CN101765640A - 热处理油组合物 - Google Patents
热处理油组合物 Download PDFInfo
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- CN101765640A CN101765640A CN200880100504A CN200880100504A CN101765640A CN 101765640 A CN101765640 A CN 101765640A CN 200880100504 A CN200880100504 A CN 200880100504A CN 200880100504 A CN200880100504 A CN 200880100504A CN 101765640 A CN101765640 A CN 101765640A
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- 238000010438 heat treatment Methods 0.000 title claims description 44
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- 239000002199 base oil Substances 0.000 claims abstract description 15
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Abstract
本发明提供:向基油中混合(A)金属系清洁分散剂及(B)碳原子数6~30的脂族羧酸而成的、冷却性能高的热处理油组合物,该组合物即使闪点高也具有优良的冷却性能。
Description
技术领域
本发明涉及热处理油组合物,详细而言,涉及在淬火加工中冷却性能高的热处理油组合物。
背景技术
淬火等热处理加工通常使用热处理液,是为了赋予金属材料所期望的硬度而进行的。因此,热处理液必须具有能够提高金属材料硬度的优良冷却性能。
以往的热处理液多使用油系的热处理液。这是因为水系的热处理液冷却性能过高,具有金属材料产生淬火裂纹的危险性,另外与油系的热处理液相比较,淬火变形大。因此,需求冷却性能高的油系热处理液,即热处理油。
热处理油划分为低油温下使用的冷油、可在高温下使用的热油以及在中间温度下使用的半热油,冷油相当于JIS K2242的1种,半热油及热油相当于2种。热油在100℃下的运动粘度通常大约为10~30mm2/s,冷油大约为6mm2/s以下。
然而,如果为了减轻淬火变形而使用热油或半热油在高油温下淬火,虽然淬火变形的减轻效果较大,但是冷却性能不足,存在不能通过淬火得到目标硬度(淬火硬度)的问题。
与此相对,使用冷油时,虽然可以得到足够的硬度,但是由于是低粘度油,因而闪点低,在淬火加工时具有着火的危险性,另外还有产生油烟而使环境恶化的问题。
即,热处理油的冷却性能的状况为:越是低粘度油,其冷却性能越高,但是低粘度油不能避免着火的危险性等。
鉴于这种状况,人们期望开发出即使闪点高、粘度高、也具有高的冷却性能的热处理油。
一方面,关于以往的热处理油的冷却性能的改良,一直以来使用的是向矿物油系基油中混合沥青、高分子化合物、或者磺酸、水杨酸等的碱土金属盐而成的、冷却性能得到提高的淬火油。但是,这种淬火油的冷却性能不足,有时不能赋予金属材料所期望的硬度。
另外,在近年来的研究中,例如,专利文献1中记载了如下组合物,该组合物在具有特定的运动粘度及组成的油中含有脂族聚烯烃和烃基取代酚、水杨酸等的碱土金属盐以及根据需要的烃基取代琥珀酸酯等。另外,专利文献2中公开了如下组合物,该组合物在具有特定的运动粘度及组成的油中含有水杨醇衍生物的碱金属盐和选自脂族聚烯烃、烃基取代酚、水杨酸等的碱土金属盐、烃基取代琥珀酸酯等的至少一种。
但是,这些组合物都含有聚异丁烯等脂族聚烯烃作为必要成分,氧化稳定性不足,同时冷却性能也未必足够。
专利文献1:日本特表2005-513200号公报
专利文献2:日本特表2005-513201号公报
发明内容
在这种状况下,本发明的目的在于提供冷却性能高的热处理油组合物,该组合物即使闪点高也具有优良的冷却性能。
