CN101983218A - 条形弹性体型件、特别是风挡刮水器片的涂层及其制备方法 - Google Patents

条形弹性体型件、特别是风挡刮水器片的涂层及其制备方法 Download PDF

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CN101983218A
CN101983218A CN2009801118440A CN200980111844A CN101983218A CN 101983218 A CN101983218 A CN 101983218A CN 2009801118440 A CN2009801118440 A CN 2009801118440A CN 200980111844 A CN200980111844 A CN 200980111844A CN 101983218 A CN101983218 A CN 101983218A
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V·杜瓦尔
Y·弗伯格
V·卡利尔
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Abstract

本发明涉及一种适于条形弹性体型件的涂层，该涂层包含嵌于聚合物基质中的固体润滑剂。本发明还涉及一种适于风挡刮水器的包含这种涂层的刮片以及一种用于制备经涂覆的条形弹性体型件的方法。该含嵌入的固体润滑剂的聚合物基质可如下制得，即通过在无聚合物粘合剂存在下聚合含固体润滑剂和低分子量的交联剂的混合物。在一个实施方例中，该基质由低分子量的交联剂即六甲氧基甲基密胺的热聚合反应制得。固体润滑剂的实例是石墨和HDPE。

Description

条形弹性体型件、特别是风挡刮水器片的涂层及其制备方法
本发明涉及一种适于条形弹性体型件的涂层，该涂层包含嵌于聚合物基质中的固体润滑剂。本发明还涉及包含该涂层的风挡刮水器的刮片以及制备按本发明涂覆过的条形弹性体型件的方法。
背景技术
风挡刮水器的刮片通常可适配于汽车挡风玻璃的轮廓，并在各种温度下保持足够的柔性。因此刮片常由弹性体型件和橡胶材料如天然橡胶或氯丁二烯制备。以外该刮片还可由如硅橡胶或聚氨酯橡胶等材料制成。
与其它材料如玻璃或塑料相比，弹性体有高的滑动摩擦系数。在风挡刮水器的刮片情况下，该风挡刮水器沿挡风玻璃水平运动所需施加的力数倍于通过与挡风玻璃接触而垂直施加在刮片型件上的压力。为减小摩擦，可为该刮片施加具有低摩擦系数的涂层。
刮片常使用于具有疏水特性的挡风玻璃上。在疏水性挡风玻璃上刮片犹如在干表面上滑动。由于该挡风玻璃的疏水性表面，在表面和刮片之间不能形成减少摩擦的水膜。适于刮片的附加涂层因此需满足滑动特性、耐磨性和无条纹刮擦的要求。
适于刮片的常用涂层含石墨或二硫化钼作为颗粒状固体润滑剂，以降低刮片在玻璃表面上的摩擦系数。石墨作为固体润滑剂的效力在很大程度上取决于其在涂层中的相对浓度。
含颗粒状石墨作为固体润滑剂的已知涂层的缺点是，由于该石墨颗粒的柔软性和所需高的相对份量而降低了在涂层中的相互粘附性。由此增加了运行中该涂层的磨损。为达到所需的低摩擦系数，涂层中的石墨份量通常调节到高于临界的颜料体积浓度。因此降低了内聚力和减小了涂层的耐久性。
使用硬质固体润滑剂来增加耐磨性会由于形成条纹和拖尾而导致较差的刮擦质量。降低石墨份量如降到低于30％会导致各石墨颗粒的表面主要由粘合剂所涂覆。由此降低了该石墨的润滑作用及增加了该涂层的摩擦系数。
US 2003/0087767 A1公开了一种在刮片边缘部分的两表面上有涂层膜的橡胶刮片，其中该涂层膜含颗粒状的固体润滑剂和粘合剂。该粘合剂在干燥或硬化后的0.5％模量为1MPa或更大，其断裂伸长为1％或更大。按该文献，该粘合剂已呈聚合物形态。为涂覆要将其溶于溶剂并涂于刮片上。需要时用硬化剂预先交联后再去除该溶剂，并形成最终涂层。但该文献未涉及该涂层的抗磨强度和该刮片的寿命。如果需使用过量有机溶剂以将粘合剂和固体润滑剂涂于刮片上，从经济角度看是不利的。再则，过量使用有机溶剂对环保也是有害的。
发明内容
本发明提供一种适于条形弹性体型件的涂层，该涂层包含嵌于聚合物基质中的固体润滑剂，并且通过在无聚合物粘合剂存在下聚合含固体润滑剂和低分子量交联剂的混合物而获得含嵌入的固体润滑剂的聚合物基质。
