CN117178077A - 用于金属冷成型的金属基材在非中性pH值下的一步预处理方法 - Google Patents
用于金属冷成型的金属基材在非中性pH值下的一步预处理方法 Download PDFInfo
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Classifications
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- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
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Abstract
本发明涉及一种用于后续金属冷成型工艺的金属基材的预处理方法,所述方法至少包括步骤(1)和(2),即提供至少一种具有至少一个至少部分由至少一种金属制成的表面的基材(步骤(1)),使步骤(1)中提供的基材的该至少一个表面与水性润滑剂组合物(B)接触(步骤(2)),其中水性润滑剂组合物(B)除水外至少包含成分(b1)‑(b4)和任选(b5),即作为(b1)的至少一种通过至少乙烯基吡咯烷酮作为至少一种单体的聚合制备的均聚物和/或共聚物,其中(b1)具有的多分散指数(PDI)在1.5‑8.0范围内,作为(b2)的至少一种蜡,作为(b3)的至少一种消泡剂和作为(b4)的(i)草酸根阴离子和/或磷酸根阴离子或者(ii)钙阳离子、氯阴离子和氢氧根阴离子,以及任选地作为(b5)的Fe(III)离子,其中(b5)在至少草酸根阴离子作为(b4)存在的情况下存在,一种可以由本发明方法获得的预处理金属基材,一种冷成型金属基材的方法以及一种如上所定义的水性润滑剂组合物(B)。
Description
本发明涉及一种用于后续金属冷成型工艺的金属基材的预处理方法,所述方法至少包括步骤(1)和(2),即提供至少一种具有至少一个至少部分由至少一种金属制成的表面的基材(步骤(1)),使步骤(1)中提供的基材的该至少一个表面与水性润滑剂组合物(B)接触(步骤(2)),其中水性润滑剂组合物(B)除水外至少包含成分(b1)-(b4)和任选(b5),即作为(b1)的至少一种通过至少乙烯基吡咯烷酮作为至少一种单体的聚合制备的均聚物和/或共聚物,其中(b1)具有的多分散指数(PDI)在1.5-8.0范围内,作为(b2)的至少一种蜡,作为(b3)的至少一种消泡剂和作为(b4)的(i)草酸根阴离子和/或磷酸根阴离子或者(ii)钙阳离子、氯阴离子和氢氧根阴离子,以及任选地作为(b5)的Fe(III)离子,其中(b5)在至少草酸根阴离子作为(b4)存在的情况下存在,一种可以由本发明方法获得的预处理金属基材,一种冷成型金属基材的方法以及一种如上所定义的水性润滑剂组合物(B)。
发明背景
金属工件的冷成型常规通过工件的轧制,如螺纹滚轧,拉拔,特别是滑动拉拔或深拉,压制、拉伸成形和/或冷镦实现,以将它们转变成具有所需形状的制品。冷成型通常在低于经受冷成型的工件的金属材料的再结晶温度的温度下,如在低于和最多450℃的温度下进行。在冷成型方法中不使用外部加热源。相反,任何发热或温度升高通常仅归因于金属工件与在成型过程中使用的加工工具之间的摩擦力和归因于由工件中的材料流生成的内摩擦力。冷成型通常导致压力增加,例如对于钢,例如在200MPa至1GPa的范围内,有时甚至高达2GPa。待冷成型的工件的温度最初处于环境温度,即在大约10-32℃。在将工件在成型前预热到例如650-1250℃范围内的温度的情况下,该成型工艺不再是“冷成型”工艺,而是“亚热(semi-hot)”成型、热成型或锻造工艺。
如果将金属工件冷成型为具有仅较低变形度的成型制品,则实施冷成型工艺所需的力相当低。为此,常规上将非反应性成型油施加到工件上。但是,在较高变形度下,通常在冷成型工艺前首先将转化涂层施加到工件的表面上,然后在上面施加另一润滑层,以防止冷成型过程中的冷焊。该两步方法例如公开于EP 0 232 929 A1,WO 94/16119A1,WO 2009/095373A1,WO 2009/095375 A1,WO 2009/095374 A1和JP S56 72090A中。
EP 0 232 929 A1涉及一种用于促进不锈钢基材的后续冷成型的两步预处理方法。在第一步骤中通过使用尤其含有草酸以及水溶性聚合物的溶液将草酸盐涂层施加到基材上。此后,在第二步骤中将润滑剂施加到草酸盐涂层上。金属皂在EP 0 232 929 A1中被指定为合适的润滑剂。WO 94/16119A1公开了一种为了后续冷成型工艺而在第一步骤中在金属表面上形成转化涂层的液体水性组合物。该组合物包含有机阳离子聚合物并可进一步包含草酸根阴离子。在第二步骤中可以通过使用尤其油基润滑剂和/或皂将润滑膜施加到转化膜上。WO 2009/095373 A1公开了一种用于促进金属基材的后续冷成型的两步预处理方法。在第一步骤中通过使用含有Ca、Mg和/或K阳离子的水性酸性磷化液形成工件表面上的磷酸盐层。在第二步骤中,施加含有有机聚合物的水性碱性润滑剂组合物。WO 2009/095375A1和WO 2009/095374 A1都公开了一种为冷成型准备金属工件的方法。在WO 2009/095375 A1的情况下通过使表面与包含至少一种水溶性、含水或结合水的氧化物和/或硅酸盐和有机聚合物的水性润滑剂组合物接触或在WO 2009/095374 A1的情况下通过使表面与包含至少两种蜡和有机聚合物的水性润滑剂组合物接触而将润滑剂涂层施加到任选带有转化涂层作为隔离层的工件的金属表面上。最后,JP S56 72090A涉及一种用于促进钢基材的后续冷成型的两步预处理方法。为此在第一步骤中将草酸盐涂层施加到基材上。通过使用尤其含有草酸和水溶性有机钛化合物以及聚乙烯基吡咯烷酮的溶液获得草酸盐涂层。在第二步骤中,将润滑剂施加到草酸盐涂层上。金属皂和固体润滑剂在JP S56 72090A中被指定为合适的润滑剂。
但是,就现有技术中已知的这些方法而言,存在若干缺点。首先,既出于生态原因又为了避免在基材上形成不期望的磷诱导δ铁素体,希望不使用磷酸盐涂膜作为转化涂膜,如在WO2009/095373A1中公开的方法中施加的转化涂膜,而是仅使用无磷酸盐体系。就现有技术中已知的润滑剂组合物而言,油基润滑剂组合物通常导致较高的VOC含量,因为相当大量的油可在其使用过程中蒸发。此外,油基润滑剂体系可能引起安全问题,因为它们易燃并且必须作为危险材料储存在>150℃的闪点下。由于这些原因,不希望使用油基润滑剂配制剂。固体润滑剂,例如基于MoS2和/或石墨的润滑剂,仅适用于具有大变形度的重度冷成型,因此这类润滑剂仅具有有限用途。此外,这样的润滑剂膜中存在的硫化物通常具有有害影响,特别是在不锈钢上。因此,出于生态原因和经济原因,使用水性润滑剂组合物都比使用固体和/或油基润滑剂更理想。
但是,现有技术的常规水性润滑剂组合物通常是碱性组合物,如EP 0232 929A1、WO 2009/095373 A1、WO 2009/095375 A1、WO 2009/095374A1和JP S56 72090A中公开的(金属)皂和皂溶液,其例如基于碱金属或碱土金属硬脂酸盐。这些仅在碱性条件下稳定并且例如在酸性介质中不稳定。此外,现有技术的碱性润滑剂组合物通常仅具有较短寿命,因此必须相当频繁地更新。这从生态角度(必须使用更大量的水和更大量的存在于该组合物中的成分)和经济角度(更高的能量成本和更换时间)看当然都是不利的。与用于在先前施加的转化涂层上提供润滑剂层的这些水性碱性润滑剂组合物相比,用于生成上述转化涂层的组合物是如上文已提到的酸性组合物。为了进行这样的两步预处理方法,通常使用两个不同的开放处理浴,将金属工件浸渍到其中,即含有水性酸性转化涂层组合物的第一个浴和含有水性碱性润滑剂组合物的第二个浴。但是,必须在这两个浸渍步骤之间包括冲洗和/或中和步骤以便在将工件从第一酸性浴中取出之后和在将其浸渍到第二碱性浴之前除去存在于工件上的任何过量酸,以尽可能长地保持这两个浴的寿命,特别是第二个浴的寿命。但是,由于经济原因和生态原因,必须进行这样的冲洗和/或中和步骤是不利的。简单混合或合并用于提供转化涂层的常规水性酸性组合物如磷酸盐和/或草酸盐组合物与用于提供润滑剂层的常规水性碱性组合物是不可能的,因为这些组合物彼此不混溶,因此将观察到不想要的相分离。此外,用于制备常规水性碱性润滑剂组合物的已知有机聚合物分散体大多在酸性环境中不稳定。因此,并不总是能够简单地使用已知的水性碱性润滑剂组合物的酸性形式。
EP 3 290 544 A1涉及一种pH值为2.0-6.5的酸性水基润滑涂布剂,其尤其含有化学转化组分如草酸和润滑组分如包括油或皂的亲脂性润滑组分。该涂布剂可进一步包含水基树脂作为粘合剂组分。EP 3 290 544 A1进一步公开了用于后续冷成型的金属基材的一步预处理方法。
JP S54 5847A涉及一种用于促进金属冷成型的润滑剂组合物。该润滑剂含有草酸以及选自水溶性有机钛化合物、乙烯基吡咯烷酮均聚物和乙烯基吡咯烷酮共聚物的至少一种成分。该润滑剂组合物可进一步含有润滑助剂。
