CN111742037A - 润滑脂组合物 - Google Patents
润滑脂组合物 Download PDFInfo
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- CN111742037A CN111742037A CN201980014428.2A CN201980014428A CN111742037A CN 111742037 A CN111742037 A CN 111742037A CN 201980014428 A CN201980014428 A CN 201980014428A CN 111742037 A CN111742037 A CN 111742037A
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Abstract
本申请涉及一种润滑脂组合物,其是含有具有生物降解性的基础油、以及包含磺酸钙复合物和脱水山梨糖醇脂肪酸酯的防锈剂的润滑脂组合物,组合物中的具有生物降解性的有机物质的合计含量为75质量%以上,防锈剂的含量为2.5~30质量%。
Description
技术领域
本发明涉及对环境的影响少、且具有对盐水的防锈性和耐水性的润滑脂组合物。
背景技术
近年来,对水资源、海洋环境的保护的关心日益高涨,例如在美国,关于入港的全部船舶中使用油的设备,施行了附有如下义务的船舶入港限制(Vessel General Permit:VGP),即,在有可能漏油的水接触部使用生物降解性、非毒性和非生物富集性受到认可的环保型润滑油(Environmentally Acceptable Lubricants:EAL)。鉴于这样的情况,以防止海洋、湖泊、河流等的污染为目标的生物降解性润滑脂的开发成为当务之急。
专利文献1公开了一种润滑剂组合物,其适于与水接触的钢缆,且对人体是安全的。然而,关于对海水等盐水的高的防锈性、耐水性,仍有改善的余地。
现有技术文献
专利文献1:日本特开2013-60541号公报
发明内容
发明要解决的课题
本发明的目的在于,提供对环境的影响少、且具有对海水等盐水的优异的防锈性和耐水性的润滑脂组合物。
用于解决课题的手段
本发明人进行了深入研究,结果发现,含有具有生物降解性的基础油、增稠剂、以及包含磺酸钙复合物和脱水山梨糖醇脂肪酸酯的防锈剂的润滑脂组合物对盐水的防锈性和耐水性优异,从而完成了本发明。
即,本发明涉及:
[1]一种润滑脂组合物,其是含有具有生物降解性的基础油、以及包含磺酸钙复合物和脱水山梨糖醇脂肪酸酯的防锈剂的润滑脂组合物,其中,组合物中的具有生物降解性的有机物质的合计含量为75质量%以上,防锈剂的含量为2.5~30质量%;
[2]根据[1]所述的润滑脂组合物,其中,磺酸钙复合物相对于脱水山梨糖醇脂肪酸酯的含量(磺酸钙复合物的含量/脱水山梨糖醇脂肪酸酯的含量)为0.5~5.0。
[3]根据[1]或[2]所述的润滑脂组合物,其是含有具有生物降解性的基础油、增稠剂、以及包含磺酸钙复合物和脱水山梨糖醇脂肪酸酯的防锈剂的润滑脂组合物,其中,组合物中的具有生物降解性的有机物质(特别是具有生物降解性的基础油和脱水山梨糖醇脂肪酸酯)的合计含量为75质量%以上,防锈剂的含量为2.5~30质量%;
[4]根据[3]所述的润滑脂组合物,其中,增稠剂的含量为2.0~20质量%。
[5]根据[3]或[4]所述的润滑脂组合物,其中,增稠剂为选自锂皂、锂复合皂和脲系化合物中的1种或2种以上的增稠剂。
[6]根据[3]~[5]中任一项所述的润滑脂组合物,其中,混合稠度为265~295。
