EP3555252B1 - Lubrification d'une transmission automatique à usure réduite sur un roulement à aiguilles - Google Patents
Lubrification d'une transmission automatique à usure réduite sur un roulement à aiguilles Download PDFInfo
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- EP3555252B1 EP3555252B1 EP17826056.8A EP17826056A EP3555252B1 EP 3555252 B1 EP3555252 B1 EP 3555252B1 EP 17826056 A EP17826056 A EP 17826056A EP 3555252 B1 EP3555252 B1 EP 3555252B1
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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
- C10M169/00—Lubricating 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
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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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
- C10M169/00—Lubricating 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
- C10M169/04—Mixtures of base-materials and additives
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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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
- C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
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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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
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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
- C10M139/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00
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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
- 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
- C10M141/12—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 compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
- C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- 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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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
- C10M2215/28—Amides; Imides
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2217/02—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2217/022—Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an amino group
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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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
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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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
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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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/049—Phosphite
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- 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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
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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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/42—Phosphor free or low phosphor content compositions
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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
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/44—Boron free or low content boron compositions
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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
- C10N2040/02—Bearings
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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
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
Definitions
- the disclosed technology relates to lubricant formulations that provide good resistance to wear. They may be especially useful when used for lubrication of a needle bearing in an automatic transmission.
- U.S. Patent Application Publication 2005/00146656, Sumiejski et al., January 20, 2005 discloses a lubricating composition useful for the lubrication of automotive transmissions.
- the lubricating composition comprises a hydrocarbyl phosphite, the condensation product of at least one fatty acid with a polyamine, a borate ester, a borated dispersant, and an oil of lubricating viscosity.
- U.S. Patent Application Publication 2007/0142237 discloses a lubricant composition, e.g., a gear oil. It contains a base oil which typically has a viscosity of 2 - 15 or 2 - 10 cSt. It also contains a boron-containing compound, which may be a nitrogen-containing compound, e.g., succinimide or a borate ester or amide, e.g., borated epoxides or borated fatty acid esters of glycerol. The amount of the boron compound may provide 5 to 500 or 11-100 ppm B. A sulfur-containing, phosphorus-containing compound is also present; dibutyl hydrogen phosphonate is disclosed.
- a lubricant composition e.g., a gear oil. It contains a base oil which typically has a viscosity of 2 - 15 or 2 - 10 cSt. It also contains a boron-containing compound, which may be a nitrogen
- U.S. Patent Application Publication 2014/0031268, Sumiejski et al., January 30, 2014 discloses a lubricant for a continuously variable transmission.
- the lubricant includes a functionalized dispersant treated with (among others) a borating agent; a di-C3-C6 alkyl phosphite, and a trialkyl borate.
- the lubricant composition may have a KV100 of up to about 12 mm 2 /s, e.g., 2-10 or 6-8.
- the dispersant may contain 0.4 to 1.2 percent by weight boron from the borating agent.
- U.S. Patent Application Publication 2014/0107001, Saccomando et al., April 17, 2014 discloses a lubricant for an automatic transmission which contains certain aromatic condensation products. It is prepared in an oil having KV100 of 1 or 2 to 8 to 10 mm 2 /s, and the overall lubricant composition may have a KV100 of 1 or 1.5 to 10 or to 15 or to 20 mm 2 /s.
- Other components that may be present include a dispersant.
- Succinimide dispersants are disclosed as well as post-treated dispersant with, e.g., boron compounds.
- a supplemental friction modifier may be present, such as fatty phosphites, borated fatty epoxides, or borated fatty acids of glycerol.
- One formulation contains 0.15% of a borate ester friction modifier and 0.30% phosphite and phosphonate friction modifiers.
- Another formulation contains 0.2% phosphite friction modifier.
- U.S. Patent Application Publication 2015/0376544, Kakao et al., December 31, 2015 discloses a lubricating composition for transmissions comprising a lubricant base oil comprising a mineral base oil having ca 100 °C kinematic viscosity of 1.5 mm 2 /s or higher and 3.5 mm 2 /s or lower and certain other defined parameters, in an amount of 50 to 97 percent by mass on the total base oil composition mass basis, and a monoester-based oil having a 100 °C kinematic viscosity of 2 to 10 mm 2 /s in an amount of 3 to 10 percent by mass; as well as a phosphorus acid ester and a boronated ashless dispersant.
- a lubricant base oil comprising a mineral base oil having ca 100 °C kinematic viscosity of 1.5 mm 2 /s or higher and 3.5 mm 2 /s or lower and certain other defined parameters, in an amount of 50 to 97 percent by
- U.S. Patent Application Publication 2016/0130524 discloses a low viscosity ester lubricant for use in high temperature applications, such as for a crankcase lubricant.
- the ester exhibits a KV100 of 1 to 4 centistokes.
- the lubricant optionally contains one or more dispersants, among those listed being alkylsuccinic derivatives. These products may be post-treated with various reagents including (among others) boron compounds such as borate esters. In one example, a low Zn dialkyl dithiophosphate is present.
- U.S. Patent Application Publication 2016/0108337 discloses a lubricant composition and method of lubricating a transmission.
- the lubricating composition may have a kinematic viscosity at 100 °C of 3.6 to 4.8 cSt or 4.0 to 4.2 cSt. It may comprise an oil of lubricating viscosity of 2.8 to 3.6 cSt.
- the lubricant contains 1.2 to 5.0% of a borated dispersant and two phosphorus-containing compounds in an amount to deliver 360 to 950 ppm of phosphorus.
- the reaction product i.e., borated dispersant
- An optional component is a friction modifier; among the list of these are included borated glycerol esters and borated fatty epoxides.
- U.S. Patent 9,090,850, Edwards et al., July 28, 2015 discloses a lubricant containing a dithiophosphate ester of the structure It may optionally contain a phosphite antiwear agent. It may optionally contain one or more boron-containing compounds, examples of which include borate esters and borated succinimide dispersants.
- the lubricant composition may have a viscosity at 100 °C between 2 and 30 cSt or between 4 and 8 cSt.
- the claimed invention therefore, solves the problem of providing good or improved bearing life or reduced bearing wear, for instance, in needle bearings, particularly when using very low viscosity lubricant fluids.
- the claimed invention provides a lubricant composition
- a lubricant composition comprising: (a) an oil having a kinematic viscosity at 100 °C of 2.2 to 3.7 mm 2 /s; (b) at least one borate ester having an alkyl group of 4 to 18 carbon atoms in an amount to provide 25 to 300, or 30 to 150, or 50 to 100, parts per million by weight boron to the composition;(c) at least one phosphorus ester in an amount to provide 150 to 650 parts per million by weight phosphorus to the composition; (d) a viscosity index modifier comprising a linear polymer viscosity modifier having dispersant functionality, wherein the linear polymer has a weight average molecular weight of 5,000 to 25,000, and wherein said linear polymer is present in an amount of 0.1 to 4 weight percent; and (e) a borated succinimide dispersant to provide 180 to 270 ppm boron to the lubricant composition; wherein the
- the claimed invention provides a lubricant composition
- a lubricant composition comprising: (a) 50 to 98 percent by weight of an oil having a kinematic viscosity at 100 °C of 2.2 to 3.7 mm 2 /s; (b) at least one borate ester having an alkyl group of 4 to 18 carbon atoms, wherein the borate ester comprises: (b-1) 0.
- the claimed invention provides a method of lubricating an automatic transmission comprising supplying thereto the lubricant composition defined herein, wherein the automatic transmission optionally contains a bearing that is lubricated by said lubricant composition.
- the base oil may be selected from any of the base oils in Groups I-V of the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (2011), namely Base Oil Category Sulfur (%) Saturates(%) Viscosity Index Group I >0.03 and/or ⁇ 90 80 to less than 120 Group II ⁇ 0.03 and ⁇ 90 80 to less than 120 Group III ⁇ 0.03 and ⁇ 90 ⁇ 120 Group IV All polyalphaolefins (PAOs) Group V All others not included in Groups I, II, III or IV
- Groups I, II and III are mineral oil base stocks. Other generally recognized categories of base oils may be used, even if not officially identified by the API: Group II+, referring to materials of Group II having a viscosity index of 110-119 and lower volatility than other Group II oils; and Group III+, referring to materials of Group III having a viscosity index greater than or equal to 130.
