CN108368375A - 不锈钢板用润滑涂料及润滑不锈钢板 - Google Patents

不锈钢板用润滑涂料及润滑不锈钢板 Download PDF

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CN108368375A
CN108368375A CN201680070393.0A CN201680070393A CN108368375A CN 108368375 A CN108368375 A CN 108368375A CN 201680070393 A CN201680070393 A CN 201680070393A CN 108368375 A CN108368375 A CN 108368375A
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stainless steel
steel plate
slip coating
mass parts
polyethylene wax
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CN108368375B (zh
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平泽淳郎
平泽淳一郎
矢野孝宜
石川伸
上力
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JFE Steel Corp
JFE Engineering Corp
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NKK Corp
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Priority claimed from PCT/JP2016/085940 external-priority patent/WO2017094893A1/ja
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Abstract

本发明的目的在于提供加压加工性(拉深性及耐擦伤性)优异的不锈钢板用润滑涂料及使用其的润滑不锈钢板；本发明提供不锈钢板用润滑涂料及使用其的润滑不锈钢板，上述不锈钢板用润滑涂料包含丙烯酸系树脂及聚乙烯蜡，上述聚乙烯蜡的熔点为115℃以上，相对于上述丙烯酸系树脂100质量份而言，不锈钢板用润滑涂料含有大于20质量份且小于等于50质量份的上述聚乙烯蜡。

Description

不锈钢板用润滑涂料及润滑不锈钢板
技术领域
本发明涉及在对不锈钢板进行加压加工时有用的、赋予表面润滑性的涂料，以及涂装有该涂料的润滑不锈钢板。
背景技术
与一般的软钢相比较，不锈钢板的强度高，在加压加工时承受来自模具的更高的面压力而发生滑动，从而钢板表面的损伤(擦伤(galling))变得显著，因此，在钢板表面上需要优异的表面润滑性。
通常为了在加工时获得润滑性而广泛使用润滑油，然而，润滑油存在滴落、而且具有挥发性从而在空气中扩散等使作业环境变差的情况。
除了润滑油以外，作为对钢板表面赋予润滑性的物质，有向树脂中添加蜡等润滑剂并通过烘烤而使其干燥而得到的固体润滑被膜。一般而言，与润滑油相比较，固体润滑被膜的润滑性、耐擦伤性优异，并且被膜自身没有挥发性，因此作业环境也可保持良好。