[7]根据[1]或[2]所述的润滑脂组合物,其是含有具有生物降解性的基础油、具有生物降解性的蜡、增粘剂、以及包含磺酸钙复合物和脱水山梨糖醇脂肪酸酯的防锈剂的润滑脂组合物,其中,组合物中的具有生物降解性的有机物质(特别是具有生物降解性的基础油、具有生物降解性的蜡和脱水山梨糖醇脂肪酸酯)的合计含量为75质量%以上,防锈剂的含量为2.5~30质量%,熔点为50℃~100℃;
[8]根据[7]所述的润滑脂组合物,其中,增粘剂的含量为1.0~25质量%;
[9]根据[7]或[8]所述的润滑脂组合物,其中,具有生物降解性的基础油和具有生物降解性的蜡的合计量中的具有生物降解性的蜡的含量为6.0~40质量%。
发明效果
本发明的润滑脂组合物对环境的影响少,且对海水等盐水具有优异的防锈性和耐水性。另外,由于未使用通常的润滑脂中使用的锌、钼等金属系的添加物,因此对生物的毒性、蓄积性的风险低。
具体实施方式
<润滑脂组合物>
本实施方式的润滑脂组合物的特征在于,含有具有生物降解性的基础油、以及包含磺酸钙复合物和脱水山梨糖醇脂肪酸酯的防锈剂。需要说明的是,上述的VGP中规定,在润滑脂组合物中含有75质量%以上的、依据作为测定有机物质的易生物降解性的标准试验法的OECD试验准则301系列、具有规定的生物分解度(例如依据OECD试验准则301B,基于微生物的生物分解度为60%以上)的有机物质,为了对应于VGP,本实施方式的润滑脂组合物也设计成这样。
(基础油)
作为基础油,优选使用依据OECD试验准则301系列具有规定的生物分解度的、判定为具有生物降解性的基础油(以下,本说明书中,有时将这样的基础油简写为“具有生物降解性的基础油”)。
具有生物降解性的基础油没有特别限定,可举出植物油、动物油、合成酯油、聚亚烷基二醇、合成烃油等,从防锈性和耐水性的观点出发,优选合成酯油和植物油。另外,从氧化稳定性、高温下的保存稳定性的观点出发,更优选合成酯油,从成本、高的生物降解率、以及毒性、蓄积性等安全性的观点出发,优选植物油。
本说明书中,“植物油”是指来自植物的油,是包括油脂的概念。本实施方式中可以使用的植物油没有特别限定,例如可举出可可脂、玉米油、花生油、葵花籽油、大豆油、椰子油、橄榄油、山茶油、红花油、油桐油、亚麻籽油、椰油、橡树油、扁桃仁油、杏仁油、蓖麻油、菜籽油、大风子油、乌桕油、棉籽油、芝麻油、棕榈油、棕榈仁油、米糠油、桐油、松节油、木棉油等,优选选自玉米油、葵花籽油、红花油、蓖麻油、亚麻籽油、大豆油、菜籽油、棉籽油、橄榄油、山茶油、桐油、松节油、椰子油和棕榈油中的1种以上。另外,也可以是将这些油多种混合而得到的物质;包括甘油二酯、甘油单酯的油脂;一部分发生了氧化、还原等改性的油。
作为市售的植物油,例如可举出大豆油KT等丸正公司制植物油;精炼大豆油、亚麻籽油等日清Oillio(株)制的植物油;大米色拉油等Boso油脂(株)制的植物油;TEXAPRINTSDCE等Cognis Japan(株)制的植物油;苎烯油、桉树油、桐油等安土产业(株)制的植物油;Hartall SR-20、Hartall SR-30、Hartall R-30等Harima化成(株)制的植物油;α-蒎烯、东洋松印、双戊烯等荒川化学公司制的松节油;丰国制油(株)制的工业一号蓖麻油等,但不限定于这些。
本说明书中,“动物油”是指来自动物的油,是包括油脂的概念。作为本实施方式中可以使用的动物油,有沙丁鱼油、鲭鱼油、鲱鱼油、秋刀鱼油、金枪鱼油、鱼肝油等由鱼类的躯体得到的鱼油;猪油脂、鸡油、黄油、牛油、牛骨油、鹿油、海豚油、马油、猪油、骨油、羊油、牛蹄油、鼠海豚油、鲨鱼油、抹香鲸油、鲸油等,优选为选自鱼油、牛油和猪油中的1种以上的油,也可以是将这些油多种混合而得到的物质;包括甘油二酯、甘油单酯的油脂;一部分发生了氧化、还原等改性的油。
