CN1108298A - 铝和铝合金热轧用含油组合物 - Google Patents

铝和铝合金热轧用含油组合物 Download PDF

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CN1108298A
CN1108298A CN94116849A CN94116849A CN1108298A CN 1108298 A CN1108298 A CN 1108298A CN 94116849 A CN94116849 A CN 94116849A CN 94116849 A CN94116849 A CN 94116849A CN 1108298 A CN1108298 A CN 1108298A
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acid
methyl
oil
weight
composition
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CN1047197C (zh
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冈本好雄
杉下幸男
安藤裕幸
松井邦昭
市本武彦
根岸政隆
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Kao Corp
Kobe Steel Ltd
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Kao Corp
Kobe Steel Ltd
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Abstract

一种铝或铝合金热轧用水分散性含油组合物，它 有极好的润滑性和乳化液稳定性，它使长期使用时产 生的热变质减到最小，该组合物含有以下组分(a)－ (d):(a)一种矿物油，(b)3－30％(重)脂肪酸或其单酯、或油和脂，(c)0.5-10％(重)磷酸(或亚磷酸)C4－C18烷基或烯基酯，以及(d)0.1－10％(重)聚合物和有机酸盐之间的盐，其中聚合物的平均分子量为10000－100000，它是式(1)表示的单体和(甲基)丙烯酰胺和/或(甲基)丙烯酸盐的共聚物。

Description

本发明涉及一种铝和铝合金热轧用水分散性含油组合物，该组合物具有极好的轧制润滑性和乳化稳定性，它可得到有极好表面质量的轧制板材。
在铝和铝合金热轧过程中，由于铝从轧制板材表面转移到轧辊表面的结果，在轧辊表面形成所谓的辊涂层。如果轧辊上有辊涂层，铝坯在与辊涂层接触的同时被轧制成。这就意味着轧制板材的表面质量随辊涂的性质而变化，而且表面的缺陷影响冷轧后板材表面的质量。因此，辊涂层的性质是很重要的。它随轧制条件（要轧制的材料、板材温度、板材表面粗糙度、轧辊温度、轧辊表面粗糙度、牵引、轧速、刷辊操作条件等）以及轧制油的种类而变化。因此，在辊涂层控制中，轧制油的选择是很重要的。
在热轧中，轧制油以乳化液的形式使用，因为足够的轧辊冷却性质是需要的。传统的铝和铝合金用热轧油是含有3-10%油组分的乳化液。它们通常用以下步骤制备：将油性能改进剂、极压添加剂、防锈剂、抗氧化剂等加到作为基础油的矿物油中;然后主要用阴离子型表面活性剂使形成的混合物乳化。油性能改进剂可包括脂肪酸、油和脂，以及脂肪族酯类。
铝和铝合金热轧用油所需的性质包括润滑性、良好的辊涂层性质、良好的表面质量、乳化液稳定性、可加工性以及废料处理性质。尤其是近年来，由于大量生产的需要以及高质量轧制铝产品的要求导致需要具有高水平润滑性、表面质量和乳化液稳定性的热轧油。但是，传统的铝和铝合金热轧用油不能完全满足所有这些要求。
