CN106917921B - 制冷剂输送用软管 - Google Patents

制冷剂输送用软管 Download PDF

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Publication number
CN106917921B
CN106917921B CN201611093128.2A CN201611093128A CN106917921B CN 106917921 B CN106917921 B CN 106917921B CN 201611093128 A CN201611093128 A CN 201611093128A CN 106917921 B CN106917921 B CN 106917921B
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China
Prior art keywords
layer
hose
polyamide
transportation
refrigerant
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Expired - Fee Related
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CN201611093128.2A
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English (en)
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CN106917921A (zh
Inventor
薮谷祐希
水谷幸治
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Sumitomo Riko Co Ltd
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Sumitomo Riko Co Ltd
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Abstract

本发明涉及制冷剂输送用软管。本发明提供耐制冷剂透过性、耐热性优异、且对在软管内流动的制冷剂、润滑油的耐提取性优异的制冷剂输送用软管。一种制冷剂输送用软管，其具备：包含氟树脂的管状的最内层1、与上述最内层(1)外周面接触而设置的聚酰胺树脂层(2)、与上述聚酰胺树脂层(2)外周面接触而设置的第一橡胶层(3a)、与上述第一橡胶层(3a)外周面接触而设置的强化层(4)和与上述强化层(4)外周面接触而设置的第二橡胶层(3b)，上述聚酰胺树脂层(2)包含碳原子相对于每1个氮原子的平均数Ca为10以下的聚酰胺树脂。

Description

制冷剂输送用软管
技术领域
本发明涉及作为用于输送汽车等车辆用的制冷剂的软管有用的、制冷剂输送用软管。
背景技术
近年来，伴随着臭氧层破坏气体的蒸散限制强化，对汽车等中使用的制冷剂输送用软管的制冷剂阻隔性(耐制冷剂透过性)的要求变严格。因此，制冷剂输送用软管的最内层的形成材料例如使用了聚酰胺树脂那样的结晶性高的树脂(例如参照专利文献1)。
现有技术文献
专利文献
专利文献1：日本特开2002-181254号公报
发明内容
发明要解决的问题
然而，聚酰胺树脂特别是在高温气氛下存在如下问题：对于软管内流动的制冷剂、润滑油，其低聚物成分容易被提取出来。由于发动机舱内为高温，因此，容易产生上述那样的问题。而且，这样的低聚物成分例如积存于制冷剂配管内的阀时，存在制冷剂的流动变差的问题。
本发明是鉴于这样的情况而作出的，本发明的目的在于，提供：耐制冷剂透过性、耐热性优异、且对在软管内流动的制冷剂、润滑油的耐提取性优异的制冷剂输送用软管。
