EP1803797B1 - Utilisation d'une composition lubrifiante pour améliorer la compatibilité d'un matériau d'étanchéité en caoutchouc acrylique dans un moteur à combustion interne - Google Patents

Utilisation d'une composition lubrifiante pour améliorer la compatibilité d'un matériau d'étanchéité en caoutchouc acrylique dans un moteur à combustion interne Download PDF

Info

Publication number
EP1803797B1
EP1803797B1 EP06256586.6A EP06256586A EP1803797B1 EP 1803797 B1 EP1803797 B1 EP 1803797B1 EP 06256586 A EP06256586 A EP 06256586A EP 1803797 B1 EP1803797 B1 EP 1803797B1
Authority
EP
European Patent Office
Prior art keywords
lubricating oil
oil composition
amount
content
use according
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
EP06256586.6A
Other languages
German (de)
English (en)
Other versions
EP1803797A2 (fr
EP1803797A3 (fr
Inventor
Yoshitaka Takeuchi
Yoshito Yamashita
Morikuni Nakazato
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.)
Chevron Japan Ltd
Original Assignee
Chevron Japan 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 Chevron Japan Ltd filed Critical Chevron Japan Ltd
Publication of EP1803797A2 publication Critical patent/EP1803797A2/fr
Publication of EP1803797A3 publication Critical patent/EP1803797A3/fr
Application granted granted Critical
Publication of EP1803797B1 publication Critical patent/EP1803797B1/fr
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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/087—Boron oxides, acids or 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • 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
    • C10M2215/062—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups bound to the aromatic ring
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/043—Mannich bases
    • 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
    • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • 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
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid 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
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
    • C10M2227/06—Organic compounds derived from inorganic acids or metal salts
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/12—Groups 6 or 16
    • 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
    • C10N2030/36—Seal compatibility, e.g. with rubber
    • 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

