CN105128823A - 条形型件和涂覆条形型件的方法 - Google Patents
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Abstract
本发明涉及条形型件和涂覆条形型件的方法。具体地，本发明涉及一种用于刮水片、特别是挡风玻璃刮水器的刮水片的条形型件，其具有由弹性材料制成的基底，且至少部分涂有降低摩擦的涂层。该涂层包括2层，其中直接涂于基底上的基层是耐磨涂层，涂于基层上的覆盖层是降低摩擦的。本发明还涉及一种用于涂覆条形型件的方法，该方法的第一步中，在型件上涂覆覆基层，在第二步中涂覆覆盖层，该基层含0－45重量%的干性润滑物质，该覆盖层含60－100重量%的干性润滑物质。在覆盖层中的干性润滑物质的份量比基层中的高。
Description
本专利申请为中国专利申请号为200880111954.2的分案申请。
技术领域
本发明涉及一种由弹性材料制成的适用于刮水片的条形型件。本发明还涉及涂覆该条形型件的方法。
背景技术
由弹性材料制成的条形型件（Strangförmige
Profile）例如用于刮水片，特别是用作挡风玻璃刮水器的刮水片。这时重要的是用作刮水片的条形型件能尽可能好地适配于汽车玻璃的外形，并且在不同温度下还要保持柔韧性。因此该刮水片通常由弹性型件制成，其中主要使用橡胶材料如天然橡胶或氯丁二烯橡胶。此外，也已知由硅橡胶或聚氨酯橡胶制成的刮水片。
但与如玻璃或塑料等材料相比，弹性体具有高的滑动摩擦系数，以致在玻璃板表面上的呈挡风玻璃刮水片形式的弹性型件的垂直固定支承力情况下，对水平移动常需耗费数倍的该支承力。如果该挡风玻璃刮水器在湿的情况下运行，则基本上不会有问题，因为通过玻璃板上的水膜在挡风玻璃刮水片和玻璃板之间形成了润滑膜，以致产生水力润滑。但如果该挡风玻璃刮水片在无水作为润滑膜时运行，如在夏天或短时间的阵雨后运行，则就会有问题。在这种条件下挡风玻璃很快变干，由此大大增加了摩擦系数。这可导致刺耳声音、颤动或甚至使挡风玻璃刮水器停运。
为降低挡风玻璃刮水片对干燥的玻璃板的摩擦系数，常对挡风玻璃刮水片的表面进行氯化处理或溴化处理，即硬化该挡风玻璃刮水片。但这需要精确的工序，并对环保也会产生问题。此外，由于这种处理方法对刮水质量会产生不利影响。
另外也已知，在挡风玻璃刮水片上施加可降低滑动摩擦系数的涂层。
例如从DE-A 10116929已知一种润滑漆成分和一种用于涂覆挡风玻璃刮水片的弹性体的润滑漆。该润滑漆成分含聚氨酯、硅氧烷以及聚酰胺粉末、聚乙烯粉末或聚酰胺溶液。该所建议的润滑漆起硬机械隔片的作用，该隔片凸出于所涂覆的表面，其缺点在于由此对刮水质量产生不利影响，特别是由于在刮水时产生浑浊和形成条纹。此外，在润滑漆中所含的填料也易于从涂层中分离，因为这些填料仅不良粘附，并且该涂层结构也显示出低的结合低粘结力。
由DE-A 10132026也已知一种用于橡胶刮水片的涂层剂。给该橡胶刮水片提供涂层膜，该涂层膜含颗粒状的固体润滑剂和粘合剂。该粘合剂的0.5%模量为1 MPa或更大，其断裂伸长率为1%或更大。但该弹性模量仅与涂层有关，与由聚合物粘合剂和石墨构成的复合材料的粘结强度无关，并因此与耐磨性无关。
发明内容
本发明的优点
由本发明构成的用于刮水片，特别是挡风玻璃刮水器的刮水片的条形型件，其具有由弹性材料制成的基底，且至少部分具有降低摩擦的涂层。按本发明该涂层包括2层，直接涂于基底上的基层是耐磨涂层，涂于基层上的覆盖层是降低摩擦的。
