CN108291058A - 橡胶组合物以及层叠体 - Google Patents
橡胶组合物以及层叠体 Download PDFInfo
- Publication number
- CN108291058A CN108291058A CN201680069918.9A CN201680069918A CN108291058A CN 108291058 A CN108291058 A CN 108291058A CN 201680069918 A CN201680069918 A CN 201680069918A CN 108291058 A CN108291058 A CN 108291058A
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- Prior art keywords
- rubber
- vulcanization
- layer
- hose
- rubber composition
- Prior art date
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Abstract
本发明的目的在于,提供一种橡胶组合物以及层叠体,其中,所述橡胶组合物不仅在利用蒸汽硫化方式进行了硫化的情况下,而且在利用烘箱硫化方式进行了硫化的情况下,也对金属表面具有优异的粘接性,并且在硫化后放置于湿热环境下的情况下也显示出优异的粘接性,所述层叠体具备具有金属表面的增强层和使用上述橡胶组合物形成的橡胶层。本发明的橡胶组合物含有:含丁二烯橡胶的二烯系聚合物和多元醇,相对于上述二烯系聚合物100质量份,上述多元醇的含量为0.5质量份以上且14质量份以下。
Description
技术领域
本发明涉及一种橡胶组合物以及层叠体。
背景技术
以往,在用于建筑机械等的软管(例如,液压软管)中,使用具备橡胶层和表面由黄铜(Brass)等金属镀敷的增强层的层叠体。另外,从防止由与带轮等旋转体的接触引起的磨耗的观点等考虑,有时会在上述橡胶层中使用耐磨耗性优异的丁二烯橡胶。
例如,在专利文献1中公开了一种液压软管,其具有:使用以丁二烯橡胶为主要成分的组合物而形成的橡胶层、和与上述(权利要求书等)橡胶层邻接的镀黄铜金属线增强层。
现有技术文献
专利文献
专利文献1:日本特开2012-51978号公报
发明内容
发明要解决的问题
再者,在制造具备橡胶层和具有金属表面的增强层的软管的情况下,通常,在增强层形成未硫化的橡胶层之后进行硫化。作为此时的硫化方式,主要有:利用蒸汽进行加热来硫化的蒸汽硫化方式、和利用烘箱进行加热来硫化的烘箱硫化方式。在此,蒸汽硫化方式为密闭系统,难以连续生产,相对于此,烘箱硫化方式为开放系统,因此,能够连续生产,从生产率的观点考虑,与蒸汽硫化方式相比,更理想的是烘箱硫化方式。
在这种情况下,本发明人在使用含有丁二烯橡胶的橡胶组合物来制造具备橡胶层和具有金属表面的增强层的软管时,发现:在利用蒸汽硫化方式进行了硫化的情况下,橡胶层与金属表面之间的粘接性未发现问题,但在利用烘箱硫化方式进行了硫化的情况下,有时橡胶层与金属表面之间的粘接性降低,其粘接性未必一定满足目前要求的水准。
另外,发现:用于建筑机械等的软管通常暴露于湿热环境下,在将所得的软管放置于湿热环境下的情况下,粘接性进一步降低。
因此,鉴于上述实际情况,本发明的目的在于提供一种橡胶组合物以及层叠体,其中,所述橡胶组合物不仅在利用蒸汽硫化方式进行了硫化的情况下,而且在利用烘箱硫化方式进行了硫化的情况下,也对金属表面具有优异的粘接性,并且在硫化后放置于湿热环境下的情况下也显示出优异的粘接性,所述层叠体具备具有金属表面的增强层和使用上述橡胶组合物而形成的橡胶层。
技术方案
本发明人对上述问题进行了深入研究,结果发现:通过配合多元醇能够解决上述问题。
即,本发明人发现:通过以下的构成能够解决上述问题。
