EP2788462B1 - Motorschmiermittel für hybrid -oder mikrohybridkraftfahrzeuge - Google Patents

Motorschmiermittel für hybrid -oder mikrohybridkraftfahrzeuge Download PDF

Info

Publication number
EP2788462B1
EP2788462B1 EP12797934.2A EP12797934A EP2788462B1 EP 2788462 B1 EP2788462 B1 EP 2788462B1 EP 12797934 A EP12797934 A EP 12797934A EP 2788462 B1 EP2788462 B1 EP 2788462B1
Authority
EP
European Patent Office
Prior art keywords
use according
internal combustion
wear
bearings
combustion engine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP12797934.2A
Other languages
English (en)
French (fr)
Other versions
EP2788462A1 (de
Inventor
Olivier Lerasle
Jérôme VALADE
Mickael DEBORD
Roger THOLLON
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TotalEnergies Marketing Services SA
Original Assignee
Total Raffinage Marketing SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Total Raffinage Marketing SA filed Critical Total Raffinage Marketing SA
Publication of EP2788462A1 publication Critical patent/EP2788462A1/de
Application granted granted Critical
Publication of EP2788462B1 publication Critical patent/EP2788462B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • 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
    • C10M137/10—Thio derivatives
    • 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
    • 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
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • 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
    • 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
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • C10M2219/068—Thiocarbamate metal salts
    • 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
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines

Definitions

  • the present invention relates to the lubrication of hybrid motor vehicle engines and micro-hybrid powered vehicles equipped with the "Stop-and-Start" system.
  • Hybrid drive systems overcome these disadvantages by implementing an electric motor and a conventional thermal internal combustion engine, in series, in parallel or in combination.
  • a hybrid vehicle starting is provided by the electric motor. Up to a speed of the order of 50 km / h, it is the electric motor that ensures the traction of the vehicle. As soon as a higher speed is reached or a strong acceleration is required, the internal combustion engine takes over. When the speed decreases or when the vehicle stops, the internal combustion engine stops and the electric motor takes over. Thus, the internal combustion engine of hybrid vehicles undergoes a significant number of stops and restarts compared to a conventional combustion engine thermal vehicles.
  • some vehicles are equipped with an automatic stop and start device (also called “Stop-and-Start” system in the English terminology, this terminology will be used below). These vehicles are generally considered “micro-hybrid” vehicles. Indeed, these vehicles are equipped with a thermal internal combustion engine and an alternator-starter or a reinforced starter which ensure the stopping and restarting of the internal combustion engine thermal when the vehicle comes to a stop.
  • Thermal internal combustion engines of microhybrid vehicles equipped with the "Stop-and-Start” system such as the internal combustion engines of hybrid vehicles, undergo a significant number of shutdowns and restarts compared to a thermal internal combustion engine. conventional vehicles.
  • the thermal internal combustion engine of hybrid vehicles or micro-hybrid vehicles undergoes, during its life, a number of stops and starts much higher than that of a conventional vehicle.
  • anti-wear compositions comprising a friction modifier have been described.
  • the demand WO2011045773 discloses the use of a kinematic viscosity motor oil at 100 ° C according to ASTM D445 of between 16 and 27 cSt, comprising at least one ester of formula (a) for the lubrication of internal combustion engines of motorized vehicles hybrids, whose maximum torque, measured between 1000 and 3000 revolutions / minute, is greater than 1000 Nm.
  • the ester of formula (a) is an organic friction modifier.
  • This particular organic friction modifier makes it possible to reduce the wear of the conrod bearings of the engine. However the reduction of wear can be further improved.
  • compositions comprising an organomolybdenum compound as a friction modifier.
  • these documents do not teach or suggest the use of such compositions to specifically reduce bearing wear in a combustion engine of hybrid and micro-hybrid vehicles.
  • the anti-wear solutions applicable to a thermal combustion engine of a conventional vehicle are not systematically transferable into a thermal combustion engine of a hybrid and micro-hybrid vehicle. .
  • the Applicant has found that the use in thermal internal combustion engines of hybrid and hybrid motor vehicles equipped with the Stop-and-Start system, lubricating compositions comprising some inorganic friction modifiers allowed to reduce considerably wear of the bearings present in said engines, this without increasing the viscosity of the compositions, which makes possible their commissioning in real conditions, which allows to increase the life of the engine, to increase the interval of time between engine parts changes.
  • the invention relates to the use of a lubricating composition comprising at least one base oil and at least one organomolybdenum compound for reducing wear of the bearings and for lubricating metal surfaces, polymeric surfaces and / or carbon surfaces.
  • a lubricating composition comprising at least one base oil and at least one organomolybdenum compound, is also described, to reduce the wear of the bearings and for the lubrication of metal surfaces, polymeric surfaces and / or amorphous carbon surfaces, motors thermal internal combustion of vehicles with hybrid and / or microhybrid motorization.
  • Micro-hybrid powered vehicles are equipped with an alternator-starter or a reinforced starter.
  • the use of the lubricant composition makes it possible to reduce the wear of the internal combustion engine, in particular the wear of the bearings of the internal combustion engine, in particular the wear of the connecting rod bearings of the combustion engine. internal heat.
  • the use of the lubricant composition makes it possible to increase the service life of the internal combustion engine, in particular the service life of the bearings of the internal combustion engine, in particular the service life of the connecting rod bearings. internal combustion engine.
  • the use of the lubricating composition makes it possible to increase the time interval between the parts changes of the internal combustion engine, in particular the time interval between the changes of the combustion engine bearings.
  • internal thermal in particular the time interval between the changes of the connecting rod bearings of the internal combustion engine thermal.
  • the lubricating composition comprises from 0.1 to 10% by weight, relative to the total weight of lubricating composition, of organomolybdenum compound, preferably from 0.5 to 8%, more preferably from 1 to 5%, more preferably more preferably from 2 to 4%.
  • the organomolybdenum compounds are chosen from dithiocarbamates and / or dithiophosphates of molybdenum, taken alone or as a mixture.
  • the organomolybdenum compounds are chosen from molybdenum dithiocarbamates of formula (I): in which R 1 , R 2 , R 3 and R 4 are, independently of one another, saturated or unsaturated linear or branched alkyl groups, preferably containing from 4 to 18 carbon atoms, preferably from 8 to 13 carbon atoms. .
