CN102675662B - 弹性体组合物和其制造方法、及使用该弹性体组合物的充气轮胎 - Google Patents
弹性体组合物和其制造方法、及使用该弹性体组合物的充气轮胎 Download PDFInfo
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- CN102675662B CN102675662B CN201210148703.XA CN201210148703A CN102675662B CN 102675662 B CN102675662 B CN 102675662B CN 201210148703 A CN201210148703 A CN 201210148703A CN 102675662 B CN102675662 B CN 102675662B
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Abstract
本发明提供具有柔软性、且低温耐久性优异的弹性体组合物及其制造方法,和使用该弹性体组合物的充气轮胎。即,提供一种弹性体组合物(C)及其制造方法,所述弹性体组合物(C)具有弹性体成分(B)分散相在热塑性树脂(A)基质中细微分散的海岛结构,热塑性树脂(A)与弹性体成分(B)的体积比满足式(Ⅰ):фd/фm>ηd/ηm(Ⅰ)(式中,фd和ηd分别表示弹性体成分(B)的体积分率和熔融粘度,фm和ηm分别表示热塑性树脂(A)的体积分率和熔融粘度),本发明还提供使用该弹性体组合物(C)的充气轮胎。
Description
本申请发明是申请号为200780007401.8、发明名称为弹性体组合物和其制造方法、及使用该弹性体组合物的充气轮胎、申请日为2007年3月2日的申请的分案申请。
技术领域
本发明涉及弹性体组合物和其制造方法、及使用该弹性体组合物的充气轮胎,更详细地说,涉及在发挥树脂的特性的同时柔软且低温耐久性优异的弹性体组合物和其制造方法,及利用该弹性体组合物的充气轮胎。
背景技术
橡胶在热塑性树脂的基质(连续相)中细微分散(分散相)而得到的热塑性弹性体组合物已经为人们所知,在满足后述式(Ⅳ)那样的条件下,树脂变成包裹橡胶的海岛结构已经为人们所知(参考特开2000-159939号公报)。为了将在热塑性树脂成为基质的状态下获得的组合物制成橡胶状弹性体,有必要尽量增加橡胶量,但如果配合大量橡胶,那么作为连续相的热塑性树脂,与作为分散相的弹性体成分的相就会逆转,所以制备的热塑性弹性体组合物不显示热塑性树脂的流动性,变得不可能成型,因此,可以配合的橡胶量有限。
发明内容
所以,本发明的目的在于,提供柔软且低温耐久性优异的弹性体组合物(C)和其制造方法、及使用该弹性体组合物(C)的充气轮胎,所述弹性体组合物(C)是将比较多量的弹性体成分(B)在比较少量的热塑性树脂(A)的基质中细微分散而形成的。
根据本发明,能够提供弹性体组合物(C)以及使用该弹性体组合物(C)的充气轮胎,所述弹性体组合物(C)是弹性体成分(B)分散相在热塑性树脂(A)基质中细微分散而形成的海岛结构,热塑性树脂(A)与弹性体成分(B)的体积比满足式(Ⅰ)。
фd/фm>ηd/ηm (Ⅰ)
(式中,фd和ηd分别表示弹性体成分(B)的体积分率和熔融粘度,фm和ηm分别表示热塑性树脂(A)的体积分率和熔融粘度)