(1)一种橡胶组合物,其含有:含丁二烯橡胶的二烯系聚合物和多元醇,
相对于上述二烯系聚合物100质量份,上述多元醇的含量为0.5质量份以上且14质量份以下。
(2)根据上述(1)所述的橡胶组合物,其中,上述多元醇为甘油。
(3)根据上述(1)或(2)所述的橡胶组合物,其中,进一步含有蜡,
相对于上述二烯系聚合物100质量份,上述蜡的含量为2质量份以上。
(4)一种层叠体,其具备:具有金属表面的增强层和设于上述金属表面上的橡胶层,
上述橡胶层是使用上述(1)至(3)中任一项所述的橡胶组合物而形成的。
(5)根据上述(4)所述的层叠体,其中,上述增强层具有编织金属线而成的编织结构或螺旋结构。
(6)根据上述(4)或(5)所述的层叠体,其中,所述层叠体为软管。发明效果
如下所示,根据本发明,能够提供一种橡胶组合物以及层叠体,其中,所述橡胶组合物不仅在利用蒸汽硫化方式进行了硫化的情况下,而且在利用烘箱硫化方式进行了硫化的情况下,也对金属表面具有优异的粘接性,并且在硫化后放置于湿热环境下的情况下也显示出优异的粘接性,所述层叠体具备具有金属表面的增强层和使用上述橡胶组合物而形成的橡胶层。
附图说明
图1是本发明的软管的一个实施方式的局部剖切立体图。
图2是制造本发明的软管的制造工序的一个实施方式的说明图。
图3是制造本发明的软管的制造工序中的硫化工序的一个实施方式的说明图。
图4是对投入至硫化装置的心轴周围的层结构的一个示例进行说明的局部剖面图。
具体实施方式
以下,对本发明的橡胶组合物、以及层叠体进行说明。
需要说明的是,在本说明书中,使用“~”表示的数值范围是指包含“~”前后记载的数值作为下限值以及上限值的范围。
[橡胶组合物]
本发明的橡胶组合物(以下,也称为“本发明的组合物”)含有:含丁二烯橡胶的二烯系聚合物和多元醇。在此,相对于上述二烯系聚合物100质量份,上述多元醇的含量为0.5质量份以上且14质量份以下。
推测为:由于本发明的组合物含有多元醇,因此能得到所期望的效果。虽然其理由尚不清楚,但大致推测如下。
根据本发明人的研究,可知:在具有金属表面的增强层使用橡胶组合物来形成未硫化的橡胶层,然后,在进行了硫化的情况下,橡胶组合物中的水分变成催化剂而进行橡胶层与金属表面之间的键结反应,其结果是,橡胶层与金属表面的粘接性提高。进而,得到了如下见解:在利用蒸汽硫化方式进行了硫化的情况下,橡胶组合物难以干燥,存在许多水分,因此,橡胶层与金属表面的成键充分进行,相对于此,在利用烘箱硫化方式进行了硫化的情况下,橡胶组合物容易干燥,存在的水分少,因此,橡胶层与金属表面的成键难以进行。
本发明是基于上述见解的发明,是通过配合多元醇来谋求促进橡胶层与金属表面的成键的发明。虽然其作用尚不清楚,但可以认为:多元醇所具有的羟基填补硫化时的因热引起的橡胶组合物中的水分减量,多元醇自身作为形成橡胶层与金属表面的键结的催化剂发挥作用。作为结果,推测为:在使用了本发明的组合物的情况下,橡胶层与金属表面之间的粘接性极其优异。
以下,对本发明的组合物中所含的各成分进行详细说明。
<二烯系聚合物>
本发明的组合物中所含的二烯系聚合物含有丁二烯橡胶(BR)。
二烯系聚合物中的丁二烯橡胶的含量优选为10质量%以上,更优选为20质量%以上,进一步优选为30质量%以上。上限没有特别限制,优选为90质量%以下,更优选为70质量%以下,进一步优选为50质量%以下。
二烯系聚合物可以含有丁二烯橡胶以外的二烯系聚合物。作为丁二烯橡胶以外的二烯系聚合物没有特别限制,可列举出:天然橡胶(NR)、异戊二烯橡胶(IR)、芳香族乙烯基-共轭二烯共聚物橡胶、丙烯腈-丁二烯共聚橡胶(NBR)、丁基橡胶(IIR)、卤化丁基橡胶(Br-IIR、Cl-IIR)、氯丁二烯橡胶(CR)、乙烯-丙烯-二烯橡胶(EPDM)、氯化聚乙烯橡胶(CM)、氯磺化聚乙烯橡胶(CSM)等,可以单独使用它们,也可以并用2种以上。
