JP5507933B2 - Engine oil composition - Google Patents
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- JP5507933B2 JP5507933B2 JP2009206201A JP2009206201A JP5507933B2 JP 5507933 B2 JP5507933 B2 JP 5507933B2 JP 2009206201 A JP2009206201 A JP 2009206201A JP 2009206201 A JP2009206201 A JP 2009206201A JP 5507933 B2 JP5507933 B2 JP 5507933B2
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- 239000000203 mixture Substances 0.000 title claims description 24
- 239000010705 motor oil Substances 0.000 title claims description 21
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 14
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 229920000193 polymethacrylate Polymers 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims 1
- 239000002199 base oil Substances 0.000 description 34
- 150000002148 esters Chemical class 0.000 description 23
- -1 dicarboxylic acid diester Chemical class 0.000 description 21
- 238000001704 evaporation Methods 0.000 description 14
- 230000008020 evaporation Effects 0.000 description 14
- 239000000446 fuel Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 9
- 239000010687 lubricating oil Substances 0.000 description 7
- 239000002480 mineral oil Substances 0.000 description 7
- 235000010446 mineral oil Nutrition 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 230000001603 reducing effect Effects 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000002783 friction material Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- MNZNJOQNLFEAKG-UHFFFAOYSA-N 2-morpholin-4-ylethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCN1CCOCC1 MNZNJOQNLFEAKG-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Lubricants (AREA)
Description
本発明は、超低粘度エステル系基油とモリブデンジチオカーバメイトを用いた省燃費性能に優れたエンジン油組成物に関する。 The present invention relates to an engine oil composition excellent in fuel saving performance using an ultra-low viscosity ester base oil and molybdenum dithiocarbamate.
近年、地球温暖化防止のために自動車の燃費を向上させ、ＣＯ2の排出を抑制する要求が非常に高まっている。自動車の燃費を向上させるにはエンジンの効率向上が重要であり、ガソリンエンジンにおいてはリーンバーン化や直噴化あるいは動弁系のローラーフォロワ化及び各種可変化技術が採用されている。一方、エンジンの摩擦を低減することも燃費向上に貢献できることから、しゅう動部品への低摩擦材料の使用やピストンリングの低張力化等、様々なアプローチで低フリクション型エンジンの開発や低燃費化が計られている。 In recent years, there has been an increasing demand for improving the fuel efficiency of automobiles and suppressing CO 2 emissions to prevent global warming. Improving engine efficiency is important for improving the fuel efficiency of automobiles. In gasoline engines, lean burn, direct injection, valve-roller roller followers, and various variable technologies are employed. On the other hand, reducing the friction of the engine can also contribute to improving fuel economy, so the development of low-friction engines and fuel efficiency are reduced by various approaches such as the use of low-friction materials for sliding parts and the lower tension of piston rings. Is measured.
一方、省燃費型エンジン油を使用することでもエンジンの燃費は向上が可能である。この省燃費型エンジン油を製造するには、ＳＡＥ（米国自動車技術会）Ｊ３００に規定されている粘度分類記載の５Ｗ−２０や０Ｗ−２０という低粘度化をはかると共に、摩擦を低下させる添加剤（摩擦調整剤、以下ＦＭと称することもある）を配合することが有効であることが知られている（非特許文献１）。 On the other hand, the fuel consumption of the engine can be improved by using fuel-saving engine oil. In order to produce this fuel-saving engine oil, an additive that lowers the friction and reduces the viscosity of 5W-20 and 0W-20 described in the viscosity classification specified in SAE (American Automotive Engineers) J300 It is known that it is effective to blend (a friction modifier, hereinafter sometimes referred to as FM) (Non-patent Document 1).
