CN100476279C - 多层管 - Google Patents
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Abstract
本发明提供一种可以获得现有多层管未曾得到的超群低透过性能的多层管。在具有包含以热塑性树脂为材料的多个树脂层的多层结构的多层管中,多个树脂层中有至少2层低透过性树脂层,且各自由不同的低透过性树脂材料构成。
Description
技术领域
本发明涉及用于汽车燃料管道的多层管,特别是涉及可以显著提高对燃料的低透过性能的多层管。
背景技术
以往一般使用将金属管的外周面用镀膜或树脂被膜被覆起来的管作为汽车燃料管道使用的管,通过改良被膜材料或被膜层的结构来强化耐腐蚀性和耐化学品性等性质。
近年来,除了上述金属管之外,已经开始使用树脂管作为该种燃料管道用的管。树脂管与金属管不同,有不生锈、加工容易、设计上的自由度大以及质量轻等优点。
树脂管用于燃料管道时,最大的问题是对汽油的低透过性能差。
现有技术涉及的多层树脂管中,为了提高低透过性能,有用低透过性的树脂形成与汽油接触的最内层,其外侧通过粘接层,在最外层使用聚酰胺树脂等的多层管。
然而,最近在欧美由于与环境问题的关系,对燃料管道的燃料透过性能的限制日益强化,现有的多层管在低透过性能上存在限制,因此,应该明确规定,强化树脂管的低透过性能成为当务之急。
发明内容
因此,本发明的目的是提供一种可以消除上述现有技术中存在的问题,能获得用现有多层管不能获得的非常高的低透过性能的多层管。
为了达到上述目的,本发明的特征在于,在具有包含多个以热塑性树脂作为材料的树脂层的多层结构的多层管中,所述多个树脂层有至少2层低透过性树脂层,各低透过性树脂层包含不同的低透过性树脂材料。
另外,本发明的特征在于,在具有包含多个以热塑性树脂作为材料的树脂被膜的多层结构的多层管中,所述树脂层有至少2层低透过性树脂层,其中,构成一层的热塑性树脂是选自乙烯-四氟乙烯(ETFE)、液晶聚合物(LCP)、聚苯硫醚(PPS)、乙烯-乙烯醇(EVOH)和聚萘二甲酸丁二醇酯(PBN)中的任意一种。
进一步地,本发明的特征在于,在具有包含多个以热塑性树脂作为材料的树脂层的多层结构的多层管中,
上述树脂层中,两个树脂层由低透过性树脂层构成,这些低透过性树脂层相应于下述a)~e)中的任意一种:
a)包含乙烯-四氟乙烯(ETFE)的低透过性树脂层和包含乙烯-乙烯醇(EVOH)的低透过性树脂层;
b)包含乙烯-四氟乙烯(ETFE)的低透过性树脂层和包含聚苯硫醚(PPS)的低透过性树脂层;
c)包含液晶聚合物(LCP)的低透过性树脂层和包含乙烯-四氟乙烯(ETFE)的低透过性树脂层;
d)包含聚萘二甲酸丁二醇酯(PBN)的低透过性树脂层和包含乙烯-四氟乙烯(ETFE)的低透过性树脂层;
e)包含聚萘二甲酸丁二醇酯(PBN)的低透过性树脂层和包含聚苯硫醚(PPS)的低透过性树脂层。
附图说明
图1是本发明第1实施方案的多层管的横截面图。
图2是本发明第1实施方案的另一构成例的多层管的横截面图。
图3是本发明第2实施方案的多层管的横截面图。
图4是本发明第2实施方案的另一构成例的多层管的横截面图。
图5是实施例涉及的多层管的透过性试验结果图。
发明的最佳实施方案
以下参照附图说明本发明多层管的一个实施方案。
第1实施方案
图1表示本发明第1实施方案的多层管的横截面。该第1实施方案涉及的多层管是由5层树脂层构成的管。与燃料直接接触的最内层第1层和第3层是以低透过性热塑性树脂作为材料的低透过性树脂层。在该第1层和第3层之间插入作为粘接层的第2层。作为最外层的第5层不是特别地以低透过性热塑性树脂作为材料的层,而是包含聚酰胺的树脂层。上述多层管通过共挤出成型法成型。