- the oil of lubricating viscosity can include natural or synthetic oils and mixtures thereof. Mixture of mineral oil and synthetic oils, e.g., polyalphaolefin oils and/or polyester oils, may be used.
- the oil of lubricating viscosity comprises an API group II or Group III oil or mixtures thereof.
- the oil of lubricating viscosity (or mixture of such oils) will be a relatively low viscosity oil, having a kinematic viscosity at 100 °C of 2.2 to 3.7 mm 2 /s, or 2.5 to 3.5 mm 2 /s, or 2.8 to 3.3 mm 2 /s.
- oil of this viscosity range permits preparation of a lubricant composition having a kinematic viscosity at 100 °C of less than or equal to 4.7 mm 2 /s, such as 3.0 to 4.6 or 3.3 to 4.3 or 3.6 to 4.1 mm 2 /s
- the amount of the oil of lubricating viscosity may be 70 to 94, or 80 to 93, or 85 to 92 percent by weight. The amount may be calculated so as to include the amount of diluent oil conventionally supplied with such additive components as detergents, dispersants, and viscosity modifiers.
- Another component of the disclosed lubricant composition is at least one borate ester having an alkyl group of 4 to 18 carbon atoms.
- Borate ester may be seen generically an ester from boric acid or an equivalent thereof with an alcohol, although they need not be formed by an esterification (condensation) reaction.
- the borate ester may be what is referred to as a borated epoxide.
- the boron-containing compound may be described as a borate ester or a borate alcohol.
- the borate ester or borate alcohol compounds are substantially the same except the borate alcohol has at least one hydroxyl group that is not esterified, and the latter may also be a borated epoxide. Therefore, as used herein the term "borate ester" is used to refer to either borate ester or borate alcohol.
- the borate ester may be prepared by the reaction of a boron compound and at least one compound selected from epoxy compounds, halohydrin compounds, epihalohydrin compounds, alcohols and mixtures thereof.
- the alcohols include dihydric alcohols, trihydric alcohols or higher alcohols, with the proviso for one embodiment that hydroxyl groups are on adjacent carbon atoms, i.e., vicinal.
- epoxy compounds is used when referring to epoxy compounds, halohydrin compounds, epihalohydrin compounds, or mixtures thereof.
- Boron compounds suitable for preparing the borate ester include the various forms such as boric acid (including metaboric acid, HBO 2 , orthoboric acid, H 3 BO 3 , and tetraboric acid, H 2 B 4 O 7 ), boric oxide, boron trioxide and alkyl borates.
- the borate ester may also be prepared from boron halides.
- the borate ester is formed by the reaction of a boron compound with an epoxy compound, dihydric alcohols, trihydric alcohols or higher alcohols.
- the borate ester may be represented by at least one of formulae (I) to (VI): wherein each R may be hydrogen or a hydrocarbyl groups, provided that the borate ester is oil soluble.
- At least two of the R groups per the above formulas are hydrocarbyl groups.
- the hydrocarbyl groups may be alkyl, aryl or cycloalkyl, wherein when any two adjacent R groups are connected in a ring.
- R is alkyl, the group may be saturated or unsaturated.
- the hydrocarbyl group is an unsaturated alkyl.
- the hydrocarbyl group is cyclic.
- the hydrocarbyl groups are mixtures of alkyl and cycloalkyl.
- the number of carbon atoms present in each R may be 4 to 18 or 6 to 12. In certain embodiments the total number of carbon atoms on the R groups typically may be 9 or more, or 10 or more, or 12 or more, or 14 or more.
- R groups include isopropyl, n-butyl, isobutyl, amyl, 2-pentenyl, 4-methyl-2-pentyl, 2-ethylhexyl, heptyl, isooctyl, nonyl, decyl, undecyl, dodecenyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups.
- the epoxy compounds useful for preparing borate esters may be represented by the formulas (VIIa) or (VIIb): or wherein
- the epoxy compounds of the invention include commercial mixtures of C 14 -C 16 epoxides or C 14 -C 18 epoxides.
- the epoxy compounds of the invention have been purified.
- suitable purified epoxy compounds may include 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxybutadecane, 1,2-epoxypentadecane 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, and 1,2-epoxyoctadecane.
- purified epoxy compounds include 1,2-epoxyhexadecane.
- a borated ester comprises a borated epoxide having 12 to 18 or 14 to 18 carbon atoms.
- the alcohols employed for esterification of an alcohol with a borating agent may include monohydric alcohols, dihydric alcohols, trihydric alcohols or higher alcohols.
- the alcohol may contain 4 to 18 carbon atoms or 6 to 16 or 6 to 12 carbon atoms.
- the borate ester may be prepared by blending the boron compound and the epoxy compounds or alcohols described above and heating them at a suitable temperature, such as at 80 °C to 250 °C, 90 °C to 240 °C, or 100 °C to 230 °C, until the desired reaction has occurred.
- the molar ratio of the boron compounds to the epoxy compounds may be 4:1 to 1:4, or 1:1 to 1:3, or 1:2.
- An inert liquid may be used in performing the reaction, such as toluene, xylene, chlorobenzene, dimethylformamide, or mixtures thereof. Water is typically formed and is distilled off during a condensation reaction. Alkaline reagents may be used to catalyze the reaction.
- suitable borate ester compounds include tripropyl borate, tributyl borate, tripentyl borate, trihexyl borate, triheptyl borate, trioctyl borate, trinonyl borate, and tridecyl borate.
- the borate ester compounds include tributyl borate, tri-2-ethylhexyl borate or mixtures thereof.
- the lubricant composition may comprise borate ester containing an alkyl group of 4 to 12 carbon atoms and a borate ester containing an alkyl group of 12 to 18 or 14 to 18 carbon atoms.
- borate ester component may comprise the reaction product of boric acid with an alcohol of 6 to 12 carbon atoms.
- the borate ester component may comprise a borated epoxide having 12 to 18 carbon atoms.
- the amount of the borate ester in the lubricant may be 0.1 to 1.1 percent by weight or 0.05 to 1.1 or 0.15 to 0.7 or 0.10 or 0.90 percent by weight, or 0.2 to 1.0 percent or 0.25 to 0.75 percent. If there are two borate esters present, one with a C4 to C12 alkyl group and one with a C14 to C18 alkyl group, the amount of the C4-C12 ester may be 0.05 to 1.0 percent by weight or 0.1 to 1, or 0.15 to 0.7 or 0.2 to 0.6 percent; and the C14 to C18 ester may be 0.05 to 1 percent by weight, or 0.075 to 0.7, or 0.15 to 0.4 percent by weight.
- the borate ester or esters will contribute to the amount of boron in the lubricant, a portion of which may come from other sources such as a borated dispersant (discussed below).
- the amount contributed by the borate ester may be 25 to 300, or 30 to 150, or 50 to 100, or 70 to 100 parts per million by weight.
- the balance of the boron may be provided by other sources such as borated dispersants, described below.
- the lubricant of the disclosed technology will also contain at least one phosphorus ester in an amount to provide 150 to 650, or 150 to 350, or 180 to 250 parts per million by weight phosphorus to the composition.
- the amount of the at least one phosphorus ester will be 0.05 to 0.4 percent by weight, or 0.1 to 0.35 percent.
- the phosphorus ester may comprise a C4 to C8 or C4 to C6 alkyl phosphite, such as dioctyl phosphite, or, alternatively, an oligomeric phosphite which is the reaction product of a monomeric phosphorous acid or ester with an alkylene diol.
- the C4 to C6 alkyl phosphite may include dialkyl phosphites such as dibutyl phosphites, dihexyl phosphite, and dicyclohexyl phosphite. Such materials are readily commercially available.
- the oligomeric phosphites are described in greater detail in PCT publication WO 2016/089565, Abraham et al. (Lubrizol), June 9, 2016 . In brief they may be described as a reaction product of (a) a monomeric phosphorous acid or an ester thereof with (b) at least two alkylene diols.
- the first alkylene diol (i) will have two hydroxy groups in a 1,4 or 1,5 or 1,6 relationship on the carbon chain, and the second alkylene diol (ii) will be an alkyl-substituted 1,3-propylene diol with one or more of the alkyl substituents on one or more of the carbon atoms of the propylene unit.
- the total number of carbon atoms in the alkyl-substituted 1,3-propylene diol will be 5 to 12.
