CN113795382A - 制冷剂软管 - Google Patents
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Abstract
本发明涉及一种制冷剂软管,该制冷剂软管至少具有以下层结构:‑内层(A),该内层用作阻挡层并且该内层由至少两个片层(A1,A2)构成,其中,至少一个片层(A1)由弹性体改性的EVOH或聚烯烃改性的EVOH或弹性体改性的EVOH和聚烯烃改性的EVOH的组合构成,以及‑至少一个加强层(B),以及‑外层(C),该外层由至少一种弹性体材料构成。
Description
技术领域
本发明涉及一种制冷剂软管,该制冷剂软管至少具有以下层结构:
-内层,该内层用作阻挡层并且由至少两个片层构成,以及
-至少一个加强层,以及
-外层,该外层由至少一种弹性体材料构成。
背景技术
安装在汽车行业空调系统中的制冷剂软管通常包含碳氟化合物作为制冷剂。当这种类型的制冷剂逸出到大气中时,会以例如酸雨、温室效应或臭氧层退化的形式对环境产生不利影响。CO2是一种更环保的制冷剂。然而,由于其分子大小以及其物理特性和化学特性,它使空调系统受到更严格的要求和需求;遵守这些要求和需求或对于这些要求和需求的解决方案尤其需要新颖的软管系统。
用于常规制冷剂的软管主要由三个不同的层组成:内部层、加强层和外部层,其中,外部层和内部层主要由弹性体材料构成,并且内部层通常被配置成由多于一个片层构成,并且另外具有整合的片层,该整合的片层由热塑性材料制成,并且该整合的片层显著改善了软管在制冷剂损失方面的阻挡特性,但同时削弱了软管的柔韧性。以下可以尤其作为用于内部层和/或外部层的弹性体使用:EPDM、EPM、BIMS、BIIR、CIIR、IIR、CM、AEM、ACM、CR、NBR、HNBR,单独或组合使用。
加强层主要由有机纤维系统(例如聚酯纱线、聚酰胺纱线、人造丝纱线、芳族聚酰胺纱线或PVOH纱线)组成,并且通常以编织或螺旋(即缠绕)形式存在。在螺旋软管的情况下,通常使用两个加强层,这两个加强层可以相同或者彼此不同。另一个弹性体层可以整合为两个缠绕纤维层之间的中间层。为了产生或优化多个不同层之间的粘附,还可以将助粘剂层添加至层结构。
内部层的热塑性片层可以在软管内部(单板软管,见图1和图2)或作为阻挡片层嵌入内部层的另外两个片层之间(阻挡软管,见图3和图4)。聚酰胺已被证明是成功的用于阻挡片层的材料。特别地,利用了冲击改性等级的PA.6,因为它们目前为空调软管的生产提供了柔韧性与阻挡功能之间的良好折衷。
因此,以上描述的软管结构为安装在有限空间中的软管提供了足够的柔韧性,同时还展现出足够好的阻挡特性以例如提供足够程度的制冷剂R134a(1,1,1,2-四氟乙烷)或R1234yf(2,3,3,3-四氟丙烯)的制冷剂损失的减少。
如上文已经提到的,所提到的软管结构必须是新设想的,用于与作为制冷剂的CO2一起使用,因为广泛使用的空调软管没有展现出相对于CO2的足够的阻挡功能。
为了优化阻挡功能,即为了进一步避免制冷剂损失,US 20040118469 A1提出了使用基于EVOH的片层,该片层相对于PA.6展现出显著更好的阻挡特性。
然而,这种类型的软管在柔韧性和暴露于动态机械负载方面存在缺点。在上述类型的软管中,由于突然负载或低温柔韧性测试期间而导致EVOH片层发生相对较快的开裂。
发明内容
因此,本发明的目的是提供一种制冷剂软管,该制冷剂软管首先具有相对于制冷剂(特别是相对于CO2)具有优化的阻挡效果的耐流体内部层的特征,并且其次具有足够的柔韧性和高的抗动态机械负载的特征。