本发明者们在锐意研究后,出乎预料地发现,向基油中混合金属系清洁分散剂和特定的脂族羧酸而成的组合物可以实现本发明目的。本发明是基于这一发现而完成的。
即,本发明提供:
(1)热处理油组合物,其是向基油中混合(A)金属系清洁分散剂以及(B)碳原子数6~30的脂族羧酸而得到的;
(2)根据上述(1)中所述的热处理油组合物,其中(A)成分的金属系清洁分散剂为选自磺酸、酚及水杨酸的金属盐中的至少一种;
(3)根据上述(1)中所述的热处理油组合物,其中(A)成分的金属为碱土金属;
(4)根据上述(1)中所述的热处理油组合物,其中脂族羧酸为碳原子数8~20的脂族单羧酸;
(5)根据上述(1)中所述的热处理油组合物,其中(A)成分的混合量按组合物基准为0.1~20质量%,(B)成分的混合量按组合物基准为0.1~20质量%;
(6)根据上述(1)中所述的热处理油组合物,其中(B)成分相对于(A)成分的混合比按质量比为0.1~2;
(7)根据上述(1)中所述的热处理油组合物,该组合物的闪点为180℃以上。
根据本发明,可以提供冷却性能高的热处理组合物,该组合物即使闪点高也具有优良的冷却性能。
发明的最佳实施方式
本发明的热处理油组合物是向基油中混合(A)金属系清洁分散剂及(B)碳原子数6~30的脂族羧酸而成的组合物。
对本发明中使用的基油并无特别限定,可以使用各种矿物油或合成油。作为矿物油,可列举出例如石蜡基系矿物油、中间基系矿物油、环烷基系矿物油等。另外,作为合成油,可以使用例如α-烯烃低聚物(碳原子数6~16的α-烯烃的低聚化物以及将其加氢而得到的产物)、碳原子数2~16的烯烃的(共)聚合物、烷基苯、烷基萘、聚苯基系烃、各种酯类(例如新戊二醇、三羟甲基丙烷、季戊四醇等多元醇的脂肪酸酯)、聚氧亚烷基二醇衍生物等。
另外,作为上述基油,优选使用100℃下的运动粘度为1~50mm2/s的基油。运动粘度低于1mm2/s,会出现容易着火的危险情况,而超过50mm2/s,由于过于粘稠而处理不便。从这些点来看,更优选上述运动粘度为1.5~45mm2/s的基油,特别优选为2~40mm2/s的基油。
另外,基油的闪点优选为150℃以上,更优选为170℃以上。为150℃以上,则着火等的危险性低,同时可以抑制在热处理加工时产生油烟。
再者,基油的粘度指数优选为85以上,更优选为95以上。另外,芳香族部分(%CA)优选为10以下,更优选为7以下,进一步优选为3以下,特别优选为1以下。如果粘度指数为85以上、芳香族部分(%CA)为10以下,则可以良好地维持热处理油组合物的氧化稳定性。
上述矿物油及合成油可以仅单独使用一种,也可以以任意比例将两种以上混合使用。
用作本发明的(A)成分的金属系清洁分散剂可使用以往公知的种种金属系清洁分散剂,没有特别的限制,合适的有例如磺酸、酚及水杨酸的金属盐。
作为上述磺酸,可列举出分子量大约为300~1500的烷基取代芳香族磺酸,具体可列举出烷基苯磺酸、烷基萘磺酸、石油磺酸等。该磺酸也可以为硫代磺酸。
作为酚,可列举出烷基酚或其硫化物、烷基酚的曼尼希反应物等;作为水杨酸,可列举出烷基水杨酸。
这些磺酸、酚及水杨酸的烷基取代基通常优选碳原子数1~20的饱和或不饱和的直链或支链烷基。另外,优选使用具有1~7个、特别是1~4个这些取代基的磺酸、酚及水杨酸。
作为上述磺酸、酚及水杨酸的金属盐等金属系清洁分散剂中的金属,可列举出碱金属以及碱土金属。其中,从冷却性能的角度考虑,优选碱土金属,可使用例如Ca、Ba、Mg,特别优选Ca、Ba。
另外,磺酸、酚及水杨酸的金属盐也适于使用它们的金属盐、和用金属氢氧化物和二氧化碳或者用金属氧化物和二氧化碳将这些金属盐进一步过碱化而得到的产物。
因此,本发明中,作为(A)成分的金属系清洁分散剂可以广泛地使用中性、碱性及过碱性的物质,例如,可使用碱值大约为0~600mgKOH/g的物质。其中,碱值为50~400mgKOH/g的物质是优选的。
需说明的是,此处所说的碱值为根据JIS K2501的“石油制品及润滑油-中和价实验法”的7中规定的高氯酸法而测定的“总碱值”。
本发明中,作为(A)成分,可以仅使用一种上述金属系清洁分散剂,也可以以任意比例将两种以上混合使用。另外,其混合量优选为组合物的0.1~20质量%。该混合量不足0.1质量%时,冷却性能提高的效果有时会不充分;而超过20质量%时,粘度上升,冷却性能恐怕会变差,并且效果饱和,成本增高。从这些理由出发,该混合量更优选为1~10质量%。