根据本发明,还提供上述弹性体组合物(C)的制造方法,该方法通过将满足式(Ⅱ)和(Ⅲ)的比率的热塑性树脂(A)、弹性体成分(B)、和增塑剂(D)混合并成型,然后使增塑剂(D)挥发、提取或迁移而除去。
фd/(фm+фl)×(ηml/ηd)<1 (Ⅱ)
ηml/ηd=0.8~1.2 (Ⅲ)
(式中,фd和ηd分别表示弹性体成分(B)的体积分率和粘度,фm表示热塑性树脂(A)的体积分率,фl表示增塑剂(D)的体积分率,ηml表示热塑性树脂(A)与增塑剂(D)的混合物的熔融粘度)
根据本发明,能够获得在发挥热塑性树脂的特性的同时柔软的弹性体,所以,在例如使用尼龙作为热塑性树脂、使用丁基类橡胶作为弹性体的情况下,能够制作兼具耐热性、低透气性、耐化学性、高动态耐久性的内衬层。由于同样的特性,也可以在软管内管、包装等中应用。
具体实施方式
本发明者们为了解决上述问题进行了研究,结果发现,通过将热塑性树脂(A)、弹性体成分(B)、增塑剂(D)按照满足式(Ⅱ)的组成混合成型,制作以树脂(A)为“海”、以弹性体(B)为“岛”的海岛结构,成型成最终形状,然后除去组成的一部分,能够得到将弹性体的比率提高到通常能够制成的界限以上的海岛结构,由此,可能得到在发挥基质热塑性树脂(A)的特性的同时,由于高弹性体量而柔软的弹性体。
向来人们公知(参考特开平9-100413号公报、特开2000-159936号公报等),为了制造弹性体成分分散在热塑性树脂成分的基质中的热塑性弹性体组合物,以下条件是必要的。即,当以形成基质(连续相)的热塑性树脂成分的体积分率为фm,以熔融混炼时的粘度为ηm,另一方面,以形成分散相的弹性体成分的体积分率为фd,以同条件下的粘度为ηd时,以
α=[фd/фm]×[ηm/ηd]
的值小于1那样的体积分率,将二者进行混炼是必要的。即,
[фd/фm]×[ηm/ηd]<1(Ⅳ)
这是因为,当上述α的值小于1时,所制造的热塑性弹性体组合物的微观结构就以热塑性树脂成分为连续相(基质)、以弹性体成分为分散相(畴,domain)而存在,因此能够按照热塑性树脂的成型法成型,但当α为1以上时,就导致该连续相与分散相逆转,所以调制的热塑性弹性体组合物不显示热塑性树脂的流动,因此不可能用树脂用成型加工机成型。另外,在配合的弹性体量多的情况下,如果在一定量以上配合,就有α大于1的倾向,导致连续相和分散相逆转。如果要在维持热塑性树脂形成的连续相和弹性体形成的分散相的关系,同时将弹性体比率进一步提高,那么使用历来公知的制造方法自然是受到限制的。
本发明是弹性体组合物及其制造方法,所述弹性体组合物是处于以热塑性树脂成分(A)为连续相(基质)、以弹性体成分(B)为分散相(domain)而存在的状态,并且将树脂中的弹性体成分(B)的体积比率提高到了用以往的制造方法不可能实现的程度。
即,弹性体组合物(C)满足下述式(I)的同时,形成在热塑性树脂成分(A)的连续相(基质)中,弹性体成分(B)成为分散相(domain)的状态。
[фd/фm]×[ηm/ηd]>1 (Ⅰ)
进而,弹性体组合物(C)的制造方法如下。
在热塑性树脂成分(A)中,将增塑剂(D)作为假树脂构成成分,满足以下条件与弹性体成分(B)一同配合。
[фd/(фm+фl)]×[ηml/ηd]<1 (Ⅱ)
ηml/ηd=0.8~1.2 (Ⅲ)
(式中,фd和ηd分别表示弹性体成分(B)的体积分率和粘度,фm表示热塑性树脂(A)的体积分率,фl表示增塑剂(D)的体积分率,ηml表示热塑性树脂(A)与增塑剂(D)的混合物的熔融粘度)
