EP0699739A2 - Composition d'huile pour moteur - Google Patents

Composition d'huile pour moteur Download PDF

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Publication number
EP0699739A2
EP0699739A2 EP95113870A EP95113870A EP0699739A2 EP 0699739 A2 EP0699739 A2 EP 0699739A2 EP 95113870 A EP95113870 A EP 95113870A EP 95113870 A EP95113870 A EP 95113870A EP 0699739 A2 EP0699739 A2 EP 0699739A2
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EP
European Patent Office
Prior art keywords
engine oil
oil composition
group
chain
amount
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95113870A
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German (de)
English (en)
Other versions
EP0699739A3 (fr
EP0699739B1 (fr
Inventor
Yasushi c/o Japan Energy Corp. Naitoh
Kenyu Akiyama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyota Motor Corp
Eneos Corp
Original Assignee
Japan Energy Corp
Toyota Motor Corp
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Application filed by Japan Energy Corp, Toyota Motor Corp filed Critical Japan Energy Corp
Publication of EP0699739A2 publication Critical patent/EP0699739A2/fr
Publication of EP0699739A3 publication Critical patent/EP0699739A3/fr
Application granted granted Critical
Publication of EP0699739B1 publication Critical patent/EP0699739B1/fr
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    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • C10N2040/28—Rotary engines

Definitions

  • the present invention relates to an engine oil composition for automobiles. More particularly, the invention relates to the long life and fuel-saving engine oil composition which can suppress the friction loss in the engine to a low level for a long time.
  • engine oil compositions have been required to possess various performances such as wear resistance, oxidation stability, and detergent dispersibility. Recently, in order to suppress the earth from getting warmer due to increase in the content of CO2 in the atmosphere, how to improve the mileage of the automobiles is an important problem. Accordingly, the fuel saving has been also strongly required with respect to the engine oils.
  • the engine oil composition is composed of a mixture of a base oil purified from petroleum, added with additives ouch as a detergent, an antioxidant, an anti-wear agent, and a viscosity index improver.
  • a viscosity index improver In order to increase the fuel efficiency (mileage) of the engine oil, for example, the viscosity of the engine oil is lowered by decreasing the viscosity of the base oil or changing the viscosity index improver.
  • friction cannot be reduced in the case of the above ordinary engine oil composition in such an area as a boundary lubricating condition where the viscosity does not contributes to mitigation of the friction. Consequently, a friction modifier (FM) has recently come to be added so as to reduce the wearing in the boundary lubricating area.
  • FM friction modifier
  • organic molybdenum compound such as molybdenum dithiocarbamate (MoDTC) and oxymolybdenum organo phosphodithioate sulfide (MoDTP) are highly effective as described in JP-B 3-23595.
  • MoDTC contains no phosphorus, increase in its addition amount does not cause decrease in the catalytic activity.
  • MoDTC has a small friction-mitigating effect, it may be considered that MoDTC is used in combination with zinc dithiophosphate (ZnDTP) as an anti-wear agent so as to supplement the wear-mitigating effect of the former.
  • ZnDTP has been frequently used, as antioxidant and anti-wear agent, in the engine oil compositions.
  • ZnDTP contains phosphorus and gives adverse influence upon the exhaust gas catalyst as mentioned above, its addition amount is limited so that good friction-mitigating effect cannot unfavorably be maintained for a long time.
  • MoDTC be used in combination with a sulfur-based extreme pressure additive (See JP-B 5-83599). This combination does not afford adverse effect upon the exhaust gas catalyst, but it encounters a practically great problem upon the engine oil composition in that wear largely occurs in the valve train system.
  • the present inventors discovered that the combination of MoDTC and ZnDTP with a polysulfide compound can remarkably prolong the performance of the low fuel consumption rate, that is, can maintain the friction-mitigating effect of the engine oil for a long time without affording adverse influence upon the exhaust gas catalyst. Based on this discovery, the inventors have accomplished the present invention.