本出願人は、ローラーフォロワ型動弁系エンジンで最適の省燃費効果を発揮する潤滑油として、１００℃における動粘度が５.５mm2/s以下、粘度指数が１２０以上、１５０℃における高温高せん断粘度が２.２mPa以上かつ２.５mPa未満のローラーフォロワ型動弁系エンジン用潤滑油組成物を提案した（特許文献１）。しかし、この潤滑油組成物は、特に粘度指数が低く、高温での粘度が低くなり耐摩耗性の点で、十分なものではなかった。
また、低粘度化を図るために、特定のジカルボン酸ジエステルを基油とし、あるいは、これにポリオールエステルを配合する潤滑油組成物（特許文献２）や特定のモノエステル化合物を含む内燃機関用潤滑油基油（特許文献３）が提案されている。しかし、エステル化合物を基油として用いると、摩擦低減に従来有効と考えられてきたモリブデンジチオカーバメイトの添加効果が十分に発揮されず、省燃費性の向上が不十分であることが分かった。
As a lubricating oil that exhibits an optimum fuel efficiency in a roller follower type valve-operated engine, the present applicant has a kinematic viscosity at 100 ° C. of 5.5 mm 2 / s or less, a viscosity index of 120 or more, and a high temperature and high temperature at 150 ° C. A lubricating oil composition for roller follower type valve-operated engines having a shear viscosity of 2.2 mPa or more and less than 2.5 mPa has been proposed (Patent Document 1). However, this lubricating oil composition has a particularly low viscosity index and a low viscosity at high temperatures, which is not sufficient in terms of wear resistance.
Further, in order to lower the viscosity, a lubricating oil composition (Patent Document 2) containing a specific dicarboxylic acid diester as a base oil or a polyol ester added thereto and a specific monoester compound is used. An oil base oil (Patent Document 3) has been proposed. However, it has been found that when an ester compound is used as a base oil, the effect of adding molybdenum dithiocarbamate, which has been considered to be effective for friction reduction, is not sufficiently exhibited, and the fuel economy is not sufficiently improved.
本発明は上記課題を解決するためになされたもので、本発明の目的は、低粘度のエステル化合物を基油として用いても、摩擦低減が十分に発揮できるエンジン油組成物を提供するである。 The present invention has been made to solve the above problems, and an object of the present invention is to provide an engine oil composition that can sufficiently exhibit friction reduction even when a low-viscosity ester compound is used as a base oil. .
本発明者は、上記課題を解決すべく鋭意研究を進めた結果、従来から一般に使用されているモリブデンジチオカーバメイトは、基油への溶解性の観点から炭素数１２〜１３のアルキル基を主とするものが用いられているが、エステル系基油を主成分とするエンジン油組成物においては、炭素数１２以上のアルキル基を有するモリブデンジチオカーバメイトが摩擦低減に寄与していないことを見出し、本発明に想到した。
すなわち、本発明は、１００℃における動粘度が３.６mm2/s以下、粘度指数が１３０以上のエステル系基油を主成分とし、炭素数６〜１０のアルキル基及び／又はアルケニル基を有するモリブデンジチオカーバメイトを全量基準で、モリブデン量として０.０３質量％以上含有するエンジン油組成物であり、好ましくは、前記エンジン油組成物が粘度指数向上剤としてポリメタクリレート系添加剤を５〜１５質量％含有し、１００℃における動粘度が８.８mm2/s以下である。
As a result of diligent research to solve the above-mentioned problems, the present inventors have generally used molybdenum dithiocarbamate mainly having an alkyl group having 12 to 13 carbon atoms from the viewpoint of solubility in a base oil. In an engine oil composition mainly composed of an ester base oil, it is found that molybdenum dithiocarbamate having an alkyl group having 12 or more carbon atoms does not contribute to friction reduction. I came up with the invention.
That is, the present invention is mainly composed of an ester base oil having a kinematic viscosity at 100 ° C. of 3.6 mm 2 / s or less and a viscosity index of 130 or more, and has an alkyl group and / or alkenyl group having 6 to 10 carbon atoms. An engine oil composition containing molybdenum dithiocarbamate in an amount of 0.03 mass% or more based on the total amount of the molybdenum dithiocarbamate. Preferably, the engine oil composition contains 5 to 15 mass of a polymethacrylate-based additive as a viscosity index improver. %, And the kinematic viscosity at 100 ° C. is 8.8 mm 2 / s or less.
本発明のエステル系基油使用の超省燃費エンジン油組成物を、最新のエンジンに使用することにより、良好な省燃費効果が得られるという格別の効果を奏する。 By using the super fuel-saving engine oil composition using the ester base oil of the present invention for the latest engine, there is a special effect that a good fuel-saving effect can be obtained.
