CN104685045B - 发动机清洗用组合物 - Google Patents

发动机清洗用组合物 Download PDF

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Publication number
CN104685045B
CN104685045B CN201380050775.3A CN201380050775A CN104685045B CN 104685045 B CN104685045 B CN 104685045B CN 201380050775 A CN201380050775 A CN 201380050775A CN 104685045 B CN104685045 B CN 104685045B
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amine
engine
washing compositions
engine washing
dispersant
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CN104685045A (zh
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河合秀敏
畑善晴
樱井武雄
西浦博之
柳昌幸
一柳昌幸
小川玲花
佐藤繁彦
松永真明
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Toyota Motor Corp
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Toyota Motor Corp
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Abstract

本发明的课题是提供用于除去在发动机内部形成的堆积物的发动机清洗用组合物。利用含有含羧酸和胺的分散剂、螯合剂、二元醇系溶剂、以及环烷油的发动机清洗用组合物能够解决上述课题。

Description

发动机清洗用组合物
技术领域
本发明涉及用于除去在发动机内部形成的堆积物的发动机清洗用组合物。
背景技术
已知如果在发动机内部形成淤泥等堆积物，则发动机功能降低。因此，采取了通过在燃料、润滑油中添加各种添加剂来抑制堆积物的形成。
例如，专利文献1公开了具有使含水硫酸钙分散在油中的功能的由羟基羧酸类构成的柴油发动机用润滑油添加剂。上述添加剂具有使淤泥的成分即硫酸钙分散在润滑油中的功能，能够减少淤泥的堆积。另外，还已知有用于清扫发动机的燃烧室的装置、组合物(例如，专利文献2和3)。
现有技术文献
专利文献
专利文献1：日本特开平9-13065号公报
专利文献2：日本特开平1-301923号公报
专利文献3：日本特开2003-214268号公报
发明内容
专利文献1中记载的添加剂是通过使堆积物的成分即硫酸钙分散在润滑油中来抑制堆积物的形成的，并不具有将已形成的堆积物除去的功能。特别是在所形成的堆积物为固体形状的情况下，难以除去该堆积物。
因此，本发明的目的是提供用于除去在发动机内部形成的堆积物的发动机清洗用组合物。
本发明人等经过深入研究，结果发现通过将含羧酸和胺的分散剂与螯合剂、二元醇系溶剂以及环烷油并用，能够有效率地除去堆积物。
即，本发明包含以下发明。
[1]一种发动机清洗用组合物，含有：含羧酸和胺的分散剂、螯合剂、二元醇系溶剂、以及环烷油。
[2]如[1]所述的发动机清洗用组合物，其中，胺是由通式：NR1R2R3[式中，R1为C8～C18烷基，R2和R3各自独立地为氢或C1～C3烷基]表示的脂肪族胺。
[3]如[2]所述的发动机清洗用组合物，其中，R2和R3为氢。
[4]如[1]～[3]中任一项所述的发动机清洗用组合物，其中，羧酸是碳原子数18～36的脂肪族多元羧酸。