在传统的轧制油中，润滑性受乳化剂的种类和数量的控制。但是，在传统的含有乳化剂的热轧油中，润滑性和乳化液稳定性有冲突，这两种性质通常不能同时满足。换句话说，当润滑性增加时，乳化液稳定性下降，因而使润滑性长期稳定性变差。同样，当乳化液稳定性提高时，又不能达到足够高的润滑性。最终，在板材表面产生缺陷。所以，使用传统的轧制油时通常不能得到轧制板材表面长期不变的质量。
日本专利申请（Kokoku）14599/1987公开了一种轧制油组合物，其中润滑性和乳化液稳定性都是令人满意的。虽然该专利申请的技术是有特色的和在统一润滑性和乳化液稳定性方面是成功的，但得到的轧制板材的表面质量不一定是令人满意的。日本专利申请（Kokai）120795/1988公开了一种类似的方法。该专利申请的技术与日本专利（Kokoku）14588/1987公开的基本上相同，但后一专利申请通过牺牲润滑性提高了表面质量。
因此，在传统的铝和铝合金热轧用油中，通常不能同时得到令人满意的润滑性、乳化液稳定性和表面质量。所以，传统的轧制油通常不适用于用现代的轧制方法大量生产铝和铝合金，同时也难以满足高质量轧制产品的要求。
由于上述原因，本发明者发现，通过用特定的聚合物化合物使特定的润滑剂组分乳化和分散的方法，可同时得到良好的润滑性、乳化液稳定性和表面质量。在这些发现的基础上，已提交了专利申请（日本专利（Kokai）145692/1990）。但是，进一步的研究揭示，这种热轧油组合物在苛刻的热轧条件下长期使用后不能避免热降解。这样的热降解使组合物的性能以及轧制铝或铝合金的表面质量变坏。
因此，轧制油组合物，当其在水中乳化时，能同时长期得到令人满意的润滑性、乳化液稳定性和表面质量仍是需要的。
因此，本发明的一个目的是提供一种铝或铝合金热轧用含油组合物，该组合物有极好的润滑性和乳化液稳定性。
本发明的另一目的是提供一种铝或铝合金热轧用含油组合物，该组合物使轧制材料得到极好的表面质量。
本发明的另一目的是提供一种铝或铝合金热轧用含油组合物，该组合物甚至在长期使用后也不会热降解。
本发明者继续了他们的研究工作，从而发现，用（ⅰ）特定单体的共聚物与（ⅱ）有机酸的盐代替日本专利申请（Kokai）145692/1990中描述的热轧油中的聚合物化合物，可明显减少长期使用后由于热降解使性能变坏，同时得到良好的润滑性、乳化液稳定性和表面质量。
通过提供一种铝或铝合金热轧用水分散性含油组合物来达到这些目的和其他一些目的，在以下优选实施方案的详细描述过程中这些目的将变得十分清楚，该组合物含有以下组分（a）-（d）：
（a）一种在40℃下粘度不大于80厘沲的矿物油，
（b）3-30%（重）选自C10-C22脂肪酸、油和脂肪，C10-C22脂肪酸与C1-C22醇组成的单酯，以及它们的混合物的化合物，
（c）0.5-10%（重）磷酸或亚磷酸的C4-C18烷基或烯基酯，
（d）0.1-10%（重）聚合物与有机酸的盐，其中
聚合物的平均分子量为10000-1000000，它为下式（1）表示的一种或多种单体和至少另外一种选自（甲基）丙烯酰胺和（甲基）丙烯酸盐的单体的共聚物：
其中，R1为氢或甲基，R2和R3各自独立地为氢或C1-C3烷基，m为0或1，n为1-3中的一个整数，以及
用下式（2）表示的有机酸：
其中，R4为C1-C5烷基、羟基-C1-C5烷基、羧基-C1-C5烷基或羧基。
从本发明以下优选实施方案的详细描述中，本发明的这些目的和其他一些目的、特征以及优点将变得很清楚。
本含油组合物通常在用于热轧以前用水乳化。因此，本含油组合物最好可分散在水中。但是，本含油组合物不限于用作铝或铝合金热轧用水包油型乳化液，还用作润滑剂和/或分散剂。
