EP3263677A1 - Composition d'huile lubrifiante biodégradable - Google Patents

Composition d'huile lubrifiante biodégradable Download PDF

Info

Publication number
EP3263677A1
EP3263677A1 EP16755611.7A EP16755611A EP3263677A1 EP 3263677 A1 EP3263677 A1 EP 3263677A1 EP 16755611 A EP16755611 A EP 16755611A EP 3263677 A1 EP3263677 A1 EP 3263677A1
Authority
EP
European Patent Office
Prior art keywords
lubricating oil
acid
base oil
mass
oil composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP16755611.7A
Other languages
German (de)
English (en)
Other versions
EP3263677B1 (fr
EP3263677A4 (fr
Inventor
Shinji Aoki
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.)
Idemitsu Kosan Co Ltd
Original Assignee
Idemitsu Kosan Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Idemitsu Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
Publication of EP3263677A1 publication Critical patent/EP3263677A1/fr
Publication of EP3263677A4 publication Critical patent/EP3263677A4/fr
Application granted granted Critical
Publication of EP3263677B1 publication Critical patent/EP3263677B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04Mixtures of base-materials and additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32Esters
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32Esters
    • C10M105/38Esters of polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04Hydroxy compounds
    • C10M129/10Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68Esters
    • C10M129/76Esters containing free hydroxy or carboxyl groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M137/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04Phosphate esters
    • C10M137/10Thio derivatives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/2805Esters used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/282Esters of (cyclo)aliphatic oolycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/283Esters of polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/283Esters of polyhydroxy compounds
    • C10M2207/2835Esters of polyhydroxy compounds used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/287Partial esters
    • C10M2207/288Partial esters containing free carboxyl groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/287Partial esters
    • C10M2207/289Partial esters containing free hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular 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
    • C10M2209/084Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064Di- and triaryl amines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/223Five-membered rings containing nitrogen and carbon only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/041Triaryl phosphates
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/047Thioderivatives not containing metallic elements
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/02Unspecified siloxanes; Silicones
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/04Molecular weight; Molecular weight distribution
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/065Saturated Compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02Pour-point; Viscosity index
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/08Resistance to extreme temperature
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10Inhibition of oxidation, e.g. anti-oxidants
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64Environmental friendly compositions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/08Hydraulic fluids, e.g. brake-fluids

