CN107614601A - 热塑性氟树脂组合物、以及交联体的制造方法 - Google Patents
热塑性氟树脂组合物、以及交联体的制造方法 Download PDFInfo
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- CN107614601A CN107614601A CN201680029801.8A CN201680029801A CN107614601A CN 107614601 A CN107614601 A CN 107614601A CN 201680029801 A CN201680029801 A CN 201680029801A CN 107614601 A CN107614601 A CN 107614601A
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- fluorocarbon resin
- thermoplastic fluorocarbon
- resin composition
- thermoplastic
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Abstract
本发明提供一种热塑性氟树脂组合物、以及交联体的制造方法。其中,所述热塑性氟树脂组合物含有:热塑性氟树脂(A),依据ASTM D2240的23℃下的肖氏D硬度为50以下;以及交联结构形成剂(B),选自由多官能性不饱和化合物(b‑1)、多胺化合物(b‑2)以及多羟基化合物(b‑3)构成的组,能够通过与热塑性氟树脂(A)的反应形成交联结构,在所述热塑性氟树脂组合物中,在含有(b‑1)的情况下,实质上不含有过氧化物化合物;在含有(b‑2)的情况下,实质上不含有吸酸剂;在含有(b‑3)的情况下,实质上不含有吸酸剂以及鎓类化合物中的至少一方。所述交联体的制造方法包含:利用电离性射线使该热塑性氟树脂组合物交联的工序。
Description
技术领域
本发明涉及一种热塑性氟树脂组合物。另外,本发明涉及一种使用了该热塑性氟树脂组合物的交联体的制造方法。
背景技术
交联橡胶是通过使用被称为交联剂等的试剂在交联性橡胶成分(弹性体形成成分)的分子链之间引起交联反应而具有交联结构的弹性体。交联橡胶利用耐热性、耐化学品性优异的特征而经常用于垫圈(Gasket)或衬垫(Packing)等密封件、软管、管等。在交联橡胶中,就氟系的交联橡胶(以下,称为氟橡胶。)而言,表示由热劣化引起的变形的压缩永久变形特性优异,适合在高温环境下使用〔例如,日本特开2005-113035号公报(专利文献1)〕。
现有技术文献
专利文献
专利文献1:日本特开2005-113035号公报
专利文献2:国际公开第2006/057331号
专利文献3:日本特开2009-138158号公报
专利文献4:日本特开2002-167454号公报
专利文献5:日本特开2002-173543号公报
发明内容
发明所要解决的问题
认识到在由交联橡胶形成的成型体的制造中存在如下问题,难以提高生产效率:
a)为了成型为规定的形状,交联反应是必不可少的,因此,不适合于挤出成型、注塑成型,难以连续地进行成型而连续生产成型体;
b)一旦形成交联结构而使形状固定,交联反应是不可逆的,即使加热也不熔融,形状也是不可逆的,因此,即使在成型后的形状存在一些不良情况时,也无法再利用成型后的材料来再次实施成型工序。
另一方面,在弹性体中,除了交联橡胶之外,有的还被称为“热塑性弹性体”。一般而言,热塑性弹性体有:1)将热塑性树脂成分与橡胶成分混合而成的组合物、2)将含有热塑性树脂成分和橡胶成分的组合物动态交联而成的组合物、3)热塑性树脂成分与橡胶成分的嵌段共聚物等。就热塑性弹性体而言,若低于其热塑性树脂成分的熔点,则热塑性树脂成分如假交联位点(pseudo-cross-linking site)般起作用,由此热塑性弹性体的形状被固定,并且使其表现出橡胶弹性,另一方面,若在热塑性树脂成分的熔点以上,则热塑性树脂成分熔融,因此,能够使热塑性弹性体发生形状变化。动态交联(dynamic cross-linking)是指,一边将热塑性树脂成分和未交联的交联性橡胶成分与交联剂一起熔融混炼、一边使交联性橡胶成分进行交联的方法。
例如,在国际公开第2006/057331号(专利文献2)中,记载了一种将含有氟树脂、交联性的氟橡胶成分以及交联剂的组合物动态交联而成的热塑性弹性体组合物。在日本特开2009-138158号公报(专利文献3)中,记载了:制备将含有氟树脂、未交联氟橡胶粒子以及交联剂的组合物动态交联而成的热塑性弹性体组合物,对其进行成型后照射伽马射线而得到成型品。