WO 2020/165035 A1公开了一种制备用于冷成型的钢和/或合金钢工件的一步预处理方法。在金属表面上的草酸盐润滑剂层通过使用含有成膜聚合物的水性酸性草酸化溶液形成。宽范围的聚合物可以用于制备该溶液。但是,该润滑剂在其他酸性溶液如磷化液中不一定稳定并且在碱性溶液中通常也不稳定。此外,它可以含有润滑油。但是,该类油的使用由于前文所述原因通常是不利的。
此外,现有技术中已知的用于冷成型的常规预处理工艺并不总是得到在工件上形成的润滑剂层的足够高的涂覆重量,或者如果在润滑剂层下方还存在隔离层如转化涂层,并不总是得到合并的润滑剂层和所述隔离层的足够高的涂覆重量。这可能导致这些层对金属基材仅不足的附着性能。此外,这可导致在冷成型之后和在冷成型过程中工具与工件的隔离无效,并导致仅无效的摩擦系数降低或甚至导致不期望的冷焊,因为只有不够高的量的涂层(如通过它们的涂覆重量测得)在冷成型工艺的过程中保持存在于工件上。
因此,出于经济原因和生态原因二者,需要简化使用水性润滑剂组合物的用于金属冷成型的常规表面预处理工艺,特别是提供需要更少处理步骤并使用水性润滑剂组合物的用于冷成型工艺的金属基材的改进水基预处理技术,所述组合物含有在酸性和碱性介质中均稳定的合适成分。同时,这样的简化预处理必须仍然得到在金属基材上形成的涂层的足够高涂覆重量,以同时确保对基材的良好附着力和在冷成型过程中有效降低摩擦系数并防止冷焊。
问题
因此,本发明的一个目的是出于经济原因和生态原因二者,提供一种使用水性润滑剂组合物的用于金属冷成型的简化表面预处理方法,特别是提供一种需要更少处理步骤并使用水性酸性润滑剂组合物的用于冷成型工艺的金属基材的改进水基预处理技术,所述组合物在酸性和碱性介质中均稳定。但是,同时要求这样的简化预处理必须仍然得到在金属基材上形成的涂层的足够高涂覆重量,以同时确保对基材的良好附着力和在冷成型过程中有效降低摩擦系数并防止任何冷焊。
解决方案
通过本申请权利要求的主题以及通过本说明书中公开的其优选实施方案,即通过本文中描述的主题解决这一目的。
本发明的第一个主题是一种用于后续金属冷成型工艺的金属基材的预处理方法,所述方法至少包括步骤(1)和(2)和任选步骤(3),即
(1)提供至少一种基材,其具有至少一个至少部分由至少一种金属和/或其
合金制成的表面,其中所述金属和/或其合金为钢、铝以及铝和/或钢的合金中的至少一种,
(2)使步骤(1)中提供的基材的该至少一个表面与具有在非中性pH范围内的pH值的水性润滑剂组合物(B)接触,其中该中性pH范围为>6.0至<8.0的pH范围,
其中水性润滑剂组合物(B)除水外至少包含相互不同的成分(b1)-(b4)和任选(b5),即
(b1)至少一种成膜聚合物,其是通过至少乙烯基吡咯烷酮作为至少一种单体的聚合制备的均聚物和/或共聚物,其中所述均聚物和/或共聚物具有的多分散指数(PDI)在1.5-8.0范围内,
(b2)至少一种蜡,
(b3)至少一种消泡剂,和
(b4)(i)草酸根阴离子和/或磷酸根阴离子或者(ii)钙阳离子、氯阴离子和氢氧根阴离子,以及
(b5)任选地,Fe(III)离子,其中成分(b5)在至少草酸根阴离子作为成分(b4)存在的情况下存在,以及
(3)任选地,干燥在已经进行步骤(2)之后得到的涂膜。
本发明的另一个主题是一种可以通过本发明方法获得的预处理金属基材。
本发明的另一个主题是一种将金属基材冷成型的方法,其特征在于其包括对本发明的预处理金属基材进行冷成型工艺的步骤。
本发明的另一个主题是如上文就本发明的预处理方法定义的水性润滑剂组合物(B)。
本发明的另一个主题是一种母料,其用于通过用水稀释该母料和如果适用的话调节pH值生产本发明的水性组合物(B)。
惊人地发现水性润滑剂组合物(B),尤其是其成分(b1)和(b2)与有机和/或无机酸,尤其是草酸和/或磷酸相容并且因此代表酸稳定组合物。同时出人意料地发现水性润滑剂组合物(B),尤其是其成分(b1)和(b2)也与有机和/或无机碱相容并且因此也代表在碱性介质中稳定的组合物。因此,有利的是取决于仅仅成分(b4)的选择,基本相同的组合物既可以用作酸性水性润滑剂组合物又可以用作碱性水性润滑剂组合物。这为最终用户提供了更大灵活性。
尤其惊人地发现因此可以将(i)草酸根和/或磷酸根阴离子作为(b4)包括在组合物(B)中,尤其是当组合物(B)的pH值在至多pH 6.0的非中性酸性范围内时,或者将(ii)钙阳离子、氯阴离子和氢氧根阴离子作为(b4)包括在组合物(B)中,尤其是当组合物(B)的pH值在8.0或更高的非中性碱性范围内时。这具有的优点是在单一步骤中组合物(B)可以作为水性酸性或碱性组合物用于本发明方法中。水性酸性或碱性组合物(B)尤其均可以仅在单一步骤中用作润滑剂组合物和转化涂层组合物,并且因此不必在施加该润滑剂之前的额外步骤中施加任何转化涂层,这当然既具有经济优势又具有生态优势。类似地,不必随后施加任何润滑助剂。
尤其惊人地发现水性润滑剂组合物(B)中存在的所有成分可配制为和配制到pH值在0.1-6.0范围内的酸性组合物中或者pH值在8.0-14.0范围内的碱性组合物中。尤其惊人地发现组合物(B)在这样的酸性条件和这样的碱性条件下均稳定并且组合物(B)中存在的该至少一种成膜聚合物(b1)以及该至少一种蜡(b2)尤其在这两种环境中在酸性条件的情况下额外存在(i)草酸根和/或磷酸根阴离子(b4)时或者在碱性条件的情况下额外存在(ii)钙阳离子、氯阴离子和氢氧根阴离子(b4)时是稳定的,甚至当这些离子以较高浓度存在于组合物(B)中时。如上所述,这为最终用户提供了更大灵活性。
进一步惊人地发现由于组合物(B)可以仅在单一步骤中既作为润滑剂组合物又作为转化涂层组合物用于本发明方法中,根本不必进行冲洗和/或中和步骤,这与其中至少在施加转化涂层组合物之后和在施加润滑剂组合物之前必须进行该冲洗和/或中和步骤的常规多步方法相反。
此外,进一步发现在步骤(2)之后得到的涂膜是合并的转化和润滑剂涂膜。因此,得到的涂膜兼具转化层和润滑剂层的性能。润滑剂涂膜可存在于转化涂膜之上。合并的层可部分分离和调整。当使用具有至少部分由铝和/或其合金制成的表面的基材时,已经发现当使用包含钙阳离子、氯阴离子和氢氧根阴离子作为成分(b4)的组合物(B)时,作为转化涂膜形成铝酸钙涂膜,因为在将组合物(B)施加于表面上之后原位形成铝酸根阴离子。
此外,惊人地发现由施加组合物(B)获得的涂层牢固地附着在基材上并表现出良好的润滑剂性能。因此,通过本发明方法预处理的基材可随后进行金属冷成型工艺,包括冷挤出和高速拉拔的拉丝。在基材的冷成型中,已经发现将组合物(B)施加到基材上而获得的涂层可有效进行用于金属冷成型的拉拔步骤。在基材如钢丝在拉丝机中的冷成型中,已经发现甚至在至多35%横截面积(在每个拉拔步骤中降低)的拉拔下可以高效地使用将组合物(B)施加到基材上而获得的润滑剂层。
此外,惊人地发现通过发明方法获得的涂布金属基材带有由施加组合物(B)获得的在金属基材上形成的涂层的足够高涂覆重量。所得涂层均匀、厚并牢固地附着在基材表面上。已经发现这样的高涂覆重量不仅确保对基材的良好附着力,还确保在冷成型过程中有效降低摩擦系数并防止任何冷焊。惊人地发现与进行其中转化涂层和润滑剂层在分开的步骤中施加的常规多步法相比,当进行仅包括一个接触步骤(步骤(2))的本发明方法时获得更高的涂覆重量。在草酸根阴离子作为(b4)存在的情况下,惊人地发现与使用硝基胍相比,额外将Fe(III)离子用作促进剂正面影响涂覆重量。
此外,已经发现由本发明方法获得的涂布金属工件具有良好的耐腐蚀性。就此而言惊人地发现当进行本发明方法时,在组合物(B)中存在任选的缓蚀剂(b6)不会以任何方式不利地影响草酸盐和/或磷酸盐和/或铝酸盐转化涂层的形成,因为形成的转化涂层具有优异的涂覆质量,尤其是当将烷基酰胺和链烷醇胺的混合物用作任选的成分(b6)时。此外,已经发现在本发明表面处理工艺过程中没有形成稳定泡沫。
此外,惊人地发现与使用常规润滑剂组合物相比,由于将该特定成膜聚合物(b1)与该至少一种蜡(b2)组合使用而尤其改进了在本发明方法的步骤(2)之后或者任选的步骤(3)之后获得的润滑剂膜的润滑剂性能。
进一步惊人地发现含有酸性水性润滑剂组合物(B)的浴具有较长寿命,特别是比含有常规碱性水性润滑剂组合物的浴长的寿命。这当然具有经济和生态优点。
发明详述
术语“包含”在本发明的意义上,特别是与本发明方法、本发明组合物(B)和用于制备组合物(B)的母料相关地,优选具有“由…组成”的含义。在这种情况下,例如关于本发明的组合物(B),除其中的必需成分(成分(b1)-(b4)、任选(b5)和水)外,在该组合物中还可含有一种或多种下文提到的其他任选组分。该原理同样适用于本发明方法中所用的组合物(B)和母料。所有组分/成分在每种情况下可以下文提到的其优选实施方案存在。这同样适用于本发明的其他主题。
存在于各组合物如组合物(B)中的任何下文所给成分以wt%(重量%)计的比例和量加起来至多为100重量%,在每种情况下基于相应组合物如组合物(B)的总重量计。