作为合成酯油,优选使用脂肪酸二酯、脂肪酸多元醇酯,更优选脂肪酸多元醇酯。作为脂肪酸二酯的具体例,例如可举出己二酸二异癸酯、壬二酸二异癸酯、癸二酸二辛酯等。作为脂肪酸多元醇酯的具体例,例如可举出新戊二醇二酯、三羟甲基丙烷三酯、三羟甲基丙烷复合酯、季戊四醇四酯、二季戊四醇六酯等。其中,优选使用BASF Japan(株)制的Synative ES TMP 05/140和05/320(三羟甲基丙烷复合酯)、Croda Japan(株)制的Priolube2089(三羟甲基丙烷油酸酯)、伊藤制油(株)制的MINERASOL LB-601(特殊蓖麻油系缩合脂肪酸酯)等高生物降解性酯油。
作为聚亚烷基二醇,例如可举出聚乙二醇、聚丙二醇、聚环氧乙烷-环氧丙烷(环氧乙烷与环氧丙烷的共聚物)、聚(甲基-亚乙基)二醇、聚丁二醇等。另外,就聚亚烷基二醇而言,使用2种以上不同的环氧烷烃而得到的聚亚烷基二醇的无规共聚物、交替共聚物、嵌段共聚物、以及它们的混合物中的任意者均可以使用。
作为合成烃油,例如可举出FT合成油。本说明书中,“FT合成油”是指包括这些的合成油:对以氢和一氧化碳作为主成分的混合气(有时也称为合成气)应用费托(FT)反应而得到的相当于石脑油、煤油、轻油的液体馏分;及通过将它们进行加氢纯化、加氢分解而得到的烃混合物;以及通过FT反应而生成液体馏分和FT蜡,将其进行加氢纯化、加氢分解,由此得到的烃混合物。需要说明的是,FT合成油在许多情况下使用相应于原料的称呼,例如,以天然气作为原料的称为GTL,以煤作为原料的称为CTL,以生物质作为原料的称为BTL。
上述的具有生物降解性的基础油可以从上述例示的例子中单独使用任1种,也可以并用2种以上。优选地,可举出1种以上的合成酯油、或者将其与1种以上的植物油混合而得到的基础油。通过并用2种以上的具有生物降解性的基础油,能够期待润滑性的提高。
具有生物降解性的基础油的含量在润滑脂组合物中优选为60质量%以上,更优选为65质量%以上,更优选为70质量%以上,进一步优选为75质量%以上,特别优选为80质量%以上。
另外,作为基础油,为了润滑性的提高等,可以并用润滑脂组合物中使用的常见的基础油中依据OECD试验准则301系列判定为不具有规定的生物降解性的基础油。但是,在润滑脂组合物中,需要使这样的基础油少于依据OECD试验准则301系列具有规定的生物降解性的全部有机物质的25质量%。
基础油的闪点优选为230℃以上,更优选为260℃以上。通过基础油的闪点为230℃以上,不易发生对润滑脂组合物的引燃。需要说明的是,本实施方式中,基础油的闪点可通过JIS K 2265 4的克利夫兰开放式(COC)算出。
基础油的动力粘度(40℃)优选为70mm2/s以上,更优选为90mm2/s以上。另外,基础油的动力粘度(40℃)优选为1000mm2/s以下,更优选为600mm2/s以下。通过基础油的动力粘度为上述范围内,从而容易将基础油的闪点维持在高温,且润滑脂组合物的流动性(泵送性)好。需要说明的是,本实施方式中,基础油的动力粘度可通过JIS K 2283算出。
(防锈剂)
作为本实施方式的防锈剂,优选使用磺酸钙复合物和脱水山梨糖醇脂肪酸酯。通过并用磺酸钙复合物和脱水山梨糖醇脂肪酸酯,可得到协同的防锈效果。
磺酸钙复合物是将磺酸钙与选自(i)碳酸钙、(ii)二山嵛酸钙、二硬脂酸钙、二羟基硬脂酸钙等高级脂肪酸钙盐、(iii)醋酸钙等低级脂肪酸钙盐、(iv)硼酸钙等中的钙盐(钙皂)组合而得到的物质。其中,优选以磺酸钙和碳酸钙为必要成分,并在其中配合了选自二山嵛酸钙、二硬脂酸钙、二羟基硬脂酸钙、硼酸钙和醋酸钙中的至少2种而得到的物质。作为磺酸钙复合物的具体例,例如可举出以出光兴产(株)制的Daphne Multilex WR、FuchsJapan(株)制的RENOLIT CXI 1、(株)Nippeco制的Calforex EP等商品名市售的磺酸钙复合物。