Definitions

  • the present invention relates to a biodegradable lubricating oil composition containing a synthetic ester base oil.
  • a biodegradable lubricating oil is required to have a high biodegradation rate, and, therefore, use of a large quantity of a mineral oil that is popularly used as a base oil in an ordinary lubricating oil is difficult. Consequently, the base oil must be selected from a limited range of a natural vegetable oil, a synthetic polyalkylene glycol base oil, a synthetic ester base oil and the like. Heretofore, among these, a synthetic ester base oil that is relatively excellent in heat stability and oxidation stability is much used.
  • PTL 1 discloses a biodegradable lubricating oil prepared by blending a phenol-based antioxidant, a low base number calcium sulfonate and a triazole compound in a base oil containing a hindered ester in an amount of 50% by mass or more for enhancing lubrication performance, oxidation stability and anticorrosion performance.
  • Performance of lubricating oil compositions is being desired to improve more year by year, and biodegradable lubricating oil compositions also have become required to have further prolonged lifetime and improved wear resistance.
  • a hindered ester is used as a base oil and different kinds of additives are blended therein, it is still difficult to sufficient improve oxidation stability for lifetime prolongation, and in addition, wear resistance could not be improved sufficiently and the performance requirements could not be satisfied.
  • the present invention has been made in consideration of the above-mentioned problems and an object thereof is to provide a biodegradable lubricating oil composition having better wear resistance and enhanced oxidation stability.
  • the present inventors have found that, when a specific synthetic ester base oil is used as a base oil and when the transmittance at 3,005 ⁇ 1 cm -1 of the lubricating oil composition is made high, the resultant lubricating oil composition added with small quantities of additives added thereto can have sufficiently improved oxidation stability and wear resistance while maintaining good biodegradability, and have completed the present invention as described below.
  • the present invention provides the following:
  • a biodegradable lubricating oil composition having good wear resistance and having enhanced oxidation stability.
  • the biodegradable lubricating oil composition of one aspect of the present invention contains at least 50% by mass or more of a synthetic ester base oil (A), as antioxidants (B), 0.1 to 3% by mass of an amine-based antioxidant (B1) and 0.1 to 3% by mass of a phenol-based antioxidant (B2), and 0.01 to 2% by mass of a sulfur-phosphorus-based extreme-pressure agent (C).
  • A synthetic ester base oil
  • B1 an amine-based antioxidant
  • B2 0.1 to 3% by mass of a phenol-based antioxidant
  • C sulfur-phosphorus-based extreme-pressure agent
  • the transmittance at 3,005 ⁇ 1 cm -1 of a 0.1 mm-thick liquid film of the composition, as measured through IR absorptiometry is 50% or more.
  • the transmittance at 3,005 ⁇ 1 cm -1 in IR absorptiometry is an index of the amount of the unsaturated bonds in the biodegradable lubricating oil composition, and when the transmittance is 50% or more, the amount of the unsaturated bonds in the composition is small.
  • the transmittance of the composition can be 50% or more.
  • a synthetic ester base oil (A) having a small amount of unsaturated bonds therein is used to thereby reduce the amount of the unsaturated bonds in the lubricating oil composition, and consequently, by adding small quantities of the specific antioxidants (B) and the extreme-pressure agent (C), the oxidation stability and the wear resistance of the resultant biodegradable lubricating oil composition can be sufficiently improved.
  • the transmittance of the lubricating oil composition is, from the viewpoint of more reducing the amount of the unsaturated bonds in the lubricating oil composition, preferably 55% or more, and for making the composition contain few unsaturated bonds, the transmittance is more preferably 60% or more.
  • the upper limit of the transmittance is 100%, but in view of the characteristics thereof, the transmittance is generally about 80% or less.
  • biodegradable lubricating oil composition The components contained on the biodegradable lubricating oil composition are described in detail hereinunder.
  • the synthetic ester base oil (A) may be adequately selected from ester bond-having synthetic base oils, and specifically may be selected from (A1) a polyol ester base oil being an ester of a polyol and an aliphatic monocarboxylic acid, (A2) a diester base oil being an ester of an aliphatic dicarboxylic acid and a monoalcohol, (A3) an ester base oil being a copolymer of an unsaturated dibasic acid ester and an ⁇ -olefin, etc.
  • the synthetic ester base oil (A) may be one kind of an ester alone or may also be a mixture of two or more kinds of esters.
  • the synthetic ester base oil (A) for use in the lubricating oil composition is, for reducing the amount of the unsaturated bonds therein to thereby increase the transmittance of the lubricating oil composition as above, preferably so selected that the transmittance at 3,005 ⁇ 1 cm -1 of a 0.1 mm-thick liquid film of the composition, as measured through IR absorptiometry, could be 50% or more, more preferably 55% or more, and even more preferably 60% or more so that the composition may contain few unsaturated bonds.
  • the upper limit of the transmittance of the synthetic ester base oil (A) is 100%, but in view of the characteristics of the synthetic ester base oil (A), the transmittance thereof is generally about 80% or less.
  • the lubricating oil composition preferably contains a larger amount of the one having a transmittance of 50% or more than the another having a transmittance of less than 50%.
  • the synthetic ester base oil (A) is contained in an amount of 50% by mass or more based on the total amount of the lubricating oil composition as above, but is preferably contained in an amount of 70% by mass or more, more preferably in an amount of 80% by mass or more, even more preferably in an amount of 90% by mass or more.
  • the content of the synthetic ester base oil (A) relative to the total amount of the lubricating oil composition is less than 99.8% by mass, but in order that the additives thereto to be mentioned below could be each in an adequate amount, the base oil content is preferably 99% by mass or less, more preferably 98% by mass or less.
  • the polyol ester base oil (A1) to be used as the synthetic ester base oil (A) includes a hindered ester, that is, an ester of a hindered polyol having one or more of quaternary carbons in the molecule where 1 to 4 methylol groups bond to at least one of the quaternary carbons, and an aliphatic monocarboxylic acid. More detailed examples of the hindered polyol include those having the following general formula (I): wherein R 1 and R 2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms, or a methylol group, and n represents an integer of 0 to 4.