本发明的预处理方法
本发明方法是一种用于后续金属冷成型工艺的金属基材的预处理方法。本发明方法至少包括步骤(1)和(2)和任选另外的步骤(3)。本发明方法可以包括一个或多个其他额外的任选步骤。
优选本发明方法除了步骤(2)外不包括任何草酸化和/或磷化步骤并且进一步除了步骤(2)外不包括任何润滑步骤。
步骤(1)
在本发明方法的步骤(1)中,提供至少一种基材,其具有至少一个至少部分由至少一种金属和/或其合金制成的表面。所述金属和/或其合金为钢、铝以及铝和/或钢的合金中的至少一种。
所用基材的表面至少部分由至少一种金属和/或其合金制成,即所述表面的至少一个区域由至少一种金属和/或其合金制成。该表面可由包含不同金属的不同区域组成。优选基材的整个表面由至少一种金属和/或其合金制成。更优选基材由至少一种金属和/或其合金组成。
优选该至少一种金属选自铝,铝合金,锌,钢,包括冷轧钢、热轧钢、热镀锌钢(镀锌钢),包括热浸镀锌钢(热浸锌钢)或电解镀锌钢,钢合金,铝和/或铝合金。
优选基材的该至少一个表面由钢、铝和/或钢和/或铝合金制成,更优选基材本身由钢、铝和/或钢和/或铝合金制成。
作为基材,可使用例如带材、片材、嵌条、线材、线圈、更复杂的成型件、套筒、型材如中空或实心型材、管、圆盘、杆、棒或圆柱体。任选的步骤(1a)、(1b)和(1c)
步骤(1)中提供的基材的表面在如下文概述在步骤(2)中用组合物(B)处理前可借助酸性、碱性或pH中性清洁组合物清洁和/或蚀刻:在本发明方法的步骤(2)之前,可进行一个或多个以下任选步骤,优选以这一顺序:步骤(1a):清洁,优选通过对至少部分由钢和/或其合金制成的表面使用碱性水性清洁组合物和/或通过对至少部分由铝和/或其合金制成的表面使用pH中性的水性清洁组合物,以及任选随后冲洗步骤(1)中提供的基材的表面,和/或
步骤(1b):对基材表面进行酸洗,即蚀刻,和随后冲洗基材表面,和/或
步骤(1c):任选通过使用不同于组合物(B)的水性活化组合物(A)活化基材表面。
替换地,可以在一个步骤中进行任选步骤(1a)和(1b)。优选步骤(1a)和(1b)都进行。步骤(1a)中包括的冲洗优选用去离子水或自来水进行。优选通过使用盐酸、氢氟酸、硫酸、硝酸和/或磷酸进行酸洗。在磷酸根阴离子作为成分(b4)存在于组合物(B)中的情况下,基材表面可以任选通过使用水性活化组合物(A)根据任选的步骤(1c)活化,例如通过使用来自Chemetall GmbH的市售活化产品V 6522。
步骤(2)
在本发明方法的步骤(2)中,使步骤(1)中提供的基材的该至少一个表面与水性润滑剂组合物(B)接触,优选浸入水性润滑剂组合物(B)中。
根据步骤(2)的处理程序,即“接触”可例如包括喷涂和/或浸涂程序。也可通过淹没表面或通过辊涂或甚至手动通过擦拭或刷涂施加组合物(B)。但是,浸渍是优选的。在这种情况下,将所用基材浸入含有组合物(B)的浴中。
优选接触步骤(2)通过将基材至少部分浸入具有20-95℃,优选45-90℃,特别是50-85℃范围的浴温的含有水性润滑剂组合物(B)的浴中进行。
处理时间,即表面与步骤(2)中所用水性组合物(B)接触的时间,优选为15秒至20分钟,更优选30秒至15分钟,最优选45秒至10分钟。
优选在进行步骤(2)之后没有进行冲洗步骤。
组合物(B)
关于组合物(B)的术语“水性”在本发明的意义上优选是指组合物(B)是含有基于其有机和无机溶剂(包括水)的总含量计至少40重量%或至少50重量%,优选至少60重量%,更优选至少70重量%,特别是至少80重量%,最优选至少90重量%或95重量%或98重量%或99重量%或甚至100重量%水的组合物。因此,除水之外,组合物(B)可含有至少一种有机溶剂,但是其量显著低于存在的水量。优选组合物(B)不含有机溶剂。因此,水优选是存在的唯一溶剂/稀释剂。
优选组合物(B)以至少40重量%的量含有水。更优选组合物(B)以至少45重量%或至少50重量%,更优选至少60重量%,甚至更优选至少70重量%,仍更优选至少80重量%的量含有水,在每种情况下基于组合物(B)的总重量计。
水性润滑剂组合物(B)具有在非中性pH范围内的pH值,其中中性pH范围为>6.0至<8.0的pH范围。换言之,水性润滑剂组合物(B)具有pH7.0+1.0或更高的pH值,即在8.0-14.0范围内的pH值,或者pH 7.0-1.0或更低的pH值,即在0-6.0如0.1-6.0范围内的pH值。若组合物(B)具有在8.0-14.0范围内的pH值,则它代表碱性组合物。若组合物(B)具有在0-6.0如0.1-6.0范围内的pH值,则它代表酸性组合物。pH值尤其可以通过选择成分(b4)及其量调节。
优选水性润滑剂组合物(B)具有在0.1-6.0,优选0.2-5.8,更优选0.5-5.5范围内的pH值,优选(i)当草酸根阴离子和磷酸根阴离子中的至少一种作为成分(b4)存在时,尤其是当基材表面至少部分由钢和/或其合金制成时,或者具有在8.0-14.0,优选9.0-14.0,更优选10.0-13.5,甚至更优选11.0-13.0范围内的pH值,优选当(ii)钙阳离子、氯阴离子和氢氧根阴离子作为成分(b4)存在时,尤其是当基材表面至少部分由铝和/或其合金制成时。
更优选水性润滑剂组合物(B)具有在0.1至<2.0,甚至更优选0.2-1.9,仍更优选0.5-1.8范围内的pH值,优选当(i)至少草酸根阴离子作为成分(b4)存在时,更优选当草酸根阴离子作为成分(b4)存在并且不存在磷酸根阴离子或者若存在磷酸根阴离子,则其存在量以g/l计低于以g/l计的草酸根阴离子量时,尤其是当基材表面至少部分由钢和/或其合金制成时,或者具有在≥2.0至6.0,甚至更优选2.2-5.8,仍更优选2.4-5.5范围内的pH值,优选(i)当至少磷酸根阴离子作为成分(b4)存在时,更优选当磷酸根阴离子作为成分(b4)存在并且不存在草酸根阴离子或者若存在草酸根阴离子,则其存在量以g/l计低于以g/l计的磷酸根阴离子量时,尤其是当基材表面至少部分由钢和/或其合金制成时,或者具有在8.0-14.0,甚至更优选9.0-14.0,仍更优选10.0-13.5,还更优选11.0-13.0范围内的pH值,优选(ii)当钙阳离子、氯阴离子和氢氧根阴离子作为成分(b4)存在时,更优选当钙阳离子、氯阴离子和氢氧根阴离子作为成分(b4)存在并且不存在草酸根阴离子和磷酸根阴离子或者若存在草酸根阴离子和磷酸根阴离子,则其各自的存在量以g/l计低于以g/l计的钙阳离子、氯阴离子和氢氧根阴离子各自的量时,尤其是当基材表面至少部分由铝和/或其合金制成时。
优选组合物(B)以溶液或分散体的形式,特别是以溶液形式存在,优选在至少40℃,特别是至少50℃的温度下。
优选组合物(B)具有在0.1-30重量%,更优选0.2-25重量%,甚至更优选0.3-20重量%,仍更优选0.4-15重量%范围内的固含量,在每种情况下基于组合物(B)的总重量计。
由于组合物(B)包含(i)草酸根和/或磷酸根阴离子或(ii)钙阳离子、氯阴离子和氢氧根阴离子中的至少一种作为成分(b4),其代表适合在基材表面上形成转化涂层的草酸化组合物、磷化组合物或形成铝酸盐的组合物。由于组合物(B)进一步包含(b2)至少一种蜡和至少一种成膜聚合物(b1),其无论如何也同时代表适合在基材表面上形成润滑涂层的润滑剂组合物。
优选组合物(B)不包含任何油如润滑油。组合物(B)除了成分(b1)和(b2)外尤其不包含任何其他润滑助剂。
组合物(B)除了水外至少包含相互不同的成分(b1)-(b4)和任选(b5)。
成分(b1)
组合物(B)包含至少一种成膜聚合物,其是通过至少乙烯基吡咯烷酮作为至少一种单体的聚合制备的均聚物和/或共聚物,其中所述均聚物和/或共聚物具有的多分散指数(PDI)在1.5-8.0.范围内。PDI以及重均分子量(Mw)根据下文在‘方法’部分公开的方法测定。
优选成膜聚合物(b1)具有的多分散指数(PDI)在1.8-7.5,更优选2.0-7.0,仍更优选2.5-6.5,甚至更优选3.0-6.0,尤其是3.5-5.5范围内。
优选成膜聚合物成分(b1)具有的重均分子量在1 000-500 000g/mol,更优选2500-400 000g/mol,甚至更优选4 000-300 000g/mol,仍更优选5500-200 000g/mol,还更优选7 000-100 000g/mol,仍更优选8 500-75000g/mol范围内。
优选成膜聚合物(b1)具有至少一个在40-200℃,更优选50-190℃,还更优选60-170℃,仍更优选70-150℃,甚至更优选80-130℃,尤其是90-120℃范围内的玻璃化转变温度(Tg)。Tg根据下文在‘方法’部分公开的方法测定。
优选该至少一种成膜聚合物是水溶性或水分散性的,更优选水溶性的。优选该至少一种成膜聚合物可溶于或可分散于组合物(B),更优选可溶于组合物(B)。