丁二烯橡胶以外的二烯系聚合物优选为芳香族乙烯基-共轭二烯共聚物橡胶,更优选为苯乙烯-丁二烯共聚物橡胶(SBR)。
在二烯系聚合物含有丁二烯橡胶以外的二烯系聚合物的情况下,二烯系聚合物中的丁二烯橡胶以外的二烯系聚合物的含量优选为10~90质量%,更优选为30~70质量%。
<多元醇>
本发明的组合物中所含的多元醇只要是具有两个以上羟基的醇就没有特别限制。
作为多元醇,例如可列举出:乙二醇、二乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,4-丁二醇、2-丁烯-1,4-二醇、2,3-丁二醇、戊二醇、己二醇、辛二醇、二羟基丙酮、1,1,1-三羟基甲基乙烷、2-乙基-2-羟基甲基-1,3-丙二醇、1,2,6-己三醇、1,2,3-己三醇、1,2,4-丁三醇、三羟甲基丙烷、抗坏血酸、异抗坏血酸、糖醇类、单糖类、二糖类、三糖类等。
作为糖醇类,可列举出:包含甘油的丙糖醇类;赤藓糖醇、苏糖醇等丁糖醇类;阿拉伯糖醇、木糖醇、核糖醇(阿东糖醇)等戊糖醇类;艾杜糖醇、半乳糖醇(卫矛醇)、葡萄糖醇(山梨醇)、甘露糖醇等己糖醇类;庚七醇(Volemitol)、甘露庚糖醇(Perseitol)等庚糖醇类等。
作为单糖类,可列举出:甘油醛、苏糖、赤藓糖、核糖、阿拉伯糖、木糖、来苏糖、阿洛糖、阿卓糖、葡萄糖、甘露糖、古洛糖、艾杜糖、半乳糖、塔罗糖等醛糖类;二羟基丙酮、赤藓酮糖、木酮糖、核酮糖、阿洛酮糖、果糖、山梨糖、塔格糖、景天庚酮糖、毒空木酮糖等酮糖类等。
作为二糖类,可列举出:蔗糖、海藻糖、异海藻糖(β,β-海藻糖)、新海藻糖(α,β-海藻糖)、半乳蔗糖(Galactosucrose)等非还原糖;乳果糖、乳糖、麦芽糖、纤维二糖、曲二糖、黑曲霉糖、异麦芽糖、槐糖、昆布二糖、龙胆二糖、松二糖、麦芽酮糖、帕拉金糖、龙胆二酮糖(Gentiobiulose)、甘露二糖、蜜二糖、车前二糖(Melibiulose)、异乳糖(Neolactose)、海葱二糖(Scillabiose)、芸香糖、芦丁酮糖(Rutinulose)、荚豆二糖、木二糖、樱草糖等还原糖等。
作为三糖类,可列举出:黑曲霉三糖、麦芽三糖、松三糖、麦芽丙酮糖(Maltotriulose)、棉子糖、蔗果三糖等。
从粘接性更优异的理由考虑,多元醇优选为下述通式(1)所示的化合物。
[化学式1]
通式(1)
在通式(1)中,R1表示氢原子或者可以包含醚键以及支链的碳数为1以上且5以下的单羟基烷基或多羟基烷基,R2表示可以包含醚键以及支链的碳数为1以上且5以下的单羟基烷基或多羟基烷基。
在上述通式(1)中,作为R1,例如可列举出:羟基甲基、1-羟基乙基、2-羟基乙基、二羟基乙基、1-羟基丙基、2-羟基丙基、3-羟基丙基、二羟基丙基、三羟基丙基、1-羟基丁基、2-羟基丁基、3-羟基丁基、4-羟基丁基、二羟基丁基、三羟基丁基、四羟基丁基、五羟基丁基、1-羟基戊基、2-羟基戊基、3-羟基戊基、4-羟基戊基、5-羟基戊基、二羟基戊基、三羟基戊基、四羟基戊基、五羟基戊基、甲氧基甲基、羟基乙氧基乙基、二羟基丙氧基甲基、二羟基丙氧基乙基、三羟基丙氧基甲基、以及三羟基丙氧基乙基等。
在上述通式(1)中,作为R2,例如可列举出:羟基甲基、1-羟基乙基、2-羟基乙基、二羟基乙基、1-羟基丙基、2-羟基丙基、3-羟基丙基、二羟基丙基、三羟基丙基、1-羟基丁基、2-羟基丁基、3-羟基丁基、4-羟基丁基、二羟基丁基、三羟基丁基、四羟基丁基、五羟基丁基、1-羟基戊基、2-羟基戊基、3-羟基戊基、4-羟基戊基、5-羟基戊基、二羟基戊基、三羟基戊基、四羟基戊基、五羟基戊基、甲氧基甲基、羟基乙氧基乙基、二羟基丙氧基甲基、二羟基丙氧基乙基、三羟基丙氧基甲基、以及三羟基丙氧基乙基等。
