WO1988006616A1 - Lubricating oil composition - Google Patents

Lubricating oil composition Download PDF

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Publication number
WO1988006616A1
WO1988006616A1 PCT/JP1988/000221 JP8800221W WO8806616A1 WO 1988006616 A1 WO1988006616 A1 WO 1988006616A1 JP 8800221 W JP8800221 W JP 8800221W WO 8806616 A1 WO8806616 A1 WO 8806616A1
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WO
WIPO (PCT)
Prior art keywords
lubricating oil
weight
oil
acid
oil composition
Prior art date
Application number
PCT/JP1988/000221
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
Masashi Dasai
Tsutomu Akita
Masaharu Sasaki
Original Assignee
Idemitsu Kosan Company Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Idemitsu Kosan Company Limited filed Critical Idemitsu Kosan Company Limited
Priority to DE8888902226T priority Critical patent/DE3876897T2/de
Priority to JP63502061A priority patent/JPH0696713B1/ja
Priority to KR1019880011351A priority patent/KR900005103B1/ko
Publication of WO1988006616A1 publication Critical patent/WO1988006616A1/ja

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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00Lubricating 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
    • C10M141/08Lubricating 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 sulfur-, selenium- or tellurium-containing compound
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    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32Esters
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    • C10M101/00Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02Petroleum fractions
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    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02Well-defined hydrocarbons
    • C10M105/04Well-defined hydrocarbons aliphatic
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    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
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    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68Esters
    • C10M129/72Esters of polycarboxylic acids
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    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68Esters
    • C10M129/74Esters of polyhydroxy compounds
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    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
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    • C10M129/86Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
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    • C10M133/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16Amides; Imides
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    • C10M133/52Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/56Amides; Imides
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    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20Thiols; Sulfides; Polysulfides
    • C10M135/22Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M135/24Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
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    • C10M135/20Thiols; Sulfides; Polysulfides
    • C10M135/22Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M135/26Thiols; Sulfides; Polysulfides containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
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    • C10M145/00Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/10Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
    • C10M145/14Acrylate; Methacrylate
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    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04Mixtures of base-materials and additives
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    • C10M169/04Mixtures of base-materials and additives
    • C10M169/044Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/02Well-defined aliphatic compounds
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    • C10M2203/022Well-defined aliphatic compounds saturated
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Definitions