  • the hydrocarbon group having 1 to 6 carbon atoms of R 1 and R 2 is preferably a linear chain or branched chain alkyl group, more preferably an alkyl group having 1 or 2 carbon atoms.
  • n is preferably an integer of 0 to 2.
  • Examples of the hindered polyol represented by the general formula (I) include a hindered polyol such as a dialkylpropanediol (where the alkyl group has 1 to 6 carbon atoms), a trimethylolalkane (where the alkane has 2 to 7 carbon atoms), a pentaerythritol, etc., and a dehydrated condensate thereof, and specifically include neopentyl glycol, 2-ethyl-2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, trimethylolethane, trimethylolpropane, trimethylolbutane, trimethylolpentane, trimethylolhexane, trimethylolheptane, pentaerythritol, 2,2,6,6-tetramethyl-4-oxa-1,7-heptanediol, 2,2,6,6,10,10-hex
  • hindered polyols trimethylolpropane, neopentyl glycol, pentaerythritol, and bimolecular or trimolecular dehydrated condensates thereof are preferred; and above all, neopentyl glycol, trimethylolpropane and pentaerythritol are more preferred.
  • the aliphatic monocarboxylic acid to be used for the polyol ester base oil (A1) includes a saturated aliphatic monocarboxylic acid having 5 to 22 carbon atoms.
  • the acyl group on the saturated aliphatic monocarboxylic acid may be linear or branched.
  • saturated aliphatic monocarboxylic acid of the type examples include a linear saturated monocarboxylic acid such as valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, etc.; a branched saturated monocarboxylic acid such as isomyristic acid, isopalmitic acid, isostearic acid, 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,3,3-trimethylbutanoic acid, 2,2,3,4-tetramethylpentanoic acid, 2,5,
  • the polyol ester is generally a complete ester where all the hydroxyl groups in a polyol are esterified, but within a range not having any negative influence on the advantageous effects of the present invention, the polyol ester for use herein may contain a small amount of an ester where a part of hydroxyl groups are not esterified and remain as such.
  • diester base oil (A2) for example, an ester of a saturated dicarboxylic acid having 6 to 12 carbon atoms and an alkyl monoalcohol having 6 to 12 carbon atoms may be used.
  • saturated dicarboxylic acid include adipic acid, pimellic acid, suberic acid, azelaic acid, sebacic acid, undecane-diacid, dodecane-diacid, etc.
  • alkyl monoalcohol examples include a branched alkyl monoalcohol such as isooctanol, isononanol, isodecanol, 2-ethylhexanole, etc.; a linear alkyl monoalcohol such as n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, etc.
  • branched alkyl monoalcohol such as isooctanol, isononanol, isodecanol, 2-ethylhexanole, etc.
  • linear alkyl monoalcohol such as n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, etc.
  • Preferred examples of the compounds include dioctyl adipate, diisononyl adipate, diisodecyl adipate, di-2-ethylhexyl azelate, diisooctyl azelate, diisononyl azelate, di-2-ethylhexyl sebacate, diisooctyl sebacate, diisononyl sebacate, di-2-ethylhexyl dodecanedioate, etc.
  • the ester to be used as the diester base oil (A2) may be an ester of one kind of alkylmonoalcohol and a saturated dicarboxylic acid, or may also be an ester of two kinds of alkylmonoalcohol and a saturated dicarboxylic acid.
  • the ester base oil (A3) is a copolymer prepared by copolymerizing an ester of an unsaturated dibasic acid and a monoalcohol, and an ⁇ -olefin.
  • the unsaturated dibasic acid to be used here includes maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc.
  • the monoalcohol includes an alkyl monoalcohol having 1 to 20 carbon atoms. Among these, an alkyl monoalcohol having 3 to 8 carbon atoms is more preferably used.
  • the alkyl group of the alkyl monoalcohol may be linear or branched.
  • the alkyl monoalcohol includes methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, etc.
  • the ⁇ -olefin is preferably one having 3 to 20 carbon atoms, more preferably 6 to 18 carbon atoms.
  • Examples of the ⁇ -olefin of the type include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, etc.
  • the ester base oil (A3) has a kinematic viscosity at 100°C of 20 to 55 mm 2 /s, more preferably 25 to 45 mm 2 /s.
  • the above-mentioned various esters for use in the component (A) are generally produced by reacting a carboxylic acid and an alcohol, and, as a result, may have an ester structure formed of the above-mentioned carboxylic acid residue and the alcohol residue. Accordingly, it is not necessary to produce the component (A) by dehydration reaction of raw materials of the above-mentioned carboxylic acid and the alcohol, and the component may be produced according to any other method using other raw materials. For example, it may be produced according to an transesterification method.
  • the synthetic ester base oil (A) contains the polyol ester base oil (A1) as the main ingredient among the above-mentioned synthetic ester base oils.
  • the synthetic ester base oil (A) preferably contains the polyol ester base oil (A1) in an amount of more than 50% by mass relative to the total amount of the synthetic ester base oil (A), more preferably in an amount of 70 to 100% by mass, even more preferably 85 to 100% by mass.
  • the synthetic ester base oil (A) contains a polyol ester base oil (A1-1) having a total carbon number of 23 to 50 in one molecule as the main ingredient among the above-mentioned polyol ester base oil (A1) for the reason of kinematic viscosity, etc.
  • the synthetic ester base oil (A) preferably contains a polyol ester base oil (A1-1) having a total carbon number of 23 to 50 in an amount of more than 50% by mass relative to the total amount of the synthetic ester base oil (A), more preferably in an amount of 70 to 100% by mass, even more preferably 75 to 100% by mass.
  • the base oil (A) may further contain an ester base oil (A1-2) having a larger total carbon number in one molecule than that of the component (A1-1) among the above-mentioned polyol ester base oil (A1), and an ester base oil (A3) of the above-mentioned copolymer as the side ingredients.
  • the ester base oil (A1-2) having a larger total carbon number in one molecule than that of the component (A1-1) includes a polyol ester base oil (A1-2) having a total carbon number of 51 to 80 in one molecule.
  • the synthetic ester base oil (A) preferably contains at least one kind of ester selected from the polyol ester base oil (A1-2) having a total carbon number of 51 to 80 in one molecule, and the ester base oil (A3) of the above-mentioned copolymer, in a ratio of less than 50% by mass relative to the total amount of the ester base oil (A), more preferably in a ratio of 1 to 30% by mass, even more preferably 3 to 25% by mass.
  • the biodegradable lubricating oil composition may be readily controlled to have an adequate viscosity without losing oxidation stability and wear resistance.