Definitions

  • the present invention relates to use of a lubricating oil composition for improving the acrylic rubber sealant compatibility with the lubricating oil composition in operation of an internal combustion engine.
  • Lubrication systems for supplying a lubricating oil are generally equipped with various sealing materials (sealants).
  • the sealing materials include resin or rubber sealants such as silicone rubber sealant, acrylic rubber sealant, fluorocarbon resin sealant, nitrile rubber sealant, hydrogenated nitrile rubber sealant and ethylene-propylene rubber sealant. According to their physical and chemical characteristics, those sealants are optionally selected to be installed in proper parts of the lubrication systems.
  • acrylic rubber sealant is particularly used as packing parts for fixation because it is not only excellent in heat resistance and oil resistance but also inexpensive,
  • lubricating oil compositions containing various additives often deteriorate resin or rubber sealants despite satisfying lubricating performance requirements.
  • Most of the additives contained in the compositions are so chemically active that they are liable to shrink the sealants and/or to impair their strength and elasticity.
  • U.S. Patent No. 6,124,247 describes a lubricating oil composition containing a borated glycerol ester and a mono-succinimide or bis-succinimide type dispersant subjected or not subjected to post-treatment with, for example, ethylene carbonate. It is stated that this oil composition has excellent compatibility with fluorocarbon elastomer, which is used as a sealant in a lubrication system of an internal-combustion engine.
  • JP-A-11-181461 describes that a lubricating oil composition containing an aliphatic amine has excellent compatibility with rubber sealants.
  • U.S. Patent No. 6,569,818 describes a lubricating oil composition containing an ashless dispersant of an alkenyl- or alkyl-succinic imide or a derivative thereof, an alkali metal or alkaline earth metal alkylsalicylate of non-sulfide or otherwise an alkali metal salt of alkylphenol derivative having a Mannich base structure, a zinc dialkyldithiophosphate, and an oxidation inhibiting phenol or amine compound. It is stated that all of the ash content, the phosphorus content and the sulfur content of the disclosed lubricating oil composition are low levels and that the lubricating oil composition gives high detergency at a high temperature.
  • U.S. Patent No. 6,569,818 is silent about a lubricating oil composition of the present invention described hereinbelow. Further, this reference neither describes nor suggests any effect that the lubricating oil composition has on sealants.
  • EP 1 452 581 A2 provides a method of improving elastomer seal compatibility and dispersancy in an internal combustion engine, said method comprising contacting the elastomer seal in the internal combustion engine with a lubricating oil composition comprising: a) a major amount of a base oil of lubricating viscosity; b) a carboxylated detergent-dispersant obtained by: (i) neutralizing alkylphenols using an alkaline earth base in the presence of at least one carboxylic acid that contains from one to four carbon atoms but in the absence of alkali base, dialcohol, and monoalcohol, forming an intermediate product; and (ii) carboxylating the intermediate product using carbon dioxide so that at least 20 mole percent of the original alkylphenol starting material has been converted to alkaline earth metal single aromatic-ring hydrocarbyl salicylate; and c) a nitrogen-containing dispersant.
  • a lubricating oil composition comprising: a) a major amount of a
  • the nitrogen-containing dispersant employed in the lubricating oil composition of EP 1 452 581 A2 is an ashless dispersant such as an alkenyl succinimide, an alkenyl succinic anhydride, an alkenyl succinate ester, and the like, or mixtures of such dispersants.
  • the present invention relates to use of a lubricating oil composition for improving acrylic rubber sealant compatibility with the lubricating oil composition in operation of an internal combustion engine, wherein the lubricating oil composition comprises:
  • the nitrogen-containing ashless dispersant in the lubricating oil composition employed in the present invention is an alkenyl- or alkyl-succinic imide or a derivative thereof.
  • the metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative in the lubricating oil composition employed in the present invention has a Mannich base structure represented by the following formula: wherein R is an alkyl group having 8 to 30 carbon atoms, and n is 0 or a positive integer.
  • the lubricating oil composition employed in the present invention may further comprise a phosphorus-containing organic compound selected from the group consisting of zinc dihydrocarbyldithiophosphates, zinc dihydrocarbylphosphates, phosphoric acid esters, phosphorous acid esters, and thiophosphoric acid esters.
  • a phosphorus-containing organic compound selected from the group consisting of zinc dihydrocarbyldithiophosphates, zinc dihydrocarbylphosphates, phosphoric acid esters, phosphorous acid esters, and thiophosphoric acid esters.
  • the lubricating oil composition employed in the present invention may further comprise a metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates in an amount of 1.0 wt.% or less in terms of the metal content.
  • a metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates in an amount of 1.0 wt.% or less in terms of the metal content.
  • the amount of metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates to the amount of metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure is in a ratio of 1:0.003 to 1:1 in terms of the metal content.
  • the lubricating oil composition employed in the present invention may further comprise a molybdenum compound selected from the group consisting of an oxymolybdenum complex prepared by the reaction between an acidic molybdenum compound and a basic nitrogen compound, sulfurized oxymolybdenum dithiocarbamate, and sulfurized oxymolybdenum dithiophosphate, in amount of 0.25 wt.% or less in terms of the molybdenum content.