另外,在日本特开2002-167454号公报(专利文献4)以及日本特开2002-173543号公报(专利文献5)中,记载了:对含有弹性体性聚合物链段和非弹性体性聚合物链段的氟系热塑性弹性体进行成型后,照射伽马射线而得到成型品。
就氟系热塑性弹性体而言,若在构成氟系热塑性弹性体的热塑性树脂成分的熔点以上,则该成分熔融,若低于熔点,则氟系热塑性弹性体的形状被固定,因此,适合于挤出成型、注塑成型,另外,能够可逆地改变形状,因此,也能够再利用成型后的材料来进行再成型。但是,含有热熔融的热塑性树脂成分的氟系热塑性弹性体与氟橡胶相比耐热性差,尤其是表示由热劣化引起的变形的压缩永久变形特性差。
本发明的目的在于,提供一种交联体的制造方法、以及该制造方法所使用的热塑性氟树脂组合物,所述方法在实施通过熔融成型进行的连续成型、以及成型工序的情况下,能够再利用成型后的材料,能够制造即使在高温环境下也显示出优异的压缩永久变形特性的交联体。
用于解决问题的方案
本发明提供以下所示的热塑性氟树脂组合物、以及交联体的制造方法。
[1]一种热塑性氟树脂组合物,其含有:
热塑性氟树脂(A),依据ASTM D2240测定出的23℃下的肖氏D硬度为50以下;以及
交联结构形成剂(B),选自由多官能性不饱和化合物(b-1)、多胺化合物(b-2)以及多羟基化合物(b-3)构成的组,能够通过与所述热塑性氟树脂(A)的反应形成交联结构,
在所述热塑性氟树脂组合物中,在含有所述多官能性不饱和化合物(b-1)的情况下,实质上不含有过氧化物化合物;在含有多胺化合物(b-2)的情况下,实质上不含有吸酸剂;在含有多羟基化合物(b-3)的情况下,实质上不含有吸酸剂以及鎓类化合物中的至少一方。
[2]根据[1]所述的热塑性氟树脂组合物,其中,
进一步含有交联性橡胶成分(C)。
[3]根据[2]所述的热塑性氟树脂组合物,其中,
所述交联性橡胶成分(C)为氟橡胶。
[4]根据[2]或[3]所述的热塑性氟树脂组合物,其中,
相对于100重量份的所述热塑性氟树脂(A),所述交联性橡胶成分(C)的含量为100重量份以下。
[5]一种交联体的制造方法,其包含:
准备[1]~[4]中任一项所述的热塑性氟树脂组合物的工序;以及
利用电离性射线使所述热塑性氟树脂组合物交联的工序。
[6]根据[5]所述的制造方法,其中,
在准备所述热塑性氟树脂组合物的工序与使所述热塑性氟树脂组合物交联的工序之间,进一步包含使所述热塑性氟树脂组合物成型的工序。
发明效果
根据本发明,能够提供一种交联体的制造方法、以及该制造方法所使用的热塑性氟树脂组合物,所述方法在实施通过熔融成型进行的连续成型、以及成型工序的情况下,能够再利用成型后的材料,所述交联体即使在高温环境下也显示出优异的压缩永久变形特性。所得的交联体可以优选用作衬垫、垫圈之类的密封件等,尤其是要求高温环境下(例如130~230℃,特别是150~200℃)的耐热劣化性的密封件等。
具体实施方式
<热塑性氟树脂组合物>
本发明的热塑性氟树脂组合物含有热塑性氟树脂(A)和交联结构形成剂(B)。热塑性氟树脂是指,含有氟原子的热塑性树脂。
(A)热塑性氟树脂
本发明的热塑性氟树脂组合物中含有的热塑性氟树脂(A)是依据ASTM D2240测定出的23℃下的肖氏D硬度为50以下的热塑性氟树脂。这是基于本发明人所获得的新见解,通过使用肖氏D硬度为50以下的热塑性氟树脂(A),能够得到高温环境下的压缩永久变形特性优异的交联体。肖氏D硬度优选为45以下。热塑性氟树脂组合物可以含有一种或两种以上的热塑性氟树脂(A),但在含有两种以上的情况下,优选所有的热塑性氟树脂(A)的肖氏D硬度均为50以下。
热塑性氟树脂(A)的具体例包含:四氟乙烯-全氟烷基乙烯基醚共聚物(PFA)、四氟乙烯-六氟丙烯共聚物(FEP)、四氟乙烯-乙烯共聚物(ETFE)、聚氯三氟乙烯(PCTFE)、氯三氟乙烯-乙烯共聚物(ECTFE)、偏氟乙烯-六氟丙烯共聚物(VDF-HFP共聚物)、偏氟乙烯-六氟丙烯-四氟乙烯共聚物(VDF-HFP-TFE共聚物)。其中,优选使用VDF-HFP共聚物、VDF-HFP-TFE共聚物等。
在本说明书中,术语“热塑性氟树脂”包含氟系热塑性弹性体。氟系热塑性弹性体是指,含有氟原子的热塑性弹性体。如上所述,热塑性弹性体有:1)将热塑性树脂成分与橡胶成分混合而成的组合物、2)将含有热塑性树脂成分和橡胶成分的组合物动态交联而成的组合物、3)热塑性树脂成分与橡胶成分的嵌段共聚物等。可以用于本发明的优选的氟系热塑性弹性体是属于上述3)的、热塑性树脂成分(热塑性的聚合物链段)与橡胶成分(弹性体性的聚合物链段)的嵌段共聚物。