- the relative molar amounts of monomeric phosphorous acid or ester thereof (a) and the total of the alkylene diols (b) will typically be in a ratio of 0.9:1.1 to 1.1:0.9
- the relative molar amounts of the first alkylene diol (i) and the alkyl-substituted 1,3-propylene diol (ii) will typically be in a ratio of 30:70 to 65:35, or alternatively 35:54 to 60:40 or 50:60 to 50:50, or 40:60 to 45:55.
- the first alkylene diol may be branched (e.g., alkyl-substituted) or unbranched and in one embodiment is unbranched.
- Unbranched that is, linear diols ( ⁇ , ⁇ -diols) include 1,4-butanediol, 1,5-pentane diol, and 1,6-hexanediol.
- Branched or substituted diols include 1,4-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 3,3-dimethyl-1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, and 2,5-dimethyl-2,5-hexanediol.
- a diol having one or more secondary hydroxy groups such as 2,5-hexanediol
- a branched or substituted diol even though the carbon chain itself may be linear.
- the location of the hydroxy groups in the 1,4-, 1,5-, or 1,6- positions may be helpful to promote oligomerization with the phosphorous species rather than formation of cyclic structures (which would be sterically disfavored).
- the first alkylene diol may be 1,6-hexanediol.
- the first alkylene dihydroxy compound (diol) may, if desired, have additional hydroxy groups, that is, more than two per molecule, or there may be exactly two. In one embodiment, there are exactly two hydroxy groups per molecule. If there are more than two hydroxy groups, care should be taken to assure that there is no excessive cyclization such as might interfere with the polymerization reaction, if there are fewer than 4 atoms separating any of the hydroxy groups. Also, care should be taken to avoid excessive branching or crosslinking in the product, which could lead to undesirable gel formation. Such problems may be avoided by careful control of reaction conditions such as control of the ratio of reagents and the order of their addition, performing the reaction under suitably dilute conditions, and reacting under low acid conditions. These conditions can be determined by the person skilled in the art with only routine experimentation.
- the second alkylene diol is an alkyl-substituted 1,3-propylene diol with one or more of the alkyl substituents thereof being on one or more of the carbon atoms of the propylene unit, the total number of carbon atoms in the alkyl-substituted 1,3-propylene diol being 5 to 12 or 6 to 12 or 7 to 11 or 8 to 18 or, in certain embodiments, 9.
- the alkyl-substituted 1,3-propylene diol may be represented by the general formula where the various R groups may be the same or different and may be hydrogen or an alkyl group, provided that at least one R is an alkyl group and that the total number of carbon atoms in the R groups is 2 to 9 or 3 to 9, so that the total carbon atoms in the diol will be 5 to 12 or 6 to 12, respectively, and likewise for the other ranges of total carbons.
- 1,3-diols means that the two hydroxy groups are in a 1,3 relationship to each other, that is, separated by a chain of 3 carbon atoms.
- a 1,3-diol may thus also be named as a 2,4- or 3,5-diol. If the 1,3-diol has one or more secondary hydroxy groups, such a molecule will be considered to be a substituted diol.
- the number of alkyl substituents is 2 and the total number of carbon atoms in the molecule is 9.
- Suitable substituents may include, for instance, methyl, ethyl, propyl, and butyl (in their various possible isomers).
- Examples of the second alkylene diol may include 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butylpropane-1,3-diol, 2-ethylhexane-1,3-diol, 2,2-dibutylpropane-1,3-diol, 2,2-diisobutylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, 2-propyl-propane-1,3-diol, 2-butylpropane-1,3-diol, 2-pentylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, 2,2-diethylpropane-1,3-diol, 2,2,4-trimethylpentane-1,3-diol, 2-methylpentane-2,4-diol, 2,4,-di
- the total amount of phosphorus in the lubricant may be in a higher range, such as 150 to 1000, or 200 to 800, parts per million by weight.
- the additional phosphorus may be provided by a different phosphorus-containing species, such as an inorganic phosphorus acid, such as phosphoric acid or phosphorous acid.
- Phosphoric acid may be commercially provided as an 85 percent by weight composition with 15 percent water, and appropriate amounts thereof may be employed.
- Other phosphorus sources may include phosphorus-treated (phosphorus-containing) dispersants such as post-treated succinimide dispersants, described below.
- the lubricant composition of the claimed invention further comprises a viscosity modifier as defined in claim 1, also referred to as a viscosity index modifier or a viscosity index improver.
- Viscosity modifiers (VMs) and dispersant viscosity modifiers (DVMs) are well known.
- VMs and DVMs may include polymethacrylates, polyacrylates, polyolefins, hydrogenated vinyl aromatic-diene copolymers (e.g., styrene-butadiene, styrene-isoprene), styrene-maleic ester copolymers, and similar polymeric substances including homopolymers, copolymers, and graft copolymers, including polymers having linear, branched, or star-like structures.
- hydrogenated vinyl aromatic-diene copolymers e.g., styrene-butadiene, styrene-isoprene
- styrene-maleic ester copolymers e.g., styrene-maleic ester copolymers, and similar polymeric substances including homopolymers, copolymers, and graft copolymers, including polymers having linear, branched, or star-like structures.
- the DVM may comprise a nitrogen-containing methacrylate polymer or nitrogen-containing olefin polymer, such as a poly(meth)acrylate containing a nitrogen-containing dispersant monomer; for example, a nitrogen-containing methacrylate polymer derived from methyl methacrylate and dimethylaminopropyl amine.
- the DVM may alternatively comprise a copolymer with units derived from an ⁇ -olefin and units derived from a carboxylic acid or anhydride, such as maleic anhydride, in part esterified with a branched primary alcohol and in part reacted with an amine-containing compound.
- Examples of commercially available VMs, DVMs and their chemical types may include the following: polyisobutylenes (such as Indopol TM from BP Amoco or Parapol TM from ExxonMobil); olefin copolymers (such as Lubrizol ® 7060, 7065, and 7067, and Lucant ® HC-2000L, HC-1100, and HC-600 from Lubrizol); hydrogenated styrene-diene copolymers (such as Shellvis TM 40 and 50, from Shell and LZ ® 7308, and 7318 from Lubrizol); styrene/maleate copolymers, which are dispersant copolymers (such as LZ ® 3702 and 3715 from Lubrizol); polymethacrylates, some of which have dispersant properties (such as those in the Viscoplex TM series from RohMax, the Hitec TM series of viscosity index improvers from Afton, and LZ ® 7702, L
- the VM or DVM may have a weight average molecular weight of 5,000 to 25,000, or 10,000 to 20,000, or 12,000 to 18,000.
- the number average molecular weight will be proportionally lower, such as 3,000 to 15,000, or 6,000 to 12,000.
- the materials in question typically have a relatively low molecular weight compared to VMs and DVMs that may be commonly used in other applications such as lubricants for internal combustion engines.
- the viscosity index modifier comprises a linear polymer viscosity modifier having dispersant functionality, wherein the linear polymer has a weight average molecular weight of 5,000 to 25,000 or 10,000 to 20,000, and wherein said linear polymer is present in an amount of 0.1 to 4 weight percent.
- the viscosity index modifier may comprise a linear polymer as described herein and a polymer with star architecture, e.g., (meth)acrylic type star polymers, as disclosed in WO 2007/127660, Lubrizol, November 8, 2007 .
- Viscosity modifiers that may be used are described in U.S. patents 5,157,088 , 5,256,752 and 5,395,539 .
- the VMs and/or DVMs may be used in the functional fluid at a concentration of up to 50% or to 20% by weight, depending on the application. Concentrations of 0.1 to 20%, or 0.5 to 20%, or 1 to 20%, or 1 to 12%, or 3 to 10%, or 0.1 to 4%, or 1 to 4%, or alternatively 20 to 40%, or 20 to 30% by weight in the lubricant composition may be used.
- the selection of the amount of viscosity modifier is within the abilities of the person of ordinary skill, and will be in an amount which, in combination with the viscosity of the base oil, will provide a lubricant composition with a kinematic viscosity at 100 °C of less than or equal to 4.7 mm 2 /s, such as 2.7 to 4.7, or 2.8 to 4.7, or 3.4 to 4.0, or 3.5 to 3.9 mm 2 /s.