本発明のエステル系基油は、１００℃における動粘度が３.６mm2/s以下、粘度指数が１３０以上のものである。１００℃における動粘度が３.６mm2/sを超えると省燃費性に劣り、粘度指数が１３０未満であれば、低温での粘度が高くなり省燃費性に劣る。
また、このエステル系基油は、１００℃における動粘度が２.０mm2/s以上のものが、蒸発ロスが少ないため好ましい。粘度指数は、高ければ高いほど好ましいが、高くなれば、一般に動粘度も高くなるため、１７０以下のものが好ましい。
なお、本発明に用いるエステル系基油や組成物の動粘度及び粘度指数は、ＪＩＳ Ｋ２２８３で測定される値である。
The ester base oil of the present invention has a kinematic viscosity at 100 ° C. of 3.6 mm 2 / s or less and a viscosity index of 130 or more. When the kinematic viscosity at 100 ° C. exceeds 3.6 mm 2 / s, the fuel efficiency is inferior. When the viscosity index is less than 130, the viscosity at low temperature is increased and the fuel efficiency is inferior.
In addition, the ester base oil having a kinematic viscosity at 100 ° C. of 2.0 mm 2 / s or more is preferable because of a small evaporation loss. The higher the viscosity index, the better. However, the higher the viscosity index, the higher the kinematic viscosity. Therefore, the viscosity index is preferably 170 or less.
The kinematic viscosity and viscosity index of the ester base oil and composition used in the present invention are values measured according to JIS K2283.
さらに、このエステル系基油は蒸発ロスが１８％以下のものが好ましい。この蒸発ロスが１８％を超えるとエンジン油組成物の蒸発ロスを１５％以下にすることが困難になる。この蒸発ロスは低ければ低いほど好ましいが、低過ぎると動粘度が高くなるため、５％以上が好ましい。なお、蒸発ロスは、−２０mmH2Oの減圧度、油温２５０℃で、供試油を１時間放置したときに蒸発する割合でＡＳＴＭ Ｄ５８００に規定された試験方法により測定される値である。 Further, the ester base oil preferably has an evaporation loss of 18% or less. If this evaporation loss exceeds 18%, it becomes difficult to reduce the evaporation loss of the engine oil composition to 15% or less. The lower the evaporation loss, the better. However, if the evaporation loss is too low, the kinematic viscosity increases, so 5% or more is preferable. The evaporation loss is a value measured by a test method defined in ASTM D5800 at a rate of evaporation when the sample oil is allowed to stand for 1 hour at a reduced pressure of −20 mmH 2 O and an oil temperature of 250 ° C.
エステル系基油を構成するエステル化合物としては、各種のエステル化合物、例えば、モノカルボン酸と１価アルコールとのエステルであるモノエステル化合物、ジカルボン酸と１価アルコールとのエステルであるジエステル化合物、モノカルボン酸と多価アルコールとのエステルであるポリオールエステル化合物のいずれからも選択することができるが、特には、炭素数４〜１２の直鎖又は分岐の飽和ジカルボン酸と炭素数７〜１２の１価のアルコールとのエステル化合物が、モリブデンジチオカーバメイトの添加効果が十分に発揮されるので好ましい。具体的には、セバシン酸ジオクチルやアジピン酸ジイソデシル等が、特に好ましい。
これらのエステル化合物は、単独で用いて、エステル系基油としてもよく、また数種類のエステル化合物を混合して、エステル系基油としてもよい。
Examples of the ester compound constituting the ester base oil include various ester compounds such as a monoester compound that is an ester of a monocarboxylic acid and a monohydric alcohol, a diester compound that is an ester of a dicarboxylic acid and a monohydric alcohol, Although it can select from any of the polyol ester compounds which are ester of carboxylic acid and a polyhydric alcohol, it is especially C4-C12 linear or branched saturated dicarboxylic acid and C7-C12 1 An ester compound with a hydric alcohol is preferable because the effect of adding molybdenum dithiocarbamate is sufficiently exhibited. Specifically, dioctyl sebacate, diisodecyl adipate and the like are particularly preferable.
These ester compounds may be used alone to form an ester base oil, or several types of ester compounds may be mixed to form an ester base oil.