  • the present invention relates to a lubricating oil composition and, more particularly, to a lubricating oil composition suitable for lubricating parts having a wet clutch such as an automatic transmission or a tractor or a wet brake.
  • the present invention relates to any lubricating oil composition. Background technology ''
  • Lubricants used for lubricating parts with wet clutches or wet brakes have good friction characteristics, oxidation stability, and resistance to oxidation. It is required to have performances such as corrosiveness and protection, and large transmission torque.
  • the friction characteristic refers to a ratio between a static friction coefficient and a dynamic friction coefficient, and it is required that the ratio is small and that the change due to temperature and aging is small. It has been reviewed.
  • the purpose of the present invention is to solve the above-mentioned conventional problems by adding a specific combination of compounds to the base oil, thereby reducing the transmission shock and increasing the transmission torque.
  • it is intended to provide a lubricating oil composition suitably used for lubrication of dynamic transmissions and the like.
  • the present invention relates to a method wherein the base oil comprises (A) an alkyl succinate ester and / or an alkyl succinate ester.
  • the lubricating oil composition of the present invention has a low friction characteristic, that is, a static friction coefficient Z, a low dynamic friction coefficient, and a small shock due to gear shifting.
  • a static friction coefficient Z a low dynamic friction coefficient
  • a small shock due to gear shifting a small shock due to gear shifting.
  • the change in friction characteristics due to oil temperature is small, and the change over time is also small. Therefore, it can be adequately adapted to downsizing of transmissions and the like.
  • FIG. 1 and 3 show ⁇ in each case up to 2 DQ0 cycles in the examples and comparative examples. / ⁇ 12. .
  • FIG. 2 is a graph showing the change with time, and FIG. 2 is a graph showing the change with temperature.
  • the base oil used in the present invention is a main component of a lubricating oil composition, and various mineral oils and oils or synthetic oils that are used in ordinary lubricating oils are used. You can do it.
  • the viscosity of the base oil is preferably 1.5 to 30 cSt at 100: 100, especially for the automatic transmission oil and the wet brake of the agricultural tractor. When used as grease oil, 2 to 20 cSt is preferred.
  • base oils are as follows: Mineral oils are 60 neutral oils obtained by solvent refining or hydrorefining, 100 neutral oils, and 150 neutral oils. Oil, 300-neutral oil, 500-neutral oil, etc.
  • synthetic oils such as polyolefins and Coal ester, dibasic acid ester, polyester, phosphoric acid ester, silicone oil, alkylbenzen, alkylgif
  • synthetic oils such as polyolefins and Coal ester, dibasic acid ester, polyester, phosphoric acid ester, silicone oil, alkylbenzen, alkylgif
  • the sulfur content is Q. Less than 5% by weight, more preferably less than Q.1% by weight, particularly preferably less than 100 PPm can be used.
  • the sulfur content exceeds Q.5% by weight because the oxidation stability decreases.
  • Mineral oil can also be used at low pour points.
  • the pour point is less than or equal to -15, more preferably less than or equal to 25 t, especially preferably less than or equal to 35. This is because the friction characteristics are further improved and the restriction on the operating temperature range is relaxed.
  • Mineral oil has an aromatic hydrocarbon content (% CA) of 20 or less, more preferably 10 or less, a total acid value of Q.
  • ImsKOH / g or less, and preferably 0.05 m 0 H Preferred conditions are / g or less.
  • the material obtained in this way can be obtained by further deepening the material.
  • the distillate refers to a crude oil obtained by distillation under normal pressure or a residue obtained by distilling the residual oil of normal pressure under reduced pressure. Although there is no particular limitation on the purification method, it can be obtained by performing any of the following 1 to 5.
  • a crude lubricating oil raw material is prepared from raffinic crude oil or intermediate base crude oil by an ordinary method and subjected to severe hydrotreating. By this treatment, a component that is not desirable in a lubricating oil fraction such as an aromatic component is removed, or a reaction is performed to convert the component into an effective component. At this time, most of sulfur and nitrogen are also removed.
  • fractional distillation is performed to obtain the required viscosity by distillation under reduced pressure.
  • a known solvent removal is carried out to remove the pour point of the usual paraffin-based oil, that is to say around -15 lOt.
  • This treatment employs a solvent removal method under severe conditions.
  • a zeolite catalyst is used, and the raffin (mainly normanorufin) adsorbed in the pores of the catalyst is used.
  • a method of catalytic hydrogenation is used to remove any that can be selectively decomposed in a hydrogen atmosphere.
  • the hydrogen pressure 5 ⁇ 300 kg / cm 2
  • the amount of hydrogen introduced (per feed distillate per unit) 30 to 3000 Nm 3 , preferably 100 to 2000 Nm 3 .
