分钟使其硬化,由此得到动态力学分析(DynamicMechanical Analysis,DMA)测定用的硬化树脂板。
另外,将得到的环氧树脂组合物一边在60℃~80℃下加热一边注入至厚度4mm、宽度10mm、长度150mm的模具中,真空脱泡后,在150℃下使其硬化60分钟,由此得到弯曲试验用的硬化树脂板。
<tanδ的测定方法>
将所述DMA测定用的硬化树脂试验板加工成试验片(长度60mm×宽度5mm),并使用动态粘弹性测定装置(TA公司制造的RSA3)在拉伸位移0.1%、频率1Hz、0℃~250℃的范围内测定动态粘弹性。对于所得到的tanδ,使用0℃-10℃的平均值作为tanδ(0℃-10℃)。另外,使用所得到的tanδ作为各温度下的损失系数,将tanδ成为最大(max)值的温度作为Tg(玻璃化转变温度)。
<硬化树脂板的弯曲特性的测定方法>
对于所述弯曲试验用的硬化树脂板,使用具备1000N测压元件(load cell)的万能试验机(岛津制作所公司制造,制品名:AGS-X)测定树脂试验板的弯曲特性。在温度23℃、湿度50%相对湿度(relative humidity,RH)的环境下,使用三点弯曲夹具,按照日本工业标准(Japanese Industrial Standards,JIS)K 7074测定试验片的弯曲强度、弯曲弹性模量(储存弹性模量:E'、损失弹性模量:E”)、弯曲应变。
将这些结果示于表1、及图1~5中。
[表1]
如表1和图1~3所示,在实施例1~3中,0℃以上的温度区域中的tanδ高于0.033,并且还抑制了机械物性的降低,Tg也实现了120℃以上。另外,在比较例中,如图4、5所示,还发现室温区域(0℃-30℃)的tanδ降低。
产业上的可利用性
通过对本发明的环氧树脂组合物进行加热硬化而得到的成型物在0℃以上的温度区域可以得到高tanδ,具有高耐热性和机械物性,同时能够得到优异的减振性、衰减性。
因此,根据本发明,能够广泛提供高耐热且减振性、衰减性优异的接着剂、纤维增强塑料成型体,例如面向洗衣机用钢板的接着剂、产业用减振材、飞机用途、运动、休闲用途的成型体等。
Claims (3)
1.一种环氧树脂组合物,包含下述成分A~成分D,
成分A:分子内具有噁唑烷酮环结构的环氧树脂;
成分B:在30℃下为液态的环氧树脂;
成分C:具有B-M结构的二嵌段共聚物,
(此处,M是包含甲基丙烯酸甲酯的均聚物或含有至少50重量%甲基丙烯酸甲酯的共聚物的嵌段,B是对于环氧树脂和嵌段M不相容且其玻璃化转变温度Tg为20℃以下的嵌段,B及M所表示的各嵌段是直接键结或经由连结基而连结);
成分D:作为双氰胺或其衍生物的胺系硬化剂,且
所述环氧树脂组合物的特征在于,各成分的调配比例满足下述式:
A/(A+B)=0.05~0.25、
C/(A+B)=0.12~0.19、
D/(A+B)=1~10、
(此处,A~D分别是成分A~成分D的含量(质量))。
2.根据权利要求1所述的环氧树脂组合物,其中,成分C的嵌段M是包含甲基丙烯酸甲酯的均聚物的结构单元,嵌段B是选自1,4-聚丁二烯、聚丙烯酸丁酯以及聚(丙烯酸2-乙基己酯)的结构单元。
3.一种硬化物,是如权利要求1或2所述的环氧树脂组合物的硬化物,其在0℃~10℃的温度区域中的tanδ为0.033以上,且Tg为120℃以上且160℃以下。
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