  • a molybdenum compound selected from the group consisting of an oxymolybdenum complex prepared by the reaction between an acidic molybdenum compound and a basic nitrogen compound, sulfurized oxymolybdenum dithiocarbamate, and sulfurized oxymolybdenum dithiophosphate, in amount of 0.25 wt.% or less in terms of the molybdenum content.
  • the lubricating oil composition employed in the present invention may further comprise an alkali metal borate in an amount of 2 wt.% or less and an oxidation inhibitor selected from the group consisting of hindered phenol compounds and diarylamine compounds in an amount of 5 wt.% or less.
  • the base oil of lubricating viscosity contains 10 wt.% or more of a mineral oil showing the following characteristics:
  • the lubricating oil composition employed in the present invention is a SAE viscosity grade selected from the group consisting of 0W20, 0W30, 5W20, 5W30 and 10W30.
  • the lubricating oil composition meets the SAE 10W-30 viscosity grade.
  • a lubricating oil composition containing a certain combination of a nitrogen-containing dispersant and a metal-containing detergent of an alkali metal salt of alkylphenol derivative having a Mannich base structure, together with a phosphorus-containing organic compound can be effectively employed for improving the acrylic rubber sealant compatibility in an internal combustion engine, if the ratio of the nitrogen-containing dispersant and a metal-containing detergent of an alkali metal salt of alkylphenol derivative having a Mannich base structure is adjusted to a specific range, i.e., in the range of from 1:0.005 to 1:2 in terms of the nitrogen content.
  • the lubricating oil composition hardly impairs the sealing performance of the acrylic rubber sealant.
  • the present invention resides in use of a certain lubricating oil composition to improve the acrylic rubber sealant compatibility with the lubricating oil composition in operation of an internal combustion engine.
  • the lubricating oil composition while meeting the lubricating performance requirements of internal combustion engines, at the same time is less detrimental to the sealing performance of acrylic rubber sealants found in internal combustion engines as compared to conventionally used lubricating oil compositions.
  • the present invention advantageously improves the acrylic rubber sealant compatibility in internal combustion engines.
  • the lubricating oil composition employed in the present invention will contain a nitrogen-containing ashless dispersant.
  • the nitrogen-containing ashless dispersant is preferably is a polyolefin-derived alkenyl- or alkyl-succinic imide or a derivative thereof.
  • the amount of the nitrogen-containing ashless dispersant is in the range of 0.01 to 0.3 wt.%, preferably 0.01 to 0.1wt.%, in terms of the nitrogen content, based on the total amount of the lubricating oil composition.
  • a representative succinic imide can be prepared by the reaction between succinic anhydride having a high molecular weight alkenyl or alkyl substituent group with polyalkylenepolyamine containing 4 to 10 nitrogen atoms on average, preferably 5 to 7 nitrogen atoms.
  • the high molecular weight alkenyl or alkyl substituent group is preferably a polybutene having a number average molecular weight of approximately 900 to 5,000.
  • the process for preparing the polybutenylsuccinic anhydride by the reaction between polybutene and maleic anhydride is generally performed by a chlorination method utilizing chlorine. While this reaction is advantageous in giving a high reaction yield, it has a disadvantageous feature in that a large amount (for instance, approximately 2,000 to 3,000 ppm) of chlorine remains in the final succinic imide product. In contrast, a thermal reaction process utilizing no chlorine can give a final reaction product having an extremely low chlorine content (such as 0 to 30 ppm). It is, therefore, preferred to use a succinic imide derived from the polybutenylsuccinic anhydride prepared by the thermal reaction process so that the chlorine content can be in the range of 0 to 30 ppm.
  • the resulting succinic imide can be further converted into a modified succinic imide by a further reaction with boric acid, alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate or organic acids.
  • boric acid alcohol, aldehyde, ketone, alkylphenol, cyclic carbonate or organic acids.
  • a boron-containing alkenyl- or alkyl-succinic imide which is produced by the reaction with boric acid or a boron-containing compound.
  • the lubricating oil composition employed in the present invention indispensably contains the ashless dispersant, whose representative example is an alkenyl- or alkyl-succinic imide or a derivative thereof.
  • the ashless dispersant ashless dispersants of alkenylbenzylamine type and alkenylsuccinic acid ester type can be also used.
  • the lubricating oil composition employed in the present invention will contain metal-containing detergent of an alkali metal or alkaline metal earth metal salt of alkylphenol derivative.
  • the metal-containing detergent of an alkali metal or alkaline metal earth metal salt of alkylphenol derivative has a Mannich base structure represented by the following formula:
  • the amount of the metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure is in the range of 0.001 to 0.4 wt.% in terms of the metal content or 0.002 to 0.1 wt.% in terms of the nitrogen content, based on the total amount of the lubricating oil composition.
  • the metal-containing detergent of an alkali metal (e.g., sodium, potassium) or alkaline earth metal (e.g., calcium, barium, magnesium) salt of alkylphenol derivative having a Mannich base structure is generally prepared by the steps of:
  • the ratio of the nitrogen-containing ashless dispersant to the metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure is in the range of from 1:0.005 to 1:2, preferably 1:0.01 to 1:0.3, in terms of the nitrogen content.
  • the lubricating oil composition employed in the present invention will contain a phosphorus-containing organic compound selected from the group consisting of zinc dihydrocarbyldithiophosphates, zinc dihydrocarbylphosphates, phosphoric acid esters, phosphorous acid esters, and thiophosphoric acid esters.
  • the amount of the phosphorus-containing organic compound is in the range of 0.001 to 0.5 wt.%, preferably 0.01 to 0.2 wt.%, in terms of the phosphorus content, based on the total amount of the lubricating oil composition.