- the lubricant composition of the claimed invention also includes one or more dispersants, including a borated succinimide dispersant, which provides additional boron content to the lubricant composition.
- a borated succinimide dispersant which provides additional boron content to the lubricant composition.
- Succinimide dispersants are sometimes referred to ashless dispersants are so-called because, as supplied, they do not contain metal and thus do not normally contribute to sulfated ash when added to a lubricant (although the boron component which borated detergents contain may contribute to sulfated ash).
- ashless dispersants may, of course, interact with ambient metals once they are added to a lubricant which includes metal-containing species.
- Ashless dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain.
- Typical ashless dispersants include N-substituted long chain alkenyl succinimides, having a variety of chemical structures including typically the simplified structure
- each R 1 is independently an alkyl group, frequently a polyisobutylene group with a molecular weight (Mn) of 500-5000 based on the polyisobutylene precursor
- R 2 are alkylene groups, commonly ethylene (C 2 H 4 ) groups.
- Such molecules are commonly derived from reaction of an alkenyl acylating agent with a polyamine.
- linkages between the two moieties is possible beside the simple imide structure shown above, including a variety of amides and quaternary ammonium salts.
- the polyamine component is known to be possible, including various cyclic structures.
- the amine portion is shown as an alkylene polyamine, although other aliphatic and aromatic mono- and polyamines may also be used.
- a variety of modes of linkage of the R 1 groups onto the imide structure are possible, including various cyclic linkages.
- the ratio of the carbonyl groups of the acylating agent to the nitrogen atoms of the amine may be 1:0.5 to 1:3, and in other instances 1: 1 to 1:2.75 or 1: 1.5 to 1:2.5.
- Succinimide dispersants are more fully described in U.S. Patents 4,234,435 and 3,172,892 and in EP 0355895 .
- Dispersants can also be post-treated by reaction with any of a variety of agents. Among these are urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, and phosphorus compounds. References detailing such treatment are listed in U.S. Patent 4,654,403 .
- borated succinimide dispersants as used in the claimed invention contain boron and supply boron to the lubricant formulation.
- Borated dispersants may be prepared by borating using a variety of agents such as any of the various forms of boric acid (including metaboric acid, HBO 2 , orthoboric acid, H 3 BO 3 , and tetraboric acid, H 2 B 4 O 7 ), boric oxide, boron trioxide, and alkyl borates.
- the borating agent is boric acid which may be used alone or in combination with other borating agents.
- the borated dispersant may be prepared by blending the boron compound and a succinimide dispersant and heating them at a suitable temperature, typically 80 °C to 250 °C, 90 °C to 230 °C, or 100 °C to 210 °C, until the desired reaction has occurred.
- An inert liquid may be used in performing the reaction.
- the liquid may include toluene, xylene, chlorobenzene, dimethylformamide, or mixtures thereof.
- the boron-containing succinimide dispersant may have a boron content of 0.5 to 1.0 weight percent, or 0.6 to 0.9, or 0.54 to 0.85, or 0.56 to 0.83 weight percent.
- the borated succinimide dispersant may also be a product containing additional functionality by post treating, for instance, prepared by heating together:
- the dispersant component may also comprise a mixture of separate dispersant species, including an untreated (non-borated) succinimide dispersant, a borated succinimide dispersant, a DMTD-treated dispersant, and a terephthalic acid-treated dispersant.
- some or all of the post treatments may be applied to some or all of the succinimide dispersant species.
- some or all of the succinimide dispersant may be borated and treated with a dimercaptothiadiazole and optionally further with terephthalic acid.
- the dispersant component may comprise 1 to 4 percent by weight of a borated succinimide dispersant that is not treated with a dimercaptothiadiazole and 0.1 to 1.5 percent weight of a borated succinimide dispersant that is treated with a dimercaptothiadiazole.
- the components to prepare the post-treated succinimide dispersant may be combined and reacted in any order.
- the borating agent may be a pretreatment process or a post-treatment process.
- boric acid and optionally also phosphoric acid
- the intermediate borated dispersant may be reacted with the mercaptothiadiazole and the dicarboxylic acid of an aromatic compound.
- the dispersant substrate, dicarboxylic acid of an aromatic compound and mercapthothiadiazole may be first reacted, and then the product treated with a borating agent (and optionally with phosphoric acid, a phosphorus acid).
- a phosphorylated succinimide dispersant may be prepared by reacting a phosphorus acid with a hydrocarbyl-substituted succinic anhydride to prepare a mixed anhydride-acid precursor, and then reacting the precursor with a polyamine to form a phosphorus-containing dispersant.
- the phosphorus-containing dispersant may thereafter be reacted with the dicarboxylic acid of an aromatic compound and mercaptothiadiazole; and with the borating agent.
- the components are typically reacted by heating the borating agent and optionally the other agents with the dispersant substrate at a sufficient time and temperature to assure solubility of resulting product, typically 80-200°C, or 90-180°C, or 120-170°C, or 150-170°C.
- the time of reaction is typically at least 0.5 hours, for instance, 1-24 hours, 2-12 hours, 4-10 hours, or 6-8 hours.
- the amount of the succinimide dispersant component (or alternatively of specifically the boron-containing succinimide dispersant) in a fully formulated lubricant of the present technology, if it is present, may be at least 0.1% of the lubricant composition, or at least 0.3% or 0.5% or 1% or 1.5%, and in certain embodiments at most 9% or 8% or 6% or 4% or 3% or 2% by weight, such as 1.1 to 5.5 or 1.0 to 3.5 percent by weight.
- the amount of boron provided to the lubricant formulation by the borated succinimide dispersant component in accordance with the invention is 180 to 270 parts per million by weight,.
- the succinimide dispersant component may provide 10 to 250 parts per million by weight, or 20 to 200, or 50 to 150 ppm, sulfur to the composition by means of the presence of a dimercaptothiadiazole moiety present therewith.
- the lubricant compositions of the disclosed technology may also include one or more foam inhibitors.
- Anti-foam agents used to reduce or prevent the formation of stable foam include silicones, fluorosilicones, or organic polymers such as acrylate polymers, fluoroacrylate polymers, or fluoromethacrylate polymers. Examples of these and additional anti-foam compositions are described in " Foam Control Agents," by Henry T. Kerner (Noyes Data Corporation, 1976), pages 125-162 . They may typically be present in amounts of 20 to 250 or 50 to 200 parts per million (excluding diluent).
- a first anti-foam agent being derived from a first anti-foam composition comprising a polydimethyl siloxane dispersed or dissolved in an aromatic oil or a naphthenic hydrocarbon solvent, the first anti-foam composition having a kinetic viscosity at 25 °C (absent solvent) in the range from 10,000 to 50,000 mm 2 /s; a second anti-foam agent being comprising a polydimethyl siloxane dispersed or dissolved in an aromatic oil or a naphthenic hydrocarbon solvent and having a kinetic viscosity at 25 °C (absent solvent) in the range from 80,000 to 120,000 mm 2 /s; and a third anti-foam agent comprising a fluorinated polysiloxane dispersed or dissolved in an aliphatic solvent or a solvent comprising a ketone (e.g., aliphatic ketone) having
- additives may also optionally be present in amounts conventionally used for automatic transmission lubricants. They include friction modifiers, antioxidants, detergents, corrosion inhibitors, extreme pressure/antiwear agents, and seal swell agents.
- Friction modifiers in the context of automatic transmission lubricants, are materials designed to provide a high, stable coefficient of friction to lubricated clutch plates, typically comprising mating plates of metal (iron) and a non-metal composition such as a cellulosic surface. Friction modifiers are well known to those skilled in the art. A list of friction modifiers that may be used is included in U.S. Patents 4,792,410 , 5,395,539 , 5,484,543 and 6,660,695 . U.S. Patent 5,110,488 discloses metal salts of fatty acids and especially zinc salts, useful as friction modifiers.
- a list of friction modifiers that may be used may include borated alkoxylated fatty amines; fatty acid amides; metal salts of fatty acids; fatty epoxides; sulfurized olefins; fatty imidazolines; fatty amines; condensation products of carboxylic acids and polyalkylene-polyamines; glycerol esters; metal salts of alkyl salicylates; borated glycerol esters; amine salts of alkylphosphoric acids; alkoxylated fatty amines; ethoxylated alcohols; oxazolines; imidazolines; hydroxyalkyl amides; polyhydroxy tertiary amines; and mixtures of two or more thereof.
