CN106833846A - 一种免脱脂汽车钢板用冲压清洗油及其制备方法 - Google Patents
一种免脱脂汽车钢板用冲压清洗油及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种免脱脂汽车钢板用冲压清洗油及其制备方法,所述冲压清洗油包括以下各组分:精制矿物油,极压抗磨剂,防锈剂,成膜剂,乳化剂,分散剂,表面活性剂,抗氧剂。该冲压清洗油集清洗、冲压、防锈一体,在钢板在线清洗冲压成型时,可去除钢板表面机械杂质,同时清洗过的钢板防锈期可达3个月;成型后的零件表面干净无冲压残渣等,无需进行清洗;拥有良好的润滑性,钢板清洗后可直接冲压成型,无需再涂冲压成型专用油;清洗冲压后的料件表面残油无需进行脱脂工序,水洗即可去除,简化了钢板成型工艺,降低了冲压油、清洗油、脱脂剂的使用量,节能环保,提高了经济效益。
Description
技术领域
本发明涉及一种免脱脂汽车钢板用冲压清洗油的技术领域,具体涉及一种具有优良清洗性、防锈性和润滑性能的免脱脂汽车钢板用冲压清洗油及其制备方法。
背景技术
冲压清洗油主要应用于汽车钢板的冲压及清洗。冲压清洗油的性能要求有:可用水洗去除、优良的清洗性、防锈性、润滑性以及后道涂装的匹配性能。目前大多数冲压清洗油使用后均需要进行脱脂工序、且不能同时兼顾清洗性与防锈性、防锈性与后道涂装的匹配性能。汽车钢板在清洗后存在清洗不净或清洗干净导致润滑不足、成型后存放周期短的情况,同时在后道涂装工序时也存在脱脂困难和残油等问题,不能完好地解决汽车钢板在线冲压成型时板面“星目”的缺陷及涂装工艺的“电泳缩孔”的缺陷。
另外冲压清洗油在冲压工序使用后,进入涂装工序,首先进入脱脂工序进行清洗表面油品,以便进行磷化及电泳工艺。脱脂工序的脱脂剂大多含有磷,对水体的影响较大,虽然经过技术改良,市场上已基本使用不含磷的脱脂剂,但对水体的污染还是存在的。如何减少水体的污染,是汽车工业面对的一个问题。
作为钢板在线冲压清洗油,简化了原有清洗和冲压的两个工序,使其一次涂油即可完成冲压工序所需的清洗、防锈、润滑、涂装匹配。其综合各个方面的性能,要求非常严苛,需要考虑的问题点:①油品需要有良好的清洗与可清洗性能;②由于清洗后板面残油相对较少,需保证此时在钢板表面的清洗油满足冲压成型的润滑需要;③成型后的料件,需要良好的防锈油,以便于存储;④成型后的料件经焊接后进入涂装工段,需保证板面油品有良好电泳漆相容性。
发明内容
本发明的目的在于克服现有技术的不足,提供一种免脱脂汽车钢板用冲压清洗油及其制备方法。通过乳化剂、表面活性剂、分散剂的复配选择,保证了良好的清洗与可清洗性能、后道涂装匹配性能;通过不同防锈剂的协同作用及成膜剂的增强作用,保证了良好的防锈性;通过不同种类精制矿物油、极压抗磨剂的复配,保证了良好的润滑性。
本发明的目的是通过以下技术方案实现的:
本发明提供了一种免脱脂汽车钢板用冲压清洗油,其特征在于,包括以下质量百分含量的各组分:精制矿物油55-86%,极压抗磨剂3-8%,防锈剂4.5-11%,成膜剂2-7%,乳化剂2-8%,分散剂1-5%,表面活性剂1-6%,抗氧剂0.1-0.5%。
优选地,所述精制矿物油为航空煤油、工业白油、变压器油、工业齿轮油、液力传动油、内燃机油、石腊基中性油、烷烃基中性油、中间基中性油中的2-4种。
优选地,所述极压抗磨剂包括硫化烯烃和二油醇亚磷酸酯,还包括硫化猪油、硫化异丁烯、二苄基二硫、硼酸酯中的1-3种;且硫化烯烃和二油醇亚磷酸酯的总含量为清洗油总含量的4-5%。
优选地,所述防锈剂为石油磺酸钙、石油磺酸钠、合成磺酸钙、合成磺酸钠、十二烯基丁二酸、咪唑啉中的1-3种。
优选地,所述成膜剂为羊毛脂镁皂、季戊四醇羊毛酸酯、氧化棉籽油、氧化蜡皂、多元醇、油酸二辛酯中的1-3种。
优选地,所述乳化剂为石油磺酸钠、聚异丁烯丁二酸酐、高分子聚醚、司本85、十二烷基苯磺酸中的1-2种。
优选地,所述分散剂为合成磺酸镁、高碱值合成磺酸钙、硫化烷基酚钙、聚异丁烯中的1-2种。
优选地,所述表面活性剂为烷基苯磺酸钠、油酸二乙醇酰胺、脂肪酸甘油酯、亚磷酸酯的1-3种。
优选地,所述抗氧剂为2、6-二叔丁基对甲酚、苯三唑衍生物、噻二唑衍生物、二甲胺抗氧剂的1-2种。
