CN103930533B - 包含三唑和噻二唑的制动液组合物 - Google Patents

包含三唑和噻二唑的制动液组合物 Download PDF

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CN103930533B
CN103930533B CN201280054041.8A CN201280054041A CN103930533B CN 103930533 B CN103930533 B CN 103930533B CN 201280054041 A CN201280054041 A CN 201280054041A CN 103930533 B CN103930533 B CN 103930533B
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braking fluid
weight
glycol
triazole
thiadiazoles
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CN103930533A (zh
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朴载润
赵昌烈
李洪基
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KD Fine Chemicals Co.,Ltd.
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Kukdong Jeyen Co Ltd
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Abstract

本发明涉及一种制动液组合物，包含：作为溶剂的甘醇化合物；作为金属防腐剂的三唑与噻二唑的混合物；以及抗氧化剂。本发明提供长期金属防腐性能及高温防腐性能提高的制动液组合物。本发明的制动液组合物的防腐性能优秀，试验片的重量变化量减少而大大改善长期耐久性，对于平衡回流沸点及湿平衡回流沸点的影响极其小，对于高温的防腐性能却很优秀。

Description

包含三唑和噻二唑的制动液组合物
技术领域
本发明涉及制动液组合物。
背景技术
本发明涉及使用于汽车系统制动装置中的汽车用制动液组合物，上述制动液组合物包含溶剂、金属防腐剂及抗氧化剂。更详细地涉及如下的制动液组合物，包含：作为溶剂的甘醇化合物；作为防腐剂的三唑与噻二唑；抗氧化剂；以及稳定剂，由此能够提高防腐性能。
制动液起到将主缸中发生的压力正确传达到轮缸的重要的作用。若在此过程中发生问题，则导致制动响应性恶化的结果。这种制动液与化学及物理性质相关，需要几种重要条件。其中，第一为高的平衡回流沸点(EquilibriumRefluxBoilingPoint，ERBP)。制动液本身是难以沸腾的液体，但制动时发生高温而根据特定情况会发生沸腾。若发生沸腾，则主缸的压力不能正确传达，且不能期待稳定的制动力。并且，在制动系统中使用频繁的盘式制动时发生的摩擦热的温度为约800℃。这种高热传达的制动液因热量被氧化而致使防腐性能下降，可成为安全事故的原因。第二为高的湿平衡回流沸点(WetEquilibriumRefluxBoilingPoint)。制动液为有吸湿性的液体，需要低的吸湿性，但吸收一定程度的水分时也不使沸点下降，其为重要。因为吸收大气中的水分而沸点下降，则因发生气阻现象(vaporlock)而会引起安全事故。并且，在广泛的温度范围内的粘度的变化量也应小。并且，制动液中添加金属防腐剂及氧化稳定剂等，以防止制动装置内的各种金属的腐蚀而使其具有耐久性。
就通常使用的制动液而言，只使用甘醇醚化合物作为溶剂，或主要使用在溶剂中添加约30～50重量％的硼酯化合物的类型。就只使用甘醇醚化合物的制动液而言，长时间使用时吸收大气中的水分而使湿沸点(wetboilingpoint)下降，导致气阻现象(vaporlock)，由此存在引起无法制动的事故的危险，且存在金属防腐性能弱的缺点。并且，就添加约30～50重量％的硼酯化合物的类型的制动液而言，由于使用硼酯化合物而使平衡回流沸点和湿沸点上升，因此安全度高于只使用甘醇醚化合物的类型。然而，吸收水分时，因硼酯化合物的水解而析出硼酸，由此存在腐蚀金属部件的缺点。借助防腐添加剂及抗氧化剂，来防止金属及非铁金属受到这种制动液引起的腐蚀。
发明内容
要解决的问题
本发明人为了解决上述以往技术的问题而努力研究的结果确认到，本发明提供如下的汽车用制动液的组合物，以往的制动液组合物中包含三唑及噻二唑的情况下，与以往制动液相比，呈现长期金属防腐性能、高温金属防腐性能及减少的重量变化量，由此完成了本发明。