另外,就磺酸钙而言,从增稠效果的观点出发,优选碱值为50mgKOH/g以上且500mgKOH/g以下,更优选碱值为300mgKOH/g以上且500mgKOH/g以下。具体而言,特别优选二烷基苯磺酸钙盐。
作为脱水山梨糖醇脂肪酸酯,例如可举出脱水山梨糖醇单油酸酯、脱水山梨糖醇三油酸酯、脱水山梨糖醇单月桂酸酯、脱水山梨糖醇三硬脂酸酯、脱水山梨糖醇单硬脂酸酯、脱水山梨糖醇单棕榈酸酯、聚氧乙烯脱水山梨糖醇单月桂酸酯、聚氧乙烯脱水山梨糖醇单油酸酯、聚氧乙烯脱水山梨糖醇单硬脂酸酯等。作为脱水山梨糖醇脂肪酸酯,例如可以使用由花王(株)以Emasol的商品名市售的脱水山梨糖醇脂肪酸酯等。需要说明的是,脱水山梨糖醇脂肪酸酯是依据OECD试验准则301系列具有生物降解性的有机物质。特别是,脱水山梨糖醇单油酸酯是规则“FDA21CFR178.3570”所规定的物质,因此只要遵守所定的规定值,则对人体的安全性高。脱水山梨糖醇脂肪酸酯优选皂化值为145~160,羟值为193~210。当皂化值和羟值脱离193~210的范围时,作为食品用成分,变得难以确保安全性。需要说明的是,脱水山梨糖醇脂肪酸酯是依据OECD试验准则301系列具有生物降解性的有机物质。特别是,脱水山梨糖醇单油酸酯是规则“FDA21CFR178.3570”所规定的物质,因此只要遵守所定的规定值,则对人体的安全性高。脱水山梨糖醇脂肪酸酯优选皂化值为145~160,羟值为193~210。当皂化值和羟值脱离193~210的范围时,作为食品用成分,变得难以确保安全性。
磺酸钙复合物相对于脱水山梨糖醇脂肪酸酯的含量(磺酸钙复合物的含量/脱水山梨糖醇脂肪酸酯的含量)优选为0.5~5.0的范围,更优选为0.7~3.0的范围,进一步优选为1.0~2.0的范围。小于0.5或大于5.0的情况下,有防锈性的协同效果变弱的倾向。
防锈剂可以适当包含除了上述的磺酸钙复合物和脱水山梨糖醇脂肪酸酯以外的其它防锈剂。作为其它防锈剂,例如为磺酸盐、羧酸、羧酸盐、酯系防锈剂、胺系防锈剂等。其它防锈剂可以从上述例示的例子中单独使用任1种,也可以并用2种以上。
磺酸盐为磺酸碱金属盐、磺酸碱土金属盐等磺酸金属盐,磺酸胺盐等。磺酸盐可通过使碱金属、碱土金属或胺与磺酸反应来制备。
作为构成磺酸盐的磺酸,优选石油磺酸和二壬基萘磺酸。作为构成磺酸盐的碱金属,可例示钠、钾等。作为碱土金属,可例示镁、钙、钡等。在它们中,作为金属盐,优选钠盐、钾盐、钙盐或钡盐,更优选钙盐。另外,磺酸盐为胺盐的情况下,就胺而言,可例示单胺、多胺、烷醇胺等。
在磺酸盐中,优选包含磺酸胺、磺酸钙或磺酸钡,更优选包含磺酸钙,进一步优选包含石油磺酸钙盐。需要说明的是,磺酸盐可以从上述例示的例子中单独使用任1种,也可以并用2种以上。
作为羧酸,例如可举出硬脂酸等单羧酸、烷基琥珀酸及其衍生物、烯基琥珀酸及其衍生物、环烷酸、松香酸(abietic acid)、羊毛脂脂肪酸等。作为羧酸盐,可举出上述的羧酸的金属盐(钙、钡、镁、铝、锌、铅等)。
作为酯系防锈剂,例如可举出聚氧乙烯月桂酸酯、聚氧乙烯油酸酯、聚氧乙烯硬脂酸酯、季戊四醇单油酸酯、琥珀酸半酯等羧酸部分酯等。酯系防锈剂由于具有良好的生物降解性,因此优选使用。
作为胺系防锈剂,例如可举出烷氧基苯胺等胺衍生物、二元羧酸部分酰胺等。
防锈剂的含量在润滑脂组合物中为2.5质量%以上,优选为3.0质量%以上,更优选为4.0质量%以上。防锈剂的含量小于2.5质量%的情况下,有对盐水的防锈性降低的倾向。另一方面,从减少非生物降解性的有机物质的观点出发,防锈剂的含量为30质量%以下,优选为25质量%以下,更优选为20质量%以下,进一步优选为15质量%以下。