  • ester base oil (A1-1) having a total carbon number of 23 to 50 one or more is adequately selected from the above-exemplified ester base oil (A1), and preferred examples thereof include an ester of neopentyl glycol (having 6 carbon atoms) with a saturated aliphatic monocarboxylic acid having 9 to 22 carbon atoms, such as pelargonic acid, capric acid, undecanoic acid, lauryl acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, isomyristic acid, isopalmitic acid, isostearic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,3,3-trimethylbutanoic acid, 2,2,3,4-tetramethylpentanoic acid, 2,5,5-trimethyl
  • an ester of pentaerythritol is preferred from the viewpoint of enhancing oxidation stability.
  • the component (A1-1) is preferably an ester of neopentyl glycol.
  • the carboxylic acid in the ester of neopentyl glycol is preferably a branched carboxylic acid, and more preferably a saturated aliphatic monocarboxylic acid having 16 to 20 carbon atoms.
  • polyol ester base oil (A1-1) a polyol ester base oil having a total carbon number of 37 to 45 in one molecule is preferred.
  • polyol ester base oil (A1-2) having a total carbon number of 51 to 80 one or more may be selected from the polyol ester base oil (A1) that is an ester of a polyol and an aliphatic monocarboxylic acid as described above, and preferred examples thereof include an ester of pentaerythritol with a saturated higher aliphatic monocarboxylic acid having 12 to 18 carbon atoms, such as lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, isomyristic acid, isopalmitic acid, isostearic acid, 2,5,5-trimethyl-2-t-butylhexanoic acid, etc.; an ester of trimethylolpropane with a saturated higher aliphatic monocarboxylic acid having 15 to 22 carbon atoms, such as pentadecanoic acid, palmitic acid,
  • component (A1-2) use of an ester of trimethylolpropane among these is preferred. Further, using an ester of pentaerythritol as the component (A1-1) is preferred along with using an ester of trimethylolpropane as the component (A1-2). Using such a mixed ester can adequately control the viscosity characteristics of the lubricating oil composition without detracting from various characteristics of the composition.
  • the total carbon number in one molecule of the polyol ester base oil (A1-2) is preferably 51 to 70.
  • the ester may be controlled to contain few unsaturated bonds therein, and for example, as the component (A1), use of an ester of a specific polyol and a saturated aliphatic monocarboxylic acid as mentioned above can attain the intended purpose.
  • the ester many commercial products are available for a saturated aliphatic monocarboxylic acid and an ester of the carboxylic acid, and such carboxylic acids or esters thereof may be adequately selected and used here.
  • some commercial products of saturated aliphatic monocarboxylic acids or esters thereof may contain unsaturated bonds, and the esters could not have a transmittance of 50% or more. This is because saturated aliphatic monocarboxylic acids are generally produced from animal oil and vegetable oil containing a large quantity of unsaturated bonds.
  • the unsaturated bonds contained in animal oil and vegetable oil are generally hydrogenated and saturated during the production process, or are generally removed by purification. Consequently, in the component (A1) in this aspect, the saturated aliphatic monocarboxylic acid to be used as the raw material is preferably one having a high hydrogenation degree or one having a high purification degree to have a small quantity of unsaturated bonds.
  • the raw materials of alkyl monoalcohols and others are preferably ones having a high hydrogenation degree or having a high purification degree.
  • the base oil of the biodegradable lubricating oil composition may be the above-mentioned synthetic ester base oil (A) alone, but may contain any other base oil component than the above-mentioned synthetic ester base oil (A) within a range not detracting from the advantageous effects of the present invention.
  • the base oil may contain at least one selected from a polyether base oil such as a polyalkylene glycol, a polyvinyl ether, etc.; a mineral oil as exemplified by a paraffinic mineral oil, a napthenic mineral oil, an intermediate base mineral oil, etc.; a synthetic hydrocarbon oil such as a polybutene, a polypropylene, an olefin copolymer, etc.
  • the content of the other base oil component than the synthetic ester base oil (A) is preferably less than 20% by mass based on the total amount of the lubricating oil composition in order that the composition may secure high biodegradability as described below, more preferably less than 10% by mass.
  • the biodegradable lubricating oil composition of this aspect contains, as antioxidants (B), both of an amine-based antioxidant (B1) and a phenol-based antioxidant (B2).
  • antioxidants (B) both of an amine-based antioxidant (B1) and a phenol-based antioxidant (B2).
  • these two antioxidants are blended in the above-mentioned specific synthetic ester base oil (A), and therefore though the amount of each component to be blended is small, the resultant composition can exhibit high oxidation stability.
  • the amine-based antioxidant (B1) includes a monoalkyldiphenylamine in which the alkyl group has 4 to 12 carbon atoms, such as mono-t-butyldiphenylamine, monooctyldiphenylamine, monononyldiphenylamine, etc.; a dialkyldiphenylamine in which the alkyl group each has 4 to 12 carbon atoms, such as 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine, 4-butyl-4'-octyldiphenylamine, etc.; a polyalkyldiphenylamine in which the alkyl group each has 1 to 10 carbon atoms, such as tetra
  • amine-based antioxidant (B1) using a dialkyldiphenylamine or an alkylphenyl- ⁇ -naphthylamine among the above is preferred, and using a dialkyldiphenylamine is more preferred.
  • the phenol-based antioxidant (B2) includes a monophenol-based antioxidant and a bisphenol-based antioxidant.
  • the monophenol-based antioxidant includes an alkyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (in which the alkyl group includes one having 4 to 20 carbon atoms, preferably 8 to 18 carbon atoms) such as n-octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 6-methylheptyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, n-octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, etc.; a 2,6-di-t-butyl-4-alkylphenol (in which the alkyl group has 1 to 4 carbon atoms) such as 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, etc.; 2,4-dimethyl-6-t-butyl
  • the bisphenol antioxidant includes 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-bis(2,6-di-t-butylphenol), 4,4'-bis(2-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 4,4'-isopropylidenebis(2,6-di-t-butylphenol), 2,2'-methylenebis(4-methyl-6-nonylphenol), 2,2'-isobutylidenebis(4,6-dimethylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol),
  • the phenol-based antioxidant is preferably a monophenol-based antioxidant among the above, and above all, an alkyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate is more preferred.
  • the biodegradable lubricating oil composition contains the amine-based antioxidant (B1) in an amount of 0.1 to 3% by mass and the phenol-based antioxidant (B2) in an amount of 0.1 to 3% by mass based on the total amount of the composition, as mentioned above.
