CN111093965A - 多层柔性软管 - Google Patents

多层柔性软管 Download PDF

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Publication number
CN111093965A
CN111093965A CN201880058592.9A CN201880058592A CN111093965A CN 111093965 A CN111093965 A CN 111093965A CN 201880058592 A CN201880058592 A CN 201880058592A CN 111093965 A CN111093965 A CN 111093965A
Authority
CN
China
Prior art keywords
layer
hose
flexible hose
zinc
adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201880058592.9A
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English (en)
Inventor
迈克尔·图姆
马丁·西内莫斯
拉尔斯·德林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ContiTech Schlauch GmbH
Original Assignee
ContiTech Schlauch GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ContiTech Schlauch GmbH filed Critical ContiTech Schlauch GmbH
Publication of CN111093965A publication Critical patent/CN111093965A/zh
Pending legal-status Critical Current

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Classifications

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    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/10—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements not embedded in the wall
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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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Abstract

本发明涉及一种多层柔性软管、尤其是多层柔性制动软管。该软管具有以下层结构：‑基于至少一种弹性体的单层或多层的外层、以及‑至少一个单层或多层的织物强度构件层、以及至少一个单层或多层的织物粘合剂层，其中，该粘合剂层包含至少一种丙烯酸锌(II)盐和/或至少一种甲基丙烯酸锌(II)盐和/或至少一种单甲基丙烯酸锌(II)盐作为粘合剂，以及基于至少一种弹性体的单层或多层的内层。