由此,首先可以制造以含有增塑剂(D)的热塑性树脂成分(A)为连续相(基质)、以弹性体成分(B)为分散相(domain)的热塑性弹性体组合物(E)。其中,通过满足式(Ⅲ),使粘度比ηml/ηd在0.8~1.2的范围,显示出能够缩小弹性体的分散粒子,通过缩小分散粒子而提高耐久性历来为人们所知。(参考特开2000-159936)
其中,фl/(фm+фl)=0.05~0.6,更优选是0.1~0.3。
这样制造的组合物(E)具有热塑性,进而使增塑剂(D)从该组合物(E)中挥发、提取或迁移,最终制造出弹性体组合物(C)。另外,该弹性体组合物(C)失去了热塑性。
作为本发明的弹性体组合物(C)的制作中所使用的热塑性树脂(A),可以使用1种或其以上的热塑性树脂,作为树脂成分,可以列举聚酰胺类树脂(例如尼龙6(N6)、尼龙66(N66)、尼龙46(N46)、尼龙11(N11)、尼龙12(N12)、尼龙610(N610)、尼龙612(N612)、尼龙6/66共聚物(N6/66)、尼龙6/66/610共聚物(N6/66/610)、尼龙MXD6(MXD6)、尼龙6T、尼龙6/6T共聚物、尼龙66/PP共聚物、尼龙66/PPS共聚物)、聚酯类树脂(例如聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸乙二醇酯(PET)、聚间苯二甲酸乙二醇酯(PEI)、PET/PEI共聚物、聚芳酯(PAR)、聚萘二甲酸丁二醇酯(PBN)、液晶聚酯、聚氧亚烷基二酰亚胺酸/聚对苯二甲酸丁二醇酯共聚物等芳香族聚酯)、聚腈类树脂(例如聚丙烯腈(PAN)、聚甲基丙烯腈、丙烯腈/苯乙烯共聚物(AS)、甲基丙烯腈/苯乙烯共聚物、甲基丙烯腈/苯乙烯/丁二烯共聚物)、聚甲基丙烯酸酯类树脂(例如聚甲基丙烯酸甲酯(PMMA)、聚甲基丙烯酸乙酯)、聚乙烯基类树脂(例如乙酸乙烯酯(EVA)、聚乙烯醇(PVA)、乙烯醇/乙烯共聚物(EVOH)、聚1,1-二氯乙烯(PVDC)、聚氯乙烯(PVC)、氯乙烯/1,1-二氯乙烯共聚物、1,1-二氯乙烯/丙烯酸甲酯共聚物),纤维素类树脂(例如乙酸纤维素、乙酸丁酸纤维素),氟类树脂(例如聚1,1-二氟乙烯(PVDF)、聚氟乙烯(PVF)、聚三氟氯乙烯(PCTFE)、四氯乙烯/乙烯共聚物(ETFE))、酰亚胺类树脂(例如芳香族聚酰亚胺(PI))等。其中,使用以尼龙为代表的线状聚酰胺树脂,可以取得耐久性与阻气性的平衡,所以优选。
另外,在构成上述弹性体组合物的基质的热塑性树脂(A)中,根据需要,也可以适当配合为了改善加工性、分散性或者此外的耐热、抗氧化性等以及其它目的而一般配合的填充剂、增强剂、加工助剂、稳定剂、抗氧化剂等。
在本发明的弹性体组合物的制作中使用的弹性体成分(B),可以是在弹性体成分中配合包括硫化类配合成分的通常橡胶配合剂而形成的弹性体组合物,或者,也可以是在弹性体成分中,配合除了硫化类配合成分以外的其它通常的橡胶配合剂的弹性体组合物。