因此，本发明的目的在于提供制动液组合物。
借助以下发明的详细说明及保护范围，本发明的其他目的及优点将会更加明确。
解决问题的手段
根据本发明的技术方案，本发明提供制动液组合物，包含：作为溶剂的甘醇化合物；作为防腐剂的三唑与噻二唑的混合物；以及抗氧化剂。
本发明人为了解决上述以往技术的问题而努力研究的结果确认到，本发明能够提供如下的汽车用制动液的组合物，以往的制动液组合物中包含三唑及噻二唑的情况下，与以往制动液相比，呈现长期金属防腐性能、高温金属防腐性能及减少的重量变化量，由此完成了本发明。
在本说明书中，术语“制动液”为使用于汽车(运输用车辆)系统制动装置的汽车的油压制动用非石油类液体，是为了将在主缸中发生的压力正确传达到轮缸而使用的液相物质。
在本发明的组合物中，溶剂包含本发明所属领域中公知的任何甘醇(glycol)化合物。优选地，上述甘醇化合物选自包含乙二醇(ethyleneglycol)、二乙二醇(diethyleneglycol)、三乙二醇(triethyleneglycol)、甲二醇(methyleneglycol)、二甲二醇(dimethyleneglycol)、三甲二醇(trimethyleneglycol)、丙二醇(propyleneglycol)、二丙二醇(dipropyleneglycol)、丁二醇(butyleneglycol)、聚亚烷基二醇(polyalkyleneglycol)、甘醇醚(glycolether)以及它们的混合物的组。更优选地，适用于本发明的组合物的甘醇化合物为乙二醇、二乙二醇、丙二醇、二丙二醇、聚亚烷基二醇或甘醇醚。
在本发明的组合物中，作为上述甘醇醚(glycolether)可利用本发明所属领域中公知的所有物质，但优选地，选自包含乙二醇乙醚(ethyleneglycolether)、二乙二醇乙醚(diethyleneglycolether)、三乙二醇乙醚(triethyleneglycolether)、乙二醇甲醚(ethyleneglycolmethylether)、二乙二醇甲醚(diethyleneglycolmethylether)、三乙二醇甲醚(triethyleneglycolmethylether)、聚乙二醇甲醚(polyethyleneglycolmethylether)、乙二醇丁醚(ethyleneglycolbutylether)、二乙二醇丁醚(diethyleneglycolbutylether)、三乙二醇丁醚(triethyleneglycolbutylether)、聚乙二醇丁醚(polyethyleneglycolbutylether)、二丙二醇甲醚(dipropyleneglycolmethylether)、聚丙二醇甲醚(polypropyleneglycolmethylether)以及它们的混合物的组。更优选地，适用于本发明的组合物的甘醇醚为乙二醇甲醚、二乙二醇甲醚、三乙二醇甲醚、聚乙二醇甲醚、乙二醇丁醚、二乙二醇丁醚、三乙二醇丁醚或聚乙二醇丁醚，最优选为三乙二醇单甲醚(triethyleneglycolmonoether)、聚乙二醇单甲醚(polyethyleneglycolmonomethylether)或聚乙二醇单丁醚(polyethyleneglycolmonobutylether)。
根据本发明的最优选的实例，本发明中所利用的作为溶剂的甘醇化合物为聚亚烷基二醇、甘醇醚的混合物。
在本发明的组合物中，以组合物的总重量作为基准，作为溶剂的甘醇化合物的含量优选为20～99重量％，更优选为40～99重量％，尤其优选为60～99重量％，进而优选为70～99重量％，最优选为85-95重量％。
利用聚亚烷基二醇及甘醇醚作为溶剂的情况下，以溶剂的总重量作为基准，聚亚烷基二醇的含量优选为1.0～80重量％，更优选为1.0～70重量％，尤其优选为5.0～50重量％，进而优选为5.0～30重量％。以溶剂的总重量作为基准，甘醇醚的含量优选为20～90重量％，更优选为30～80重量％，尤其优选为50～80重量％，进而优选为70～85重量％。
根据本发明的优选实例，在本发明的组合物还包含作为溶剂的含硼化合物。优选地，上述含硼化合物选自包含硼酸(boricacid)、硼化合物、硼酸钠(sodiumborate)及硼酸钾(potassiumborate)的组。更优选为硼化合物，尤其优选为硼酯化合物。最优选为三2-[2-(2-甲氧基乙氧基)乙氧基]乙基]硼酸盐(tris[2-[2-(2-methoxyethoxy)ethoxy]ethyl]orthoborate)。
本发明的制动液组合物必须包含作为金属防腐剂的三唑与噻二唑的混合物。如在以下实施例中证明，三唑与噻二唑的混合物在长期金属防腐性能及高温金属防腐性能中呈现优秀的性能(performance)。