  • the organomolybdenum compounds are chosen from molybdenum dithiophosphates of formula (II): in which R 5 , R 6 , R 7 and R 8 are independently of each other linear or branched, saturated or unsaturated alkyl groups, preferably containing from 4 to 18 carbon atoms, preferably from 8 to 13 carbon atoms. .
  • the metal surface is an alloy.
  • the alloy is steel.
  • the alloy comprises as base element tin (Sn), lead (Pb), copper (Cu), aluminum (Al), cadmium (Cd), silver ( Ag) or zinc (Zn).
  • an alloy comprising lead (Pb) and copper (Cu).
  • the polymeric surface comprises polytetrafluoroethylene.
  • the kinematic viscosity at 100 ° C of the lubricating composition is between 5.6 and 12.5 cSt.
  • the present invention relates to the reduction of the wear of the bearings and the lubrication of the internal combustion engines of vehicles with hybrid or micro-hybrid powertrain.
  • the thermal internal combustion engine undergoes, during its life, a number of stops and starts much higher than in a conventional vehicle (phenomenon of "Stop-and-Start") .
  • vehicle with micro-hybrid powertrain means vehicles comprising a thermal internal combustion engine, but no electric motor such as hybrid vehicles, the "hybrid” character being provided by the presence of the Stop and Start system provided by an alternator. -starter or a reinforced starter which ensure the stopping and restarting of the engine when the vehicle comes to rest and then restarts.
  • the present invention is more preferably aimed at the lubrication of internal combustion engines of vehicles equipped with hybrid or micro-hybrid systems circulating in an urban environment, where the Stop-and-Start phenomenon and the resulting wear are increased.
  • a fixed part comprising the engine block, the cylinder head, the cylinder head gasket, the liner and various parts ensuring the assembly and sealing of these different parts.
  • a movable part comprising the crankshaft, the connecting rod and its bearings, the piston and its segments.
  • the role of the connecting rod is to transmit to the crankshaft the forces received by the piston, transforming a reciprocating rectilinear motion into a circular motion in one direction.
  • a connecting rod has two circular bores, one of small diameter, called small end, and the other of large diameter called big end. Between these two bores, is the body of the connecting rod connecting the small end and the small end.
  • the small end is engaged around the axis of the piston, the friction between the small end and the axis of the piston is reduced by the interposition between the two moving parts of a circular ring covered or made of anti-metal. friction (bronze, for example), or bearings (usually needle).
  • crankpin crankpin The big end, it, encloses the crankpin crankpin.
  • the friction between the crankpin and crankpin assembly is reduced by the existence of an oil film and the interposition between the crankpin and the crankpin, pads. In this case we speak of big-end bearings.
  • crankshaft is a rotating part. Its positioning and maintenance are achieved by a number of bearings, called trunnions. So we have a fixed part, the bearing crankshaft, which encloses a moving part, the crankshaft journal. Lubrication between these two parts is imperative and pads are put in place to resist the forces applied to these bearings. In this case we speak of trunnion bushings (or bearings of shaft line or crankshaft bearings).
  • the role of the bearing in the case of a big end or a trunnion, is to allow a good rotation of the crankshaft.
  • the pads are thin shells in the shape of a half-cylinder. These are parts that are extremely sensitive to lubrication conditions. If there is contact between the bushing and the rotating shaft, crankpin or pin, the energy released systematically leads to significant wear or engine breakage. The generated wear can also play the role of amplifying the phenomenon and the severity of the contact.
  • the bearings are subject to several types of wear in the motors.
  • the different types of wear encountered in motors are: adhesive wear or wear through metal-to-metal contact, abrasive wear, corrosive wear, fatigue wear, or complex forms of wear ( contact corrosion, cavitation erosion, electrical wear).
  • the pads are subject in particular to adhesive wear, the invention is particularly useful for improving this type of wear but the invention can nevertheless be applied to the other types of wear mentioned above.
  • Surfaces that will be susceptible to wear are metal-like surfaces, or metallic-type surfaces coated with another layer which may be either a polymer or an amorphous carbon layer. . Wear occurs at the interface between said surfaces that come into contact when the oil film becomes insufficient.
  • the metal type surface may be a surface made of a pure metal such as tin (Sn) or lead (Pb). Most of the time, the metal type surface will be a metal type alloy, based on a metal and at least one other metal element or not. A frequently used alloy is steel, iron alloy (Fe) and carbon (C). The bearings used in the automotive industry, are mostly bearings whose support is made of steel, a support coated or not with another metal alloy.
  • the other metal alloys constituting the metal surfaces according to the invention are alloys comprising as base element tin (Sn), lead (Pb), copper (Cu) or aluminum (Al).
  • Cadmium (Cd), silver (Ag) or zinc (Zn) may also be basic elements of the metal alloys constituting the metal surfaces according to the invention.
  • To these basic elements will be added other elements chosen from antimony (Sb), arsenic (As), chromium (Cr), indium (In), magnesium (Mg), nickel (Ni), platinum (Pt) or silicon (Si).
  • Preferred alloys are based on the following combinations Al / Sn, Al / Sn / Cu, Cu / Sn, Cu / Al, Sn / Sb / Cu, Pb / Sb / Sn, Cu / Pb, PB / Sn / Cu, Al / Pb / Si, Pb / Sn, Pb / In, Al / Si, Al / Pb.
  • the preferred combinations are Sn / Cu, Sn / Al, Pb / Cu or Pb / Al combinations.
  • Copper and lead-based alloys are preferred alloys, and are also known as cupro-lead or white metal alloys.