  • the present invention relates to the engine oil composition
  • the engine oil composition comprising (1) at least one oil selected from the group consisting of a mineral oil and a synthetic lubricant as a base oil; (2) a molybdenum dithicarbamate in an amount of 50 to 2000 ppm by weight when calculated as molybdenum (Mo), relative to the total weight of the engine oil composition; (3) zinc dithiophosphate in an amount of 0.01 to 0.2 wt% when calculated as phosphorus (P), relative to the total amount of the engine oil composition; and (4) an ashless organic polysulfide compound in an amount of 0.01 to 0.4 wt% when calculated as sulfur (S), relative to the total amount of the engine oil composition.
  • This engine oil composition is a long life and low fuel consumption engine oil composition which can maintain the friction loss at a low level for a long time.
  • the base oil to be used in the engine oil composition according to the present invention is a mineral oil and/or a synthetic oil.
  • the base oil which is used, in the engine oil composition, as a base component occupying a great part of the engine oil composition, any base oil may be used.
  • a lubricant base oil which is producing by obtaining a cut through distilling an ordinary pressure distillation residue of such as a paraffinic crude oil under reduced pressure, treating the resulting cut through extraction with a solvent such as furfural, purification by hydrogenation and dewaxing with a solvent such as MEK/toluene, a lubricant base oil produced by obtaining a deasphalted oil by deasphalting the above pressure-reduced distillation residue and treating it by any of the above appropriate processes, a highly purified base oil obtained through isomerization of slack wax and dewaxing an appropriate cut of the isomerized oil with a solvent of MEK/toluene, or an appropriate mixture thereof.
  • an ⁇ -olefin oligomer a diester synthesized from a dibasic acid such as an adipic acid and a primary alcohol, a polyol ester synthesized from a higher alcohol such as neopentyl glycol, trimethylol propane or pentaerithritol and a monobasic acid, an alkyl benzene or a polyoxyalkylene glycol or an appropriate mixture thereof.
  • a mixed oil obtained by appropriately combining the mineral oil with the synthetic oil may be used as a base oil for the engine oil composition according to the present invention.
  • the molybdenum dithiocarbamate (MoDTC) to be used as an additive in the present invention is a compound expressed by the following formula (1)
  • R1 through R4 independently denote a straight-chain or branched-chain alkyl group or a straight-chain or branched-chain alkenyl group having four to eighteen carbons
  • X1 through X4 independently denote an oxygen atom or a sulfur atom, the ratio between the number of the oxygen atom or atoms and that of the sulfur atom or atoms with respect to X1 through X4 being 1/3 to 3/1.
  • the alkyl group is preferred.
  • butyl group, 2-ethylhexyl group, isotridecyl group or stearyl group may be recited.
  • These four R1 through R4 existing in one molecule may be identical with or different from each other.
  • two or more MoDTCs differing in terms of R1 through R4 may be used in a mixed state.
  • MoDTC is used in the addition amount of 50 to 2000 ppm by weight, preferably 300 to 1000 ppm by weight, when calculated as molybdenum (Mo), relative to the total weight of the engine oil composition. If the addition amount is less than 50 ppm by weight, the friction-reducing effect is small, whereas if it is more than 2000 ppm by weight, the friction-reducing effect is saturated and the cost increases.
  • the zinc dithiophosphate (ZnDTP) to be used as an additive in the present invention is a compound expressed by the formula (2):
  • R5 and R6 independently denote a straight-chain or branched chain alkyl group or a straight-chain or branched chain aryl group having three to eighteen carbon atoms.
  • an alkyl group particularly, a primary alkyl group is preferred from the standpoint that the friction-mitigating performance must be maintained for a long time. More specifically, for example, propyl group, butyl group, pentyl group, hexyl group, octyl group and lauryl group may be recited.
  • These two R5 and R6 existing in one molecule may be identical with or different from each other. Further, two or more kinds of ZnDTPs differing in terms of R5 and R6 may be used in a mixed state.
