EP1299509B1 - Friction modifier additive combination - Google Patents
Friction modifier additive combination Download PDFInfo
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- EP1299509B1 EP1299509B1 EP01949345A EP01949345A EP1299509B1 EP 1299509 B1 EP1299509 B1 EP 1299509B1 EP 01949345 A EP01949345 A EP 01949345A EP 01949345 A EP01949345 A EP 01949345A EP 1299509 B1 EP1299509 B1 EP 1299509B1
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- fatty
- amine
- oil
- carbon atoms
- lubricant formulation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M133/10—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms cycloaliphatic
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/10—Macromolecular 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
- C10M145/12—Macromolecular 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
- C10M145/14—Acrylate; Methacrylate
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular 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 type
- C10M2209/084—Acrylate; Methacrylate
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/044—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms having cycloaliphatic groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/08—Amides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/08—Amides
- C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/26—Amines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
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- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
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- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
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- 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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
Definitions
- This invention relates to a combination of additives that provides friction modifier benefits to lubricants and functional fluids, especially to power transmission fluids such as gear oils, automatic transmission fluids and fluids for continually variable transmissions.
- ATF automatic transmission fluid
- All ATFs should possess high oxidation stability, good viscometrics and low temperature properties, as well as good corrosion protection, anti-foaming and air separation properties.
- the friction properties measured by friction coefficients displayed in a graph, are key to providing satisfactory performance.
- the friction property of the ATF must be balanced such that there is sufficient friction to provide adequate power transmission whilst minimising shudder both on start up of the engine (the so called “green shudder”) and over the lifetime of the ATF. Excessive shudder causes driver discomfort and gives rise to an unacceptable noise level.
- the Original Equipment Manufacturer (hereafter "OEM”) specifies a minimum friction coefficient at a plate sliding speed of 5 rpm of 0.123 to provide the necessary power transmission to the axle, together with the requirement that the friction coefficient does not decrease with increasing plate sliding speed, ie the gradient of the curve in the graph of friction coefficient against increasing sliding speed is positive or zero; it must not be negative.
- the latter requirements is to minimise green shudder to an acceptable time period of no more than 0.2 hours (12 minutes).
- the ATF will function without noticeable shudder (once any green shudder has ceased) for at least 150,000 km o f automotive transmission operation.
- the minimum hours according to the Zahnradfarbik Friedrichschafen (hereafter "ZF”) ec3 test as defined is in the region of >100 hours.
- ATFs used hitherto containing conventional friction modifiers do not meet these requirements.
- FM friction modifiers
- ETHOMEEN® T-12 a tallow amine supplied by AKZO Chemicals, when incorporated in an ATF formulation at a treat level of 0.15% by wt. does not always meet the requirement for friction coefficient vs. sliding speed (0.123 at 5 rpm) and never achieves a durability of >100 hours.
- Prior published EP-A-0 713 908 describes an oil-based power transmission fluid composition, especially ATFs which contains inter alia at least one oil-soluble friction modifier which may be selected from aliphatic amines, aliphatic fatty acid amides, aliphatic carboxylic acids, aliphatic carboxylic esters, aliphatic carboxylic ester amides, aliphatic phosphonates, aliphatic phosphates, aliphatic thiophosphates and aliphatic thiophosphates etc wherein the aliphatic group contains more than 8 carbon atoms to render the compound suitably oil soluble.
- ATFs which contains inter alia at least one oil-soluble friction modifier which may be selected from aliphatic amines, aliphatic fatty acid amides, aliphatic carboxylic acids, aliphatic carboxylic esters, aliphatic carboxylic ester amides, aliphatic phosphonates, aliphatic phosphates, ali
- compositions of this invention are said to have the capability of exhibiting a positive slope in the plot of coefficient of friction versus sliding speed in the low speed SAE No. 2 Friction Test when performed with Ford Engineering Material Specification WSP-M2CZAA-A. Also, in clutch friction durability tests performed using the above method involving 20,000 cycles, the following results were achieved: ⁇ D in the range of 0.130-0.170; ⁇ S values (at 0.25 seconds) in the range of 0.110-0.155; low speed dynamic friction values in the range of 0.130-0.170; S1/D values in the range of 0.90-1.16; and stop times, in seconds, in the range of 0.70-1.0. It would be evident to those skilled in the art that this SAE-test cannot be read across for European OEMs, and hence it is not suitable for European design because it is a laboratory test rig which did not produce the specific results initially and, therefore, had to be abandoned.
- WO 99/02628 discloses friction modifiers including alkoxylated amines and a polyamide compound which is the reaction product of a polyamine containing from 2 to 60 total carbon atoms and from 3 to 15 nitrogen atoms with at least one of the nitrogen atoms present in the form of a primary amine group and at least two of the remaining nitrogen atoms present in the form of primary or secondary amine group and a carboxylic anhydride.