  • the surfaces affected by wear are polymeric surfaces.
  • the pads will be steel and will include in addition this polymeric surface.
  • the polymers that can be used are either thermoplastics such as polyamides, polyethylenes, fluoropolymers such as tetrafluoroethylenes, in particular polytetrafluoroethylenes (PTFE), or thermosetting agents such as polyimides and phenoplasts.
  • the surfaces concerned by the wear are surfaces of amorphous carbon type.
  • the bearings will be made of steel and will include in addition this amorphous carbon type surface.
  • the surfaces of amorphous carbon type are also called DLC, or Diamond Like Carbon or Diamond Like Coating, whose carbons are sp 2 and sp 3 hybridizations.
  • the surfaces affected by wear are not ceramic surfaces. This type of ceramic coating is used very little in the field of vehicles because of their fragility and recyclability constraints applied to modern engines.
  • the lubricant compositions used in the invention comprise at least one friction modifier chosen from organomolybdenum compounds. These compounds are, as their name indicates, compounds based on molybdenum, carbon and hydrogen, but these compounds also contain sulfur and phosphorus, and also oxygen and nitrogen.
  • the organomolybdenum compounds according to the invention are, for example, molybdenum dithiophosphates, molybdenum dithiocarbamates, molybdenum dithiophosphinates, molybdenum xanthates, molybdenum thioxanthates, and various organic molybdenum complexes such as molybdenum carboxylates, molybdenum esters, the molybdenum amides, obtainable by reacting molybdenum oxide or ammonium molybdates with fatty substances, glycerides or fatty acids, or fatty acid derivatives (esters, amines, amides ).
  • Organomolybdenum compounds which are suitable for the lubricating compositions according to the present invention are for example described in the application EP2078745 , from paragraph [0036] to paragraph [062].
  • Preferred organomolybdenum compounds are molybdenum dithiophosphates and / or molybdenum dithiocarbamates.
  • molybdenum dithiocarbamates have been found to be very effective in reducing pad wear.
  • These molybdenum dithiocarbamates have the following general formula (I) in which R 1 , R 2 , R 3 or R 4 are independently of each other linear or branched alkyl groups, saturated or unsaturated, comprising 4 to 18 carbon atoms, preferably 8 to 13.
  • molybdenum dithiophosphates have the following general formula (II) in which R 5 , R 6 , R 7 or R 8 are independently of each other linear or branched alkyl groups, saturated or unsaturated, comprising 4 to 18 carbon atoms, preferably 8 to 13.
  • the lubricating compositions according to the invention may comprise between 0.1 and 10% by weight, relative to the total mass of lubricating composition, of organomolybdenum compound, preferably between 0.5 and 8%, more preferably between 1 and 5% more preferably between 2 and 4%.
  • the Applicant has shown that the use of these organomolybdenum compounds, in a motor oil, can significantly reduce the wear of the connecting rod bearings on the engines of hybrid or micro-hybrid vehicles, without changing the consumption. of fuel or reducing fuel consumption.
  • organomolybdenum compounds that can be used according to the invention comprise from 1 to 30% by weight of molybdenum, relative to the total mass of organomolybdenum compound, preferably from 2 to 20%, more preferably from 4 to 10%, even more preferably from 8 to 10% by weight. at 5%.
  • organomolybdenum compounds which can be used according to the invention comprise from 1 to 30% by weight of sulfur, relative to the total weight of organomolybdenum compound, preferably from 2 to 20%, more preferably from 4 to 10%, even more preferably from 8 to 10% by weight. at 5%.
  • organomolybdenum compounds which can be used according to the invention comprise from 1 to 10% by weight of phosphorus, with respect to the total weight of organomolybdenum compound, preferably from 2 to 8%, more preferably from 3 to 6%, even more preferably from 4 to 10% by weight. at 5%.
  • the lubricating compositions used according to the present invention comprise one or more base oils, generally representing from 50% to 90% by weight, relative to the total mass of the lubricating composition, preferably from 60% to 85%, more preferably from 65 to 80%, even more preferably 70 to 75%.
  • the base oil (s) used in the lubricant compositions according to the present invention may be oils of mineral or synthetic origin of groups I to V according to the classes defined in the API classification (or their equivalents according to the ATIEL classification) as summarized below, alone or as a mixture.
  • oils may be oils of vegetable, animal or mineral origin.
  • the mineral base oils according to the invention include all types of bases obtained by atmospheric distillation and vacuum of crude oil, followed by refining operations such as solvent extraction, desalphating, solvent dewaxing, hydrotreatment, hydrocracking and hydroisomerization, hydrofinishing.
  • the base oils of the compositions according to the present invention may also be synthetic oils, such as certain esters of carboxylic acids and alcohols, or polyalphaolefins.
  • the polyalphaolephines used as base oils are obtained from monomers having from 4 to 32 carbon atoms (for example octene, decene), and a viscosity at 100 ° C. of between 1.5 and 15 cSt (measured according to ASTM D 445). Their weight average molecular weight is typically between 250 and 3000 (measured according to ASTM D5296).
  • Mixtures of synthetic and mineral oils may also be employed, for example when formulating multigrade oils to avoid cold start problems.
  • the lubricating compositions can comprise improving polymers of viscosity index (VI improving), such as, for example, polymeric esters, olefins copolymers (OCP), homopolymers or copolymers of styrene, butadiene or isoprene, polymethacrylates. (LDCs).