作为本发明的(B)成分的碳原子数6~30的脂族羧酸,优选使用具有直链或支链的饱和或不饱和脂族单羧酸及脂族二羧酸。
上述脂族单羧酸的具体例子可列举出例如己酸(羊油酸)、庚酸、辛酸(羊脂酸)、壬酸、癸酸(羊蜡酸)、十一烷酸、十二烷酸、十三烷酸、十四烷酸(肉豆蔻酸)、十五烷酸、十六烷酸(棕榈酸)、十七烷酸、十八烷酸(硬脂酸)、十九烷酸、二十烷酸、二十一烷酸、二十二烷酸、二十三烷酸、二十四烷酸、二十五烷酸、二十六烷酸、二十七烷酸、二十八烷酸、二十九烷酸、三十烷酸等饱和脂肪酸(这些饱和脂肪酸可以为直链状或支链状),己烯酸、庚烯酸、辛烯酸、壬烯酸、癸烯酸、十一烯酸、十二烯酸、十三烯酸、十四烯酸、十五烯酸、十六烯酸、十七烯酸、十八烯酸(包括油酸)、十八烷二烯酸(包括亚油酸)、十八烷三烯酸(包括亚麻酸)、十九烯酸、二十烯酸、二十一烯酸、二十二烯酸、二十三烯酸、二十四烯酸、二十五烯酸、二十六烯酸、二十七烯酸、二十八烯酸、二十九烯酸、三十烯酸等不饱和脂肪酸(这些不饱和脂肪酸可以为直链状或支链状,另外双键的位置也是任意的)等。
上述脂族二羧酸的具体例子可列举出例如辛二酸(软木酸)、壬二酸(杜鹃花酸)、癸二酸(皮脂酸)、十一烷二酸、十二烷二酸、十三烷二酸、十四烷二酸、十六烷二酸、十八烷二酸、二十烷二酸、二十二烷二酸、二十四烷二酸、二十六烷二酸、二十八烷二酸等饱和脂族二羧酸(这些二羧酸可以为直链状或支链状)、以及与这些饱和脂族二羧酸对应的不饱和脂族二羧酸(这些不饱和脂肪酸可以为直链状或支链状,另外双键的位置也是任意的)等。
在这些脂族羧酸中,从冷却性能的观点出发,优选碳原子数8~20的脂族单羧酸,具体例子可列举出辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、异硬脂酸、油酸、亚油酸、亚麻酸等。
在本发明中,作为(B)成分,可以仅使用一种上述脂族羧酸,也可以以任意比例将两种以上混合使用。另外,其混合量优选为组合物的0.1~20质量%。该混合量不足0.1质量%,冷却性能提高的效果有时会不充分;而超过20质量%,效果饱和,有时得不到与成本相抵的效果。从这些理由出发,该混合量更优选1~10质量%。
本发明中,(B)成分的脂族羧酸相对于(A)成分的金属系清洁分散剂的混合比按脂族羧酸/金属系清洁分散剂的质量比优选0.1~2,更优选0.2~1.5。混合比在此范围内时,能够得到良好的冷却性能。
基本上,本发明的热处理油组合物是通过混合基油、(A)成分及(B)成分而制备的,可以根据需要进一步混合热处理油中惯用的添加剂,例如蒸汽膜破裂剂、光亮改善剂、抗氧化剂等。
作为上述蒸汽膜破裂剂,可以列举出例如乙烯-丙烯共聚物等乙烯-α-烯烃共聚物(α-烯烃的碳原子数为3~20)、1-己烯、1-辛烯、1-癸烯、1-十二烯、1-十四烯、1-十六烯、1-十八烯等碳原子数为5~20的α-烯烃的聚合物、聚丙烯、聚丁烯、聚异丁烯等碳原子数为3或4的烯烃聚合物等各种聚烯烃类以及这些聚烯烃类的加氢产物;聚甲基丙烯酸酯、ポリメタアクリレ一ト、聚苯乙烯、石油树脂等高分子化合物以及沥青等。其中,特别是从冷却性、稳定性的观点出发,优选沥青,而从光亮性的观点出发,优选乙烯-丙烯共聚物等乙烯-α-烯烃共聚物、聚丁烯、聚异丁烯。这些蒸汽膜破裂剂的数均分子量通常优选为800~100,000。另外其混合量通常为热处理油组合物的0.5~10质量%。
上述光亮改善剂可列举出以往公知的油脂或油脂脂肪酸、烷基或烯基琥珀酸酰亚胺、取代羟基芳香族羧酸酯衍生物等。抗氧化剂可列举出以往公知的胺系抗氧化剂、受阻酚系抗氧化剂等。
本发明的热处理油组合物是将上述成分混合而成的,对其性状并无特别限制,组合物的闪点优选180℃以上,更优选190℃以上。另外,本发明组合物的闪点进一步优选200℃以上、220℃以上、240℃以上、250℃以上、260℃以上等更高的温度。如果是闪点这样高的组合物,可以适当地用作高油温热处理中使用的热油、半热油。
组合物的闪点如果为200℃以上,按照消防法对危险物的分类就相当于第四石油类,因此可以缓和因指定数量的控制而带来的约束,如果组合物的闪点为250℃以上,可作为指定可燃物(非危险物)处理,具有可进一步缓和消防法的约束的效果。
本发明的热处理油组合物即使是闪点高(例如为250℃以上)的组合物,也具有优良的冷却性能。