蜡被广泛用作润滑剂，特别是低熔点的蜡由于摩擦系数低而经常使用。然而，另一方面，蜡具有难以固化的缺点，在为了提高润滑性而大量添加蜡的情况下，即便要通过烘烤炉等而将涂料干燥，仍存在蜡没有固化而使得被膜保持粘性的问题。
专利文献1在其权利要求1中记载了一种脱膜型润滑钢板，所述脱膜型润滑钢板包含：(a)特定的丙烯酸树脂，(b)金属皂等和(c)熔点Tm为70≤Tm≤150℃的聚乙烯系蜡，其中，成分(b)和成分(c)的组合作为混合润滑剂，并且相对于(a)的固体成分而言成分(c)为3～20重量％。该文献公开了以下的发明：具有(b)金属皂等与(c)特定的高熔点聚乙烯系蜡组合而成的混合润滑剂的润滑钢板在拉深性、耐擦伤性方面优异。在比较例7中显示出下述结果：在仅使用特定的高熔点蜡的单独的润滑剂的情况下，耐擦伤性变差。另外，在比较例9、12中显示出下述结果：若特定的高熔点蜡的配合量大于20重量％，则其与钢板的密合性变差，拉深性、耐擦伤性变差(参见段落[0021]、表2(其中的3))。
专利文献2中记载了在特定的丙烯酸树脂中含有熔点为60℃以上的有机固态蜡作为润滑剂(权利要求1)的、加工性、耐擦伤性优异的不锈钢冷轧钢板(权利要求5)。关于蜡的含量，记载了相对于涂料组成物的全部树脂固体成分而言为1～10质量％左右(段落[0038])，实施例中使用的蜡为低熔点(68℃～107℃)、且使用量为少量(相对于丙烯酸系树脂100质量份而言为2.04～11.1质量份)。在专利文献2的发明中，是基于下述技术理解而开发的发明：高熔点蜡自身的摩擦系数高，因此为了降低摩擦系数而使用摩擦系数更低的、比较而言低熔点的蜡。
专利文献2的发明虽然得到了作为润滑不锈钢板的效果，但在不锈钢的连续加压时、剧烈的深拉深成型时，仍有改良的必要。
另外，若为了提高润滑特性而相对于树脂固体成分添加大于20重量％的熔点小于115℃的低熔点蜡时，则由于蜡的熔点低，因而涂料在干燥后仍未固化从而保持粘性，当处理钢板时，涂装附着于周边，从而存在涂装的润滑效果降低、而且周边需要清扫的问题。
现有技术文献
专利文献
专利文献1：日本特开平9-156029号公报
专利文献2：日本特开2008-248076号公报
发明内容
发明要解决的课题
本发明的目的在于，解决上述现有技术的问题点，并提供对强度比一般的软钢更高的不锈钢板赋予优异的加压加工性的润滑涂料、以及使用该润滑涂料的润滑不锈钢板。
用于解决课题的手段
本发明人等为解决上述现有技术的课题，详细地研究了润滑涂料的组成，结果与专利文献2中的上述构思相反，意外地发现：如使用相对于丙烯酸系树脂100质量份而言大于20质量份的大量的高熔点蜡时，当不使用专利文献1的混合润滑剂而使用在专利文献1中结果不好的、在润滑涂料中大量的高熔点蜡时，对于不锈钢而言，与作为专利文献2的发明的基础的技术构思相反，可得到充分的深拉深性及耐擦伤性，从而完成了本发明。
即，本发明提供以下构成。
(1)、不锈钢板用润滑涂料，其包含丙烯酸系树脂及聚乙烯蜡，上述聚乙烯蜡的熔点为115℃以上，相对于上述丙烯酸系树脂100质量份而言，上述不锈钢板用润滑涂料含有大于20质量份且小于等于50质量份的聚乙烯蜡。
(2)、如(1)中记载的不锈钢板用润滑涂料，相对于上述丙烯酸系树脂100质量份而言，进一步含有1质量份～10质量份的有机钙化合物。