[5]如[1]～[4]中任一项所述的发动机清洗用组合物，其中，分散剂所含的羧酸与胺的混合物的胺值为40～260mgKOH/g，酸值为10～160mgKOH/g。
[6]如[1]～[5]中任一项所述的发动机清洗用组合物，其中，螯合剂进一步包含胺。
本说明书包含本申请的优先权基础即日本国专利申请2012-214130号的说明书和/或附图中记载的内容。
根据本发明，能够有效地除去在发动机内部形成的堆积物。
具体实施方式
＜分散剂＞
本发明中使用的分散剂含有羧酸和胺。
在本说明书中，“清洗”是指将已形成的堆积物除去。此外，专利文献1中，作为抑制堆积物形成的效果(即，预防效果)，使用“清洁”的用语，但在本说明书中明确区分“清洗”与“清洁”。清洗剂和清洁剂由于使用的情况、目的、效果等不同，所以在用途上能够明确区分。
通过使用含有上述分散剂的本发明的发动机清洗用组合物，能够除去发动机内部的堆积物。除去的堆积物的种类没有特别限定，可除去半固体形状(粘性形状)、固体形状等的堆积物。特别是因热而固化成的有机性污垢即固体形状的堆积物难以采用现有方法除去，因此上述分散剂适用于除去这种固体形状的堆积物的用途。
对于堆积物的成分，也不限定于含有硫酸钙，只要是在发动机内部形成的堆积物就能够广泛地应用本发明。
在本说明书中，羧酸是指1分子中具有1个以上羧基的化合物。没有特别限定，但优选为脂肪族羧酸，特别优选为碳原子数18～36的脂肪族羧酸。另外，优选为1分子中具有2个以上(例如2～6个)羧基的多元羧酸，特别优选为1分子中具有2个羧基的二羧酸。这些羧酸可以是饱和羧酸也可以是不饱和羧酸。应予说明，也可以使用分子中不具有羟基的羧酸。
作为具体的羧酸，可举出二聚酸、蓖麻油酸、枸橼酸、苯六甲酸、葡萄糖酸、己二酸、1,8-辛烷二羧酸、1,10-癸烷二羧酸、二十烷二酸、酒石酸、苹果酸、邻苯二甲酸、马来酸、对苯二甲酸、硬脂酸、月桂酸、肉豆蔻酸、山萮酸、水杨酸等。羧酸可以单独使用1种也可以组合2种以上使用。
在本发明中，胺优选为脂肪族胺。特别优选使用由通式：NR1R2R3[式中，R1为C8～C18烷基，R2和R3各自独立地为氢或C1～C3烷基]表示的脂肪族胺。R1为C8～C18烷基、R2和R3均为氢的脂肪族胺在清洗性能方面特别优异。
作为具体的胺，可举出辛胺、壬胺、癸胺、十一胺、十二胺(月桂胺)、十三胺、十四胺、十五胺、十六胺、十七胺和十八胺(硬脂胺)以及这些化合物中与氮原子键合的氢中的1个或2个被甲基取代而成的胺等。胺可以单独使用1种也可以组合2种以上使用。
上述分散剂可以进一步包含溶剂。溶剂的种类没有特别限定，可使用通常使用的溶剂。特别优选使用有机溶剂，例如可举出芳香油、二甲苯、矿物油精、异链烷烃、己烷、丁基溶纤剂等。溶剂可以单独使用1种也可以组合2种以上使用。
在上述分散剂中，通过将胺值和酸值调节在一定范围内，能够进一步提高清洗性能。
具体而言，分散剂的胺值优选为20～130mgKOH/g，更优选为50～120mgKOH/g，特别优选为80～110mgKOH/g。另外，酸值优选为5～80mgKOH/g，更优选为10～60mgKOH/g，特别优选为15～40mgKOH/g。分散剂的胺值和酸值可根据除羧酸和胺以外的任意成分的存在而改变。
另一方面，分散剂所含的羧酸与胺的混合物的胺值优选为40～260mgKOH/g，更优选为100～240mgKOH/g，特别优选为160～220mgKOH/g。另外，酸值优选为10～160mgKOH/g，更优选为20～120mgKOH/g，特别优选为30～80mgKOH/g。
胺值可根据JIS K7237中规定的方法测定。酸值可根据JIS K0070中规定的方法测定。
羧酸与胺的重量比优选为1：0.5～1：4，特别优选为1：1～1：3。
分散剂中优选含有合计为20～80重量％的羧酸和胺，更优选含有30～70重量％，特别优选含有40～60重量％。