本组分（a）的例子包括各种形式矿物油，如锭子油、机加工油、透平油、汽缸油、中性油等。其中，烷烃系列的矿物油由于其耐热性和润滑性是优选的。矿物油在40℃下的粘度最好不大于80厘沲。超过80厘沲的粘度可能使板材的表面质量变坏。组分（a）作为基础油，所以它在含油组合物中的数量不受特别地限制。但是，优选的是，该组分的加入量为38-96.4%（重），优选50-96.4%（重），更优选60-85%（重）。
组分（b）的例子包括动物和植物脂肪和油，例如鲸油、牛油、猪脂、菜籽油、蓖麻油、棕榈油和椰子油。C10-C22脂肪酸的例子包括癸酸、月桂酸、硬脂酸、异硬脂酸、油酸和芥酸。脂肪酸单酯包括C10-C22脂肪酸和选自C1-C22脂族一元醇、乙二醇、三甲醇丙烷、季戊四醇、甘油等的醇的单酯。脂肪酸单酯的具体例子包括癸酸甲酯、硬脂酸丁酯、油酸月桂酯、芥酸2-乙基己酯、单油酸季戊四醇酯、单油酸甘油酯等。
组分（b）用作油性能改进剂。组分（b）可为单一的化合物，也可为含有各种适用化合物的混合物。优选的是，组分（b）的数量为含油组合物的3-30%（重），更优选10-25%（重）。小于3%（重）的数量可能使润滑性降低，而大于30%（重）的数量可能使轧制产品的表面质量变坏。当油和/或脂肪作为唯一的组分（b）源时，油和/或脂的数量按含油组合物的总重量计最好是不大于20%（重）。
组分（c）是磷酸或亚磷酸的一种或多种C4-C18烷基或烯基酯。组分（c）的例子包括磷酸二丁酯、磷酸单辛酯、磷酸三油基酯、磷酸三丁酯、磷酸二异辛酯和磷酸三油基酯。在单酯、二酯和三酯中，特别优选的是磷酸单和二烷基酯、磷酸单和二烯基酯、亚磷酸单和二烷基酯和亚磷酸单和二烯基酯。
优选的是，组分（c）的数量为含油组合物的0.5-10%（重），更优选为1-5%（重）。小于0.5%（重）的数量在提高轧制板材的表面质量方面可能无效，而大于10%（重）的数量可能不能得到明显的改进。
组分（d）聚合物的例子包括式（1）表示的单体和（甲基）丙烯酰胺的共聚物、式（1）表示的单体和（甲基）丙烯酸盐的共聚物，以及式（1）表示的单体、（甲基）丙烯酰胺和（甲基）丙烯酸盐的共聚物。优选的是，式（1）表示的单体在聚合物中的摩尔百分含量为50-90%，（甲基）丙烯酰胺在聚合物中的摩尔百分含量为0-20%以及（甲基）丙烯酸盐在聚合物中的摩尔百分含量为10-50%。
在组分（d）的有机酸中，R4为C1-C5烷基、羟基-C1-C5烷基或羧基。其中，羟基-C1-C5烷基是特别优选的。R4COO-的具体例子包括乙酸根、丙酸根、丁酸根、戊酸根、癸酸根、甘醇酸根、乳酸根、羟丙烯酸根、草酸根、丙二酸根、琥珀酸根、谷氨酸根、己二酸根等。特别优选的是甘醇酸根、乳酸根和丙烯酸根。
在式（1）单体中胺的例子包括二甲氨乙基丙烯酰胺、二甲氨丙基丙烯酰胺、二乙氨甲基丙烯酰胺、二甲氨乙基甲基丙烯酰胺、二甲氨丙基甲基丙烯酰胺和二乙氨甲基甲基丙烯酰胺，其中所有的都是其中m＝1的式（1）的化合物，以及烯丙胺、二甲氨甲基乙烯、二乙氨甲基乙烯、二甲氨甲基丙烯、二乙氨甲基丙烯，它们都是其中m＝0的式（1）的化合物。在这些胺中，m＝1的式（1）化合物是特别优选的。特别优选的单体（1）的例子包括二甲氨丙基甲基丙烯酰胺和二乙氨丙基丙烯酰胺，以及最优选的共聚物中和产物是用甘醇酸的中和产物。
（甲基）丙烯酸盐的例子包括碱金属盐，如（甲基）丙烯酸钠和（甲基）丙烯酸钾，以及有机胺盐，如（甲基）丙烯酸单乙醇铵、（甲基）丙烯酸二乙醇铵和（甲基）丙烯酸三乙醇铵。
优选的是，组分（d）聚合物的平均分子量为10000-1000000。低于这一范围的平均分子量可能使乳化液稳定性变差，而高于这一范围的平均分子量可能使该组合物高度粘稠，以致难以处理。更优选的平均分子量为30000-300000。
在聚合物制备中，可以使用式（2）的有机酸中和的式（1）的单体。例如，可通过用甘醇酸中和的二甲氨丙基甲基丙烯酰胺与共聚单体聚合的方法得到共聚物（d）。