本发明还提供了一种免脱脂汽车钢板用冲压清洗油的制备方法,包括以下步骤:
在反应釜中加入精制矿物油、防锈剂和极压抗磨剂,搅拌均匀后,升温至60-90℃,保温30min;加入成膜剂、乳化剂、分散剂,搅拌均匀后,降温至50℃以下,加入表面活性剂、抗氧剂,使其充分溶解,即制得所述一种免脱脂汽车钢板用冲压清洗油。
本发明所述精制矿物油是提供清洗、防锈、润滑性能的主要组分,也是其他添加剂的载体;极压抗磨剂能更好的在钢板表面成膜,在冲压成型时保护形变部位的钢板无拉毛或开裂的现象;防锈剂能够更好的吸附在金属表面,形成保护膜,隔绝水分与空气和金属接触,有效抑制锈蚀的产生;成膜剂可提高油品在金属表面的附着力,从而确保防锈性及润滑性;分散剂、乳化剂、表面活性剂可促进金属表面杂质的清除,保证油品的清洗与可清洗性能,同时可使油品与涂装工序中碱性脱脂及阴离子电泳漆电泳达到很好的匹配性。因此,本发明制备的冲压清洗油的具有优良的清洗与可清洗性、防锈性、润滑性以及后道涂装的匹配性能。
与现有技术相比,本发明具有如下的有益效果:
本发明的冲压清洗油集清洗、冲压、防锈一体,在钢板在线清洗冲压成型时,可去除钢板表面机械杂质及锈蚀,同时清洗过的钢板防锈期可达3个月;成型后的零件表面干净无冲压残渣等,无需进行清洗;拥有良好的润滑性,钢板清洗后可直接冲压成型,无需再涂冲压成型专用油;清洗冲压后的料件表面残油无需进行脱脂工序,水洗即可去除,简化了钢板成型工艺,降低了冲压油、清洗油、脱脂剂的使用量,节能环保,提高了经济效益。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变化和改进。这些都属于本发明的保护范围。
实施例1
本实施例提供了一种免脱脂汽车钢板用冲压清洗油及其制备方法,所述冲压清洗油所选各个组分的具体物质及重量百分比如下:
(1)精制矿物油为航空煤油、烷烃基中性油、石腊基中性油,其质量百分比分别为:20%,20%,30%;
(2)极压抗磨剂为硫化猪油、硫化烯烃、二油醇亚磷酸酯,其重量百分比为2%,1%,4%;
(3)防锈剂为石油磺酸钙、合成磺酸钙、咪唑啉,其重量百分比为3%,4%,2%;
(4)成膜剂为羊毛脂镁皂、氧化蜡皂,其重量百分比为3%,0.8%;
(5)乳化剂为石油磺酸钠、聚异丁烯丁二酸酐,其重量百分比为2%,2%;
(6)分散剂为高碱值合成磺酸钙、聚异丁烯,其重量百分比为1.5%,1%;
(7)表面活性剂为烷基苯磺酸钠、脂肪酸甘油酯,其重量百分比为2.4%,0.8%。
(8)抗氧剂为2、6-二叔丁基对甲酚、苯三唑衍生物,其重量百分比为0.2%,0.3%。
其制备方法为:在反应釜中加入精制矿物油、防锈剂和极压抗磨剂,搅拌均匀后,升温至60-90℃,保温30min;加入成膜剂、乳化剂、分散剂,搅拌均匀后,降温至50℃以下,加入表面活性剂、抗氧剂,使其充分溶解,即制得所述一种免脱脂汽车钢板用冲压清洗油。
实施例2
本实施例提供了一种免脱脂汽车钢板用冲压清洗油及其制备方法,所述冲压清洗油所选各个组分的具体物质及重量百分比如下:
(1)精制矿物油为航空煤油、烷烃基中性油、石腊基中性油,其质量百分比分别为:30%,10%,17%;
(2)极压抗磨剂为硫化猪油、硫化烯烃、二油醇亚磷酸酯,其重量百分比为4%,2%,2%;
(3)防锈剂为石油磺酸钙、合成磺酸钙、咪唑啉,其重量百分比为3%,4%,3%;
(4)成膜剂为羊毛脂镁皂、氧化蜡皂,其重量百分比为3%,4%;
(5)乳化剂为石油磺酸钠、聚异丁烯丁二酸酐,其重量百分比为5%,2%;
(6)分散剂为高碱值合成磺酸钙、聚异丁烯,其重量百分比为3%,2%;
(7)表面活性剂为烷基苯磺酸钠、脂肪酸甘油酯,其重量百分比为2.4%,3.2%。
(8)抗氧剂为2、6-二叔丁基对甲酚、苯三唑衍生物,其重量百分比为0.1%,0.3%。
所述制备方法与实施例1相同。
对比例1
本对比例提供了一种免脱脂汽车钢板用冲压清洗油及其制备方法,所述冲压清洗油所选各个组分的具体物质及重量百分比与实施例1基本相同,不同之处仅在于:本对比例中,所述极压抗磨剂为硫化猪油、二油醇亚磷酸酯,其重量百分比为2%,5%。
对比例2