本发明的一个实施方式的润滑脂组合物含有具有生物降解性的基础油、增稠剂、以及包含磺酸钙复合物和脱水山梨糖醇脂肪酸酯的防锈剂。设为这样的配合的润滑脂组合物具有良好的操作性和储藏稳定性,优选用于钢缆等的维护用。
(增稠剂)
作为本实施方式的增稠剂,从没有大的缺点且性能平衡(例如耐水性、剪切稳定性等)良好的观点出发,优选使用锂皂。作为锂皂,例如可举出由碳数10~28的脂肪酸和碳数10~28的羟基酸合成的锂皂。
作为碳数10~28的脂肪酸,可例示月桂酸、棕榈酸、硬脂酸、亚油酸、花生酸、肉豆蔻酸、十五烷酸、十七烷酸、油酸、花生四烯酸、山嵛酸等,从稠度收率(润滑脂变硬的程度)良好的观点出发,优选硬脂酸。作为碳数10~28的羟基酸,可例示12-羟基硬脂酸、12-羟基月桂酸、16-羟基棕榈酸等,从容易获取、廉价的方面出发,优选12-羟基硬脂酸。
作为锂皂,更具体而言,例如可例示月桂酸锂、硬脂酸锂、12-羟基硬脂酸锂、和它们的混合物等。锂皂可以单独使用上述中的任1种,也可以并用2种以上。
作为锂皂以外的其它增稠剂,例如可举出脲系化合物,锂复合皂、钙皂、钠皂、铝皂等金属皂,对苯二酸酰胺钠、氟、有机化膨润土、硅胶等,优选脲系化合物和锂复合皂。更优选包含锂皂的增稠剂,更优选仅由锂皂构成的增稠剂。
锂复合皂没有特别限定。举例来说,就锂复合皂而言,可举出以锂作为金属源、通过具有至少1个羟基的碳数12~24的脂肪族单羧酸、碳数2~12的脂肪族二羧酸和氢氧化锂的反应而形成的物质,优选通过12-羟基硬脂酸和壬二酸的混合物与氢氧化锂的反应而形成的物质。
脲系化合物没有特别限定。举例来说,脲系化合物为下述通式(I)所示的双脲化合物。式中,R2表示碳数6~15的芳香族系烃基,R1和R3表示碳数6~18的芳香族烃基,环己基、碳数7~12的烷基环己基或碳数8~22的烷基。
[化学式1]
上述双脲化合物可以通过利用公知的方法使胺与二异氰酸酯化合物反应来得到。作为胺,例如可举出碳数6~18的芳香族胺、环己胺、碳数7~12的烷基环己胺、碳数8~22的烷基胺、以及它们的混合物等。作为二异氰酸酯化合物,例如可举出4,4′-二苯基甲烷二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯等。其中,从获取性优异的方面出发,优选4,4′-二苯基甲烷二异氰酸酯、2,6-甲苯二异氰酸酯,另外,从耐热性优异的方面出发,优选4,4′-二苯基甲烷二异氰酸酯。
增稠剂的含量没有特别限定,在润滑脂组合物中,优选为2.0质量%以上,更优选为5.0质量%以上,进一步优选为8.0质量%以上。增稠剂的含量小于2.0质量%的情况下,得到的润滑脂组合物过于软质,因此有飞散、泄漏或者引起过度的油分离的倾向。另一方面,从减少非生物降解性的有机物质的观点出发,增稠剂的含量优选为20质量%以下,更优选为18质量%以下,进一步优选为15质量%以下,特别优选为12质量%以下。
需要说明的是,使用增稠剂的方式中,优选将增粘剂(特别是聚异丁烯)的用量设为小于1.0质量%,更优选设为小于0.5质量,进一步优选设为小于0.1质量%,特别优选不使用增粘剂。增粘剂的用量为1.0质量%以上的情况下,润滑脂的粘度变高,有因拉丝等导致操作性降低的风险。
就本实施方式的润滑脂组合物的混合稠度而言,从操作性的观点出发,优选为220~340的范围,更优选为265~295(2号)的范围。需要说明的是,本实施方式中,混合稠度的值为基于JIS K 22207在25℃的环境下使安装于稠度计的圆锥向润滑脂组合物下落,将以5秒进入的深度(mm)乘以10倍的值。