作为上述通式(1)所示的化合物,例如可列举出:乙二醇、丙二醇、丁二醇、戊二醇、二乙二醇、三乙二醇、甘油、1,2,6-三羟基己烷、二甘油、三羟甲基丙烷、季戊四醇、山梨醇以及己三醇等。其中,从粘接性更优异的理由考虑,优选乙二醇、二乙二醇、甘油、己三醇、二甘油、山梨醇,更优选甘油。
多元醇的分子量没有特别限制,优选为50~1000,更优选为70~300。
多元醇的沸点没有特别限制,优选为100~400℃,更优选为100~300℃。需要说明的是,上述沸点是指1atm下的值。
在本发明的组合物中,相对于上述的二烯系聚合物100质量份,多元醇的含量为0.5质量份以上且14质量份以下。其中,优选为1.0~10质量份。<任意成分>
本发明的组合物可以含有二烯系聚合物、多元醇以外的成分。作为这样的成分,例如可列举出:填料、增塑剂、软化剂、抗老化剂、有机系活性剂、抗氧化剂、抗静电剂、阻燃剂、硫化促进剂、交联促进助剂、硫化延迟剂、臭氧劣化剂、加工油(芳香油)、粘接助剂、蜡、脂肪酸酯、硫化剂(例如,硫)等。
作为填料,例如可列举出:炭黑、二氧化硅(白炭黑)、粘土、滑石、氧化铁、氧化锌(ZnO)、氧化钛、氧化钡、氧化镁、碳酸钙、碳酸镁、碳酸锌、硫酸钡、云母(Mica)以及硅藻土等。它们可以单独使用1种,也可以并用2种以上。作为炭黑,可以根据用途适当选择使用。作为炭黑,优选ISAF级以及FEF级等。作为二氧化硅,例如可列举出:结晶性二氧化硅、沉淀二氧化硅、无定形二氧化硅(例如,高温处理二氧化硅)、气相二氧化硅、锻烧二氧化硅、沉淀二氧化硅、粉碎二氧化硅、以及熔融二氧化硅等。特别是,已知二氧化硅与炭黑同样地生成碳凝胶(结合橡胶),可以根据需要适当使用。作为粘土,可列举出:硬质粘土、叶蜡石粘土、高岭土粘土、以及煅烧粘土等。
作为增塑剂,例如可列举出:邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二丁酯(DBP)、己二酸二辛酯(DOA)、琥珀酸异癸酯、二乙二醇二苯甲酸酯、季戊四醇酯、油酸丁酯、乙酰基蓖麻油酸甲酯、磷酸三甲苯酯、磷酸三辛酯、偏苯三酸酯、己二酸丙二醇聚酯、以及己二酸丁二醇聚酯、环烷油等。它们可以单独使用1种,也可以并用2种以上。
作为软化剂,具体而言,例如可列举出:芳香系油、环烷系油、石蜡系油、石油树脂、植物油、以及液态橡胶等。它们可以单独使用1种,也可以并用2种以上。
作为抗老化剂,例如可列举出:N-(1,3-二甲基丁基)-N′-苯基-对苯二胺(6PPD)、N,N′-二萘基-对苯二胺(DNPD)、N-异丙基-N′-苯基-对苯二胺(IPPD)、苯乙烯化苯酚(SP)、以及2,2,4-三甲基-1,2-二氢喹啉聚合物(RD)等。它们可以单独使用1种,也可以并用2种以上。
作为有机系活性剂,例如可列举出:硬脂酸、油酸、月桂酸、硬脂酸锌等。它们可以单独使用1种,也可以并用2种以上。
作为抗氧化剂,例如可列举出:丁基羟基甲苯(BHT)、丁基羟基苯甲醚(BHA)。
作为抗静电剂,例如可列举出:季铵盐;聚乙二醇、环氧乙烷衍生物等亲水性化合物。
作为阻燃剂,例如可列举出:氯代烷基磷酸酯、甲基膦酸二甲酯、溴磷化合物、聚磷酸铵、新戊基溴-聚醚、以及溴化聚醚等。另外,作为非卤素系阻燃剂,例如可列举出:氢氧化铝、氢氧化镁、磷酸三甲苯酯、以及磷酸甲苯二苯酯。
作为交联促进助剂,可以同时使用一般橡胶用助剂。作为橡胶用助剂,例如可以使用:锌白;硬脂酸、油酸、它们的锌盐。
作为粘接助剂,例如可列举出:三嗪硫醇系化合物(例如,2,4,6-三巯基-1,3,5-三嗪、6-丁基氨基-2,4-二巯基-1,3,5-三嗪)、间苯二酚、甲酚、间苯二酚-福尔马林胶乳、单羟甲基三聚氰胺、单羟甲基脲、亚乙基马来酰亚胺、环烷酸钴、硬脂酸钴、叔碳酸钴、以及十二烷酸钴等。它们可以单独使用1种,或者也可以并用2种以上。
本发明的组合物优选含有蜡。
蜡没有特别限制,例如可列举出:植物性蜡(米糠蜡、小烛树蜡、巴西棕榈蜡、日本蜡、漆蜡、甘蔗蜡、棕榈蜡等)、矿石系蜡(褐煤蜡、地蜡(Ozokerite)和纯地蜡(Ceresin)、由油页岩(Oil shale)得到的蜡等)、动物性蜡(蜂蜡等)等。其中,优选微晶蜡、石蜡。