在该至少一种成膜聚合物(b1)是共聚物的情况下,至少一种带有至少一个烯属不饱和基团,优选至少一个乙烯基并且不同于乙烯基吡咯烷酮的其他单体可用于制备成分(b1)。优选使用至少一种不同于乙烯基吡咯烷酮的其他乙烯基单体。但是,这样的其他单体可以还或者替换地带有至少一个(甲基)丙烯酸酯基团。这包括(甲基)丙烯酸基团。但是,优选不使用具有酸基的单体。该其他单体可以是离聚物。该其他单体也可以是乙烯、丙烯、丁烯、苯乙烯等。术语“(甲基)丙烯酰基”是指“丙烯酰基”和/或“甲基丙烯酰基”。类似地,“(甲基)丙烯酸酯”是指丙烯酸酯和/或甲基丙烯酸酯。
优选成膜聚合物(b1)是由乙烯基吡咯烷酮制备的均聚物或者由乙烯基吡咯烷酮以及至少一种选自(甲基)丙烯酸酯单体、乙烯基胺、乙烯醇、乙烯基甲酰胺、乙烯基己内酰胺、乙酸乙烯酯和乙烯基咪唑的单体制备的共聚物。优选衍生于该至少一种不同于乙烯基吡咯烷酮的其他单体的结构单元在该共聚物中的量为至多50mol%。优选衍生于乙烯基吡咯烷酮的结构单元在该共聚物中的量为至少50mol%,更优选至少60mol%或至少70mol%或至少75mol%。
最优选聚乙烯基吡咯烷酮均聚物以及乙烯基吡咯烷酮和乙酸乙烯酯的共聚物。示例性聚合物为来自德国BASF SE的K 17P。
优选该至少一种成膜聚合物(b1)以在0.05-20重量%,更优选0.10-15重量%,甚至更优选0.15-10重量%,仍更优选0.20-7.5重量%,特别是0.25-5.0重量%范围内的量存在于组合物(B)中,在每种情况下基于组合物(B)的总重量计。
成分(b2)
组合物(B)包含至少一种蜡作为不同于成分(b1)的成分(b2)。
如术语“蜡”已经暗示,该至少一种蜡在室温(23℃)下是固体物质。本领域技术人员熟悉术语“蜡”。所述术语例如由German Society for Fat Science(DGF)在DGF标准方法M-I 1(75)(2015)中定义。优选用作成分((b2)的该至少一种蜡符合蜡的这一定义。根据这一定义的蜡可在20℃下捏合,具有坚实(固体)到脆性的硬度,具有粗晶到细晶结构,颜色为半透明到不透明但不是玻璃态或玻璃状,在40℃以上的温度下熔化而不分解,在其熔点以上为轻微液态并在其熔点以上具有低粘度,具有高度依赖于温度的稠度和溶解度,并可在轻微压力下被抛光。优选地并且根据DGF的定义(DGF标准方法M-I 1(75)),如果一种物质没有满足超过一种上述性能,则该物质不是蜡。
优选该至少一种蜡(b2)是水溶性或水分散性的,更优选水分散性的。优选该至少一种蜡(b2)可溶于或可分散于组合物(B)。
优选组合物(B)可通过使用该至少一种蜡(b2)的水分散体或水溶液进行制备获得。
优选该至少一种蜡(b2)具有在30-170℃,更优选40-165℃,尤其优选60-160℃范围内的熔点。
组合物(B)优选包含多于一种蜡作为成分(b2)。优选组合物(B)包含至少两种,更优选至少三种不同的蜡作为成分(b2)。优选该至少两种或至少三种不同的蜡至少在它们的熔化温度(熔点)方面彼此不同。优选至少两种蜡的熔点之间相差至少20℃。
优选该至少一种蜡(b2)以在0.1-20重量%,更优选0.5-15重量%,甚至更优选0.75-12.5重量%,仍更优选1.0-10.0重量%,特别是1.5-9.0重量%,最优选2.0-7.5重量%范围内的量存在于组合物(B)中,在每种情况下基于组合物(B)的总重量计。
优选该至少一种蜡(b2)选自阳离子蜡、阳离子稳定化蜡和非离子蜡。“阳离子稳定化蜡”优选是通过酸性介质中,如组合物(B)中的阳离子基团稳定化或通过至少一种阳离子表面活性剂稳定化的蜡。
优选该至少一种蜡(b2)通过至少一种乳化剂稳定化。例如,该至少一种蜡(b2)可通过阳离子乳化剂稳定化(阳离子稳定化)或可通过非离子乳化剂稳定化(非离子稳定化)。阳离子乳化剂的实例是烷氧基化硬脂胺,如乙氧基化硬脂胺,和/或聚烷氧基化牛脂胺,如聚乙氧基化牛脂胺。非离子乳化剂的实例是醇,包括例如二乙氨基乙醇。
优选该至少一种蜡(b2)选自聚烯烃蜡(包括聚乙烯蜡,特别是HDPE(高密度聚乙烯)和/或聚丙烯蜡),天然蜡,包括植物和动物蜡,如褐煤蜡、蜂蜡和/或巴西棕榈蜡,石蜡(石油衍生蜡)以及它们的混合物。
在本文中,术语“烯烃”主要是指聚烯烃中典型的烯烃,优选具有2-8个碳原子的链烯烃,尤其是具有2-6个碳原子的链烯烃,尤其是具有2-4个碳原子的链烯烃,尤其是具有末端双键的那些。在本发明上下文中,优选的代表是乙烯、丙烯、1-丁烯和异丁烯。在本发明上下文中,乙烯和丙烯是特别优选的烯烃单体。术语“聚烯烃”通常被理解为是指单一类型烯烃单体的均聚物(例如乙烯均聚物)或至少两种烯烃单体的共聚物(例如包含或由乙烯、丙烯、1-丁烯和/或异丁烯组成的混合物的聚合物)。聚烯烃因此含有一种或多种类型的烯烃单体,因此是均聚物或共聚物。但是,它们也可能另外含有聚合或接枝的一种或多种不同于烯烃单体的烯属不饱和单体,特别是带有羧酸基团的烯属不饱和单体。如果具有羧基或羧酸酐基团的不同烯属不饱和单体用于烯烃单体的聚合或接枝,其用量使得含有羧基的作为成分(a5)的聚烯烃蜡具有在3-50,优选5-40,特别优选8-35,非常特别优选10-25,特别优选13-20mg KOH/g范围内的酸值。聚烯烃蜡优选选自氧化聚乙烯蜡、氧化聚丙烯蜡、氧化聚(乙烯-共-丙烯)蜡和氧化乙烯-烯烃共聚物、乙烯-(甲基)丙烯酸共聚物和不同于上述共聚物的乙烯和/或丙烯聚合物,其已用例如马来酸酐接枝(转化成水解形式,并带有游离COOH基团)。当然,其他烯属不饱和酸如丙烯酸也可用于接枝。
所用的石蜡优选是微晶的。
可购得并且可使用的示例性蜡是例如来自德国BYK Chemie的1041、来自BYK Chemie的561、来自BYK Chemie的517、来自MünzingChemie的O-33a和来自德国Clariant的KST。
成分(b3)
组合物(B)包含至少一种消泡剂作为成分(b3)。优选该消泡剂不含聚硅氧烷。因此,优选硅氧烷和/或聚硅氧烷单元不存在于(b3)中。
优选(b3)以0.01-5.0重量%,更优选0.01-4.0重量%,甚至更优选0.01-3重量%,尤其是0.05-1.5重量%的量存在于组合物(B)中,在每种情况下基于组合物(B)的总重量计。
成分(b4)
组合物(B)包含(i)草酸根阴离子和磷酸根阴离子中的至少一种或者包含(ii)钙阳离子、氯阴离子和氢氧根阴离子作为成分(b4)。优选组合物(B)精确地包含草酸根阴离子和磷酸根阴离子中的一种,即草酸根或磷酸根阴离子,或者包含钙阳离子、氯阴离子和氢氧根阴离子。
当组合物(B)的pH值在至多pH 6.0的非中性酸性范围内时,草酸根和/或磷酸根阴离子优选作为(b4)存在于组合物(B)中。当组合物(B)的pH值在pH值为8.0或更高的非中性碱性范围内时,钙阳离子、氯阴离子和氢氧根阴离子优选作为(b4)存在于组合物(B)中。
优选草酸根阴离子(b4)以在2-500g/l,更优选5-100g/l,尤其是10-50g/l草酸范围内的量存在于组合物(B)中,在每种情况下作为草酸二水合物计算。在这种情况下,优选不存在额外的磷酸根阴离子。
如上文所述在草酸根阴离子(b4)存在于组合物(B)中的情况下,组合物(B)优选具有在0.1至<2.0,甚至更优选0.2-1.9,仍更优选0.5-1.8范围内的pH值。这在草酸根阴离子作为唯一成分(b4)存在并且不存在磷酸根阴离子或者若存在磷酸根阴离子,则其存在量以g/l计低于以g/l计的草酸根阴离子量时,尤其是当基材表面至少部分由钢和/或其合金制成时尤其适用。
在本发明的意义上,“草酸”也指草酸的单和双去质子化形式。同样,在本发明的意义上,“草酸盐”也指其单和双质子化形式,其中双质子化形式是草酸。优选使用草酸二水合物,因为它便宜且吸湿性差。
优选磷酸根阴离子(b4)以在2-500g/l,特别优选4-320g/l,最特别优选8-200g/l,尤其是12-120g/l范围内的量存在于组合物(B)中,在每种情况下作为PO4计算。在这种情况下,优选不存在额外的草酸根阴离子。
如上文所述在磷酸根阴离子(b4)存在于组合物(B)中的情况下,组合物(B)优选具有在≥2.0至6.0,甚至更优选2.2-5.8,仍更优选2.4-5范围内的pH值。这在磷酸根阴离子作为唯一成分(b4)存在并且不存在草酸根阴离子或者若存在草酸根阴离子,则其存在量以g/l计低于以g/l计的磷酸根阴离子量时,尤其是当基材表面至少部分由钢和/或其合金制成时尤其适用。
若关于重量浓度(例如g/l)使用术语“作为X计算”,其中X是特定的指定化学化合物,则这应该如下理解:如果是另一化学化合物(非X),其应该以由在每种情况下指明的特定重量浓度(例如g/l)考虑其摩尔质量后对X计算的摩尔浓度使用。
优选钙阳离子以在0.05-15.0g/l,更优选0.07-10.0g/l,甚至更优选0.10-7.5g/l,尤其是0.20-5.0g/l,还更优选0.30-2.5g/l,尤其是0.40-2.0g/l或0.50-1.5g/l范围内的量作为(b4)的一部分存在于组合物(B)中,在每种情况下作为金属计算。优选氯阴离子以在0.10-15.0g/l,更优选0.50-10.0g/l,甚至更优选0.70-7.0g/l,尤其是0.80-5.0g/l,还更优选0.9-4.0g/l,尤其是1.0-3.0g/l范围内的量作为(b4)的一部分存在于组合物(B)中,在每种情况下作为氯化钠计算。优选氢氧根离子以在0.01-6.0g/l,更优选0.02-5.0g/l,甚至更优选0.03-3.0g/l,尤其是0.04-1.5g/l,还更优选0.05-0.8g/l,尤其是0.10-0.6g/l范围内的量作为(b4)的一部分存在于组合物(B)中,在每种情况下作为氢氧化钠计算。