本发明的另一实施方式的润滑脂组合物含有具有生物降解性的基础油、具有生物降解性的蜡、增粘剂、以及包含磺酸钙复合物和脱水山梨糖醇脂肪酸酯的防锈剂,且具有50℃~100℃的熔点。这样的润滑脂组合物特别适于钢缆的制造。当熔点小于50℃时,在高温下的使用中,有润滑脂从钢缆滴落的问题。另一方面,当熔点大于100℃时,有促进油剂的劣化的倾向,另外,有钢缆生产线中的涂布变得困难等问题。熔点优选为55℃~95℃,更优选为60℃~90℃,进一步优选为65℃~85℃。需要说明的是,对于配合了增稠剂的上述的润滑脂组合物而言,当反复进行加热熔融和冷却时,除了有润滑脂的软化、油分离等无法维持作为润滑脂的状态的情况以外,还有添加剂劣化、防锈性降低的风险,但对于配合了具有生物降解性的蜡和增粘剂的本实施方式的润滑脂组合物而言,即使在加热熔融后冷却,也能够维持润滑脂的状态和防锈性。
(蜡)
作为蜡,优选使用依据OECD试验准则301系列具有规定的生物分解度的、判定为具有生物降解性的蜡(以下,本说明书中,有时将这样的蜡简写为“具有生物降解性的蜡”)。具有生物降解性的蜡可以用作代替具有生物降解性的基础油的物质,且可以为了将润滑脂组合物的熔点调节为上述的范围而适量含有。
作为具有生物降解性的蜡,可以使用公知的植物系蜡、动物系蜡、石油系蜡等。作为植物系蜡,例如可举出米蜡、巴西棕榈蜡、小烛树蜡等。作为动物系蜡,例如可举出蜂蜡、羊毛脂、鲸蜡等。作为石油系蜡,例如可举出微晶蜡、石蜡等。另外,可以使用虽然是合成蜡但具有生物降解性的物质。
具有生物降解性的基础油和具有生物降解性的蜡的合计含量在润滑脂组合物中优选为60质量%以上,更优选为65质量%以上,更优选为70质量%以上,进一步优选为75质量%以上,特别优选为80质量%以上。
具有生物降解性的基础油和具有生物降解性的蜡的合计量中的具有生物降解性的蜡的含量优选为6.0质量%以上,更优选为6.5质量%以上,进一步优选为10质量%以上,特别优选为12质量%以上。另外,该含量优选为40质量%以下,更优选为35质量%以下,进一步优选为30质量%以下,特别优选为25质量%以下。
(增粘剂)
作为本实施方式中能够使用的增粘剂,没有特别限定,可以适当选择聚丁烯、聚异丁烯(polyisobutene)、聚异丁烯、α烯烃共聚物等在润滑脂中通常使用的增粘剂。增粘剂可以为依据OECD试验准则301系列具有规定的生物分解度的、判定为具有生物降解性的增粘剂(例如聚异丁烯等)。
增粘剂在润滑脂组合物中优选为1.0质量%以上,更优选为3.0质量%以上,进一步优选为5.0质量%以上,特别优选为7.0质量%以上。另外,增粘剂的含量优选为25质量%以下,更优选为20质量%以下,进一步优选为15质量%以下,特别优选为12质量%以下。增粘剂的含量为上述范围内的情况下,有使附着性提高而不对泵送性产生影响的优点。
需要说明的是,使用具有生物降解性的蜡和增粘剂的方式中,优选将增稠剂(特别是铝复合皂)的使用量设为小于1.0质量%,更优选设为小于0.5质量%,进一步优选设为小于0.1质量%,特别优选不使用增稠剂。增稠剂的用量为1.0质量%以上的情况下,当反复进行加热熔融和冷却时,除了有润滑脂的软化、油分离等无法维持作为润滑脂的状态的情况以外,还有添加剂劣化、防锈性降低的风险。
(任意成分)
本实施方式的润滑脂组合物在不损害本实施方式的效果的范围内,可进一步含有任意成分。作为任意成分,可举出耐磨耗剂、抗氧化剂、极压添加剂、染料、色相稳定剂、结构稳定剂、金属减活剂、抗氧化剂、粘度指数提高剂等。
含有耐磨耗剂的情况下,作为耐磨耗剂,可例示亚甲基二硫代氨基甲酸酯、硫系耐磨耗剂、磷系耐磨耗剂等。耐磨耗剂可以从上述例示的例子中单独使用任1种,也可以并用2种以上。需要说明的是,本实施方式的润滑脂组合物即使在不配合耐磨耗剂的情况下,也可发挥优异的耐磨耗性。
就磷系耐磨耗剂而言,可例示以亚磷酸三丁酯和亚磷酸三油基酯等作为代表的亚磷酸酯类;以磷酸三甲苯酯和磷酸氢二月桂酯等作为代表的磷酸酯类;以磷酸二丁酯辛胺盐和磷酸二月桂酯辛胺盐等作为代表的磷酸胺类;以硫代磷酸三苯酯和烷基化硫代磷酸酯等作为代表的硫代磷酸酯类;以磷酸钙作为代表的固体润滑剂;以及亚磷酸氢二苯酯等。