(3)、如(1)或(2)中记载的不锈钢板用润滑涂料，其中，上述聚乙烯蜡为中密度聚乙烯蜡或高密度聚乙烯蜡。
(4)、(1)至(3)中任一项中记载不锈钢板用润滑涂料的制造方法，其中，使用水系溶剂将上述聚乙烯蜡乳化并进行添加。
(5)、润滑不锈钢板的制造方法，其中，在不锈钢板上涂布(1)至(3)中任一项中记载的不锈钢板用润滑涂料，进行热风干燥，从而形成以干燥后的质量计每面为0.5～2.5g/m2的润滑被膜。
(6)、润滑不锈钢板，所述润滑不锈钢板具有以干燥后的质量计每面为0.5～2.5g/m2的上述(1)至(3)中任一项所述的不锈钢板用润滑涂料。
发明效果
通过使用本发明的润滑涂料，可提供加压加工性(深拉深性及耐擦伤性)优异的润滑不锈钢板。
附图说明
图1：为说明本发明的摩擦系数及擦伤性的评价方法的示意图。
具体实施方式
<不锈钢板用润滑涂料>
本发明的不锈钢板用润滑涂料为含有丙烯酸系树脂的水性涂料，并且是相对于丙烯酸系树脂100质量份而言，含有大于20质量份且小于等于50质量份的熔点为115℃以上的聚乙烯蜡的不锈钢板用润滑涂料。
(丙烯酸系树脂)
本发明中使用的丙烯酸系树脂没有特别限定。优选使用将在下述1.至5.组成的组中选择的1种或2种以上作为单体进行聚合或共聚而得到的丙烯酸系树脂：1.丙烯酸、甲基丙烯酸、马来酸、马来酸酐、衣康酸、富马酸等脂肪酸；2.将上述1.的脂肪酸进行甲基化、乙基化、异丙基化、丁基化、2-乙基己基化等而得到的酯；3.上述1.的脂肪酸与氨等的酰胺；4.苯乙烯；5.在上述1.的脂肪酸中加成聚氧乙烯而得到的物质。作为聚合或共聚的方法，可例示溶液聚合法、乳液聚合法或悬浮聚合法等。作为向丙烯酸系树脂中添加的添加剂，相对于上述丙烯酸系树脂100质量份而言，通常在涂料中广泛使用的表面活性剂、防锈剂、极压剂、pH调节剂等合计可含有10质量份以下。润滑涂料的溶剂可以是水系或有机溶剂中的任一者，但优选水系溶剂。
(熔点115℃以上的聚乙烯蜡)
所用的聚乙烯蜡为熔点115℃以上的聚乙烯蜡即可，无限定。优选使用中密度～高密度聚乙烯蜡(密度0.930g/cm3以上)。若熔点小于115℃，则在相对于上述丙烯酸系树脂100质量份而言添加大于20质量份的情况下，由于涂料干燥后不易固化而产生粘性，因此，采用熔点115℃以上的聚乙烯蜡。特别优选为熔点为120℃以上的高密度聚乙烯蜡(密度0.942g/cm3以上)，进一步优选为熔点为130℃以上的聚乙烯蜡。熔点优选为145℃以下。若熔点过高，则会变硬，在加压加工时通过与模具的接触而存在被膜的剥离变大的情况。
对于熔点115℃以上的聚乙烯蜡而言，由于当将乳化的聚乙烯蜡添加在含有丙烯酸系树脂的水性涂料中时，其会均匀地混合在含丙烯酸系树脂的水性涂料中，所得的润滑涂料的特性优异，因此是优选的。
乳化后的聚乙烯蜡的平均粒径优选小于1.0μm。这是由于平均粒径小的聚乙烯蜡更均匀地分散在被膜中。为了进一步均匀地分散，平均粒径更优选为0.2μm以下。
对于添加量而言，了解到对于加压加工时的面压升高的不锈钢板而言，相对于上述丙烯酸系树脂100质量份而言添加大于20质量份(与采用软钢的情况相比添加量更多)会有效。此外，还了解到熔点高达115℃以上的聚乙烯蜡由于蜡自身的摩擦系数高，因此，若添加量相对于上述丙烯酸系树脂100质量份而言为20质量份以下，则作为润滑被膜的摩擦系数不会充分地降低、得不到充分的润滑性提高效果。另一方面，即便添加大于50质量份的量，润滑性提高效果也会饱和。因而，设为大于20质量份且小于50质量份。相对于树脂固体成分而言熔点115℃以上的聚乙烯蜡的添加量越多，则作为被膜的摩擦系数变得越小，但若摩擦系数过小，则卷材可能由于自重而破坏、在板的搬运过程中坠落，更优选的是，相对于上述丙烯酸系树脂100质量份而言为40质量份以下、进一步优选为30质量份以下，由此在不锈钢的通常的加压加工中可获得充分的润滑性。