  • Examples of the phosphorus-containing organic compounds include zinc dihydrocarbyldithiophosphates, zinc dihydrocarbylphosphates, phosphoric acid esters, phosphorous acid esters, and thiophosphoric acid esters in which each ester is generally derived from the corresponding acid and an alkylalcohol having 3 to 18 carbon atoms or an alkylarylalcohol having an alkyl group of 3 to 18 carbon atoms.
  • a zinc dihydrocarbyldithiophosphate (zinc dialkyldithiophosphate)
  • the amount of the additive is preferably in the range of 0.01 to 0.1 wt.% in terms of the phosphorus content, based on the total amount of the lubricating oil composition. From the viewpoint of reducing the phosphorus content and the sulfur content, the amount preferably is in the range of 0.01 to 0.06 wt.%, based on the total amount of the lubricating oil composition.
  • the zinc dialkyldithiophosphate preferably has an alkyl group of 3 to 18 carbon atoms or an alkylaryl group having an alkyl group of 3 to 18 carbon atoms. It is particularly preferred for the zinc dialkyldithiophosphate to have an alkyl group derived from a secondary alcohol having 3 to 18 carbon atoms or an alkyl group derived from a mixture of a primary alcohol having 3 to 18 carbon atoms and a secondary alcohol having 3 to 18 carbon atoms, because the zinc dialkyldithiophosphate having that alkyl group is particularly effective in wear reduction.
  • a zinc dialkyldithiophosphate derived from a primary alcohol is also excellent in heat resistance.
  • the zinc dithiophosphates can be used singly, but it is preferred to use a mixture mainly comprising a secondary alkyl-type and/or a primary alkyl type.
  • the lubricating oil composition employed in the present invention may further contain another metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates in an amount of 1.0 wt.% or less in terms of the metal content, based on the total amount of the lubricating oil composition.
  • another metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates in an amount of 1.0 wt.% or less in terms of the metal content, based on the total amount of the lubricating oil composition.
  • the amount of the metal-containing detergent selected from the group consisting of alkali metal or alkaline earth metal salicylates, carboxylates, phenates and sulfonates to the amount of the metal-containing detergent of an alkali metal or alkaline earth metal salt of alkylphenol derivative having a Mannich base structure is in a ratio of 1:0.003 to 1:1 in terms of the metal content, based on the total amount of the lubricating oil composition.
  • the lubricating oil composition employed in the present invention may further contain an oxidation inhibitor selected from the group consisting of hindered phenol compounds and diarylamine compounds in an amount of 5 wt.% or less, based on the total amount of the lubricating oil composition.
  • an oxidation inhibitor selected from the group consisting of hindered phenol compounds and diarylamine compounds in an amount of 5 wt.% or less, based on the total amount of the lubricating oil composition.
  • diarylamine-type oxidation inhibitors are particularly advantageous.
  • hindered phenol-type oxidation inhibitors effectively prevent deterioration caused by NO x oxidation.
  • hindered phenol oxidation inhibitors examples include 2,6-di-t-butyl-p-cresol, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-methylenebis(6-t-butyl-o-cresol), 4,4'-isopropylidenebis(2,6-di-t-butylphenol), 4,4'-bis(2,6-di-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-thiobis(2-methyl-6-t-butylphenol), 2,2-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, and octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate.
  • diarylamine oxidation inhibitors examples include an alkyldiphenylamine containing a mixture of alkyl groups having 4 to 9 carbon atoms, p,p'-dioctyldiphenylamine, phenyl- ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, alkylated ⁇ -naphthylamine, and alkylated phenyl- ⁇ -naphthylamine.
  • Each of the hindered phenol compounds and the diarylamine compounds can be used singly or in combination.
  • Other oil soluble oxidation inhibitors can be employed in combination.
  • the lubricating oil composition employed in the present invention may further contain a molybdenum compound selected from the group consisting of an oxymolybdenum complex prepared by the reaction between an acidic molybdenum compound and a basic nitrogen compound, sulfurized oxymolybdenum dithiocarbamate, and sulfurized oxymolybdenum dithiophosphate, in an amount of 0.25 wt.% or less in terms of the molybdenum content, based on the total amount of the lubricating oil composition.
  • a molybdenum compound selected from the group consisting of an oxymolybdenum complex prepared by the reaction between an acidic molybdenum compound and a basic nitrogen compound, sulfurized oxymolybdenum dithiocarbamate, and sulfurized oxymolybdenum dithiophosphate
  • the molybdenum-containing compound mainly functions as a friction modifier, an oxidation inhibitor or an anti-wear agent in the lubricating oil composition employed in the present invention. In addition, it also improves detergency at a high temperature.
  • the molybdenum-containing compound is preferably in an amount of 10 to 2,500 ppm in terms of the molybdenum content.
  • Examples of the molybdenum-containing compounds include sulfur-containing molybdenum complex of succinimide, sulfurized oxymolybdenum dithiocarbamate, sulfurized oxymolybdenum dithiophosphate, amine molybdenum complex compound, oxymolybdenum diethylate amide, and oxymolybdenum monoglyceride. Sulfur-containing molybdenum complex of succinimide is particularly effective in improving the detergency at a high temperature.
  • the lubricating oil composition employed in the present invention may further contain an alkali metal borate in an amount of 2 wt.% or less, based on the total amount of the lubricating oil composition.
  • the alkali metal borate hydrate is also effective in improving the detergency at a high temperature and in giving a base number.
  • the term "alkali metal borate hydrate" in the present invention means a compound representatively prepared by the method disclosed in U.S. Patent Nos. 3,929,650 and 4,089,790 .