  • the content of these antioxidants (B1) and (B2) is controlled to be each 0.1% by mass or more so that the biodegradable lubricating oil composition can be given high oxidation stability.
  • the content thereof is controlled to be each 3% by mass or less so that the biodegradable lubricating oil composition can exhibit the advantageous effects commensurate with the content and reduction in the biodegradability of the composition owing to the antioxidants (B) therein can be prevented.
  • the amine-based antioxidant (B1) is often a factor of reducing the biodegradability of the lubricating oil composition, but in this aspect, the antioxidant is used along with the above-mentioned specific synthetic ester base oil (A), and therefore even a small amount of the amine-based antioxidant (B1) can sufficiently enhance the oxidation stability of the composition. Consequently, in this aspect, the reduction in the biodegradability can be minimized.
  • the content of the amine-based antioxidant (B1) is preferably 0.2 to 2.5% by mass, more preferably 0.3 to 1.8% by mass.
  • the content of the phenol-based antioxidant (B2) is preferably 0.2 to 2.5% by mass, more preferably 0.3 to 1.5% by mass.
  • the biodegradable lubricating oil composition of this aspect further contains a sulfur-phosphorus-based extreme-pressure agent (C).
  • a sulfur-phosphorus-based extreme-pressure agent (C) is added thereto, and therefore the lubricating oil composition can sufficiently exhibit extreme-pressure performance and can better wear resistance thereof.
  • the sulfur-phosphorus-based extreme-pressure agent (C) to be used includes monothiophosphates, dithiophosphates, trithiophosphates, monothiophosphate amine salts, dithiophosphate amine salts, monothiophosphites, dithiophosphites, trithiophosphites, etc. Among these, dithiophosphates are preferred.
  • dithiophosphates having a terminal carboxyl group are preferred among dithiophosphates.
  • the sulfur-phosphorus-based extreme-pressure agent (C) can have an increased polarity, and therefore in this aspect using the above-mentioned specific synthetic ester base oil (A) as the base oil, the sulfur-phosphorus-based extreme-pressure agent (C) can readily exhibit the function of an extreme-pressure agent.
  • dithiophosphate having a terminal carboxyl group examples include compounds represented by the following general formula (II): wherein R 3 represents a linear or branched alkylene group having 1 to 8 carbon atoms, and R 4 and R 5 each independently represent a hydrocarbon group having 3 to 20 carbon atoms.
  • R 3 is, from the viewpoint of bettering solubility in base oil, preferably a linear or branched alkylene group having 1 to 8 carbon atoms, more preferably a linear or branched alkylene group having 2 to 4 carbon atoms, and even more preferably a branched alkylene group.
  • -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 CH 3 )-, CH 2 CH(CH 3 )CH 2 - and -CH 2 CH(CH 2 CH 2 CH 3 )- are preferred; -CH 2 CH(CH 3 )- and -CH 2 CH(CH 3 )CH 2 - are more preferred; and -CH 2 CH(CH 3 )- is even more preferred.
  • R 4 and R 5 each are, from the viewpoint of bettering extreme-pressure performance and bettering solubility in base oil, preferably a linear or branched alkyl group having 3 to 8 carbon atoms, more preferably a linear or branched alkyl group having 4 to 6 carbon atoms.
  • the group is preferably selected from the group consisting propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl and 2-ethylhexyl groups.
  • isobutyl and t-butyl are more preferred.
  • the biodegradable lubricating oil composition contains the sulfur-phosphorus-based extreme-pressure agent (C) in an amount of 0.01 to 2% by mass based on the total amount of the composition, as mentioned above.
  • the content of the sulfur-phosphorus-based extreme-pressure agent (C) is 0.01% by mass or more, the lubricating oil composition can be given extreme-pressure property to better wear resistance thereof.
  • the content is 2% by mass or less, the composition can exhibit the effect commensurate with the content to thereby prevent the biodegradability and the oxidation stability of the biodegradable lubricating oil composition from being lowered owing to the sulfur-phosphorus-based extreme-pressure agent (C).
  • the content of the sulfur-phosphorus-based extreme-pressure additive (C) is preferably 0.02 to 1% by mass, more preferably 0.03 to 0.5% by mass.
  • the biodegradable lubricating oil composition of this aspect may contain a viscosity index improver.
  • the viscosity index improver includes a polymethacrylate, a dispersive polymethacrylate, an olefin copolymer (for example, an ethylene-propylene copolymer, etc.), a dispersive olefin copolymer, a styrene copolymer (for example, a styrene-diene copolymer, a styrene-isoprene copolymer, etc.), etc.
  • a polymethacrylate is preferred.
  • the polymethacrylate usable as a viscosity index improver generally has a weight-average molecular weight of 10,000 to 70,000, preferably 20,000 to 55,000.
  • the weight-average molecular weight is a value measured through gel permeation chromatography and derived from a calibration curve drawn using polystyrene.
  • the content of the viscosity index improver is preferably 0.1 to 10% by mass based on the total amount of the lubricating oil composition, more preferably 0.5 to 5% by mass.
  • the biodegradable lubricating oil composition of this aspect may further contain a triazole compound.
  • the triazole compound acts as a metal inactivator, and imparts an anticorrosive effect against non-ferrous metals to the biodegradable lubricating oil composition.
  • Specific examples of the triazole compound include benzotriazole, carboxybenzotriazole, 3-aminotriazole, 4-aminotriazole, 2,5-diaminotriazole, 3-mercaptotriazole, and N-dialkyl (with 3 to 12 carbon atoms)aminomethyl-1,2,3-benzotriazole such as N-diethylaminomethyl-1,2,3-benzotriazole, etc. Those having a benzotriazole skeleton (benzotriazole compounds) are preferred.
  • the content of the triazole compound is preferably 0.01 to 1% by mass based on the total amount of the lubricating oil composition, more preferably 0.02 to 0.5% by mass.
  • the biodegradable lubricating oil composition may contain at least one selected from an alkaline earth metal sulfonate and a succinate, as a rust inhibitor. Containing a rust inhibitor, the biodegradable lubricating oil composition can have an increased corrosion-resistant effect against metals such as iron, etc.
  • the alkaline earth metal sulfonate is one prepared by sulfonating an alkylaromatic compound followed by converting it into an alkaline earth metal salt thereof, and includes a calcium sulfonate, a magnesium sulfonate and a barium sulfonate. Among these, a calcium sulfonate is preferred.
  • the alkaline earth metal sulfonate preferably has a low basicity, and specifically the total base number (TBN) thereof is preferably 0 to 100 mgKOH/g, more preferably 0 to 50 mgKOH/g. The total base number is measured according to a perchloric acid method of JIS K-2501. Using an alkaline earth metal sulfonate, the composition can additionally exhibit a detergent-dispersant effect.