在汽车中，大多使用具有疏水表面的挡风玻璃板。在挡风玻璃刮水器在疏水表面上运行时，其表现犹如在干表面上滑动。由于挡风玻璃板的斥水特性，在挡风玻璃板表面和挡风玻璃刮水器的刮水片之间不能形成润滑的水膜。通过本发明的涂层不仅改进了滑动特性，而且增加了耐磨性。该挡风玻璃板可无条纹和无浑浊地刮水。
在一个优选实施方案中，该降低摩擦的覆盖层含干性润滑物质。适合用作干性润滑物质的例如是石墨、聚四氟乙烯、聚丙烯、聚乙烯、二硫化钼或这些物质中至少两种的混合物。干性润滑物质的效力主要与其在涂层中的相对浓度有关。该干性润滑物质的含量越高，则摩擦系数越低。但较高含量的干性润滑物质同时又会导致粘结强度下降和由此降低涂层的耐磨性。通过本发明的含两层的涂层的解决方案，除降低摩擦系数外还可同时实现提高耐磨性。通过降低摩擦的覆盖层可将条形型件用于在疏水玻璃板上工作的挡风玻璃刮水器的刮水片。
该干性润滑物质的粒度优选为0.1－15 µm，尤其是0.1－5 µm。
为降低摩损，如果该涂层优良地粘附在条形型件的弹性材料上是特别有利的。低摩擦系数可通过含较大份量的干性润滑物质的上层即覆盖层实现。同时为增加耐磨性，需要使直接施涂在条形型件上的第一涂层即基层比覆盖层具有明显更高的耐磨性。
为使刮水片在玻璃板上有足够低的摩擦系数，在覆盖层中的干性润滑物质的份量优选为该层的60－100重量%。特别优选是，该干性润滑物质的份量为75－95重量%。干性润滑物质的这种份量导致具有按本发明构成的刮水片的挡风玻璃刮水器在干的玻璃上也不产生刺耳声、颤动或甚至粘住。
在本发明的一个实施方案中，该耐磨的基层也含干性润滑物质。在基层中该干性润滑物质的份量比在覆盖层中的干性润滑物质的份量低。通过基层中干性润滑物质的较低份量可增加该基层的粘结强度。增加粘结强度例如可通过较大份量的粘合剂和在基层材料中的交联剂实现。特别是为提高耐磨性，该基层在硬化后含一种交联的聚合物。
为达到足够的耐磨性，在基层中的干性润滑物质的份量优选比覆盖层中的干性润滑物质的份量低至少30重量%，其均按硬化后的层计。特别优选是，在基层中的干性润滑物质的份量比盖层中的干性润滑物质的份量低至少50重量%。
为实现足够的耐磨性，该涂层优选含至少一种交联的聚合物，在基层中的该交联的聚合物的份量比在覆盖层中的高。如果该覆盖层含未交联的聚合物或甚至根本不含粘合剂是特别优选的。
由于覆盖层仅含小份量的交联的聚合物或甚至完全不含交联的聚合物或完全不含粘合剂，该干性润滑物质在运行时在基层中均匀分布。这可实现其本上平的表面，由此实现在挡风玻璃板上的均匀支承。由此产生优良的刮水质量，并且实现长的使用寿命，并由于在挡风玻璃板和刮水片的涂层之间的耐久的优良润滑界面而在疏水的挡风玻璃板上仅有小的颤动。特别是如在湿的疏水玻璃板上的测试表明，通过含干性润滑物质的覆盖层实现了持久不变的低摩擦系数。
通过降低摩擦的覆盖层的保护作用也进一步改进了基层的耐磨性。
本发明还涉及一种用于涂覆条形型件的方法，该方法的第一步中，在型件上涂覆基层，在第二步中涂覆覆盖层。该基层含0－45重量%的干性润滑物质，该覆盖层含60－100重量%的干性润滑物质。优选是该基层含30－45重量%的干性润滑物质，该覆盖层含75－95重量%的干性润滑物质。按本发明，在覆盖层中的干性润滑物质的份量大于在基层中的干性润滑物质的份量。
由弹性材料构成的未经涂覆的条形型件例如通过挤出、注塑或模压按专业人员所熟知的常用工艺制备。