本発明においては、上記エステル系基油を主成分として用いるものであり、エステル系基油を単独で用いてもよいが、他の潤滑油基油、例えば、ポリアルファオレフィンや粘度指数が１２０以上の鉱油系基油などを配合してもよい。しかし、エンジン油組成物中に、エステル系基油が３０質量％以上、特には５０質量％以上、さらには８０質量％以上含まれていることが好ましい。 In the present invention, the ester base oil is used as a main component, and the ester base oil may be used alone, but other lubricating base oils such as polyalphaolefin and viscosity index are 120 or more. Mineral oil base oil or the like may be blended. However, it is preferable that the ester base oil is contained in the engine oil composition at 30% by mass or more, particularly 50% by mass or more, and more preferably 80% by mass or more.
この場合のポリアルファオレフィンは、重合度や側鎖の長さの違いにより多種のものが存在するが、一般に潤滑油用として用いられているものを用いることができる。すなわち、ＣＨ2＝ＣＨ−（ＣＨ2）n−ＣＨ3の構造式で表されるα‐オレフィンが３〜５分子程度重合したもので、側鎖長のｎが６〜１２の分子を主成分としたもので、具体的には、１−オクテンオリゴマー、１‐デセンオリゴマー等の炭素数４〜１６、好ましくは炭素数８〜１２のα−オレフィンのオリゴマー又はそれらの水素化物等が好適である。 In this case, various polyalphaolefins exist depending on the degree of polymerization and the length of the side chain, but those generally used for lubricating oils can be used. That, CH 2 = CH- (CH 2 ) n in which α- olefin represented by the structural formula of -CH 3 are polymerized about 3-5 molecules, mainly of molecules of n side chain length 6-12 Specifically, α-olefin oligomers having 4 to 16 carbon atoms, preferably 8 to 12 carbon atoms such as 1-octene oligomers and 1-decene oligomers, or hydrides thereof are suitable. .
鉱油系基油としては、原油を常圧蒸留して得られる常圧残油を減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、水素化精製等の処理を１つ以上行って精製したもの、あるいはワックス異性化鉱油、ＧＴＬ ＷＡＸ（ガストゥリキッドワックス）を異性化する手法で製造される基油等が好適である。なお、鉱油系基油中の硫黄分は、特に制限はないが、０.２質量％以下であることが好ましく、０.０５質量％以下であることがさらに好ましい。この鉱油系基油は、蒸発ロスの低減と省燃費性とを鑑み、粘度指数が１２０以上のものを用いることが好ましい。 Mineral oil base oils include solvent oil removal, solvent extraction, hydrocracking, solvent dewaxing, hydrogen removal of lubricating oil fractions obtained by vacuum distillation of atmospheric residue obtained by atmospheric distillation of crude oil. A base oil produced by a method of isomerizing a wax isomerized mineral oil or GTL WAX (gas-trimmed wax) is suitable. The sulfur content in the mineral oil base oil is not particularly limited, but is preferably 0.2% by mass or less, and more preferably 0.05% by mass or less. In view of reduction of evaporation loss and fuel efficiency, it is preferable to use a mineral oil base oil having a viscosity index of 120 or more.
本発明においては、ポリアルファオレフィン及び鉱油系基油は、それぞれ単独で、エステル系基油に配合しても、また両者を共に配合しても良い。このポリアルファオレフィン及び／又は鉱油系基油の配合量は、両者の合計量として、エンジン油組成物全量基準で、好ましくは、７０質量％以下、より好ましくは５０質量％以下、特に好ましくは２０質量％以下とする。配合量が、７０質量％を超えると、エンジン油組成物の粘度指数を２５０以上にすることが困難となるので、好ましくない。 In the present invention, the polyalphaolefin and the mineral base oil may be used alone or in the ester base oil, or both may be added together. The blending amount of the polyalphaolefin and / or mineral oil base oil is preferably 70% by mass or less, more preferably 50% by mass or less, particularly preferably 20%, based on the total amount of the engine oil composition as the total amount of both. Less than mass%. If the blending amount exceeds 70% by mass, it is difficult to make the viscosity index of the engine oil composition 250 or more, which is not preferable.