- EP 0748862 relates to lubrication composition, that may be used as automatic or manual transmission fluid, comprising a major amount of an oil of lubricating viscosity and at least one metal free thiophosphorus acid ester, at least one amine salt of the thiophosphorus acid ester, or a mixture thereof, wherein the metal free thiophosphorus acid ester contains at least one hydrocarbyl terminated oxyalkylene group, at least one hydrocarbyl terminated polyoxyalkylene group, or a mixture thereof.
- EP 812900 discloses a lubricating oil composition for automatic transmission comprising a sulfur-containing antioxidant or an amine type antioxidant, a phosphate or its amine salt and a reaction product of a carboxylic acid and an amine wherein the amine type antioxidant is chosen from alkylarylamines.
- WO 97/04049 discloses a friction modifier including an alkoxylated amine and a polyamide which is the reaction product of a carboxylic acids or anhydride with a polyamine containing from 2 to 60 total carbon atoms and from 3 to 15 nitrogen atoms with at least one of the nitrogen atom present in the form of a primary amine group and at least two of the remaining nitrogen atoms present in the form of primary or secondary amine groups.
- the present invention provides a friction modifier additive combination comprising (a) an oil-soluble fatty amine compound and (b) an oil-soluble fatty amide compound.
- the fatty amine compound is a tertiary amine compound, of formula (I) below: wherein:
- the substituent group R is suitably an alkyl group containing from 10 to 18 carbon atoms, preferably from 12 to 14 carbon atoms.
- the substituent group R is suitably derived from a fatty acid which is usually a naturally occurring substance and therefore may contain a mixture of carbon chain lengths, in which case the average chain length of the substituent group R is more preferably within the carbon atom ranges specified above.
- the substituent groups R 1 and R 2 are each independently an alkylene group as stated above and these groups suitably have 1 to 4 carbon atoms, most preferably 2 carbon atoms such as eg a -CH 2 -CH 2 - grouping.
- the groupings -R 1 O- and -R 2 O- are preferably oxyethylene groups and correspondingly -R 1 OH and -R 2 OH are ethylenehydroxy groups.
- the number of oxyalkylene groups represented by x and y are each independently suitably 0, 1 or 2 and are preferably 0.
- Suitable fatty amine compounds include a coco-bis(2-hydroxyethyl)amine, a polyoxyethylene(5)coco-amine, a tallow-bis(2-hydroxyethyl)amine, a polyoxyethylene(5)tallow amine, a tallow/oleyl-bis(2-hydroxyethyl)amaine and an oleyl-bis- (2-hydroxyethyl)amine.
- Such compounds are commercially available from eg AKZO Chemicals.
- Particularly preferred are compounds such as eg the coco-bis(2-hydroxyethyl)amine (ETOMEEN® C/12) which contains a mixture of C 8 to C 18 alkyl groups, with C 12 groups predominating sold by Akzo Chemicals.
- the fatty amide compound is a tertiary amide of the formula (II) wherein R, R 1 , R 2 , x and y are each independently as defined above for formula (I), both in respect of general and preferred embodiments.
- Suitable fatty amide compounds include the compound polyoxyethylene(5)oleamide sold under the trade name ETHOMID® 0/15 (ex Akzo Chemicals) which contains a mixture of C 12 to C 18 alkyl groups predominating in C 18 groups; and a fatty acid amide derived from lauric acid sold as COMPERLAN® LD (ex Henkel).
- the friction modifier additive combination according to the present invention comprises a mixture of (a) a bis(hydroxyethyl) fatty amine wherein the fatty group comprises an alkyl group which has 12 to 14 carbon atoms and (b) a bis(hydroxyethyl) fatty amide wherein the fatty group comprises an alkyl group which has 12 to 18 carbon atoms.
- the present invention provides a lubricant or functional fluid formulation comprising a major amount of base oil of lubricating viscosity and a minor amount of a friction modifier additive combination as defined above.
- the lubricant or functional fluid is suitably useable as a power transmission fluid, preferably as an automatic transmission fluid (ATF).
- ATF automatic transmission fluid
- the following description will focus on ATF formulations although it will be understood that the compositions of the present invention are not limited to such fluids but embraces within its scope other lubricant and functional fluids.
- ATFs typically have a kinematic viscosity at 100°C (KV 100 ) ranging from 2-15 mm 2 /s, preferably from 4-10 mm 2 /s, more preferably from 5-8 mm 2 /s measured according to the standard test procedure of ASTM D-446.
- the Brookfield viscosity at - 40°C is suitably less than 50,000 mPa s, preferably from 4,000-20,000 mPa s, and more preferably from 5,000-18,000 mPa s measured according to the standard test procedure of ASTM D-2983.
- the viscosity index is suitably in the range from 100-200, preferably from 150-200 measured according to the standard test procedure of ASTM D-2270.
- the amount of base oil contained in the ATF ranges from 50% by weight to 99.9%, suitably from 60-95% by weight and preferably from 70-90% by wt, based on the total weight of the ATF formulation.