可以使用市售品作为热塑性氟树脂(A)。肖氏D硬度为50以下的热塑性氟树脂(A)的具体例包含:均以商品名表示,“Kynar UltraFlex B”、“Kynar UltraFlex C”(均为阿科玛公司制、由VDF-HFP共聚物形成的热塑性树脂);“THV 220G”(3M公司制、由VDF-HFP-TFE共聚物形成的热塑性树脂);“DAI-EL Thermoplastic”(大金工业(株)制、由ETFE共聚物与VDF系共聚物的嵌段共聚物形成的热塑性弹性体)。
热塑性氟树脂(A)是能够在后述的交联结构形成剂(B)的存在下、通过照射电离性射线进行交联的热塑性树脂。热塑性氟树脂(A)可以具有或不具有不饱和基团、羟基、氨基、羰基、卤素基团等交联性位点(cross-linkable site)。在通过照射电离性射线进行的交联中,即使不具有交联性位点,热塑性氟树脂(A)也能够进行交联。
(B)交联结构形成剂
本发明的热塑性氟树脂组合物含有交联结构形成剂(B)作为必需成分。在本说明书中,“交联结构形成剂”是指,能够通过与热塑性氟树脂(A)的反应,与热塑性氟树脂(A)一起形成交联结构的试剂,其中,所述反应通过照射电离性射线而进行。
交联结构形成剂(B)例如是选自由多官能性不饱和化合物(b-1)、多胺化合物(b-2)以及多羟基化合物(b-3)构成的组中的试剂。交联结构形成剂(B)可以含有选自(b-1)、(b-2)以及(b-3)中的两种以上的交联结构形成剂,但通常仅含有选自它们中的一种。交联结构形成剂(B)可以根据热塑性氟树脂(A)的交联体系进行选择。热塑性氟树脂组合物优选含有多官能性不饱和化合物(b-1)。
多官能性不饱和化合物(b-1)可以是在利用过氧化物交联体系使交联性橡胶成分交联来制造氟橡胶的情况等中、通常用作“共交联剂(co-cross-linking agent)”的多官能性不饱和化合物。交联结构形成剂(B)可以含有一种或两种以上的多官能性不饱和化合物(b-1)。
多官能性不饱和化合物(b-1)的具体例包含:氰尿酸三烯丙酯、三烯丙基异氰脲酸酯(TAIC)、1,3,5-三丙烯酰基六氢-1,3,5-三嗪(Triacrylformal)、偏苯三酸三烯丙酯、N,N’-间苯撑双马来酰亚胺、对苯二甲酸二炔丙酯、邻苯二甲酸二烯丙酯、四烯丙基对苯二甲酸酯酰胺(tetraallyl terephthalate amide)、磷酸三烯丙酯、双马来酰亚胺、氟化三烯丙基异氰脲酸酯(1,3,5-三(2,3,3-三氟-2-丙烯基)-1,3,5-三嗪-2,4,6-三酮)、三(二烯丙基胺)-S-三嗪、亚磷酸三烯丙酯、N,N-二烯丙基丙烯酰胺、1,6-二乙烯基十二氟己烷、六烯丙基磷酰胺、N,N,N’,N’-四烯丙基邻苯二甲酰胺、N,N,N’,N’-四烯丙基丙二酰胺、三乙烯基异氰脲酸酯、2,4,6-三乙烯基甲基三硅氧烷、三(5-降冰片烯-2-亚甲基)氰尿酸酯、亚磷酸三烯丙酯。其中,从热塑性氟树脂(A)的交联性、以及所得的交联体的物性、尤其是压缩永久变形特性的方面考虑,多官能性不饱和化合物(b-1)优选含有三烯丙基异氰脲酸酯(TAIC)。
相对于100重量份的热塑性氟树脂(A),热塑性氟树脂组合物中的多官能性不饱和化合物(b-1)的含量(在使用两种以上的多官能性不饱和化合物(b-1)的情况下为其合计量)例如为0.1~20重量份,优选为0.2~10重量份,更优选为1~8重量份。若多官能性不饱和化合物(b-1)的含量过小,则通过照射电离性射线进行的热塑性氟树脂(A)的交联不会充分进行,所得的交联体的压缩永久变形特性可能会降低。若多官能性不饱和化合物(b-1)的含量过大,则热塑性氟树脂组合物的成型性可能会降低。
在热塑性氟树脂组合物含有多官能性不饱和化合物(b-1)的情况下,热塑性氟树脂组合物实质上不含有过氧化物化合物(有机过氧化物)是关键。该过氧化物化合物是在利用过氧化物交联体系使交联性橡胶成分交联来制造氟橡胶的情况等中、通常用作“交联剂”的化合物,该过氧化物化合物是在利用过氧化物交联体系使交联性橡胶成分受热交联的情况下作为必需成分而含有的、引发交联反应的试剂或者引发所需的试剂。该过氧化物化合物的具体例包含:1,1-双(叔丁基过氧基)-3,5,5-三甲基环己烷、2,5-二甲基己烷-2,5-二氢过氧化物、二叔丁基过氧化物、叔丁基枯基过氧化物、过氧化二异丙苯、α,α-双(叔丁基过氧基)对二异丙基苯、2,5-二甲基-2,5-二(叔丁基过氧基)己烷、2,5-二甲基-2,5-二(叔丁基过氧基)-3-己炔、过氧化苯甲酰、叔丁基过氧苯(t-butylperoxybenzene)、叔丁基过氧马来酸(t-butylperoxymaleic acid)、叔丁基过氧异丙基甲酸酯(t-butylperoxyisopropylcarbonate)。