＜发动机清洗用组合物＞
本发明涉及含有上述分散剂的发动机清洗用组合物。本发明的发动机清洗用组合物除分散剂外还含有螯合剂、二元醇系溶剂和环烷油。通过并用这些成分，能够发挥清洗性能。应予说明，在不对本发明的效果产生不良影响的限度内，也可以含有其他成分。
螯合剂的种类没有特别限定，可使用通常使用的螯合剂。例如可使用氨基羧酸盐作为螯合剂。作为氨基羧酸盐，例如可举出乙二胺四乙酸盐、次氮基三乙酸盐、二亚乙基三胺五乙酸盐、羟基乙基乙二胺三乙酸盐等。螯合剂可以单独使用1种也可以组合2种以上使用。
发动机清洗用组合物中优选含有3～30重量％的螯合剂，更优选含有4～20重量％，特别优选含有5～10重量％。
二元醇系溶剂的种类没有特别限定，可使用通常使用的二元醇系溶剂。例如，作为二元醇系溶剂，可举出环氧乙烷(E.O.)系二元醇醚、环氧丙烷(P.O.)系二元醇醚、二烷基二元醇醚等。
作为E.O.系二元醇醚，可举出甲基乙二醇(MG)、甲基二乙二醇(MDG)、甲基三乙二醇(MTG)、甲基聚乙二醇(MPG)、异丙基乙二醇(iPG)、异丙基二乙二醇(iPDG)、丁基乙二醇(BG)、丁基二乙二醇(BDG)、丁基三乙二醇(BTG)、异丁基乙二醇(iBG)、异丁基二乙二醇(iBDG)、己基乙二醇(HeG)、己基二乙二醇(HeDG)、2-乙基己基乙二醇(EHG)、2-乙基己基二乙二醇(EHDG)、烯丙基乙二醇(AG)、烯丙基乙二醇-H(AG-H)、苯基乙二醇(PhG)、苯基二乙二醇(PhDG)、苯基乙二醇-H(PhG-H)、苄基乙二醇(BzG)、苄基二乙二醇(BzDG)等。
作为P.O.系二元醇醚，可举出甲基丙二醇(MFG)、甲基亚丙基二乙二醇(MFDG)、甲基亚丙基三乙二醇(MFTG)、丙基丙二醇(PFG)、丙基亚丙基二乙二醇(PFDG)、丁基丙二醇(BFG)、丁基亚丙基二乙二醇(BFDG)、丁基亚丙基三乙二醇(BFTG)、苯基丙二醇(PhFG)、甲基丙二醇乙酸酯(MFG-AC)等。
作为二烷基二元醇醚，可举出二甲基乙二醇(DMG)、二甲基二乙二醇(DMDG)、二甲基三乙二醇(DMTG)、甲基乙基二乙二醇(MEDG)、二乙基二乙二醇(DEDG)、二丁基二乙二醇(DBDG)、二甲基亚丙基二乙二醇(DMFDG)等。
另外，可举出乙二醇(EG)、丙二醇(PG)等。
特别是在配合于发动机清洗用组合物时，优选使用相溶的二元醇系溶剂。通过使用这样的二元醇系溶剂，能够充分发挥发动机清洗用组合物的清洗效果。
另外，优选使用沸点为220℃以上、优选250℃以上、特别优选270℃以上的二元醇系溶剂。作为沸点的上限，例如可举出400℃、370℃、340℃等。这样的二元醇系溶剂即使在高温条件下也不蒸发，因此能够防止分散剂和螯合剂的凝胶化。由此，能够维持发动机清洗用组合物的清洗效果。
二元醇系溶剂可以单独使用1种也可以组合2种以上使用。
发动机清洗用组合物中优选含有30～80重量％的二元醇系溶剂，更优选含有35～70重量％，特别优选含有40～60重量％。
环烷油的种类没有特别限定，可使用通常使用的环烷油。例如可使用40℃时的运动粘度为5～50mm2/s、优选为5～30mm2/s、特别优选为5～15mm2/s的环烷油。环烷油可以单独使用1种也可以组合2种以上使用。
发动机清洗用组合物中优选含有10～50重量％的环烷油，更优选含有15～40重量％，特别优选含有20～30重量％。
发动机清洗用组合物中优选含有合计为3～30重量％的分散剂所含的羧酸和胺，更优选含有4～20重量％，特别优选含有5～10重量％。
本发明的发动机清洗用组合物在不损害本发明的效果的范围内可以含有进一步的成分。
＜冲洗油＞
本发明的发动机清洗用组合物可以和与该组合物为相溶性的冲洗油混合使用。使用发动机清洗用组合物清洗发动机时，需要在分解发动机后进行清洗。但是，将发动机清洗用组合物与冲洗油混合使用时，通过向发动机内部注入混合物来代替发动机油并运转一定时间，能够除去在发动机内部形成的堆积物。采用该方法不需要分解发动机，因此能够简便地除去堆积物。