如上文所述在钙阳离子、氯阴离子和氢氧根阴离子(b4)存在于组合物(B)中的情况下,组合物(B)优选具有在8.0-14.0,甚至更优选9.0-14.0,仍更优选10.0-13.5,还更优选11.0-13.0范围内的pH值。这在钙阳离子、氯阴离子和氢氧根阴离子作为唯一成分(b4)存在并且不存在草酸根阴离子和磷酸根阴离子或者若存在草酸根阴离子和/或磷酸根阴离子,则其各自的存在量以g/l计低于以g/l计的钙阳离子、氯阴离子和氢氧根阴离子各自的量时,尤其是当基材表面至少部分由铝和/或其合金制成时尤其适用。
任选的成分(b5)
组合物(B)可以任选包含Fe(III)离子(即铁(III)阳离子)作为成分(b5)。在草酸根阴离子作为成分(b4)存在的情况下,成分(b5)必然存在于组合物(B)中。
作为成分(b5)的Fe(III)离子用作草酸化促进剂。铁(III)阳离子源在本发明的意义上优选为水溶性铁(III)盐如硝酸铁(III)。还可以将适合产生铁(III)阳离子的与氧化剂结合的水溶性铁(II)盐用作铁(III)阳离子源。
优选铁(III)的含量作为硝酸铁(III)计算在0.0004-2g/l,更优选0.04-2g/l,尤其优选0.4-2g/l范围内。
当草酸根阴离子存在于其中时,优选组合物(B)不包含硝基胍。
任选的成分(b6)
组合物(B)可以进一步包含至少一种优选不同于成分(b1)-(b4)和任选的成分(b5)中每一种的缓蚀剂作为任选的成分(b6)。
术语“缓蚀剂”是本领域熟练技术人员已知的术语。所述术语例如在Lexikon,Lacke und Druckfarben 1998,Georg Thieme Verag,10.Auflage”中定义。
优选用作成分(b6)的缓蚀剂是烷基酰胺、胺和链烷醇胺。合适成分(b6)的实例是吗啉、苄胺、丁炔二醇、二异丙胺亚硝酸盐、吗啉亚硝酸盐、2-(2-十七碳-8-烯基-2-咪唑啉-1-基)乙醇、二环己胺亚硝酸盐、环己胺苯甲酸盐、二环己胺辛酸盐、胍铬酸盐、六亚甲基亚胺苯甲酸盐、二环己胺苯甲酸盐、乙基苯胺、巯基苯并三唑、吡啶、松香胺、苯基吖啶、六亚甲基四胺、壬基苯氧基乙酸、琥珀酸半酯和炔二醇如丁炔二醇。
优选该至少一种缓蚀剂优选以在0.01-5.0重量%,更优选0.05-4.0重量%,甚至更优选0.1-3重量%,尤其是0.1-1.5重量%范围内的量存在于组合物(B)中,在每种情况下基于组合物(B)的总重量计。
任选的成分(b7)
组合物(B)可以进一步包含至少一种任选的成分(b7),当(B)包含磷酸根阴离子作为成分(b4)时其为至少一种磷化促进剂并且优选不同于成分(b1)-(b4)以及任选的成分(b5)和(b6)中的每一种。优选将硝酸盐用作(b7)并且以在1-600g/l,特别优选4-450g/l,最特别优选8-300g/l,尤其是16-200g/l范围内的量存在,特别是作为硝酸根阴离子。
尤其当(B)包含磷酸根阴离子作为成分(b4)时,额外的或替换的促进剂选自氯酸盐、胍、羟胺、亚硝酸盐、硝基苯、磺酸盐、过硼酸盐、过氧化物、过氧硫酸和其他含硝基的促进剂。硝酸盐的低或中等含量可以对电解磷化具有促进效果并且因此可以是有利的。
尤其当(B)包含磷酸根阴离子作为成分(b4)时,组合物(B)可以进一步包含在0.1-200g/l,特别优选1-150g/l,最特别优选3-100g/l,尤其是6-70g/l范围内的至少一种选自有机酸和膦酸及其盐和酯的成分。这些成分尤其可以用作络合剂。
尤其当(B)包含磷酸根阴离子作为成分(b4)时,组合物(B)可以进一步包含至少一种选自Zn、Mg、Ca、Ni、Cu和/或Mn的阳离子,优选在4-100g/L,特别优选5-60g/L,最特别优选8-50g/L范围内。
本文就组合物(B)提到的阳离子和阴离子的含量可以借助ICP-OES(电感耦合等离子体的光学发射光谱)监测和测定。所述方法在下文详细描述。但是,游离氟阴离子的含量借助氟化物电极测定。
任选的成分(b8)
任选地,组合物(B)可以包含至少一种其他成分(b8)。所述至少一种其他成分(b8)优选选自增稠剂、颜料、填料、表面活性剂及其混合物。成分(b8)可以基于组合物(B)的总重量计以0.01-10重量%的量存在于组合物(B)中。优选任选的成分(b8)不同于成分(b1)-(b4)以及任选的成分(b5)、(b6)和(b7)中的每一种。
增稠剂的实例是多糖、聚硅氧烷、聚乙烯酰胺、聚丙烯酰胺和聚二醇。
颜料和填料的实例是氮化硼、石墨和硫化钼。但是,特别由于石墨和硫化钼是固体润滑剂并且它们的使用与在引言部分中概述的缺点有关,优选在组合物(B)中不存在这样的颜料,特别是既不存在石墨也不存在硫化钼。
表面活性剂的实例是脂肪醇烷氧基化物,尤其是脂肪醇乙氧基化物。
任选步骤(3)
本发明方法的任选步骤(3)是其中任选地干燥在步骤(2)后获得的涂膜的步骤。
干燥步骤(3)可优选例如在15-100℃,更优选18-95℃,特别是20-90℃的温度下进行。
本发明的预处理基材
本发明的另一主题是一种可以通过本发明方法获得的预处理金属基材。
上文关于本发明的预处理方法描述的所有优选实施方案也是预处理基材的优选实施方案。这当然同样适用于如上文联系本发明方法的步骤(1)概述的基材本身的实施方案。
在步骤(2)之后或任选在步骤(3)之后获得的涂膜是合并的转化和润滑剂涂膜。因此,所得涂膜兼具转化层和润滑剂层的性能。
优选可以通过本发明方法获得的预处理金属基材含有通过进行步骤(2)获得的转化涂膜,并进一步含有也通过进行步骤(2)获得的在所述转化涂膜上的润滑剂涂膜。但是,在步骤(2)之后或任选在步骤(3)之后获得的涂膜也可能是化学不均匀的。
优选在进行步骤(2)和任选步骤(3)之后存在于基材表面上的涂膜具有在1.0-40.0g/m2的范围内,优选5.0-35.0g/m2,更优选10.0-30.0g/m2范围内的涂覆重量。测定涂覆重量的方法公开在实施例部分中。
本发明的冷成型方法
本发明的另一主题是一种将金属基材冷成型的方法,其特征在于其包括对本发明的预处理金属基材进行冷成型工艺的步骤,优选通过拉拔。
可以进行现有技术中已知的所有可能的冷成型工艺,特别是轧制,如螺纹滚轧或敲打(beating),例如用于螺母或螺栓坯,拉拔,特别是例如焊接或无缝管、空心型材、实心型材、线材或杆的滑动拉拔(拉伸压缩成型),例如在拉丝或管材拉拔的过程中,或例如带材或金属片材的深拉、例如空心或实心体的压制如冷挤出(压力成形)、拉伸成形(成形为量块/最终尺寸)和/或冷镦,例如由线段冷镦成紧固件,如螺母。
要由本发明的预处理金属基材形成的最常见成型体是带材、片材、嵌条、线材、线圈、更复杂的成型件、套筒、型材如中空或实心型材、管、圆盘、杆、棒或圆柱体。
优选在冷成型工艺后获得的冷成型基材仍带有在进行步骤(2)和任选步骤(3)之后获得的涂膜的至少一部分:由于在步骤(2)或任选步骤(3)之后获得的存在于预处理基材上的涂膜的涂覆重量的量,所述涂膜“经得住”常规冷成型工艺。例如,这在冷成型后在预处理和冷成型的基材上留下涂覆重量的至少10%,优选至少15%,特别优选至少20%,特别是如果基材经过拉拔。
但是,可以从冷成型基材上除去涂膜,例如通过使用水性清洁组合物。因此,在冷成型工艺后,优选清洁所得基材,以从基材上除去转化和润滑剂涂膜,例如借助碱性清洁剂、酸或酸洗剂。
本发明的组合物(B)
本发明的另一主题是如上文联系本发明的预处理方法定义的水性润滑剂组合物(B)。
上文关于本发明方法及其步骤(2)中所用组合物(B)和其中所含成分描述的所有优选实施方案也是本发明组合物(B)的优选实施方案。
本发明的母料
本发明的另一主题是一种母料,其用于通过用水稀释母料和如果适用的话调节pH值而生产本发明的水性组合物(B)。
上文关于本发明方法和本发明组合物(B)和其中所含成分描述的所有优选实施方案也是本发明的母料的优选实施方案。
如果使用母料生产根据本发明的水性组合物(B),则母料通常以所需比例含有要生产的水性组合物(B)的成分,但浓度更高。这样的母料优选用水稀释到如上文公开的成分的浓度以形成水性组合物(B)。如果必要,可在母料稀释后调节水性组合物(B)的pH值。
当然,也可将任何任选组分进一步加入用于稀释母料的水中,或在用水稀释母料后加入任何任选组分。但是优选母料已含有所有必要的组分。
优选母料用水和/或水溶液以1:5,000至1:10,更优选1:1,000至1:10,最优选1:300至1:10,甚至更优选1:150至1:50的比率稀释以产生组合物(B)。
方法
1.总酸(TA)