  • ZnDTP is added in an amount of 0.01 to 0.2 wt%, preferably 0.04 to 0.2 wt%, more preferably 0.04 to 0.1 wt% when calculated as phosphorus (P), relative to the total amount of the engine oil composition. If the addition amount is less than 0.01 wt%, the wear-preventing performance of the engine oil composition for the valve train system is deteriorated. On the other hand, if it is more than 0.2 wt%, influence of the phosphorus component upon the catalytic activity for the exhaust gas becomes greater.
  • the ashless organic polysulfide compound to be used in the present invention includes organic compounds expressed by the following formulae, such as sulfides of oils or fats or polyolefins, in which a sulfur atom group having two or more sulfur atoms adjoining and bonded together is present in a molecular structure.
  • R7 and R8 independently denote a straight-chain, branched-chain, alicyclic or aromatic hydrocarbon group in which a straight chain, a branched chain, an alicyclic unit and an aromatic unit may be selectively contained in any combined manner.
  • An unsaturated bond may be contained, but a saturated hydrocarbon group is preferred.
  • alkyl group, aryl group, alkylaryl group, benzyl group, and alkylbenzyl group are preferred.
  • R9 and R10 independently denote a straight-chain, branched-chain alicyclic or aromatic hydrocarbon group which has two bonding sites and in which a straight chain, a branched chain, an alicyclic unit and an aromatic unit may be selectively contained in any combined manner.
  • An unsaturated bond may be contained, but a saturated hydrocarbon group is preferred.
  • alkylene group is preferred.
  • R11 and R12 independently denote a straight-chain or branched-chain hydrocarbon group.
  • "x" and "y” denote independently an integer of two or more.
  • sulfurized sperm oil sulfurized pinene oil, sulfurized soybean oil, sulfurized polyolefin, dialkyl disulfide, dialkyl polysulfide, dibenzyl disulfide, di-tertiary butyl disulfide, polyolefin polysulfide, thiadiazol type compound such as bis-alkyl polysulfanyl thiadiazole, and sulfurized phenol.
  • dialkyl polysulfide, dibenzyl disulfide, and thiadiazol type compound are preferred.
  • bis-alkyl polysulfanyl thiadiazole is preferred.
  • a metal-containing compound such as Ca phenate having a polysulfide bond is used.
  • this compound has a large coefficient of friction, it is not suitable.
  • the above organic polysulfide compound is an ashless compound containing no metal, and exhibits excellent performance in maintaining a low coefficient of friction for a long time when used in combination with MoDTC and ZnDTP.
  • polysulfide compound The above ashless organic polysulfide compound (hereinafter referred to briefly as “polysulfide compound”) is added in an amount of 0.01 to 0.4 wt%, preferably 0.1-0.3 wt%, more preferably 0.2-0.3 wt%, when calculated as sulfur (S), relative to the total amount of the engine oil composition. If the addition amount is less than 0.01 wt%, it is difficult to attain the intended effect, whereas if it is more than 0.4 wt%, there is a danger that corrosive wear increase. Needless to say, only one kind of the above polysulfide compound may be used, and two kinds of such polysulfide compounds may also be used in combination.
  • engine oil additives other than the above may be appropriately added to the engine oil composition according to the present invention so as to improve the total performance.
  • metallic detergents such as sulfonate, phenate and salicylate of alkaline earth metals such as Ca, Mg and Ba and alkali metals such as Na
  • ashless dispersants such as alkenyl succinic acid imide, succinic acid esters and benzylamine
  • phenolic anti-oxidant such as bisphenol
  • amine-based anti-oxidant such as diphenylamine
  • viscosity index improvers such as olefin copolymer or polymetacrylate.
  • other engine oil additives such as a pour point depressant, anti-corrosion agent and antifoaming agent may be appropriately added.
  • a lubricant in each of Examples and Comparative Examples was prepared by using Mineral Oils 1 or 2 having the following properties as a base oil.
  • Sulfur-based additive 1 means an additive containing the polysulfide compound used in the present invention, and includes a thiadiazole type polysulfide compound having the following formula.
  • the content of sulfur in the sulfur-based additive is 36 wt%.