- the amount of friction modifier additive combination present in the ATF formulation (ie the total amount of fatty amine and fatty amide) is broadly in the range from 0.05-1.2% by weight. Within this range the specific amount used will depend not only upon the friction properties desired but also, at least to some extent, upon the design of the automatic transmission. Thus the amount of friction modifier additive combination used is suitably in the range from 0.1-1% by weight, preferably from 0.2-0.8% by weight and more preferably from 0.3-0.6% by weight.
- the amount of fatty amine compound in this friction modifier additive combination is suitably in the range from 0.03-1.0% by weight, preferably from 0.05-0.8% by weight and more preferably from 0.1-0.6% by weight.
- the fatty amide compound in the additive combination is suitably from 0.05-0.8% by weight, preferably from 0.05-0.5% by weight and more preferably from 0.08-0.3% by weight.
- the weight ratio of the fatty amine to fatty amide in the additive combination is suitably in the range from 0.5:1 to 10:1, preferably from 1:1 to 8:1 and more preferably from 2:1 to 6:1.
- the amounts of the fatty amine and fatty amide in the additive combination are with respect to the active ingredients in such compounds.
- the compounds specified above are generally liquids at room temperature and within conventional lubricant additive handling and blending temperatures, and are therefore usually supplied and used in neat, 100% active ingredient form. However, if desired, they may be diluted with a solvent, such as eg mineral oil, which is inert under the conditions especially with respect to the performance of the lubricant.
- the base oil of the ATF or other lubricant or functional fluid according to the invention may be a mineral oil, a synthetic oil or mixtures thereof.
- the base oils are suitably selected from refined mineral oils, for example, a solvent refined and/or hydrotreated oils, oils derived from coal tar or shale, vegetable oils, animal oils, hydrocracked oils, hydroisomerised oils, poly-alphaolefins (PAO), esters, alkylbenzenes, polyglycols, alkylene oxide polymers, silicone oils and the like.
- the base oil comprises a mineral oil
- it is suitably a solvent refined and/or hydrotreated oil.
- suitable oils of this type include inter alia solvent refined mineral oils in the range of 50N to 150N, preferably 80N to 130N.
- Such mineral oils are available, for example, from Esso under the trade name Esso Solvent Neutral.
- the base oil is a severely refined mineral oil such as eg white oil
- these may be one of the varieties supplied by Esso under the trade names MARCOL® 52 and 172, PRIMOL® 352, PLASTOL® 135 and 352, and BAYOL® 52.
- the base oils used may also be a hydrocracked or hydroisomerised oils such as eg a hydroisomerised paraffin.
- the base oil is a synthetic oil
- it is preferably a PAO produced by the oligomerisation of 1-alkenes which suitably contain 6-20 carbon atoms, preferably 8-14 carbon atoms.
- PAOs produced from 1-decene are particularly preferred.
- the KV 100 of the PAO selected is usually determined by the viscosity desired in the final lubricant formulation and is suitably in the range from 2-8mm 2 /s, preferably from 4-6mm 2 /s.
- Such PAOs are commercially available eg from ExxonMobil.
- the base oil is a mix of mineral oils and synthetic oils, eg a mixture of one or more solvent refined mineral oils with PAOs; or a mixture of solvent refined mineral oil with white oil, a hydrocracked oil or a hydroisomerised oil as stated above.
- the base oil is a mixture of solvent refined mineral oil, a PAO and white oil.
- the functional fluid formulations of the present invention may also contain other optional additives depending upon the intended use of the functional fluid.
- additives include inter alia viscosity index improvers, pour point depressants, antioxidants, anti-wear agents, extreme pressure additives, dispersants, detergents, corrosion inhibitors, erosion inhibitors, anti-foaming agents, seal swell conditioning agents (seal fix), anti-pitting agents and the like.
- Such additives are all commercially available, the choice of one or more of these and the amounts of each used depending upon the intended end use of the functional fluid.
- a viscosity index improver would typically be included in the functional fluids at a treat level of 2-15% by weight based on active ingredient (ie excluding solvent and carrier fluids, if any), preferably from 2-10% by weight, and the other additives would typically be included in the functional fluids at a treat level of 0.01-5% by weight based on active ingredient.
- the optional additives recited above may be added individually to the base oil, or, two or more may be pre-mixed with a carrier fluid such as eg a mineral oil, to form an additive concentrate and can then be blended with the base oil.
- a carrier fluid such as eg a mineral oil
- the friction modifier additive combination according to the invention may also be pre-mixed with or without other additives into an additive concentrate.
- the friction modifier additive combination and lubricating oil formulations produced therefrom are particularly effective when used in automatic transmission fluids, especially for automatic transmissions equipped with an electronically controlled converter clutch.
- Tests 1-4 above passed the Electronically controlled converter clutch (ECCC) tests on the Mannesmann Sachs (MS) German for Geregelte Wandlerkupplung (hereafter "GWK").