含有耐磨耗剂的情况下,耐磨耗剂的含量没有特别限定。举例来说,耐磨耗剂在润滑脂组合物中优选为0.1质量%以上,更优选为0.5质量%以上。另外,耐磨耗剂优选为5质量%以下,更优选为3质量%以下。通过耐磨耗剂的含量为上述范围内,可对得到的润滑脂组合物赋予优异的耐磨耗性。
含有抗氧化剂的情况下,作为抗氧化剂,可举出胺系抗氧化剂等。胺系抗氧化剂优选为芳香族胺化合物。就芳香族胺化合物而言,可例示二苯胺、烷基化二苯胺、吩噻嗪、N-苯基-α-萘胺、p,p′-二氨基二苯基甲烷、2-羟基丁醛-α-萘胺、对十二烷基苯基-1-萘胺等。
含有抗氧化剂的情况下,抗氧化剂的含量没有特别限定。举例来说,抗氧化剂在润滑脂组合物中优选为0.1质量%以上,更优选为0.5质量%以上。另外,抗氧化剂优选为5质量%以下,更优选为3质量%以下。通过抗氧化剂的含量为上述范围内,可对得到的润滑脂组合物赋予优异的抗氧化性。
含有极压添加剂的情况下,作为极压添加剂,可例示二硫代氨基甲酸钼、二硫代磷酸钼、硫代磷酸酯、硫化油脂、二苄基硫、二丁二硫等。其中,优选硫化油脂。极压添加剂可以从上述例示的例子中单独使用任1种,也可以并用2种以上。
含有极压添加剂的情况下,极压添加剂的含量没有特别限定。举例来说,极压添加剂在润滑脂组合物中优选为0.1质量%以上,更优选为0.5质量%以上。另外,极压添加剂优选为5质量%以下,更优选为3质量%以下。通过极压添加剂的含量为上述范围内,可对得到的润滑脂组合物赋予优异的耐负荷性。
本实施方式的润滑脂组合物即使在偶然漏出到海洋、河流中的情况下生物富集性也低,对人体是安全的。另外,具有与工业用润滑剂同程度或其以上的防锈性、耐水性、疏水性、附着性,在室外等也可以使用。特别是由于具有对海水等盐水的优异的防锈性和耐水性,因此优选用于水闸的闸门的升降时使用的钢缆、船舶用钢缆等与水接触的钢缆。需要说明的是,配合了增稠剂的润滑脂组合物特别优选用于维护用,配合了具有生物降解性的蜡和增粘剂的润滑脂组合物特别优选用于钢缆生产线的初始填充用。
实施例
以下,通过实施例更具体地说明本发明。本发明不受这些实施例的任何限定。
以下,汇总示出实施例和比较例中使用的各种材料。
合成酯油:BASF Japan(株)制的Synative ES TMP 05/320(三羟甲基丙烷复合酯,动力粘度(40℃):326mm2/s)
植物油:丰国制油(株)制的工业用一号蓖麻油(动力粘度40℃):240mm2/s)
蜡:日本精蜡(株)制的Paraffin Wax 155F
锂皂:通过羟基硬脂酸和12-羟基硬脂酸与氢氧化锂的反应而形成的锂皂
锂复合皂:通过12-羟基硬脂酸和壬二酸的混合物与氢氧化锂的反应而形成的锂复合皂
双脲化合物:通过环己胺和硬脂胺的混合物与4,4’-二苯基甲烷二异氰酸酯的反应而形成的双脲化合物
增粘剂:出光兴产(株)制的出光聚丁烯2000H
磺酸钙复合物:出光兴产(株)制的Daphne Multilex WR
脱水山梨糖醇脂肪酸酯1:花王(株)制的Emasol O-10V(脱水山梨糖醇单油酸酯)
脱水山梨糖醇脂肪酸酯2:花王(株)制的Emasol O-30V(脱水山梨糖醇三油酸酯)
(实施例1~10和比较例1~5)
按照表1记载的处方,制备润滑脂组合物。对于得到的润滑脂组合物,进行以下的评价。将评价结果示于表1。
<混合稠度的测定>
依据JIS K 2220 7,在25℃的环境下使安装于稠度计的圆锥向试验用润滑脂组合物下落,测定以5秒进入的深度(mm),将测定的值乘以10倍的结果作为混合稠度。
<中性盐水喷雾试验>