- Non-borated fatty epoxides may also be useful as supplemental friction modifiers.
- Borated amines that may be used are disclosed in U.S. Patent 4,622,158 .
- Borated amine friction modifiers (including borated alkoxylated fatty amines) may be prepared by the reaction of a boron compounds, as described above, with the corresponding amines, including simple fatty amines and hydroxy containing tertiary amines.
- the amines useful for preparing the borated amines may include commercial alkoxylated fatty amines known by the trademark "ETHOMEEN” and available from Akzo Nobel, such as bis[2-hydroxyethyl]-cocoamine, polyoxyethylene[10]cocoamine, bis[2-hydroxyethyl]soyamine, bis[2-hydroxyethyl]-tallowamine, polyoxyethylene-[5]tallowamine, bis[2-hydroxyethyl]oleylamine, bis[2-hydroxyethyl]octadecylamine, and polyoxyethylene[15]octadecylamine.
- ETHOMEEN commercial alkoxylated fatty amines known by the trademark "ETHOMEEN” and available from Akzo Nobel, such as bis[2-hydroxyethyl]-cocoamine, polyoxyethylene[10]cococoamine, bis[2-hydroxyethyl]soyamine, bis[2-hydroxyethyl]-tallowamine, polyoxyethylene-[5
- Alkoxylated fatty amines and fatty amines themselves may be useful as friction modifiers. These amines are commercially available.
- Borated fatty acid esters of glycerol may be prepared by borating a fatty acid ester of glycerol with a boron source such as boric acid.
- Fatty acid esters of glycerol themselves may be prepared by a variety of methods well known in the art. Many of these esters, such as glycerol monooleate and glycerol tallowate, are manufactured on a commercial scale.
- Commercial glycerol monooleates may contain a mixture of 45% to 55% by weight monoester and 55% to 45% by weight diester.
- Fatty acids may be used in preparing the above glycerol esters; they may also be used in preparing their metal salts, amides, and imidazolines, any of which may also be used as friction modifiers.
- the fatty acids may contain 6 to 24 carbon atoms, or 8 to 18 carbon atoms.
- a useful acid may be oleic acid.
- the amides of fatty acids may be those prepared by condensation with ammonia or with primary or secondary amines such as diethylamine and diethanolamine.
- Fatty imidazolines may include the cyclic condensation product of an acid with a diamine or polyamine such as a polyethylenepolyamine.
- the friction modifier may be the condensation product of a C8 to C24 fatty acid with a polyalkylene polyamine, for example, the product of isostearic acid with tetraethylenepentamine.
- the condensation products of carboxylic acids and polyalkyleneamines may be imidazolines or amides.
- the fatty acid may also be present as its metal salt, e.g., a zinc salt.
- These zinc salts may be acidic, neutral, or basic (overbased).
- These salts may be prepared from the reaction of a zinc containing reagent with a carboxylic acid or salt thereof.
- a useful method of preparation of these salts is to react zinc oxide with a carboxylic acid.
- Useful carboxylic acids are those described hereinabove. Suitable carboxylic acids include those of the formula RCOOH where R is an aliphatic or alicyclic hydrocarbon radical. Among these are those wherein R is a fatty group, e.g., stearyl, oleyl, linoleyl, or palmityl.
- zinc salts wherein zinc is present in a stoichiometric excess over the amount needed to prepare a neutral salt.
- Salts wherein the zinc is present from 1.1 to 1.8 times the stoichiometric amount, e.g., 1.3 to 1.6 times the stoichiometric amount of zinc, may be used.
- These zinc carboxylates are known in the art and are described in U.S. Patent 3,367,869 .
- Metal salts may also include calcium salts. Examples may include overbased calcium salts.
- Sulfurized olefins are also well known commercial materials used as friction modifiers.
- a suitable sulfurized olefin is one which is prepared in accordance with the detailed teachings of U.S. Patents 4,957,651 and 4,959,168 . Described therein is a cosulfurized mixture of 2 or more reactants selected from the group consisting of at least one fatty acid ester of a polyhydric alcohol, at least one fatty acid, at least one olefin, and at least one fatty acid ester of a monohydric alcohol.
- the olefin component may be an aliphatic olefin, which usually will contain 4 to 40 carbon atoms. Mixtures of these olefins are commercially available.
- the sulfurizing agents useful in the process of the present invention include elemental sulfur, hydrogen sulfide, sulfur halide plus sodium sulfide, and a mixture of hydrogen sulfide and sulfur or sulfur dioxide.
- Metal salts of alkyl salicylates include calcium and other salts of long chain (e.g. C12 to C16) alkyl-substituted salicylic acids.
- Amine salts of alkylphosphoric acids include salts of oleyl and other long chain esters of phosphoric acid, with amines such as tertiary-aliphatic primary amines, sold under the tradename Primene TM .
- Eighty-five percent phosphoric acid is a suitable material for addition to the fully-formulated compositions to increase frictional properties and can be included at a level of 0.01-0.3 weight percent based on the weight of the composition, such as 0.03 to 0.2 or to 0.1 percent.
- the amount of supplemental friction modifier may be 0.01 to 10 or 5 percent by weight of the lubricating composition, 0.1 to 2.5 percent by weight of the lubricating composition, such as 0.1 to 2.0, 0.2 to 1.75, 0.3 to 1.5 or 0.4 to 1 percent. In some embodiments, however, the amount of friction modifier is present at less than 0.2 percent or less than 0.1 percent by weight, for example, 0.01 to 0.1 percent.
- Antioxidants encompass phenolic antioxidants, which may be hindered phenolic antioxidants, one or both ortho positions on a phenolic ring being occupied by bulky groups such as t-butyl.
- the para position may also be occupied by a hydrocarbyl group or a group bridging two aromatic rings.
- the para position is occupied by an ester-containing group, such as, for example, an antioxidant of the formula wherein R 3 is a hydrocarbyl group such as an alkyl group containing, e.g., 1 to 18 or 2 to 12 or 2 to 8 or 2 to 6 carbon atoms; and t-alkyl can be t-butyl.
- Such antioxidants are described in greater detail in U.S. Patent 6,559,105 .
- Antioxidants also include aromatic amines.
- an aromatic amine antioxidant can comprise an alkylated diphenylamine such as nonylated diphenylamine or a mixture of a di-nonylated and a mono-nonylated diphenylamine.
- Antioxidants also include sulfurized olefins such as mono- or disulfides or mixtures thereof. These materials generally have sulfide linkages of 1 to 10 sulfur atoms, e.g., 1 to 4, or 1 or 2.
- Materials which can be sulfurized to form the sulfurized organic compositions of the present invention include oils, fatty acids and esters, olefins and polyolefins made thereof, terpenes, or Diels-Alder adducts. Details of methods of preparing some such sulfurized materials can be found in U.S. Pat. Nos. 3,471,404 and 4,191,659 .
- Molybdenum compounds can also serve as antioxidants, and these materials can also serve in various other functions, such as antiwear agents or friction modifiers.
- U.S. Patent 4,285,822 discloses lubricating oil compositions containing a molybdenum- and sulfur-containing composition prepared by combining a polar solvent, an acidic molybdenum compound and an oil-soluble basic nitrogen compound to form a molybdenum-containing complex and contacting the complex with carbon disulfide to form the molybdenum- and sulfur-containing composition.
- antioxidants will, of course, depend on the specific antioxidant and its individual effectiveness, but illustrative total amounts can be 0.01 to 5 percent by weight or 0.15 to 4.5 percent or 0.2 to 4 percent.
- Detergents are typically overbased materials, otherwise referred to as overbased or superbased salts, which are generally homogeneous Newtonian systems having by a metal content in excess of that which would be present for neutralization according to the stoichiometry of the metal and the detergent anion.
- the amount of excess metal is commonly expressed in terms of metal ratio, that is, the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound.
- Overbased materials are prepared by reacting an acidic material (such as carbon dioxide) with an acidic organic compound, an inert reaction medium (e.g., mineral oil), a stoichiometric excess of a metal base, and a promoter such as a phenol or alcohol.
- the acidic organic material will normally have a sufficient number of carbon atoms, to provide oil-solubility.