- ECCC Electronically controlled converter clutch
- MS Mannesmann Sachs
- GWK Garnier Wandlerkupplung
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Abstract
Description
- This invention relates to a combination of additives that provides friction modifier benefits to lubricants and functional fluids, especially to power transmission fluids such as gear oils, automatic transmission fluids and fluids for continually variable transmissions.
- Power transmissions for automotive vehicles, for example automatic transmissions, are being continually developed to improve their performance. There is a new generation of automatic transmissions currently being produced which are equipped with an electronically controlled converter clutch (hereafter "ec3"). The design provides a more compact and lighter automatic transmission that enables together with the ec3 a fuel saving of up to 10% and exhibits superior shift comfort.
- The new automatic transmission designs place higher demands on the automatic transmission fluid (hereafter "ATF"). All ATFs should possess high oxidation stability, good viscometrics and low temperature properties, as well as good corrosion protection, anti-foaming and air separation properties. In addition, the friction properties, measured by friction coefficients displayed in a graph, are key to providing satisfactory performance. The friction property of the ATF must be balanced such that there is sufficient friction to provide adequate power transmission whilst minimising shudder both on start up of the engine (the so called "green shudder") and over the lifetime of the ATF. Excessive shudder causes driver discomfort and gives rise to an unacceptable noise level.
- For the recently developed automatic transmissions equipped with an electronically controlled converter clutch, these friction requirements are even more demanding. Typically, the Original Equipment Manufacturer (hereafter "OEM") specifies a minimum friction coefficient at a plate sliding speed of 5 rpm of 0.123 to provide the necessary power transmission to the axle, together with the requirement that the friction coefficient does not decrease with increasing plate sliding speed, ie the gradient of the curve in the graph of friction coefficient against increasing sliding speed is positive or zero; it must not be negative. The latter requirements is to minimise green shudder to an acceptable time period of no more than 0.2 hours (12 minutes). Furthermore, it is preferred that the ATF will function without noticeable shudder (once any green shudder has ceased) for at least 150,000 km o f automotive transmission operation. The minimum hours according to the Zahnradfarbik Friedrichschafen (hereafter "ZF") ec3 test as defined is in the region of >100 hours.
- ATFs used hitherto containing conventional friction modifiers (hereafter "FM"), such as fatty acids, fatty amines and fatty alcohols, do not meet these requirements. For example, ETHOMEEN® T-12, a tallow amine supplied by AKZO Chemicals, when incorporated in an ATF formulation at a treat level of 0.15% by wt. does not always meet the requirement for friction coefficient vs. sliding speed (0.123 at 5 rpm) and never achieves a durability of >100 hours.
- Prior published EP-A-0 713 908 describes an oil-based power transmission fluid composition, especially ATFs which contains inter alia at least one oil-soluble friction modifier which may be selected from aliphatic amines, aliphatic fatty acid amides, aliphatic carboxylic acids, aliphatic carboxylic esters, aliphatic carboxylic ester amides, aliphatic phosphonates, aliphatic phosphates, aliphatic thiophosphates and aliphatic thiophosphates etc wherein the aliphatic group contains more than 8 carbon atoms to render the compound suitably oil soluble. The compositions of this invention are said to have the capability of exhibiting a positive slope in the plot of coefficient of friction versus sliding speed in the low speed SAE No. 2 Friction Test when performed with Ford Engineering Material Specification WSP-M2CZAA-A. Also, in clutch friction durability tests performed using the above method involving 20,000 cycles, the following results were achieved: µD in the range of 0.130-0.170; µS values (at 0.25 seconds) in the range of 0.110-0.155; low speed dynamic friction values in the range of 0.130-0.170; S1/D values in the range of 0.90-1.16; and stop times, in seconds, in the range of 0.70-1.0. It would be evident to those skilled in the art that this SAE-test cannot be read across for European OEMs, and hence it is not suitable for European design because it is a laboratory test rig which did not produce the specific results initially and, therefore, had to be abandoned.
- WO 99/02628 discloses friction modifiers including alkoxylated amines and a polyamide compound which is the reaction product of a polyamine containing from 2 to 60 total carbon atoms and from 3 to 15 nitrogen atoms with at least one of the nitrogen atoms present in the form of a primary amine group and at least two of the remaining nitrogen atoms present in the form of primary or secondary amine group and a carboxylic anhydride.
- EP 0748862 relates to lubrication composition, that may be used as automatic or manual transmission fluid, comprising a major amount of an oil of lubricating viscosity and at least one metal free thiophosphorus acid ester, at least one amine salt of the thiophosphorus acid ester, or a mixture thereof, wherein the metal free thiophosphorus acid ester contains at least one hydrocarbyl terminated oxyalkylene group, at least one hydrocarbyl terminated polyoxyalkylene group, or a mixture thereof. EP 812900 discloses a lubricating oil composition for automatic transmission comprising a sulfur-containing antioxidant or an amine type antioxidant, a phosphate or its amine salt and a reaction product of a carboxylic acid and an amine wherein the amine type antioxidant is chosen from alkylarylamines. WO 97/04049 discloses a friction modifier including an alkoxylated amine and a polyamide which is the reaction product of a carboxylic acids or anhydride with a polyamine containing from 2 to 60 total carbon atoms and from 3 to 15 nitrogen atoms with at least one of the nitrogen atom present in the form of a primary amine group and at least two of the remaining nitrogen atoms present in the form of primary or secondary amine groups.