  • the catalyst used in this case is a carrier such as aluminum, silica, silica, alumina, zeolite, activated carbon, and voxyite.
  • Use metals such as Group VI and Group VI of the Periodic Table, preferably Kontor, Nickel, Moribden, Tungsten, etc.
  • the catalyst component supported by a known method is used.
  • the catalyst is pre-sulfurized in advance.
  • the distillate is subjected to various treatments after being subjected to the hydrotreatment, but when the distillate is subjected to the second or third stage of the hydrogenation treatment,
  • the hydrotreating conditions may be set within the above range, and the conditions in the first to third stages may be the same or different. However, usually, the conditions are more strictly applied to the second stage than the first stage, and to the third stage rather than the second stage.
  • the alkaline distillation is performed as a process to improve the stability of the distillate by removing a trace amount of acidic substances, and the pressure is reduced by adding an alcohol such as NaOH or KOH. This is done by distillation.
  • Sulfuric acid washing is generally performed as a finishing step for petroleum products, and includes aromatic hydrocarbons, especially polycyclic aromatic hydrocarbon olefins, It is applied to improve the properties of distillate oil by removing sulfur compounds.
  • Q ⁇ 5 to 5% by weight of concentrated sulfuric acid is added to the treated oil and the treatment is performed at a temperature of room temperature to 60 ° C. Sum up.
  • the properties of the distillate obtained by the above treatment are as follows.
  • the kinematic viscosity is 1.5 to 30 cSc (at 100), the sulfur content is less than 0.5 wt%, and the pour point is below -15. It has an aromatic hydrocarbon content (% C A ) of about 20% or less and a total acid value of 0.1 lmsKQH / g or less.
  • synthetic oils polyolefins and condensed and / or Z or non-condensed ring saturated hydrocarbons are preferred.
  • saturated hydrocarbons there are various types of such saturated hydrocarbons, and in particular, saturated hydrocarbons having a cyclohexyl group and a z or decalyl group. And those having 1 to 40 carbon atoms (! To 40.
  • specific examples of the saturated hydrocarbon having a cyclohexyl group and / or a dextrin group include: 2 — methyl 2, 4 — dicyclohexylpentanine; cyclohexylmethyldecalin; 11 (methyldecalyl) 2,4-Dicyclohexylbentan; disodecylcyclohexane, and the like.
  • the base oil may be added with a viscosity index improver, corrosion inhibitor, etc., if necessary.
  • an alkenyl succinate ester / or an alkyl succinate ester is used as the component (A).
  • Alkenyl succinate ester or alkyl succinate as the succinic acid ester, those represented by the following general formula [I] can be particularly effectively used.
  • R 1 is an alkyl group or an alkyl group having 6 to 30 carbon atoms, preferably 12 to 24 carbon atoms.
  • R 2 and R 3 are hydrogen, an alkyl group having 1 to 20 carbon atoms, and a hydroxyalkyl group having 1 to 20 carbon atoms.
  • R 4 is an alkylene group having 1 to 4 carbon atoms
  • R 5 is an alkyl group having 1 to 20 carbon atoms or a hydroxy-substituted product thereof
  • n is an integer of 0 to 6
  • X is 1 or 2.
  • R 2 and R 3 are the same even if the same level is different, but a good level is excluded when both R 2 and R 3 are hydrogen.
  • alkenyl succinate esters and alkyl succinate esters include octadecenyl succinate monomethyl ester. Ter, octadecenyl dimethyl succinate, octadecenyl monosuccinate, octadecenyl succinate Dioctylester octarate, octadecane Monooctyl ester octyl octyl octanoate, octyl decyl ester octyl octyl octyl acrylate, octadecenyl monooctyl octyl succinate, octa octyl ester Dinonylester decenyl succinate, Monolauryl ester octadecenyl succinate, Octadecenyl succinate, Dilaurate succinate Lilester, monolau
  • the component (A) there is any one of an alkyl succinate ester and an alkyl succinate ester. Alternatively, these mixtures are added, but the amount of added calories differs depending on the properties of the intended lubricating oil composition and cannot be uniquely determined. However, it is usually from Q.05 to 5.0% by weight, preferably from 0.1 to 3.0% by weight. If the amount is less than Q.05% by weight, a sufficient effect cannot be obtained, and if it exceeds 5.0% by weight, the oxidation stability deteriorates, so that it is not preferable.
  • a fatty acid ester of a polyhydric alcohol is used as the component (B).
  • the polyvalent alcohols are glycerin, trimethylolpropane, and benzene: 3 slits, solvit. Glycerin is particularly preferred.
  • fatty acids having 8 to 30 carbon atoms are available.
  • fatty acids include belargonic acid, rauric acid, palmitic acid, stearic acid, behenic acid, pendecylenic acid, and oleic acid. Acid, linoleic acid, linolenic acid, etc.
  • esters include monoglyceride monooleate, diglyceride oleate, and monoglymate stearate. Examples include partial esters of polyhydric alcohols such as cerides and diglyceride stearate.
  • the amount of the component (B) is about 0.05 to 5% by weight, preferably 0.01 to 3% by weight. Q. If the amount is less than 0.05% by weight, the friction characteristics cannot be improved to + minutes. on the other hand,
  • the lubricating oil composition of the present invention is basically obtained by blending the above components (A) and (B) with a base oil.