用于解决问题的方案
为了达成上述目的，本发明的制冷剂输送用软管采用如下构成：具备包含氟树脂的管状的最内层、与上述最内层外周面接触而设置的聚酰胺树脂层、与上述聚酰胺树脂层外周面接触而设置的第一橡胶层、与上述第一橡胶层外周面接触而设置的强化层和与上述强化层外周面接触而设置的第二橡胶层，上述聚酰胺树脂层包含碳原子相对于每1个氮原子的平均数Ca为10以下的聚酰胺树脂。
即，本发明人等为了解决前述课题而反复深入研究。在该研究的过程中，为了形成耐热性、耐制冷剂透过性优异的软管，研究了：设置包含碳原子相对于每1个氮原子的平均数Ca为10以下的聚酰胺树脂的聚酰胺树脂层。然而，以上述聚酰胺树脂层作为最内层时，担心如上述那样的低聚物成分对制冷剂、润滑油的提取，因此，研究了在上述聚酰胺树脂层的内周面进一步设置氟树脂层。而且，为了提高对制冷剂输送用软管要求的耐弯曲性、耐热性、耐水性、强度等，研究了：在上述聚酰胺树脂层的外周面依次层叠第一橡胶层、强化层、第二橡胶层。其结果发现：可以达成期望的目的，可以发挥作为制冷剂输送用软管的优异的性能，从而完成了本发明。
发明的效果
本发明的制冷剂输送用软管为具备包含氟树脂的管状的最内层、与上述最内层外周面接触而设置的聚酰胺树脂层、与上述聚酰胺树脂层外周面接触而设置的第一橡胶层、与上述第一橡胶层外周面接触而设置的强化层和与上述强化层外周面接触而设置的第二橡胶层的制冷剂输送用软管，上述聚酰胺树脂层包含碳原子相对于每1个氮原子的平均数Ca为10以下的聚酰胺树脂。因此，耐制冷剂透过性、耐热性优异，且对在软管内流动的制冷剂、润滑油的耐提取性优异，还可以消除在制冷剂配管内提取物(聚酰胺树脂的低聚物成分)积存而制冷剂的流动变差的问题。另外，通过形成上述那样的橡胶层构成，本发明的制冷剂输送用软管的耐弯曲性、耐水性、强度等也优异。
特别是，上述最内层包含熔融粘度为500～3000Pa·s的氟树脂时，软管的柔软性变得更优异。
另外，上述最内层包含选自由乙烯-四氟乙烯共聚物(ETFE)、聚偏二氟乙烯(PVDF)、乙烯-四氟乙烯-六氟丙烯共聚物(EFEP)、四氟乙烯-全氟(烷基乙烯基醚)-氯三氟乙烯共聚物(CPT)、四氟乙烯-六氟丙烯共聚物(FEP)和氯三氟乙烯-乙烯共聚物(ECTFE)组成的组中的至少一种氟树脂时，软管的柔软性与耐提取性的均衡性变得更优异。
另外，上述最内层包含选自由马来酸酐改性氟树脂、衣康酸酐改性氟树脂和柠康酸酐改性氟树脂组成的组中的至少一种时，与聚酰胺树脂层的层间粘接性变得更优异。
另外，上述最内层的厚度为0.05～0.25mm的范围时，软管的柔软性变得更优异而不会破坏耐提取性。
另外，上述最内层的弹性模量为600～900MPa的范围时，软管的耐弯曲性变得更优异。
另外，在位于与上述聚酰胺树脂层的界面的最内层外周面具有羟基时，聚酰胺树脂层与最内层的层间粘接性变得更优异。
另外，上述聚酰胺树脂层包含选自由聚酰胺6、聚酰胺610和聚酰胺66组成的组中的至少一种聚酰胺树脂时，耐制冷剂透过性变得更优异。
另外，上述聚酰胺树脂层为分散有包含弹性体的岛相的聚酰胺树脂层时，软管的柔软性等变得更优异。
另外，以上述最内层的厚度达到上述聚酰胺树脂层的厚度以上的方式构成时，软管的柔软性等变得更优异。
另外，以上述最内层的弹性模量达到上述聚酰胺树脂层的弹性模量以上的方式构成时，软管的柔软性等变得更优异。
附图说明
图1为示意性示出本发明的制冷剂输送用软管的截面的说明图。
附图标记说明
1 最内层
2 聚酰胺树脂层
3a 第一橡胶层
3b 第二橡胶层
4 强化层
具体实施方式
接着，对本发明的实施方式进行详细说明。但是，本发明不限定于该实施方式。