- The present invention provides a friction modifier additive combination comprising (a) an oil-soluble fatty amine compound and (b) an oil-soluble fatty amide compound.
- It has been found that by combining a fatty amine with a fatty amide, the friction properties of a lubricant or functional fluid containing the same are improved. For example, by formulating an ATF using the amine/amide friction modifier combination of the present invention it is possible to achieve a friction coefficient at 5 rpm of at least 0.123 together with a positive or zero gradient in the graph of friction coefficient versus sliding speed. After the end of the green shudder, if any, the ATF can operate for 150 hours or more before the onset of shudder.
-
- R is an alkyl group containing from 8 to 24 carbon atoms or any aryl group containing one or more alkyl substituents containing from 8 to 24 carbon atoms;
- R1 and R2 are each independently an alkylene group containing from 1-8 carbon atoms; and x and y are each independently 0 or an integer from 1 to 5.
-
- The substituent group R is suitably an alkyl group containing from 10 to 18 carbon atoms, preferably from 12 to 14 carbon atoms. The substituent group R is suitably derived from a fatty acid which is usually a naturally occurring substance and therefore may contain a mixture of carbon chain lengths, in which case the average chain length of the substituent group R is more preferably within the carbon atom ranges specified above.
- The substituent groups R1 and R2 are each independently an alkylene group as stated above and these groups suitably have 1 to 4 carbon atoms, most preferably 2 carbon atoms such as eg a -CH2-CH2- grouping. The groupings -R1O- and -R2O- are preferably oxyethylene groups and correspondingly -R1OH and -R2OH are ethylenehydroxy groups.
- The number of oxyalkylene groups represented by x and y are each independently suitably 0, 1 or 2 and are preferably 0.
- Specific examples of suitable fatty amine compounds include a coco-bis(2-hydroxyethyl)amine, a polyoxyethylene(5)coco-amine, a tallow-bis(2-hydroxyethyl)amine, a polyoxyethylene(5)tallow amine, a tallow/oleyl-bis(2-hydroxyethyl)amaine and an oleyl-bis- (2-hydroxyethyl)amine. Such compounds are commercially available from eg AKZO Chemicals. Particularly preferred are compounds such as eg the coco-bis(2-hydroxyethyl)amine (ETOMEEN® C/12) which contains a mixture of C8 to C18 alkyl groups, with C12 groups predominating sold by Akzo Chemicals.
-
- Specific examples of suitable fatty amide compounds include the compound polyoxyethylene(5)oleamide sold under the trade name ETHOMID® 0/15 (ex Akzo Chemicals) which contains a mixture of C12 to C18 alkyl groups predominating in C18 groups; and a fatty acid amide derived from lauric acid sold as COMPERLAN® LD (ex Henkel).
- In a preferred embodiment, the friction modifier additive combination according to the present invention comprises a mixture of (a) a bis(hydroxyethyl) fatty amine wherein the fatty group comprises an alkyl group which has 12 to 14 carbon atoms and (b) a bis(hydroxyethyl) fatty amide wherein the fatty group comprises an alkyl group which has 12 to 18 carbon atoms.
- In another embodiment, the present invention provides a lubricant or functional fluid formulation comprising a major amount of base oil of lubricating viscosity and a minor amount of a friction modifier additive combination as defined above. The lubricant or functional fluid is suitably useable as a power transmission fluid, preferably as an automatic transmission fluid (ATF). To illustrate the invention, the following description will focus on ATF formulations although it will be understood that the compositions of the present invention are not limited to such fluids but embraces within its scope other lubricant and functional fluids.
- ATFs typically have a kinematic viscosity at 100°C (KV100) ranging from 2-15 mm2/s, preferably from 4-10 mm2/s, more preferably from 5-8 mm2/s measured according to the standard test procedure of ASTM D-446. The Brookfield viscosity at - 40°C is suitably less than 50,000 mPa s, preferably from 4,000-20,000 mPa s, and more preferably from 5,000-18,000 mPa s measured according to the standard test procedure of ASTM D-2983. The viscosity index is suitably in the range from 100-200, preferably from 150-200 measured according to the standard test procedure of ASTM D-2270.
- Generally, the amount of base oil contained in the ATF ranges from 50% by weight to 99.9%, suitably from 60-95% by weight and preferably from 70-90% by wt, based on the total weight of the ATF formulation.
- The amount of friction modifier additive combination present in the ATF formulation (ie the total amount of fatty amine and fatty amide) is broadly in the range from 0.05-1.2% by weight. Within this range the specific amount used will depend not only upon the friction properties desired but also, at least to some extent, upon the design of the automatic transmission. Thus the amount of friction modifier additive combination used is suitably in the range from 0.1-1% by weight, preferably from 0.2-0.8% by weight and more preferably from 0.3-0.6% by weight.