  • An acid amide or a boron derivative thereof can be added to improve the physical properties of all.
  • the acid amide is obtained by the reaction of a carboxylic acid having 12 to 30 carbon atoms with an amine compound, and thus, specifically, isostearic acid. Or oleic acid, and tetraethylamine, triethylenetetramine, tetraethylenepentamine, hexaethylene Examples of the reaction product with benzylamine are listed.
  • acid amide also includes a reaction product of an acid amide with a boron compound (boric acid, borate, borate ester). More specifically, boric acid is further added to the above-mentioned acid amide, for example, the reaction product of isostearic acid and tetraethylenpentamicin. You can list what you got from the reaction.
  • the amount added is from 0.01 to 10% by weight, preferably from 0.05 to 3% by weight. If the amount is less than 0.01% by weight, a sufficient effect of improving the frictional properties and the effect of cleaning and dispersing cannot be obtained. On the other hand, if the amount exceeds 10% by weight, the static friction coefficient decreases and the transmission torque decreases. Is not desirable because it becomes smaller.
  • an antioxidant for example, an antioxidant, a fining dispersant, a viscosity index improver, and the like can be appropriately added.
  • the antioxidant generally used compounds such as phenol compounds, amine compounds, and zinc dithiophosphate may be used.
  • the amount added is 0.01 to 3% by weight, preferably 0.05 to 2% by weight. If the content is less than 1% by weight, there will be no effect. No significant improvement is observed.
  • ashless detergents and metal detergents can be used as detergent dispersants.
  • alkenyl quinoimide imide, sulfonate, and finate are preferred, for example, polybutenyl octamate imidium, calcium sulfo imide, and the like.
  • Net Norium Surnet, Calumium Finite, Norimu Finete, Calum Salicitate, etc. It is mentioned.
  • the addition amount is 0.1 to 10% by weight, preferably 0.5 to 5% by weight. If it is less than 0.1% by weight, the dispersibility is insufficient, and if it exceeds 10% by weight, the frictional characteristics are undesirably deteriorated.
  • the viscosity index improver there is no particular limitation on the viscosity index improver, but it is possible to use a polymer atalylate, an aged refin copolymer, or the like.
  • a polymethacrylate having a molecular weight of 100,000 or less, preferably 50,000 or less, which has excellent shear stability and can prevent a change in viscosity for a long period of time is suitable.
  • the amount added is 0.5 to 15% by weight, preferably 2 to 10% by weight. Q. If the amount is less than 5% by weight, no improvement in viscosity-temperature characteristics is observed. If the amount is more than 15% by weight, a low-viscosity base oil is used, resulting in a decrease in wear resistance and the like. Nare, 0
  • Mineral oil I having a kinematic viscosity of 5 cSt and a sulfur content of 200 ppm in 1 Q0 t as a base oil and a polymethacrylate (molecular weight 42,000) 4.0% by weight
  • Table 1 shows the base oil to which 4.0% by weight of libbutenyl succinic acid imid (boribitol base molecular weight 1 QQ 0) and 0.5% by weight of acid amide were added. A predetermined amount of the compound was added to obtain a lubricating oil composition.
  • the obtained lubricating oil composition was tested by the following method.
  • Oil temperature 50, 8o, loo, 120
  • the dynamic friction coefficient at a rotational speed of 1200 rpm under the above experimental conditions was 12 . 0 , ⁇ is the static friction coefficient when stopping. Measured as. / ⁇ 2. . was calculated. This ⁇ . / ⁇ i 2 . .
  • the frictional characteristics were evaluated by measuring the time-dependent changes and temperature changes of the values.
  • the lubricating oil compositions shown in Table 1 were prepared in the same manner as in Examples 1-2 and Comparative Examples 1-2, except that mineral oil II having the following properties was used as the base oil. And tested. ⁇ at each time up to 2000 cycles. / ⁇ 12. . Fig. 3 shows the time-dependent changes of. Table 1 shows the results of the durability test and the temperature dependency test. Properties of Mineral Oil II
  • the lubricating oil compositions shown in Table 1 were tested in the same manner as in Examples 1 and 2 and Comparative Examples 1 and 2. Table 1 shows the results of the durability test and temperature dependence test.
  • the polymer acrylate molecular weight
  • the polybutenyl succinate imid polybutyl group molecular weight: 1,000
  • 0.5% by weight of acid amide Power 0.5% by weight of acid amide Power.
  • Type A A 2 A 3 B 2 200 2000 50 "C 120 * C
  • Synthetic oil IV 2 — Methyl 2,4 — Dicyclohexylbentan (Kinematic viscosity at 100 ° C 3.7 cSt)
  • the lubricating oil composition of the present invention has a lubricating oil for an automatic transmission, a wet clutch such as a tractor, or a wet brake. It is extremely effective as a lubricating oil for all parts.
  • composition having such properties is used for lubricating oils such as shock absorbers, power steering, hydraulic suspensions, and the like. It is also effective as a dual-purpose oil for multiple purposes.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)
PCT/JP1988/000221 1987-03-02 1988-02-29 Lubricating oil composition WO1988006616A1 (en)