为实现耐磨的涂层，如果基层的涂层剂含至少一种粘合剂和至少一种交联剂是优选的。该粘合剂优选是基于聚氨酯的粘合剂。例如带羟基官能团的聚酯-聚氨酯树脂适合用作粘合剂。例如含高亚氨基含量的甲基化的蜜胺-氨基塑料可用作硬化剂。其它适用的粘合剂例如是聚丙烯酸酯树脂、聚酯-聚氨酯树脂、聚醚-聚氨酯树脂、聚酯树脂、聚酰胺树脂、聚酰胺-酰亚胺树脂，其它适用的硬化剂例如是异氰酸酯交联剂、环氧化物交联剂、硅烷交联剂、聚氮丙啶交联剂、碳二亚胺交联剂。
用于覆盖层的涂层材料除含干性润滑物质外还优选含不交联的粘合剂，如基于丙烯酸酯、甲基丙烯酸酯和苯乙烯的粘合剂。此外，用于覆盖层的涂层材料还可含添加剂如增稠剂和分散剂，以产生稳定的分散体。例如可使用市售的表面活性剂作为分散剂。
在本发明方法的第一实施方案中，在涂覆覆盖层前硬化基层。为此该基层例如首先经干燥，以去除溶剂。接着硬化该层。在硬化时粘合剂和硬化剂交联，从而形成耐磨的交联层。用于去除溶剂的干燥优选在50－100℃的温度下进行1－5分钟。硬化优选在75－160℃的温度下进行5－15分钟。或者，也可在室温下硬化至少6天。由此得到交联的和耐水的膜。该膜厚度优选为0.2－5 µm。
该基层经硬化后涂覆覆盖层。涂覆覆盖层后对其进行干燥，以去除溶剂。该干燥优选在50－150℃的温度下进行。在使用不交联的粘合剂时得到不交联的覆盖层。
在第二实施方案中，将覆盖层涂于尚未硬化的基层上。涂覆覆盖层后，将两层一同干燥和硬化。或者也可先干燥基层，然后涂覆覆盖层并接着一同硬化该两层。
在一个实施方案中，在硬化后将涂层涂于条形型件上。这使得可以首先制备条形型件，然后涂以涂层。
但如果在未硬化的条形型件上涂以涂层则是优选的。该型件接着与涂层一同硬化。由此可将在硬化时引入的能量同时用于涂层的硬化和/或热交联。另外，涂层材料的硬化以非常短的时间完成。此外，由于条形型件的未硬化的弹性材料的较高的反应性，实现了基层的涂层材料与构成基底的弹性体的更好的交联。
为避免覆盖层发生交联并由此降低滑动特性，优选是在未硬化的弹性体材料上涂覆该涂层的基层，接着再硬化该弹性体材料，然后涂覆降低磨擦系数的覆盖层。
此外，优选的是将该条形型件设计成双型件，在双型件上涂以基层，接着将该双型件分成两单型件，并再涂以覆盖层。在以双型件形式制备刮水片时，该两型件通常沿该刮水片的刮水棱相互连结。然后通过沿刮水棱切断该型件以分成两单型件。由此该切断面仅涂有覆盖层。与具有基层和覆盖层的涂层相比，这导致改进的刮水质量。
分离成单型件后涂覆降低摩擦的第二层。因为该降低摩擦的层仅少量交联或完全不交联，所以在刮水棱上形成均匀的膜。
具体实施方式
实施例
对比实施例
一种水性涂层组合物含聚酯-聚氨酯分散体、甲基化的亚氨基蜜胺氨基塑料交联剂、作为干性润滑剂的石墨和增稠剂。将该涂层组合物涂于弹性体基底上。该弹性体基底是由氯化橡胶组合物经注塑制成的双刮水器型件。在初始干燥蒸发水性溶剂后，在150℃硬化该涂层组合物10 min。形成4 µm厚的交联的和耐水的膜。
经硬化的基层组合物含54.6重量%的羟基官能化的聚酯-聚氨酯树脂(Bayer Material
Science的Bayhydrol PT
241®)的交联树脂组合物（其平均羟基含量为2.5%，与含高亚氨含量的甲基化的蜜胺氨基塑料硬化剂(Cytec的Cymel 303 LF®)交联）、34.0重量%的石墨、10.6重量%的聚乙烯(HDPE)和0.8重量%的丙烯酸酯增稠剂。
如此制备的基层在喷有水以摸拟下雨条件的疏水挡风玻璃板上的刮水实验中实验30分钟。起初的刮水质量不太好，在长时间中显现条纹和浑浊。在5分钟后所记录的颤动幅度开始增大，并达到大于14 mm的水平。