- The amount of fatty amine compound in this friction modifier additive combination is suitably in the range from 0.03-1.0% by weight, preferably from 0.05-0.8% by weight and more preferably from 0.1-0.6% by weight. The fatty amide compound in the additive combination is suitably from 0.05-0.8% by weight, preferably from 0.05-0.5% by weight and more preferably from 0.08-0.3% by weight.
- The weight ratio of the fatty amine to fatty amide in the additive combination is suitably in the range from 0.5:1 to 10:1, preferably from 1:1 to 8:1 and more preferably from 2:1 to 6:1.
- The amounts of the fatty amine and fatty amide in the additive combination are with respect to the active ingredients in such compounds. The compounds specified above are generally liquids at room temperature and within conventional lubricant additive handling and blending temperatures, and are therefore usually supplied and used in neat, 100% active ingredient form. However, if desired, they may be diluted with a solvent, such as eg mineral oil, which is inert under the conditions especially with respect to the performance of the lubricant.
- The base oil of the ATF or other lubricant or functional fluid according to the invention may be a mineral oil, a synthetic oil or mixtures thereof. The base oils are suitably selected from refined mineral oils, for example, a solvent refined and/or hydrotreated oils, oils derived from coal tar or shale, vegetable oils, animal oils, hydrocracked oils, hydroisomerised oils, poly-alphaolefins (PAO), esters, alkylbenzenes, polyglycols, alkylene oxide polymers, silicone oils and the like.
- Where the base oil comprises a mineral oil, it is suitably a solvent refined and/or hydrotreated oil. Examples of suitable oils of this type include inter alia solvent refined mineral oils in the range of 50N to 150N, preferably 80N to 130N. Such mineral oils are available, for example, from Esso under the trade name Esso Solvent Neutral.
- Where the base oil is a severely refined mineral oil such as eg white oil, these may be one of the varieties supplied by Esso under the trade names MARCOL® 52 and 172, PRIMOL® 352, PLASTOL® 135 and 352, and BAYOL® 52. The base oils used may also be a hydrocracked or hydroisomerised oils such as eg a hydroisomerised paraffin.
- Where the base oil is a synthetic oil, it is preferably a PAO produced by the oligomerisation of 1-alkenes which suitably contain 6-20 carbon atoms, preferably 8-14 carbon atoms. PAOs produced from 1-decene are particularly preferred. The KV100 of the PAO selected is usually determined by the viscosity desired in the final lubricant formulation and is suitably in the range from 2-8mm2/s, preferably from 4-6mm2/s. Such PAOs are commercially available eg from ExxonMobil.
- In a preferred embodiment, the base oil is a mix of mineral oils and synthetic oils, eg a mixture of one or more solvent refined mineral oils with PAOs; or a mixture of solvent refined mineral oil with white oil, a hydrocracked oil or a hydroisomerised oil as stated above. In a particularly preferred embodiment, the base oil is a mixture of solvent refined mineral oil, a PAO and white oil.
- The functional fluid formulations of the present invention may also contain other optional additives depending upon the intended use of the functional fluid. Such additives include inter alia viscosity index improvers, pour point depressants, antioxidants, anti-wear agents, extreme pressure additives, dispersants, detergents, corrosion inhibitors, erosion inhibitors, anti-foaming agents, seal swell conditioning agents (seal fix), anti-pitting agents and the like. Such additives are all commercially available, the choice of one or more of these and the amounts of each used depending upon the intended end use of the functional fluid. Thus, eg, a viscosity index improver would typically be included in the functional fluids at a treat level of 2-15% by weight based on active ingredient (ie excluding solvent and carrier fluids, if any), preferably from 2-10% by weight, and the other additives would typically be included in the functional fluids at a treat level of 0.01-5% by weight based on active ingredient.
- The optional additives recited above may be added individually to the base oil, or, two or more may be pre-mixed with a carrier fluid such as eg a mineral oil, to form an additive concentrate and can then be blended with the base oil. The friction modifier additive combination according to the invention may also be pre-mixed with or without other additives into an additive concentrate.
- Of the optional additives recited above:
- the dispersants are suitably ashless dispersants such as eg polyalkenyl succinic anhydrides, polyalkenyl succinimides and derivatives thereof wherein the polyalkenyl group is derived from a long chain polyolefm such as eg polyisobutylene;
- the extreme pressure additives are suitably phosphorus- or zinc-based;
- the antioxidants are suitably aminic and/or phenolic type;
- the pitting booster is suitably sulphurised fatty oil eg Sulperm® 307 (ex Ferro Corporation);
- the anti-foam agents are suitably silicon based; and
- the viscosity index improver is suitably acrylic based such as eg a polymethylmethacrylate.