  • the alkenyl succinate includes a half ester of an alkenylsuccinic acid with an alcohol such as a polyalcohol, etc.
  • One of the rust inhibitors may be used singly or two or more kinds thereof may be used in combination.
  • the content of the rust inhibitor is preferably within a range of 0.01 to 1.0% by mass based on the total amount of the lubricating oil composition, more preferably 0.03 to 0.5% by mass.
  • the biodegradable lubricating oil composition may contain any other extreme-pressure additive than the sulfur-phosphorus-based extreme-pressure agent (C).
  • the other extreme-pressure agent includes a phosphorus-based extreme-pressure agent such as a phosphate, e.g., tricresyl phosphate (TCP), an acidic phosphate amine salt, a phosphite, etc.
  • the content of the phosphorus-based extreme-pressure agent is preferably 0.1 to 2% by mass based on the total amount of the lubricating oil composition, more preferably 0.2 to 1.5% by mass.
  • the biodegradable lubricating oil composition may contain any other additive than the above, such as an ashless dispersant, a pour point depressant, an anti-foam agent, a surfactant, a demulsifier, etc.
  • Examples of the ashless dispersant include a succinimide, a boron-containing succinimide, a benzylamine, a boron-containing benzylamine, etc.
  • the pour point depressant includes an ethylene-vinyl acetate copolymer, a condensate of a chloroparaffin and a naphthalene, a condensate of a chloroparaffin and a phenol, a polymethacrylate, a polyalkylstyrene, etc.
  • the anti-foam agent may be a silicone anti-foam agent or a non-silicone anti-foam agent.
  • the biodegradable lubricating oil composition of this aspect preferably has a biodegradation rate of 60% or more as measured in a degradation test for chemical substances with microbes according to the 301B test of the OECD Test Guideline, more preferably 70% or more.
  • the specific synthetic ester base oil (A) is used as the main component, and the amount of various additives of the antioxidants (B1) and (B2) and the sulfur-phosphorus-based extreme-pressure agent (C) is controlled to be a predetermined amount or less, and the biodegradation rate of the composition can be thereby increased.
  • the kinematic viscosity at 40°C of the biodegradable lubricating oil composition is preferably 10 to 150 mm 2 /s, more preferably 15 to 100 mm 2 /s.
  • the viscosity index of the composition is preferably 130 or more, more preferably 135 or more. Having a kinematic viscosity and a viscosity index each falling within the range, the biodegradable lubricating oil composition can be adequately used as a lubricating oil in various uses to be mentioned hereinunder.
  • the biodegradable lubricating oil composition of this aspect can be favorably used, for example, for a hydraulic fluid that is a power transmission fluid for use for power transmission, power control, buffer or the like in a hydraulic system; a lubricating oil or a universal oil for transmissions of agricultural tractors, or construction or civil engineering machines; an oil for chain saws; a 2-cycle engine oil; an industrial gear oil for wind-power generation, etc.
  • the composition is more preferably used as a hydraulic fluid.
  • a production method for the biodegradable lubricating oil composition in this aspect includes blending at least 0.1 to 3% by mass of an amine-based antioxidant (B1), 0.1 to 3% by mass of a phenol-based antioxidant (B2) and 0.01 to 2% by mass of a sulfur-phosphorus-based extreme-pressure agent (C) in 50% by mass or more of a synthetic ester base oil (A) to produce a biodegradable lubricating oil composition wherein the transmittance at 3,005 ⁇ 1 cm -1 of a 0.1 mm-thick liquid film of the composition, as measured through IR absorptiometry, is 50% or more.
  • any other components than these components (A), (B1), (B2) and (C) may be blended in the biodegradable lubricating oil composition.
  • a lubricating oil composition was introduced between potassium bromide cells via a 0.1 mm-thick spacer to form a 0.1 mm-thick liquid film therebetween, and the transmittance thereof at 4,000 to 400 cm -1 was measured at a resolution of 4 cm -1 for a number of 16 scans, and then the transmittance at 3,005 ⁇ 1 cm -1 was read to be the transmittance of the lubricating oil composition.
  • the load bearing performance of the lubricating oil composition was evaluated under the test conditions of a load of 294 N, a rotating speed of 1,200 rpm, a temperature of 50°C, and for a test period of 30 minutes. The result was expressed as the wear track (mm) by the test steel ball.
  • the lubricating oil composition was tested at a test temperature of 150°C and under a pressure of 620 kPa, and the time taken until the pressure lowered by 175 kPa from the maximum pressure was measured.
  • the tested composition when the RBOT value is 250 minutes or more, the tested composition is evaluated as good "A" since its oxidation stability is sufficient in use, for example, as a compression hydraulic oil, but when the value is less than 250 minutes, the tested composition is evaluated as not good "B” since the oxidation stability thereof is insufficient.
  • a copper/iron catalyst was made to exist in a sample oil, and the sample oil was aged at a test temperature of 130°C for a test period of 168 hours.
  • a value calculated by dividing the kinematic viscosity at 40°C of the aged oil by the kinematic viscosity at 40°C of the unaged oil was referred to as a viscosity ratio.
  • the acid value of the aged oil was subtracted from the acid value of the unaged oil to give an acid value increase.
  • Biodegradable lubricating oil compositions were prepared in the blending formulation shown in Table 1, and tested to determine and evaluate the properties thereof. The results are shown in Table 1.
  • the synthetic ester base oil (A) having a high transmittance was used in order that the transmittance at 3,005 ⁇ 1 cm -1 of the lubricating oil composition could be 50% or more, and the amine-based antioxidant (B1), the phenol-based antioxidant (B2) and the sulfur-phosphorus-based extreme-pressure agent (C) were contained each in a predetermined amount, and therefore, the RBOT value of the composition was sufficiently large and, in addition, the viscosity increase and the acid value increase in the ISOT test could be prevented from increasing, that is, the oxidation stability of the composition was good in various environments. Further, the wear loss in the Shell wear test was small, and the wear resistance of the composition was good.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
EP16755611.7A 2015-02-27 2016-02-25 Composition d'huile lubrifiante biodégradable Active EP3263677B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015039470A JP6669343B2 (ja) 2015-02-27 2015-02-27 生分解性潤滑油組成物
PCT/JP2016/055590 WO2016136867A1 (fr) 2015-02-27 2016-02-25 Composition d'huile lubrifiante biodégradable