作为这样的弹性体成分,可以列举天然橡胶、合成聚异戊二烯橡胶(IR)、环氧化天然橡胶、丁苯橡胶(SBR)、聚丁二烯橡胶(BR)、丁腈橡胶(NBR)、氢化NBR、氢化SBR那样的二烯类橡胶及其氢化合物;乙丙橡胶(EPDM,EPM)、马来酸改性乙烯-α-烯烃共聚物(M-PO)、丁基橡胶(IIR)、异丁烯与芳香族乙烯基化合物或二烯类单体共聚物、丙烯酸酯橡胶(ACM)、离聚物那样的烯烃类橡胶;Br-IIR、Cl-IIR、异丁烯-对甲基苯乙烯共聚物的溴化物(Br-IPMS)、氯丁二烯橡胶(CR)、氯醚橡胶(CHC,CHR)、氯磺化聚乙烯(CSM)、氯化聚乙烯(CM)、马来酸改性氯化聚乙烯(M-CM)那样的含卤素橡胶;甲基乙烯基硅橡胶、二甲基硅橡胶、甲基苯基乙烯基硅橡胶那样的硅橡胶;聚硫橡胶那样的含硫橡胶;1,1-二氟乙烯类橡胶、含氟乙烯基醚类橡胶、四氟乙烯-丙烯类橡胶、含氟硅类橡胶、含氟磷腈类橡胶那样的氟橡胶;苯乙烯类弹性体、烯烃类弹性体、聚酯类弹性体、聚氨酯类弹性体、聚酰胺类弹性体那样的热塑性弹性体等。
构成本发明的弹性体组合物(C)的分散相的上述弹性体成分(B)可以动态硫化,动态硫化的情况下的硫化剂、硫化助剂、和硫化条件(温度、时间)等,可以根据添加的弹性体成分(B)的组成适当确定,并没有特别限制。作为硫化剂,可以使用一般的橡胶硫化剂(交联剂)。具体地,作为硫类硫化剂,可以示例粉末硫、沉淀性硫、高分散性硫、表面处理硫、不溶性硫、二硫代二吗啉、烷基苯酚二硫化物等,例如,可以使用0.5~4重量份[相当于100重量份弹性体成分(聚合物)的重量份]左右。
另外,作为有机过氧化物类的硫化剂,可以示例过氧化苯甲酰、叔丁基过氧化氢、2,4-二氯过氧化苯甲酰、2,5-二甲基-2,5-二(叔丁基过氧化)己烷、2,5-二甲基己烷-2,5-二(过氧化苯甲酸酯)等,例如,可以使用1~20重量份左右。进而,作为酚树脂类的硫化剂,可以示例烷基酚树脂的溴化物,含有氯化锡、氯丁二烯等卤素供体与烷基酚树脂的混合交联剂等,例如,可以使用1~20重量份左右。
作为其它的配合成分,可以示例氧化锌(5重量份左右)、氧化镁(4重量份左右)、一氧化铅(10~20重量份左右)、对苯醌二肟、对二苯甲酰苯醌二肟、四氯对苯醌、聚对二亚硝基苯(2~10重量份左右)、二氨基二苯甲烷(0.2~10重量份左右).
另外,根据需要,可以添加硫化促进剂。作为硫化促进剂,例如,可以使用0.5~2重量份左右的醛氨类、胍类、噻唑类、次磺酰胺类、秋兰姆类、二硫酸盐类、硫脲类等一般的硫化促进剂。此外,作为硫化促进助剂,可以并用一般的橡胶用助剂,例如,可以使用硬脂酸、油酸和它们的Zn盐(2~4重量份左右)等。
进而,在形成分散相的弹性体成分(B)中,除了上述配合剂之外,为了改善分散性、耐热性等以及其它目的,根据需要还可以适当配合一般配合的软化剂、抗老化剂、加工助剂等配合剂。
作为在本发明的制造方法中所使用的增塑剂(D),可以使用烷基苯磺酰胺、邻苯二甲酸二烯丙酯、邻苯二甲酸二辛酯、癸二酸二辛酯、己二酸二辛酯、邻苯二甲酸二异癸酯、邻苯二甲酸丁苄酯、磷酸三甲苯酯、偏苯三酸异壬酯等酯类,甲醇、乙醇、2-丙醇等醇类,石蜡油、环烷烃油、芳香油等石油类油,等等,从沸点高、与树脂的相容性的方面出发,优选烷基苯磺酰胺。
在本发明中,弹性体(B)在基质树脂(A)中细微分散的弹性体组合物(C)的制造方法,可以按照例如如下来实施。首先,预先使用一般的捏合机、班伯里混炼机等,根据需要与配合剂一起,将弹性体混炼直到得到均匀混合状态,来制作弹性体成分(B)。这时,在弹性体成分(B)中,也可添加适当量的碳黑、油、其它碳酸钙等填充剂。另外,在必要的情况下,还可以添加弹性体的硫化剂或交联剂、硫化助剂、硫化促进剂等。接着,将构成基质的热塑性树脂(A)与增塑剂(D),以及根据需要配合的抗老化剂等的配合剂投入到双螺杆混炼机等中进行混炼,制作将构成基质的热塑性树脂成分(A)。将这样制作的树脂成分(A)与弹性体成分(B)投入到双螺杆混炼机等中,进行熔融混炼。在使用弹性体成分(B)中没有配合硫化类配合剂的弹性体成分(B)的情况下,在混炼已经充分完成的阶段添加硫化类配合剂,进一步混炼使弹性体成分动态交联,能够获得热塑性弹性体组合物(E)。