  • the alkali metal borate in the form of dispersed fine particles.
  • the carbonation reaction is preferably conducted further in the presence of an ashless dispersant such as succinic imide.
  • the alkali metal preferably is potassium or sodium.
  • alkali metal borate hydrate additive is a suspension comprising a mixture of neutral calcium sulfonate and succinic imide and fine particles of KB 3 O 5 •H 2 O having sizes of approximately 0.3 ⁇ m or less.
  • the potassium can be replaced with sodium.
  • the additive is also preferably used in consideration of water resistance.
  • the lubricating oil composition employed in the present invention may further contain a viscosity index improver in an amount of 20 wt.% or less, preferably 1 to 20 wt.%, based on the total amount of the lubricating oil composition.
  • a viscosity index improver include polymer compounds such as polyalkyl methacrylate, ethylene-propylene copolymer, styrene-butadiene copolymer, and polyisoprene.
  • dispersant-type viscosity index improvers which can be obtained by modifying the above polymers so that they can function as dispersants, and multi-functional viscosity index improvers.
  • the viscosity index improvers can be used singly or in combination.
  • the lubricating oil composition employed in the present invention may further contain various other auxiliary additives.
  • auxiliary additives include zinc dithiocarbamate, methylenebis(dibutyldithiocarbamate), an oil-soluble copper compound, a sulfur-containing compound (e.g., sulfurized olefin, sulfurized ester, polysulfide), and an organic amide compound (e.g., oleyl amide). They function as oxidation inhibitors or anti-wear agents. It is also preferred to incorporate metal deactivators such as benzotriazole compounds and thiadiazole compounds.
  • a nonionic surface active agent of polyoxyalkylene such as a copolymer of polyoxyethylenealkylphenyl ether, ethylene oxide and propylene oxide can be added as a rust preventing agent or an demulsifier. It is also possible to incorporate various amines, amides, amine salts or derivatives thereof, and aliphatic acid esters of polyhydric alcohols or their derivatives. They serve as friction modifiers. It is further possible to incorporate various compounds that function as defoaming agents or pour point depressants. Each auxiliary additive is added to the lubricating oil composition employed in the present invention preferably in an amount of 3 wt.% or less, preferably 0.001 to 3 wt.% , based on the total amount of the lubricating oil composition.
  • the base oil used in the lubricating oil composition employed in the present invention generally is a mineral or synthetic oil showing a kinematic viscosity of 2 to 50 mm 2 /s at 100°C. There are no specific conditions with respect to the mineral or synthetic oil, but the base oil has a sulfur content of preferably 0.1 wt.% or less, more preferably 0.03 wt.% or less, most preferably 0.005 wt.% or less.
  • the mineral base oil is preferably subjected to properly combined treatments.
  • the mineral lubricant distillate thereof is preferably subjected to treatments such as solvent refining and hydrogenation processing in combination.
  • it is preferred to use a highly hydrogen-refined (hydrocracked) base oil having, for example, a viscosity index of 100 to 150, an aromatic component content of 5 wt.% or less, a nitrogen content of 50 ppm or less, and a sulfur content of 50 ppm or less).
  • a high viscosity index-base oil prepared by isomerization or hydrocracking of synthetic wax synthesized from slack wax (crude wax) of mineral oil or natural gas.
  • any of the above mineral or synthetic base oils may be used singly, but two or more of the mineral base oils or two or more of the synthetic base oils can be used in combination, if desired. Further, the mineral and synthetic base oils can be used in combination at any ratios, if desired, to prepare the appropriate base oil of lubricating viscosity.
  • a major amount of base oil of lubricating viscosity as defined herein comprises 40 wt % or more.
  • Preferred amounts of base oil comprise 40 to 99.9 wt %, preferably greater than 50 to 97 wt %, more preferably 60 to 97 wt % of the lubricating oil composition.
  • the lubricating oil composition employed in the present invention can be prepared by adding the additives independently or all at once to the base oil. Otherwise, an additive concentrate comprising the additives in high concentrations can be beforehand prepared and then mixed it with a base oil to prepare the lubricating oil composition employed in the present invention.
  • the below-mentioned additives and the base oil of lubricating viscosity were mixed to give the lubricating oil composition employed in the present invention.
  • the lubricating oil composition was SAE viscosity grade 10W30. Also shown below are the contents of each element (Ca, P, N) in the lubricating oil composition, the ratio between the nitrogen content attributable to all the dispersants and that attributable to the detergent A (Mannich base calcium phenate), and the ratio between the metal content attributable to all the detergents and that attributable to the detergent A (Mannich base calcium phenate).
  • Example 1 The procedures of Example 1 were repeated except for changing the amount of the detergent A (Mannich base calcium phenate) into 1.16 wt.% (content in terms of calcium: 0.03 wt.%, content in terms of nitrogen: 0.018 wt.%) and for changing the residual amount of the base oil of lubricating viscosity so that the total amount of the lubricating oil composition is 100 wt.%.
  • the prepared lubricating oil composition was SAE viscosity grade 10W30.
  • Comparative Example A was prepared according to the procedures of Example 1 except for not adding the detergent A (Mannich base calcium phenate) and for changing the amount of the base oil of lubricating viscosity so that the total amount of the lubricating oil composition is 100 wt.%.
  • the prepared lubricating oil composition was SAE viscosity grade 10W30.
  • the contents of each element (Ca, P, N) in the lubricating oil composition are shown below.
  • Example 2 Comparative Example A Volume change(%) -7 to +5 +2 0 +2 Hardness change -5 to +8 +3 +4 +3 Tensile strength change(%) -15 to +18 +2 +2 -4 Elongation change(%) -35 to +10 -23 -19 -35