-
- The friction modifier additive combination and lubricating oil formulations produced therefrom are particularly effective when used in automatic transmission fluids, especially for automatic transmissions equipped with an electronically controlled converter clutch.
- The present invention is further illustrated with reference to the following Examples.
- The following formulation was tested for its performance as an ATF in which all the amounts in the columns are % by weight:
COMPONENTS Test No. 1 Test No. 2 Test No. 3 Test No. 4 Mineral base oil (SN90) 10.0 10.0 10.0 10.0 White oil (Hydrovis® 3) 30.0 30.0 30.0 30.0 PAO 4 30.0 30.0 30.0 30.0 Hydrocracked base oil (Nexbase 3030) 14.87 14.89 14.67 14.77 X-9077 5.6 5.6 5.6 5.6 Pitting booster (Sulperm® 307) 0.4 0.4 0.4 0.4 Pour point depressant (Viscoplex® 1-311) 0.2 0.2 0.2 0.2 VI Improver (Viscoplex® 0-030) 8.5 8.5 8.5 8.5 Parabar® 10100 0.03 0.03 0.03 0.03 Fatty amine (Ethomeen® C/12) 0.3 0.3 0.5 0.4 Fatty amide (Comperlan® LD 30) 0.1 0.08 0.1 0.1 - The formulations in Tests 1-4 above passed the Electronically controlled converter clutch (ECCC) tests on the Mannesmann Sachs (MS) German for Geregelte Wandlerkupplung (hereafter "GWK"). The formulations shown above achieved a green shudder of 0 hours and a shudder resistance time of 110 hours or above (as against a specification time of a minimum of 100 hours) thereby meeting the demanding GWK requirements from MS and ZF.
Claims (14)
- A friction modifier additive combination comprising(a) an oil-soluble fatty amine compound of formula (I): wherein:R is an alkyl group containing from 8 to 24 carbon atoms or any aryl group containing one or more alkyl substituents containing from 8 to 24 carbon atoms;R1 and R2 are each independently an alkylene group containing from 1-8 carbon atoms; and x and y are each independently 0 or an integer from 1 to 5, and
- A combination according to Claim 1, wherein the substituent groups R1 and R2 are each independently an alkylene group and have 1 to 4 carbon atoms.
- A combination according to Claim 1 or 2, wherein the number of oxyalkylene groups represented by x and y are each independently suitably 0, 1 or 2 and are preferably 0.
- A combination according to any one of Claims 1 to 3, wherein the fatty amine is selected from the group of coco-bis(2-hydroxyethyl)amine, a polyoxyethylene(5)coco-amine and an oleyl-bis- (2-hydroxyethyl)amine, and mixtures thereof.
- A combination according to any one of Claims 1 to 4, comprising a mixture of (a) a bis(hydroxyethyl)fatty amine wherein the fatty group comprises an alkyl group which has 12 to 14 carbon atoms and (b) a bis (hydroxyethyl) fatty amide wherein the fatty group comprises an alkyl group which has 12 to 18 carbon atoms.
- A lubricant formulation comprising a major amount of base oil of lubricating viscosity and a minor amount of a friction modifier additive combination as defined in any one of the preceding Claims 1-5.
- A lubricant formulation according to Claim 6, wherein said formulation is an automatic transmission fluid having a kinematic viscosity at 100°C (KV 100) ranging from 2-15 mm2 /s measured according to the standard test procedure of ASTM D-446, a Brookfield viscosity at -40°C of less than 50,000 mPa s measured according to the standard test procedure of ASTM D-2983 and a viscosity index in the range from 100-200 measured according to the standard test procedure of ASTM D-2270.
- A lubricant formulation according to Claim 6 or 7, wherein the total amount of the fatty amine and fatty acid amide present as the friction modifier additive combination is in the range from 0.05-1.2% by weight.
- A lubricant formulation according to any one of the preceding Claims 6 to 8, wherein the base oil comprises a poly-alpha-olefin (PAO) having a KV100 in the range from 2-8mm2/s.
- A lubricant formulation according to any one of the preceding Claims 6 to 9, wherein said formulation comprises a mixture of a solvent refined mineral oil, a PAO and white oil.
- A lubricant formulation according to any one of the preceding Claims 6 to 10, wherein said formulation comprises a viscosity index improver at a level of 2-15% by weight based on active ingredient.
- A lubricant formulation according to Claim 11, wherein the viscosity index improver is a polymethylmethacrylate.
- Use of the lubricant formulation according to any one of Claims 6 to 12 as a power transmission fluid.
- Use of the lubricant formulation according to any one of Claims 6 to 12 as an automatic transmission fluid (ATF).