(其他添加物)
相对于上述丙烯酸系树脂100质量份而言，通常在涂料中广泛使用的表面活性剂、防锈剂、极压剂、pH调节剂等合计可含有1O质量份以下。水性涂料的溶剂为以水为主体的溶剂，虽然也可以含有少量的有机溶剂，但由于可尽量降低润滑涂料中的挥发性有机溶剂产生量，因此优选水系溶剂。
由本发明首次发现以下情况。
1)对于以专利文献2的基本的技术构思而按照规定量使用摩擦系数小的低熔点蜡的润滑涂料而言，在不锈钢板的高面压力的加压加工时，当相对于上述丙烯酸系树脂100质量份而言添加20质量份以下的蜡时，存在得不到充分的耐擦伤性的情况，在不锈钢板的高面压力的加压加工中，需要进一步提高耐擦伤性。
对于熔点115℃以上的高熔点聚乙烯蜡，其自身的摩擦系数比低熔点聚乙烯蜡高，因此，当以与低熔点聚乙烯蜡等量程度添加时，摩擦阻力可能不会充分降低，在使用高熔点聚乙烯蜡的情况下，若相对于上述丙烯酸系树脂100质量份而言添加超过20质量份的量，则由于丙烯酸树脂的比率降低，因此摩擦系数高的丙烯酸树脂的贡献变小，并且显现出高熔点聚乙烯蜡摩擦系数降低效果，因此可得到以往未曾得到的优异的润滑性。
对此的理由尚不清楚，据认为如下所述。
与低熔点的蜡相比，高熔点的蜡的粘度高、在模具与钢板的接触滑动时易于残留在其间隙中，因此可推定对深拉深性及擦伤具有效果。
2)本申请的擦伤性的评价如实施例中说明的那样，为不同于专利文献1、2的评价方法。在专利文献1中，观察方管(square tube)拉深的擦伤，在专利文献2中通过埃里克森杯突(Erichsen cupping)(圆管拉深)的擦伤进行评价。作为评价的等级(模具与板的接触面压力)，大致为本申请＞专利文献1＞专利文献2，本申请的“对同一供试材料以高面压力(约200MPa)连续滑动20次，摩擦系数也不上升”的评价对于不锈钢而言为适合的评价方法。其理由在于，对于不锈钢而言，存在通过一次加压没有完成成型加工而进行多次加压成型的情况，因此，通过严苛的加压成型的评价方法首次能够适当地评价不锈钢的耐擦伤性。不存在进行过这种严苛的加压成型的评价的现有技术。
(有机钙化合物)
在不锈钢板的加压成型时，存在通过一次加压没有完成、而通过多次加压来进行成型的情况。此时，存在涂装由于初始的加压而受到损伤、此后摩擦系数逐渐上升而擦伤的现象。为了提高耐擦伤性，根据需要，添加有机钙化合物。
对于有机钙化合物而言，使用含有6质量％以上的钙的有机钙化合物。例如，硬脂酸钙、油酸钙、月桂酸钙等脂肪酸为C12～C18的脂肪酸钙。或者，高碱性烷基苯磺酸钙、高碱性烷基萘磺酸钙、高碱性烷基芳基磺酸钙等高碱性石油磺酸钙。
对于有机钙化合物而言，若相对于上述丙烯酸系树脂100质量份而言添加1～10质量份，则可得到改善擦伤性的效果，根据需要进行添加。若小于1质量份，则得不到改善擦伤性的效果。即便添加大于10质量份的量，效果也已饱和。
(不锈钢)
本发明的不锈钢板用润滑涂料与不锈钢的种类无关，可应用于所有不锈钢板，可得到深拉深加工性和耐擦伤性优异的润滑不锈钢板。特别适于拉深加工所用的铁素体系不锈钢板的加压加工。