上面所说的冷却性能,具体而言,可以用基于JIS K 2242的银试片的冷却曲线中从800℃到300℃的冷却时间(秒数)(以下有时称为“300℃秒数”)来表示,该冷却时间越短则冷却性能越好,这表明通过淬火加工可以得到具有充分硬度的淬火加工物。
本发明的热处理油组合物的300℃秒数极短,即使是闪点为260℃左右的相当于热油、半热油的组合物,其冷却时间也可以达到6.0秒以下,进一步可达到5.0秒以下、4.0以下。另外,如果是闪点为190℃左右的相当于冷油的组合物,则300℃秒数可以达到3.5秒左右。
与具有同程度的闪点的公知的热处理油相比,上述冷却性能是相当高的性能。
实施例
接下来通过实施例进一步详细说明本发明,但是本发明并不受到这些例子的任何限定。需说明的是,热处理油组合物的性状及性能根据以下方法而求出。
(1)冷却性能
基于JIS K 2242中规定的冷却性能试验,将加热至810℃的规定的银试片投入试料(热处理油)中,测定银试片的冷却曲线。将该冷却曲线的从800℃冷却至300℃所需要的冷却时间(300℃秒数)作为冷却性能进行测定。该秒数越小则表示冷却性能越高。
(2)特性秒数
测定到达上述(1)中按JIS K 2242测定的冷却曲线中的特性温度(蒸汽膜阶段终止的温度)的时间(秒数)。
(3)100℃下的运动粘度
基于JIS K 2283进行测定。
(4)闪点
基于JIS K 2256(C.O.C法)进行测定。
(5)淬火实验
在下述实验条件下进行淬火,测定淬火处理物的硬度(淬火硬度)。
[淬火实验条件]
被加工材(试验片):SCM420、φ15mm×30mmL
加热温度:850℃×30分钟、纯氮气气氛
淬火条件:油温120℃、无搅拌、冷却时间3分钟
[硬度测定方法]
硬度测定位置:半径的1/2位置的测定、r=3.75mm
硬度测定机器:维氏硬度计
实施例1~17及比较例1~6
使用表1中所示的基油及添加剂,按照表1所示的比例混合,调和热处理油组合物,求出其性状及性能。结果显示于表1。另外,关于实施例6及比较例6的热处理油组合物,进行淬火实验,将其结果(淬火硬度)显示于表1。
[注]
1)矿物油-1:氢化精制矿物油(相当于ISO-100)、100℃运动粘度=90mm2/s、粘度指数=104、%CA=3.0、闪点=260℃
2)矿物油-2:氢化精制矿物油(相当于ISO-10)、100℃运动粘度=14mm2/s、粘度指数=99、%CA=6.0、闪点=190℃
3)蒸汽膜破裂剂:沥青、100℃运动粘度=500mm2/s、闪点=340℃
从表1可知,闪点为260℃左右的本发明的热处理油组合物(实施例1~16)的300℃秒数为6.0秒以下,较短,冷却性能优良。
与此相对,未混合本发明的(A)、(B)的任一个或两个成分的热处理油组合物(比较例1~3)及混合蒸汽膜破裂剂替代(A)、(B)成分的比较例4的热处理油组合物,它们的300℃秒数均为9.4秒以上,冷却性能低劣。另外,闪点为250℃左右的市售热处理油(比较例6)的300℃秒数也为7.5秒,与闪点为260℃左右的本发明的热处理油相比,冷却性能低劣。
关于由本发明热处理油(实施例6、300℃秒数为5.0秒)和市售热处理油(比较例6、300℃秒数为7.5秒)的淬火实验得到的淬火硬度,前者为476Hv,而后者为420Hv,因此可以明确把握本发明与比较例的淬火性能的差别。
闪点为190℃左右、相当于冷油的本发明的热处理油组合物(实施例17),其300℃秒数为3.5秒,与闪点同样为190℃左右、混合了蒸汽膜破裂剂替代(A)、(B)成分的比较例5的热处理油(300℃秒数为5.1秒)相比,冷却性能格外优良。
产业上的可利用性
根据本发明,可以提供冷却性能高的热处理油组合物,该组合物即使闪点高也具有优良的冷却性能。因此,为了减轻淬火变形,在使用所谓的热油或半热油于高油温下进行淬火时,也可有效地用作具有必要的冷却性能的热处理油。
Claims (7)
1.热处理油组合物,其是向基油中混合(A)金属系清洁分散剂以及(B)碳原子数6~30的脂族羧酸而得到的。
2.根据权利要求1中所述的热处理油组合物,其中(A)成分的金属系清洁分散剂为选自磺酸、酚及水杨酸的金属盐中的至少一种。
3.根据权利要求1中所述的热处理油组合物,其中(A)成分的金属为碱土类金属。