Publications (3)

Publication Number Publication Date
EP3263677A1 true EP3263677A1 (fr) 2018-01-03
EP3263677A4 EP3263677A4 (fr) 2018-07-25
EP3263677B1 EP3263677B1 (fr) 2022-04-27

Family

ID=56788450

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16755611.7A Active EP3263677B1 (fr) 2015-02-27 2016-02-25 Composition d'huile lubrifiante biodégradable

Country Status (4)

Country Link
US (1) US20180044606A1 (fr)
EP (1) EP3263677B1 (fr)
JP (1) JP6669343B2 (fr)
WO (1) WO2016136867A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108587748A (zh) * 2018-06-07 2018-09-28 芜湖市欧贝润滑剂有限责任公司 一种抗磨防锈链条润滑脂
CN108753426A (zh) * 2018-07-10 2018-11-06 河南倍佳润滑科技股份有限公司 一种特高温食品级合成链条油组合物
WO2019040576A1 (fr) * 2017-08-25 2019-02-28 Exxonmobil Research And Engineering Company Lubrifiants sans cendres pour moteurs destinés à des applications haute température

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3555243A1 (fr) * 2016-12-19 2019-10-23 ExxonMobil Research and Engineering Company Composition et procédé de prévention ou de réduction du cognement d'un moteur et moteurs à allumage commandé avec compression de pré-allumage
BR112020019106A2 (pt) * 2018-03-21 2020-12-29 Cargill, Incorporated Estrutura de compósito polimérico reforçada com fibra, e, método para produzir uma estrutura de compósito polimérico reforçada com fibra
CN112941536B (zh) * 2021-01-27 2023-06-09 浙江丹弗中绿科技股份有限公司 一种抗磨环保型发动机清洗油及其制备方法
CN115109630B (zh) * 2021-11-30 2023-01-17 北京福润联石化科技开发有限公司 配合二氟甲烷制冷剂使用的冷冻机油组合物及其应用

Family Cites Families (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4919833A (en) * 1987-05-21 1990-04-24 Ciba-Geigy Corporation Functional fluids
JPH05331481A (ja) * 1992-05-29 1993-12-14 Tonen Corp 2サイクルエンジン用潤滑油組成物
TW279839B (fr) * 1992-06-02 1996-07-01 Ciba Geigy Ag
KR100245894B1 (ko) * 1992-08-28 2000-03-02 웨인 씨 제쉬크 자연 분해성 2-사이클 엔진 오일 조성물 및 에스테르 기본 원료
GB9408235D0 (en) * 1994-04-26 1994-06-15 Castrol Ltd Lubricant composition
JPH07305079A (ja) * 1994-05-12 1995-11-21 Lion Corp 潤滑油
DE69523067T2 (de) * 1994-12-08 2002-06-27 Exxonmobil Chem Patents Inc Biologisch abbaubare synthetische verzweigte ester und damit hergestelltes schmiermittel
DE59703420D1 (de) * 1996-07-15 2001-05-31 Ciba Sc Holding Ag Beta-Dithiophosphorylierte Propionsäure in Schmierstoffen
DE59813902D1 (de) * 1997-09-18 2007-03-29 Ciba Sc Holding Ag Schmierstoffzusammensetzungen mit Thiophosphorsäureestern und Dithiophosphorsäureestern
US5880075A (en) * 1997-09-22 1999-03-09 Exxon Chemical Patents Inc Synthetic biodegradable lubricants and functional fluids
JP2000160177A (ja) * 1998-11-30 2000-06-13 Idemitsu Kosan Co Ltd 2サイクルエンジン油組成物
US6551968B2 (en) * 2001-01-05 2003-04-22 Hatco Corporation Biodegradable polyneopentyl polyol based synthetic ester blends and lubricants thereof
AU2002303357A1 (en) * 2001-05-17 2002-11-25 Exxonmobil Chemical Patents, Inc. Biodegradable synthetic lubricants
US6620772B2 (en) * 2001-07-13 2003-09-16 Renewable Lubricants, Inc. Biodegradable penetrating lubricant
US7517837B2 (en) * 2003-05-22 2009-04-14 Anderol, Inc. Biodegradable lubricants
US8183190B2 (en) * 2003-08-20 2012-05-22 Cognis Ip Management Gmbh Complex polyol esters with improved performance
JP4827381B2 (ja) * 2004-01-30 2011-11-30 出光興産株式会社 生分解性潤滑油組成物
US7579306B2 (en) * 2005-03-02 2009-08-25 Chemtura Corporation Method for improving the oxidative stability of industrial fluids
JP2006265494A (ja) * 2005-03-25 2006-10-05 Nippon Oil Corp 潤滑油組成物
US20090186789A1 (en) * 2006-05-15 2009-07-23 Mitsuhiro Nagakari Lubricating oil composition
JP5313483B2 (ja) * 2006-11-06 2013-10-09 出光興産株式会社 ウォームギヤ油組成物
JP5095177B2 (ja) * 2006-11-06 2012-12-12 出光興産株式会社 生分解性潤滑油組成物
JP5199679B2 (ja) * 2008-01-08 2013-05-15 Jx日鉱日石エネルギー株式会社 難燃性油圧作動油組成物
JP5465921B2 (ja) * 2009-05-15 2014-04-09 出光興産株式会社 生分解性潤滑油組成物
JP2011137089A (ja) * 2009-12-28 2011-07-14 Lion Corp 潤滑油基油
JP5848002B2 (ja) * 2010-01-18 2016-01-27 Jx日鉱日石エネルギー株式会社 潤滑油組成物
US8980808B2 (en) * 2011-08-03 2015-03-17 Cognis Ip Management Gmbh Lubricant compositions with improved oxidation stability and service life
JP5759836B2 (ja) * 2011-09-02 2015-08-05 出光興産株式会社 生分解性潤滑油組成物
CN104302612B (zh) * 2012-02-28 2017-07-18 马来西亚国家石油公司 物质的润滑剂组合物及其制备方法
US20140194331A1 (en) * 2013-01-10 2014-07-10 Washington State University High performance biohydraulic fluid
JP5695229B2 (ja) * 2014-01-23 2015-04-01 出光興産株式会社 生分解性潤滑油組成物
JP6255265B2 (ja) * 2014-02-06 2017-12-27 コスモ石油ルブリカンツ株式会社 油圧作動油組成物
WO2016014417A1 (fr) * 2014-07-21 2016-01-28 Elevance Renewable Sciences, Inc. Esters de polyols insaturés utilisés dans des applications de fluides hydrauliques
JP5913478B2 (ja) * 2014-08-11 2016-04-27 Jxエネルギー株式会社 油圧作動油組成物