此外,对于待添加到热塑性树脂成分(A)或弹性体成分(B)中的各种配合剂,可以在上述双螺杆混炼之前预先混合,也可以添加到上述双螺杆混炼中。进而,还可以将基质树脂与弹性体、各种配合剂、增塑剂在双螺杆混炼机等中一次混炼,但这种情况下,必须在将基质树脂与增塑剂充分混炼之后加入弹性体。作为与这些弹性体成分(B)、基质树脂成分(A)的混炼和弹性体组合物的熔融混炼的条件,只要温度为热塑性树脂的熔融温度以上即可。另外,混炼时的剪断速度优选为500~7500每秒钟,混炼时间优选为30秒钟~10分钟左右。
接着使用单螺杆挤出机的前端的T型平缝口模(sheeting dies)、直线或十字头结构的胶管模、吹塑成型用的圆筒模等,将得到的热塑性弹性体组合物(E)成型成薄片、薄膜或管状,然后通过烘箱加热来挥发、与橡胶等叠层热压来迁移、使用甲醇等溶剂来提取等,除去增塑剂(D)的一部分或全部,从而获得弹性体组合物(C)的成型体。如果要作为充气轮胎或软管等的低透气层使用,可以将含有增塑剂的上述热塑性弹性体组合物(E),用与橡胶叠层的状态贴附在轮胎或软管的例如最内层,成型成最终形状,然后通过热压使增塑剂(D)迁移到橡胶中,来获得由弹性体组合物(C)构成的低透气层。该层由于是以树脂为基质、橡胶为分散相,且橡胶量非常多,所以能够形成发挥树脂的特性,例如低透气性、耐热性、耐化学性,同时柔软且动态耐久性像橡胶那样良好的材料层。
实施例
以下,通过实施例更详细的说明本发明,但不言而喻,本发明的范围不受这些实施例限制。
实施例1~7和比较例1~7
试样的调制
在表Ⅰ所示的配合中,将弹性体和交联剂用密闭型班伯里混炼机(神户制钢所制造)在100℃混合2分钟,制作复合物,用橡胶造粒机(森山制作所制造)加工成颗粒状。向树脂颗粒中加入树脂用增塑剂(丁基苯磺酰胺,大八化学工业制造BM-4),使其相对于树脂约为30重量%(фl/(фm+фl)=0.26),用双螺杆混炼机(日本制钢所制造)混炼,将得到的加入了增塑剂的树脂与橡胶颗粒再次用双螺杆混炼机(日本制钢所制造)混炼,制作加入了增塑剂的弹性体组合物的颗粒(动态硫化的)。将制作的颗粒用T型模成型机成型成片状,用甲醇提取除去增塑剂,然后用真空烘箱在70℃干燥12小时,完全除去甲醇,得到弹性体组合物的薄片。
实施例8
在表Ⅰ所示的配合中,将弹性体和交联剂用密闭型班伯里混炼机(神户制钢所制造)在100℃混合2分钟,制作弹性体组合物,用橡胶造粒机(森山制作所)制成颗粒状。向树脂颗粒中加入树脂用增塑剂(丁基苯磺酰胺,大八化学工业制造BM-4),使其相对于树脂约为30重量%,用双螺杆混炼机(日本制钢所制造)混炼,将得到的加入了增塑剂的树脂与橡胶颗粒再次用双螺杆混炼机(日本制钢所制造)混炼,制作加入了增塑剂的弹性体组合物的颗粒(动态硫化的)。将制作的颗粒用T型模成型机成型成片状,用真空烘箱在180℃干燥30分钟,挥发除去增塑剂,得到弹性体组合物的薄片。
实施例9