总酸(TA)是存在的二价阳离子以及游离和结合的草酸和/或磷酸的总和。其使用pH计和电极通过0.1M NaOH的消耗测定。为此,将10ml组合物吸移到合适的容器,例如300ml锥形烧瓶中并用25ml去离子水稀释。然后用0.1M NaOH滴定至pH为9。每10ml稀释组合物消耗的毫升数对应于总酸分数(TA)。
2.游离酸(FA)和Fischer总酸(TAF)
游离酸(FA)使用pH计和电极通过0.1M NaOH的消耗测定。为此,将5ml组合物吸移到合适的容器,例如300ml锥形烧瓶中并用50ml去离子水稀释。然后用0.1M NaOH滴定至pH为4。每10ml稀释组合物消耗的毫升数对应于游离酸分数(FA)。在FA滴定之后将40mL 30%草酸钾溶液加入该溶液中。然后用0.1M NaOH滴定至pH为9。每10ml稀释组合物消耗的毫升数对应于Fischer总酸分数(TAF)。
3.固含量
根据DIN EN ISO 3251(日期:2019年6月)测定非挥发分(固体或固含量)。这涉及将1克样品称到预先干燥的铝盘中,并将带有样品的盘在干燥箱中在130℃下干燥60分钟,将其在干燥器中冷却,然后再称重。相对于所用样品的总量计的残留物相当于非挥发分。
4.ICP-OES
根据DIN EN ISO 11885(日期:2009年9月1日)使用电感耦合等离子体原子发射光谱法(ICP-OES)测定受分析的样品中某些元素的量。
4.碱性点
碱性点使用pH计和电极通过0.05M硫酸的消耗测定。为此,将5ml组合物吸移到合适的容器,例如300ml锥形烧瓶中并用50ml去离子水稀释。然后用0.05M硫酸滴定至pH为4.5。
5.钙点
钙点通过滴定0.1M EDTA溶液测定。
6.玻璃化转变温度(Tg)
玻璃化转变温度(Tg)通过差示扫描量热法(DSC)测定。通过DSC分析10mg聚合物样品。温度程序设定为从-50℃到210℃并且选择加热/冷却速率为10℃/Min。
7.多分散指数(PDI)和重均分子量(Mw)
Mw(重均分子量)和PDI以及Mn(数均分子量)的测定通过装有RI和UV检测器的凝胶渗透色谱法(GPC)进行。将聚合物样品溶于移动相中并将所得滤液用微孔过滤器0.45μm过滤。洗脱条件如下:移动相:DMF 100体积%0.01% LiBr;流速:1mL/min;柱:VarianAquagel OH混合H,8μm,3*30cm;检测:RI(浓度检测器Agilent)+在290nm下的UV;样品浓度:在移动相中约0.5重量%;注入回路:100μL。
实施例
下列实施例进一步例示本发明但不应被解释为限制其范围。
1.本发明和对比润滑剂组合物
1.1实施例I1(本发明)
在高速混合机中在搅拌下制备用于钢和/或合金钢预处理的含磷酸根阴离子的酸稳定水性聚合物润滑剂组合物I1。在表1中给出这种润滑剂的组成。它具有约2.5的pH值。
表1:含磷酸盐的润滑剂实施例I1的组成
聚合物1是由BASF SE市购的聚乙烯基吡咯烷酮均聚物。聚合物1具有约4.5的多分散指数(PDI)和约100-110℃的玻璃化转变温度(Tg)。聚合物水溶液2含有由BASF SE市购的聚乙烯基吡咯烷酮共聚物。水性蜡分散体1含有由BYK Chemie市购的聚丙烯蜡。水性蜡分散体2含有由Münzing Chemie市购的聚乙烯蜡。水性蜡分散体3含有由Michelman市购的微晶蜡。蜡4是可分散在水性介质中的褐煤蜡。将烷基酰胺和链烷醇胺的混合物用作缓蚀剂。Z 3100是由Chemetall GmbH市购的含有磷酸根阴离子的产品,其用于进行磷酸锌处理。I1的磷化点(游离酸(FA)加Fischer总酸(TFA))为20。
1.2实施例I2(本发明)
在高速混合机中在搅拌下制备用于钢和/或合金钢预处理的含草酸根阴离子的酸稳定水性聚合物润滑剂组合物I2。在表2中给出这种润滑剂的组成。它具有约1.0的pH值。
表2:含草酸盐的润滑剂实施例I2的组成
聚合物1、聚合物水溶液2、水性蜡分散体1、2和3及蜡4以及缓蚀剂已经在上面就润滑剂实施例I1说明。Hybrid Z 4100是市售含草酸产品(Chemetall GmbH),其不含磷酸盐。Additive H 7104是由Chemetall GmbH市购的含Fe(NO3)3产品并且与Hybrid Z4100组合用作草酸化促进剂。
Hybrid Z 4100在I2中的浓度为33g/L并且Additive H7104在I2中的浓度为23.6g/L。I2的总酸(TA)值为55。
1.3实施例I3(本发明)
在高速混合机中在搅拌下制备用于钢和/或合金钢预处理的含磷酸根阴离子的酸稳定水性聚合物润滑剂组合物I3。在表3中给出这种润滑剂的组成。它具有约5.5的pH值。
表3:含磷酸盐的润滑剂实施例I3的组成
聚合物1、聚合物水溶液2、水性蜡分散体1、2和3及蜡4以及缓蚀剂已经在上面就润滑剂实施例I1说明。Z 3911是由Chemetall GmbH市购的含磷酸盐产品,其用于进行磷酸铁处理。Additive H 7201是用于进行磷酸铁处理的市售添加剂。I3的总酸(TA)为15且碱性点为0.7。
1.4实施例I4(本发明)
在高速混合机中在搅拌下制备用于铝和/或铝合金预处理的碱稳定水性聚合物润滑剂组合物I4。在表4中给出这种润滑剂的组成。它具有约12.0的pH值。
表4:润滑剂实施例I4的组成
聚合物1、聚合物水溶液2、水性蜡分散体1、2和3及蜡4以及缓蚀剂已经在上面就润滑剂实施例I1说明。Z 3900是由Chemetall GmbH市购的产品,包含氯化钙、氯化钠和氢氧化钙。I4的钙点在15-20范围内。
1.5实施例I5(对比)
将由Chemetall GmbH市售的产品L 6332用作对比组合物I5,其为含蜡水性碱性聚合物润滑剂。L 6332具有9.5的pH值并且在酸溶液中不稳定。在L 6332中将不含任何衍生于乙烯基吡咯烷酮的单体单元的酸官能共聚物用作成膜聚合物。
1.5实施例I6(对比)
在高速混合机中在搅拌下制备用于钢和/或合金钢预处理的含草酸根阴离子的酸稳定水性聚合物润滑剂组合物I6。该润滑剂的组成及其pH值与实施例I2的润滑剂的组成和pH值相同,不同的是没有使用Additive H 7104,但使用包含硝基胍的市售草酸化促进剂。
2.本发明和对比方法
2.1在单一步骤中对钢和/或合金钢进行磷酸锌处理和用酸稳定水性聚合物润滑剂I1处理(本发明)
作为金属工件,使用以下基材:
a)由2.0mm热轧钢(HRS)制成的片材(DC11(编号1.0332);基材S1),
b)由回火钢制成的具有27mm直径和13mm高度的嵌条(C15(编号1.0401);基材S2),和
c)由钢制成的具有11.0mm直径的线段(C15(编号1.0401);基材S3)。
将各工件在90℃下浸渍在含有可获自Chemetall GmbH的351的50g/L水性清洁溶液的清洁浴中10分钟,然后用冷自来水冲洗1分钟。此后,表面净化的工件随后使用15重量%HCl溶液酸洗1分钟,随后用冷自来水冲洗1分钟。然后在室温下将工件用从Chemetall GmbH得到的V 6522最佳地活化1分钟。
然后,在单一步骤中将工件浸入在60℃下的含有润滑剂实施例I1的浴中10分钟。
最后,将所得涂布工件在85℃下用空气干燥。
在这一工艺过程中没有形成固体泡沫。在I1的反应浴中产生的淤渣是粉末状的并且可容易地从反应浴中除去。
2.2在单一步骤中对钢和/或合金钢的草酸化处理和用酸稳定水性聚合物润滑剂I2(本发明)或I6(对比)处理
作为金属工件,使用以下基材:
a)由0.8mm冷轧钢(CRS)制成的片材(DC05(编号1.0332);基材S4),
b)由2.0mm热轧钢(HRS)制成的片材(DC11(编号1.0332);基材S1),
c)由回火钢制成的具有27mm直径和13mm高度的嵌条(C15(编号1.0401);基材S2),和
d)由钢制成的具有11.0mm直径的线段(C15(编号1.0401);基材S3)。
将各工件在85℃下浸渍在含有可获自Chemetall GmbH的351的50g/L水性清洁溶液的清洁浴中10分钟,然后用冷自来水冲洗1分钟。此后,表面净化的工件随后使用15重量%HCl溶液酸洗1分钟,随后用冷自来水冲洗1分钟。
然后,在单一步骤中将工件浸入在85℃下的含有润滑剂实施例I2或I6的浴中8分钟。
最后,将所得涂布工件在85℃下用空气干燥。
在这一工艺过程中没有形成固体泡沫。在I2和I6的反应浴中产生的淤渣是粉末状的并且可容易地从反应浴中除去。
2.3在单一步骤中对钢和/或合金钢进行磷酸铁处理和用酸稳定水性聚合物润滑剂I3处理(本发明)
作为金属工件,使用以下基材:
a)由2.0mm热轧钢(HRS)制成的片材(DC11(编号1.0332);基材S1),
b)由钢制成的无缝管(编号1.0050,基材S5)
将各工件在85℃下浸渍在含有可获自Chemetall GmbH的351的50g/L水性清洁溶液的清洁浴中10分钟,然后用冷自来水冲洗1分钟。此后,表面净化的工件随后使用15重量%HCl溶液酸洗1分钟,随后用冷自来水冲洗1分钟。
然后,在单一步骤中将工件浸入在70℃下的含有润滑剂实施例I3的浴中10分钟。
最后,将所得涂布工件在85℃下用空气干燥。