在本说明书中,“实质上不含有过氧化物化合物”是指,过氧化物化合物的含量相对于100重量份的热塑性氟树脂(A)为0.1重量份以下。
根据实质上不含有过氧化物化合物的本发明的热塑性氟树脂组合物,通过由照射电离性射线进行的交联,能够得到即使在高温环境下也显示出优异的压缩永久变形特性的交联体。另外,本发明的热塑性氟树脂组合物能够加热熔融,并且实质上不含有过氧化物化合物,由此,即使在成型时加热熔融也不进行交联。因此,本发明的热塑性氟树脂组合物容易实现使用了例如挤出成型、注塑成型之类的熔融成型的连续成型。另外,还能够在成型后的形状存在一些不良情况时,对该成型体进行热熔融,再次实施成型工序等,再利用成型后的材料。这样的材料的再利用有利于削减制造成本。
以上这样的本发明的热塑性氟树脂组合物的优点,在该组合物进一步含有氟橡胶等后述的交联性橡胶成分(C)的情况下也可得到。对此,在如专利文献2以及3所记载的、将含有氟树脂、未交联氟橡胶以及交联剂的组合物动态交联(一边使氟树脂、未交联氟橡胶以及交联剂熔融混炼,一边利用交联剂对未交联氟橡胶进行热交联)而成的热塑性弹性体组合物的情况下,能够通过提高氟树脂的含有率来提高热熔融性、成型性,但即使利用热或者利用电离性射线使该热塑性弹性体组合物进一步交联,也难以得到优异的压缩永久变形特性。在如专利文献4以及5所记载的、利用电离性射线使含有弹性体性聚合物链段和非弹性体性聚合物链段的氟系热塑性弹性体交联的方法中,也难以得到优异的压缩永久变形特性。
多胺化合物(b-2)可以是在利用多胺交联体系使交联性橡胶成分交联来制造氟橡胶的情况等中、通常用作“交联剂”的多胺化合物。交联结构形成剂(B)可以含有一种或两种以上的多胺化合物(b-2)。
多胺化合物(b-2)的具体例包含:六亚甲基二胺氨基甲酸酯、N,N’-二亚肉桂基-1,6-六亚甲基二胺、4,4’-双(氨基环己基)甲烷氨基甲酸酯。其中,从热塑性氟树脂(A)的交联性、以及所得的交联体的物性、尤其是压缩永久变形特性的方面考虑,多胺化合物(b-2)优选含有N,N’-二亚肉桂基-1,6-六亚甲基二胺。
相对于100重量份的热塑性氟树脂(A),热塑性氟树脂组合物中的多胺化合物(b-2)的含量(在使用两种以上的多胺化合物(b-2)的情况下为其合计量)例如为0.1~20重量份,优选为0.2~10重量份,更优选为1~8重量份。若多胺化合物(b-2)的含量过小,则通过照射电离性射线进行的热塑性氟树脂(A)的交联不会充分进行,所得的交联体的压缩永久变形特性可能会降低。若多胺化合物(b-2)的含量过大,则热塑性氟树脂组合物的成型性可能会降低。
在热塑性氟树脂组合物含有多胺化合物(b-2)的情况下,热塑性氟树脂组合物实质上不含有吸酸剂(acid acceptor)是关键。该吸酸剂与在利用多胺交联体系使交联性橡胶成分交联来制造氟橡胶的情况等中、通常用作“吸酸剂”的物质相同,该吸酸剂是在利用多胺交联体系使交联性橡胶成分受热交联的情况下作为必需成分而含有的、引发交联反应的试剂或者引发所需的试剂。该吸酸剂的具体例包含:二价金属的氧化物、二价金属的氢氧化物、二价金属的氧化物与弱酸金属盐的混合物、二价金属的氢氧化物与弱酸金属盐的混合物。作为二价金属,可列举出镁、钙、锌、铅等。作为弱酸金属盐,可列举出硬脂酸、苯甲酸、碳酸、草酸、亚磷酸等之类的弱酸的金属盐。
在本说明书中,“实质上不含有吸酸剂”是指,吸酸剂的含量相对于100重量份的热塑性氟树脂(A)为0.1重量份以下。
另外,实质上不含有吸酸剂的本发明的热塑性氟树脂组合物也能够实现与上述的实质上不含有过氧化物化合物的热塑性氟树脂组合物同样的效果。即使在该组合物进一步含有后述的交联性橡胶成分(C)的情况下,也能够实现该效果。
多羟基化合物(b-3)可以是在利用多元醇交联体系使交联性橡胶成分交联来制造氟橡胶的情况等中、通常用作“交联剂”的多羟基化合物。交联结构形成剂(B)可以含有一种或两种以上的多羟基化合物(b-3)。从所得的交联体的压缩永久变形特性的观点考虑,多羟基化合物(b-3)优选含有多羟基芳香族化合物。