作为形成低透过性树脂层的热塑性树脂,合适的包括例如乙烯-四氟乙烯(ETFE)、液晶聚合物(LCP)、聚苯硫醚(PPS)、乙烯-乙烯醇(EVOH)、聚萘二甲酸丁二醇酯(PBN)和聚偏二氟乙烯(PVDF)等。
第1层的材料和第3层的材料使用不同种类的低透过性树脂。例如,如果第1层的材料使用对普通汽油的低透过性大的乙烯-四氟乙烯(ETFE),则第3层的材料使用对醇调合汽油低透过性大的乙烯-乙烯醇(EVOH),这样就组合使用低透过性不同的材料。
另外,材料中以液晶聚合物(LCP)作为主体时,通过以该LCP碎粉末与PA11、PA12、ETFE、PPS、PBN、EVOH以及其它热塑性树脂混合的树脂作为材料,可以使进行共挤出时的树脂温度控制变得容易。即,单独使用LCP时,熔点明显高于其它树脂,共挤出时的温度控制困难,通过混合LCP碎粉末可以消除这一缺陷。
对于该低透过性树脂的混合物,不限于LCP,可以使用将LCP、ETFE、PPS、PBN和EVOH中的任意一种树脂的粉碎物与其它任意的热塑性树脂混合得到的树脂。
其次,图2是表示由5层树脂层构成的管的构成例的横截面图。该多层管中,最内层第1层和最外层第5层是包含不同种类的低透过性热塑性树脂的层,第3层是没有低透过性的树脂层,第2层、第4层由粘接层构成。
如上所述,使最内层第1层为低透过性树脂层时,另一低透过性树脂层可以是第3层和第5层中的任意一层。
也可以在第1层的材料使用低透过性热塑性树脂与碳等导电性填料的混合物,这样不仅得到低透过性,而且赋予导电性。由此可以使燃料和第1层之间的摩擦导致的静电消散到外部。
使第1层具有导电性时,作为低透过性树脂层的第5层不赋予导电性。第1层通过赋予导电性,其低透过性能降低,但用第5层可以充分弥补低透过性能,从而可以使导电性时总体管的低透过性能的影响达到最低限。
第2实施方案
其次,图3表示本发明第2实施方案的多层管的横截面。该第2实施方案涉及的多层管是由6层树脂层构成的管。
最内层第1层是往非低透过性热塑性树脂,例如聚酰胺中混合碳等填料赋予了导电性的树脂层。第2层和第4层是以低透过性热塑性树脂作为材料的低透过层。第3层和第5层为粘接层。作为最外层的第6层不是特别地以低透过性热塑性树脂作为材料的层,而是包含聚酰胺的树脂层。上述由6层构成的管通过共挤出成型法成型。第2层的材料和第4层的材料使用不同种类的低透过性树脂,这点与第1实施方案相同。
作为构成低透过性树脂层材料的热塑性树脂,合适的包括例如乙烯-四氟乙烯(ETFE)、液晶聚合物(LCP)、聚苯硫醚(PPS)、聚萘二甲酸丁二醇酯(PBN)和聚偏二氟乙烯(PVDF)等。
另外,作为各低透过性树脂层的树脂,除单独使用上述热塑性树脂之外,也可以用任一树脂的粉碎粉末与除此之外的任意热塑性树脂的混合物作为材料。
通过如上所述构成的多层管,可以确保导电性以使第1层的静电逃逸到外面,可以设置第2层、第4层两层低透过性树脂层,并且可以使其分别具有不同的低透过性。
其次,图4表示由6层树脂层构成的多层管的构成例的横截面。该多层管中,最内层第1层是包含在低透过性热塑性树脂中混合碳等填料的材料的层。其它层与图3的多层管相同。通过该多层管可以提高导电性,同时进一步提高低透过性能。
实施例
下面就图3的第2实施方案说明对第2层和第4层的低透过性树脂层材料使用图5所示的材料组合的实施例。
各实施例中,管内径为6.0mm,第1层(聚酰胺)的壁厚度为0.2mm,第2层的壁厚度为0.1mm,第3层(粘接层)的壁厚度为0.1mm,第4层的壁厚度为0.2mm,第5层(粘接层)的壁厚度为0.1mm,第6层(聚酰胺)的壁厚度为0.3mm。