在本发明的组合物中,蜡的含量没有特别限制,相对于上述的二烯系聚合物100质量份,优选为2质量份以上。上限没有特别限制,优选为10质量份以下。
<橡胶组合物的制备方法>
本发明的组合物可以通过以往公知的制造方法进行制造。例如可列举出:使用班伯里密炼机、以及捏合机等密闭式混合机、辊等辊式混炼机、挤出机、以及双螺杆挤出机等对上述的各成分进行混炼的方法。
[层叠体]
本发明的层叠体具备:具有金属表面的增强层和设于上述金属表面上的橡胶层。在此,橡胶层是使用上述的本发明的组合物形成的。
如上所述,本发明的组合物对金属表面显示出优异的粘接性,因此,本发明的层叠体适合用于软管(特别是,高压软管、液压软管)。
[软管]
以下,对本发明的层叠体为软管的情况进行详细说明。
图1是本发明的软管的一个实施方式的局部剖切立体图。如图1所示,软管1形成为圆筒状,具有:在内部供流体通过的内部橡胶层11、设于内部橡胶层11的外侧的增强层12、以及设于增强层12的外侧的外部橡胶层13。在此,增强层12具有金属表面。另外,内部橡胶层11及/或外部橡胶层13是使用上述的本发明的组合物形成的。增强层12配设为夹入在内部橡胶层11与外部橡胶层13之间。内部橡胶层11、增强层12以及外部橡胶层13通过内部橡胶层11以及外部橡胶层13的硫化而被粘接固定。
以下,首先对各层进行说明,然后对制造本发明的软管的具体例进行详细说明。
<增强层>
增强层是用于对软管的强度进行保持的层,从与橡胶层的粘接性的观点考虑,具有金属表面。增强层是钢线材编织而成的金属线编织层,优选金属线的表面镀有黄铜。需要说明的是,在图1所示的示例中,将增强层设为一层,但也可以设置层间配置有中间橡胶层的多个增强层。就增强层而言,除了金属线编织层以外,也可以形成为在内部橡胶层周围以螺旋状卷绕钢线材金属线而成的螺旋金属线。形成增强层的材料以及编法、织法或者卷绕法可以根据用途,例如根据耐压力进行适当选择。在液压软管等中,优选通过金属线编织层形成增强层。增强层优选具有编织金属线而成的编织结构或螺旋结构。
作为金属线材料,例如可列举出:钢琴线(碳钢)、硬钢线以及不锈钢线等。作为金属线材料,从加工性以及强度等观点考虑,特别优选钢琴线(碳钢)以及硬钢线。
为了提高与橡胶层的粘接性,优选增强层的表面镀有金属。该金属镀层是对钢琴线以及硬钢线实施了黄铜(Brass)涂布而成的。对于黄铜涂层而言,在钢金属线上镀有铜,在铜上镀有锌,施加热扩散处理而形成黄铜涂层。
<橡胶层>
橡胶层是使用上述的本发明的组合物而形成的。从耐候性的观点考虑,优选至少外部橡胶层是使用上述的本发明的组合物形成的。优选内部橡胶层是使用以耐油性优异的丙烯腈丁二烯橡胶(NBR)为主要成分的橡胶组合物形成的。
使用本发明的组合物形成橡胶层的方法没有特别限制,例如可列举出:在增强层的金属表面上形成橡胶组合物的层之后进行硫化的方法等。通过硫化,橡胶之间利用硫等硫化剂而被交联,被赋予弹性和拉伸强度,并且,在与增强层的界面,金属与硫化剂(例如,硫)键结,橡胶层与增强层被粘接。
在使用硫作为硫化剂的情况下,在形成作为橡胶组合物的混炼胶时,硫优选预先与其他材料一起进行配合。需要说明的是,就硫的配合而言,只要通过硫形成二烯系聚合物的分子链之间通过硫被交联,通过橡胶层与增强层的界面中的金属与硫的键结等,橡胶层与增强层被粘接,则并不限定于在混炼胶制备时配合。
作为硫化方法,可列举出:在硫的存在下以规定温度、规定时间对橡胶组合物进行加热处理的方法等。作为硫化温度,优选130℃以上且180℃以下。作为硫化时间,优选30分钟以上且240分钟以下。通过该范围的温度与时间的组合,能够得到更优异的物性,例如弹性、拉伸强度、外观、橡胶-金属界面的粘接性以及橡胶-金属界面的橡胶附着率。