聚合物粘合剂意指其分子的分子量≥1000g/mol的粘合剂。不存在这种聚合物粘合剂意指不加入该粘合剂或仅加入在工艺上不可避免量的该粘合剂。例如其含量可≤0.1重量％或≤0.01重量％。
本发明中的低分子量交联剂是至少双官能团的单体化合物或低聚化合物。其分子量≤1000g/mol，优选≤500g/mol。该交联剂分子通过反应性基团可相互发生粘合。该反应性基团也可被封闭，以致在加热时才释放出并参与反应。该交联剂的聚合例如可经热、自由基或辐射诱导进行。缩聚反应和加聚反应均属聚合概念之内。聚合结束后，存在一种其中嵌有固体润滑剂的聚合物基质。该固体润滑剂宜以颗粒状态存在。其平均粒度为≥0.1μm-≤15μm。
按本发明已知，以高含量存在的软性固体润滑剂和耐磨基质的相互矛盾的要求可如此协调，即为形成基质不使用聚合物粘合剂，而代之的是将交联剂本身聚合。甚至在固体润滑剂与基质的高体积比情况下，在基质内也存在足够的内聚力以粘合固体润滑剂。同时该基质是如此坚固，以致改进了耐磨强度。通过不使用聚合物粘合剂可简化制备方法，因为无待计量加入的成分。
在该涂层的一个实施方案中，该固体润滑剂的材料选自石墨、二硫化钼、六方形氮化硼、玻璃微球、聚四氟乙烯、聚乙烯和/或聚丙烯。特别优选是天然大晶形石墨，因为由其鳞状结构提供了特别低的摩擦系数。天然大晶形石墨和高密度聚乙烯(HDPE)的组合也是优选的。
在该涂层的另一个实施方案中，低分子量交联剂选自完全烷氧基化的密胺衍生物、部分烷氧化的密胺衍生物和/或六甲氧基甲基密胺。特别优选是六甲氧基甲基密胺。该所述的交联剂也可在有利实现的工艺条件下可于无粘合剂时聚合成基质。所得基质具有所需的对固体润滑剂的粘聚性，同时具有耐磨性所需的硬度。此外，这种交联剂的优点是，需要时也可与共溶剂一起溶于水中。
在该涂层的另一个实施方案中，聚合物基质中的固体润滑剂对聚合的交联剂的相体积比为≥0.3-≤9.0。该比值也可为≥0.4-≤3.0或≥1.0-≤1.5。在该体积比下可达特别好的润滑特性且同时达到特别好的耐磨性。
此外，本发明的目的是提供一种含本发明的涂层的风挡刮水器的刮片。该刮片的基材例如可为橡胶、氯丁二烯、硅橡胶、弹性体聚氨酯或其它弹性体。本发明的涂层经干燥和硬化后的膜厚可有利地为≥1μm-≤10μm、≥2μm-≤8μm或≥4μm-≤6μm。
在风挡刮水器的刮片的一个实施方案中，在聚合的涂层上和/或在未涂覆的表面上具有另一层含固体润滑剂的层。在该层中的固体润滑剂不嵌于经交联的聚合物基质中。由于该固体润滑剂不固定，所以其可较快地或较均匀地分布在经涂覆的表面上和起初未经涂覆的表面上。可如此制得这种刮片，即首先对该刮片的双型件提供按本发明的交联涂层，然后将该型件分离成两单型件。这时该截面是在风挡刮水器运行时贴于挡风玻璃上的面。该经干燥的另一层的组成可例如为≥4重量％-≤15重量％的未交联的粘合剂、≥0.5重量％-≤4重量％的增稠剂、≥1.0重量％-≤11重量％的表面活性剂和≥80重量％-≤90重量％的石墨。
本发明还涉及一种用于制备经涂覆的条形弹性体型件的方法，该型件具有权利要求1-4之一的涂层，该方法包括下列步骤：
a)将含固体润滑剂和低分子量交联剂的混合物涂于型件上，
b)加热到≥100℃-≤200℃的温度。
在步骤a)中涂覆该弹性体型件。这特别可通过浸涂或喷涂进行。在待涂混合物中的固体润滑剂的含量例如可为≥5重量％-≤25重量％或≥9重量％-≤21重量％。可聚合的低分子量的交联剂的含量例如可为≥5重量％-≤15重量％或≥7重量％-≤10重量％。
在步骤b)中该可聚合的低分子量的交联剂热聚合。由此形成嵌入有固体润滑剂颗粒的聚合物基质。热聚合反应可进行≥3分钟-≤25分钟或≥10分钟-≤15分钟。该加热也可在≥140℃-≤160℃的温度下进行。在热聚合反应前还可有干燥步骤，以从涂层混合物中去除溶剂。
在该方法的一个实施方案中，在步骤a)的混合物中的固体润滑剂的材料选自石墨、二硫化钼、六方形氮化硼、玻璃微球、聚四氟乙烯、聚乙烯和/或聚丙烯。此外，在步骤a)的混合物中的低分子量交联剂选自完全烷氧基化的密胺衍生物、部分烷氧基化的密胺衍生物和/或六甲氧基甲基密胺。上面已说明选用这些材料的优点。