Landscapes

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

Claims (15)

  1. Utilisation d'une composition d'huile lubrifiante pour améliorer la compatibilité d'un joint en caoutchouc acrylique avec la composition d'huile lubrifiante pendant l'opération d'un moteur à combustion interne, où la composition d'huile lubrifiante comprend :
    a) une quantité majeure d'une huile de base à viscosité lubrifiante,
    b) un dispersant contenant de l'azote et sans teneur en cendres en une quantité de 0,01 à 0,3 pour cent en poids en termes du contenu en azote, sur la base du poids total de la composition d'huile lubrifiante,
    c) un détergent contenant un métal d'un sel de métal alcalin ou alcalino-terreux d'un dérivé d'alkylphénole ayant une structure de base de Mannich en une quantité de 0,001 à 0,04 pour cent en poids en termes du contenu en métal, sur la base du poids total de la composition d'huile lubrifiante, et
    d) un composé organique contenant du phosphore en une quantité de 0,001 à 0,5 pour cent en poids en termes du contenu en phosphore, sur la base du poids total de la composition d'huile lubrifiante,
    où le rapport des composantes b) à c) est dans la plage entre 1:0,005 et 1:2 en termes du contenu en azote ;
    et où l'amélioration de la compatibilité d'un joint en caoutchouc acrylique est une amélioration du change en élongation mesuré selon le test d'affinité CEC-L-39-T-96 pour les caoutchoucs d'étanchéité.
  2. Utilisation selon la revendication 1, dans laquelle le dispersant contenant de l'azote et sans teneur en cendres est un imide succinique d'alcényle ou d'alkyle ou un de ses dérivés.
  3. Utilisation selon la revendication 1, dans laquelle le détergent contenant un métal d'un sel de métal alcalin ou alcalino-terreux d'un dérivé d'alkylphénole ayant une structure de base de Mannich est représenté par la formule suivante :
    Figure imgb0005
     dans laquelle R est un groupe alkyle ayant 8 à 30 atomes de carbone, et n est 0 ou un nombre entier positif.
  4. Utilisation selon la revendication 1, dans laquelle le composé organique contenant du phosphore est sélectionné parmi le groupe constitué par les dihydro-carbyldithiophosphates de zinc, les dihydrocarbylphosphates de zinc, les esters d'acide phosphorique, les esters d'acide phosphoreux, et les esters d'acide thiophosphorique.
  5. Utilisation selon la revendication 1, dans laquelle la quantité du dispersant contenant de l'azote et sans teneur en cendres est dans la plage de 0,01 à 0,1 pour cent en poids en termes du contenu en azote, sur la base du poids total de la composition d'huile lubrifiante.
  6. Utilisation selon la revendication 1, dans laquelle la quantité du détergent contenant un métal d'un sel de métal alcalin ou alcalino-terreux d'un dérivé d'alkylphénole ayant une structure de base de Mannich est dans la plage de 0,002 à 0,1 pour cent en poids en termes du contenu en azote, sur la base du poids total de la composition d'huile lubrifiante.
  7. Utilisation selon la revendication 1, dans laquelle la quantité du composé organique contenant du phosphore est dans la plage de 0,01 à 0,2 pour cent en poids en termes du contenu en phosphore, sur la base du poids total de la composition d'huile lubrifiante.
  8. Utilisation selon la revendication 1, dans laquelle la composition d'huile lubrifiante comprend en plus un détergent contenant un métal sélectionné parmi le groupe constitué par les salicylates, les carboxylates, les phénates et les sulfonates d'un métal alcalin ou métal alcalino-terreux en une quantité de 1,0 pour cent en poids ou moins en termes de contenu en métal, sur la base du poids total de la composition d'huile lubrifiante.
  9. Utilisation selon la revendication 8, dans laquelle la quantité du détergent contenant un métal sélectionné parmi le groupe constitué par les salicylates, les carboxylates, les phénates et les sulfonates d'un métal alcalin ou métal alcalino-terreux et la quantité du détergent contenant un métal d'un sel de métal alcalin ou alcalino-terreux d'un dérivé d'alkylphénole ayant une structure de base de Mannich sont dans un rapport de 1:0,003 à 1:1 en termes du contenu en métal.
  10. Utilisation selon la revendication 1, dans laquelle la composition d'huile lubrifiante comprend en plus un composé de molybdène sélectionné parmi le groupe constitué par un complexe oxymolybdène préparé par la réaction entre un composé de molybdène acide et un composé d'azote basique, un dithiocarbamate d'oxymolybdène sulfurisé, et un dithiophosphate d'oxymolybdène sulfurisé, en une quantité de 0,25 pour cent en poids ou moins en termes du contenu en molybdène, sur la base du poids total de la composition d'huile lubrifiante.
  11. Utilisation selon la revendication 1, dans laquelle la composition d'huile lubrifiante comprend en plus un borate de métal alcalin en une quantité de 2 pour cent en poids ou moins, sur la base du poids total de la composition d'huile lubrifiante.
  12. Utilisation selon la revendication 1, dans laquelle la composition d'huile lubrifiante comprend en plus un inhibiteur d'oxydation sélectionné parmi le groupe constitué par des composés stériquement empêchés et de diarylamine en une quantité de 5 pour cent en poids ou moins, sur la base du poids total de la composition d'huile lubrifiante.
  13. Utilisation selon la revendication 1, dans laquelle l'huile de base comprend 10 pour cent en poids ou plus d'une huile minérale ayant les charactéristiques suivantes :
    - 17 pour cent en poids ou moins de perte d'évaporation selon ASTM D-5800,
    - 90 pour cent en poids ou plus de contenu saturé,
    - 10 pour cent en poids ou moins de composante aromatique,
    - 0,01 pour cent en poids ou moins de contenu en soufre, et
    - un indice de viscosité de 120 ou plus.
  14. Utilisation selon la revendication 1, dans laquelle la composition d'huile lubrifiante a un degré de viscosité SAE sélectionné parmi le groupe constitué par 0W20, 0W30, 5W20, 5W30 et 10W30.
  15. Utilisation selon la revendication 14, dans laquelle la composition d'huile lubrifiante a un degré de viscosité SAE de 10W30.
EP06256586.6A 2005-12-27 2006-12-27 Utilisation d'une composition lubrifiante pour améliorer la compatibilité d'un matériau d'étanchéité en caoutchouc acrylique dans un moteur à combustion interne Active EP1803797B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2005375974A JP4955998B2 (ja) 2005-12-27 2005-12-27 潤滑油組成物