  • VI improving polymers of viscosity index
  • OCP olefins copolymers
  • LDCs polymethacrylates.
  • the lubricant compositions according to the present invention may contain from 0 to 20%, or from 5 to 15%, or from 7 to 10% by weight, based on the total weight of the lubricating composition, of improving polymers.
  • viscosity index (VI improvers) by examples chosen from polymeric esters, olefins copolymers (OCP), homopolymers or copolymers of styrene, butadiene or isoprene, polymethacrylates (PMA).
  • the lubricant compositions according to the invention preferably have a viscosity index value or VI, measured according to ASTM D2270 greater than 130, preferably greater than 140, preferably greater than 150.
  • the lubricant compositions according to the invention have a kinematic viscosity (KV100) at 100 ° C. according to ASTM D445, of between 3.8 cSt and 26.1 cSt, preferably between 5.6 and 12.5 cSt, which corresponds, according to the SAE J 300 classification, to grades 20 (5.6 to 9.3 cSt) or 30 (9.3 to 12.5 cSt) hot.
  • KV100 kinematic viscosity
  • the lubricant compositions according to the invention are multigrade engine oils grade 0W or 5W cold, and 20 or 30 hot according to classification SAE J 300.
  • the lubricant compositions for engines used according to the invention may furthermore contain all types of additives suitable for use as engine oil.
  • additives can be introduced individually and / or included in packages of additives used in commercial lubricant formulations, performance levels as defined by the ACEA (Association of European Automobile Manufacturers) and / or the API. (American Petroleum Institute).
  • ACEA Association of European Automobile Manufacturers
  • API API.
  • These additive packages are concentrates comprising about 30% by weight of dilution base oil.
  • the lubricant compositions according to the invention may contain, in particular and without limitation, anti-wear and extreme pressure additives, antioxidants, overbased or non-overbased detergents, pour point improvers, dispersants, defoamers, thickeners ...
  • the anti-wear and extreme pressure additives protect the friction surfaces by forming a protective film adsorbed on these surfaces.
  • the most commonly used is zinc dithiophosphate or ZnDTP. This category also contains various phosphorus, sulfur, nitrogen, chlorine and boron compounds.
  • anti-wear additives there is a wide variety of anti-wear additives, but the most used category in engine oils is that of phosphosulfur additives such as metal alkylthiophosphates, particularly zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates or ZnDTPs.
  • the preferred compounds are of formula Zn ((SP (S) (OR 9 ) (OR 10 )) 2 , or R 9 and R 10 are linear or branched, saturated or unsaturated alkyl groups, preferably containing from 1 to 18 atoms
  • the ZnDTP is typically present at levels of the order of 0.1 to 2% by weight, based on the total weight of the lubricating composition.
  • Amine phosphates, polysulfides, especially sulfur olefins, are also commonly used antiwear additives.
  • the anti-wear and extreme-pressure additives are generally present in the compositions for motor lubricants at contents of between 0.5 and 6% by weight, preferably between 0.7 and 2%, preferably between 1 and 1.5%. relative to the total mass of the lubricating composition.
  • Antioxidants delay the degradation of oils in service, which can result in the formation of deposits, the presence of sludge, or an increase in the viscosity of the oil. They act as free radical inhibitors or destroyers of hydroperoxides.
  • antioxidants are phenolic and / or amine antioxidants.
  • Phenolic antioxidants may be ashless, or may be in the form of neutral or basic metal salts. Typically, these are compounds containing a sterically hindered hydroxyl group, for example when two hydroxyl groups are in the ortho or para position of each other, or when the phenol is substituted by an alkyl group comprising at least 6 carbon atoms. .
  • Amino compounds are another class of antioxidants that can be used alone or possibly in combination with phenolic compounds.
  • Typical examples are aromatic amines, of formula R 11 R 12 R 13 N, where R 11 is an optionally substituted aromatic group, or aromatic group, R 12 is an optionally substituted aromatic group, R 13 is hydrogen, or an alkyl or aryl group, or a group of the formula R 14 S (O) x R 15 , where R 14 and R 15 are alkylene, alkenylene, or aralkylene groups, and x is 0, 1 or 2.
  • Sulfurized alkyl phenols or their alkali and alkaline earth metal salts are also used as antioxidants.
  • antioxidants are that of oil-soluble copper compounds, for example copper thio- or dithiophosphates, copper and carboxylic acid salts, dithiocarbamates, sulphonates, phenates, acetylacetonates of copper.
  • the copper salts I and II, succinic acid or anhydride are used.
  • These compounds are typically present in the engine lubricating compositions in amounts of between 0.1 and 5% by weight, preferably between 0.3 and 2%, even more preferably between 0.5 and 1, 5%, based on the total mass of the lubricating composition.
  • Detergents reduce the formation of deposits on the surface of metal parts by dissolving secondary products of oxidation and combustion, and allow the neutralization of some acid impurities from combustion and found in the oil.
  • the detergents commonly used in the formulation of lubricating compositions are typically anionic compounds having a long lipophilic hydrocarbon chain and a hydrophilic head.
  • the associated cation is typically a metal cation of an alkali or alkaline earth metal.
  • the detergents are preferably chosen from alkali metal or alkaline earth metal salts of carboxylic acids, sulphonates, salicylates and naphthenates, as well as the salts of phenates, preferably of calcium, magnesium, sodium or barium.
  • metal salts may contain the metal in an approximately stoichiometric amount or in excess (in an amount greater than the stoichiometric amount). In the latter case, we are dealing with so-called overbased detergents.