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DE8888902226T DE3876897T2 (de) 1987-03-02 1988-02-29 Schmieroelzusammensetzung.
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Cited By (2)

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JP2777750B2 (ja) * 1990-07-31 1998-07-23 エクソン・ケミカル・パテンツ・インク 内燃機関の燃料の経済性を改善するための、アミン/アミド及びエステル/アルコール摩擦緩和剤の相乗性ブレンド
JP2000219888A (ja) * 1999-02-02 2000-08-08 Idemitsu Kosan Co Ltd 潤滑油組成物

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EP0373454A1 (en) * 1988-12-08 1990-06-20 Idemitsu Kosan Company Limited Lubricating oil composition for power control
JP2602102B2 (ja) * 1989-09-20 1997-04-23 日本石油株式会社 内燃機関用潤滑油組成物
EP0454395B1 (en) * 1990-04-23 1996-05-29 Ethyl Petroleum Additives, Inc. Automatic transmission fluids and additives therefor
DE69102217T2 (de) * 1990-07-09 1994-09-15 Texaco Development Corp Verwendung von einem besonderen Ester.
US5282990A (en) * 1990-07-31 1994-02-01 Exxon Chemical Patents Inc. Synergistic blend of amine/amide and ester/alcohol friction modifying agents for improved fuel economy of an internal combustion engine
KR100240365B1 (ko) * 1993-12-20 2000-01-15 만셀 케이쓰 로드니 유성 조성물의 마찰 내구성을 개선시키는 방법, 이에 사용되는 조성물 및 첨가제 농축물
EP0856042B9 (en) * 1995-10-18 2011-12-21 Infineum USA L.P. Automatic transmission with an automatic transmission fluid of improved friction durability
US5750476A (en) * 1995-10-18 1998-05-12 Exxon Chemical Patents Inc. Power transmitting fluids with improved anti-shudder durability

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JP2000219888A (ja) * 1999-02-02 2000-08-08 Idemitsu Kosan Co Ltd 潤滑油組成物

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KR900005103B1 (ko) 1990-07-19
JPH0696713B1 (pt) 1994-11-30
DE3876897D1 (de) 1993-02-04
DE3876897T2 (de) 1993-06-03
EP0305538B1 (en) 1992-12-23
EP0305538A1 (en) 1989-03-08
EP0305538A4 (en) 1989-08-16

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