依据JIS K 2246 6.35,考察将以试验用润滑脂组合物覆盖的试验片(覆膜制作方法依据JIS K 2220 21)在35℃的环境下在喷雾有中性盐水的装置内保持规定时间后的锈蚀发生度。将锈蚀发生度仍为0%的盐水的喷雾时间示于表1。将120小时以上作为性能目标值。
<水系耐水度试验>
依据JIS K 2220 16,在38℃和79℃的环境下测定相对于试验前的润滑脂的量100质量%的、经水冲洗后的润滑脂的质量。该质量越小,则耐水性越优异。
<离油度>
依据JIS K 2220 11,测定在100℃静置24小时后的离油度。该质量越小,则储存稳定性越优异。
[表1]
根据表1的结果可知,本发明的润滑脂组合物具有对盐水的优异的防锈性、耐水性和储藏稳定性。
(实施例11~17和比较例6~10)
按照表2记载的处方,制备润滑脂组合物。对于得到的润滑脂组合物,进行以下的评价。将评价结果示于表2。
<熔点的测定>
依据JIS K 2235,测定润滑脂组合物的熔点。
<中性盐水喷雾试验>
依据JIS K 2246 6.35,考察将以试验用润滑脂组合物覆盖的试验片(覆膜制作方法依据JIS K 2220 21)在35℃的环境下在喷雾有中性盐水的装置内保持规定时间后的锈蚀发生度。将锈蚀发生度为0%的盐水的喷雾时间示于表2。将240小时以上作为性能目标值。
[表2]
根据表2的结果可知,本发明的润滑脂组合物具有对盐水的优异的防锈性。
产业上的可利用性
本发明的润滑脂组合物对环境的影响少,且具有对海水等盐水的优异的防锈性和耐水性,因此特别是作为与水接触的钢缆用的润滑剂是有用的。
Claims (9)
1.一种润滑脂组合物,其是含有具有生物降解性的基础油、以及包含磺酸钙复合物和脱水山梨糖醇脂肪酸酯的防锈剂的润滑脂组合物,
组合物中的具有生物降解性的有机物质的合计含量为75质量%以上,
防锈剂的含量为2.5质量%~30质量%。
2.根据权利要求1所述的润滑脂组合物,其中,磺酸钙复合物相对于脱水山梨糖醇脂肪酸酯的含量,即磺酸钙复合物的含量/脱水山梨糖醇脂肪酸酯的含量为0.5~5.0。
3.根据权利要求1或2所述的润滑脂组合物,其是含有具有生物降解性的基础油、增稠剂、以及包含磺酸钙复合物和脱水山梨糖醇脂肪酸酯的防锈剂的润滑脂组合物,其中,
组合物中的具有生物降解性的有机物质的合计含量为75质量%以上,
防锈剂的含量为2.5质量%~30质量%。
4.根据权利要求3所述的润滑脂组合物,其中,增稠剂的含量为2.0质量%~20质量%。
5.根据权利要求3或4所述的润滑脂组合物,其中,增稠剂为选自锂皂、锂复合皂和脲系化合物中的1种或2种以上的增稠剂。
6.根据权利要求3~5中任一项所述的润滑脂组合物,其中,混合稠度为265~295。
7.根据权利要求1或2所述的润滑脂组合物,其是含有具有生物降解性的基础油、具有生物降解性的蜡、增粘剂、以及包含磺酸钙复合物和脱水山梨糖醇脂肪酸酯的防锈剂的润滑脂组合物,其中,
组合物中的具有生物降解性的有机物质的合计含量为75质量%以上,
防锈剂的含量为2.5质量%~30质量%,
熔点为50℃~100℃。
8.根据权利要求7所述的润滑脂组合物,其中,增粘剂的含量为1.0质量%~25质量%。
9.根据权利要求7或8所述的润滑脂组合物,其中,具有生物降解性的基础油和具有生物降解性的蜡的合计量中的具有生物降解性的蜡的含量为6.0质量%~40质量%。
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CN115652309A (zh) * | 2022-11-04 | 2023-01-31 | 北美防锈技术(上海)有限公司 | 一种采用生物基原料制备的可生物降解金属防锈脂 |
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