Description

多层柔性软管
技术领域
本发明涉及一种多层柔性软管、尤其是多层柔性制动软管。
背景技术
制动软管用于机动车辆的制动系统中，以便藉由制动踏板产生静态的制动流体柱，该制动流体柱旨在将压力无损耗地传递至车轮制动缸。脚所消耗的力在制动软管或制动管线中传递是无摩擦且无损耗的。为了弥合从车身到车轮(即制动缸)的间隙，需要柔性的过渡，以便在压缩和回弹之间建立平衡。为此，通常安装柔性制动软管，柔性制动软管具有至少一个强度构件层和基于至少一种橡胶混合物的至少一个层。与刚性制动管线相比，柔性制动管线是可伸长的，并且这种特性随更迭的环境条件而改变。柔性制动软管体积方面的变化是藉由踏板行程来平衡，这导致压力点不断改变。
因为温度、体积和压力值不断变化，软管必须在其整个寿命上具有用于各个层粘附的限定的最小值。只有这样，才可以确保制动软管完美且安全地起作用。通常使用特定的粘合体系来使各个层彼此粘附。
所使用的粘合体系通常是间苯二酚-甲醛体系，该间苯二酚-甲醛体系因此构成了橡胶加工工业的当前现有技术。弹性体混合物中的间苯二酚-甲醛粘合体系通常也称为RFS(间苯二酚-甲醛-二氧化硅)，并且水性聚合物分散体通常称为RFL(间苯二酚-甲醛-胶乳)。
尤其是间苯二酚-甲醛体系(RF体系)与EPDM弹性体之间的粘附最多只能视为平均水平。相比之下，EPM弹性体与RF体系之间根本不会发生粘合。
粘合体系的间苯二酚和甲醛组分被分类为对环境和健康有害。因此，在未来几年，这两种物质的使用可能会受到显著地限制和/或与严格的规章相关联。
发明内容
因此，本发明的目的是提供一种多层柔性软管、尤其是多层柔性制动软管，该制动软管以改善的各层的粘附为特征，尤其是强度构件层与基于至少一种弹性体的层之间的粘附，并且该制动软管符合适用测试标准的要求。
此目的实现在于该多层柔性软管具有至少以下层：
-基于至少一种弹性体的单层(einlagige)或多层(mehrlagige)的外层，以及
-至少一个单层或多层的织物强度构件层，以及
-至少一个单层或多层的织物粘合剂层，其中，该粘合剂层包含至少一种丙烯酸锌(II)盐和/或至少一种甲基丙烯酸锌(II)盐和/或至少一种单甲基丙烯酸锌(II)盐作为粘合剂，以及
-基于至少一种弹性体的单层或多层的内层。
已经发现，包含所提及的至少一种酸锌(II)盐的粘合剂层明显改善了层之间的粘附，并且满足了动态性能的要求。
在优选的实施例中，因此可以部分或全部省去在粘合剂层中RF体系的使用。粘合剂层中RF体系的量更优选为0phr。
关于外层和内层的定量和/或定性成分，该外层和内层可以彼此相同或不同。它们可以各自为单层或多层的形式。
为了实现最大可能的柔性，这两个层基于至少一种弹性体和其他混合物成分进行构造。弹性体可以包括可以单独或组合使用的橡胶和/或热塑性弹性体。
特别地应提及以下橡胶组分：乙烯-丙烯共聚物(EPM)、乙烯-丙烯-二烯单体共聚物(EPDM)、丁腈橡胶(NBR)、(部分)氢化的丁腈橡胶(HNBR)、氟橡胶(FPM或FKM)、氯丁橡胶(CR)、天然橡胶(NR)、苯乙烯-丁二烯橡胶(SBR)、异戊二烯橡胶(IR)、丁基橡胶(IIR)、溴化丁基橡胶(BIIR)、氯化丁基橡胶(CIIR)、丁二烯橡胶(BR)、氯化聚乙烯(CM)、氯磺化聚乙烯(CSM)、聚环氧氯丙烷(ECO)、乙烯-乙酸乙烯酯橡胶(EVA)、丙烯酸酯橡胶(ACM)、硅酮橡胶(MVQ)、氟化的甲基硅酮橡胶(MFQ)、全氟橡胶(FFPM或FFKM)、聚氨酯(PU)。特别重要的是EPM或EPDM，因为它们相对于制动流体具有特别好的稳定性。
这些混合物成分包括至少一种交联剂或一种交联剂体系。
其他附加的混合物成分通常是一种填充剂和/或加工助剂和/或增塑剂和/或老化稳定剂，还以及可选的其他添加剂(例如，纤维、颜料)。这里也参考橡胶混合技术的一般现有技术。
强度构件层可以是单层或多层的形式。用于织物强度构件层的材料可以是本领域中已知的任何合适的材料，其优选地选自下组，该组由以下组成：聚酰胺(PA)、例如PA6、PA6.6、PA11、PA12、PA6.10、PA6.12、和/或共聚酰胺和/或聚酯(PES)和/或人造丝和/或聚乙烯对苯二甲酸乙二醇酯(PET)和/或聚萘二甲酸乙二醇酯(PEN)和/或聚对苯二甲酸丁二醇酯(PBT)和/或聚碳酸酯(PC)和/或不饱和聚酯树脂(UP)和/或聚(1,4-环己烷二亚甲基对苯二酸酯)(PCDT)和/或棉和/或人造短纤维和/或聚乙烯醇(PVAL)和/或聚氧苯并萘甲酸酯和/或聚乙烯醇缩醛(PVA)和/或聚醚醚酮(PEEK)和/或聚-2,6-萘二甲酸乙二醇酯(PEN)和/或聚亚苯基和/或聚苯醚(PPO)和/或聚苯硫醚(PPS)和/或聚苯醚和/或聚苯并恶唑(PBO)和/或聚恶二唑(POD)和/或聚醚酰亚胺(PEI)和/或间芳族聚酰胺和/或对芳族聚酰胺和/或玻璃和/或玄武岩和/或金属和/或碳和/或陶瓷和/或碳和/或羊毛和/或棉和/或聚丙烯和/或三聚氰胺和/或改性黏胶纤维和/或石材和/或高结晶聚合物纤维和/或含氟聚合物，例如氟硅酮、聚四氟乙烯(PTFE)和全氟乙烯丙烯(FEP)、和/或含氟共聚物，例如聚(偏二氟乙烯-共六氟丙烯)(VDF/HFP)、聚(偏二氟乙烯-共六氟丙烯-共四氟乙烯)(TFB)、聚(偏二氟乙烯-共四氟乙烯-共全氟甲基乙烯基醚)(VDF/TFE/PMVE)、聚(四氟乙烯-共丙烯)(TFE/P)和聚(偏二氟乙烯-共氯三氟乙烯共聚物)(VDF/CTFE)。
此处，用于强度构件层的材料可以单独使用或组合使用，这意味着所谓的混合系统也是可能的。
尤其对于制动软管，优选单独或组合使用具有特别好的动态性能并且同时展现出小的体积增加的材料，例如PVAL或人造丝或PES或芳族聚酰胺。
此处的织物强度构件层可以用至少一种粘附促进剂，例如粘附促进浸入进行改性。然而，在本发明的上下文中，优选的是，当织物强度构件层没有任何粘附促进的改性，尤其是没有RF体系时，这意味着在织物强度构件层中的粘附促进剂、尤其是RF体系的量为0phr。
强度构件层可以是编织物、环形针织物、辫状物或拉环针织物。
对于本发明重要的是，该软管包含至少一个单层或多层的织物粘合剂层，其中该粘合剂层包含至少一种丙烯酸锌(II)盐和/或至少一种甲基丙烯酸锌(II)盐和/或至少一种单甲基丙烯酸锌(II)盐作为粘附促进剂。
所提及的可以单独或组合使用的粘附促进剂的总量优选为10phr至100phr、更优选为20phr至80phr、最优选为20phr至50phr。
就其定性和/或定量组成而言，粘合剂层的成分优选是相同的，尤其关于橡胶、填充剂和交联剂的类型和量，除了所提及的粘附促进剂和过氧化物交联所需的助剂。这进一步降低了软管生产期间的复杂性。
粘合剂层优选包含至少一种过氧化物作为硫化剂。
尤其借助于所提及的粘合剂和过氧化物的组合，实现了与织物强度构件结合的附加丙烯酸酯-聚合物网络。该网络以及刚性的共价键也具有柔性的离子键，并且因此保证了软管的动态性能。
过氧化物的总量优选为3phr至7phr、更优选为3phr至6phr、最优选为4phr至5phr。
在优选的实施例中，粘合剂层还包含至少一种填充剂。这可以是技术人员已知的任何填充剂，例如，炭黑、石墨、碳纳米管(CNT)、二氧化硅、硅酸钙和硅酸铝、硅藻土、高岭土、石灰石、沸石、环糊精、长石和/或滑石粉、白垩、氧化铝凝胶、纤维(短纤维和长纤维、玻璃、碳或芳族聚酰胺纤维)、晶须(氧化铝、碳化硅)、云母、磁铁矿、氧化锌、芯/壳填充剂、沥青、硬橡胶粉尘、氯化物、碳酸盐、硫酸盐、碱金属和碱土金属的氧化物和氢氧化物、Al(OH)3、PVC、聚合物粉末(例如PE或PTFE粉末)、油膏、无机和有机颜料、有机或无机酸、玻璃珠、锯屑、坚果壳粉，其中的每一种都可以单独使用或组合使用。令人惊讶地发现，白垩的使用引起粘附改善，并且在此同时可以部分或全部省去溶剂的使用。
粘合剂混合物可以在软管的生产过程中应用为挤出层或共挤出层、应用为压延片或以橡胶溶液的形式应用。
软管还可以附加地包含至少一个另外的中间层，优选地基于至少一种橡胶。
该软管优选地可以是制动软管、离合器软管、冷却水软管、输送软管、加油软管、化学软管、可加热的软管、饮用水软管、食品软管、歧管软管、燃料软管、离岸和海洋软管、燃料舱软管、空调软管或油漆喷涂软管。
具体实施方式
现在参考在表1a和表1b中汇总的对比实例和工作实例对本发明进行详细地阐述。
表1a示出了在实验室规模下使用具有二丙烯酸锌(ZDA)的浓度系列的T测试的性能。
在此，在各自情况下将基于EPDM橡胶并且具有不同量的ZDA的粘合剂层施加到由PVAL制成的织物强度构件上。在此，织物强度构件在一种情况下配备有RF体系浸入，而在一种情况下不包含RF体系浸入。
根据ASTM D2229的所谓的T测试是织物强度构件插入物与橡胶混合物之间的粘附测试。T测试确定静态粘附。在该测试中，将待测试的细丝放置到橡胶基质中，然后该橡胶基质在压力和温度的影响下发生硫化。测量以90°角将细丝从橡胶中拉出所需的力，并且通常以牛顿为单位报告，其中根据细丝厚度的硫化块的宽度为5mm或10mm。
所列出的值已被标准化为不将ZDA施加至具有RF浸入的PVAL强度构件的粘合剂层。因此，大于100％的值表示改善的粘附。
表1b示出了从PVAL的强度构件层与软管中的粘合剂层之间的撕裂传播阻力[N/mm]确定的分离力，该软管所具有的外层和内层各自由基于120℃热老化后的EPDM的橡胶混合物制成。此处，一行中的值被标准化为新制成的分离力。
Figure BDA0002405637490000061
表1a
Figure BDA0002405637490000062
表2b。

Claims (5)

1.一种多层柔性软管，其特征在于，该多层柔性软管至少具有以下层结构：
-基于至少一种弹性体的单层或多层的外层，以及
一至少一个单层或多层的织物强度构件层，以及
-至少一个单层或多层的织物粘合剂层，其中，该粘合剂层包含至少一种丙烯酸锌(II)盐和/或至少一种甲基丙烯酸锌(II)盐和/或至少一种单甲基丙烯酸锌(II)盐作为粘合剂，以及
-基于至少一种弹性体的单层或多层的内层。
2.如权利要求1所述的多层柔性软管，其特征在于，该外层基于至少一种EPM或EPDM橡胶。
3.如权利要求1或2所述的多层柔性软管，其特征在于，该内层基于至少一种EPM或EPDM橡胶。
4.如权利要求1至3中任一项所述的多层柔性软管，其特征在于，该单层或多层的织物强度构件层由人造丝、PVAL、芳族聚酰胺、聚酰胺或所提及材料的混合变体组成。
5.如权利要求1至4中任一项所述的多层柔性软管，其特征在于，该多层柔性软管为制动软管。
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DE102017215964A1 (de) 2019-03-14
US10969039B2 (en) 2021-04-06

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