多羟基芳香族化合物的具体例包含:2,2-双(4-羟基苯基)丙烷(双酚A)、2,2-双(4-羟基苯基)全氟丙烷(双酚AF)、间苯二酚、1,3-二羟基苯、1,7-二羟基萘、2,7-二羟基萘、1,6-二羟基萘、4,4’-二羟基联苯、4,4’-二羟基芪、2,6-二羟基蒽、对苯二酚、邻苯二酚、2,2-双(4-羟基苯基)丁烷(双酚B)、4,4-双(4-羟基苯基)戊酸、2,2-双(4-羟基苯基)四氟二氯丙烷、4,4-二羟基二苯基砜、4,4’-二羟基二苯基酮、三(4-羟基苯基)甲烷、3,3’,5,5’-四氯双酚A、3,3’,5,5’-四溴双酚A。这些多羟基芳香族化合物可以为碱金属盐、碱土金属盐等。
相对于100重量份的热塑性氟树脂(A),热塑性氟树脂组合物中的多羟基化合物(b-3)的含量(在使用两种以上的多羟基化合物(b-3)的情况下为其合计量)例如为0.1~20重量份,优选为0.2~10重量份,更优选为1~8重量份。若多羟基化合物(b-3)的含量过小,则通过照射电离性射线进行的热塑性氟树脂(A)的交联不会充分进行,所得的交联体的压缩永久变形特性可能会降低。若多羟基化合物(b-3)的含量过大,则热塑性氟树脂组合物的成型性可能会降低。
在热塑性氟树脂组合物含有多羟基化合物(b-3)的情况下,热塑性氟树脂组合物实质上不含有吸酸剂以及鎓类化合物中的至少一方是关键。该吸酸剂以及鎓类化合物分别与在利用多元醇交联体系使交联性橡胶成分交联来制造氟橡胶的情况等中、通常用作“吸酸剂”、“鎓类化合物”的物质相同,该吸酸剂以及鎓类化合物分别是利用多元醇交联体系使交联性橡胶成分受热交联的情况下作为必需成分而含有的、引发交联反应的试剂或者引发所需的试剂。吸酸剂的具体例与上述的物质相同。鎓类化合物的具体例包含:季铵盐、季鏻盐、氧鎓化合物、锍化合物。
在本说明书中,“实质上不含有吸酸剂以及鎓类化合物中的至少一方”是指,吸酸剂以及鎓类化合物中的至少一方的含量相对于100重量份的热塑性氟树脂(A)为0.1重量份以下。
另外,实质上不含有吸酸剂以及鎓类化合物的本发明的热塑性氟树脂组合物也能够实现与上述的实质上不含有过氧化物化合物的热塑性氟树脂组合物相同的效果。即使在该组合物进一步含有后述的交联性橡胶成分(C)的情况下,也能够实现该效果。
(C)交联性橡胶成分
本发明的热塑性氟树脂组合物可以进一步含有交联性橡胶成分(C)。就进一步含有交联性橡胶成分(C)的热塑性氟树脂组合物而言,也能够得到即使在高温环境下也显示出优异的压缩永久变形特性的交联体,另外,也能够实现使用了例如挤出成型、注塑成型之类的熔融成型的连续成型,也能够再利用成型后的材料。进一步含有交联性橡胶成分(C)在例如要求柔韧性的用途中是有利的。
交联性橡胶成分(C)是能够通过交联反应形成具有上述的交联结构的弹性体(交联橡胶)的橡胶成分,其具体例包含:乙烯-丙烯橡胶(EPM)、乙烯-丙烯-二烯橡胶(EPDM)、丁腈橡胶(NBR;丙烯腈丁二烯橡胶)、氢化丁腈橡胶(HNBR;氢化丙烯腈丁二烯橡胶)、丁基橡胶(IIR)、氟橡胶(FKM)、全氟弹性体(FFKM)、丙烯酸橡胶、硅橡胶。其中,优选使用氟橡胶(FKM)、全氟弹性体(FFKM)。交联性橡胶成分(C)既可以仅使用一种,也可以并用两种以上。
氟橡胶(FKM)的具体例包含:偏氟乙烯(VDF)-六氟丙烯(HFP)系聚合物;偏氟乙烯(VDF)-六氟丙烯(HFP)-四氟乙烯(TFE)系聚合物;四氟乙烯(TFE)-丙烯(Pr)系聚合物;偏氟乙烯(VDF)-丙烯(Pr)-四氟乙烯(TFE)系聚合物;乙烯(E)-四氟乙烯(TFE)-全氟甲基乙烯基醚(PMVE)系聚合物;偏氟乙烯(VDF)-四氟乙烯(TFE)-全氟甲基乙烯基醚(PMVE)系聚合物、偏氟乙烯(VDF)-全氟甲基乙烯基醚(PMVE)系聚合物。
全氟弹性体(FFKM)的具体例包含四氟乙烯(TFE)-全氟甲基乙烯基醚(PMVE)系聚合物。
交联性橡胶成分(C)可以具有或不具有碳-碳不饱和基团、腈基、羟基、氨基、羰基、卤素基团等交联性位点。在通过照射电离性射线进行的交联中,即使不具有交联性位点,交联性橡胶成分(C)也能够进行交联。
相对于100重量份的热塑性氟树脂(A),热塑性氟树脂组合物中的交联性橡胶成分(C)的含量(在使用两种以上的交联性橡胶成分(C)的情况下为其合计量)优选为100重量份以下,更优选为80重量份以下(例如70重量份以下)。若交联性橡胶成分(C)的含量过大,则热塑性氟树脂组合物的成型性可能会降低。在热塑性氟树脂组合物含有交联性橡胶成分(C)的情况下,相对于100重量份的热塑性氟树脂(A),交联性橡胶成分(C)的含量例如为5重量份以上、10重量份以上、或者20重量份以上。