在表Ⅰ所示的配合中,将弹性体和交联剂用密闭型班伯里混炼机(神户制钢所制造)在100℃混合2分钟,制作弹性体组合物,用橡胶造粒机(森山制作所)加工成颗粒状。向树脂颗粒中加入树脂用增塑剂(丁基苯磺酰胺,大八化学工业制造BM-4),使其相对于树脂约为30重量%,用双螺杆混炼机(日本制钢所制造)混炼,将得到的加入了增塑剂的树脂与橡胶颗粒再次用双螺杆混炼机(日本制钢所制造)混炼,制作加入了增塑剂的弹性体组合物的颗粒(动态硫化的)。将制作的颗粒用T型模成型机成型成片状,用下述组成的橡胶复合物的2mm的薄片夹持,在180℃热压15分钟,使增塑剂挥发和迁移到橡胶复合物中而除去,得到弹性体组合物的薄片。
橡胶复合物的组成
用以下的试验方法测定得到的薄片的物性,结果示于表Ⅰ。
物性评价试验法
透气度:依照JIS K 7126“(塑料薄膜和薄片的气体透过度试验方法(A)法)”。
试片:使用在各例中制成的薄膜试样。
试验气体:空气(N2:O2=8:2)
试验温度:30℃
为了维持空气压,为20×10-12(cm3·cm/cm2·sec·cmHg)以下是良好的,优选为15×10-12(cm3·cm/cm2·sec·cmHg)以下。
M50(-20℃):依照JIS K6251在-20℃测定。
动态疲劳(-20℃)
-20℃的应变试验:使用JIS 3号哑铃,用应变试验机(上岛制作所制造)在-20℃以下施以40%的重复变形。以根据威布尔图表(Weibull chart)得到的破裂率70%的点为超过100万次的为合格。
表Ⅰ注解
*1:Exxon Mobile Chemicals制造IPMS(Exxon89-4)(粘度:200Pa·s)
*2:三井化学(株)制造Mah-EPM(タフマ一MP0620)(粘度:120Pa·s)
*3:Bayer制造Br-IIR(Bromobutyl X2)(粘度:20Pa·s)
*4:Exxon Mobile Chemicals制造IIR(Exxon Butyl268)(粘度:80Pa·s)
*5:BASF制造PIB(Oppanol B100)(粘度:300Pa·s)
*6:正同化学(株)制造氧化锌(亜鉛3号)
*7:日本油脂(株)制造硬脂酸(ビ一ズステアリン酸)
*8:宇部兴产(株)制造尼龙6,66(ウベナイロン5033B)(粘度:500Pa·s)
*9:宇部兴产(株)制造尼龙6(ウベナイロン1030B)(粘度:500Pa·s)
*10:ARKEMA(株)制造尼龙11(リルサンBESNOTL)(粘度:200Pa·s)
加入了增塑剂的尼龙的粘度
加入了增塑剂的尼龙11:150Pa·s
加入了增塑剂的尼龙6:170Pa·s
加入了增塑剂的尼龙6,66:200Pa·s
比较例8~13
将弹性体和交联剂用密闭型班伯里混炼机(神户制钢所制造)在100℃混合2分钟,制作复合物,用橡胶造粒机(森山制作所制造)加工成颗粒状。将复合物的颗粒与树脂颗粒用双螺杆混炼机(日本制钢所)混炼。一部分由于橡胶比率过高,而发生相反转,不能够混炼。将制作的颗粒用T型模成型机成型成片状,得到热塑性弹性体组合物的薄片。如上述那样测定得到的薄片的物性,结果示于表Ⅱ。
比较例14~16
将弹性体和交联剂用密闭型班伯里混炼机(神户制钢所制造)在100℃混合2分钟,制作复合物,用橡胶造粒机(森山制作所制造)加工成颗粒状。向树脂颗粒中加入树脂用增塑剂(丁基苯磺酰胺,大八化学工业制造BM-4),使其相对于树脂约为30重量%,用双螺杆混炼机(日本制钢所制造)混炼,将制成的加入了增塑剂的树脂与橡胶颗粒再次用双螺杆混炼机(日本制钢所制造)混炼,制作加入了增塑剂的弹性体组合物的颗粒。将制作的颗粒用T型模成型机成型成片状,得到热塑性弹性体组合物的薄片。如上述那样测定得到的薄片的物性,结果示于表Ⅲ。