4.根据权利要求1中所述的热处理油组合物,其中脂族羧酸为碳原子数8~20的脂族单羧酸。
5.根据权利要求1中所述的热处理油组合物,其中(A)成分的混合量按组合物基准为0.1~20质量%,(B)成分的混合量按组合物基准为0.1~20质量%。
6.根据权利要求1中所述的热处理油组合物,其中(B)成分相对于(A)成分的混合比按质量比为0.1~2。
7.根据权利要求1中所述的热处理油组合物,该组合物的闪点为180℃以上。
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CN103667629A (zh) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | 低温回火方法 |
CN103667628A (zh) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | 热处理方法 |
CN104245968A (zh) * | 2012-03-16 | 2014-12-24 | 出光兴产株式会社 | 热处理油组合物 |
CN109722511A (zh) * | 2019-02-20 | 2019-05-07 | 张丹 | 一种高性能淬火油 |
TWI675911B (zh) * | 2015-02-18 | 2019-11-01 | 日商出光興產股份有限公司 | 熱處理油組成物 |
CN111868269A (zh) * | 2018-03-28 | 2020-10-30 | 出光兴产株式会社 | 热处理油组合物 |
CN111886349A (zh) * | 2018-03-28 | 2020-11-03 | 出光兴产株式会社 | 热处理油组合物 |
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KR101070878B1 (ko) | 2009-04-24 | 2011-10-06 | 에쓰대시오일 주식회사 | 산화안정성이 개선된 열처리유 |
JP5930981B2 (ja) * | 2013-02-06 | 2016-06-08 | 出光興産株式会社 | 熱処理油組成物 |
JP6569145B2 (ja) * | 2015-02-18 | 2019-09-04 | 出光興産株式会社 | 熱処理油組成物 |
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CN103667629A (zh) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | 低温回火方法 |
CN103667628A (zh) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | 热处理方法 |
TWI675911B (zh) * | 2015-02-18 | 2019-11-01 | 日商出光興產股份有限公司 | 熱處理油組成物 |
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CN111868269A (zh) * | 2018-03-28 | 2020-10-30 | 出光兴产株式会社 | 热处理油组合物 |
CN111886349A (zh) * | 2018-03-28 | 2020-11-03 | 出光兴产株式会社 | 热处理油组合物 |
CN109722511A (zh) * | 2019-02-20 | 2019-05-07 | 张丹 | 一种高性能淬火油 |
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JP2009029950A (ja) | 2009-02-12 |
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CN101765640B (zh) | 2013-06-12 |
WO2009016942A1 (ja) | 2009-02-05 |
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