在该方法的另一个实施方案中，该步骤a)的混合物还含聚丙烯酸酯增稠剂、丁基乙二醇和水。基于环保、工艺安全性和成本原因，水是优选的主溶剂。在涂层混合物中的水的含量例如可为≥50重量％-≤90重量％或≥60重量％-≤80重量％。丁基乙二醇用作共溶剂，以便低分子交联剂如特别是六甲氧基甲基密胺可保持呈溶液状态。在涂层混合物中的丁基乙二醇的含量例如可为≥10重量％-≤20重量％或≥14重量％-≤16重量％。聚丙烯酸酯增稠剂用于调节涂层混合物的粘度，以使在非极性基底表面上可构成连续涂层。此外，由于提高的粘度该石墨颗粒较好地保持在分散体中。在涂层混合物中的增稠剂含量例如可为≥1重量％-≤5重量％或≥2重量％-≤3重量％。
在该方法的另一个实施方案中，在步骤b)中经加热后，在经聚合的涂层上和/或未经涂覆的表面上涂以一种含固体润滑剂的混合物。此外，使该经涂覆的型件在≥50℃-≤100℃的温度下干燥。这例如可在将先前经涂覆的双型件分离成两个单型件后进行。该未经涂覆的表面是截面。该温度的选择要使不发生粘合剂交联，而是仅从混合物中去除溶剂。另一合适的温度范围是≥80℃-≤90℃。由于固体润滑剂不固定，所以其可较快地或较均匀地分布在经聚合的涂层上和起初未经涂覆的截面上。
按下面的实施例进一步说明本发明。
实施例1
将含甲基化的亚氨基-密胺-氨基塑料、润滑剂石墨填料和增稠剂的水性涂层组合物涂于弹性基底上。该涂层组合物具有下列配方：
                        重量份
Cymel 303               10.0
石墨                    9.0
聚丙烯酸酯增稠剂        3.0
丁基乙二醇              14.0
去离子水                64.0
总计：                  100.0
Cymel 303是Cytec公司的六甲氧基甲基密胺的商品名。
在此实施例中，弹性基底是刮片的双型件，其由氯化橡胶混合物通过注塑而制成。该双型件经初始干燥以去除溶剂后在150℃下硬化10分钟。得到4μm厚的膜，其具有下列的石墨成分和聚合物基质成分的组成：
                             重量％    体积％
聚合的Cymel 303的固态级分    51.5      67.4
石墨的固态级分               47.3      31.0
增稠剂                       1.2       1.6
总计                         100.0     100.0
经硬化后将该双型件分离成两个单型件。对截面的检测表明截面的涂层无受损或剥落。
石墨对聚合的交联剂的体积相比为0.46。由此得到该涂层的优良的滑动特性。该石墨颗粒由聚合物基质牢固地相互粘合，由此不仅在疏水性玻璃表面上而且在亲水性的玻璃表面上均得到优良的抗磨强度。
实施例2
将含甲基化的亚氨基-密胺-氨基塑料、润滑剂石墨填料和增稠剂的水性涂层组合物涂于弹性基底上。该涂层组合物具有下列配方：
                        重量份
Cymel 303               10.0
石墨                    21.0
聚丙烯酸酯增稠剂        3.0
丁基乙二醇              14.0
去离子水                52.0
总计：                  100.0
在此实施例中，弹性基底是刮片的双型件，其由氯化橡胶混合物通过注塑而制成。该双型件经初始干燥以去除溶剂后在150℃下硬化10分钟。得到4μm厚的膜，其具有下列的石墨成分和聚合物基质成分的组成：
                             重量％      体积％
聚合的Cymel 303的固态级分    31.6        47.7
石墨的固态级分               67.7        51.2
增稠剂                       0.7    1.1
总计：                       100.0       100.0
经硬化后将该双型件分离成两个单型件。对截面的检测表明该截面的涂层无受损或剥落。
石墨对聚合的交联剂的体积相比增加到1.08。由此得到该涂层的优良的滑动特性。该石墨颗粒由聚合物基质更牢固地相互粘合，由此不仅在疏水性玻璃表面上而且在亲水性的玻璃表面上均得到优良的抗磨强度。