表Ⅲ
*1:参考表Ⅰ注解
*2:丁基苯磺酰胺,(大八化学制造BM-4)
轮胎试验
用得到的薄片进行以下的轮胎试验。结果示于表Ⅳ。
表Ⅳ
漏气试验:在内衬层中使用各例所记载的材料(厚度0.15mm),制作195/65/R15尺寸的轮胎,在气压250KPa、25℃的气氛下,测定经3个月后的内压变化,与使用丁基橡胶/天然橡胶为80/20重量%的标准内衬层的轮胎相比较,以内压保持率为相同或更好的轮胎为合格,以低于同等的轮胎为不合格。
-20℃动态耐久试验:在内衬层中使用各例所记载的材料(厚度0.15mm),制作195/65/R15尺寸的轮胎,在气压120KPa、-20℃气氛气下,施以4.8kN的负荷,在金属转鼓上走行30000km。走行后观察内衬层,以发生破裂的轮胎为不合格。
工业可利用性
根据本发明,能够获得发挥热塑性树脂的特性的同时柔软的弹性体,所以能够制作兼具例如耐热性、低透气性、耐化学性、高动态耐久性的内衬层,由于同样的特性,也能够在充气轮胎的其它部位、软管内管、包装等中应用。
Claims (6)
1.一种不显示热塑性的弹性体组合物(C)的制造方法,通过将满足式(Ⅱ)和(Ⅲ)的比率的热塑性树脂(A)、弹性体成分(B)和增塑剂(D)混合并成型,然后使增塑剂(D)挥发、提取或迁移而除去,从而制造弹性体组合物(C),
фd/(фm+фl)×(ηml/ηd)<1 (Ⅱ)
ηml/ηd=0.8~1.2 (Ⅲ)
式中,фd和ηd分别表示弹性体成分(B)的体积分率和粘度,фm表示热塑性树脂(A)的体积分率,фl表示增塑剂(D)的体积分率,ηml表示热塑性树脂(A)与增塑剂(D)的混合物的熔融粘度,
并且,所述弹性体组合物(C)是弹性体成分(B)分散相在热塑性树脂(A)基质中细微分散的海岛结构,热塑性树脂(A)与弹性体成分(B)的体积比满足式(I):
фd/фm>ηd/ηm (I)
上式中,фd和ηd分别表示弹性体成分(B)的体积分率和熔融粘度,фm和ηm分别表示热塑性树脂(A)的体积分率和熔融粘度,
所述热塑性树脂(A)选自聚酰胺类树脂、聚酯类树脂、聚腈类树脂、聚甲基丙烯酸酯类树脂、聚乙烯基类树脂、纤维素类树脂、氟类树脂和酰亚胺类树脂,
所述增塑剂(D)选自烷基苯磺酰胺、邻苯二甲酸二烯丙酯、邻苯二甲酸二辛酯、癸二酸二辛酯、己二酸二辛酯、邻苯二甲酸二异癸酯、邻苯二甲酸丁苄酯、磷酸三甲苯酯、偏苯三酸异壬酯、甲醇、乙醇、2-丙醇、石蜡油、环烷烃油和芳香油。
2.如权利要求1所述的弹性体组合物(C)的制造方法,热塑性树脂(A)是聚酰胺类树脂。
3.如权利要求1所述的弹性体组合物(C)的制造方法,弹性体成分(B)的体积比率为55~95%。
4.如权利要求2所述的弹性体组合物(C)的制造方法,热塑性树脂(A)是选自尼龙6、尼龙6/66共聚物、尼龙11、尼龙12、尼龙6/10共聚物和尼龙6/12共聚物中的至少一种的热塑性树脂。
5.如权利要求1所述的弹性体组合物(C)的制造方法,弹性体成分(B)是选自异戊二烯-对甲基苯乙烯共聚物的溴化物、马来酸酐改性乙烯-α-烯烃共聚物、丁基橡胶、卤化丁基橡胶和聚异戊二烯橡胶中的至少一种弹性体。
6.如权利要求1所述的弹性体组合物(C)的制造方法,增塑剂(D)是烷基苯磺酰胺。
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