本发明的制冷剂输送用软管如图1所示那样，为具备包含氟树脂的管状的最内层1、与上述最内层1外周面接触而设置的聚酰胺树脂层2、与上述聚酰胺树脂层2外周面接触而设置的第一橡胶层3a、与上述第一橡胶层3a外周面接触而设置的强化层4和与上述强化层4外周面接触而设置的第二橡胶层3b的制冷剂输送用软管，上述聚酰胺树脂层2包含碳原子相对于每1个氮原子的平均数Ca为10以下的聚酰胺树脂。
作为用作上述最内层1的形成材料的氟树脂，没有特别限定，从提高软管的柔软性的观点出发，优选使用熔融粘度为500～3000Pa·s的氟树脂，更优选使用熔融粘度为800～2000Pa·s的氟树脂。需要说明的是，上述熔融粘度是依据JIS K7199、通过毛细管流变仪、在280℃、剪切速度121.6sec-1的条件下测定的熔融粘度。
而且，上述氟树脂中，从软管的柔软性与耐提取性的均衡性的观点出发，优选使用：乙烯-四氟乙烯共聚物(ETFE)、聚偏二氟乙烯(PVDF)、乙烯-四氟乙烯-六氟丙烯共聚物(EFEP)、四氟乙烯-全氟(烷基乙烯基醚)-氯三氟乙烯共聚物(CPT)、四氟乙烯-六氟丙烯共聚物(FEP)和氯三氟乙烯-乙烯共聚物(ECTFE)。而且，这些氟树脂可以单独使用或组合2种以上使用。
另外，从与聚酰胺树脂层2的层间粘接性的观点出发，上述氟树脂优选使用马来酸酐改性氟树脂、衣康酸酐改性氟树脂、柠康酸酐改性氟树脂。作为基于上述改性的氟树脂的适合的例子，可以使用与上述同样的物质。
需要说明的是，使用如上述那样经过改性的氟树脂时，为了进一步提高与聚酰胺树脂层2的层间粘接性，优选将最内层1和聚酰胺树脂层2进行共挤出成形。
另外，上述最内层1外周面具有羟基时，与聚酰胺树脂层2的层间粘接性也变得更优异。上述羟基是通过对上述最内层1外周面进行等离子体处理而导入的，可以通过X射线光电子能谱分析来确认。
作为上述聚酰胺树脂层2的形成材料，如上述那样，可以使用碳原子相对于每1个氮原子的平均数Ca为10以下的聚酰胺树脂。优选使用碳原子相对于每1个氮原子的平均数Ca为6～10的聚酰胺树脂。需要说明的是，Ca的值可以如下求出：根据上述聚酰胺树脂1分子中的氮原子数和碳原子数，计算相对于每1个氮原子的碳原子数，从而求出。
作为上述那样的聚酰胺树脂，例如可以举出：聚酰胺6(Ca＝6)、聚酰胺610(Ca＝8)、聚酰胺46(Ca＝5)、聚酰胺66(Ca＝6)、聚酰胺1010(Ca＝10)、聚酰胺612(Ca＝9)、聚酰胺1012(Ca＝11)、聚酰胺6T(Ca＝7)、聚酰胺6T-6I(Ca＝7)、聚酰胺66-6T(Ca＝7)、聚酰胺66-6T-6I(Ca＝7)、聚酰胺6T-2MPMDT(Ca＝7)、聚酰胺9T(Ca＝8.5)、聚酰胺10T(Ca＝9)、聚酰胺11T(Ca＝9.5)等。它们可以单独使用或组合2种以上使用。其中，从耐制冷剂透过性更优异的方面出发，适合使用聚酰胺6、聚酰胺610、聚酰胺66。
另外，上述聚酰胺树脂层2为分散有包含弹性体的岛相的聚酰胺树脂层时，软管的柔软性等更优异，故优选。作为上述弹性体，例如可以举出：乙烯-α-烯烃共聚物、离聚物树脂、改性聚烯烃(马来酸酐改性乙烯-丁烯共聚物等)、聚醚酰胺弹性体、聚酯酰胺弹性体、聚醚酯酰胺弹性体、聚醚酯弹性体、丙烯酸类橡胶、乙烯/丙烯系橡胶、丁基橡胶、腈橡胶、氟橡胶、硅橡胶等。其中，从柔软性、耐冲击性的观点出发，优选使用乙烯-α-烯烃共聚物。
形成上述那样的海岛结构的聚酰胺树脂层时，作为其材料，从耐制冷剂透过性的观点出发，优选的是，将聚酰胺树脂与弹性体以重量比计为聚酰胺树脂/弹性体＝95/5～55/45的比例进行混合。
需要说明的是，可以根据需要，在上述聚酰胺树脂层2的形成材料中适当配混填充剂、增塑剂、防老剂等添加剂。