实施例3
将含甲基化的亚氨基-密胺-氨基塑料、润滑剂石墨填料、聚乙烯分散体和增稠剂的水性涂层组合物涂于弹性基底上。该涂层组合物具有下列配方：
                        重量份
Cymel 303               10.0
石墨                    9.0
HDPE-分散体             8.8
聚丙烯酸酯增稠剂        3.0
丁基乙二醇              15.8
去离子水                72.4
总计：                  119.0
高密度聚乙烯(HDPE)分散体的固含量为35％。
在此实施例中，弹性基底是刮片的双型件，其由氯化橡胶混合物通过注塑而制成。该双型件经初始干燥以去除溶剂后在150℃下硬化10分钟。得到4μm厚的膜，其具有下列的润滑剂成分和聚合物基质成分的组成：
                             重量％      体积％
聚合的Cymel 303的固态级分    44.3        55.6
石墨的固态级分               40.7        25.5
HDPE的固态级分               14.0        17.6
增稠剂                       1.0    1.3
总计：                       100.0       100.0
经硬化后将该双型件分离成两个单型件。对截面的检测表明该截面的涂层无受损或剥落。
润滑剂(石墨和HDPE)对聚合的交联剂的体积相比为0.78。由此得到该涂层的优良的滑动特性。该石墨颗粒由聚合物基质牢固地相互粘合，由此不仅在疏水性玻璃表面上而且在亲水性的玻璃表面上均得到优良的抗磨强度。
实施例4
将含甲基化的亚氨基-密胺-氨基塑料、润滑剂石墨-填料、聚乙烯分散体和增稠剂的水性涂层组合物涂于弹性基底上。该涂层组合物具有下列配方：
                        重量份
Cymel 303               7.0
石墨                    9.0
HDPE分散体              8.8
聚丙烯酸酯增稠剂        2.5
丁基乙二醇              15.8
去离子水                56.9
总计：                  100.0
高密度聚乙烯(HDPE)分散体的固含量为35％。
在此实施例中，弹性基底是刮片的双型件，其由氯化橡胶混合物通过注塑而制成。该双型件经初始干燥以去除溶剂后在150℃下硬化10分钟。得到4μm厚的膜，其具有下列的润滑剂成分和聚合物基质成分的组成：
                             重量％      体积％
聚合的Cymel 303的固态级分    35.9        46.9
石墨的固态级分               47.0        30.8
HDPE的固态级分               16.1        21.0
增稠剂                       1.0         1.3
总计：                       100.0       100.0
经硬化后将该双型件分离成两个单型件。对截面的检测表明该截面的涂层无受损或剥落。
润滑剂(石墨和HDPE)对聚合的交联剂的体积相比增加到1.10。由此得到该涂层的优良的滑动特性。该石墨颗粒仍由聚合物基质牢固地相互粘合，由此不仅在疏水性玻璃表面上而且在亲水性的玻璃表面上均得到优良的抗磨强度。
实施例5
实施例1的涂层经涂覆和硬化。该双型件经切割和分离成单型件后，在单型件上喷涂石墨分散体。该首先涂覆的含石墨的经聚合的涂层现作为基层。该石墨分散体在90℃下经干燥，以去除水性溶剂。得到未交联的盖层，该盖层不仅覆盖该单型件的基层也覆盖其截面。经干燥后的盖层含4.6重量％的聚合物粘合剂、3.4重量％的增稠剂、10.2重量％的表面活性剂和81.8重量％的石墨。
该双涂层的刮片在疏水性的汽车挡风玻璃上测试30分钟。在玻璃上喷水，以模拟下雨。在测试中所记录的振幅保持为小于8mm的恒定的低水平。该刮片在挡风玻璃上安静并无燥声运行。该刮片的质量保持优异。