组分（d）共聚物可单独使用或两种或多种一起使用。组分（d）的数量按含油组合物的总重量计为0.1-10%（重），优选0.5-5%（重）。超过10%（重）的数量是不利的，因为耐压负荷的性能可能变差，而且组合物的防过热咬合性可能变坏。
如果需要的话，铝和铝合金热轧用含油组合物根据需要还可含有已知的添加剂，如防锈/防腐蚀剂、抗氧化剂以及用于改善最初乳化能力的乳化剂。
防锈/防腐蚀剂的例子包括烯基琥珀酸及其衍生物（如盐和C1-C5烷基酯）、脂肪酸（如油酸）、酯类（如脱水山梨醇单油酸酯）和胺类。它们可加到本含油组合物中，其数量按组合物的总重量计不大于2%（重）。
抗氧剂的例子包括酚类化合物（如2，4-二叔丁基对-甲酚）和芳族胺（如苯基-α-萘胺）。它们可加到本含油组合物中，其数量按组合物的总重量计不大于5%（重）。
乳化剂的例子包括阴离子型表面活性剂（油酸三乙醇铵和石油磺酸钠）和非离子型表面活性剂（如聚（氧乙烯）壬基苯基醚）。它们可加到本含油组合物中，其数量按含油组合物的总重量计不大于2%（重）。
在使用前，铝和铝合金热轧用含油组合物可用水稀释并乳化。稀释比不受特别限制，但优选的是稀释到含油组合物的浓度为乳化液的1-30%（重）。
组分（d）的聚合物最好能有有利的电内聚力、空间阻碍和保护胶体作用，并且能耐高温。本含油组合物能在苛刻的轧制条件下长期维持乳化颗粒的均匀分散以及适合颗粒尺寸的不变颗粒分布。所以，最初良好的轧制润滑性可长期维持。另外，组分（d）最好能有有利的辊涂层控制作用，以及组分（d）最好还能有有利的薄而均匀的辊涂层。因此，可得到有最少缺陷的铝或铝合金表面以及均匀的质量。
在以下例证性实施方案的描述中，本发明的其他一些特征将变得很清楚，这些实施方案用于说明本发明，并不打算用来限制本发明。
现在通过实施例来描述本发明，但不应把它们作为对本发明的限制。
实施例1
含油组合物（本发明产品1-5和对比产品1-6）按以下描述配制，和按已知方法制备。聚合物称为“聚合物分散剂”。
本发明产品1：
组分(a):  %(重)
烷烃系列矿物油(70厘沲/40℃)  61.5
组分(b):
油酸  15.0
猪脂  15.0
组分(c):
亚磷酸二月桂酯  3.0
组分(d):
聚合物分散剂(A):醋酸与二甲氨
丙基丙烯酰胺/丙烯酰胺/丙烯酸钠
的80/5/15共聚物的中和产物(分子
量为400000)  2.0
其他:
磷酸三羟甲苯酯  2.0
抗氧化剂(2,4-二叔丁基对甲酚)  1.0
非离子型表面活性剂(I):聚氧乙烯壬
基苯基醚(亲水亲油平衡为12.4)  0.5
合计  100.0
本发明产品2:
组分(a):  %(重)
烷烃系列矿物油(60厘沲/40℃)  73.0
组分(b):
异硬脂酸  15.0
月桂酸  2.0
硬脂酸丁酯  5.0
组分(c):
磷酸三油基酯  1.0
组分(d):
聚合物分散剂(B):甘醇酸与二甲氨
丙基甲基丙烯酰胺/甲基丙烯酸钠的
85/15共聚物的中和产物(分子量为
80000)  3.0
其他:
抗氧化剂(2,4-二叔丁基甲酚)  1.0
合计  100.0
本发明产品3:
组分(a):  %(重)
烷烃系列的矿物油(20厘沲/40℃)  80.5
组分(b):
月桂酸  5.0
棕榈油  5.0
油酸油基酯  5.0
组分(c):
磷酸二油基酯  2.5
组分(d):
聚合物分散剂(c):乳酸与二甲氨
甲基乙烯/丙烯酸三乙醇铵的75/25
共聚物的中和产物(分子量为100000)  0.5
其他:
抗氧化剂(2,4-二叔丁基对甲酚)  1.0
防锈/防腐蚀剂(C18烯基琥珀酸) 0.5
合计  100.0
本发明产品4:
组分(a):  %(重)