本发明中可利用的三唑包含本发明所属领域中公知的多种三唑(triazole)，优选地，上述三唑选自包含苯并三唑(benzotriazole)、甲苯基三唑(tolytriazole)、辛基三唑(octyltriazole)、癸基三唑(decyltriazole)、十二烷基三唑(dodecyltriazole)以及它们的混合物的组，更优选地，三唑为苯并三唑或甲苯基三唑。
本发明中可利用的噻二唑包含本发明所属领域中公知的多种噻二唑，优选地选自包含2,5-二硫基-1,3,4-噻二唑(2,5-Dimercapto-1,3,4-thiadiazole)、2-硫基-5-烃基硫代-1,3,4-噻二唑(2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazole)、2-硫基-5-烃基二硫代-1,3,4-噻二唑(2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazole)、2,5-双(烃基硫代)1,3,4-噻二唑(2,5-bis(hydrocarbylthio)-1,3,4-thiadiazole)、2,5-双(烃基二硫代)1,3,4-噻二唑(2,5-bis(hydrocarbyldithio)-1,3,4-thiadiazole)及它们的混合物的组。更优选地，噻二唑为2,5-二硫基-1,3,4-噻二唑(2,5-Dimercapto-1,3,4-thiadiazole)。
在本发明的组合物中，以组合物总重量作为基准，作为上述金属防腐剂的三唑与噻二唑的混合物的优选的含量为0.1～10重量％，更优选的含量为0.5～10重量％。作为上述金属防腐剂，三唑与噻二唑的混合物中，作为上述两种成分的三唑:噻二唑的重量比为0.1:1～1:0.1。
本发明的制动液组合物包含抗氧化剂。适合于本发明的抗氧化剂包含本发明所属领域中公知的多种抗氧化剂。根据本发明的优选的实例，本发明的制动液组合物包含选自包含二丁基羟基甲苯(dibutylhydroxytoluene)、丁基羟基茴香醚(butylhydroxyanisole)及磷酸三苯酯(triphenylphosphate)的组中的一种或一种以上的抗氧化剂。更优选地，利用为本发明的抗氧化剂为二丁基羟基甲苯。
在本发明的组合物中，以组合物总重量作为基准，抗氧化剂的优选的含量为0.1～5.0重量％，更优选的含量为0.1～5.0重量％。
包含甘醇化合物、作为金属防腐剂的三唑与噻二唑的混合物及抗氧化剂的本发明的制动液组合物中，优选地，甘醇化合物的含量为85～99重量％，防腐剂的含量为0.1～10.0重量％及抗氧化剂的含量为0.1～5.0重量％。
根据本发明的优选的实例，本发明的制动液组合物还包含作为金属防腐剂的胺化合物。优选地，上述胺选自烷基二乙醇胺(alkyldiethanolamine)(例如，甲基二乙醇胺(methyldiethanolamine))、单乙醇胺(monoethanolamine)、二乙醇胺(diethanolamine)、三乙醇胺(triethanolamine)、二环己胺(dicyclohexylamine)、吗啉(morpholin)、苯基吗啉(phenylmorpholin)、乙醇胺(ethanolamine)、二-(2-乙基己基)胺(di(2-ethylhexyl)amine)、二正丁胺(di-N-butylamine)、单戊胺(monoamylamine)、二戊胺(diamylamine)、二辛胺(dioctylamine)、水杨基单乙醇胺(salicylmonoethanolamine)及二-β-萘基-对苯二胺(di-beta-naphthyl-p-phenylenediamine)。
在本发明的组合物中，以组合物的总重量作为基准，追加胺化合物的优选含量为0.1～10重量％，更优选的含量为0.1～5.0重量％。
根据本发明的优选的实例，本发明的制动液组合物在溶剂中还包含含硼化合物。更优选地，上述含硼化合物选自包含硼酸(boricacid)、硼酸钠(sodiumborate)及硼酸钾(potassiumborate)的组，尤其优选地，选自包含硼酯化合物的组。最优选为三[2-[2-(2-甲氧基乙氧基)乙氧基]乙基]硼酸盐(tris[2-[2-(2-methoxyethoxy)ethoxy]ethyl]orthoborate)。
在本发明的组合物中，以组合物的总重量作为基准，含硼化合物的含量优选为10～70重量％，更优选为10～50重量％，尤其优选为10～40重量％。
本发明的制动液组合物对于金属材质的长期金属防腐性能及对于高温的高温金属防腐性能很优秀。因此，本发明的制动液组合物的长期金属防腐性能优秀，从而提高对于金属材质的耐腐性，解决高温时制动液沸腾的问题，并且防止因这种问题而导致的周边金属部件的腐蚀，并防止因热量而导致的氧化。