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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GB0011931 | 2000-05-17 | ||
GBGB0011931.3A GB0011931D0 (en) | 2000-05-17 | 2000-05-17 | Friction modifier additive combination |
PCT/EP2001/005656 WO2001088067A2 (en) | 2000-05-17 | 2001-05-17 | Friction modifier additive combination |
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EP1299509A2 EP1299509A2 (en) | 2003-04-09 |
EP1299509B1 true EP1299509B1 (en) | 2004-08-25 |
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EP01949345A Expired - Lifetime EP1299509B1 (en) | 2000-05-17 | 2001-05-17 | Friction modifier additive combination |
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EP (1) | EP1299509B1 (en) |
AT (1) | ATE274567T1 (en) |
AU (1) | AU7052501A (en) |
DE (1) | DE60105165T2 (en) |
ES (1) | ES2227234T3 (en) |
GB (1) | GB0011931D0 (en) |
PT (1) | PT1299509E (en) |
WO (1) | WO2001088067A2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7989408B2 (en) | 2007-04-10 | 2011-08-02 | Exxonmobil Research And Engineering Company | Fuel economy lubricant compositions |
US8299005B2 (en) | 2006-05-09 | 2012-10-30 | Exxonmobil Research And Engineering Company | Lubricating oil composition |
US10947474B2 (en) | 2017-11-30 | 2021-03-16 | Valvoline Licensing And Intellectual Property Llc | Friction modifier for motor oil |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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TR200906533A2 (en) | 2009-08-25 | 2010-03-22 | Nnt Nanoteknoloji̇ Bor Ür.Ve Ser.Malz | Nano lubricant additive composition and production process produced by detonation technology and argon regime. |
US20150111801A1 (en) * | 2013-10-18 | 2015-04-23 | Chevron Oronite Company Llc. | Lubricating oil composition for protection of silver bearings in medium speed diesel engines |
CN114540103B (en) * | 2020-11-24 | 2023-04-25 | 中国石油化工股份有限公司 | Friction modifier composition, application thereof and industrial gear oil |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CA2095921A1 (en) * | 1991-09-16 | 1993-03-17 | The Lubrizol Corporation | Oil compositions |
US5858929A (en) * | 1995-06-09 | 1999-01-12 | The Lubrizol Corporation | Composition for providing anti-shudder friction durability performance for automatic transmissions |
US5622923A (en) * | 1995-06-16 | 1997-04-22 | The Lubrizol Corporation | Lubricating compositions, functional fluids and greases containing thiophosphorus esters or their salts with a oxyalkylene group, and methods of using the same |
US5866519A (en) * | 1995-07-17 | 1999-02-02 | Exxon Chemical Patents Inc. | Automatic transmission fluids of improved viscometric properties |
US5641733A (en) * | 1995-07-17 | 1997-06-24 | Exxon Chemical Patents Inc. | Automatic transmission fluids of improved viscometric properties |
US5646099A (en) * | 1995-07-17 | 1997-07-08 | Exxon Chemical Patents Inc. | Automatic transmission fluids of improved viscometric properties |
CA2217862A1 (en) * | 1995-07-17 | 1997-02-06 | Ricardo Alfredo Bloch | Partial synthetic transmission fluids with improved low temperature properties |
JP4334623B2 (en) * | 1996-06-12 | 2009-09-30 | 出光興産株式会社 | Lubricating oil composition for automatic transmission |
US6613722B1 (en) * | 1997-03-07 | 2003-09-02 | Exxon Chemical Patents Inc. | Lubricating composition |
-
2000
- 2000-05-17 GB GBGB0011931.3A patent/GB0011931D0/en not_active Ceased
-
2001
- 2001-05-17 EP EP01949345A patent/EP1299509B1/en not_active Expired - Lifetime
- 2001-05-17 AU AU70525/01A patent/AU7052501A/en not_active Abandoned
- 2001-05-17 ES ES01949345T patent/ES2227234T3/en not_active Expired - Lifetime
- 2001-05-17 PT PT01949345T patent/PT1299509E/en unknown
- 2001-05-17 AT AT01949345T patent/ATE274567T1/en active
- 2001-05-17 WO PCT/EP2001/005656 patent/WO2001088067A2/en active IP Right Grant
- 2001-05-17 DE DE60105165T patent/DE60105165T2/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8299005B2 (en) | 2006-05-09 | 2012-10-30 | Exxonmobil Research And Engineering Company | Lubricating oil composition |
US7989408B2 (en) | 2007-04-10 | 2011-08-02 | Exxonmobil Research And Engineering Company | Fuel economy lubricant compositions |
US10947474B2 (en) | 2017-11-30 | 2021-03-16 | Valvoline Licensing And Intellectual Property Llc | Friction modifier for motor oil |
Also Published As
Publication number | Publication date |
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DE60105165D1 (en) | 2004-09-30 |
PT1299509E (en) | 2005-01-31 |
ES2227234T3 (en) | 2005-04-01 |
ATE274567T1 (en) | 2004-09-15 |
AU7052501A (en) | 2001-11-26 |
GB0011931D0 (en) | 2000-07-05 |
WO2001088067A2 (en) | 2001-11-22 |
WO2001088067A3 (en) | 2002-04-11 |
DE60105165T2 (en) | 2005-09-08 |
EP1299509A2 (en) | 2003-04-09 |
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