  • the excess metal providing the overbased detergent character is in the form of oil-insoluble metal salts, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate, preferably calcium, magnesium, sodium or barium.
  • the lubricant compositions according to the present invention may contain any type of detergent known to those skilled in the art, neutral or overbased.
  • the more or less overbased character of the detergents is characterized by the base number BN (base number or BN in English terminology), measured according to the ASTM D2896 standard, and expressed in mg of KOH per gram.
  • Neutral detergents have a BN between about 0 and 80 mg KOH / g.
  • the BN of the lubricant composition containing detergents is measured by ASTM D2896 and expressed as mg KOH per gram of lubricant.
  • the amounts of detergents included in the motor oils according to the invention are adjusted so that the BN of said oils, measured according to ASTM D2896, is between 5 and less than or equal to 20 mg of KOH per gram of d motor oil, preferably between 8 and 15 mg of KOH per gram of engine oil
  • Pour point depressant additives improve the cold behavior of oils by slowing the formation of paraffin crystals. They are for example alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes, alkylated polystyrene. They are generally present in the oils according to the invention at contents of between 0.1 and 0.5% by weight, relative to the mass of lubricating composition.
  • Dispersants such as succinimides, PIB (polyisobutene) succinimides, Mannich bases ensure the maintenance in suspension and evacuation of insoluble solid contaminants formed by the secondary oxidation products that are formed when the engine oil is in use.
  • the dispersant level is typically between 0.5 and 10% by weight, preferably between 1 and 5%, relative to the total weight of the lubricant composition.
  • a method for reducing bearing wear and for lubricating metal surfaces, polymeric surfaces and / or amorphous carbon surfaces, thermal internal combustion engines of hybrid and / or microhybrid vehicles by the use of a lubricating composition comprising at least one base oil and at least one organomolybdenum compound is also described.
  • the set of characteristics and preferences presented for the lubricant composition according to the invention also applies to the method according to the invention.
  • the system tested includes a 4-cylinder diesel engine with a maximum torque of 200 Nm from 1750 to 2500 rpm. It is of the Stop-and-Start type and includes an alternator-starter between the clutch and the gearbox of the vehicle.
  • the engine oil is maintained at about 100 ° C in these tests.
  • the wear is followed by a usual technique of radiotracers, consisting of irradiating the surface of the connecting rod bearings whose wear is to be tested, and measuring during the test the increase in radioactivity of the engine oil, that is, the rate of loading of the oil into irradiated metal particles. This speed is directly proportional to the wear speed of the bearings.
  • the results are based on a comparative analysis of these damage rates (reference oil and test oil) and are validated by a frame with a reference oil in order to integrate positive or negative surface adaptation elements to the speed of damage.
  • the damage rates of the oils tested are all compared to the rate of damage of the reference oil and quantified as a speed ratio named Usure in Table I below.
  • the lubricant composition A is a grade 5W30 reference lubricant composition.
  • the lubricating composition B is an additive composition with an anti-wear known ZnDTP, zinc dithiophosphate of formula (III) wherein R 16 is an alkyl group comprising from 1 to 24 carbon atoms.
  • the lubricant composition C is an additive lubricant composition with a known anti-wear ZnDTC, a zinc diamyldithiocarbamate.
  • the lubricating composition D is a lubricant composition according to the prior art, and in particular according to the application WO2011045773 wherein the ester-type organic friction modifier which has the general formula (a) R (OH) m (COOR '(OH) p (OOCR ") q ) n with m equal to 1, p equal to 0, q equal to 0, n equal to 3 and R 'is an ethyl group.
  • the lubricating composition E is a lubricating composition according to the invention with, as friction modifier, an organomolybdenum compound of general formula (I) with R 1 , R 2 , R 3 and R 4 which are alkyl groups of 13 and / or 18 atoms. of carbon, the amount of molybdenum by weight, relative to the weight of the compound, is 10%, the amount of sulfur by weight, relative to the weight of the compound, is 11%.
  • the lubricating composition F is a lubricating composition according to the invention with, as friction modifier, an organomolybdenum compound of general formula (II) with R 5 , R 6 , R 7 and R 8 which are alkyl groups of 8 carbon atoms.
  • quantity of molybdenum by weight, relative to the weight of the compound is 9%
  • the amount of sulfur by weight, relative to the weight of the compound is 10.1%
  • the amount of phosphorus in mass, relative to to the mass of the compound is 3.2%.
  • the base oil used is a blend of Group III base oils with a viscosity number of 171.
  • the polymer used is a styrene polymer / butadiene linear mass M w equal to 139,700, mass M n equal to 133 000, of polydispersity index equal to 1.1, PSSI (permanent stability index at shear or Permanent Shear Stability Index in English terminology) equal to 15, 8% active ingredient in a Group III base oil.
  • the antioxidant is an amine antioxidant of alkylarylamine structure.
  • the PPD or Depressant Point in English terminology
  • pour point depressant is polymethacrylate type.
  • the additive package used includes conventional anti-wear, anti-oxidant, dispersant and detergent additives.
  • the lubricant composition A is taken as a reference.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (14)