  • R13 and R14 independently denote the same meanings as R7 and R8 do, respectively.
  • Sulfur-based additive 2 means an additives containing a sulfurized oil and fat type polysulfide compounds, and the content of sulfur in the sulfur-based additive 2 is 10.5 wt%.
  • Sulfur-based additive 3 means an additives containing a dibenzyl disulfide, and the content of sulfur in the sulfur-based additive 3 is 25.5 wt%.
  • ZnDTP1 is a primary alkyl compound of the above formula (2) in which R5 and R6 are 2-ethylhexyl groups.
  • ZnDTP2 means secondary alkyl compounds of the above formula (2) in which R5 and R6 are isopropyl groups or isohexyl groups or a mixture of these compounds each having the respective two above alkyl groups.
  • Additive package includes metallic detergent, ashless dispersant, phenolic anti-oxidant, amine-based anti-oxidant, viscosity index improver, anti-corrosion agent and antifoaming agent.
  • the coefficient of friction was measured under the following conditions by using an SRV tester.
  • test pieces a ball made of SUJ-2 (bearing steel material, Japanese Industrial Standards), and having 10 mm in diameter and a disc made of SUJ-2 were used.
  • Table 2 Test conditions Break in conditions Actual test conditions Load (N) 10 200 Amplitude (mm) 1.5 1.5 Frequency (Hz) 50 50 Temperature (°C) 40 80 Time (min) 10 30
  • the coefficient of friction is the average coefficient of friction determined in the friction test during the final 20 minutes.
  • the used oil compositions are oil compositions obtained when the oil was subjected to running in simulation with an actual car driving.
  • the engine was operated under an AMA running mode at an oil temperature of 100°C and a water temperature of 100°C, and the engine oil composition was sampled after the lapse of 160 hours (corresponding to 4000 km) and 400 hours (corresponding to 10000 km).
  • the thus obtained used oil compositions were subjected to the above friction test.
  • Each engine oil composition was subjected to the valve train system wear test according to JASO (Japanese Automobile Standards organization) M328-91. Then, scuffing of a rocker arm was evaluated, and a worn amount of a cam nose was measured.
  • JASO Japanese Automobile Standards organization
  • Example 1 Example 2
  • Example 3 Example 4
  • Mineral oil 1 84.5 83.1 84.3 - 85.0
  • Mineral oil 2 - - - 84.5 - MoDTC additive 2.0 2.0 2.0 2.0 Content of Mo in oil composition 0.08 0.08 0.08 0.08 0.08
  • Sulfur-based additive 1 0.6 - - 0.6 0.6
  • Metallic detergent 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Ash-based dispersant 4.0 4.0 4.0 4.0 4.0 4.0 4.0 Phenolic anti-oxidant 0.8 0.8 0.8 0.8 0.8 Amine-based anti-oxidant 0.4 0.4 0.4 0.4
  • Examples 1 through 3 in Table 3 are engine oil compositions which all used Mineral Oil 1 and also employed a thiadiazole compound, a sulfurized oil and fat type compound and dibenzyl disulfide as the polysulfide compound, respectively.
  • Example 4 is the same engine oil composition as in Example 1 except that Mineral Oil 1 was replaced by more highly purified Mineral Oil 2.
  • a secondary alkyl type was used as ZnDTP.
  • Comparative Example 1 is an engine oil composition containing no polysulfide compound
  • Comparative Example 2 is an engine oil composition containing much ZnDTP
  • Comparative Example 3 is an engine oil composition containing no ZnDTP
  • Comparative Example 4 is the same engine oil composition as Comparative Example 1 except that the base oil was replaced by highly purified Mineral Oil 2.
  • Comparative Example 5 is an engine oil composition containing no MoDTC
  • Comparative Example 6 is an engine oil composition containing neither MoDTC nor polysulfide compound
  • Comparative Example 7 is an engine oil composition containing neither ZnDTP nor polysulfide compound.
  • Comparative Example 8 is an engine oil composition containing neither MoDTC nor ZnDTP.