Publications (3)

Publication Number Publication Date
EP1803797A2 EP1803797A2 (fr) 2007-07-04
EP1803797A3 EP1803797A3 (fr) 2010-07-28
EP1803797B1 true EP1803797B1 (fr) 2014-12-03

Family

ID=37944351

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06256586.6A Active EP1803797B1 (fr) 2005-12-27 2006-12-27 Utilisation d'une composition lubrifiante pour améliorer la compatibilité d'un matériau d'étanchéité en caoutchouc acrylique dans un moteur à combustion interne

Country Status (5)

Country Link
US (1) US20070184992A1 (fr)
EP (1) EP1803797B1 (fr)
JP (1) JP4955998B2 (fr)
CA (1) CA2572041C (fr)
SG (1) SG133568A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080128184A1 (en) * 2006-11-30 2008-06-05 Loper John T Lubricating oil compositions having improved corrosion and seal protection properties
US20090247438A1 (en) * 2008-03-31 2009-10-01 Exxonmobil Research And Engineering Company Hydraulic oil formulation and method to improve seal swell
US20100081591A1 (en) * 2008-09-30 2010-04-01 Chevron Oronite Company Llc Lubricating oil compositions
US8993496B2 (en) 2010-03-31 2015-03-31 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility
US8901050B2 (en) * 2010-03-31 2014-12-02 Chevron Oronite Company Llc Method for improving copper corrosion performance
US8716202B2 (en) * 2010-12-14 2014-05-06 Chevron Oronite Company Llc Method for improving fluorocarbon elastomer seal compatibility
CA2852715C (fr) * 2011-12-16 2020-09-22 Chevron Oronite Company Llc Detergents melanges destines a des huiles a moteur diesel
EP3369802B1 (fr) * 2017-03-01 2019-07-10 Infineum International Limited Améliorations apportées et relatives à des compositions de lubrification