作为形成上述聚酰胺树脂层2外周的橡胶层(第一橡胶层3a和第二橡胶层3b)的材料，例如可以使用：在丁基橡胶(IIR)、氯化丁基橡胶(Cl-IIR)、溴化丁基橡胶(Br-IIR)等卤代丁基橡胶、丙烯腈-丁二烯橡胶(NBR)、氯丁橡胶(CR)、乙烯-丙烯-二烯橡胶(EPDM)、乙烯-丙烯橡胶(EPM)、氟橡胶(FKM)、环氧氯丙烷橡胶(ECO)、丙烯酸类橡胶、硅橡胶、氯化聚乙烯橡胶(CPE)、氨基甲酸酯橡胶等橡胶中适当配混了硫化剂、炭黑等而成的材料。其中，从制冷剂的低透过性更优异、且来自外部的耐水性变优异的方面出发，适合使用丁基橡胶(IIR)、卤代丁基橡胶。而且，它们可以单独使用或组合2种以上使用。
另外，如图1那样，设置于第一橡胶层3a与第二橡胶层3b之间的强化层4例如可以如下形成：通过螺旋编结、针编结、编带编结等对聚对苯二甲酸乙二醇酯(PET)、聚萘二甲酸乙二醇酯(PEN)、芳族聚酰胺、聚酰胺(尼龙)、聚乙烯醇(维尼纶)、人造丝、金属线等强化丝进行编结，从而形成。
此处，如前述图1所示那样的、本发明的制冷剂输送用软管例如可以如下那样制作。即，首先，分别准备上述的最内层1用材料、聚酰胺树脂层2用材料。接着，将上述最内层1用材料和聚酰胺树脂层2用材料共挤出成形为软管状。此时，也可以使用芯棒。另外，上述最内层1包含对聚酰胺树脂层2缺乏层间粘接性的材料时，首先，可以将最内层1用材料挤出成形为软管状，对其外周面进行等离子体处理，然后将聚酰胺树脂层2进行挤出成形。然后，在上述聚酰胺树脂层2的外周面进行第一橡胶层3a的挤出成形，然后在其外周面对强化丝进行编带编结等而形成强化层4，进而在上述强化层4的外周面进行第二橡胶层3b的挤出成形。然后，将其在规定的条件(优选170℃×30～60分钟)下进行硫化，然后抽出芯棒。如此，可以制作目标层结构的制冷剂输送用软管。
本发明的制冷剂输送用软管中，软管内径优选为5～40mm的范围。另外，上述最内层1的厚度优选为0.05～0.25mm的范围，特别优选为0.1～0.2mm。即，这是由于，上述最内层1的厚度过薄时，难以得到期望的耐提取性，上述最内层1的厚度过厚时，有破坏软管的柔软性的担心。
另外，以上述最内层1的厚度达到上述聚酰胺树脂层2的厚度以上的方式构成时，软管的柔软性等变得更优异，故优选。
另外，上述最内层1的弹性模量优选为600～900MPa的范围时，软管的耐弯曲性变得更优异，故优选。需要说明的是，上述弹性模量是依据ASTM D790测定的。
而且，以上述最内层1的弹性模量达到上述聚酰胺树脂层2的弹性模量以上的方式构成时，软管的柔软性等变得更优异，故优选。
本发明的制冷剂输送用软管可以适合用于空调/散热器等中使用的二氧化碳、氟利昂、代替氟利昂、丙烷等制冷剂的输送用软管。而且，上述制冷剂输送用软管不仅可以用于汽车而且还可以优选用于其他输送机械(飞机、铲车、挖掘机、起重机等产业用输送车辆、铁道车辆等)等。
实施例
接着，对本发明的实施例与比较例一起进行说明。但是，本发明不限定于这些实施例。
首先，先于实施例和比较例，作为树脂层材料，准备下述所示的材料。需要说明的是，下述材料中，熔融粘度是指，依据JIS K 7199、通过毛细管流变仪、在280℃、剪切速度121.6sec-1的条件下测定的熔融粘度。另外，Ca是指，聚酰胺树脂中的碳原子相对于每1个氮原子的平均数。
〔氟树脂1〕
将内容积为13升的带搅拌机的聚合槽脱气，投入1-氢十三氟己烷8500g、1,3-二氯-1,1,2,2,3-五氟丙烷3650g和CH2＝CH(CF2)4F 26g，压入四氟乙烯(以下，也称为“TFE”)2100g和乙烯(以下，也称为“E”)1.2g，将聚合槽内升温至66℃，投入作为聚合引发剂的过氧化新戊酸叔丁酯0.5质量％的1-氢十三氟己烷溶液48mL，使聚合开始。然后，以聚合中的压力达到一定的方式，连续地投入TFE/E＝70/30(摩尔比)的组成的单体混合气体，以相对于TFE/E的单体混合气体为0.7摩尔％的方式连续地投入CH2＝CH(CF2)4F。聚合开始3小时后，在投入单体混合气体900g的时刻，将聚合槽内温降温至室温，并且吹扫至常压。将如此得到的浆料用玻璃过滤器抽滤，在120℃下使其干燥15小时，得到950g的乙烯-四氟乙烯共聚物(ETFE1)。