- Overbased detergents may be characterized by Total Base Number (TBN, ASTM D2896), the amount of strong acid needed to neutralize all of the material's basicity, expressed as mg KOH per gram of sample. Since overbased detergents are commonly provided in a form which contains diluent oil, for the purpose of this document, TBN is to be recalculated to an oil-free basis by dividing by the fraction of the detergent (as supplied) that is not oil. Some useful detergents may have a TBN of 100 to 800, or 150 to 750, or, 400 to 700.
- the metal compounds useful in making the basic metal salts are generally any Group 1 or Group 2 metal compounds (CAS version of the Periodic Table of the Elements). Examples include alkali metals such as sodium, potassium, lithium, copper, magnesium, calcium, barium, zinc, and cadmium. In one embodiment the metals are sodium, magnesium, or calcium.
- the anionic portion of the salt can be hydroxide, oxide, carbonate, borate, or nitrate.
- the lubricant can contain an overbased sulfonate detergent.
- Suitable sulfonic acids include sulfonic and thiosulfonic acids, including mono- or polynuclear aromatic or cycloaliphatic compounds.
- Certain oil-soluble sulfonates can be represented by R 2 -T-(SO 3 - ) a or R 3 -(SO 3 - ) b , where a and b are each at least one; T is a cyclic nucleus such as benzene or toluene; R 2 is an aliphatic group such as alkyl, alkenyl, alkoxy, or alkoxyalkyl; (R 2 )-T typically contains a total of at least 15 carbon atoms; and R 3 is an aliphatic hydrocarbyl group typically containing at least 15 carbon atoms.
- the groups T, R 2 , and R 3 can also contain other inorganic or organic substituents.
- the sulfonate detergent may be a predominantly linear alkylbenzenesulfonate detergent having a metal ratio of at least 8 as described in paragraphs [0026] to [0037] of US Patent Application 2005065045 .
- the phenols useful in making phenate detergents can be represented by (R 1 ) a -Ar-(OH) b , where R 1 is an aliphatic hydrocarbyl group of 4 to 400 or 6 to 80 or 6 to 30 or 8 to 25 or 8 to 15 carbon atoms; Ar is an aromatic group such as benzene, toluene or naphthalene; a and b are each at least one, the sum of a and b being up to the number of displaceable hydrogens on the aromatic nucleus of Ar, such as 1 to 4 or 1 to 2. Phenate detergents are also sometimes provided as sulfur-bridged species.
- the overbased material is an overbased saligenin detergent.
- Overbased saligenin detergents are commonly overbased magnesium salts which are based on saligenin derivatives.
- Saligenin detergents are disclosed in greater detail in U.S. Patent 6,310,009 , with special reference to their methods of synthesis (Column 8 and Example 1).
- Salixarate derivatives and methods of their preparation are described in greater detail in U.S. patent number 6,200,936 and PCT Publication WO 01/56968 . It is believed that the salixarate derivatives have a predominantly linear, rather than macrocyclic, structure, although both structures are intended to be encompassed by the term "salixarate.”
- Overbased glyoxylic detergents and their methods of preparation are disclosed in greater detail in U.S. Patent 6,310,011 and references cited therein.
- the overbased detergent can also be an overbased salicylate, e.g., an alkali metal or alkaline earth metal salt of a substituted salicylic acid.
- Overbased salicylate detergents and their methods of preparation are disclosed in U.S. Patents 4,719,023 and 3,372,116 .
- Other overbased detergents can include overbased detergents having a Mannich base structure, as disclosed in U.S. Patent 6,569,818 .
- the hydrocarbyl substituents on hydroxy-substituted aromatic rings in the above detergents are free of or substantially free of C 12 aliphatic hydrocarbyl groups (e.g., less than 1%, 0.1%, or 0.01% by weight of the substituents are C 12 aliphatic hydrocarbyl groups).
- such hydrocarbyl substituents contain at least 14 or at least 18 carbon atoms.
- the amount of the overbased detergent, in the formulations of the present technology, if it is present, may typically be at least 0.6 weight percent on an oil-free basis, or 0.7 to 5 weight percent or 1 to 3 weight percent or 0.05 to 0.55 weight percent. Either a single detergent or multiple detergents can be present. As alternatively expressed, the amount of overbased calcium detergent may be an amount suitable to deliver 110 to 550 parts per million by weight, or 175 or 400 or 175 to 300 ppm.
- Corrosion inhibitors often refer to copper (or "yellow metal") corrosion inhibitors.
- Such materials include triazole compounds such as tolyltriazole, derivatives of tolyltriazole, imidazoline compounds, thiadiazoles, carboxylic acids and their salts or esters, and alkanolamines.
- Antiwear agents may also be included, in addition to or supplemental to the phosphorus esters described in detail above.
- Examples include phosphorus-containing antiwear/extreme pressure agents such as phosphoric acid esters and salts thereof, phosphorus-containing carboxylic acids, esters, ethers, and amides; and phosphites.
- a phosphorus antiwear agent may be present in an amount to deliver 0.01 to 0.2 or 0.015 to 0.15 or 0.02 to 0.1 or 0.025 to 0.08 percent phosphorus.
- Non-phosphorus-containing anti-wear agents include borate esters (including borated epoxides), dithiocarbamate compounds, molybdenum-containing compounds, and sulfurized olefins.
- Extreme pressure (EP) agents include some of the materials listed elsewhere herein as well as other sulfur- and chlorosulfur-containing EP agents, chlorinated hydrocarbon EP agents, and phosphorus EP agents.
- EP agents include chlorinated wax; sulfurized olefins (such as sulfurized isobutylene), organic sulfides and polysulfides such as dibenzyldisulfide, bis-(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons such as the reaction product of phosphorus sulfide with turpentine or methyl oleate; phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, e.g., dibutyl phosphit
- Seal swell agents include oil-soluble esters and oil-soluble sulfones, sulfolanes, such as isodecyl sulfolane, benzyl esters, lactones, nitriles, phenolic materials, or phthalate esters.
- condensation product is intended to encompass esters, amides, imides and other such materials that may be prepared by a condensation reaction of an acid or a reactive equivalent of an acid (e.g., an acid halide, anhydride, or ester) with an alcohol or amine, irrespective of whether a condensation reaction is actually performed to lead directly to the product.
- an acid e.g., an acid halide, anhydride, or ester
- a particular ester may be prepared by a transesterification reaction rather than directly by a condensation reaction.
- the resulting product is still considered a condensation product.
- each chemical component described is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated.
- each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, byproducts, derivatives, and other such materials which are normally understood to be present in the commercial grade.
- hydrocarbyl substituent or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character.
- hydrocarbyl groups include:
- Needle bearings are a species of roller bearing in which the rollers have a high length-to-diameter ratio, such as at least 3:1 or 4:1 and up to, for instance, 10:1.
- the rollers may be used in a compression bearing, and the rollers may be oriented radially with respect to the axis of rotation of the bearing. Needle bearings may have a higher load capacity than other roller bearings.
- the invention herein is useful for lubricating a transmission such as an automatic transmission; the method of which comprises supplying thereto the lubricant composition as described herein. It may be particularly useful wherein the automatic transmission contains a bearing, such as a needle bearing, that is lubricated by the lubricant composition.
- a bearing such as a needle bearing
- Example 1 (outside scope of claimed invention) A mineral oil-based formulation, containing:
- Example 2 A mineral oil-based formulation, containing:
- Example 3 (outside scope of claimed invention) A mineral oil-based formulation, containing:
- Example 4 (outside scope of claimed invention) A mineral oil-based formulation, containing:
- Example 5 is a commercially available sample of automatic transmission fluid included for comparison. It is a sample of Shell TM ATF134FE, a high performance automatic transmission fluid commercially available from Shell.
- Example 6 is also a commercially available sample of automatic transmission fluid included for comparison. It is Toyota WS (World Standard) automatic transmission fluid used commercially by Toyota TM .
- examples 1 to 4 are subjected to needle bearing testing on a Uisseel TM bearing rig.
- a 100 mL sample of each lubricant is evaluated using a bearing with 12 thrust needle rollers, running 6 tests per sample, with an applied load of 10,000 N, at a speed of 1.1-1.5 m/s (which corresponds to 12,250 rpm needle revolutions and a shaft speed of about 700 rpm), at 120 °C, with a maximum pressure of 2.6 GPa.