在湿的旋转的疏水玻璃板上实验时，该基层的摩擦系数随时间增大，并在30
cm/s的速度下经30分钟后为0.60。
实施例
1
在双型件上涂覆相应于对比实施例的基层。该基层经硬化后，将该双型件切断成两个单型件。在单型件上喷洒石墨分散体，以涂覆基层和切断面。该石墨分散体在90℃下经干燥，以去除水性溶剂。得到未交联的覆盖层。该覆盖层含4.6重量%的固态粘合剂聚合物、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，其均按干的覆盖层计。
在湿的旋转的疏水玻璃板上的实验表明，该包括两层的涂层有稳定的低摩擦系数，即所测定的摩擦系数在实验中保持恒定。
该包括两层的涂层的摩擦系数经30分钟后为0.4 (在30 cm/s的速度下)。
在挡风玻璃板刮水器实验中，也将该涂有两层涂层的刮水片在汽车的疏水性挡风玻璃板上实验30分钟。在挡风玻璃板上喷水以模拟下雨。在整个实验期间所记录的颤动幅度保持非常低(小于5 mm)，并且该刮水片在挡风玻璃板上平滑运行且无噪声。刮水质量保持优异。
实施例
2
在由氯化橡胶材料制成的刮水片上首先涂覆相应于对比实施例的基层。在该基层上施加干的石墨粉，其涂在单型件的基层的表面上。具有包括两层的涂层的刮水片在疏水性挡风玻璃板上进行刮水实验30分钟，在该玻璃板上喷有水以摸拟下雨。在实验期间所记录的颤动幅度为2－4 mm。
Claims (13)
1.用于刮水片、特别是挡风玻璃刮水器的刮水片的条形型件，其具有由弹性材料制成的基底，且至少部分具有降低摩擦的涂层，其特征在于，该涂层包括2层，其中具有直接涂于基底上的基层是耐磨涂层，涂于基层上的覆盖层是降低摩擦的。
2. 权利要求1的条形型件，其特征在于，所述降低摩擦的覆盖层含干性润滑物质。
3. 权利要求2的条形型件，其特征在于，所述干性润滑物质是石墨、聚四氟乙烯、聚丙烯、聚乙烯、二硫化钼或这些物质中至少两种的组合物。
4. 权利要求2或3的条形型件，其特征在于，在覆盖层中的干性润滑物质的份量为硬化后的层的60－100重量%。
5. 权利要求1－4之一的条形型件，其特征在于，耐磨的第一涂层也含干性润滑物质，在基层中该干性润滑物质的份量比覆盖层中的干性润滑物质的份量低。
6. 权利要求5的条形型件，其特征在于，在基层中的干性润滑物质的份量比覆盖层中的干性润滑物质的份量低至少30重量%，其均按硬化后的层计。
7. 权利要求1－6之一的条形型件，其特征在于，所述涂层含交联的聚合物，在基层中的该交联的聚合物的份量比在覆盖层中的高。
8. 用于涂覆条形型件的方法，该方法的第一步中，在型件上涂覆基层，在第二步中涂覆覆盖层，其中基层含0－45重量%的干性润滑物质，覆盖层含60－100重量%的干性润滑物质。
9. 权利要求8的方法，其特征在于，所述基层在涂覆覆盖层前经硬化。
10.权利要求8的方法，其特征在于，覆盖层涂于尚未硬化的基层上，并且两层一同经硬化。
11.权利要求8－10之一的方法，其特征在于，在由弹性体材料形成条形型件后，在条形型件上涂覆涂层，接着硬化带涂层的型件。
12.权利要求8－10之一的方法，其特征在于，经硬化后将涂层涂于条形型件上。
13.权利要求8－12之一的方法，其特征在于，将所述条形型件设计成双型件，在双型件上涂以基层，接着将该双型件分成两单型件，并随后涂以覆盖层。
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Application publication date: 20151209 |