然后，将如上述那样得到的ETFE1和熔融粘度1200Pa·s的马来酸改性ETFE(AH2000、旭硝子株式会社制造)以重量比计为ETFE1：AH2000＝2：1进行共混，得到熔融粘度600Pa·s的氟树脂1。
〔氟树脂2〕
将如上述那样得到的ETFE1和熔融粘度1200Pa·s的马来酸改性ETFE(AH2000、旭硝子株式会社制造)以重量比计为ETFE1：AH2000＝1：2进行共混，得到熔融粘度800Pa·s的氟树脂2。
〔氟树脂3〕
熔融粘度1200Pa·s的马来酸改性ETFE(AH2000、旭硝子株式会社制造)
〔氟树脂4〕
将熔融粘度1200Pa·s的马来酸改性ETFE(AH2000、旭硝子株式会社制造)和熔融粘度1700Pa·s的ETFE(C88AXP、旭硝子株式会社制造)以重量比计为AH2000：C88AXP＝2：1进行共混，得到熔融粘度1400Pa·s的氟树脂4。
〔氟树脂5〕
熔融粘度1700Pa·s的ETFE(C88AXP、旭硝子株式会社制造)
〔聚酰胺树脂1〕
聚酰胺6(Ca：6)(CM1017、东丽株式会社制造)
〔聚酰胺树脂2〕
聚酰胺610(Ca：8)(CM2006、东丽株式会社制造)
〔聚酰胺树脂3〕
聚酰胺12(Ca：12)(3030B、Ube Industries,Ltd.制造)
〔弹性体1〕
乙烯-α-烯烃共聚物(TAFMER MH7020、三井化学株式会社制造)
[实施例1]
在金属制的芯棒(外径12.7mm)上，将包含氟树脂1的最内层(厚度0.15mm)和包含聚酰胺树脂1与弹性体1的混合物(以重量比计设为聚酰胺树脂1/弹性体1＝70/30的比例的混合物)的外层(厚度0.15mm)进行共挤出成形。然后，在上述外层(聚酰胺树脂层)的外周面，通过EPDM的挤出成形，形成第一橡胶层(厚度1.6mm)，然后在该橡胶层外周面通过芳族聚酰胺丝的编带编结形成强化层，进而在上述强化层的外周面通过EPDM的挤出成形，形成第二橡胶层(厚度1.0mm)。然后，硫化后，从该层叠软管体抽出芯棒，切成长尺寸的成形品，从而制作目标制冷剂输送用软管(参照图1)。需要说明的是，对上述外层(聚酰胺树脂层)进行电子显微镜观察，结果确认了分散有包含弹性体1的岛相。
[实施例2]
作为最内层的材料，使用氟树脂2代替氟树脂1。除此之外，与实施例1同样地制作目标制冷剂输送用软管。
[实施例3]
作为最内层的材料，使用氟树脂3代替氟树脂1。除此之外，与实施例1同样地制作目标制冷剂输送用软管。
[实施例4]
作为最内层的材料，使用氟树脂4代替氟树脂1。除此之外，与实施例1同样地制作目标制冷剂输送用软管。
[实施例5]
作为外层(聚酰胺树脂层)的材料，使用聚酰胺树脂2与弹性体1的混合物(以重量比计设为聚酰胺树脂2/弹性体1＝70/30的比例的混合物)代替聚酰胺树脂1与弹性体1的混合物。除此之外，与实施例1同样地制作目标制冷剂输送用软管。需要说明的是，对上述外层(聚酰胺树脂层)进行电子显微镜观察，结果确认了分散有包含弹性体1的岛相。
[实施例6]
在金属制的芯棒(外径12.7mm)上，将包含氟树脂5的最内层(厚度0.15mm)进行挤出成形，然后对上述最内层外周面进行等离子体处理。之后，对上述最内层外周面，将包含聚酰胺树脂1与弹性体1的混合物(以重量比计设为聚酰胺树脂1/弹性体1＝70/30的比例的混合物)的外层(厚度0.15mm)进行挤出成形。然后，在上述外层(聚酰胺树脂层)的外周面，通过EPDM的挤出成形，形成第一橡胶层(厚度1.6mm)，然后在该橡胶层外周面，通过芳族聚酰胺丝的编带编结形成强化层，进而在上述强化层的外周面，通过EPDM的挤出成形，形成第二橡胶层(厚度1.0mm)。然后，硫化后，从该层叠软管体抽出芯棒，切成长尺寸的成形品，制作目标制冷剂输送用软管。需要说明的是，对上述外层(聚酰胺树脂层)进行电子显微镜观察，结果确认了分散有包含弹性体1的岛相。