<润滑不锈钢板的制造方法>
将本发明的不锈钢板用润滑涂料涂布于不锈钢板表面并进行干燥。涂布方法没有限定，可例示喷雾涂布、辊涂机涂布、浸渍涂布、毛刷涂布等方法。本发明涂料的固体成分(丙烯酸系树脂+聚乙烯蜡+钙化合物)浓度可结合所用的涂布方法、干燥方法来调节。优选为1质量％～50质量％。涂料的干燥方法可使用一般的烘烤炉等，但本发明的润滑涂料由于易于固化，因此，可通过简便的热风干燥而使其充分固化。涂装根据钢板的使用用途而在钢板的单面或两面进行，干燥后的附着量优选为每面0.5～2.5g/m2。
若干燥后的附着量为0.5g/m2～2.5g/m2，则不易发生被膜的损伤，耐擦伤性优异，润滑效果充分且滑动时的被膜的剥离少，不会发生剥离的物质堆积在加压模具中而对加压加工产生造成不良影响的情况。干燥后的附着量更优选为0.8g/m2以上、2.0g/m2以下，进一步优选为1.5g/m2以下。
(摩擦阻力)
摩擦系数随测定方法而有不同，对于本发明中得到的润滑被膜的同一样品，根据测定方法的不同其绝对值也会不同，因此，不能通过绝对值进行评价，通常，摩擦系数经相对比较为高值时，则滑动性变差，因此加压性降低。另一方面，若摩擦系数过低，则当将钢带卷成卷时，存在卷材由于自重而破坏的情况，而且过于滑动而对板的操作带来障碍。
实施例
以下，利用实施例、比较例具体说明本发明，但本发明不限于这些实施例、比较例。
(实施例1～18，比较例1～6)
制备表1的组成的含有丙烯酸树脂的水性涂料，通过喷雾均匀地涂布于不锈钢板(SUS444的(19质量％Cr-2质量％Mo-0.4质量％Nb)2D精轧)上，将通过烘干机的热风而干燥的涂装施于板的两面，对其特性进行评价。需要说明的是，各涂料均将固体成分(丙烯酸树脂+聚乙烯蜡+钙化合物)浓度调节为10质量％。将其结果示于表1。对于聚乙烯蜡，将乳化的聚乙烯蜡混合在水性涂料中使用。
<评价方法>
1.对于摩擦系数而言，使用图1所示的装置(即，在曲率5为R20的上下的模具之间，夹持厚度1.5mm×长度200mm×宽度20mm的供试材料，在以推压负荷方向6推压的状态下在拉拔负荷方向8上拉拔，从而对拉拔负荷进行测定的滑动试验机)测定拉拔负荷。摩擦系数利用拉拔负荷/推压负荷求出。关于试验条件，在模具：材质SKD11、曲率R20、样品宽度20mm、滑动距离：100mm、拉拔速度：20mm/秒、推压负荷：3920N的条件下进行。模具与供试材料的接触面积为约20mm2(20mm宽度×约1mm)，面压力为约200MPa(＝3920N/20mm2)。
2.关于有无粘性，以面压力0.01MPa将无被膜的不锈钢压靠于润滑被膜形成后的不锈钢板上，通过用荧光X射线测定C计数量，从而对在剥离后在无被膜的不锈钢板的表面上是否有转移而来的润滑被膜进行评价。在未发现C量的增加的情况下，评价为无粘性。在无被膜的不锈钢板的表面存在C量的增加的情况下，评价为有粘性。
3.关于深拉深性，利用极限深拉深比(LDR(＝Limiting Drawing Ratio))测定进行评价。向圆板形的试验片中压入圆筒形的冲头(直径d＝33mm)，求出在没有断裂的情况下所完整拉深出的最大的试验片直径(D(mm))，由D/d的计算式求出。在冲头肩R为3mm、冲头送入速度为1mm/秒、压边负荷为10kN、压边装置肩R为3mm的条件下进行。
4.关于耐擦伤性，使用图1中记载的滑动试验机，在没有中途模具研磨的条件下将一个供试材料连续滑动20次，将摩擦系数不上升的情况评价为耐擦伤性良好。所谓摩擦系数不上升，是指“对同一供试材料以高面压力(约200MPa)连续滑动20次，第20次的摩擦系数仍小于0.15”，将这种情况评价为耐擦伤性良好，将“0.15以上”评价为不良。
表1的有机钙化合物的种类，
A：硬脂酸钙
B：高碱性石油磺酸钙
表1的树脂的种类，
丙烯酸1：苯乙烯+甲基丙烯酸丁酯+甲基丙烯酸+烯键式不饱和羧酸的共聚物(质量比25∶30∶24∶21)
丙烯酸2：苯乙烯+甲基丙烯酸丁酯+甲基丙烯酸的共聚物(质量比25∶51∶24)
表1的P系添加剂，
*)油酸磷酸酯(极压剂)
<实施例、比较例的评价>
由表1的结果可知，在实施例1～18中，当相对于上述丙烯酸系树脂100质量份而言以比以往的量更多的特定量添加高熔点的聚乙烯蜡时，可得到对不锈钢板具有优异的加工性的润滑涂料。在表1的实施例1、3、5、6、15、17中，即便没有添加有机钙化合物，耐擦伤性仍然优异，但当添加有机钙化合物时，耐擦伤性进一步提高。在比较例1、4、6中，当高熔点的聚乙烯蜡的量相对于树脂而言少时，耐擦伤性变差。在比较例5中可知，当低熔点的聚乙烯蜡相对于上述丙烯酸系树脂100质量份而言大量添加时，润滑涂料具有粘性。在比较例2、3中可知，当使用低熔点蜡时，虽然摩擦系数降低，但作为不锈钢用的润滑涂料，耐擦伤性低。另外，在比较例1、2、3、4、6的聚乙烯蜡的添加量低的情况下，结果为LDR值比实施例低、深拉深性变差。
产业上的可利用性
若将本发明的不锈钢用润滑涂料涂布于不锈钢板，则可得到深拉深、耐擦伤性等加工性优异的润滑不锈钢板。当使用本发明的不锈钢用润滑涂料时，能够容易地通过高面压力的加压成型来加工不锈钢板，因此，耐腐蚀性、高温特性优异的不锈钢的应用能够以汽车、家电、厨房领域为中心扩大，在工业上是有用的。尤其是对于铁素体系不锈钢而言，由于不含Ni，因此与奥氏体系不锈钢相比，价格便宜，而且还具有不用担心发生应力腐蚀裂纹(SCC)这样的优点，因此，是可期待今后需求增加的材料。与软钢相比，铁素体系不锈钢大量地含有Cr，因此缺乏延展性、拉伸性(stretch formability)变差，故而存在可成型范围受限的问题，但当利用本发明的不锈钢用润滑涂料时，能够实现宽范围的成型加工，能够有效发挥出该材料的特性从而得到工业制品。
附图标记说明
1：供试材料 2：下模具 3：上模具 5：曲率 6：推压负荷方向 8：拉拔负荷方向

Claims (5)

1.不锈钢板用润滑涂料，其包含丙烯酸系树脂及聚乙烯蜡，所述聚乙烯蜡的熔点为115℃以上，相对于所述丙烯酸系树脂100质量份而言，所述不锈钢板用润滑涂料含有大于20质量份且小于等于50质量份的所述聚乙烯蜡。
2.如权利要求1所述的不锈钢板用润滑涂料，相对于所述丙烯酸系树脂100质量份而言，进一步含有1质量份～10质量份的有机钙化合物。
3.权利要求1或2所述的不锈钢板用润滑涂料的制造方法，其中，使用水系溶剂将所述聚乙烯蜡乳化并进行添加。
4.润滑不锈钢板的制造方法，其中，在不锈钢板上涂布权利要求1或2所述的不锈钢板用润滑涂料，进行热风干燥，从而形成以干燥后的质量计每面为0.5～2.5g/m2的润滑被膜。
5.润滑不锈钢板，所述润滑不锈钢板具有以干燥后的质量计每面为0.5～2.5g/m2的权利要求1或2所述的不锈钢板用润滑涂料。
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