  • Comparison between Example 1 and Comparative Example 1, between Example 2 and Comparative Example 2 and between Example 4 and Comparative Example 4 reveals that when the polysulfide compound was used in combination, the coefficient of friction particularly after the passage of 400 hours remarkably decreased.
  • Comparison between Example 3 and Comparative Example 3 reveals that in Comparative Example 3, since no ZnDTP was used in combination, the coefficient of friction after the passage of 400 hours was not only high, but also the worn amount of the cam nose consipicuously increased.
  • Comparison between Example 5 and Comparative Examples 5 and 6 reveals that in Comparative Examples 5 and 6, since no MoDTC was used in combination, the coefficient of friction was high from the beginning.
  • the engine oil composition of the present invention is characterized in that MoDTC and ZnDTP are combined with the ashless organic polysulfide compound in the respectively specified addition amounts, and that a low coefficient of friction can be maintained in a long-term use even without addition of a large amount of particularly MoDTP or ZnDTP. Therefore, when the engine oil composition according to the present invention is charged into and used in the automobile, spectacular effects can be exhibited with respect to fuel consumption saving and environmental maintenance.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP95113870A 1994-09-05 1995-09-04 Composition d'huile pour moteur Expired - Lifetime EP0699739B1 (fr)

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EP0768366A1 (fr) * 1995-10-11 1997-04-16 Tonen Corporation Composition d'huile lubrifiante
EP0822246A2 (fr) * 1996-08-02 1998-02-04 Tonen Corporation Composition d'huile lubrifiante
EP0889030A1 (fr) * 1997-07-05 1999-01-07 RHEIN-CHEMIE RHEINAU GmbH Polysulfides, procédé pour leur préparation et leur utilisation
EP1013750A2 (fr) * 1998-12-21 2000-06-28 Tonen Corporation Composition d'huile lubrifiante pour des moteurs diesel
EP1027412A1 (fr) * 1997-11-12 2000-08-16 Exxon Chemical Patents Inc. Controle d'usure avec des dispersants utilisant des polymeres poly alfa-olefines
US6300291B1 (en) 1999-05-19 2001-10-09 Infineum Usa L.P. Lubricating oil composition
US6855675B1 (en) 1995-05-24 2005-02-15 Tonengeneral Sekiyu K.K. Lubricating oil composition
WO2010036892A2 (fr) * 2008-09-26 2010-04-01 Greengold Lubricants, Llc Composition lubrifiante et procédés de fabrication de celle-ci
US8592356B2 (en) 2007-05-29 2013-11-26 Idemitsu Kosan Co., Ltd. Lubricant composition for internal combustion engine
CN111286390A (zh) * 2020-02-14 2020-06-16 中国地质大学（北京） 一种含有纳米级碳基固体添加剂的新型汽车发动机润滑油及其制备方法
CN114555763A (zh) * 2019-07-08 2022-05-27 马来西亚国家石油公司 减少摩擦和磨损的添加剂
US20220259515A1 (en) * 2019-07-26 2022-08-18 Adeka Corporation Lubricating oil additive and lubricating oil composition containing same
US12006485B2 (en) * 2019-07-26 2024-06-11 Adeka Corporation Lubricating oil additive and lubricating oil composition containing same

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GB9716283D0 (en) * 1997-08-01 1997-10-08 Exxon Chemical Patents Inc Lubricating oil compositions
JP4559550B2 (ja) * 1998-08-07 2010-10-06 出光興産株式会社 内燃機関用潤滑油組成物