在这一工艺过程中没有形成固体泡沫。在I3的反应浴中产生的淤渣是粉末状的并且可容易地从反应浴中除去。
2.4在单一步骤中对铝和/或铝合金用碱稳定水性聚合物润滑剂I4处理(本发明)
作为金属工件,使用以下基材:由回火铝制成的具有27mm直径和13mm高度的嵌条(1050A,基材S6)。
将各工件在55℃下浸渍在含有可获自Chemetall GmbH的T 5550的20g/L水性清洁溶液的清洁浴中10分钟,然后用冷自来水冲洗1分钟。此后,表面净化的工件随后使用35g/LP4304酸溶液酸洗1分钟,随后用冷自来水冲洗1分钟。
然后,在单一步骤中将工件浸入在75℃下的含有润滑剂实施例I4的浴中10分钟。
最后,将所得涂布工件在85℃下用空气干燥。
在这一工艺过程中没有形成固体泡沫。在I4的反应浴中产生的淤渣是粉末状的并且可容易地从反应浴中除去。
2.5在以两个步骤(加冲洗)进行(i)磷酸锌处理并随后(ii)冲洗之后用常规碱性聚合物润滑剂I5处理钢和/或合金钢(对比)
作为金属工件,使用以下基材:
a)由2.0mm热轧钢(HRS)制成的片材(DC11(编号1.0332);基材S3),
b)由钢制成的具有11.0mm直径的线段(C15(编号1.0401);基材S1)。
将各工件在85℃下浸渍在含有可获自Chemetall GmbH的351的50g/L水性清洁溶液的清洁浴中10分钟,然后用冷自来水冲洗1分钟。此后,表面净化的工件随后使用15重量%HCl溶液酸洗1分钟,随后用冷自来水冲洗1分钟。然后在室温下将工件用从Chemetall GmbH得到的V 6522最佳地活化1分钟。
将工件在60℃下浸入含有来自Chemetall GmbH的市售产品Z3100的磷酸锌处理浴中10分钟。该磷酸锌处理浴的磷酸盐点为20,与润滑剂I1的情况相同。然后将磷酸锌处理工件用自来水冲洗以中和表面。在冲洗之后将工件在60℃下浸入含有常规对比水性碱性润滑剂I5的浴中2分钟。
最后,将所得涂布工件在85℃下用空气干燥。
2.6在以两个步骤(加冲洗)进行(i)草酸化处理并随后(ii)冲洗之后用常规碱性聚合物润滑剂I5处理钢和/或合金钢(对比)
a)由0.8mm冷轧钢(CRS)制成的片材(DC05(编号1.0332);基材S2),
b)由钢制成的具有11.0mm直径的线段(C15(编号1.0401);基材S1)。
将各工件在85℃下浸渍在含有可获自Chemetall GmbH的351的50g/L水性清洁溶液的清洁浴中10分钟,然后用冷自来水冲洗1分钟。此后,表面净化的工件随后使用15重量%HCl溶液酸洗1分钟,随后用冷自来水冲洗1分钟。
将工件在85℃下浸入含有来自Chemetall GmbH的市售产品Hybrid Z4100和Additive H 7104的草酸化浴中10分钟。该草酸化浴的总酸(TA)为55,与I2相同。然后将草酸化工件用自来水冲洗以中和表面。在冲洗之后将工件在60℃下浸入含有常规对比水性碱性润滑剂I5的浴中2分钟。
最后,将所得涂布工件在85℃下用空气干燥。
3.涂布基材的性能
3.1获自如条目2.1(本发明)—使用润滑剂I1中概述的一步法的涂布基材
各涂布工件上的所得涂层均匀、厚并牢固地附着在各工件的处理表面上。涂层显示出非常好的抗腐蚀稳定性并且在任何钢表面上不存在颜色褐变。通过该方法形成的顶涂层是聚合物润滑剂层,形成的底涂层是磷酸锌转化涂层。
将润滑工件称重。然后用二甲苯洗涤聚合物润滑剂涂层以使其脱离,随后用水洗涤。然后将工件干燥并称重。用含有NaOH、三乙胺和EDTA的碱性溶液(来自Chemetall GmbH的PL 83)洗涤磷酸盐涂层以使其脱离。最后用水冲洗工件,干燥并再次称重。在不同基材表面上的涂覆重量列于表5中。这些数据涉及使用润滑剂I1。
表5:在不同基材表面(S1、S2和S3)上的涂覆重量,以g/m2计
基材 | 聚合物润滑剂涂覆重量[g/m2] | 磷酸锌涂覆重量[g/m2)] | 总计[g/m2] |
S1 | 2.7 | 8.0 | 10.7 |
S2 | 5.0 | 8.7 | 13.7 |
S3 | 2.9 | 8.1 | 11.0 |
以不同拉拔速度(三个平行操作I、II和III)进行涂布基材S3的拉拔试验以证明冷成型性能。结果示于表6中。操作I的拉拔试验使用30m/min的拉拔速度和在各步骤中20%的横截面积减小。操作II以60m/min的拉拔速度和在各步骤中20%的横截面积减小进行。这些数据也涉及使用润滑剂I1。
表6:涂布基材S3的拉拔性能的测试参数
这两个平行操作均显示出良好的拉拔性能。在基材S3上的涂层显示出非常好的润滑性能。此外,涂层显示出非常好的抗腐蚀稳定性。在拉拔之后均匀涂层仍存在于钢丝表面上并且钢丝基材S3在其钢表面上没有显示出划痕或其他可见缺陷。剩余的聚合物润滑剂涂覆重量和磷酸锌涂覆重量列于表7中。聚合物润滑剂涂层具有良好的润滑性能并且因此适合在高速拉拔下金属冷成型。
表7:在拉拔之后涂布基材S3的剩余涂覆重量
聚合物润滑剂涂覆重量[g/m2] | 磷酸锌涂覆重量[g/m2] | 总计[g/m2] | |
操作I | 1.0 | 3.9 | 4.9 |
操作II | 0.7 | 2.8 | 3.5 |
将涂布基材S2冷挤出。冷挤出是成功的。在冷挤出基材上不存在划痕或其他可见缺陷。
已经证明涂层具有高质量并且非常适合在高拉拔速度下冷成型和冷挤出。剩余的涂层仍牢固地附着在基材的金属表面上。
在冷成型工艺后,剩余涂层可使用碱性清洁剂,例如来自Chemetall GmbH的含有Additive H 7375的S 5171,或使用酸性清洁剂,例如来自Chemetall GmbH的含有Additive H7390的Additive H7132洗涤,这不会损害任何所需性能。
3.2获自如条目2.2(本发明)—使用润滑剂I2中概述的一步法的涂布基材
各涂布工件上的所得涂层均匀、厚并牢固地附着在各工件的处理表面上。涂层显示出非常好的抗腐蚀稳定性并且在任何钢表面上不存在颜色褐变。通过该方法形成的顶涂层是聚合物润滑剂层,形成的底涂层是草酸盐转化涂层。
在不同基材上的涂覆重量通过上文在条目3.1中所述方法测定并且列于表8中。这些数据涉及使用润滑剂I2。
表8:在不同基材表面(S1、S2和S3)上的涂覆重量,以g/m2计
以不同拉拔速度(三个平行操作I、II和III)进行涂布基材S1的拉拔试验以证明冷成型性能。结果示于表9中。操作I的拉拔试验使用30m/min的拉拔速度和在各步骤中20%的横截面积减小。操作II以60m/min的拉拔速度和在各步骤中20%的横截面积减小进行。操作III以40m/min的拉拔速度和在各步骤中35%的横截面积减小进行。这些数据也涉及使用润滑剂I2。
表9:涂布基材S3的拉拔性能的测试参数
nd=未测定
所有三个平行操作均显示出良好的拉拔性能。钢丝上的涂层显示出非常好的润滑性能。在拉拔之后均匀涂层仍存在于钢丝表面上并且钢丝在钢表面上没有显示出划痕或其他可见缺陷。在进行拉拔试验之后剩余的涂覆重量列于表10中。在拉拔之后,总的剩余涂覆重量全部仍高于6g/m2。钢丝甚至仍可以进行拉拔而减少直径。这些数据也涉及使用润滑剂I2。
表10:在拉拔之后涂布基材S3的剩余涂覆重量
聚合物润滑剂涂覆重量[g/m2] | 草酸盐涂覆重量[g/m2] | 总涂覆重量[g/m2] | |
操作I | 3.2 | 3.8 | 7.0 |
操作II | 3.4 | 5.2 | 8.6 |
操作III | 2.7 | 3.6 | 6.3 |
将涂布基材S2冷挤出。冷挤出是成功的。在冷挤出基材上不存在划痕或其他可见缺陷。
已经证明涂层具有高质量并且非常适合在高拉拔速度下冷成型和冷挤出。剩余的涂层仍牢固地附着在基材的金属表面上。
在冷成型工艺后,剩余涂层可使用碱性清洁剂,例如来自Chemetall GmbH的含有Additive H 7375的S 5171,或使用酸性清洁剂,例如来自Chemetall GmbH的含有Additive H7390的Additive H7132洗涤,这不会损害任何所需性能。
3.3获自如条目2.3(本发明)—使用润滑剂I3中概述的一步法的涂布基材
各涂布工件上的所得涂层均匀、厚并牢固地附着在各工件的处理表面上,这特别适合管材行业。涂层显示出非常好的抗腐蚀稳定性并且在任何钢表面上不存在颜色褐变。通过该方法形成的顶涂层是聚合物润滑剂层,形成的底涂层是磷酸铁涂层。
在不同基材上的涂覆重量通过上文在条目3.1中所述方法测定并且列于表11中。这些数据涉及使用润滑剂I3。
表11:在不同基材表面(S1和S5)上的涂覆重量,以g/m2计
基材 | 聚合物润滑剂涂覆重量[g/m2] | 磷酸铁涂覆重量[g/m2)] | 总计[g/m2] |
S1 | 2.1 | 1.1 | 3.2 |
S5 | 2.1 | 0.9 | 3.0 |
3.4获自如条目2.4(本发明)—使用润滑剂I4中概述的一步法的涂布基材
各涂布工件上的所得涂层均匀、厚并牢固地附着在各工件的处理表面上。涂层显示出非常好的抗腐蚀稳定性并且在任何铝表面上不存在颜色褐变。通过该方法形成的顶涂层是聚合物润滑剂层,形成的底涂层是铝酸钙转化涂层。