(D)其他成分
本发明的热塑性氟树脂组合物根据需要可以含有:填充剂(增强剂)、加工助剂、抗老化剂、抗氧化剂、硫化促进剂、稳定剂、硅烷偶联剂、阻燃剂、脱模剂、蜡类、润滑剂等添加剂。填充剂的具体例包含:炭黑、二氧化硅、氧化铝、氧化锌、二氧化钛、粘土、滑石、硅藻土、硫酸钡、硅酸化合物(硅酸盐等)、碳酸钙、碳酸镁、氧化钙、云母、石墨、氢氧化铝、树脂微粒。加工助剂的具体例包含:热塑性氟树脂(A)以外的热塑性树脂、液体橡胶、油(石蜡系油等)、增塑剂、软化剂、增粘剂。添加剂既可以仅使用一种,也可以并用两种以上。
(E)热塑性氟树脂组合物的制备
本发明的热塑性氟树脂组合物可以通过将热塑性氟树脂(A)、交联结构形成剂(B)、以及任意添加的交联性橡胶成分(C)、其他添加剂均匀混炼进行制备。作为混炼机,例如,可以使用开炼机(open roll)之类的混炼机(mixing roll);捏合机、班伯里密炼机之类的密炼机(mixer);双螺杆挤出机之类的挤出机等。就这些配合剂而言,既可以同时混合并进行混炼,也可以以对一部分的配合剂进行混炼、然后对剩余的配合剂进行混炼这样的方式,分成多个阶段对全部的配合剂进行混炼。混炼时的温度既可以为常温,也可以在加热下,但从混炼的均匀性的观点考虑,优选在热塑性氟树脂(A)的熔融温度或其附近、或者熔融温度以下的温度下进行混炼。
<交联体的制造方法>
以上述的热塑性氟树脂组合物为原料的交联体可以优选通过包含如下工序的方法进行制造:
(1)准备上述的本发明的热塑性氟树脂组合物的工序〔以下,称为工序(1)。〕;以及
(2)利用电离性射线使热塑性氟树脂组合物交联的工序〔以下,称为工序(2)。〕。优选在工序(1)与工序(2)之间进一步包含:
(3)将热塑性氟树脂组合物成型为所期望的形状的工序〔以下,称为工序(3)。〕。
工序(1)既可以是以某种方式获得本发明的热塑性氟树脂组合物的工序,也可以是制备该组合物的工序。制备方法如上所述。
进行热塑性氟树脂组合物的成型的工序(3)可以利用通常的方法来进行。本发明的热塑性氟树脂组合物能够加热熔融,并且实质上不含有引发通过热进行的交联反应的试剂或引发所需的试剂,因此,即使在成型时加热熔融也不进行交联。因此,根据本发明的热塑性氟树脂组合物,能够实现使用了例如挤出成型、注塑成型之类的熔融成型的连续成型。由此,能够实现交联成型体的连续生产、进而能够削减制造成本。可以通过加压成型等其他成型法进行热塑性氟树脂组合物的成型。热塑性氟树脂组合物的成型温度例如为150~320℃。
另外,根据能够加热熔融、并且即使在成型时加热熔融也不进行交联的本发明的热塑性氟树脂组合物,还能够在成型后的形状存在一些不良情况时,对该成型体进行热熔融,再次实施成型工序等,再利用成型后的材料。
在工序(2)中,热塑性氟树脂组合物或其成型体利用电离性射线进行交联,从而得到交联体(或交联成型体)。电离性射线并不特别限制,但可以优选使用电子射线、γ射线。电离性射线的照射量优选为10~500kGy,更优选为30~200kGy。若照射量小于10kGy,则存在如下趋势:无法得到足够的交联度,无法得到所期望的压缩永久变形特性,根据情况无法得到进一步的机械强度。另一方面,将照射量设为500kGy以下,在不损害柔韧性的方面是有利的。另外,若照射量大于500kGy,则恐怕会在交联体产生由电离性射线引起的劣化。
本发明的交联体的制造方法实质上不包含通过热对热塑性氟树脂组合物或其成型体进行交联的工序。这是由于,热塑性氟树脂组合物实质上不含有引发通过热进行的交联反应的试剂或引发所需的试剂。假如含有该试剂,则在热塑性氟树脂组合物进一步含有交联性橡胶成分(C)的情况下,在成型时的加热熔融时等,热塑性氟树脂组合物会被动态交联处理,其结果是,所得的交联体的压缩永久变形特性会降低。
在利用电离性射线进行交联处理之后,根据需要,可以使用烘箱(电炉、真空电炉)等对交联体施加热处理。在交联体为例如真空密封用途的密封件的情况下,能够通过热处理来减少释放气体成分,因此,有时能够提高密封性。热处理的温度通常为100~320℃(例如170~230℃左右、或者170~200℃左右)。