  1. Verwendung einer Schmierzusammensetzung umfassend mindestens ein Basisöl und mindestens eine Organomolybdänverbindung zur Verringerung des Lagerverschleißes und zur Schmierung von Metalloberflächen, von Polymeroberflächen und/oder von amorphen Kohlenstoffoberflächen, von thermischen Verbrennungsmotoren von Fahrzeugen mit Microhybrid-Motorisierung ausgestattet mit einem Anlassergenerator oder einem verstärkten Anlasser.
  2. Verwendung gemäß Anspruch 1 zur Verringerung des Lagerverschleißes der Pleuelstange des thermischen Verbrennungsmotors.
  3. Verwendung gemäß einem der Ansprüche 1 oder 2 zur Erhöhung der Lebensdauer des thermischen Verbrennungsmotors, insbesondere der Lebensdauer der Lager des thermischen Verbrennungsmotors, insbesondere der Lebensdauer der Lager der Pleuelstange des thermischen Verbrennungsmotors.
  4. Verwendung gemäß einem der Ansprüche 1 bis 3 zur Erhöhung des Zeitabstandes zwischen den Wechseln der Lager des thermischen Verbrennungsmotors, insbesondere des Zeitabstandes zwischen den Wechseln der Lager der Pleuelstange des thermischen Verbrennungsmotors.
  5. Verwendung gemäß einem der Ansprüche 1 bis 4, wobei die Schmierzusammensetzung von 0,1 bis 10 Massenprozent, bezogen auf die Gesamtmasse der Schmierzusammensetzung, an Organomolybdänverbindung umfasst, vorzugsweise von 0,5 bis 8 %, bevorzugter von 1 bis 5 %, noch bevorzugter von 2 bis 4 %.
  6. Verwendung gemäß einem der Ansprüche 1 bis 5, wobei die Organomolybdänverbindungen ausgewählt sind aus Molybdändithiocarbamaten und/oder -dithiophosphaten, allein genommen oder als Mischung.
  7. Verwendung gemäß einem der Ansprüche 1 bis 6, wobei die Organomolybdänverbindungen ausgewählt sind aus den Molybdändithiocarbamaten der Formel (I):
    Figure imgb0008
     wobei R1, R2, R3, R4 unabhängig voneinander lineare oder verzweigte, gesättigte oder ungesättigte Alkylgruppen sind, enthaltend vorzugsweise von 4 bis 18 Kohlenstoffatome, vorzugsweise von 8 bis 13.
  8. Verwendung gemäß einem der Ansprüche 1 bis 6, wobei die Organomolybdänverbindungen ausgewählt sind aus den Molybdändithiophosphaten der Formel (II):
    Figure imgb0009
     wobei R5, R6, R7, R8 unabhängig voneinander lineare oder verzweigte, gesättigte oder ungesättigte Alkylgruppen sind, enthaltend vorzugsweise von 4 bis 18 Kohlenstoffatome, vorzugsweise von 8 bis 13.
  9. Verwendung gemäß einem der Ansprüche 1 bis 8, wobei die Metalloberfläche eine Legierung ist.
  10. Verwendung gemäß Anspruch 9, wobei die Legierung Stahl ist.
  11. Verwendung gemäß Anspruch 9, wobei die Legierung als Basiselement Zinn (Sn), Blei (Pb), Kupfer (Cu), Aluminium (Al), Cadmium (Cd), Silber (Ag) oder Zink (Zn) umfasst.
  12. Verwendung gemäß Anspruch 11, wobei die Legierung Blei (Pb) und Kupfer (Cu) umfasst.
  13. Verwendung gemäß einem der Ansprüche 1 bis 8, wobei die Polymeroberfläche Polytetrafluorethylen umfasst.
  14. Verwendung gemäß einem der Ansprüche 1 bis 13, wobei die kinematische Viskosität der Schmierzusammensetzung bei 100 °C, gemessen gemäß der Norm ASTM D445, zwischen 5,6 und 12,5 cST liegt.
EP12797934.2A 2011-12-09 2012-12-07 Motorschmiermittel für hybrid -oder mikrohybridkraftfahrzeuge Active EP2788462B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1161380A FR2983867B1 (fr) 2011-12-09 2011-12-09 Lubrifiant moteur pour vehicules a motorisation hybride ou micro-hybride
PCT/EP2012/074786 WO2013083777A1 (fr) 2011-12-09 2012-12-07 Lubrifiant moteur pour vehicules a motorisation hybride ou micro-hybride