DE60020044T3 (de) * 1999-09-21 2008-12-18 Infineum International Ltd., Abingdon Multigrad Schmiermittelzusammensetzungen für Motorgehäuse
JP5414955B2 (ja) * 1999-09-21 2014-02-12 インフィニューム インターナショナル リミテッド 潤滑油組成物
JP2006016453A (ja) * 2004-06-30 2006-01-19 Nippon Oil Corp 内燃機関用潤滑油組成物
JP5175462B2 (ja) 2006-09-04 2013-04-03 出光興産株式会社 内燃機関用潤滑油組成物
JP2010189657A (ja) * 2010-04-26 2010-09-02 Tonengeneral Sekiyu Kk 内燃機関用潤滑油組成物
JP5105557B2 (ja) * 2010-04-26 2012-12-26 東燃ゼネラル石油株式会社 内燃機関用潤滑油組成物
JPWO2014156325A1 (ja) * 2013-03-29 2017-02-16 Ｊｘエネルギー株式会社 潤滑油組成物

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Cited By (21)

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Publication number Priority date Publication date Assignee Title
US6855675B1 (en) 1995-05-24 2005-02-15 Tonengeneral Sekiyu K.K. Lubricating oil composition
EP0768366A1 (fr) * 1995-10-11 1997-04-16 Tonen Corporation Composition d'huile lubrifiante
EP0822246A2 (fr) * 1996-08-02 1998-02-04 Tonen Corporation Composition d'huile lubrifiante
EP0822246A3 (fr) * 1996-08-02 1998-04-15 Tonen Corporation Composition d'huile lubrifiante
EP0889030A1 (fr) * 1997-07-05 1999-01-07 RHEIN-CHEMIE RHEINAU GmbH Polysulfides, procédé pour leur préparation et leur utilisation
EP1027412A1 (fr) * 1997-11-12 2000-08-16 Exxon Chemical Patents Inc. Controle d'usure avec des dispersants utilisant des polymeres poly alfa-olefines
EP1027412A4 (fr) * 1997-11-12 2002-01-02 Exxonmobil Chem Patents Inc Controle d'usure avec des dispersants utilisant des polymeres poly alfa-olefines
EP1013750A3 (fr) * 1998-12-21 2000-11-15 Tonen Corporation Composition d'huile lubrifiante pour des moteurs diesel
US6207625B1 (en) 1998-12-21 2001-03-27 Tonen Corporation Lubricant oil composition for diesel engines (LAW913)
EP1013750A2 (fr) * 1998-12-21 2000-06-28 Tonen Corporation Composition d'huile lubrifiante pour des moteurs diesel
US6300291B1 (en) 1999-05-19 2001-10-09 Infineum Usa L.P. Lubricating oil composition
US8592356B2 (en) 2007-05-29 2013-11-26 Idemitsu Kosan Co., Ltd. Lubricant composition for internal combustion engine
WO2010036892A3 (fr) * 2008-09-26 2010-07-01 Greengold Lubricants, Llc Composition lubrifiante et procédés de fabrication de celle-ci
US8211329B2 (en) 2008-09-26 2012-07-03 Greengold Lubricants, Llc Lubricant composition and methods of manufacture thereof
WO2010036892A2 (fr) * 2008-09-26 2010-04-01 Greengold Lubricants, Llc Composition lubrifiante et procédés de fabrication de celle-ci
CN114555763A (zh) * 2019-07-08 2022-05-27 马来西亚国家石油公司 减少摩擦和磨损的添加剂
CN114555763B (zh) * 2019-07-08 2024-05-07 马来西亚国家石油公司 减少摩擦和磨损的添加剂
US20220259515A1 (en) * 2019-07-26 2022-08-18 Adeka Corporation Lubricating oil additive and lubricating oil composition containing same
US12006485B2 (en) * 2019-07-26 2024-06-11 Adeka Corporation Lubricating oil additive and lubricating oil composition containing same
CN111286390A (zh) * 2020-02-14 2020-06-16 中国地质大学（北京） 一种含有纳米级碳基固体添加剂的新型汽车发动机润滑油及其制备方法
CN111286390B (zh) * 2020-02-14 2021-09-28 中国地质大学（北京） 一种含有纳米级碳基固体添加剂的新型汽车发动机润滑油及其制备方法

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DE69515093D1 (de) 2000-03-23
JPH0873878A (ja) 1996-03-19
JP2971748B2 (ja) 1999-11-08
EP0699739A3 (fr) 1997-03-19
DE69515093T2 (de) 2000-07-13
EP0699739B1 (fr) 2000-02-16

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