烷烃系列矿物油(30厘沲/40℃)  69.5
组分(b):
油酸  20.0
油酸月桂酯  5.0
组分(c):
磷酸二丁酯  2.5
组分(d):
聚合物分散剂(D):琥珀酸与二
乙氨丙基丙烯酰胺/丙烯酰胺/
丙烯酸钾的70/10/20共聚物的
中和产物(分子量为300000)  1.0
其他:
抗氧剂(2,4-二叔丁基对甲酚)  1.0
防锈/防腐蚀剂(C18烯基琥珀酸) 1.0
合计  100.0
本发明产物5
组分(a):  %(重)
烷烃系列矿物油(30厘沲/40℃)  77.0
组分(b):
油酸  5.0
硬脂酸丁酯  10.0
组分(c):
亚磷酸三异辛酯  5.0
组分(d):
聚合物分散剂(E):甘醇酸与二甲氨
丙基甲基丙烯酰胺/丙烯酰胺/丙烯
酸钠的84/1/15共聚物的中和产物(分子量为50000)  1.0
其他:
抗氧化剂(2,4-二叔丁基对甲酚)  1.0
防锈/防腐蚀剂(C18烯基琥珀酸) 1.0
合计  100.0
对比产品1：
商业上可购的铝热轧含油组合物（阴离子型表面活性剂）
对比产品2:  %(重)
矿物油(30厘沲/40℃)  82.5
油酸  5.0
牛油  5.0
磷酸三羟甲苯酯  2.5
抗氧化剂(2,4-二叔丁基对甲酚)  1.0
防锈/防腐蚀剂(C18烯基琥珀酸) 1.0
非离子型表面活性剂(I)  3.0
合计  100.0
对比产品3:  %(重)
矿物油(100厘沲/40℃)  51.0
油酸  10.0
棕榈油  10.0
硬脂酸丁酯  20.0
磷酸三羟甲苯酯  5.0
抗氧化剂(2,4-二叔丁基对甲酚)  1.0
防锈/防腐蚀剂(C18烯基琥珀酸) 1.0
聚合物分散剂(A)  2.0
合计  100.0
对比产品4:  %(重量)
烷烃系列矿物油(20厘沲/40℃)  80.5
油酸  5.0
油酸月桂酯  10.0
磷酸单辛酯  2.5
抗氧化剂(2,4-二叔丁基对甲酚)  1.0
聚合物分散剂(E):磷酸与二甲
氨乙基甲基丙烯酸酯/甲基丙烯酸
癸酯/丙烯酸钠的6/1/1共聚物
的中和产物(分子量为300000)  1.0
合计  100.0
对比产品5:  %(重)
烷烃系列矿物油(20厘沲/40℃)  80.5
月桂酸  5.0
棕榈油  5.0
油酸油基酯  5.0
磷酸二油基酯  2.5
聚合物分散剂(G):磷酸与二甲氨
乙基甲基甲基丙烯酰胺/丙烯酸钠
/乙烯基磺酸钠的3/1/1共聚物的
中和产物(分子量为200000)  0.5
抗氧化剂(2,4-二叔丁基对甲酚)  1.0
防锈/防腐蚀剂(C18烯基琥珀酸) 0.5
合计  100.0
对比产品6:  %(重)
矿物油(20厘沲/40℃)  84.0
牛油  10.0
亚磷酸三辛酯  5.0
聚合物分散剂(H):甘醇酸与二甲氨
乙基甲基丙烯酸酯/丙烯酸钠的6/1
共聚物的中和产物(分子量为500000)  1.0
合计  100.0
试验实施例1-轧制试验
使用实施例1得到的含油组合物，按照以下描述的方法评价轧制润滑性和轧制板材的表面质量。从牵引和轧制负荷可了解轧制润滑性。表面质量由轧制板数和表面的粗糙度（在宽度的方向）来决定。
试验方法
使用二辊式轧制机（直径200毫米×宽200毫米，轧辊材料：球轴承钢，HS（肖氏硬度）＝65），研究了每种轧制含油组合物的轧制润滑性和得到的表面质量。
轧制条件
轧制材料：纯铝材（宽80毫米×长700毫米×厚3.5毫米）
轧辊的粗糙度：用砂纸沿轧制方向研磨轧辊的表面使其Ra（粗糙剖面的平均高度）为0.3-0.4微米。
板材温度：480℃
轧制速度：50米/分钟
减薄比：40%和60%（用于研究轧制润滑性），60%（用于研究轧制板材的表面质量）
轧制板数：对于每一减薄比来说，5块板（用于研究轧制润滑性）和100块板（用于研究表面质量）。