作为硫化方式,例如可列举出:在增强层的金属表面上形成橡胶组合物的层之后封入高压容器内并在蒸气釜内进行交联的蒸汽硫化方式;将利用尼龙布等覆盖的增强层在热风干燥炉内进行硫化的烘箱硫化方式等。一般而言,蒸汽硫化方式是间歇式处理,烘箱硫化方式是连续式处理。从生产率的观点考虑,优选为连续式处理的烘箱硫化方式。
需要说明的是,不言而喻,也可以将本发明适用于通过以往公知的其他硫化方式来制造橡胶制品。作为其他硫化方式,例如可列举出:加压硫化、蒸汽硫化、以及热水硫化(hot water cure)等。
上述内部橡胶层的厚度例如优选0.2mm以上且4.0mm以下,更优选0.5mm以上且2.0mm以下。同样地,上述外部橡胶层的厚度例如优选0.2mm以上且4.0mm以下,更优选0.5mm以上且2.0mm以下。
<制造方法>
以下,参照图2以及图3,对制造本发明的软管的方法的具体例进行说明。
图2是制造本发明的软管的制造工序的一个实施方式的说明图,图3是制造本发明的软管的制造工序中的硫化工序的一个实施方式的说明图。
如图2所示,软管通过形成内部橡胶层11的橡胶材料的挤出工序(步骤S101)、增强层12的编织工序(步骤S102)、外部橡胶层13的挤出/硫化工序(步骤S103)、以及心轴101的抽出工序(步骤S104)来得到。所制造的软管经过水压检查、进一步经过检查卷取工序,被捆包、出货。
首先,在步骤S101中,在从开卷机100抽出的心轴101的外周面,通过第一挤出机102覆盖未硫化内部橡胶层103。未硫化内部橡胶层103卷绕于卷取开卷机104。
接着,在步骤S102中,以覆盖从卷取开卷机104抽出的未硫化内部橡胶层103的方式,将通过编织机105进行编织而形成增强层的带增强层的未硫化内部橡胶层106卷绕于卷取开卷机107。对于该增强层的帘线,使用金属线。就金属线而言,为了使与橡胶的粘接性良好,而使用镀有黄铜的钢线。需要说明的是,增强层可以通过将金属线呈螺旋状卷绕在形成于心轴101的周围的未硫化内部橡胶层103的周围来形成。
接着,在步骤S103中,在从卷取开卷机107抽出的带增强层的未硫化内部橡胶层106的增强层上,通过第二挤出机108覆盖未硫化的外部橡胶层而形成软管前体109,将所形成的软管前体109卷绕于卷取机110。在此,在软管前体109离开第二挤出机108之后、卷绕于卷取机110的期间,通过硫化装置111实施硫化工序,将硫化后的软管利用卷取机110来卷取,但硫化工序也可以设于将软管前体109利用卷取机110来卷取之后。另外,在硫化装置111的前后,设有用于向软管前体109拆装尼龙布等保护布的缠绕装置113以及解缠装置114。需要说明的是,在图2中,通过缠绕装置113缠绕有尼龙布的带尼龙布软管前体115为硫化后、拆下尼龙布之前的带尼龙布软管112。对于硫化工序将在下面进行说明。
接着,在步骤S104中,在硫化后,通过心轴抽出装置117自从卷取机110开卷的解缠后的软管116抽取心轴101而完成软管118。
如图3所示,离开第二挤出机108的软管前体109通过缠绕装置113在周围卷绕有尼龙布119。由尼龙布119覆盖的带尼龙布软管前体115被搬入至硫化装置111内。硫化装置111是利用热风120来使硫化进行的热风循环型的连续硫化装置。该硫化方式为烘箱硫化方式。硫化方式也可以为蒸汽硫化方式等烘箱硫化方式以外的硫化方式,但从生产率提高的观点考虑,优选为烘箱硫化方式。
图4是对投入至硫化装置的心轴周围的层结构的一个示例进行说明的局部剖面图。如图4所示,在心轴101周围形成有未硫化内部橡胶层103,进而在其周围形成有增强层12,进而在其周围形成有未硫化外部橡胶层121。在未硫化外部橡胶层121的周围卷绕有尼龙布119,在该状态下被加热,进行硫化工序。