冲洗油含有无灰分散剂、金属清洁剂、二烷基二硫代磷酸锌、消泡剂和基础油。应予说明，在对本发明的发动机清洗用组合物的效果不产生不良影响的限度内，也可以含有其他成分。
无灰分散剂的种类没有特别限定，可使用通常使用的无灰分散剂。例如，作为无灰分散剂，可举出琥珀酰亚胺、琥珀酸酯、苄胺、琥珀酰胺、共聚系聚合物等。无灰分散剂可以单独使用1种也可以组合2种以上使用。
金属清洁剂的种类没有特别限定，可使用通常使用的金属清洁剂。例如，作为金属清洁剂，可举出有机酸的碱土金属盐等，更具体而言，可举出中性或过碱性金属(Ba、Ca、Mg)磺酸盐、过碱性金属(Ba、Ca、Mg)酚盐、过碱性金属(Ca、Mg)水杨酸盐、膦酸盐等。金属清洁剂可以单独使用1种也可以组合2种以上使用。
二烷基二硫代磷酸锌可以单独使用1种也可以组合2种以上使用。
消泡剂的种类没有特别限定，可使用通常使用的消泡剂。例如，作为消泡剂，可举出硅油、油醇、鲸蜡醇、磷酸三丁酯、高级醇、烷基酯、聚甲基丙烯酸酯等。消泡剂可以单独使用1种也可以组合2种以上使用。
基础油的种类只要与本发明的发动机清洗用组合物为相溶性就没有特别限定。例如，作为基础油，可举出天然矿物油、合成油等，更具体而言，可举出石蜡系烃、芳香族烃、环烷系烃、烯烃低聚物、聚丁烯、烷基苯、环烷烃类、二酯、多元醇酯、磷酸酯、聚乙二醇、苯醚、聚硅氧烷、硅酸酯、卤化碳等。基础油可以单独使用1种也可以组合2种以上使用。
上述冲洗油的粘度指数优选为150以下。更具体而言，可举出0～150、30～140、60～130、90～120等。粘度指数可根据JIS K2283中规定的方法测定。通过使用具有上述粘度指数的冲洗油，能够进一步提高与发动机清洗用组合物的相溶性。
上述冲洗油的磷含量优选为0.09重量％以上。更具体而言，可举出0.09～1重量％、0.1～0.5重量％、0.11～0.2重量％等。通过增加磷含量，能够防止发动机的磨损。
本发明的发动机清洗用组合物可与上述冲洗油组合使用。发动机清洗用组合物和冲洗油可以以处于各自被混合的状态的发动机清洗用配合剂的形式提供。为配合剂时，发动机清洗用组合物与冲洗油的体积比例如优选为5：1～1：1，特别优选为4：1～2：1。发动机清洗用配合剂中的磷含量例如优选为0.025重量％以上，更具体而言，优选为0.025～0.3重量％、0.03～0.1重量％等。
另外，发动机清洗用组合物和冲洗油也可以以处于各自分离的状态的发动机清洗用试剂盒的形式提供。消费者可以在使用之前将试剂盒中具备的发动机清洗用组合物与冲洗油适当混合而使用。为试剂盒时，优选以通过混合发动机清洗用组合物和冲洗油而得到的发动机清洗用配合剂中的磷含量例如为0.025重量％以上，更具体而言为0.025～0.3重量％、0.03～0.1重量％等的方式，具备发动机清洗用组合物和冲洗油。
＜发动机的清洗方法＞
通过使用本发明的发动机清洗用组合物，能够除去发动机内部的堆积物。另外，堆积物并不局限于半固体形状的堆积物，也可以是难以除去的固体形状的堆积物。
发动机的清洗可通过将发动机清洗用组合物用于分解取出的发动机而进行。清洗的方法没有特别限定，以发动机与发动机清洗用组合物接触的方式进行即可。例如可通过将发动机浸渍于装有发动机清洗用组合物的容器来进行清洗。另外，通过在高温条件下清洗，能够提高清洗效率。例如优选在50～200℃、70～150℃、90～120℃进行清洗。
混合发动机清洗用组合物和冲洗油而成的发动机清洗用配合剂可以代替发动机油直接注入到发动机内部。而且，通过运转一定时间，能够除去在发动机内部形成的堆积物。在该实施方式中，无需将发动机分解、取出，因此能够使清洗操作明显简单化。另外，由于不需要发动机的分解，所以还能够防止发动机的损伤。此外，由于清洗操作简便，所以不必依赖具有专门技能的人员，一般消费者就能够独自实施。