[比较例1]
在金属制的芯棒(外径12.7mm)上，将包含聚酰胺树脂1与弹性体1的混合物(以重量比计设为聚酰胺树脂1/弹性体1＝70/30的比例的混合物)的最内层(厚度0.15mm)进行挤出成形。然后，在上述最内层的外周面，通过EPDM的挤出成形，形成第一橡胶层(厚度1.6mm)，然后在该橡胶层外周面，通过芳族聚酰胺丝的编带编结，形成强化层，进而在上述强化层的外周面，通过EPDM的挤出成形，形成第二橡胶层(厚度1.0mm)。然后，硫化后，从该层叠软管体抽出芯棒，切成长尺寸的成形品，制作目标制冷剂输送用软管。
[比较例2]
在金属制的芯棒(外径12.7mm)上，将包含聚酰胺树脂3与弹性体1的混合物(以重量比计设为聚酰胺树脂3/弹性体1＝70/30的比例的混合物)的最内层(厚度0.15mm)进行挤出成形。然后，在上述最内层的外周面，通过EPDM的挤出成形，形成第一橡胶层(厚度1.6mm)，然后在该橡胶层外周面，通过芳族聚酰胺丝的编带编结，形成强化层，进而在上述强化层的外周面，通过EPDM的挤出成形，形成第二橡胶层(厚度1.0mm)。然后，硫化后，从该层叠软管体抽出芯棒，切成长尺寸的成形品，制作目标制冷剂输送用软管。
[比较例3]
作为外层(聚酰胺树脂层)的材料，使用聚酰胺树脂3与弹性体1的混合物(以重量比计设为聚酰胺树脂3/弹性体1＝70/30的比例的混合物)代替聚酰胺树脂1与弹性体1的混合物。除此之外，与实施例1同样地制作目标制冷剂输送用软管。
[比较例4]
作为最内层的材料，使用聚烯烃树脂(B241、Prime Polymer Co.,Ltd.制造)代替氟树脂1。除此之外，与实施例1同样地制作目标制冷剂输送用软管。
[比较例5]
作为最内层的材料，使用马来酸改性聚烯烃树脂(Admer QF551、三井化学株式会社制造)代替氟树脂1。除此之外，与实施例1同样地制作目标制冷剂输送用软管。
关于如此得到的、实施例和比较例的制冷剂输送用软管，依据下述基准，进行各特性的评价。将其结果一并示于后述的表1和表2。
《耐制冷剂透过性》
将实施例和比较例的各软管沿长度方向切开，然后冲裁成圆盘状，制作样品片。然后，在低温(-35℃以下)下，将封入了代替氟利昂气体(HFC-134a)的杯子的开口部用该样品片封闭，将其放置在90℃的烘箱中。然后，将杯子内的代替氟利昂气体减少量与时间一起作图，通过其斜率，算出相对于样品片的透过面积的、每1天的代替氟利昂气体透过量(HFC-134a透过系数、mg·mm/cm2·天)。然后，将每1天的代替氟利昂气体透过量为0.3mg·mm/cm2·天以下的情况评价为○。
《弹性模量》
依据ASTM D 790测定制冷剂输送用软管的树脂层(最内层/外层)的弹性模量(MPa)。
《耐提取性》
在软管长400mm的制冷剂输送用软管中，封入制冷剂(HFC-134a)50g与油(DaphneHermetic Oil)30g的混合液，在软管的两端开口部加盖，之后，将该软管在150℃的烘箱中放置168小时。之后，将取出的提取液取出到滤纸上使其干燥，用显微镜观察上述滤纸上的提取物的有无。然后，将没有确认到提取物的情况评价为○、将确认到提取物的情况评价为×。
《耐热性》
将包含制冷剂输送用软管的树脂层(最内层/外层)的材料的试验片(JIS5号哑铃)放置在150℃的吉尔恒温箱中168小时，使其热老化，然后对180°弯曲、试验片中是否有龟裂产生、折叠等异常进行外观观察。然后，将最内层/外层的试验片均未见异常的情况评价为○，将最内层/外层中的至少一者的试验片可见异常的情况评价为×。
《层间粘接性》
将制冷剂输送用软管切成10mm宽，制作条状的样品。然后，将各样品的树脂层间(最内层与外层的层间)部分地剥离，将该部分分别夹持于拉伸试验机的夹头，在气氛温度23℃、拉伸速度25mm/分钟的条件下，测定90°剥离强度(N/cm)。然后，将上述剥离强度为30N/cm以上的情况评价为○，将上述剥离强度小于30N/cm的情况评价为×。