- the test results are presented in terms of L10 and L50, fitting data to a Weibull analysis.
- L10 indicates the number of revolutions with a 10 percent probability of failure of the bearing (as determined by pit formation, typically detected as vibration), and L50 indicates the number of revolutions with a 50 percent probability of failure.
- the results, reported in terms of revolutions (cycles) are shown in the following table: L10 L50 KV100 (cSt) KV40 (cSt) Ex 1 285,000 920,000 4.27 17.7 Ex 2 592,000 2,100,000 3.84 15.7 Ex 3 700,000 2,000,000 3.82 15.5 Ex 4 163,000 610,000 3.84 15.8 Ex 5 42,000 255,000 5.30 23.8 Ex 6 148,000 500,000 4.35 18.1
- the transitional term "comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
- the term also encompass, as alternative embodiments, the phrases “consisting essentially of” and “consisting of,” where “consisting of” excludes any element or step not specified and “consisting essentially of” permits the inclusion of additional un-recited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.
- the expression “consisting of” or “consisting essentially of,” when applied to an element of a claim, is intended to restrict all species of the type represented by that element, notwithstanding the presence of "comprising" elsewhere in the claim.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- General Details Of Gearings (AREA)
Claims (14)
- Composition lubrifiante comprenant :(a) une huile ayant une viscosité cinématique à 100 °C de 2,2 à 3,7 mm2/s ;(b) au moins un ester de borate ayant un groupe alkyle de 4 à 18 atomes de carbone en une quantité pour fournir 25 à 300, ou 30 à 150, ou 50 à 100, parties par million en poids de bore à la composition ;(c) au moins un ester de phosphore en une quantité pour fournir 150 à 650 parties par million en poids de phosphore à la composition ;(d) un modificateur d'indice de viscosité comprenant un modificateur de viscosité polymère linéaire ayant une fonctionnalité de dispersant, dans laquelle le polymère linéaire a une masse moléculaire moyenne en poids de 5 000 à 25 000, et dans laquelle ledit polymère linéaire est présent en une quantité de 0,1 à 4 pour cent en poids ; et(e) un dispersant succinimide boré pour fournir 180 à 270 ppm de bore à la composition lubrifiante ;
dans laquelle la viscosité cinématique à 100 °C de la composition lubrifiante est inférieure ou égale à 4,7 mm2/s. - Composition lubrifiante selon la revendication 1, dans laquelle :la quantité de l'au moins un ester de borate (b) est de 0,1 à 1,1 pour cent en poids, ou 0,15 à 0,7 pour cent en poids ; etla quantité de l'au moins un ester de phosphore (c) est de 0,05 à 0,40 pour cent en poids.
- Composition lubrifiante selon la revendication 1, dans laquelle l'huile du composant (a) comprend une huile du groupe II ou du groupe III de l'API ou des mélanges de celles-ci.
- Composition lubrifiante selon l'une quelconque des revendications 1 à 3, dans laquelle (b) l'au moins un composant ester de borate comprend un ester de borate contenant un groupe alkyle de 4 à 12 atomes de carbone et un ester de borate contenant un groupe alkyle de 14 à 18 atomes de carbone.
- Composition lubrifiante selon l'une quelconque des revendications 1 à 3, dans laquelle (b) l'au moins un composant ester de borate comprend un époxyde boré ayant 12 à 18 atomes de carbone.
- Composition lubrifiante selon l'une quelconque des revendications 1 à 4, dans laquelle (b) l'au moins un composant ester de borate comprend le produit de réaction d'acide borique avec un alcool de 6 à 12 atomes de carbone.
- Composition lubrifiante selon l'une quelconque des revendications 1 à 6, dans laquelle (c) l'ester de phosphore comprend un phosphite d'alkyle en C4 à C6 tel que le dibutylphosphite ou un phosphite oligomère qui est le produit de réaction d'un acide ou ester de phosphore monomère avec un alkylène-diol.
- Composition lubrifiante selon l'une quelconque des revendications 1 à 7 dans laquelle (d) le modificateur d'indice de viscosité comprend un poly(méth)acrylate contenant un monomère dispersant contenant de l'azote.
- Composition lubrifiante selon l'une quelconque des revendications 1 à 8, dans laquelle (e) le dispersant succinimide est en outre traité avec un dimercaptothiadiazole.
- Composition selon l'une quelconque des revendications 1 à 9, dans laquelle la quantité de (e) le dispersant succinimide contenant du bore est de 1,0 à 3,5 pour cent en poids.
- Composition lubrifiante selon l'une quelconque des revendications 1 à 10, dans laquelle (e) le composant dispersant succinimide contenant du bore fournit 10 à 250 parties par million en poids de soufre à la composition au moyen de la présence d'un fragment dimercaptothiadiazole présent avec celui-ci.
- Composition lubrifiante selon l'une quelconque des revendications 1 à 11, dans laquelle (e) le dispersant succinimide contenant du bore a une teneur en bore de 0,6 à 0,9 pour cent en poids, ou 0,54 à 0,85, ou 0,56 à 0,83 pour cent en poids.
- Composition lubrifiante comprenant :(a) 50 à 98 pour cent en poids d'une huile ayant une viscosité cinématique à 100 °C de 2,2 à 3,7 mm2/s ;(b) au moins un ester de borate ayant un groupe alkyle de 4 à 18 atomes de carbone, dans laquelle l'ester de borate comprend :(b-1) 0,1 à 1,0 pour cent en poids d'un ester de borate contenant un groupe alkyle en C4 à C12 ;(b-2) 0,15 à 0,40 pour cent en poids d'un ester de borate contenant un groupe alkyle en C14 à C18 ;(c) au moins un ester de phosphore en une quantité pour fournir 150 à 650 parties par million en poids de phosphore à la composition ;(e) un dispersant succinimide boré en une quantité pour fournir 180 à 270 ppm de bore à la composition lubrifiante, dans laquelle le dispersant succinimide boré comprend :(e-1) 1,0 à 4,0 pour cent en poids d'un dispersant succinimide boré non traité avec un dimercaptothiadiazole ; et(e-2) 0,1 à 1,5 pour cent en poids d'un dispersant succinimide boré qui est traité avec un dimercaptothiadiazole ;
dans laquelle la quantité de bore fournie par les composants (b-1), (b-2), (e-1) et (e-2) est d'au moins 180 parties par million en poids de la composition ; et dans laquelle la viscosité cinématique à 100 °C de la composition lubrifiante est inférieure ou égale à 4,7 mm2/s. - Procédé de lubrification d'une transmission automatique comprenant la fourniture à celle-ci de la composition lubrifiante selon l'une quelconque des revendications 1 à 13, dans lequel la transmission automatique contient facultativement un palier qui est lubrifié par ladite composition lubrifiante.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201662435279P | 2016-12-16 | 2016-12-16 | |
| PCT/US2017/066290 WO2018112135A1 (fr) | 2016-12-16 | 2017-12-14 | Lubrification d'une transmission automatique à usure réduite sur un roulement à aiguilles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3555252A1 EP3555252A1 (fr) | 2019-10-23 |
| EP3555252B1 true EP3555252B1 (fr) | 2024-05-08 |
Family
ID=60937913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP17826056.8A Active EP3555252B1 (fr) | 2016-12-16 | 2017-12-14 | Lubrification d'une transmission automatique à usure réduite sur un roulement à aiguilles |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20200080017A1 (fr) |
| EP (1) | EP3555252B1 (fr) |
| JP (1) | JP7145857B2 (fr) |
| CN (1) | CN110088255A (fr) |
| CA (1) | CA3045129A1 (fr) |