轧制油的条件：
乳化液中油的浓度：2%（体）
温度：60℃
搅拌：高速混合器，12000转/分钟
喷射量：2升/分钟
试验实施例2-乳化液稳定性试验
试验方法
将轧制含油组合物和水混合达到预定的浓度（2%（体），5升，60℃），然后用高速混合器在12000转/分钟下搅拌制得乳化液。加入100ppm铝粉（325目），并将得到的混合物搅拌5小时制得试验乳化液。将加热的铝板（材料：纯铝板，宽80毫米×长150毫米×厚5毫米，500℃）浸没在该乳化液中，5秒钟后取出。重复浸没（高速混合器：12000转/分钟），在此期间，用库耳特颗粒计数器测量乳化液的颗粒尺寸，从平均颗粒尺寸（体积分布）对浸没板的数目的变化评价乳化液长期稳定性。
结果
试验实施例1和2的结果列入表1。
Figure 941168492_IMG4
正如表1所示，与对比产品相比，本组合物（1-5）显示极好的轧制润滑性，得到的轧制产品的表面粗糙度减少，有极好的表面质量。
另外，本组合物有极好的长期乳化液稳定性。从实施例1和2的试验数据结果，已证实本含油组合物满足轧制润滑性、轧制产品的表面质量以及乳化液轧制润滑性、轧制产品的表面质量以及乳化液长期稳定性所有三项要求。但是，对比产品1有较差的轧制润滑性，产品2有较差的轧制润滑性和稳定性，产品3有较差的表面质量，产品4-6有较差的乳化液稳定性。
本热轧含油组合物具有适合的颗粒尺寸和高的润滑性。所以，该组合物使沉降数量的变化减到最小，而且组合物是新鲜组合物时，也有极好的润滑性。后一特性使新鲜含油组合物进入轧制机后立即就能轧制高强度材料。另外，还可降低轧制含油组合物在水包油型乳化液中的浓度。还有，因为组合物具有极好的长期润滑性和辊涂层控制作用，它们可避免在长期使用后出现的沉降或滑移时变坏等一些问题，这些问题是使用传统的轧制油不可避免的。因此，用不变的方式可在整个时间内得到极好的轧制产品的表面质量。此外，由于聚合物分散剂的功能，可减少对贮槽和轧制机周围的外罩的污染，使废水处理性质得到改善。

Claims (5)

1、一种可分散在水中的含油组合物，它含有以下组分(a)-(d)：
(a)一种40℃粘度不大于80厘沲的矿物油，
(b)3-30%(重)选自C10-C22脂肪酸、油和脂、C10-C22脂肪酸和C1-C22醇的单酯，以及它们的混合物的化合物，
(c)0.5-10%(重)磷酸C4-C18烷基或烯基酯或亚磷酸C4-C18烷基或C4-C18烯基酯，
(d)0.1-10%(重)聚合物与有机酸的盐，其中
聚合物的平均分子量为10000-1000000，它是下式(1)表示的一种或多种单体和选自(甲基)丙烯酰胺和(甲基)丙烯酸盐的至少另一种单体的共聚物，
其中，R1为氢或甲基，R2和R3各自独立地为氢或C1-C3烷基，
m为0或1，n为1-3中的一个整数，以及
用下式(2)表示的有机酸：
其中，R4为C1-C5烷基、羟基-C1-C5烷基、羧基-C1-C5烷基或羧基。
2、根据权利要求1的组合物，其中R4为羟基C1-C5烷基。
3、根据权利要求1的组合物，其中组分（d）含有50-90%（摩尔）式（1）的单体、0-20%（摩尔）（甲基）丙烯酰胺和10-50%（摩尔）（甲基）丙烯酸盐。
4、根据权利要求2的组合物，其中组分（d）含有50-90%式（1）的单体、0-20%（摩尔）（甲基）丙烯酰胺和10-50%（摩尔）（甲基）丙烯酸盐。
5、根据权利要求1的组合物，其中式（1）中的m为1。
CN94116849A 1993-10-08 1994-10-07 铝和铝合金热轧用含油组合物 Expired - Lifetime CN1047197C (zh)

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