在热塑性氟树脂组合物不含有交联性橡胶成分(C)的情况下,通过本发明得到的交联体以及交联成型体由交联后的热塑性氟树脂(A)(以及任意含有的添加剂)构成。另外,在热塑性氟树脂组合物进一步含有交联性橡胶成分(C)的情况下,通过本发明得到的交联体可以采用交联后的热塑性氟树脂(A)与交联后的交联性橡胶成分(C)(即交联橡胶)的海岛结构。交联后的热塑性氟树脂(A)以及交联橡胶中的哪一种为基质,取决于热塑性氟树脂(A)以及交联性橡胶成分(C)的配合比率等。存在如下趋势:配合比率更高的成分为基质。除了海岛结构之外,通过本发明得到的交联体以及交联成型体还可以具有共连续结构(co-continuous structure)、柱状结构(cylinder structure)、片晶结构(lamellarstructure)等结构形态。
通过本发明得到的交联体以及交联成型体可以应用于要求耐热性的各种构件,其中,可以优选用作衬垫、垫圈之类的密封件等,尤其是要求200℃或200℃以上的高温环境下的耐热劣化性的密封件等。密封件的形状根据其用途进行适当选择,其代表例是剖面形状为O形的O形密封圈。
实施例
以下,举出实施例以及比较例对本发明进行更详细的说明,但本发明不受这些实施例的限定。对于以下的实施例以及比较例,按照如下方法测定出压缩永久变形。
(压缩永久变形的测定)
依据JIS K 6262,以压缩率25%将试样(A568-214O形密封圈)夹在铁板之间,在200℃×72小时的条件下用电炉进行加热后,进行压缩释放,基于下述公式计算出冷却30分钟后的试样的压缩永久变形。
压缩永久变形(%)={(T0-T1)/(T0-T2)}×100%
T0为试验前的试样的高度,T1为冷却30分钟后的试样的高度,T2为垫块(Spacer)的厚度(高度)。将结果示于表1。
<实施例1>
按照表1所示的配合组成(表1中的配合量的单位为重量份。),利用开炼机对规定量的各配合成分进行混炼。混炼温度设为140℃。接着,在230℃下对所得的热塑性氟树脂组合物进行挤出成型,得到了密封件(O形密封圈)形状的成型体。容易挤出成型(熔融成型)为密封件形状。然后,以80kGy的照射量照射射线(γ射线),得到了作为交联成型体的密封件(O形密封圈)。照射射线前的成型体显示出热熔融性,也容易使该成型体热熔融并再次进行成型。
<实施例2~5、比较例1~3>
除了将热塑性氟树脂组合物的配合成分及其配合量设为如表1所示以外,与实施例1同样地制作出作为交联成型体的密封件。在实施例2~5、比较例1~3的任一个中,均容易挤出成型(熔融成型)为密封件形状。另外,照射射线前的成型体显示出热熔融性,也容易使该成型体热熔融并再次进行成型。
<比较例4>
按照表1所示的配合组成,利用开炼机对交联结构形成剂(B)和交联性橡胶成分(C)进行混炼而得到了混炼物。按照表1所示的配合组成,利用LABO PLASTOMILL〔(株)东洋精机制作所制〕对该混炼物、热塑性氟树脂(A)以及过氧化物进行混炼。此时的混炼温度设为200℃,转速设为50rpm。接着,在230℃下对所得的热塑性氟树脂组合物进行挤出成型,得到了密封件(O形密封圈)形状的成型体。容易挤出成型(熔融成型)为密封件形状。然后,以80kGy的照射量照射射线(γ射线),得到了作为交联成型体的密封件(O形密封圈)。
[表1]
在实施例以及比较例中使用的各配合成分的详情如下。
〔1〕热塑性氟树脂a-1:由VDF-HFP共聚物形成的热塑性树脂(阿科玛公司制的“Kynar UltraFlex B”,依据ASTM D2240测定出的23℃下的肖氏D硬度:40),
〔2〕热塑性氟树脂a-2:作为偏氟乙烯(VDF)系聚合物与四氟乙烯-乙烯系聚合物(ETFE)的嵌段聚合物的氟系热塑性弹性体〔大金工业(株)制“DAI-EL Thermoplastic T-530”,依据ASTM D2240测定出的23℃下的肖氏D硬度:18〕,
〔3〕热塑性氟树脂a-3:由VDF-HFP共聚物形成的热塑性树脂(阿科玛公司制的“Kynar 2850-00”,依据ASTM D2240测定出的23℃下的肖氏D硬度:73),
〔4〕交联结构形成剂b-1:三烯丙基异氰脲酸酯〔日本化成公司制“TAIC”〕,
〔5〕交联性橡胶成分c-1:偏氟乙烯(VDF)-六氟丙烯(HFP)-四氟乙烯(TFE)系聚合物〔大金工业(株)制“DAI-EL G902”〕,
〔6〕交联性橡胶成分c-2:偏氟乙烯(VDF)-六氟丙烯(HFP)系聚合物,
〔7〕过氧化物d-1:5-二甲基-2,5-二(叔丁基过氧基)己烷〔日油(株)制“Perhexa25B”〕。
Claims (6)
1.一种热塑性氟树脂组合物,其含有:
热塑性氟树脂(A),依据ASTM D2240测定出的23℃下的肖氏D硬度为50以下;以及
交联结构形成剂(B),选自由多官能性不饱和化合物(b-1)、多胺化合物(b-2)以及多羟基化合物(b-3)构成的组,能够通过与所述热塑性氟树脂(A)的反应形成交联结构,