《柔软性》
将制冷剂输送用软管缠绕于直径200mm的管状筒(芯棒)，根据该缠绕程度，进行柔软性的评价。即，根据上述缠绕，将软管的树脂层没有弯折(弯曲)的情况评价为○。
《MIT试验》
将制冷剂输送用软管切成10mm宽，制作条状的样品。然后，依据JIS P8115，对于各样品，在气氛温度120℃、载荷250g、弯曲角度135°、试验循环175cpm下进行MIT试验。然后，将往复弯曲次数为10000次以上也不产生样品断裂的情况评价为○。
[表1]
[表2]
根据上述表的结果可知，实施例的软管的耐制冷剂透过性、耐热性均优异，并且耐提取性优异。另外，实施例的软管的树脂层中的层间粘接性也高，在柔软性、MIT试验中也可以得到良好的结果。
与此相对，比较例1、2的软管变为耐提取性等差的结果。具备包含聚酰胺12的合金的外层的比较例3的软管为耐热性评价差的结果。具备包含聚烯烃树脂的最内层的比较例4的软管为耐热性、层间粘接性评价差的结果。具备包含酸改性聚烯烃树脂的最内层的比较例5的软管为耐热性评价差的结果。
产业上的可利用性
本发明的制冷剂输送用软管可以适合用于空调/散热器等中使用的二氧化碳、氟利昂、代替氟利昂、丙烷等制冷剂的输送用软管。而且，上述制冷剂输送用软管不仅可以用于汽车还可以优选用于其他输送机械(飞机、铲车、挖掘机、起重机等产业用输送车辆、铁道车辆等)等。

Claims (7)

1.一种制冷剂输送用软管，其特征在于，具备：包含氟树脂的管状的最内层、与所述最内层外周面接触而设置的聚酰胺树脂层、与所述聚酰胺树脂层外周面接触而设置的第一橡胶层、与所述第一橡胶层外周面接触而设置的强化层和与所述强化层外周面接触而设置的第二橡胶层，所述聚酰胺树脂层包含碳原子相对于每1个氮原子的平均数Ca为10以下的聚酰胺树脂，所述聚酰胺树脂层为分散有包含弹性体的岛相的聚酰胺树脂层，
所述最内层包含熔融粘度为500～3000Pa·s的氟树脂，
所述氟树脂选自由马来酸酐改性氟树脂、衣康酸酐改性氟树脂和柠康酸酐改性氟树脂组成的组中的至少一种，
所述马来酸酐改性氟树脂、衣康酸酐改性氟树脂和柠康酸酐改性氟树脂中的氟树脂选自由乙烯-四氟乙烯共聚物ETFE、聚偏二氟乙烯PVDF、乙烯-四氟乙烯-六氟丙烯共聚物EFEP、四氟乙烯-全氟(烷基乙烯基醚)-氯三氟乙烯共聚物CPT、四氟乙烯-六氟丙烯共聚物FEP和氯三氟乙烯-乙烯共聚物ECTFE组成的组中的至少一种。
2.根据权利要求1所述的制冷剂输送用软管，其中，所述最内层的厚度为0.05～0.25mm的范围。
3.根据权利要求1所述的制冷剂输送用软管，其中，所述最内层的弹性模量为600～900MPa的范围。
4.根据权利要求1所述的制冷剂输送用软管，其中，在位于与所述聚酰胺树脂层的界面的最内层外周面具有羟基。
5.根据权利要求1所述的制冷剂输送用软管，其中，所述聚酰胺树脂层包含选自由聚酰胺6、聚酰胺610和聚酰胺66组成的组中的至少一种聚酰胺树脂。
6.根据权利要求1所述的制冷剂输送用软管，其中，以所述最内层的厚度达到所述聚酰胺树脂层的厚度以上的方式构成。
7.根据权利要求1所述的制冷剂输送用软管，其中，以所述最内层的弹性模量达到所述聚酰胺树脂层的弹性模量以上的方式构成。
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JP2001050434A (ja) * 1999-08-11 2001-02-23 Yokohama Rubber Co Ltd:The 冷媒輸送用ホース
CN102686926A (zh) * 2010-10-08 2012-09-19 东海橡塑工业株式会社 制冷剂输送用软管

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