清洗所需的运转发动机的时间根据堆积物的状态和量而不同，例如可以设为1～10小时、1.5～7小时、2～4小时。
另外，也可通过对燃烧室直接喷洒发动机清洗用组合物而除去在燃烧室内形成的堆积物。通过将对燃烧室喷洒发动机清洗用组合物和向发动机注入发动机清洗用配合剂这两种方式组合，能够同时除去曲轴箱和燃烧室的堆积物。
实施例
以下，使用实施例和比较例更详细地说明本发明，但本发明的技术范围并不限定于此。
＜分散剂的制备＞
(1)将月桂胺(20重量份)、二聚酸(29重量份)和芳香油(51重量份)在60℃搅拌3小时进行混合。所得分散剂(o)的胺值为56mgKOH/g，酸值为59mgKOH/g。
(2)与上述同样地制备分散剂(p)～(x)。各分散剂的组成、胺值和酸值如表1所示。应予说明，分散剂(n)为共荣社化学株式会社制的FLORENE G-600。另外，二聚酸为共轭亚油酸的二聚体。
[表1]
＜清洗试验1＞
按表2所示的比例将上述制备的各分散剂与环烷油、二元醇系溶剂(HeG)和螯合剂混合，制备清洗用组合物。应予说明，螯合剂(b)为Chubuchelest株式会社制的MZ-2，溶剂的含量为35重量％。
[表2]
分散剂 12wt％
环烷油 24wt％
HeG 48wt％
螯合剂(b) 16wt％
将附着有堆积物的汽油发动机的活塞的油环浸渍于清洗用组合物中，在100℃放置。测定堆积物被完全除去所需的时间。将结果作为清洗性能示于表1。
另外，采用上述方法研究分散剂的效果。如表3所示，如果不使用分散剂(n)，则即使经过11小时以上，油环的堆积物仍未被除去。应予说明，螯合剂(a)为Chubuchelest株式会社制的MZ-8，溶剂的含量为50重量％。
[表3]
分散剂(n) 环烷油 HeDG 螯合剂(a) 清洗性能
实施例 12wt％ 20wt％ 48wt％ 20wt％ 9h
比较例 - 20wt％ 48wt％ 32wt％ ×(＞11h)
<清洗试验2>
将附着有堆积物的汽油发动机的活塞的油环浸渍于清洗用组合物中，在100℃放置1～9小时。通过目视观察堆积物的除去。将结果示于表4和5(◎：100％除去；○：除去50％以上；△：除去低于50％；×：完全无法除去)。应予说明，螯合剂(c)为乙二胺四乙酸、二丁胺与溶剂(乙二醇)的混合物，溶剂的含量为59重量％。
并用了分散剂与螯合剂的实施例1～8在9小时以内就可见堆积物的除去功能。另一方面，未并用分散剂与螯合剂的比较例1～2即使经过9小时，堆积物仍未被除去。
[表4]
[表5]
比较例1 比较例2
环烷油 20 20
HeDG 48 48
分散剂(n) - 32
螯合剂(a) 32 -
合计(wt％) 100 100
试验时间 9h 9h
除去结果 × ×
将本说明书中引用的全部出版物、专利和专利申请直接作为参考引入本说明书中。

Claims (4)

1.一种发动机清洗用组合物，含有：
含羧酸和胺的分散剂；
选自氨基羧酸盐的螯合剂；
二元醇系溶剂；以及
环烷油；
所述羧酸是碳原子数18～36的脂肪族多元羧酸，
胺是由通式：NR1R2R3表示的脂肪族胺，
式中，
R1为C8～C18烷基，
R2和R3各自独立地为氢或C1～C3烷基。
2.根据权利要求1所述的发动机清洗用组合物，其中，R2和R3为氢。
3.根据权利要求1或2所述的发动机清洗用组合物，其中，分散剂所含的羧酸与胺的混合物的胺值为40～260mgKOH/g，酸值为10～160mgKOH/g。
4.根据权利要求1～3中任一项所述的发动机清洗用组合物，其中，螯合剂进一步包含胺。
CN201380050775.3A 2012-09-27 2013-09-26 发动机清洗用组合物 Expired - Fee Related CN104685045B (zh)

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