如上所述,硫化温度优选为130℃以上且180℃以下,硫化时间、即在硫化装置111内的硫化时间优选为30分钟以上且240分钟以下。在该温度范围以及硫化时间下,可得到内部橡胶层以及外部橡胶层与增强层的粘接性更良好的软管。在此,通过使用上述的本发明的组合物形成内部橡胶层及/或外部橡胶层,能够制造内部橡胶层及/或外部橡胶层与金属制的增强层的粘接性良好的软管。
另外,在上述实施方式中,举例示出了利用连续处理方式进行的制造工序,但也可以通过利用其他工序制造出橡胶层和增强层之后进行贴合的方法来制造。
<用途>
本发明的软管能够适用于各种用途。作为本发明的软管的用途,例如能够适合用作汽车用空调软管、动力转向软管、用于建筑车辆的液压系统等的液压软管等。
另外,例如也能够将本发明同样用于传送带等其他橡胶层叠体中。
实施例
以下,通过实施例,对本发明进行更详细的说明,但本发明并不限定于这些实施例。
<橡胶组合物的制备>
使用班伯里密炼机,将下述表1所示的成分按下述表1所示的比例(质量份)进行混炼,制备出橡胶组合物。
需要说明的是,在表1中,关于SBR的量,上段的值为SBR(充油品)的量(单位:质量份),下段的值为SBR所含的SBR的净含量(单位:质量份)。
<软管的制作>
首先,在外径34mm的心轴上,将镀黄铜的金属线卷绕成编织层状而形成了具有金属表面的增强层。接着,在增强层的金属表面上,贴合了由所得的各橡胶组合物制备出的厚度2.5mm的未硫化片。进而,以覆盖未硫化片的外侧的方式卷绕尼龙66制的固化胶带(保护布),利用蒸汽硫化方式(在142℃的蒸汽釜内,90分钟)或者烘箱硫化方式(在142℃的常压烘箱内,135分钟)进行了硫化。如此,得到了具备具有金属表面的增强层和设于增强层的金属表面上的橡胶层(外侧橡胶层)的软管。
<粘接性的评价>
对于所得的软管(蒸汽硫化方式、烘箱硫化方式)评价了剥离力(kN/m)以及橡胶附着率(%)。将结果示于表1(湿热老化试验前)。
在此,剥离力(kN/m)是指,从增强层剥离外侧橡胶层(剥离速度50mm/分钟)时所需的每单位宽度(m)的力的大小(kN)。
另外,橡胶附着率是指,剥离掉外侧橡胶层时外侧橡胶层残留于增强层表面的比例,是将相对于增强层整个表面积的残留橡胶层的面积比率以百分率表示的值。
剥离力(kN/m)以及橡胶附着率(%)的数值是10次测定的平均值。
从粘接性的观点考虑,优选剥离力为3.5kN/m以上、且橡胶附着率为70%以上。
另外,将所得的软管(蒸汽硫化方式、烘箱硫化方式)在湿热环境(50℃、相对湿度95%)下放置1周后,同样评价了粘接性。将结果示于表1(湿热老化试验后)。
<耐起霜性的评价>
将所得的软管(烘箱硫化方式、湿热老化试验前)在25℃的环境下放置了6周。然后,观察或者实际触摸外侧橡胶层的表面,按以下的基准评价了蜡的耐起霜性。将结果示于表1。优选为A或B,更优选为A。
·A:与硫化时大致相同未观察到起霜。
·B:轻微观察到蜡的起霜。
·C:显著确认到蜡的起霜。
上述表1所示的各成分的详情如下。
·SBR:苯乙烯丁二烯橡胶(Taipol1723)(充油品:相对于橡胶100质量份含有充油的油37.5质量份。SBR的净含量为72.7质量%)
·BR:丁二烯橡胶(NIPOL BR 1220)
·C.B:ISAF级炭黑(SHOBLACK N220、Cabot Japan公司制)
·增塑剂:芳香系油(A/O MIX 2010、三共油化工业公司制)
·氧化锌:氧化锌JIS#3(正同化学工业公司制)
·硬脂酸:硬脂酸
·抗老化剂:N-苯基-N′-(1,3-二甲基丁基)-对苯二胺(Ozonon 6C、精工化学公司制)
·WAX1:微晶蜡(HI-MIC-1080、日本精蜡公司制)
·WAX2:石蜡(OZOACE-0015、日本精蜡公司制)
·脂肪酸酯:脂肪酸酯(NEW AID EG-ROLL、精工化学公司制)
·多元醇:甘油(分子量:92、沸点:290℃、精制甘油、阪本药品工业公司制)
·硫:硫(细井化学工业公司制)
·硫化促进剂1:N-叔丁基苯并噻唑-2-次磺酰胺(Nocceler NS-P、大内新兴化学工业公司制)