在不同基材上的涂覆重量通过上文在条目3.1中所述方法测定。用含有10% HNO3的酸溶液洗涤铝酸钙涂层以使其脱离。最后,用水冲洗工件,干燥并再次称重。
在铝嵌条(S6)上的涂覆重量在表12中给出。这些数据涉及使用润滑剂I4。
表12:在铝嵌条表面(S6)上的涂覆重量,以g/m2计
基材 | 聚合物润滑剂涂覆重量[g/m2] | 铝酸钙涂覆重量[g/m2)] | 总计[g/m2] |
S6 | 8.2 | 5.3 | 13.5 |
3.5比较获自如条目2.1中概述的本发明一步法的涂布基材和获自如条目2.5中概述的常规多步法的涂布基材—使用常规润滑剂I5处理钢
获自如条目2.1中概述的一步法的涂层性能与获自如条目2.5中概述的常规多步法的涂层相当或者稍好。但是,在本发明方法的情况下仅需进行一个工艺步骤并且因此无需在对比方法情况下的冲洗步骤,在本发明一步法的情况下获得的总涂覆重量比在对比多步法的情况下要高。
3.6比较获自如条目2.2中概述的本发明一步法的涂布基材和获自如条目2.6中概述的常规多步法的涂布基材—使用常规润滑剂I5处理钢
获自如条目2.2中概述的一步法的涂层性能与获自如条目2.6中概述的常规多步法的涂层相当或者稍好。但是,在本发明方法的情况下仅需进行一个工艺步骤并且因此无需在对比方法情况下的冲洗步骤,在本发明一步法的情况下获得的总涂覆重量比在对比多步法的情况下要高。
3.7获自如条目2.2(本发明)—使用润滑剂I6中概述的一步法的涂布基材
由表8可见,发现在使用润滑剂I2的情况下基材S1-S3上的草酸盐涂覆重量在7.7-12.5g/m2范围内,出人意料地发现在使用润滑剂I6的情况下以与条目2.2中所述相同的方式观察到的草酸盐涂覆重量显著更低,即仅在4.0-6.0g/m2范围内。因此,该效果与在I2中使用Fe(III)离子作为促进剂,而在I6中使用硝基胍有关,这是出人意料的。
Claims (15)
1.一种用于后续金属冷成型工艺的金属基材的预处理方法,所述方法至少包括步骤(1)和(2)和任选步骤(3),即
(1)提供至少一种基材,其具有至少一个至少部分由至少一种金属和/或其合金制成的表面,其中所述金属和/或其合金为钢、铝以及铝和/或钢的合金中的至少一种,
(2)使步骤(1)中提供的基材的所述至少一个表面与具有在非中性pH范围内的pH值的水性润滑剂组合物(B)接触,其中所述中性pH范围为>6.0至<8.0的pH范围,
其中所述水性润滑剂组合物(B)除水外至少包含相互不同的成分(b1)-(b4)和任选(b5),即
(b1)至少一种成膜聚合物,其是通过至少乙烯基吡咯烷酮作为至少一种单体的聚合制备的均聚物和/或共聚物,其中所述均聚物和/或共聚物具有的多分散指数(PDI)在1.5-8.0范围内,
(b2)至少一种蜡,
(b3)至少一种消泡剂,和
(b4)(i)草酸根阴离子和/或磷酸根阴离子或者(ii)钙阳离子、氯阴离子和氢氧根阴离子,以及
(b5)任选地,Fe(III)离子,其中成分(b5)在至少草酸根阴离子作为成分(b4)存在的情况下存在,以及
(3)任选地,干燥在已经进行步骤(2)之后得到的涂膜。
2.根据权利要求1的方法,其特征在于成膜聚合物(b1)具有的多分散指数(PDI)在1.8-7.5,优选2.0-7.0,更优选2.5-6.5,甚至更优选3.0-6.0,尤其是3.5-5.5范围内。
3.根据权利要求1或2的方法,其特征在于成膜聚合物(b1)具有至少一个在40-200℃,优选50-190℃,更优选60-170℃,仍更优选70-150℃,甚至更优选80-130℃,尤其是90-120℃范围内的玻璃化转变温度(Tg)。
4.根据前述权利要求中任一项的方法,其特征在于成膜聚合物(b1)是由乙烯基吡咯烷酮制备的均聚物或者由乙烯基吡咯烷酮和至少一种选自(甲基)丙烯酸酯单体、乙烯基胺、乙烯醇、乙烯基甲酰胺、乙烯基己内酰胺、乙酸乙烯酯和乙烯基咪唑的单体制备的共聚物。
5.根据前述权利要求中任一项的方法,其特征在于成膜聚合物(b1)以在0.05-20重量%,优选0.10-15重量%范围内的量存在于组合物(B)中,在每种情况下基于组合物(B)的总重量计。
6.根据前述权利要求中任一项的方法,其特征在于所述水性润滑剂组合物(B)具有在0.1-6.0,优选0.2-5.8,更优选0.5-5.5范围内的pH值,优选当(i)草酸根阴离子和磷酸根阴离子中的至少一种作为成分(b4)存在时,尤其是当所述基材表面至少部分由钢和/或其合金制成时,或者具有在8.0-14.0,优选9.0-14.0,更优选10.0-13.5,甚至更优选11.0-13.0范围内的pH值,优选当(ii)钙阳离子、氯阴离子和氢氧根阴离子作为成分(b4)存在时,尤其是当所述基材表面至少部分由铝和/或其合金制成时。
7.根据前述权利要求中任一项的方法,其特征在于所述水性润滑剂组合物(B)具有在0.1至<2.0,优选0.2-1.9,更优选0.5-1.8范围内的pH值,优选当至少草酸根阴离子作为成分(b4)存在时,更优选当草酸根阴离子作为成分(b4)存在并且不存在磷酸根阴离子或者若存在磷酸根阴离子,则其存在量以g/l计低于以g/l计的草酸根阴离子量时,尤其是当所述基材表面至少部分由钢和/或其合金制成时,或者具有在≥2.0至6.0,优选2.2-5.8,更优选2.4-5.5范围内的pH值,优选当至少磷酸根阴离子作为成分(b4)存在时,更优选当磷酸根阴离子作为成分(b4)存在并且不存在草酸根阴离子或者若存在草酸根阴离子,则其存在量以g/l计低于以g/l计的磷酸根阴离子量时,尤其是当所述基材表面至少部分由钢和/或其合金制成时,或者具有在8.0-14.0,优选9.0-14.0,更优选10.0-13.5,甚至更优选11.0-13.0范围内的pH值,优选当至少钙阳离子、氯阴离子和氢氧根阴离子作为成分(b4)存在时,更优选当钙阳离子、氯阴离子和氢氧根阴离子作为成分(b4)存在并且不存在草酸根阴离子和磷酸根阴离子或者若存在草酸根阴离子和磷酸根阴离子,则其各自的存在量以g/l计低于以g/l计的钙阳离子、氯阴离子和氢氧根阴离子各自的量时,尤其是当所述基材表面至少部分由铝和/或其合金制成时。
8.根据前述权利要求中任一项的方法,其特征在于所述至少一种蜡(b2)选自聚烯烃蜡,优选聚乙烯蜡和聚丙烯蜡,石蜡和天然蜡,优选褐煤蜡、蜂蜡和巴西棕榈蜡及其混合物,其中所述至少一种蜡(b2)优选以在0.1-20重量%,更优选0.5-15重量%范围内的量存在于组合物(B)中,在每种情况下基于组合物(B)的总重量计。
9.根据前述权利要求中任一项的方法,其特征在于组合物(B)进一步包含至少一种不同于成分(b1)-(b4)和任选的成分(b5)中的每一种的缓蚀剂作为成分(b6)。
10.根据前述权利要求中任一项的方法,其特征在于消泡剂成分(b3)是不含聚硅氧烷的消泡剂。
11.根据前述权利要求中任一项的方法,其特征在于接触步骤(2)通过将所述基材至少部分浸入含有所述水性润滑剂组合物(B)且具有在20-95℃,优选30-90℃,尤其是55-85℃范围内的浴温的浴中而进行。
12.一种可以通过根据权利要求1-11中任一项的方法得到的预处理金属基材。
13.根据权利要求12的预处理金属基材,其特征在于在已经进行步骤(3)之后存在于所述基材表面上的所述涂膜具有在1.0-40.0g/m2,优选5.0-35.0g/m2,更优选10.0-30.0g/m2范围内的涂覆重量。
14.一种将金属基材冷成型的方法,其特征在于它包括对根据权利要求12或13的预处理金属基材进行冷成型工艺的步骤,优选通过拉拔进行。
15.如权利要求1-10中任一项所定义的水性润滑剂组合物(B)。
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JPS5672090A (en) | 1979-11-19 | 1981-06-16 | Nippon Parkerizing Co Ltd | Surface treatment of metal |
JPS62170484A (ja) | 1986-01-21 | 1987-07-27 | Nippon Parkerizing Co Ltd | ステンレス鋼の冷間加工用潤滑処理方法 |
JP3193798B2 (ja) | 1993-01-13 | 2001-07-30 | 日本パーカライジング株式会社 | 金属冷間加工用の複合皮膜形成用金属表面処理液及び複合皮膜形成方法 |
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TWI457431B (zh) | 2008-01-30 | 2014-10-21 | Chemetall Gmbh | 將金屬表面施以一種潤滑劑組成物的方法 |
TWI457432B (zh) | 2008-01-30 | 2014-10-21 | Chemetall Gmbh | 將金屬表面施以一含蠟的潤滑劑組成物的方法 |
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