使用普通汽油和醇调合汽油作为透过性试验的介质,进行CARB、DBL规定的燃料透过性试验。◎、○、△表示低透过性能的评价。
◎表示对普通汽油、醇调合汽油两者的低透过性能都很好;
○表示对普通汽油的低透过性能好;
△表示对醇调合汽油的低透过性能好。
作为总体的趋势是,在低透过性树脂层中,使1层为LCP的管可以不分介质地谋求提高低透过性能。另外发现,使1层为EVOH的管对醇调合汽油的低透过性能提高。
另外发现,通过使两层中的一层(优选第1层)为ETFE,原来对提高对普通汽油的低透过性能有效、而对醇的低透过性能较弱的ETFE的性质通过在另一层中使用PPS、PBN和LCP中的任意一种得到弥补,从而可以不分燃料种类而表现低透过性能。
还发现,通过将对醇调合汽油低透过性较弱而对普通汽油较强的EVOH与其它树脂PPS、LCP中的任意一种组合,可以不分燃料种类而表现低透过性能。
另外,在这些树脂的组合中,发挥最佳低透过性能的是PPS与LCP的组合。
通过以上说明可知,通过本发明可以获得现有多层管未曾得到的超群低透过性能。另外,通过组合低透过性树脂,可以提高对特定燃料的低透过性能,或弥补对特定燃料低透过性能弱的树脂的透过性能,或在获得低透过性的同时赋予导电性,从而强化多方面的低透过性能。
Claims (2)
1.多层管,该管具有包含以热塑性树脂作为材料的多个树脂层的多层结构,其特征在于:
所述多个树脂层中有至少2层低透过性树脂层,且各低透过性树脂层包含不同的低透过性树脂材料;
上述低透过性树脂层各自包含选自乙烯-四氟乙烯(ETFE)、液晶聚合物(LCP)、聚苯硫醚(PPS)、乙烯-乙烯醇(EVOH)和聚萘二甲酸丁二醇酯(PBN)的低透过性树脂材料;
并且具有包含下述混合树脂的低透过性树脂层,该混合树脂是将乙烯-四氟乙烯(ETFE)、液晶聚合物(LCP)、聚苯硫醚(PPS)、乙烯-乙烯醇(EVOH)和聚萘二甲酸丁二醇酯(PBN)中的任一种树脂粉碎,并与该树脂之外的任意热塑性树脂混合得到的混合树脂;
被粉碎的上述任一种树脂为液晶聚合物(LCP)。
2.权利要求1所述的多层管,其特征在于:所述低透过性树脂层中,一层含有导电性材料,并构成最内层的树脂层。
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JP2002338173A JP2004169851A (ja) | 2002-11-21 | 2002-11-21 | 多層チューブ |
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US (1) | US20060011251A1 (zh) |
EP (1) | EP1580473A4 (zh) |
JP (1) | JP2004169851A (zh) |
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CN1714252A (zh) | 2005-12-28 |
WO2004046600A1 (ja) | 2004-06-03 |
JP2004169851A (ja) | 2004-06-17 |
EP1580473A1 (en) | 2005-09-28 |
EP1580473A4 (en) | 2006-12-27 |
US20060011251A1 (en) | 2006-01-19 |
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