这个目的经由至少具有以下层结构的制冷剂软管来实现:
-内层,该内层用作阻挡层并且该内层由至少两个片层构成,其中,至少一个片层由弹性体改性的EVOH或聚烯烃改性的EVOH或弹性体改性的EVOH和聚烯烃改性的EVOH的组合构成,以及
-至少一个加强层,以及
-外层,该外层由至少一种弹性体材料构成。
出人意料地,已经发现,与未改性的EVOH相比,使用特殊改性的EVOH提供了增强的柔韧性,并且与此相关联,提高了动态机械强度。
本发明中的阻挡层由至少两个片层构成,并且具有由弹性体改性的或聚烯烃改性的EVOH或两者的组合构成的至少一个片层。这个片层形成了所谓的软管的阻挡片层。此处阻挡片层(不包括用来改性的弹性体和相应地聚烯烃的含量)中存在的EVOH的乙烯含量在10%与44%之间,在此优选27%与29%之间的较小含量,以保持最大化的阻挡效果和最大化的熔点。改性的EVOH包括按重量计5%至40%的弹性体或聚烯烃或两者的组合,在此优选按重量计10%的弹性体,以首先提供足够的柔韧性并相应地对EVOH进行冲击改性,同时保持整个材料的最大化的阻挡效果。用于改性的弹性体优选为非极性弹性体,此外,该非极性弹性体针对相容性而被完全或在某种程度上改性,以便该非极性弹性体能够参与到与EVOH的均质复合物中。使用马来酸酐接枝弹性体可以实现特别好的结果。然而,也可以设想通过其他官能团对弹性体或聚烯烃进行其他改性,只要这些官能团能够参与到EVOH的键合中。
为了在足够的阻挡效果与软管刚度之间达成良好的折衷,阻挡片层的片层厚度优选在0.02mm与0.3mm之间。
阻挡层(下文中也称为内部层)还包括在所描述的阻挡片层旁边的至少一个另一个第二片层。以下材料可以用作此另一个第二片层的聚合材料:聚酰胺、聚烯烃、热塑性弹性体和其他弹性体,及其组合。除这些之外,可以尤其包括以下材料:PP、PE、PMP、TPC、PA6、PA66、PA11、PA12、PA46、PA610、PA9T、PA6T、EPM、EPDM、BR、IIR、BIIR、CIIR、BIMS。当使用聚酰胺时,优选为冲击改性聚酰胺,例如经由与马来酸酐接枝聚烯烃的反应挤出,以增强材料的柔韧性并减少暴露于机械负载(例如在突然负载或软管加强的情况下)时的开裂。
该另一个第二片层的厚度优选在0.05mm与0.5mm之间,特别优选在0.15mm与0.3mm之间。
在特别优选的实施例中,该内部层由所提到的两个片层组成,其中,形成该软管最内片层的另一个第二片层用作该阻挡片层的保护层,并且在适当选择材料的情况下,也可以对该阻挡片层的阻挡功能作出积极贡献。材料的选择可能需要对材料的相容性进行改性,以便该材料能够参与到阻挡片层的粘附中。这同样可以通过举例经由马来酸酐接枝来实现。
在另一个特别优选的实施例中,该内部层由三个片层组成,其中,形成该软管最内层的另一个第二片层用作该阻挡片层的保护层(与该内部层的双片层结构类比),并且该附加第三片层优选地由至少一种弹性体构成。以下优选地用作弹性体:EPDM、EPM、BIMS、BIIR、CIIR、IIR、CM、AEM、ACM、CR、NBR、或HNBR或这些的组合。经由添加层状硅酸盐、石墨烯或其他具有高纵横比的层状填料,可以优化附加第三片层的阻挡特性。该第三片层优选地以挤出的形式存在。
存在附加第三片层的情况下,该附加第三片层的厚度优选在0.2mm与2mm之间,特别优选在0.2mm与0.5mm之间。
本发明的软管还包括至少一个加强层和一个外层(即外部层)。