Publications (2)

Publication Number Publication Date
EP2788462A1 EP2788462A1 (de) 2014-10-15
EP2788462B1 true EP2788462B1 (de) 2019-12-04

Family

ID=47297299

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12797934.2A Active EP2788462B1 (de) 2011-12-09 2012-12-07 Motorschmiermittel für hybrid -oder mikrohybridkraftfahrzeuge

Country Status (7)

Country Link
EP (1) EP2788462B1 (de)
JP (1) JP2015500367A (de)
KR (1) KR20140110852A (de)
CN (1) CN103975047A (de)
ES (1) ES2764736T3 (de)
FR (1) FR2983867B1 (de)
WO (1) WO2013083777A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6666430B2 (ja) * 2015-08-14 2020-03-13 ヴァンダービルト ケミカルズ、エルエルシー 硫黄含有有機モリブデン化合物、硫黄非含有有機モリブデン化合物、およびトリアゾールを含む潤滑剤組成物用添加剤
CN105132107B (zh) * 2015-09-11 2019-04-09 中国石油化工股份有限公司 一种用于纯电动车变速箱的润滑油组合物
JP6667493B2 (ja) * 2017-12-12 2020-03-18 株式会社豊田中央研究所 摺動システム

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2778646B2 (ja) * 1988-09-27 1998-07-23 高木特殊工業株式会社 滑り軸受
JPH08210343A (ja) * 1994-11-28 1996-08-20 Nissan Motor Co Ltd 内燃機関のコンロッド軸受構造
JPH08177844A (ja) * 1994-12-26 1996-07-12 Nissan Motor Co Ltd 内燃機関の潤滑システム
JPH08261227A (ja) * 1995-03-20 1996-10-08 Nissan Motor Co Ltd 内燃機関のコンロッド軸受構造
JP2004019682A (ja) * 2002-06-12 2004-01-22 Taiho Kogyo Co Ltd エンジンの軸受装置
US6821932B2 (en) * 2002-12-17 2004-11-23 Ethyl Corporation Delivering molybdenum from a lubricant source into a fuel combustion system
EP1471130A1 (de) * 2003-04-23 2004-10-27 Ethyl Petroleum Additives Ltd Eine Kraftstoffzusammensetzung, die eine Molybdenumquelle und metallhaltiges Detergent enthält und deren Verwendung in Zweitaktmotoren
US7134427B2 (en) * 2003-05-22 2006-11-14 Afton Chemical Intangibles Llc Delivery of organomolybdenum via vapor phase from a lubricant source into a fuel combustion system
JP4334986B2 (ja) * 2003-12-05 2009-09-30 コスモ石油ルブリカンツ株式会社 エンジン油組成物
DE102006013399A1 (de) * 2005-12-21 2007-07-05 Mahle International Gmbh Pleuel für einen Verbrennungsmotor und Verfahren zu seiner Herstellung
JP2009063154A (ja) * 2007-09-10 2009-03-26 Nsk Ltd 転動装置
US20090163392A1 (en) 2007-12-20 2009-06-25 Boffa Alexander B Lubricating oil compositions comprising a molybdenum compound and a zinc dialkyldithiophosphate
EP2177596A1 (de) * 2008-10-20 2010-04-21 Castrol Limited Verfahren zum Betrieb eines Hybridmotors
US9441181B2 (en) * 2009-07-23 2016-09-13 International Technology Center Lubricant and synergistic additive formulation
KR101080763B1 (ko) * 2009-09-21 2011-11-07 현대자동차주식회사 장수명 가솔린 엔진오일 조성물
FR2951456B1 (fr) 2009-10-16 2011-12-09 Total Raffinage Marketing Lubrifiant moteur

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
JP2015500367A (ja) 2015-01-05
ES2764736T3 (es) 2020-06-04
EP2788462A1 (de) 2014-10-15
KR20140110852A (ko) 2014-09-17
FR2983867A1 (fr) 2013-06-14
WO2013083777A1 (fr) 2013-06-13
CN103975047A (zh) 2014-08-06
FR2983867B1 (fr) 2014-08-22

Similar Documents

Publication Publication Date Title
EP2844726B1 (de) Schmiermittelzusammensetzung für einen motor
EP3697876B1 (de) Verwendung einer zusammensetzung zur kühlung und schmierung eines antriebssystems eines fahrzeuges
EP2986693B1 (de) Schmiermittelzusammensetzung auf der basis von metallnanopartikeln
EP2920283B1 (de) Schmiermittelzusammensetzung
EP2844725A1 (de) Motorschmiermittel für fahrzeuge mit einem hybrid- oder mikrohybridmotor
WO2017149119A1 (fr) Composition lubrifiante à base d'amines neutralisées et de molybdène
EP2788462B1 (de) Motorschmiermittel für hybrid -oder mikrohybridkraftfahrzeuge
EP2958980A1 (de) Schmiermittelzusammensetzung auf der basis von aminierten verbindungen
FR3000103A1 (fr) Composition lubrifiante a base d'ether de polyglycerol
WO2019202150A1 (fr) Composition lubrifiante pour moteurs industriels a potentiel fe amplifie
EP2488618B1 (de) Verwendung eines motorschmiermittels
WO2018077780A1 (fr) Composition lubrifiante
WO2024056827A1 (fr) Utilisation d'un monoester dans une composition lubrifiante pour transmissions de
EP4314214A1 (de) Schmierung eines wiederaufladbaren hybridfahrzeugmotors und hybridfahrzeug mit bereichserweiterer

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140530

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RIN1 Information on inventor provided before grant (corrected)

Inventor name: DEBORD, MICKAEL

Inventor name: THOLLON, ROGER

Inventor name: VALADE, JEROME

Inventor name: LERASLE, OLIVIER

17Q First examination report despatched

Effective date: 20150617

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20190509

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAL Information related to payment of fee for publishing/printing deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR3

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

INTC Intention to grant announced (deleted)
GRAR Information related to intention to grant a patent recorded

Free format text: ORIGINAL CODE: EPIDOSNIGR71

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAL Information related to payment of fee for publishing/printing deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR3

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAR Information related to intention to grant a patent recorded

Free format text: ORIGINAL CODE: EPIDOSNIGR71

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

INTG Intention to grant announced

Effective date: 20191015

INTG Intention to grant announced

Effective date: 20191022

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1209412

Country of ref document: AT

Kind code of ref document: T

Effective date: 20191215

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012066241

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200304

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200305

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200304

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20200124

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20200124

Year of fee payment: 8

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2764736

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20200604

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20200528

Year of fee payment: 8

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200404

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012066241

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1209412

Country of ref document: AT

Kind code of ref document: T

Effective date: 20191204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191207

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191207

26N No opposition filed

Effective date: 20200907

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191231

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191231

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20121207

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20210101

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20201231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210101

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20220222

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201208

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20191204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201231

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20221223

Year of fee payment: 11

Ref country code: FR

Payment date: 20221222

Year of fee payment: 11

Ref country code: DE

Payment date: 20221213

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20221228

Year of fee payment: 11

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602012066241

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20231207