Claims (10)

1.用于条形弹性体型件的涂层，该涂层包含嵌于聚合物基质中的固体润滑剂，其特征在于，通过在无聚合物粘合剂存在的情况下聚合含固体润滑剂和低分子量交联剂的混合物而获得所述含嵌入的固体润滑剂的聚合物基质。
2.权利要求1的涂层，其中固体润滑剂的材料选自石墨、二硫化钼、六方形氮化硼、玻璃微球、聚四氟乙烯、聚乙烯和/或聚丙烯。
3.权利要求1或2的涂层，其中低分子量交联剂选自完全烷氧基化的密胺衍生物、部分烷氧基化的密胺衍生物和/或六甲氧基甲基密胺。
4.权利要求1-3之一的涂层，其中聚合物基质中的固体润滑剂对聚合的交联剂的相体积比为≥0.3至≤9.0。
5.用于风挡刮水器的刮片，其包含权利要求1-4之一的涂层。
6.权利要求5的用于风挡刮水器的刮片，其中在聚合的涂层上和/或在未涂覆的表面上具有另一层含固体润滑剂的层，在该层中的固体润滑剂未嵌于经交联的聚合物基质中。
7.用于制备经涂覆的条形弹性体型件的方法，其中该型件具有权利要求1-4之一的涂层，该方法包括下列步骤：
a)将含固体润滑剂和低分子量交联剂的混合物涂于型件上，
b)加热到≥100℃至≤200℃的温度。
8.权利要求7的方法，其中在步骤a)的混合物中的固体润滑剂的材料选自石墨、二硫化钼、六方形氮化硼、玻璃微球、聚四氟乙烯、聚乙烯和/或聚丙烯，此外，在步骤a)的混合物中的低分子量交联剂选自完全烷氧基化的密胺衍生物、部分烷氧基化的密胺衍生物和/或六甲氧基甲基密胺。
9.权利要求7或8的方法，其中步骤a)的混合物还含聚丙烯酸酯增调剂、丁基乙二醇和水。
10.权利要求7-9之一的方法，其中在步骤b)中经加热后，在经聚合的涂层上和/或未经涂覆的表面上还涂以一种含固体润滑剂的混合物，其中该经涂覆的型件在≥50℃至≤100℃的温度下经干燥。
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CN111356753B (zh) * 2017-11-14 2022-05-17 株式会社丰田自动织机 滑动构件及其制造方法

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EP2271704A1 (de) 2011-01-12
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US8575078B2 (en) 2013-11-05
DE102008000928A1 (de) 2009-10-08
RU2497845C2 (ru) 2013-11-10
CN101983218B (zh) 2013-11-13
KR101623763B1 (ko) 2016-05-24
JP2011516645A (ja) 2011-05-26
JP5431450B2 (ja) 2014-03-05
KR20100133401A (ko) 2010-12-21
RU2010144616A (ru) 2012-05-10
EP2271704B1 (de) 2016-04-13
WO2009121651A1 (de) 2009-10-08

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