该加强层通过编织或螺旋而被施加。对于压力要求不严格的应用也可以针织。根据压力要求,以下是适合作为加强层的材料:优选地芳族聚酰胺,例如,对芳族聚酰胺或间芳族聚酰胺、聚酰胺、PET或PVOH或以混合系统形式存在的这些的组合。
本发明的外层由至少一种弹性体材料构成,该弹性体材料优选为EPDM、EPM、BIMS、BIIR、CIIR、IIR、CM、AEM、ACM、CR、NBR或HNBR,或其组合。通过添加层状硅酸盐、石墨烯或其他具有高纵横比的层状填料,可以优化外层的阻挡特性。该外层优选地以挤出的形式存在。
该外层的厚度优选在0.2mm与2mm之间,特别优选在0.7mm与1.5mm之间。
在特别优选的实施例中,该制冷剂软管还包括至少一个中间层。该中间层优选地由至少一种弹性体材料构成,该弹性体材料可以有利地为EPDM、EPM、BIMS、BIIR、CIIR、IIR、CM、AEM、ACM、CR、NBR或HNBR,或其组合。通过添加层状硅酸盐、石墨烯或其他具有高纵横比的层状填料,可以优化中间层的阻挡特性。该中间层优选地以挤出的形式存在。
该中间层的厚度优选在0.1mm与1.5mm之间,特别优选在0.2mm与0.7mm之间。
优选地,在所有层之间具有足够好的粘附性,在优选的实施例中,该粘附性是经由在这些片层之间和/或这些层之间薄的助粘剂层的整合来提供的。
该制冷剂软管的这些单独片层和/或层优选地以挤出的形式被施加在心轴上。然后对软管进行硫化或部分硫化,并将其从心轴上移除。该部分硫化的软管可以用于模制软管生产,并在成形过程中最终硫化。
具体实施方式
现在参考实验结果和图表基于工作示例对本发明进行说明。
实验结果
表1示出了基于现有技术的制冷剂软管V1和本发明的制冷剂软管E1的多个不同物理测试结果。测试结果基于DIN规范74106获得。评估“+”意味着测试通过;评估“-”意味着测试未通过。
此处的软管结构如下:
另一个第二内部片层A2:PA6(有机合金LT5050,Arkema),片层厚度为0.3mm
阻挡片层A1:弹性体改性的EVOH(Eval LA170B,Kuraray)(E1)或未改性的EVOH(Evasin 2951F,Arkema)(V1),片层厚度为0.1mm
附加第三内部片层A3:BIIR,片层厚度为1.1mm
加强层B:编织的对芳族聚酰胺,
外层C:EPM,层厚度为0.85mm至1mm
表1
本发明的制冷剂软管E1适合作为用于在空调系统的低温区域中(用于非常短期在最高130℃)使用的制冷剂软管,并且CO2作为制冷剂。本发明的制冷剂软管具有高水平的阻挡特性、耐呈压缩机油的形式的流体、良好的低温柔韧性以及相对于突然负载的良好性能的特征。具有未改性的EVOH的对比软管V1仅在短时间暴露于突然负载之后失效,并且没有展现出高的低温柔韧性。
图表
图1示出了呈现有技术的单板软管形式的制冷剂软管,该制冷剂软管具有:编织加强层B;内部层A的双片层结构,其中,内部层A的热塑性片层A1由聚酰胺组成,并且该热塑性片层作为阻挡片层形成内部层A的最内片层,并且内部层具有内部层A的另一个第二片层A2;以及外层C。
图2示出了呈现有技术的单板软管形式的制冷剂软管,该制冷剂软管具有:两个螺旋加强层B1、B2;内部层A的双片层结构,其中,内部层A的热塑性片层A1由聚酰胺组成,并且该热塑性片层作为阻挡片层形成内部层A的最内片层,并且内部层具有内部层A的另一个第二层A2;附加的弹性体中间层D;以及外层C。
图3示出了呈现有技术的阻挡软管形式的制冷剂软管,该制冷剂软管具有:编织加强层B;内部层A的三片层结构,其中,由聚酰胺制成的内部层的热塑性片层A1作为阻挡片层被嵌入在内部层A的另外两个片层A2、A3之间,并且内部层具有内部层A的另一个第二层A2、内部层A的附加第三层A3;以及外层C。