在所述热塑性氟树脂组合物中,在含有所述多官能性不饱和化合物(b-1)的情况下,实质上不含有过氧化物化合物;在含有多胺化合物(b-2)的情况下,实质上不含有吸酸剂;在含有多羟基化合物(b-3)的情况下,实质上不含有吸酸剂以及鎓类化合物中的至少一方。
2.根据权利要求1所述的热塑性氟树脂组合物,其中,
进一步含有交联性橡胶成分(C)。
3.根据权利要求2所述的热塑性氟树脂组合物,其中,
所述交联性橡胶成分(C)为氟橡胶。
4.根据权利要求2或3所述的热塑性氟树脂组合物,其中,
相对于100重量份的所述热塑性氟树脂(A),所述交联性橡胶成分(C)的含量为100重量份以下。
5.一种交联体的制造方法,其包含:
准备权利要求1~4中任一项所述的热塑性氟树脂组合物的工序;以及
利用电离性射线使所述热塑性氟树脂组合物交联的工序。
6.根据权利要求5所述的制造方法,其中,
在准备所述热塑性氟树脂组合物的工序与使所述热塑性氟树脂组合物交联的工序之间,进一步包含使所述热塑性氟树脂组合物成型的工序。
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- 2016-04-28 WO PCT/JP2016/063380 patent/WO2016190050A1/ja active Application Filing
- 2016-04-28 KR KR1020177036247A patent/KR102414274B1/ko active IP Right Grant
- 2016-04-28 US US15/572,228 patent/US20180112045A1/en not_active Abandoned
- 2016-04-28 EP EP16799758.4A patent/EP3305845B1/en active Active
- 2016-05-06 TW TW105114198A patent/TWI718147B/zh active
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2019
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2022
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CN109749315A (zh) * | 2019-01-25 | 2019-05-14 | 上海杜实新材料科技有限公司 | 一种辐照交联氟橡胶组合物及其制备方法和应用 |
CN110157124A (zh) * | 2019-05-10 | 2019-08-23 | 上海杜实新材料科技有限公司 | 一种耐硫化氢腐蚀的四丙氟橡胶组合物及其应用 |
CN112409731A (zh) * | 2020-10-21 | 2021-02-26 | 浙江巨化技术中心有限公司 | 一种3d打印专用含氟树脂组合物及其制备方法 |
CN112409731B (zh) * | 2020-10-21 | 2023-02-24 | 浙江巨化技术中心有限公司 | 一种3d打印用含氟树脂组合物及其制备方法 |
Also Published As
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EP3305845B1 (en) | 2021-08-04 |
JP2016222752A (ja) | 2016-12-28 |
KR20180012782A (ko) | 2018-02-06 |
KR102414274B1 (ko) | 2022-06-28 |
US20200055999A1 (en) | 2020-02-20 |
TWI718147B (zh) | 2021-02-11 |
EP3305845A4 (en) | 2018-12-05 |
US20220251310A1 (en) | 2022-08-11 |
US20180112045A1 (en) | 2018-04-26 |
EP3305845A1 (en) | 2018-04-11 |
WO2016190050A1 (ja) | 2016-12-01 |
TW201704325A (zh) | 2017-02-01 |
JP6712445B2 (ja) | 2020-06-24 |
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