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019040576A1 (fr) * 2017-08-25 2019-02-28 Exxonmobil Research And Engineering Company Lubrifiants sans cendres pour moteurs destinés à des applications haute température
CN108587748A (zh) * 2018-06-07 2018-09-28 芜湖市欧贝润滑剂有限责任公司 一种抗磨防锈链条润滑脂
CN108753426A (zh) * 2018-07-10 2018-11-06 河南倍佳润滑科技股份有限公司 一种特高温食品级合成链条油组合物
CN108753426B (zh) * 2018-07-10 2021-05-28 河南倍佳润滑科技股份有限公司 一种特高温食品级合成链条油组合物

Also Published As

Publication number Publication date
JP6669343B2 (ja) 2020-03-18
JP2016160326A (ja) 2016-09-05
EP3263677B1 (fr) 2022-04-27
WO2016136867A1 (fr) 2016-09-01
EP3263677A4 (fr) 2018-07-25
US20180044606A1 (en) 2018-02-15

Similar Documents

Publication Publication Date Title
EP3263677B1 (fr) Composition d'huile lubrifiante biodégradable
EP2142624B1 (fr) Composition de mélange lubrifiant
JP4466850B2 (ja) 軸受用潤滑油
EP2392637B1 (fr) Composition d'huile lubrifiante pour transmission automatique
EP3013925B1 (fr) Compositions lubrifiantes contenant des composés à base d'isoprène
JP5095177B2 (ja) 生分解性潤滑油組成物
JPWO2009148110A1 (ja) 潤滑油組成物およびその用途
EP3668959B1 (fr) Composition lubrifiante pour une transmission de véhicule électrique hybride
JP5184068B2 (ja) 難燃性油圧作動油組成物
JP2011162652A (ja) 潤滑油組成物
JPWO2007116725A1 (ja) 潤滑油基油
EP2080799A1 (fr) Graisse lubrifiante
JP2010006950A (ja) 工業用潤滑油組成物
JP5416879B2 (ja) 潤滑油組成物
US11492566B2 (en) Ether-based lubricant compositions, methods and uses
JP4447147B2 (ja) 軸受用潤滑油
EP3555248B1 (fr) Composition lubrifiante à base d' un éther et son utilisation
JP2015140367A (ja) 潤滑油組成物
WO2023190163A1 (fr) Composition d'huile lubrifiante
AU2022327545A1 (en) Use of hemimellitic ester as a base oil for lubricant compositions

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20170818

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

AX Request for extension of the european patent

Extension state: BA ME

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: IDEMITSU KOSAN CO.,LTD.

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20180621

RIC1 Information provided on ipc code assigned before grant

Ipc: C10N 40/08 20060101ALN20180615BHEP

Ipc: C10N 30/00 20060101ALN20180615BHEP

Ipc: C10N 30/10 20060101ALN20180615BHEP

Ipc: C10M 169/04 20060101AFI20180615BHEP

Ipc: C10N 30/08 20060101ALN20180615BHEP

Ipc: C10N 30/06 20060101ALN20180615BHEP

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

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20210222

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: 20211129

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

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

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

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602016071505

Country of ref document: DE

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1486955

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220515

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1486955

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220427

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

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: 20220427

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: 20220829

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: 20220727

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: 20220427

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: 20220427

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: 20220728

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: 20220427

Ref country code: ES

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: 20220427

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: 20220727

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: 20220427

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: 20220427

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: 20220427

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: 20220427

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: 20220827

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602016071505

Country of ref document: DE

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

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: 20220427

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: 20220427

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: 20220427

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: 20220427

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: 20220427

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: 20220427

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: 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: 20220427

26N No opposition filed

Effective date: 20230130

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: 20220427

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: 20220427

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20230228

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

Effective date: 20230225

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: 20230225

Ref country code: LI

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

Effective date: 20230228

Ref country code: CH

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

Effective date: 20230228

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: GB

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

Effective date: 20230225

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

Ref country code: IT

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: 20220427

Ref country code: IE

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

Effective date: 20230225

Ref country code: GB

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

Effective date: 20230225

Ref country code: FR

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

Effective date: 20230228

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: 20230228

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

Ref country code: NL

Payment date: 20240108

Year of fee payment: 9

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

Ref country code: DE

Payment date: 20231229

Year of fee payment: 9