图4示出了呈现有技术的阻挡软管形式的制冷剂软管,该制冷剂软管具有:两个螺旋加强层B1、B2;内部层A的三片层结构,其中,由聚酰胺制成的内部层A的热塑性片层A1作为阻挡片层被嵌入在内部层A的另外两个片层A2、A3之间,并且内部层具有内部层A的另一个第二片层A2、内部层A的附加第三片层A3;附加的弹性体中间层D;以及外层C。
图5示出了本发明的制冷剂软管,该制冷剂软管具有:编织或针织加强层B;内部层A的三片层结构,其中,由弹性体改性的EVOH或聚烯烃改性的EVOH制成的内部层A的阻挡片层A1被嵌入在内部层A的另外两个片层A2、A3之间,并且内部层具有内部层A的另一个第二片层A2、内部层A的附加第三片层A3;以及外层C。内部层A的另外两个片层A2、A3的材料不同于阻挡片层A1的材料。
图6示出了本发明的制冷剂软管,该制冷剂软管具有:两个螺旋加强层B1、B2;内部层A的三片层结构,其中,由弹性体改性的EVOH或聚烯烃改性的EVOH制成的内部层A的阻挡片层A1被嵌入在内部层A的另外两个片层A2、A3之间,并且内部层具有内部层A的另一个第二片层A2、内部层A的附加第三片层A3;附加中间层D;以及外层C。内部层A的另外两个片层A2、A3的材料不同于阻挡片层的材料。
附图标记清单
(说明书的一部分)
A 内部层
A1 内部层的阻挡片层
A2 内部层的另一个第二片层
A3 内部层的附加第三片层
B 单一加强层
B1 第一加强层
B2 第二加强层
D 弹性体中间层
C 外层
Claims (6)
1.一种制冷剂软管,该制冷剂软管至少具有以下层结构:
-内层(A),该内层用作阻挡层并且该内层由至少两个片层(A1,A2)构成,其中,至少一个片层(A1)由弹性体改性的EVOH或聚烯烃改性的EVOH或弹性体改性的EVOH和聚烯烃改性的EVOH的组合构成,以及
-至少一个加强层(B),以及
-外层(C),该外层由至少一种弹性体材料构成。
2.如权利要求1所述的制冷剂软管,其特征在于,该内层(A)由两个层(A1,A2)组成。
3.如权利要求1所述的制冷剂软管,其特征在于,该内层(A)由三个层(A1,A2,A3)组成。
4.如权利要求1至3中任一项所述的制冷剂软管,其特征在于,该改性的EVOH中存在的EVOH中的乙烯含量在10mol%与44mol%之间。
5.如权利要求1至4中任一项所述的制冷剂软管,其特征在于,该改性的EVOH中的弹性体含量包括相容弹性体或完全由该相容弹性体组成。
6.如权利要求5所述的制冷剂软管,其特征在于,该相容弹性体是非极性弹性体。
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DE102019203254.0A DE102019203254A1 (de) | 2019-03-11 | 2019-03-11 | Kältemittelschlauch |
PCT/EP2020/051843 WO2020182360A1 (de) | 2019-03-11 | 2020-01-27 | Kältemittelschlauch |
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WO2020182360A1 (de) | 2020-09-17 |
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