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4713189A (en) * 1986-08-20 1987-12-15 Texaco, Inc. Precoupled mono-succinimide lubricating oil dispersants and viton seal additives
US5370805A (en) * 1993-11-18 1994-12-06 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. Chlorine-free diesel engine lubricating composition
EP0684298A3 (fr) * 1994-05-23 1996-04-03 Lubrizol Corp Compositions pour accroître la durée de conservation de joints d'étanchéité et des lubrifiants et fluides fonctionnels les contenant.
FR2762848B1 (fr) * 1997-05-05 2000-02-04 Chevron Res & Tech Utilisation de composes borates pour ameliorer la compatibilite d'huiles lubrifiantes avec des elastomeres fluorocarbones
JP3261340B2 (ja) * 1997-05-30 2002-02-25 東燃ゼネラル石油株式会社 潤滑油組成物
JP4107702B2 (ja) * 1997-12-19 2008-06-25 昭和シェル石油株式会社 シール材適合性に優れた潤滑油組成物
JP3722472B2 (ja) * 2000-06-02 2005-11-30 シェブロンテキサコジャパン株式会社 潤滑油組成物
US6569818B2 (en) * 2000-06-02 2003-05-27 Chevron Oronite Company, Llc Lubricating oil composition
EP1439217B1 (fr) * 2001-10-12 2012-06-20 Nippon Oil Corporation Composition d'huile de lubrification pour un moteur a combustion
JP4066132B2 (ja) * 2001-10-15 2008-03-26 株式会社Ａｄｅｋａ 潤滑剤及び潤滑性組成物
JP4011967B2 (ja) * 2002-05-07 2007-11-21 シェブロンジャパン株式会社 潤滑油組成物
CN100500817C (zh) * 2002-08-27 2009-06-17 新日本石油株式会社 润滑油组合物
US7285516B2 (en) * 2002-11-25 2007-10-23 The Lubrizol Corporation Additive formulation for lubricating oils
US20040171501A1 (en) * 2003-02-27 2004-09-02 Leeuwen Jeroen Van Method for improving elastomer compatibility
US7985592B2 (en) * 2004-02-13 2011-07-26 Chevron Oronite Company Llc High throughput screening methods for lubricating oil compositions

Also Published As

Publication number Publication date
CA2572041A1 (fr) 2007-06-27
JP2007177052A (ja) 2007-07-12
EP1803797A2 (fr) 2007-07-04
US20070184992A1 (en) 2007-08-09
JP4955998B2 (ja) 2012-06-20
EP1803797A3 (fr) 2010-07-28
SG133568A1 (en) 2007-07-30
CA2572041C (fr) 2015-02-17

Similar Documents

Publication Publication Date Title
EP2011855B1 (fr) Composition d'huile lubrifiante économisant du carburant pour la lubrification de moteurs diesel
EP2610333B1 (fr) Compositions d'huile lubrifiante économique de carburant pour moteurs à combustion interne
EP1167497B1 (fr) Composition d'huile lubrifiante pour moteurs diesel
EP2236590B1 (fr) Composition d'huile lubrifiante
EP1803797B1 (fr) Utilisation d'une composition lubrifiante pour améliorer la compatibilité d'un matériau d'étanchéité en caoutchouc acrylique dans un moteur à combustion interne
EP2574657B1 (fr) Composition d'une huile lubrifiante
JP5431641B2 (ja) 低硫黄低リン潤滑油組成物
CA2327384A1 (fr) Composition d'huile de lubrification pour moteur a combustion interne, particulierement adaptee a un moteur a essence
JP2007138166A (ja) 高負荷ディーゼルエンジン用低硫黄低リン潤滑油組成物
JP2003336089A (ja) 潤滑油組成物
EP2428550B1 (fr) Composition d'huile lubrifiante
US9102896B2 (en) Fuel economical lubricating oil composition for internal combustion engines
JP2004197002A (ja) 潤滑油組成物
JP2006182986A (ja) 潤滑油組成物
EP1676902B1 (fr) Composition d'huile lubrifiante à stabilité à l'oxydation améliorée à haute température
JPH11106776A (ja) 潤滑油組成物
EP2457985B1 (fr) Composition d'huile lubrifiante pour lubrifier des moteurs d'automobile
US7687444B2 (en) Lubricating oil composition having improved oxidation stability at high temperatures

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

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

17P Request for examination filed

Effective date: 20110124

AKX Designation fees paid

Designated state(s): DE FR GB NL

17Q First examination report despatched

Effective date: 20120301

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20140630

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602006043861

Country of ref document: DE

Effective date: 20150115

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602006043861

Country of ref document: DE

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

26N No opposition filed

Effective date: 20150904

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 10

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 11

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

Ref country code: NL

Payment date: 20161212

Year of fee payment: 11

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 12

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20180101

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: 20180101

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602006043861

Country of ref document: DE

Representative=s name: HL KEMPNER PATENTANWAELTE, SOLICITORS (ENGLAND, DE

Ref country code: DE

Ref legal event code: R082

Ref document number: 602006043861

Country of ref document: DE

Representative=s name: HL KEMPNER PATENTANWALT, RECHTSANWALT, SOLICIT, DE

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230530

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

Ref country code: GB

Payment date: 20231102

Year of fee payment: 18

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

Ref country code: FR

Payment date: 20231108

Year of fee payment: 18

Ref country code: DE

Payment date: 20231031

Year of fee payment: 18