本発明に用いるモリブデンジチオカーバメイト（MoDTC）は、炭素数６〜１０のアルキル基及び／又はアルケニル基を有するものであり、次の構造のものが使用できる。 Molybdenum dithiocarbamate (MoDTC) used in the present invention has an alkyl group and / or alkenyl group having 6 to 10 carbon atoms, and those having the following structure can be used.
なお、炭素数が１０を超えるアルキル基及び／又はアルケニル基を有するモリブデンジチオカーバメイトは、エステル系基油に非常に良く溶解し、摩擦界面で、MoS2を形成し難くなること、逆に、炭素数が６未満のアルキル基及び／又はアルケニル基を有するものは、エステル系基油に対する溶解度が低いため、摩擦界面でのMoS2形成ができないことによるものと推測される。したがって、炭素数６未満、１１以上のアルキル基及び／又はアルケニル基を有するモリブデンジチオカーバメイトは含まれていないことが好ましい。具体的には、モリブデンジチオカーバメイトの全質量に対してこの範囲外のモリブデンジチオカーバメイトは、２０質量％以下、特には５質量％以下が好ましい。 Molybdenum dithiocarbamate having an alkyl group and / or alkenyl group having more than 10 carbons dissolves very well in an ester base oil, making it difficult to form MoS 2 at the friction interface. Those having an alkyl group and / or alkenyl group having a number of less than 6 are presumably due to the fact that MoS 2 cannot be formed at the friction interface because of its low solubility in ester base oil. Therefore, it is preferable that molybdenum dithiocarbamate having an alkyl group and / or alkenyl group having less than 6 carbon atoms and 11 or more carbon atoms is not included. Specifically, molybdenum dithiocarbamate outside this range is preferably 20% by mass or less, particularly preferably 5% by mass or less, based on the total mass of molybdenum dithiocarbamate.
炭素数６〜１０の直鎖及び又は分岐のアルキル基及び／又はアルケニル基を有するモリブデンジチオカーバメイトは、エンジン油組成物の全量基準で、モリブデン量として０.０３質量％以上、好ましくは０.０８質量％以下、より好ましくは、０.０４５〜０.０７５質量％含まれていることにより、良好な摩擦低減効果をエンジン油組成物に付与することができる。 The molybdenum dithiocarbamate having a linear and / or branched alkyl group and / or alkenyl group having 6 to 10 carbon atoms is 0.03 mass% or more, preferably 0.08, in terms of the amount of molybdenum, based on the total amount of the engine oil composition. By containing 0.045 to 0.075% by mass, more preferably, a good friction reducing effect can be imparted to the engine oil composition.
本発明のエンジン油組成物は、高い省燃費効果を達成するために、１００℃における動粘度が８.８mm2/s以下が好ましく、蒸発ロスの観点から６.０mm2/s以上のものがより好ましい。また、粘度指数が２００℃以上のものが好ましく、２６０以上がより好ましく好ましい。粘度指数が低いと高温での粘度が低くなり、摩耗が発生しやすくなり、粘度指数は高ければ高いほどよいが、高くなれば一般に動粘度も高くなるため、３５０以下であることが好ましい。さらに、蒸発ロスが１８％以下、特には１３〜１８％が好ましい。蒸発ロスが多いと、使用中に動粘度が上昇し、省燃費効果が低下する。この蒸発ロスは、低ければ低いほど良いが、低すぎると粘度を低くすることが難しくなるので、３％以上とすることが好ましい。 Engine oil composition of the present invention, in order to achieve a high fuel economy effect, is preferably 8.8 mm 2 / s or less kinematic viscosity at 100 ° C., those in terms of the evaporation loss of more than 6.0 mm 2 / s More preferred. Moreover, a viscosity index of 200 ° C. or higher is preferable, and 260 or higher is more preferable. If the viscosity index is low, the viscosity at high temperature becomes low and wear tends to occur. The higher the viscosity index, the better. However, the higher the viscosity, the higher the kinematic viscosity, so 350 or less is preferable. Further, the evaporation loss is preferably 18% or less, particularly 13 to 18%. When the evaporation loss is large, the kinematic viscosity increases during use, and the fuel saving effect decreases. The lower the evaporation loss, the better. However, if the evaporation loss is too low, it is difficult to lower the viscosity.