效果
归纳本发明的特征及优点如下。
(a)本发明的制动液组合物，其特征在于，利用三唑与噻二唑的混合物作为金属防腐剂，并包含抗氧化剂。
(b)本发明提供长期金属防腐性能及高温防腐性能提高的制动液组合物。
(c)本发明的制动液组合物由于防腐性能优秀，且试验片的重量变化量减少而大大改善长期耐久性，对于平衡回流沸点及湿平衡回流沸点的影响极其小，对于高温的防腐性能却很优秀。
具体实施方式
以下，通过实施例对本发明进行更详细的说明。这些实施例只是用于更具体地说明本发明，根据本发明的要旨，本发明的范围不局限于这些实施例，这对于本发明所属领域普通技术人员而言是显而易见的。
实施例
制备例
制备具有如以下表1的组成成分的本发明的制动液组合物。
表1
根据表1的组成成分，分别制备实施例及比较例的制动液组合物。上述硼酯化合物为三[2-[2-(2-甲氧基乙氧基)乙氧基]乙基]硼酸盐。此时，在常温(25℃)下，将各成分搅拌及混合1小时，并利用高精度过滤方法(5μm)来进行过滤，由此制备实施例及比较例的制动液组合物。
实验例
在实验例中，对于实施例及比较例的制动液组合物(表1)进行长期金属腐蚀试验、高温金属腐蚀试验、抗氧化试验、平衡回流沸点及湿平衡回流沸点试验，来实施性能评价，其结果表示在以下表2～表5。
表2
基于组合物含量的长期金属腐蚀试验(100℃×1000hr)
为了评价对于长期耐久性的制动液的优秀性，实施如下的试验。根据KSM2141规格进行长期金属腐蚀试验，在100℃下，观察经过1000小时之后的结果。
上述测定结果如表2所示，可确认到，长期耐久腐蚀性评价结果表明，包含三唑和噻二唑的制动液的重量变化量与比较例(即，不包含三唑和噻二唑的组合的制动液)相比优秀3～16倍以上。由此可确认到三唑和噻二唑提高了制动液的金属防腐性能。
表3
基于组合物含量的高温金属腐蚀性试验(120℃×120hr)
为了评价对于高温耐久性的制动液的优秀性，实施如下的试验。根据KSM2141规格进行高温腐蚀试验，在120℃下，观察经过120小时后的结果。
上述测定结果如表3所示，可确认到，高温耐久腐蚀性评价结果表明，含有三唑和噻二唑的混合物的制动液的重量变化量，与比较例(即，不包含三唑和噻二唑的组合的制动液)相比优秀5～8倍以上。由此可确认到三唑和噻二唑提高对于高温的制动液的金属防腐性能。
表4
基于组合物含量的抗氧化性试验(23℃×70hr+70℃×168hr)
为了评价对于抗氧化性的制动液的优秀性，实施如下的试验。根据KSM21415.9的步骤实施抗氧化性试验，在23℃下进行70小时，在70℃下放置168小时后，测定金属试验片的外观及重量变化量。上述试验为在制动液中添加过氧化苯甲酰(benzoylperoxide)和橡胶来评价防腐性能的试验，与锡板相接的铝金属和铸铁金属片的外表面不应该因制动液而发生能够肉眼识别出的腐蚀。
上述测定结果如表4所示，可确认到，含有实施例的三唑和噻二唑的制动液与比较例(即，不包含三唑和噻二唑的组合的制动液)相比，对于过氧化苯甲酰的抗氧化性优秀约2～7倍以上。由此可确认到三唑和噻二唑提高制动液的抗氧化性。
表5
基于组合物含量的平衡回流沸点及湿平衡回流沸点试验
为了评价对于平衡回流沸点及湿平衡回流沸点的制动液的优秀性，实施如下的试验。根据KSM21415.1.1,5.1.4.的步骤进行平衡回流沸点及湿平衡回流沸点试验。上述测定结果如表5所示，可确认到，平衡回流沸点及湿平衡回流沸点试验结果表明，试样都表现等同水准的结果值。由此判断为平衡回流沸点和湿平衡回流沸点不受本发明的组合物添加种类的大影响。

Claims (2)

1.一种制动液组合物，其特征在于，包含：基于组合物的总重量，
(a)作为溶剂的甘醇化合物85-99重量％；
(b)作为金属防腐剂的、三唑与噻二唑的混合物0.5-10重量％和胺化合物0.1-5.0重量％；以及
(c)抗氧化剂0.1-5.0重量％，
其中，作为溶剂的甘醇化合物包含聚亚烷基二醇5.0-30重量％和甘醇醚70-85重量％，基于溶剂的总重量，
其中，甘醇醚为选自聚乙二醇单甲醚、聚乙二醇单丁醚和三乙二醇单甲醚中的一种或多种，
其中，三唑为苯并三唑或甲苯基三唑；
其中，噻二唑为2,5-二硫基-1,3,4-噻二唑；
其中，胺化合物为选自烷基二乙醇胺、环己胺和三乙醇胺中的两种；
其中，抗氧化剂为二丁基羟基甲苯。
2.根据权利要求1所述的制动液组合物，其特征在于，上述制动液组合物还包含作为溶剂的含硼化合物。
CN201280054041.8A 2011-11-04 2012-01-31 包含三唑和噻二唑的制动液组合物 Active CN103930533B (zh)

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