·硫化促进剂2:二苯基胍(Soxinol D-G、住友化学公司制)
根据表1可知,与不含有多元醇的比较例1相比,含有规定量多元醇的实施例1至5不仅在利用蒸汽硫化方式进行了硫化的情况下,而且在利用烘箱硫化方式进行了硫化的情况下也显示出优异的粘接性。另外,在硫化后将样品放置于湿热环境下的情况下也显示出优异的粘接性。其中,多元醇的含量相对于二烯系聚合物100质量份为10质量份以下的实施例1至4显示出优异的耐起霜性。其中,多元醇的含量相对于二烯系聚合物100质量份为2.5质量份以上的实施例4在利用烘箱硫化方式进行了硫化的情况下显示出更优异的粘接性。
另一方面,虽然含有多元醇但多元醇的含量相对于二烯系聚合物100质量份小于0.5质量份的比较例2与比较例1同样在利用烘箱硫化方式进行了硫化的情况下的粘接性不充分。另外,虽然含有多元醇但多元醇的含量相对于二烯系聚合物100质量份大于14质量份的比较例3在利用蒸汽硫化方式进行了硫化的情况下的粘接性不充分。
另外,不含有多元醇而增加了硫含量的比较例4以及5在硫化(烘箱硫化方式)后将样品放置于湿热环境下的情况下的粘接性不充分。
符号说明
1 软管
11 内部橡胶层
12 增强层
13 外部橡胶层
100 开卷机
101 心轴
102 第一挤出机
103 未硫化内部橡胶层
104 卷取开卷机
105 编织机
106 带增强层的未硫化内部橡胶层
107 卷取开卷机
108 第二挤出机
109 软管前体
110 卷取机
111 硫化装置
112 带尼龙布软管
113 缠绕装置
114 解缠装置
115 带尼龙布软管前体
116 软管
117 心轴抽出装置
118 软管
119 尼龙布
120 热风
121 未硫化外部橡胶层
Claims (6)
1.一种橡胶组合物,所述橡胶组合物含有:含丁二烯橡胶的二烯系聚合物和多元醇,
相对于所述二烯系聚合物100质量份,所述多元醇的含量为0.5质量份以上且14质量份以下。
2.根据权利要求1所述的橡胶组合物,其中,
所述多元醇为甘油。
3.根据权利要求1或2所述的橡胶组合物,其中,
进一步含有蜡,
相对于所述二烯系聚合物100质量份,所述蜡的含量为2质量份以上。
4.一种层叠体,所述层叠体具备:具有金属表面的增强层和设于所述金属表面上的橡胶层,
所述橡胶层是使用权利要求1至3中任一项所述的橡胶组合物而形成的。
5.根据权利要求4所述的层叠体,其中,
所述增强层具有编织金属线而成的编织结构或螺旋结构。
6.根据权利要求4或5所述的层叠体,其中,
所述层叠体为软管。
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PCT/JP2016/082011 WO2017094411A1 (ja) | 2015-12-02 | 2016-10-28 | ゴム組成物及び積層体 |
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US20190047183A1 (en) * | 2017-08-10 | 2019-02-14 | G. B. Kirby Meacham | Rubber-Steel Composite Structures |
KR102628623B1 (ko) * | 2017-10-17 | 2024-01-24 | 니폰 세이로 가부시키가이샤 | 고무 조성물용 표면 개질제 및 이것을 함유하는 고무 조성물 |
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CN108291058B (zh) | 2021-05-28 |
WO2017094411A1 (ja) | 2017-06-08 |
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