本発明のエンジン油組成物には、粘度指数向上剤としてポリメタクリレート系添加剤を５〜１５質量％、特には８〜１５質量％配合することが好ましい。この場合のポリメタクリレートは、非分散型、分散型のいずれも使用できる。非分散型ポリメタクリレートは、ポリメタクリレート化合物の重合体を用いるもので、一方、分散型ポリメタクリレートは、アルキルメタクリレートモノマーと、極性モノマーとの共重合で得られるものである。極性モノマーとしては、ジエチルアミノエチルメタクリレート、２−メチル−５−ビニルピロリドン、Ｎ−ビニルピロリドン、モルホリノエチルメタクリレートから選ばれる１種以上が好適に使用できる。
また、ポリマーの分子量であるが、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によりポリスチレン換算値として求められた重量平均分子量において、１５０,０００以上のものが好ましく、２００,０００以上がさらに好ましい。重量平均分子量が小さいと、粘度指数向上効果が小さい。重量平均分子量の上限は、特に制限されるものではないが、１,０００,０００を超えると剪断安定性が低下し、粘度指数向上効果が低下する。このため、重量平均分子量１５０,０００〜１,０００,０００のものが好適である。
The engine oil composition of the present invention preferably contains 5 to 15 mass%, particularly 8 to 15 mass% of a polymethacrylate-based additive as a viscosity index improver. In this case, the polymethacrylate can be either non-dispersed or dispersed. Non-dispersed polymethacrylate uses a polymer of a polymethacrylate compound, while dispersed polymethacrylate is obtained by copolymerization of an alkyl methacrylate monomer and a polar monomer. As the polar monomer, one or more selected from diethylaminoethyl methacrylate, 2-methyl-5-vinylpyrrolidone, N-vinylpyrrolidone, and morpholinoethyl methacrylate can be preferably used.
Moreover, although it is the molecular weight of a polymer, in the weight average molecular weight calculated | required as a polystyrene conversion value by GPC (gel permeation chromatography), a thing of 150,000 or more is preferable and 200,000 or more is more preferable. When the weight average molecular weight is small, the effect of improving the viscosity index is small. The upper limit of the weight average molecular weight is not particularly limited, but when it exceeds 1,000,000, the shear stability is lowered and the effect of improving the viscosity index is lowered. For this reason, the thing of a weight average molecular weight 150,000-1,000,000 is suitable.
本発明のエンジン油には、所望により、アルキルジチオリン酸亜鉛（ＺｎＤＴＰ）、フェノール化合物、ジフェニルアミン化合物等の酸化防止剤、Ｃａ、Ｍｇ、Ｂａ、Ｎａ等の金属スルホネート、フェネート、サリシレート、ホスホネート等の清浄剤、アルケニルコハク酸イミド等の無灰系分散剤、その他流動点降下剤や防錆剤等の添加剤を添加することができる。 In the engine oil of the present invention, as desired, zinc alkyldithiophosphate (ZnDTP), antioxidants such as phenolic compounds and diphenylamine compounds, metal sulfonates such as Ca, Mg, Ba, and Na, phenates, salicylates, phosphonates, etc. An additive such as an ashless dispersant such as an alkenyl succinimide, a pour point depressant or a rust inhibitor may be added.
次に、実施例により本発明を具体的に説明する。
用いたエステル系基油と鉱油系基油の性状を表１に示す。
Next, the present invention will be described specifically by way of examples.
Table 1 shows the properties of the ester base oil and the mineral oil base oil used.