本对比例提供了一种免脱脂汽车钢板用冲压清洗油及其制备方法,所述冲压清洗油所选各个组分的具体物质及重量百分比与实施例1基本相同,不同之处仅在于:本对比例中,所述极压抗磨剂为硫化猪油、硫化烯烃、二油醇亚磷酸酯,其重量百分比为5%,1%,1%。
对比例3
本对比例提供了一种免脱脂汽车钢板用冲压清洗油及其制备方法,所述冲压清洗油所选各个组分的具体物质及重量百分比与实施例1基本相同,不同之处仅在于:本对比例中,所述精制矿物油为石腊基中性油,其质量百分比分别为:70%。
效果验证
以实施例1、实施例2作为本发明物的组合物,对比的参照物为道达尔公司生产的冲压清洗油(法国产),定义为组合物A,以及对比例1-3制备的组合物为测试样品。
针对本发明物的特点,对冲压清洗油清洗性、防锈性、润滑性、可清洗性、电泳漆匹配性进行重点评价。
(1)清洗性评价具体如下:
先用清洁度测量仪对干净整洁的白色打印纸进行测定,所测得的数据作为基数A,再用冲压清洗油清洗过的钢板表面上,选取三个以上不同位置的点作为检测点,分别用工业用胶带(剪成小块)在这些检测点上粘贴取样,然后放在白色打印纸上,用清洁度测量仪对胶带进行测定,测得数据B。清洁度以三个试验结果的算术平均值作为测定结果。
表1清洗性
样品名称 | 清洗性 |
实施例1 | 98% |
实施例2 | 99% |
组合物A | 98% |
对比例1 | 98% |
对比例2 | 96% |
对比例3 | 95% |
表1所示的清洗性数据可知:实施例1、实施例2的清洗性与组合物A、对比例1相当,对比例2和3略差。
(2)防锈性评价具体如下:
冷轧板涂冲压清洗油,沥油24h后放入恒温恒湿箱中,测试条件为:50℃×95%RH,测试时间15天,观察记录锈蚀情况。
表2防锈性
样品名称 | 防锈性 |
实施例1 | 无锈蚀 |
实施例2 | 无锈蚀 |
组合物A | 少量锈蚀 |
对比例1 | 少量锈蚀 |
对比例2 | 少量锈蚀 |
对比例3 | 少量锈蚀 |
表2所示的防锈性数据可知:实施例1、实施例2的防锈性均优于组合物A和对比例。
(3)润滑性评价具体如下:
测试油品的最大无卡咬负荷Pd。仪器:四球摩擦试验机
表3润滑性
样品名称 | Pd |
实施例1 | 450kg |
实施例2 | 450kg |
组合物A | 350kg |
对比例1 | 400kg |
对比例2 | 420kg |
对比例3 | 410kg |
表3所示的润滑性数据可知:实施例1、实施例2的润滑性均优于组合物A和对比例。
(4)可清洗性评价具体如下:
钢板涂冲压清洗油,放置14天后,使用40℃纯水冲洗,以水润湿面积(脱脂率)为评价。
表4脱脂性
表4所示的可清洗性数据可知:实施例1、实施例2的可清洗性均优于组合物A和对比例。
(5)电泳漆匹配性评价具体如下:
取汽车厂涂装车间电泳漆,向电泳漆中加入200ppm的油品,搅拌24h后,进行泳板试验,烘干后观察板面缩孔的情况。
表5电泳漆匹配性
样品名称 | 电泳漆匹配性 |
实施例1 | 无缩孔 |
实施例2 | 无缩孔 |
组合物A | 少量缩孔 |
对比例1 | 无缩孔 |
对比例2 | 无缩孔 |
对比例3 | 少量缩孔 |
表5所示的电泳漆匹配性数据可知:实施例1、实施例2的电泳漆匹配性均优于组合物A和对比例3。
综上所述,从表1-5的结果可知,实施例1和2制备的清洗油综合性能明显要好于对比例。
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变化或修改,这并不影响本发明的实质内容。在不冲突的情况下,本申请的实施例和实施例中的特征可以任意相互组合。
Claims (10)
1.一种免脱脂汽车钢板用冲压清洗油,其特征在于,包括以下重量百分含量的各组分:精制矿物油55-86%,极压抗磨剂3-8%,防锈剂4.5-11%,成膜剂2-7%,乳化剂2-8%,分散剂1-5%,表面活性剂1-6%,抗氧剂0.1-0.5%。
2.根据权利要求1所述的免脱脂汽车钢板用冲压清洗油,其特征在于,所述精制矿物油为航空煤油、工业白油、变压器油、工业齿轮油、液力传动油、内燃机油、石腊基中性油、烷烃基中性油、中间基中性油中的2-4种。
3.根据权利要求1所述的免脱脂汽车钢板用冲压清洗油,其特征在于,所述极压抗磨剂包括硫化烯烃和二油醇亚磷酸酯,还包括硫化猪油、硫化异丁烯、二苄基二硫、硼酸酯中的1-3种;且硫化烯烃和二油醇亚磷酸酯的总含量为清洗油总含量的4-5%。
4.根据权利要求1所述的免脱脂汽车钢板用冲压清洗油,其特征在于,所述防锈剂为石油磺酸钙、石油磺酸钠、合成磺酸钙、合成磺酸钠、十二烯基丁二酸、咪唑啉中的1-3种。
5.根据权利要求1所述的免脱脂汽车钢板用冲压清洗油,其特征在于,所述成膜剂为羊毛脂镁皂、季戊四醇羊毛酸酯、氧化棉籽油、氧化蜡皂、多元醇、油酸二辛酯中的1-3种。
6.根据权利要求1所述的免脱脂汽车钢板用冲压清洗油,其特征在于,所述乳化剂为石油磺酸钠、聚异丁烯丁二酸酐、高分子聚醚、司本85、十二烷基苯磺酸中的1-2种。
7.根据权利要求1所述的免脱脂汽车钢板用冲压清洗油,其特征在于,所述分散剂为合成磺酸镁、高碱值合成磺酸钙、硫化烷基酚钙、聚异丁烯中的1-2种。
8.根据权利要求1所述的免脱脂汽车钢板用冲压清洗油,其特征在于,所述表面活性剂为烷基苯磺酸钠、油酸二乙醇酰胺、脂肪酸甘油酯、亚磷酸酯的1-3种。
9.根据权利要求1所述的免脱脂汽车钢板用冲压清洗油,其特征在于,所述抗氧剂为2、6-二叔丁基对甲酚、苯三唑衍生物、噻二唑衍生物、二甲胺抗氧剂的1-2种。
10.一种根据权利要求1所述的免脱脂汽车钢板用冲压清洗油的其制备方法,其特征在于,包括以下步骤:
在反应釜中加入精制矿物油、防锈剂和极压抗磨剂,搅拌均匀后,升温至60-90℃,保温30min;加入成膜剂、乳化剂、分散剂,搅拌均匀后,降温至50℃以下,加入表面活性剂、抗氧剂,使其充分溶解,即制得所述一种免脱脂汽车钢板用冲压清洗油。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103571585A (zh) * | 2013-11-12 | 2014-02-12 | 广西大学 | 汽车板材构件冲压成型润滑剂 |
CN103589481A (zh) * | 2013-10-17 | 2014-02-19 | 安徽顺驰电缆有限公司 | 一种金属加工清洗皂化液 |
CN103695114A (zh) * | 2013-12-14 | 2014-04-02 | 广西大学 | 薄钢板冲压成型的润滑剂 |
CN103849451A (zh) * | 2014-02-27 | 2014-06-11 | 宝山钢铁股份有限公司 | 一种用于二次冷轧机组的具有高效清洗能力的平整液 |
US20140194333A1 (en) * | 2013-01-04 | 2014-07-10 | Exxonmobil Research And Engineering Company | Method for improving engine fuel efficiency |
CN106190463A (zh) * | 2016-07-06 | 2016-12-07 | 安徽红桥金属制造有限公司 | 一种用于加工冲压件的耐高温防锈油及制备方法 |
-
2017
- 2017-01-23 CN CN201710051524.7A patent/CN106833846B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140194333A1 (en) * | 2013-01-04 | 2014-07-10 | Exxonmobil Research And Engineering Company | Method for improving engine fuel efficiency |
CN103589481A (zh) * | 2013-10-17 | 2014-02-19 | 安徽顺驰电缆有限公司 | 一种金属加工清洗皂化液 |
CN103571585A (zh) * | 2013-11-12 | 2014-02-12 | 广西大学 | 汽车板材构件冲压成型润滑剂 |
CN103695114A (zh) * | 2013-12-14 | 2014-04-02 | 广西大学 | 薄钢板冲压成型的润滑剂 |
CN103849451A (zh) * | 2014-02-27 | 2014-06-11 | 宝山钢铁股份有限公司 | 一种用于二次冷轧机组的具有高效清洗能力的平整液 |
CN106190463A (zh) * | 2016-07-06 | 2016-12-07 | 安徽红桥金属制造有限公司 | 一种用于加工冲压件的耐高温防锈油及制备方法 |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107287047A (zh) * | 2017-06-16 | 2017-10-24 | 中国人民解放军第五七九工厂 | 一种燃气‑空气通道的水溶液清洗剂 |
CN108048171A (zh) * | 2017-12-29 | 2018-05-18 | 南京科润工业介质股份有限公司 | 余热发黑膜专用防锈油及其制备方法 |
CN108531255A (zh) * | 2018-05-28 | 2018-09-14 | 湖北三环化学新材料股份有限公司 | 一种冲压清洗防锈油及其制备方法 |
CN108570346A (zh) * | 2018-05-29 | 2018-09-25 | 苏州德莱美润滑油有限公司 | 一种不锈钢高温拉伸油及其制备方法 |
CN108531279A (zh) * | 2018-06-12 | 2018-09-14 | 上海加美实业有限公司 | 一种易清洗可深度拉伸用冲压油 |
CN108913284A (zh) * | 2018-08-09 | 2018-11-30 | 嘉兴市国龙石油化工有限公司 | 一种碳钢板易清洗无氯深冲压拉伸油及其制备方法 |
CN109370734A (zh) * | 2018-11-29 | 2019-02-22 | 郑州正赢石化有限公司 | 一种通用乳化油 |
CN109943404A (zh) * | 2019-04-24 | 2019-06-28 | 上海尤希路化学工业有限公司 | 高品位环保型镜面加工磨削油 |
CN110157520A (zh) * | 2019-06-12 | 2019-08-23 | 北京汽车集团越野车有限公司 | 一种润滑剂及其制备方法 |
EP3812362A1 (de) * | 2019-10-21 | 2021-04-28 | Richard Geiss GmbH | Lösemittelstabilisator, gemisch für die entfettung von metallteilen und verwendung des lösemittelstabilisators sowie verfahren zum stabilisieren eines lösemittels und verfahren für die entfettung von metallteilen |
CN111593361A (zh) * | 2020-06-02 | 2020-08-28 | 中国石油化工股份有限公司 | 高闪点洗涤油组合物、制备方法及用途 |
CN111826226A (zh) * | 2020-07-16 | 2020-10-27 | 常州市九鑫铜业有限公司 | 一种钢管拉拔油及其制备方法和应用 |
CN114196461A (zh) * | 2020-09-17 | 2022-03-18 | 中国石油化工股份有限公司 | 一种用于重负荷车桥的清洗油组合物及其制备方法与应用 |
CN113736544A (zh) * | 2021-08-10 | 2021-12-03 | 希玛石油制品(镇江)有限公司 | 一种环保水溶性不锈钢薄板冲压油及其制备方法 |
CN113736544B (zh) * | 2021-08-10 | 2022-06-07 | 希玛石油制品(镇江)有限公司 | 一种环保水溶性不锈钢薄板冲压油及其制备方法 |
CN115058275A (zh) * | 2022-06-29 | 2022-09-16 | 黎光泰富(苏州)科技有限公司 | 一种易清洗型成型油 |
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