| WO (1) | WO2018112135A1 (fr) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10640723B2 (en) | 2018-03-16 | 2020-05-05 | Afton Chemical Corporation | Lubricants containing amine salt of acid phosphate and hydrocarbyl borate |
| FR3112793B1 (fr) * | 2020-07-22 | 2023-04-28 | Total Marketing Services | Composition lubrifiante pour transmission automobile. |
| FR3112791B1 (fr) * | 2020-07-22 | 2023-04-28 | Total Marketing Services | Composition lubrifiante pour transmission automobile aux propriétés anticorrosion améliorées. |
| JP7570907B2 (ja) * | 2020-12-07 | 2024-10-22 | Eneos株式会社 | 潤滑油組成物 |
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| DE1248643B (de) | 1959-03-30 | 1967-08-31 | The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) | Verfahren zur Herstellung von öllöslichen aeylierten Aminen |
| US3197405A (en) | 1962-07-09 | 1965-07-27 | Lubrizol Corp | Phosphorus-and nitrogen-containing compositions and process for preparing the same |
| GB1142195A (en) | 1965-06-18 | 1969-02-05 | British Petroleum Co | Alkaline lubricating oil |
| GB1105217A (en) | 1965-10-05 | 1968-03-06 | Lubrizol Corp | Process for preparing basic metal phenates |
| US3471404A (en) | 1967-03-06 | 1969-10-07 | Mobil Oil Corp | Lubricating compositions containing polysulfurized olefin |
| CA1064463A (fr) | 1975-03-21 | 1979-10-16 | Kirk E. Davis | Produit chimique sulfure |
| US4234435A (en) | 1979-02-23 | 1980-11-18 | The Lubrizol Corporation | Novel carboxylic acid acylating agents, derivatives thereof, concentrate and lubricant compositions containing the same, and processes for their preparation |
| US4285822A (en) | 1979-06-28 | 1981-08-25 | Chevron Research Company | Process for preparing a sulfurized molybdenum-containing composition and lubricating oil containing the composition |
| US4622158A (en) | 1983-11-09 | 1986-11-11 | The Lubrizol Corporation | Aqueous systems containing organo-borate compounds |
| US4594378A (en) | 1985-03-25 | 1986-06-10 | The Lubrizol Corporation | Polymeric compositions, oil compositions containing said polymeric compositions, transmission fluids and hydraulic fluids |
| GB8531626D0 (en) | 1985-12-23 | 1986-02-05 | Shell Int Research | Grease composition |
| US4741848A (en) | 1986-03-13 | 1988-05-03 | The Lubrizol Corporation | Boron-containing compositions, and lubricants and fuels containing same |
| US5110488A (en) | 1986-11-24 | 1992-05-05 | The Lubrizol Corporation | Lubricating compositions containing reduced levels of phosphorus |
| US4792410A (en) | 1986-12-22 | 1988-12-20 | The Lubrizol Corporation | Lubricant composition suitable for manual transmission fluids |
| IN172215B (fr) | 1987-03-25 | 1993-05-08 | Lubrizol Corp | |
| US5157088A (en) | 1987-11-19 | 1992-10-20 | Dishong Dennis M | Nitrogen-containing esters of carboxy-containing interpolymers |
| US4957651A (en) | 1988-01-15 | 1990-09-18 | The Lubrizol Corporation | Mixtures of partial fatty acid esters of polyhydric alcohols and sulfurized compositions, and use as lubricant additives |
| US4959168A (en) | 1988-01-15 | 1990-09-25 | The Lubrizol Corporation | Sulfurized compositions, and additive concentrates and lubricating oils containing same |
| GB8818711D0 (en) | 1988-08-05 | 1988-09-07 | Shell Int Research | Lubricating oil dispersants |
| BR8907130A (pt) | 1988-10-24 | 1991-02-13 | Exxon Chemical Patents Inc | Composicao de oleo lubrificante,fluido de transmissao de forca,concentrado de aditivo,processo para melhorar a modificacao de atrito de um oleo lubrificante,composicao de sal de amina e sal |
| US6310011B1 (en) | 1994-10-17 | 2001-10-30 | The Lubrizol Corporation | Overbased metal salts useful as additives for fuels and lubricants |
| AU710294B2 (en) * | 1995-09-12 | 1999-09-16 | Lubrizol Corporation, The | Lubrication fluids for reduced air entrainment and improved gear protection |
| EP0954517B1 (fr) | 1997-11-13 | 2003-02-05 | Lubrizol Adibis Holdings (Uk) Limited | Calixarenes salicycliques et leur utilisation comme additifs pour lubrifiants |
| EP1254100A1 (fr) | 2000-02-07 | 2002-11-06 | Bp Oil International Limited | Calixarenes et leur utilisation en tant qu'additifs de lubrification |
| US6559105B2 (en) | 2000-04-03 | 2003-05-06 | The Lubrizol Corporation | Lubricant compositions containing ester-substituted hindered phenol antioxidants |
| US6310009B1 (en) | 2000-04-03 | 2001-10-30 | The Lubrizol Corporation | Lubricating oil compositions containing saligenin derivatives |
| US6569818B2 (en) | 2000-06-02 | 2003-05-27 | Chevron Oronite Company, Llc | Lubricating oil composition |
| CN1173019C (zh) * | 2001-08-24 | 2004-10-27 | 中国石油天然气股份有限公司 | 一种手动变速箱油添加剂组合物 |
| ATE292667T1 (de) | 2001-11-05 | 2005-04-15 | Lubrizol Corp | Schmiermittelzusammensetzung mit verbesserter brennstoffersparnis |
| US6660695B2 (en) | 2002-03-15 | 2003-12-09 | Infineum International Ltd. | Power transmission fluids of improved anti-shudder properties |
| US20050014656A1 (en) | 2003-07-16 | 2005-01-20 | The Lubrizol Corporation | Transmission lubricating compositions with improved performance, containing acid/polyamine condensation product |
| US7439213B2 (en) * | 2004-10-19 | 2008-10-21 | The Lubrizol Corporation | Secondary and tertiary amines as friction modifiers for automatic transmission fluids |
| US20070142237A1 (en) | 2005-11-09 | 2007-06-21 | Degonia David J | Lubricant composition |
| CN101479368A (zh) | 2006-04-24 | 2009-07-08 | 卢布里佐尔公司 | 星形聚合物润滑组合物 |
| JP5288861B2 (ja) * | 2008-04-07 | 2013-09-11 | Jx日鉱日石エネルギー株式会社 | 潤滑油組成物 |
| WO2010126760A2 (fr) * | 2009-04-30 | 2010-11-04 | The Lubrizol Corporation | Esters phosphorés polymères pour des applications de lubrifiant |
| EP2661482B1 (fr) * | 2011-01-04 | 2016-12-28 | The Lubrizol Corporation | Fluide de transmission variable en continu ayant une durabilité anti-vibrations prolongée |
| SG192237A1 (en) | 2011-01-31 | 2013-08-30 | Lubrizol Corp | Lubricant composition comprising anti-foam agents |
| JP6100243B2 (ja) | 2011-05-12 | 2017-03-22 | ザ ルブリゾル コーポレイションThe Lubrizol Corporation | 潤滑添加剤としての芳香族イミドおよびエステル |
| JP5988891B2 (ja) | 2013-02-19 | 2016-09-07 | Jxエネルギー株式会社 | 変速機用潤滑油組成物 |
| US20160108337A1 (en) | 2013-05-14 | 2016-04-21 | The Lubrizol Corporation | Lubricating Composition and Method of Lubricating a Transmission |
| US10208269B2 (en) | 2013-12-23 | 2019-02-19 | Exxonmobil Research And Engineering Company | Low viscosity ester lubricant and method for using |
| US9090850B1 (en) | 2014-06-19 | 2015-07-28 | Afton Chemical Corporation | Phosphorus anti-wear compounds for use in lubricant compositions |
| BR112017009936B1 (pt) | 2014-11-12 | 2022-08-30 | The Lubrizol Corporation | Ésteres de fósforo misturados para aplicações lubrificantes |
-
2017
- 2017-12-14 CN CN201780077263.4A patent/CN110088255A/zh active Pending
- 2017-12-14 US US16/469,693 patent/US20200080017A1/en not_active Abandoned
- 2017-12-14 WO PCT/US2017/066290 patent/WO2018112135A1/fr not_active Ceased
- 2017-12-14 JP JP2019531660A patent/JP7145857B2/ja active Active
- 2017-12-14 EP EP17826056.8A patent/EP3555252B1/fr active Active
- 2017-12-14 CA CA3045129A patent/CA3045129A1/fr active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018112135A1 (fr) | 2018-06-21 |
| CN110088255A (zh) | 2019-08-02 |
| EP3555252A1 (fr) | 2019-10-23 |
| JP7145857B2 (ja) | 2022-10-03 |
| JP2020502318A (ja) | 2020-01-23 |
| US20200080017A1 (en) | 2020-03-12 |
| CA3045129A1 (fr) | 2018-06-21 |
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