表１の基油を用いて試作した供試油について、その配合量と性状を表２に示す。配合量は質量％で示す。
なお、モリブデンジチオカーバメイト、粘度指数向上剤は次のものを用いた。
MoDTC1：アルキル基Rが２−エチルヘキシル基であり、酸素原子と硫黄原子との比が１／３から３／１であるモリブデンジチオカーバメイト、このMoDTC1は、炭素数８のアルキル基を有するモリブデンジチオカーバメイトをモリブデン量として４.１質量％含有する。
MoDTC2：アルキル基Rが２−エチルヘキシル基及びイソトリデシル基が混在したもので、酸素原子と硫黄原子との比が１／３から３／１であるモリブデンジチオカーバメイト、これは、アルキル基Rが２−エチルヘキシル基である化合物と、アルキル基Rがイソトリデシル基である化合物と、アルキル基Rが２−エチルヘキシル基とイソトリデシル基が混在した化合物が、２：１：３のモル比で混在するものである。このMoDTC2は、炭素数８のアルキル基を有するモリブデンジチオカーバメイトをモリブデン量として１.５質量％含有する。
PMA：ポリスチレン換算の重量平均分子量が２４５,０００のポリメタクリレート
なお、その他の添加剤は、清浄剤、分散剤などを組み合わせた市販のパッケージ添加剤である。
Table 2 shows the blending amounts and properties of the test oils made using the base oil of Table 1. A compounding quantity is shown by the mass%.
In addition, the following were used for the molybdenum dithiocarbamate and the viscosity index improver.
MoDTC1: Molybdenum dithiocarbamate whose alkyl group R is a 2-ethylhexyl group and the ratio of oxygen atom to sulfur atom is 1/3 to 3/1. Is contained in an amount of 4.1% by mass as molybdenum.
MoDTC2: Molybdenum dithiocarbamate in which the alkyl group R is a mixture of 2-ethylhexyl group and isotridecyl group, and the ratio of oxygen atom to sulfur atom is 1/3 to 3/1. A compound having an ethylhexyl group, a compound in which the alkyl group R is an isotridecyl group, and a compound in which the alkyl group R is a mixture of 2-ethylhexyl group and isotridecyl group are mixed in a molar ratio of 2: 1: 3. This MoDTC2 contains 1.5% by mass of molybdenum dithiocarbamate having an alkyl group having 8 carbon atoms as the amount of molybdenum.
PMA: Polymethacrylate having a polystyrene-equivalent weight average molecular weight of 245,000 Other additives are commercially available package additives in combination with detergents, dispersants and the like.
次に、各供試油について、ＳＲＶ試験での摩擦係数を測定した。試験条件は荷重４００Ｎ、振動数５０Hz、振幅１.５mmで行なった。この結果を表２の最下段に示した。 Next, the friction coefficient in the SRV test was measured for each sample oil. The test conditions were a load of 400 N, a frequency of 50 Hz, and an amplitude of 1.5 mm. The results are shown at the bottom of Table 2.
以上の結果から明らかなように、実施例の供試油では、モリブデンジチオカーバメイトによる摩擦低減効果が得られるとともに、−３５℃におけるＣＣＳ粘度が非常に低く、特に低温領域において優れた省燃費性を発揮することは明らかである。一方、比較例１の供試油は、低温領域での摩擦低減効果は十分であるが、実施例の供試油と比較して高油温時の摩擦低減効果が不十分である。さらに、比較例２、３の供試油は、実施例の供試油と比較して−３５℃におけるＣＣＳ粘度が高く、低温領域における摩擦低減効果が不十分である。 As is clear from the above results, the sample oils of the examples have the effect of reducing friction by molybdenum dithiocarbamate, have a very low CCS viscosity at −35 ° C., and have excellent fuel economy especially in the low temperature range. It is clear that it works. On the other hand, the test oil of Comparative Example 1 has a sufficient friction reducing effect in a low temperature region, but has a poor friction reducing effect at a high oil temperature compared to the test oil of the Example. Furthermore, the sample oils of Comparative Examples 2 and 3 have a higher CCS viscosity at −35 ° C. than the sample oils of Examples, and the friction reducing effect in the low temperature region is insufficient.
本発明は、高性能の内燃機関用エンジン、例えば、ローラーフォロワ型エンジンや低摩擦材を用いたスリッパー型動弁系エンジン等の最新のエンジン用潤滑油として利用することができる。 INDUSTRIAL APPLICABILITY The present invention can be used as the latest lubricating oil for engines such as high performance engines for internal combustion engines, such as roller follower type engines and slipper type valve operating engines using low friction materials.
Claims (2)
The engine oil composition according to claim 1, comprising 5 to 15% by mass of a polymethacrylate-based additive as a viscosity index improver.
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|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |