EP3666860B1 - Anti-flaking agent and lubricant composition comprising the same - Google Patents

Anti-flaking agent and lubricant composition comprising the same Download PDF

Info

Publication number
EP3666860B1
EP3666860B1 EP19206606.6A EP19206606A EP3666860B1 EP 3666860 B1 EP3666860 B1 EP 3666860B1 EP 19206606 A EP19206606 A EP 19206606A EP 3666860 B1 EP3666860 B1 EP 3666860B1
Authority
EP
European Patent Office
Prior art keywords
dimethyl
compound
ether
malonate
flaking
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
EP19206606.6A
Other languages
German (de)
French (fr)
Other versions
EP3666860A1 (en
Inventor
Satoshi Noyama
Makoto Hayama
Daming Dong
Keiji Nakayama
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.)
Kyodo Yushi Co Ltd
Original Assignee
Kyodo Yushi 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 Kyodo Yushi Co Ltd filed Critical Kyodo Yushi Co Ltd
Publication of EP3666860A1 publication Critical patent/EP3666860A1/en
Application granted granted Critical
Publication of EP3666860B1 publication Critical patent/EP3666860B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C10M127/00Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon
    • C10M127/04Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon well-defined aromatic
    • 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
    • C10M127/00Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon
    • C10M127/06Alkylated aromatic hydrocarbons
    • 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
    • C10M129/06Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/08Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least 2 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
    • 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
    • C10M129/16Ethers
    • 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
    • C10M129/70Esters of monocarboxylic 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
    • 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
    • C10M129/72Esters of polycarboxylic 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
    • 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
    • C10M133/16Amides; Imides
    • 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
    • C10M133/22Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms containing a carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones
    • 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
    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • 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
    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • 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
    • 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
    • C10M171/00Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • 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
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06Well-defined aromatic 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
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006Petroleum or coal fractions, e.g. tars, solvents, bitumen 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
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/04Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
    • 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
    • C10M2207/021Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/022Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms containing at least two 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
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/0406Ethers; Acetals; Ortho-esters; Ortho-carbonates 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
    • C10M2207/04Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/046Hydroxy ethers
    • 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
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
    • 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
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • 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
    • C10M2207/281Esters of (cyclo)aliphatic monocarboxylic 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
    • C10M2207/282Esters 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
    • C10M2207/285Esters of aromatic polycarboxylic 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
    • C10M2207/287Partial 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
    • 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
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033Polyethers, i.e. containing di- or higher polyoxyalkylene groups 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
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms 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
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms 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
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/109Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
    • 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
    • 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
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
    • 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
    • C10M2215/08Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
    • 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
    • C10M2215/08Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
    • C10M2215/082Amides [having hydrocarbon substituents containing less than thirty carbon atoms] containing hydroxyl groups; Alkoxylated 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
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/086Imides [having hydrocarbon substituents containing less than thirty carbon atoms]
    • 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
    • C10M2215/10Amides of carbonic or haloformic 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
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/10Amides of carbonic or haloformic acids
    • C10M2215/102Ureas; Semicarbazides; Allophanates
    • 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
    • C10M2215/16Nitriles
    • 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
    • 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
    • C10M2215/224Imidazoles
    • 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
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/045Polyureas; Polyurethanes
    • 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
    • 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
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066Thiocarbamic type compounds
    • C10M2219/068Thiocarbamate metal 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
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/084Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof
    • 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
    • C10M2219/10Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106Thiadiazoles
    • 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
    • C10M2223/047Thioderivatives not containing metallic elements
    • 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
    • C10N2020/02Viscosity; 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
    • C10N2020/00Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01Physico-chemical properties
    • C10N2020/077Ionic Liquids
    • 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
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10Form in which the lubricant is applied to the material being lubricated semi-solid; greasy

Definitions

  • the present invention relates to a novel anti-flaking agent which can be contained in a lubricant applicable to a metal surface of e.g. a rolling bearing.
  • the present invention also relates to a lubricant composition containing the anti-flaking agent.
  • a peculiar early abnormal flaking involving formation of white etching area occurring on the rolling surface of a rolling bearing has been a problem since the mid-1980s because it reduces the fatigue life of the rolling bearing.
  • Such flaking is called white flaking, white band flaking, brittle flaking, hydrogen brittle flaking, or hydrogen embrittlement flaking.
  • Patent Literature 1 introduces a hydrogen hypothesis, for example. Specifically, the hypothesis is as follows: when grease is used under a high load, the grease decomposes to generate hydrogen; the hydrogen penetrates into the steel material of the rolling bearing and reacts with carbide at the grain boundaries; and as a result, the steel material becomes brittle.
  • Patent Literature 1 reports that, when a grease composition contains a specific compound containing at least one sulfur atom such as a thiazole derivative, a sulfurized oil and/or fat, or a sulfurized olefin, it is possible to deal with the problem of white band flaking, that is, the intrusion of hydrogen generated by decomposition of the lubricant into the metal.
  • a specific compound containing at least one sulfur atom such as a thiazole derivative, a sulfurized oil and/or fat, or a sulfurized olefin
  • Patent Literature 2 reports an additive which is a passivating oxidizer such as a nitrite, where the additive is added to the grease to oxidize the metal surface and suppress the catalytic activity of the surface, thereby suppressing the generation of hydrogen due to the decomposition of the lubricant.
  • Patent Literature 3 reports a technique of combining a passivating oxidizer with an organic sulfonate.
  • Patent Literature 4 reports a technique of allowing grease to contain a specific amount of an azo compound.
  • Patent Literature 5 reports a technique that suppresses the generation of hydrogen from grease by using a phenyl ether-based synthetic oil as the base oil of the grease.
  • the present inventors considered that the suppression of triboplasma generation could prevent white band flaking of e.g. a rolling bearing.
  • an object of the present invention is to provide an anti-flaking agent capable of suppressing white band flaking of e.g. a rolling bearing, and a lubricant composition containing the anti-flaking agent.
  • the present inventors measured the amount of hydrogen generated using a candidate compound for a base oil accounting for a large percentage of the lubricant composition or the grease composition, and have found that a compound having a specific volume resistivity of 1.0 ⁇ 10 10 ⁇ cm or less can effectively suppress hydrogen generation. Based on this knowledge, the present inventors have completed an invention which can effectively prevent white band flaking of e.g. a rolling bearing.
  • the present invention provides the following use.
  • the present invention also provides the following lubricant composition.
  • the anti-flaking agent and lubricant composition of the present invention can prevent white band flaking effectively (20% or less as compared with n-hexadecane).
  • FIG. 1 is a schematic view of an apparatus, used in Examples, for generating hydrogen gas by triboplasma.
  • the specific volume resistivity represents a ratio between a DC electric field (V/m) applied to the sample at 25°C and a current per unit cross-sectional area applied to the sample at that time, and is equal to the resistance between opposing faces of a cubic sample with one side being 1 cm.
  • the specific volume resistivity can be measured based on the testing methods of electrical insulating oils specified in JIS C2101.
  • the dielectric constant ⁇ is a coefficient representing the relationship between the electric charge in the substance and the force given thereby.
  • the dielectric constant ⁇ was measured at 25°C with E4991B Impedance Analyzer (Keysight Technologies).
  • the "Hansen solubility parameters" are each an index indicating the solubility of a certain solute in a certain solvent, and include three components: the dispersion term ( ⁇ D), the polar term ( ⁇ P), and the hydrogen bond term ( ⁇ H).
  • the dispersion term ( ⁇ D) represents the effect due to the dispersion force
  • the polar term ( ⁇ P) represents the effect due to the force between dipoles
  • the hydrogen bond term ( ⁇ H) represents the effect due to the hydrogen bond force. Details of the definitions and calculation methods for the Hansen solubility parameters are described in the following literature: Charles M. Hansen, "Hansen Solubility Parameters: A Users Handbook," CRC Press, 2007 .
  • white band flaking refers to a peculiar early abnormal flaking involving formation of white etching area.
  • the term "white band flaking” is synonymous with a term called e.g. white flaking, white band flaking, brittle flaking, hydrogen brittle flaking, or hydrogen embrittlement flaking in the art.
  • the life can be estimated based on the life calculation formula defined in the standards (ISO281, JIS B-1518).
  • the lifetime is reached in a shorter time than the calculated lifetime. In the actual market, it has been reported that the life is reached at about 1/10 to 1/20 of the calculated life.
  • White band flaking is one type of internal origin damage, and shows a specific phenomenon in which a white band is observed when the metal structure after the occurrence is etched with a nital solution.
  • the compound used in the present invention is a compound having a specific volume resistivity of 1.0 ⁇ 10 10 ⁇ cm or less, and is a diester as defined above.
  • the present inventors have found that a compound having such a physical property can suppress hydrogen generation by plasma.
  • the experimental methods and results are described in detail in the Examples section, the present inventors systematically examined the influence of the carbon chain length of ester on the amount of hydrogen generated. Then, as regards the length of the carbon chain derived from the dibasic fatty acid constituting the ester with methanol (R 2 OOC-R 1 -COOR 2 ) (that is, R 1 ), no hydrogen was generated when the number of carbon atoms was 6 or less.
  • the specific volume resistivity was measured and found to be 9.0 ⁇ 10 9 ⁇ cm. Moreover, when the specific volume resistivity was measured while changing the number of carbon atoms of R 1 , it was found that the specific volume resistivity increased as the number of carbon atoms of R 1 increased.
  • the present inventors examined the influence of the length of the carbon chain derived from the alcohol constituting the ester with sebacic acid (that is, R 2 ) on the amount of hydrogen generated. Then, it was found that the specific volume resistivity increased as the number of carbon atoms of R 2 increased. This tendency was also observed in the case of monoesters.
  • the present inventors have also found that a specific aromatic compound can effectively suppress hydrogen generation even when the compound has a specific volume resistivity exceeding 1.0 ⁇ 10 10 ⁇ cm.
  • the compound of the present invention is at least one selected from the group consisting of (A) a compound having a specific volume resistivity of 1.0 ⁇ 10 10 ⁇ cm or less, wherein the compound (A) is a diester selected from the group consisting of dimethyl phthalate, dimethyl maleate, diethyl malonate, dibutyl malonate, and dihexyl malonate.
  • the compound (A) preferably has a specific volume resistivity of 5.0 ⁇ 10 9 ⁇ cm or less.
  • the compound (A) is preferably liquid at 25°C.
  • the compound (A) preferably has a dielectric constant ⁇ of 3.0 or more at 500 MHz (25°C) and 1 GHz (25°C).
  • the compound (A) preferably has a Hansen solubility parameter polar term ⁇ p of 3.5 or more.
  • ⁇ p is expressed by the following formula, and ⁇ p increases as the dielectric constant ⁇ increases.
  • the dielectric constant ⁇ of oil affects electron wave absorption, and it is said that the larger the diel ectric constant ⁇ and the larger the dielectric loss tangent, the more effectively electron waves can be absorbed, which can be a countermeasure against electron wave noise.
  • ⁇ p 2 12108 V 2 ⁇ ⁇ 1 2 ⁇ + n D 2 n D 2 + 2 ⁇ 2
  • ⁇ p is preferably 4.0 or more.
  • the Hansen solubility parameter polar term ⁇ p is preferably 20 or less.
  • ⁇ p is preferably 3.5 or more, and the reason is as follows. Such a value makes it possible to achieve a conductivity to an extent sufficient to prevent charging and a high dielectric constant, and it is therefore considered that white band flaking can be suppressed through suppression of triboplasma generation.
  • the flash point of the compound of the present invention is preferably 70°C or lower because there is a risk of ignition by plasma generated due to friction of the lubrication portion.
  • the flash point can be measured based on JIS K2265.
  • the compound can be used alone as a lubricant composition, can also be used as a lubricant or a base oil of a grease, or can be mixed with a conventional base oil as a lubricant or a base oil of a grease to form a lubricant composition.
  • the conventional base oil one having a specific volume resistivity exceeding 1.0 ⁇ 10 10 ⁇ cm can be used.
  • One containing a saturated or unsaturated hydrocarbon group having 12 or more carbon atoms in total is preferable, and specific examples thereof include mineral oils and synthetic oils.
  • the mineral oil it is possible to use a paraffinic mineral oil, a naphthenic mineral oil, or a mixture thereof. It is preferable to contain a highly refined mineral oil (that is, a mineral oil which has been subjected to dewaxing treatment to reduce wax component precipitation at low temperature, thereby lowering its pour point as compared with the pour point of unrefined mineral oils (-5°C to -20°C, measured according to JIS K 2269)).
  • Examples of synthetic oils include synthetic hydrocarbons, ester oils, ether oils, glycol oils, silicone oils, and fluorinated oils.
  • Examples of synthetic hydrocarbon oils include poly alpha olefins ("PAOs") and polybutene. Among these, poly alpha olefins are preferable.
  • Examples of ester oils include diesters, trimellitate esters, and polyol esters.
  • Examples of ether oils include alkyl diphenyl ethers ("ADEs”), dialkyl diphenyl ethers, and polypropylene glycol.
  • Examples of glycol oils include polypropylene glycol and polypropylene alkyl ethers.
  • hydrogen generation can be effectively suppressed even when the compound is in a small amount, for example more than 0.1% by mass, preferably more than 1% by mass, more preferably 2% by mass or more, and further preferably 3% by mass or more based on the total mass of the lubricant composition.
  • the content of the compound in the lubricant composition of the present invention can be, for example, 40% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, or 3% by mass or less.
  • ester oils such as diesters and polyol esters
  • ether oils such as alkyl phenyl ether oils
  • glycol oils such as water-insoluble polyalkylene glycols
  • silicone oils fluorinated oils, and the like.
  • mineral oils, synthetic oils, hydrocarbon oils, phenyl ether oils, and alkyl phenyl ether oils are preferable.
  • the kinematic viscosity at 40°C of the base oil in the lubricant composition of the present invention is preferably 10 to 500 mm 2 /s.
  • the kinematic viscosity at 40°C of the base oil is less than 10 mm 2 /s, it may be impossible to achieve a sufficient oil film at low speed or high temperature.
  • the kinematic viscosity at 40°C of the base oil exceeds 500 mm 2 /s, there is a risk that the torque may rise at high speed or low temperature.
  • the range is more preferably 50 to 200 mm 2 /s and further preferably 60 to 130 mm 2 /s. Note that the kinematic viscosity of the base oil can be measured based on JIS K2283.
  • the content of the base oil in the lubricant composition of the present invention is preferably 60 to 99.9 parts by mass, more preferably 90 to 99.9 parts by mass, and further preferably 97 to 99.9 parts by mass relative to 100 parts by mass in total of the base oil and the anti-flaking agent.
  • the content of the base oil is preferably in such ranges because of excellence in lubricity and low volatility.
  • the lubricant composition of the present invention may further contain a general-purpose additive as necessary.
  • a general-purpose additive for example, a rust inhibitor, a load-bearing additive, an antioxidant, and the like can be contained as necessary.
  • the content of these optional additives is usually 0.5 to 5% by mass based on the total mass of the lubricant composition of the present invention.
  • Examples of the rust inhibitor include inorganic rust inhibitors and organic rust inhibitors.
  • Examples of the inorganic rust inhibitors include inorganic metal salts such as sodium silicate, lithium carbonate, potassium carbonate, and zinc oxide.
  • Examples of the organic rust inhibitors include benzoates such as sodium benzoate and lithium benzoate, sulfonates such as calcium sulfonate and zinc sulfonate, carboxylates such as zinc naphthenate and sodium sebacate, succinic acid derivatives such as succinic acid, succinic anhydride, and succinic acid half ester, sorbitan esters such as sorbitan monooleate and sorbitan trioleate, and fatty acid amine salts.
  • load-bearing additive examples include phosphorus-containing ones such as phosphate esters, sulfur-based ones such as polysulfide and sulfurized oils and/or fats, phosphorus-sulfur-based ones such as phosphorothioates, thiocarbamates, thiophosphates, and organic phosphate esters.
  • the antioxidant is known to suppress oxidative degradation of grease, and examples thereof include phenol-based antioxidants and amine-based antioxidants.
  • phenol-based antioxidants examples include 2,6-di-tert-butyl-p-cresol (BHT), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 2,6-di- tert -butyl-phenol, 2,4-dimethyl-6-tert-butylphenol, tert-butylhydroxyanisole (BHA), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-methylenebis(2,3-di- tert -butylphenol), 4,4'-thiobis(3-methyl-6- tert -butylphenol), and octadecyl-3-(3,5-di- tert -butyl-4-hydroxyphenyl)propionate. Among these, octadecyl-3-(3,5-di- ter
  • amine-based antioxidants examples include N-n-butyl-p-aminophenol, 4,4'-tetramethyl-di-aminodiphenylmethane, ⁇ -naphthylamine, N -phenyl- ⁇ -naphthylamine, phenothiazine, and alkyl diphenylamines. Among these, alkyl diphenylamines are preferable.
  • the lubricant composition of the present invention can be used as lubricating oil, conductive oil, dynamic pressure oil, and the like.
  • the lubricant composition of the present invention is effective in preventing flaking wear.
  • the lubricant composition of the present invention may further contain a thickener to form a grease composition.
  • the content of the compound (A) and/or (B) is preferably more than 0.1% by mass, more preferably more than 1% by mass, further preferably 2% by mass or more, and particularly preferably 3% by mass or more based on the total mass of the grease composition of the present invention, and the upper limit can be, for example, 40% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, or 3% by mass or less.
  • the grease composition of the present invention may further contain a general-purpose additive as necessary.
  • additives which can be used include ones described for the lubricant composition.
  • the content of the optional additive is usually 0.1 to 5% by mass based on the total mass of the grease composition of the present invention.
  • the worked penetration of the grease composition of the present invention is preferably 200 to 300 and more preferably 220 to 280.
  • the worked penetration exceeds 300, leakage due to high-speed rotation increases, which may result in failure to satisfy a sufficient lubrication life.
  • the worked penetration is less than 200, the fluidity of the grease is deteriorated, which may result in failure to satisfy a sufficient lubrication life.
  • the term "penetration" refers to a 60-stroke worked penetration. The penetration can be measured according to JIS K2220-7.
  • the content of the thickener is preferably 5 to 25% by mass and more preferably 10 to 20% by mass based on the total mass of the grease composition of the present invention.
  • the content is less than 5% by mass, the grease is soft and may leak, which could result in failure to satisfy a sufficient lubrication life.
  • the content is more than 25% by mass, the fluidity is inferior and thus it becomes difficult for the grease to enter the lubrication portion, which could result in failure to satisfy a sufficient lubrication life.
  • the content of the base oil is preferably 60 to 90% by mass and more preferably 70 to 90% by mass based on the total mass of the grease composition of the present invention.
  • the content of the base oil is preferably in such ranges because of excellence in lubricity and low volatility.
  • the grease composition of the present invention is used in various rolling bearings for industrial machines and automobiles.
  • industrial machines include rolling bearings in various motors for industrial machines, reducers and hydraulic equipment of industrial robots, main shafts and reducers of wind power generators, and peripherals of elevator hoists.
  • the use for automobiles is preferably a rolling bearing for automobile electrical equipment and auxiliaries.
  • automobile electrical equipment and auxiliaries include alternators, electromagnetic clutches for automobile air conditioners, intermediate pulleys, idler pulleys, and tension pulleys.
  • the amount of hydrogen generated was measured according to the method described in Nouyama, Nakayama, et al., Manuscript Preparation for Tribology Conference, Tokyo (2017), 185 .
  • a triboplasma generator ( Fig. 1 ) was used capable of generating triboplasma between the needle and the flat plate electrode.
  • the needle was the cathode and the flat plate was the anode.
  • the material of the needle was SCM435 steel and the apex angle of the needle was 120°.
  • the needle was arranged perpendicular to the anode flat plate, and was fixed at a position where the distance between the tip of the needle and the upper surface of the anode was 50 ⁇ m.
  • the distance between the needle and the flat plate electrode was controlled by a micrometer.
  • the material of the anode flat plate was SPCC steel.
  • the anode flat plate constituted the bottom portion inside the container.
  • the container was charged with the anti-flaking agent and the like of Examples or Comparative Examples, and the needle was in contact with the anti-flaking agent and the like inside the container.
  • the anode flat plate and the cathode needle were connected by a high voltage power source. The voltage and current when a voltage was applied was measurable by an oscilloscope.
  • the container and the needle were surrounded by a larger casing (hereinafter referred to as the "atmosphere control chamber") so as to cover both.
  • the top portion of the atmosphere control chamber had an opening provided therein, and the gas inside the atmosphere control chamber was collectable through a microsyringe.
  • the upper side portion of the atmosphere control chamber also had an opening provided therein so as to introduce dry air therethrough.
  • the gas inside the atmosphere control chamber was detectable by a semiconductor sensor.
  • Dry air was introduced for 30 seconds to replace the gas inside the atmosphere control chamber.
  • the atmosphere control chamber was subjected to discharging for 30 seconds while monitoring the current value and the voltage value with an oscilloscope, and then left for 20 seconds to collect the generated gas through a microsyringe.
  • the collected gas was introduced into gas chromatography to measure the amount of hydrogen gas. Note that the gas chromatography was measured using a gas chromatograph GC-2010 (manufactured by Shimadzu Corporation), a column RT-Msieve ⁇ 0.43 mm ⁇ 30 m, and a detector TCD.
  • the amount of hydrogen generated for each compound was calculated with the amount of hydrogen generated for n-hexadecane set to 100%.
  • Examples 1 to 38 are examples of the anti-flaking agent
  • Examples 39 to 71 are examples of the lubricating oil composition containing the anti-flaking agent.
  • Example 42 is a mixture of 3.0% by mass of dimethyl malonate of Example 3 and 97.0% by mass of poly alpha olefin of Comparative Example 8, and indicates that, even when the specific volume resistivity of the mixture exceeds 1.0 ⁇ 10 10 ⁇ cm, the amount of hydrogen generated can be suppressed to 0% if a predetermined amount of the anti-flaking agent of the present application having a specific volume resistivity of 1.0 ⁇ 10 10 ⁇ cm or less is contained.
  • Aromatic Hydrocarbon Compound Diphenylmethane 100 Diphenylpropane 100 Cis -1,2-Diphenylethylene 100 Monoester Methyl Myristate Dimethyl Phthalate 100 Dimethyl Maleate 100 Dimethyl Malonate 100 Dimethyl Succinate 100 Dimethyl Glutarate 100 Dimethyl Adipate 100 Diester Dimethyl Suberate 100 Dimethyl Sebacate Diethyl Malonate Dibutyl Malonate Dihexyl Malonate Dihexyl Sebacate Di-2-Ethylhexyl Sebacate Triester Tributyl Trimellitate Tetraester Pentaerythritol Glycol Tetraethylene Glycol Tripropylene Glycol Tetraethylene Glycol Dimethyl Ether Poly (

Landscapes

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

Description

    [Technical Field]
  • The present invention relates to a novel anti-flaking agent which can be contained in a lubricant applicable to a metal surface of e.g. a rolling bearing. The present invention also relates to a lubricant composition containing the anti-flaking agent.
  • [Background Art]
  • A peculiar early abnormal flaking involving formation of white etching area occurring on the rolling surface of a rolling bearing has been a problem since the mid-1980s because it reduces the fatigue life of the rolling bearing. Such flaking is called white flaking, white band flaking, brittle flaking, hydrogen brittle flaking, or hydrogen embrittlement flaking.
  • Although the mechanism of how such flaking takes place has not yet been elucidated, Patent Literature 1 introduces a hydrogen hypothesis, for example. Specifically, the hypothesis is as follows: when grease is used under a high load, the grease decomposes to generate hydrogen; the hydrogen penetrates into the steel material of the rolling bearing and reacts with carbide at the grain boundaries; and as a result, the steel material becomes brittle. Patent Literature 1 reports that, when a grease composition contains a specific compound containing at least one sulfur atom such as a thiazole derivative, a sulfurized oil and/or fat, or a sulfurized olefin, it is possible to deal with the problem of white band flaking, that is, the intrusion of hydrogen generated by decomposition of the lubricant into the metal.
  • The mechanism of how flaking takes place is also explained from the viewpoint of the formation of a new metal surface. Specifically, the mechanism is as follows: when the metal transfer surface wears, a new surface is easily formed by the wear; the newly formed surface brings about catalysis to chemically decompose the grease; and as a result, a large amount of hydrogen is generated, and the generated hydrogen penetrates into the steel to finally produce cracks on the metal surface. Patent Literature 2 reports an additive which is a passivating oxidizer such as a nitrite, where the additive is added to the grease to oxidize the metal surface and suppress the catalytic activity of the surface, thereby suppressing the generation of hydrogen due to the decomposition of the lubricant. Patent Literature 3 reports a technique of combining a passivating oxidizer with an organic sulfonate. Patent Literature 4 reports a technique of allowing grease to contain a specific amount of an azo compound. Patent Literature 5 reports a technique that suppresses the generation of hydrogen from grease by using a phenyl ether-based synthetic oil as the base oil of the grease.
  • [Citation List] [Patent Literature]
    • [Patent Literature 1] International Publication No. WO2015/016376
    • [Patent Literature 2] Japanese Patent Application Publication No. Hei 3-210394
    • [Patent Literature 3] Japanese Patent Application Publication No. Hei 5-263091
    • [Patent Literature 4] Japanese Patent Application Publication No. 2002-130301
    • [Patent Literature 5] Japanese Patent Application Publication No. Hei 3-250094
  • [Summary of Invention] [Technical Problems]
  • Meanwhile, it is known that plasma is generated in a minute range of several µm to several mm on the friction surface (Nakayama, K., Yagasaki, F., Tribology Letters (2018)). Such plasma is called "triboplasma." Discharge luminescence and electric corrosion also take place on an elastohydrodynamic lubrication (EHL) thin film of grease formed on rolling bearings. From these facts, there is a report suggesting that discharge plasma is generated on an EHL thin film (Nakayama and Tanaka: Manuscript Preparation for Tribology Conference, Tokyo (2016) A2).
  • The present inventors considered that the suppression of triboplasma generation could prevent white band flaking of e.g. a rolling bearing.
  • In view of the above, an object of the present invention is to provide an anti-flaking agent capable of suppressing white band flaking of e.g. a rolling bearing, and a lubricant composition containing the anti-flaking agent.
  • [Solution to Problems]
  • The present inventors measured the amount of hydrogen generated using a candidate compound for a base oil accounting for a large percentage of the lubricant composition or the grease composition, and have found that a compound having a specific volume resistivity of 1.0 × 1010 Ω·cm or less can effectively suppress hydrogen generation. Based on this knowledge, the present inventors have completed an invention which can effectively prevent white band flaking of e.g. a rolling bearing.
  • Specifically, the present invention provides the following use.
    1. [1] Use as an anti-flaking agent of at least one selected from the group consisting of (A) a compound having a specific volume resistivity of 1.0 × 1010 Ω·cm or less, wherein the compound (A) is a diester selected from the group consisting of dimethyl phthalate, dimethyl maleate, diethyl malonate, dibutyl malonate, and dihexyl malonate.
  • The present invention also provides the following lubricant composition.
    • [2] A lubricant composition comprising a diester selected from the group consisting of dimethyl maleate, dibutyl malonate, and dihexyl malonate and least one conventional base oil selected from the group consisting of mineral oils and synthetic oils.
    • [3] The lubricant composition according to 2 described above, wherein the base oil is at least one selected from the group consisting of mineral oils, synthetic hydrocarbon oils, and ether oils.
    • [4] The lubricant composition according to any one of 2 to 3 described above, wherein a content of the compound exceeds 0.1% by mass based on a total mass of the composition.
    • [5] The lubricant composition according to any one of 2 to 3 described above, wherein a content of the compound exceeds 1% by mass based on a total mass of the composition.
    • [6] The lubricant composition according to any one of 2 to 3 described above, wherein a content of the compound is 2% by mass or more based on a total mass of the composition.
    • [7] The lubricant composition according to any one of 2 to 3 described above, wherein a content of the compound is 3% by mass or more based on a total mass of the composition.
    • [8] The lubricant composition according to any one of 2 to 3 described above, wherein a content of the compound is 40% by mass or less based on a total mass of the composition.
    • [9] The lubricant composition according to any one of 2 to 8 described above, further comprising a thickener.
  • The anti-flaking agent and lubricant composition of the present invention can prevent white band flaking effectively (20% or less as compared with n-hexadecane).
  • [Brief Description of Drawings]
  • [Fig. 1] Fig. 1 is a schematic view of an apparatus, used in Examples, for generating hydrogen gas by triboplasma.
  • [Description of Embodiments] [Definitions]
  • In the present specification, the specific volume resistivity represents a ratio between a DC electric field (V/m) applied to the sample at 25°C and a current per unit cross-sectional area applied to the sample at that time, and is equal to the resistance between opposing faces of a cubic sample with one side being 1 cm. The specific volume resistivity can be measured based on the testing methods of electrical insulating oils specified in JIS C2101.
  • In the present specification, the dielectric constant ε is a coefficient representing the relationship between the electric charge in the substance and the force given thereby. The dielectric constant ε was measured at 25°C with E4991B Impedance Analyzer (Keysight Technologies).
  • In the present specification, the "Hansen solubility parameters" are each an index indicating the solubility of a certain solute in a certain solvent, and include three components: the dispersion term (δD), the polar term (δP), and the hydrogen bond term (δH). The dispersion term (δD) represents the effect due to the dispersion force, the polar term (δP) represents the effect due to the force between dipoles, and the hydrogen bond term (δH) represents the effect due to the hydrogen bond force. Details of the definitions and calculation methods for the Hansen solubility parameters are described in the following literature: Charles M. Hansen, "Hansen Solubility Parameters: A Users Handbook," CRC Press, 2007.
  • In the present specification, "white band flaking" refers to a peculiar early abnormal flaking involving formation of white etching area. In the present specification, the term "white band flaking" is synonymous with a term called e.g. white flaking, white band flaking, brittle flaking, hydrogen brittle flaking, or hydrogen embrittlement flaking in the art. Normally, for rolling fatigue, the life can be estimated based on the life calculation formula defined in the standards (ISO281, JIS B-1518). However, in the case where white band flaking takes place, the lifetime is reached in a shorter time than the calculated lifetime. In the actual market, it has been reported that the life is reached at about 1/10 to 1/20 of the calculated life. White band flaking is one type of internal origin damage, and shows a specific phenomenon in which a white band is observed when the metal structure after the occurrence is etched with a nital solution.
  • [Compound Used as Anti-Flaking Agent]
  • The compound used in the present invention is a compound having a specific volume resistivity of 1.0 × 1010 Ω·cm or less, and is a diester as defined above. The present inventors have found that a compound having such a physical property can suppress hydrogen generation by plasma. Although the experimental methods and results are described in detail in the Examples section, the present inventors systematically examined the influence of the carbon chain length of ester on the amount of hydrogen generated. Then, as regards the length of the carbon chain derived from the dibasic fatty acid constituting the ester with methanol (R2OOC-R1-COOR2) (that is, R1), no hydrogen was generated when the number of carbon atoms was 6 or less. Conversely, when the number of carbon atoms was 8 (that is, when the dibasic acid was sebacic acid), hydrogen was generated. However, the amount generated was only 17% compared with n-hexadecane used as a standard substance. It was considered that triboplasma was generated in the case of using dimethyl sebacate. Thus, the specific volume resistivity was measured and found to be 9.0 × 109 Ω·cm. Moreover, when the specific volume resistivity was measured while changing the number of carbon atoms of R1, it was found that the specific volume resistivity increased as the number of carbon atoms of R1 increased. Table 1
    Number of Carbon Atoms of R1 Amount of Hydrogen Generated, %* Specific Volume Resistivity, Ω·cm
    Dimethyl Malonate 1 0 6.6 × 107
    Dimethyl Adipate 4 0 4.0 × 109
    Dimethyl Sebacate 8 17 9.0 × 109
    * The amount of hydrogen generated for n-hexadecane is set to 100.
  • On the other hand, the present inventors examined the influence of the length of the carbon chain derived from the alcohol constituting the ester with sebacic acid (that is, R2) on the amount of hydrogen generated. Then, it was found that the specific volume resistivity increased as the number of carbon atoms of R2 increased. This tendency was also observed in the case of monoesters. Table 2
    Number of Carbon Atoms of R2 Amount of Hydrogen Generated, %* Specific Volume Resistivity, Ω·cm
    Dimethyl Sebacate 1 17 9.0 × 109
    Dihexyl Sebacate 6 95 9.0 × 1011
    Di(2-Ethylhexyl)Sebacate 8 100 2.4 × 1012
    * The amount of hydrogen generated for n-hexadecane is set to 100.
  • The present inventors have also found that a specific aromatic compound can effectively suppress hydrogen generation even when the compound has a specific volume resistivity exceeding 1.0 × 1010 Ω·cm.
  • Therefore, the compound of the present invention is at least one selected from the group consisting of (A) a compound having a specific volume resistivity of 1.0 × 1010 Ω·cm or less, wherein the compound (A) is a diester selected from the group consisting of dimethyl phthalate, dimethyl maleate, diethyl malonate, dibutyl malonate, and dihexyl malonate.
  • (Compound (A))
  • The compound (A) preferably has a specific volume resistivity of 5.0 × 109 Ω·cm or less.
  • In addition, the compound (A) is preferably liquid at 25°C.
  • In addition, the compound (A) preferably has a dielectric constant ε of 3.0 or more at 500 MHz (25°C) and 1 GHz (25°C).
  • In addition, the compound (A) preferably has a Hansen solubility parameter polar term δp of 3.5 or more.
  • The term δp is expressed by the following formula, and δp increases as the dielectric constant ε increases. Generally, it is said that the dielectric constant ε of oil affects electron wave absorption, and it is said that the larger the diel ectric constant ε and the larger the dielectric loss tangent, the more effectively electron waves can be absorbed, which can be a countermeasure against electron wave noise. δ p 2 = 12108 V 2 ε 1 2 ε + n D 2 n D 2 + 2 μ 2
    Figure imgb0001
  • It has been found that a compound having a specific volume resistivity of 1.0 × 1010 Ω·cm has a δp of 3.5 or more. Therefore, it is considered that, when δp is 3.5 or more, hydrogen generation can be prevented and white band flaking can be prevented. The term δp is preferably 4.0 or more. The Hansen solubility parameter polar term δp is preferably 20 or less.
  • The term δp is preferably 3.5 or more, and the reason is as follows. Such a value makes it possible to achieve a conductivity to an extent sufficient to prevent charging and a high dielectric constant, and it is therefore considered that white band flaking can be suppressed through suppression of triboplasma generation.
  • The flash point of the compound of the present invention is preferably 70°C or lower because there is a risk of ignition by plasma generated due to friction of the lubrication portion. The flash point can be measured based on JIS K2265.
  • [Lubricant Composition]
  • Since being liquid at room temperature, the compound can be used alone as a lubricant composition, can also be used as a lubricant or a base oil of a grease, or can be mixed with a conventional base oil as a lubricant or a base oil of a grease to form a lubricant composition.
  • (Conventional Base Oil)
  • As the conventional base oil, one having a specific volume resistivity exceeding 1.0 × 1010 Ω·cm can be used. One containing a saturated or unsaturated hydrocarbon group having 12 or more carbon atoms in total is preferable, and specific examples thereof include mineral oils and synthetic oils. As the mineral oil, it is possible to use a paraffinic mineral oil, a naphthenic mineral oil, or a mixture thereof. It is preferable to contain a highly refined mineral oil (that is, a mineral oil which has been subjected to dewaxing treatment to reduce wax component precipitation at low temperature, thereby lowering its pour point as compared with the pour point of unrefined mineral oils (-5°C to -20°C, measured according to JIS K 2269)). Examples of synthetic oils include synthetic hydrocarbons, ester oils, ether oils, glycol oils, silicone oils, and fluorinated oils. Examples of synthetic hydrocarbon oils include poly alpha olefins ("PAOs") and polybutene. Among these, poly alpha olefins are preferable. Examples of ester oils include diesters, trimellitate esters, and polyol esters. Examples of ether oils include alkyl diphenyl ethers ("ADEs"), dialkyl diphenyl ethers, and polypropylene glycol. Examples of glycol oils include polypropylene glycol and polypropylene alkyl ethers.
  • In the case of use in combination with a mineral oil or synthetic hydrocarbon (especially poly alpha olefin), hydrogen generation can be effectively suppressed even when the compound is in a small amount, for example more than 0.1% by mass, preferably more than 1% by mass, more preferably 2% by mass or more, and further preferably 3% by mass or more based on the total mass of the lubricant composition. The content of the compound in the lubricant composition of the present invention can be, for example, 40% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, or 3% by mass or less. Considering the compatibility with the compounds described above, preferable conventional oils are ester oils such as diesters and polyol esters, ether oils such as alkyl phenyl ether oils, glycol oils such as water-insoluble polyalkylene glycols, silicone oils, fluorinated oils, and the like. From the viewpoints of resin resistance and heat resistance, mineral oils, synthetic oils, hydrocarbon oils, phenyl ether oils, and alkyl phenyl ether oils are preferable.
  • The kinematic viscosity at 40°C of the base oil in the lubricant composition of the present invention (that is, the compound (A) and/or (B) alone, or a mixture oil with the conventional oil) is preferably 10 to 500 mm2/s. When the kinematic viscosity at 40°C of the base oil is less than 10 mm2/s, it may be impossible to achieve a sufficient oil film at low speed or high temperature. Meanwhile, when the kinematic viscosity at 40°C of the base oil exceeds 500 mm2/s, there is a risk that the torque may rise at high speed or low temperature. For the same reasons, the range is more preferably 50 to 200 mm2/s and further preferably 60 to 130 mm2/s. Note that the kinematic viscosity of the base oil can be measured based on JIS K2283.
  • The content of the base oil in the lubricant composition of the present invention is preferably 60 to 99.9 parts by mass, more preferably 90 to 99.9 parts by mass, and further preferably 97 to 99.9 parts by mass relative to 100 parts by mass in total of the base oil and the anti-flaking agent. The content of the base oil is preferably in such ranges because of excellence in lubricity and low volatility.
  • (Optional Additive)
  • The lubricant composition of the present invention may further contain a general-purpose additive as necessary. For example, a rust inhibitor, a load-bearing additive, an antioxidant, and the like can be contained as necessary. The content of these optional additives is usually 0.5 to 5% by mass based on the total mass of the lubricant composition of the present invention.
  • Examples of the rust inhibitor include inorganic rust inhibitors and organic rust inhibitors. Examples of the inorganic rust inhibitors include inorganic metal salts such as sodium silicate, lithium carbonate, potassium carbonate, and zinc oxide. Examples of the organic rust inhibitors include benzoates such as sodium benzoate and lithium benzoate, sulfonates such as calcium sulfonate and zinc sulfonate, carboxylates such as zinc naphthenate and sodium sebacate, succinic acid derivatives such as succinic acid, succinic anhydride, and succinic acid half ester, sorbitan esters such as sorbitan monooleate and sorbitan trioleate, and fatty acid amine salts.
  • Examples of the load-bearing additive include phosphorus-containing ones such as phosphate esters, sulfur-based ones such as polysulfide and sulfurized oils and/or fats, phosphorus-sulfur-based ones such as phosphorothioates, thiocarbamates, thiophosphates, and organic phosphate esters.
  • The antioxidant is known to suppress oxidative degradation of grease, and examples thereof include phenol-based antioxidants and amine-based antioxidants.
  • Examples of the phenol-based antioxidants include 2,6-di-tert-butyl-p-cresol (BHT), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-phenol, 2,4-dimethyl-6-tert-butylphenol, tert-butylhydroxyanisole (BHA), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 4,4'-methylenebis(2,3-di-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. Among these, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate is preferable.
  • Examples of the amine-based antioxidants include N-n-butyl-p-aminophenol, 4,4'-tetramethyl-di-aminodiphenylmethane, α-naphthylamine, N-phenyl-α-naphthylamine, phenothiazine, and alkyl diphenylamines. Among these, alkyl diphenylamines are preferable.
  • The lubricant composition of the present invention can be used as lubricating oil, conductive oil, dynamic pressure oil, and the like. The lubricant composition of the present invention is effective in preventing flaking wear.
  • [Grease Composition]
  • The lubricant composition of the present invention may further contain a thickener to form a grease composition.
  • For the same reasons as described for the lubricant composition, the content of the compound (A) and/or (B) is preferably more than 0.1% by mass, more preferably more than 1% by mass, further preferably 2% by mass or more, and particularly preferably 3% by mass or more based on the total mass of the grease composition of the present invention, and the upper limit can be, for example, 40% by mass or less, 20% by mass or less, 10% by mass or less, 5% by mass or less, or 3% by mass or less.
  • Examples of the thickener which can be used in the grease composition of the present invention include urea-based thickeners typified by diurea, lithium soap-based thickeners typified by lithium soap and lithium complex soap, and solid thickeners such as bentonite and silica gel. Urea-based thickeners and lithium soap-based thickeners are preferable.
  • The grease composition of the present invention may further contain a general-purpose additive as necessary. Examples of additives which can be used include ones described for the lubricant composition. The content of the optional additive is usually 0.1 to 5% by mass based on the total mass of the grease composition of the present invention.
  • (Penetration)
  • The worked penetration of the grease composition of the present invention is preferably 200 to 300 and more preferably 220 to 280. When the worked penetration exceeds 300, leakage due to high-speed rotation increases, which may result in failure to satisfy a sufficient lubrication life. Meanwhile, when the worked penetration is less than 200, the fluidity of the grease is deteriorated, which may result in failure to satisfy a sufficient lubrication life. Note that, in the present specification, the term "penetration" refers to a 60-stroke worked penetration. The penetration can be measured according to JIS K2220-7.
  • (Content of Thickener)
  • The content of the thickener is preferably 5 to 25% by mass and more preferably 10 to 20% by mass based on the total mass of the grease composition of the present invention. When the content is less than 5% by mass, the grease is soft and may leak, which could result in failure to satisfy a sufficient lubrication life. Meanwhile, when the content is more than 25% by mass, the fluidity is inferior and thus it becomes difficult for the grease to enter the lubrication portion, which could result in failure to satisfy a sufficient lubrication life.
  • (Content of Base Oil)
  • The content of the base oil is preferably 60 to 90% by mass and more preferably 70 to 90% by mass based on the total mass of the grease composition of the present invention. The content of the base oil is preferably in such ranges because of excellence in lubricity and low volatility.
  • [Bearing]
  • The grease composition of the present invention is used in various rolling bearings for industrial machines and automobiles. Examples for industrial machines include rolling bearings in various motors for industrial machines, reducers and hydraulic equipment of industrial robots, main shafts and reducers of wind power generators, and peripherals of elevator hoists. The use for automobiles is preferably a rolling bearing for automobile electrical equipment and auxiliaries. Examples of the automobile electrical equipment and auxiliaries include alternators, electromagnetic clutches for automobile air conditioners, intermediate pulleys, idler pulleys, and tension pulleys.
  • [Examples] [Hydrogen Generation Test and Measurement of Amount of Hydrogen Generated]
  • The amount of hydrogen generated was measured according to the method described in Nouyama, Nakayama, et al., Manuscript Preparation for Tribology Conference, Tokyo (2017), 185.
  • Specifically, a triboplasma generator (Fig. 1) was used capable of generating triboplasma between the needle and the flat plate electrode. The needle was the cathode and the flat plate was the anode. The material of the needle was SCM435 steel and the apex angle of the needle was 120°. The needle was arranged perpendicular to the anode flat plate, and was fixed at a position where the distance between the tip of the needle and the upper surface of the anode was 50 µm. The distance between the needle and the flat plate electrode was controlled by a micrometer. The material of the anode flat plate was SPCC steel. The anode flat plate constituted the bottom portion inside the container. The container was charged with the anti-flaking agent and the like of Examples or Comparative Examples, and the needle was in contact with the anti-flaking agent and the like inside the container. The anode flat plate and the cathode needle were connected by a high voltage power source. The voltage and current when a voltage was applied was measurable by an oscilloscope. The container and the needle were surrounded by a larger casing (hereinafter referred to as the "atmosphere control chamber") so as to cover both. The top portion of the atmosphere control chamber had an opening provided therein, and the gas inside the atmosphere control chamber was collectable through a microsyringe. The upper side portion of the atmosphere control chamber also had an opening provided therein so as to introduce dry air therethrough. The gas inside the atmosphere control chamber was detectable by a semiconductor sensor.
  • Dry air was introduced for 30 seconds to replace the gas inside the atmosphere control chamber. After the gas inside the atmosphere control chamber was replaced with dry air, the atmosphere control chamber was subjected to discharging for 30 seconds while monitoring the current value and the voltage value with an oscilloscope, and then left for 20 seconds to collect the generated gas through a microsyringe. The collected gas was introduced into gas chromatography to measure the amount of hydrogen gas. Note that the gas chromatography was measured using a gas chromatograph GC-2010 (manufactured by Shimadzu Corporation), a column RT-Msieve φ0.43 mm × 30 m, and a detector TCD. The amount of hydrogen generated for each compound was calculated with the amount of hydrogen generated for n-hexadecane set to 100%.
  • Tables 3 to 10 present the results. Examples 1 to 38 are examples of the anti-flaking agent, and Examples 39 to 71 are examples of the lubricating oil composition containing the anti-flaking agent. Example 42 is a mixture of 3.0% by mass of dimethyl malonate of Example 3 and 97.0% by mass of poly alpha olefin of Comparative Example 8, and indicates that, even when the specific volume resistivity of the mixture exceeds 1.0 × 1010 Ω·cm, the amount of hydrogen generated can be suppressed to 0% if a predetermined amount of the anti-flaking agent of the present application having a specific volume resistivity of 1.0 × 1010 Ω·cm or less is contained.
  • Examples 1 to 3, 6 to 11, 15 to 39 and 41 to 71 are comparative. Table 3
    Ex. Ex. Ex. Ex. Ex. Ref. Ex. Ref. Ex. Ref. Ex. Ref. Ex. Ref. Ex.
    1 2 3 4 5 6 7 8 9 10
    Aromatic Hydrocarbon Compound Diphenylmethane 100
    Diphenylpropane 100
    Cis-1,2-Diphenylethylene 100
    Monoester Methyl Myristate
    Dimethyl Phthalate 100
    Dimethyl Maleate 100
    Dimethyl Malonate 100
    Dimethyl Succinate 100
    Dimethyl Glutarate 100
    Dimethyl Adipate 100
    Diester Dimethyl Suberate 100
    Dimethyl Sebacate
    Diethyl Malonate
    Dibutyl Malonate
    Dihexyl Malonate
    Dihexyl Sebacate
    Di-2-Ethylhexyl Sebacate
    Triester Tributyl Trimellitate
    Tetraester Pentaerythritol
    Glycol Tetraethylene Glycol
    Tripropylene Glycol
    Tetraethylene Glycol Dimethyl Ether
    Poly (Oxyethylene)Glycol
    Polypropylene Glycol Monobutyl Ether
    Poly(Oxypropylene, Oxybutylene)Glycol
    S-cont. cmd. Dibutyl Sulfoxide
    2,2'-Thiodiethanol
    P-cont. cmd. Trimethyl Phosphate
    N-cont. cmd. Formamide
    N-Methylformamide
    N-tert-Butylformamide
    Tetramethylurea
    Tetraethylurea
    General Antistatic Agent Poly(Oxyethylene)Alkylamine
    Glycerin Aliphatic Ester Monocaprylin
    Ionic Liquid (N-(Methoxyethyl)-1-Methylpyrrolidinium Bis(Trifluoromethylsulfonyl)Imide)
    Liquid Crystal 4-Cyano-4'-Pentylbiphenyl
    Mineral Oil P-Based Mineral Oil
    Synthetic Hydrocarbon PAO
    Ether ADE
    Alkyl Tetraphenyl Ether
    Pentaphenyl Ether
    Tetraphenyl Ether
    SP-cont. cmd. Alkylated Triphenyl Phosphorothioate
    NS-Based Compound Dimercaptothiadiazole Derivative
    MoDTC
    Fatty Acid Amine Salt Oleic Acid Dicycloamine Salt
    Number of Aromatic Carbon Atoms % 92 80 86 60 0 0 0 0 0 0
    Specific Volume Resistivity Ω·cm 3.6E+12 1.3E+13 7.5E+12 3.0E+08 9.4E+06 2.2E+07 2.7E+07 6.0E+07 1.1E+09 5.8E+08
    Dielectric Constant 500 MHz 3.2 - - 8.8 10.2 11.2 8.5 9.1 7.9 -
    Dielectric Constant 1 GHz 3.3 - - 8.0 10.1 11.3 8.5 9.1 8.0 -
    Hansen Parameter Polar Force δP 1.0 2.1 1.9 7.8 10.4 7.0 6.6 6.4 5.6 5.1
    Amount of Hydrogen Generated % 2 3 2 0 0 0 0 0 0 0
    Table 4
    Ref. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex.
    11 12 13 14 15 16 17 18 19 20
    Aromatic Hydrocarbon Compound Diphenylmethane
    Diphenylpropane
    Cis-1,2-Diphenylethylene
    Monoester Methyl My ristate
    Dimethyl Phthalate
    Dimethyl Maleate
    Dimethyl Malonate
    Dimethyl Succinate
    Dimethyl Glutarate
    Dimethyl Adipate
    Diester Dimethyl Suberate
    Dimethyl Sebacate 100
    Diethyl Malonate 100
    Dibutyl Malonate 100
    Dihexyl Malonate 100
    Dihexyl Sebacate
    Di-2-Ethylhexyl Sebacate
    Triester Tributyl Trimellitate
    Tetraester Pentaerythritol
    Glycol Tetraethylene Glycol 100
    Tripropylene Glycol 100
    Tetraethylene Glycol Dimethyl Ether 100
    Poly (Oxyethylene)Glycol 100
    Polypropylene Glycol Monobutyl Ether 100
    Poly(Oxypropylene, Oxybutylene)Glycol
    S-cont. cmd. Dibutyl Sulfoxide 100
    2,2'-Thiodiethanol
    P-cont. cmd. Trimethyl Phosphate
    N-cont. cmd. Formamide
    N-Methylformamide
    N-tert-Butylformamide
    Tetramethylurea
    Tetraethylurea
    General Antistatic Agent Poly (Oxyethylene)Alkylamine
    Glycerin Aliphatic Ester Monocaprylin
    Ionic Liquid (N-(Methoxyethyl)-1-Methylpyrrolidiniu m Bis(Trifluoromethylsulfonyl)Imide)
    Liquid Crystal 4-Cyano-4'-Pentylbiphenyl
    Mineral Oil P-Based Mineral Oil
    Synthetic Hydrocarbon PAO
    Ether ADE
    Alkyl Tetraphenyl Ether
    Pentaphenyl Ether
    Tetraphenyl Ether
    SP-cont. cmd. Alkylated Triphenyl Phosphorothioate
    NS-Based Compound Dimercaptothiadiazole Derivative
    MoDTC
    Fatty Acid Amine Salt Oleic Acid Dicycloamine Salt
    Number of Aromatic Carbon Atoms % 0 0 0 0 0 0 0 0 0 0
    Specific Volume Resistivity Ω·cm 3.5E+09 4.1E+06 4.1E+08 4.4E+09 6.8E+06 2.0E+07 3.5E+07 3.1E+06 9.3E+09 3.1E+06
    Dielectric Constant 500 MHz 6.4 9.0 - - 15.6 7.8 9.0 18.1 4.6 47.6
    Dielectric Constant 1 GHz 6.4 9.0 - - 12.3 6.3 9.0 13.9 4.3 47.3
    Hansen Parameter Polar Force δP 4.5 6.0 4.4 3.8 9.4 7.8 6.0 9.4 7.8 16.4
    Amount of Hydrogen Generated % 17 0 0 1 0 0 0 0 6 0
    Table 5
    Ex. 21 Ex.22 Ex.23 Ex.24 Ex.25 Ex.26 Ex.27 Ex.28 Ex.29 Ex.30
    Aromatic Hydrocarbon Compound Diphenylmethane
    Diphenylpropane
    Cis-1,2-Diphenylethylene
    Monoester Methyl Myristate
    Dimethyl Phthalate
    Dimethyl Maleate
    Dimethyl Malonate
    Dimethyl Succinate
    Dimethyl Glutarate
    Dimethyl Adipate
    Diester Dimethyl Suberate
    Dimethyl Sebacate
    Diethyl Malonate
    Dibutyl Malonate
    Dihexyl Malonate
    Dihexyl Sebacate
    Di-2-Ethylhexyl Sebacate
    Triester Tributyl Trimellitate
    Tetraester Pentaerythritol
    Glycol Tetraethylene Glycol
    Tripropylene Glycol
    Tetraethylene Glycol Dimethyl Ether
    Poly(Oxyethylene)Glycol
    Polypropylene Glycol Monobutyl Ether
    Poly(Oxypropylene, Oxybutylene)Glycol
    S-cont. cmd. Dibutyl Sulfoxide
    2,2'-Thiodiethanol 100
    P-cont. cmd. Trimethyl Phosphate 100
    N-cont. cmd. Formamide 100
    N-Methylformamide 100
    N-tert-Butylformamide 100
    Tetramethylurea 100
    Tetraethylurea 100
    General Antistatic Agent Poly(Oxyethylene)Alkylamine 100
    Glycerin Aliphatic Ester Monocaprylin 100
    Ionic Liquid (N-(Methoxyethyl)-1-Methylpyrroli dinium Bis(Trifluoromethylsulfonyl)Imide) 100
    Liquid Crystal 4-Cyano-4'-Pentylbiphenyl
    Mineral Oil P-Based Mineral Oil
    Synthetic Hydrocarbon PAO
    Ether ADE
    Alkyl Tetraphenyl Ether
    Pentaphenyl Ether
    Tetraphenyl Ether
    SP-cont. cmd. Alkylated Triphenyl Phosphorothioate
    NS-Based Compound Dimercaptothiadiazole Derivative
    MoDTC
    Fatty Acid Amine Salt Oleic Acid Dicycloamine Salt
    Number of Aromatic Carbon Atoms % 0 0 0 0 0 0 0 0 0 0
    Specific Volume Resistivity Ω·cm <1.6E+06 4.4E+06 <1.6E+06 <1.6E+06 <1.6E+06 1.9E+06 1.7E+06 <1.6E+06 2.8E+08 <1.6E+06
    Dielectric Constant 500 MHz 23.0 28.7 107.7 158.4 - 24.5 - 7.5 7.2 -
    Dielectric Constant 1 GHz 15.5 27.5 104.2 117.3 - 24.1 - 6.5 6.0 -
    Hansen Parameter Polar Force δP 8.8 10.5 26.2 18.8 11.8 8.2 7.9 7.2 6.8 18.0
    Amount of Hydrogen Generated % 0 0 0 0 0 0 0 0 0 0
    Table 6
    Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex.
    31 32 33 34 35 36 37 38 39 40
    Aromatic Hydrocarbon Compound Diphenylmethane
    Diphenylpropane
    Cis-1,2-Diphenylethylene
    Monoester Methyl Myristate
    Dimethyl Phthalate 3.0
    Dimethyl Maleate 3.0
    Dimethyl Malonate
    Dimethyl Succinate
    Dimethyl Glutarate
    Dimethyl Adipate
    Diester Dimethyl Suberate
    Dimethyl Sebacate
    Diethyl Malonate
    Dibutyl Malonate
    Dihexyl Malonate
    Dihexyl Sebacate
    Di-2-Ethylhexyl Sebacate
    Triester Tributyl Trimellitate
    Tetraester Pentaerythritol
    Glycol Tetraethylene Glycol
    Tripropylene Glycol
    Tetraethylene Glycol Dimethyl Ether
    Poly(Oxyethylene)Glycol
    Polypropylene Glycol Monobutyl Ether
    Poly(Oxypropylene, Oxybutylene)Glycol
    S-cont. cmd. Dibutyl Sulfoxide
    2,2'-Thiodiethanol
    P-cont. cmd. Trimethyl Phosphate
    N-cont. cmd. Formamide
    N-Methylformamide
    N-tert-Butylformamide
    Tetramethylurea
    Tetraethylurea
    General Antistatic Agent Poly(Oxyethylene)Alkylamine
    Glycerin Aliphatic Ester Monocaprylin
    Ionic Liquid (N-(Methoxyethyl)-1-Methylpyrrolidiniu m Bis(Trifluoromethylsulfonyl)Imide)
    Liquid Crystal 4-Cyano-4'-Pentylbiphenyl 100
    Mineral Oil P-Based Mineral Oil
    Synthetic Hydrocarbon PAO 97.0 97.0
    Ether ADE
    Alkyl Tetraphenyl Ether 100
    Pentaphenyl Ether 100
    Tetraphenyl Ether 100
    SP-cont. cmd. Alkylated Triphenyl Phosphorothioate 100
    NS-Based Compound Dimercaptothiadiazole Derivative 100
    MoDTC 100
    Fatty Acid Amine Salt Oleic Acid Dicycloamine Salt 100
    Number of Aromatic Carbon Atoms % 35 60 100 100 40 11 0 0 - -
    Specific Volume Resistivity Ω·cm 2.4E+08 2.4E+14 7.9E+12 3.1E+13 3.5E+12 <1.6E+06 2.8E+08 1.3E+07 - -
    Dielectric Constant 500 MHz - - - - - 5.0 2.3 4.0 - -
    Dielectric Constant 1 GHz - - - - - 4.5 2.4 4.0 - -
    Hansen Parameter Polar Force δP 4.4 29.1 4.9 3.5 3.6 6.8 - - - -
    Amount of Hydrogen Generated % 12 16 1 1 1 0 0 0 0 0
    Table 7
    Ex.41 Ex.42 Ex.43 Ex.44 Ex.45 Ex.46 Ex.47 Ex.48 Ex.49 Ex.50
    Aromatic Hydrocarbon Compound Diphenylmethane
    Diphenylpropane
    Cis-1,2-Diphenylethylene
    Monoester Methyl Myristate
    Dimethyl Phthalate
    Dimethyl Maleate
    Dimethyl Malonate 3.0 3.0 40.0
    Dimethyl Succinate 5.0 10.0
    Dimethyl Glutarate 5.0
    Dimethyl Adipate
    Diester Dimethyl Suberate
    Dimethyl Sebacate
    Diethyl Malonate 10.0
    Dibutyl Malonate
    Dihexyl Malonate
    Dihexyl Sebacate
    Di-2-Ethylhexyl Sebacate 60.0
    Triester Tributyl Trimellitate
    Tetraester Pentaerythritol
    Glycol Tetraethylene Glycol 1.0
    Tripropylene Glycol 10.0
    Tetraethylene Glycol Dimethyl Ether 10.0
    Poly(Oxyethylene)Glycol
    Polypropylene Glycol Monobutyl Ether
    Poly(Oxypropylene, Oxybutylene)Glycol
    S-cont. cmd. Dibutyl Sulfoxide
    2,2'-Thiodiethanol
    P-cont. cmd. Trimethyl Phosphate
    N-cont. cmd. Formamide
    N-Methylformamide
    N-tert-Butylformamide
    Tetramethylurea
    Tetraethylurea
    General Antistatic Agent Poly(Oxyethylene)Alkylamine
    Glycerin Aliphatic Ester Monocaprylin
    Ionic Liquid (N-(Methoxyethyl)-1-Methy lpyrrolidinium Bis(Trifluoromethylsulfonyl)Imide)
    Liquid Crystal 4-Cyano-4'-Pentylbiphenyl
    Mineral Oil P-Based Mineral Oil 97.0
    Synthetic Hydrocarbon PAO 97.0 95.0 95.0 90.0 99.0 90.0 90.0
    Ether ADE 90.0
    Alkyl Tetraphenyl Ether
    Pentaphenyl Ether
    Tetraphenyl Ether
    SP-cont. cmd. Alkylated Triphenyl Phosphorothioate
    NS-Based Compound Dimercaptothiadiazole Derivative
    MoDTC
    Fatty Acid Amine Salt Oleic Acid Dicycloamine Salt
    Number of Aromatic Carbon Atoms % - - - - - - - - - -
    Specific Volume Resistivity Ω·cm 5.7E+14 2.3E+13 - - - - - - - -
    Dielectric Constant 500 MHz - - - - - - - - - -
    Dielectric Constant 1 GHz - - - - - - - - - -
    Hansen Parameter Polar Force δP - - - - - - - - - -
    Amount of Hydrogen Generated % 0 0 0 0 0 0 0 0 0 0
    Table 8
    Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex.
    51 52 53 54 55 56 57 58 59 60
    Aromatic Hydrocarbon Compound Diphenylmethane
    Diphenylpropane
    Cis-1,2-Diphenylethylene
    Monoester Methyl My ristate
    Dimethyl Phthalate
    Dimethyl Maleate
    Dimethyl Malonate
    Dimethyl Succinate
    Dimethyl Glutarate
    Dimethyl Adipate
    Diester Dimethyl Suberate
    Dimethyl Sebacate
    Diethyl Malonate
    Dibutyl Malonate
    Dihexyl Malonate
    Dihexyl Sebacate
    Di-2-Ethylhexyl Sebacate 99.0 97.0 90.0
    Triester Tributyl Trimellitate
    Tetraester Pentaerythritol
    Glycol Tetraethylene Glycol
    Tripropylene Glycol
    Tetraethylene Glycol Dimethyl Ether
    Poly (Oxyethylene)Glycol 1.0 0.5 1.0
    Polypropylene Glycol Monobutyl Ether
    Poly(Oxypropylene, Oxybutylene)Glycol
    S-cont. cmd. Dibutyl Sulfoxide 3.0 3.0 3.0
    2,2'-Thiodiethanol 3.0
    P-cont. cmd. Trimethyl Phosphate 10.0 10.0 10.0
    N-cont. cmd. Formamide
    N-Methylformamide
    N-tert-Butylformamide
    Tetramethylurea
    Tetraethylurea
    General Antistatic Agent Poly(Oxyethylene)Alkylamine
    Glycerin Aliphatic Ester Monocapry lin
    Ionic Liquid (N-(Methoxyethyl)-1-Methylpyrrolidinium Bis(Trifluoromethylsulfonyl)Imide)
    Liquid Crystal 4-Cyano-4'-Pentylbiphenyl
    Mineral Oil P-Based Mineral Oil
    Synthetic Hydrocarbon PAO 99.5 97.0 97.0 90.0
    Ether ADE 99.0 97.0 90.0
    Alkyl Tetraphenyl Ether
    Pentaphenyl Ether
    Tetraphenyl Ether
    SP-cont. cmd. Alkylated Triphenyl Phosphorothioate
    NS-Based Compound Dimercaptothiadiazole Derivative
    MoDTC
    Fatty Acid Amine Salt Oleic Acid Dicycloamine Salt
    Number of Aromatic Carbon Atoms % - - - - - - - - - -
    Specific Volume Resistivity Ω·cm - - - - - - - - - -
    Dielectric Constant 500 MHz - - - - - - - - - -
    Dielectric Constant 1 GHz - - - - - - - - - -
    Hansen Parameter Polar Force δP - - - - - - - - - -
    Amount of Hydrogen Generated % 0 0 0 0 0 0 0 0 0 0
    Table 9
    Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex.
    61 62 63 64 65 66 67 68 69 70 71
    Aromatic Hydrocarbon Compound Diphenylmethane
    Diphenylpropane
    Cis-1,2-Diphenylethylene
    Monoester Methyl My ristate
    Dimethyl Phthalate
    Dimethyl Maleate
    Dimethyl Malonate
    Dimethyl Succinate
    Dimethyl Glutarate
    Dimethyl Adipate
    Diester Dimethyl Suberate
    Dimethyl Sebacate
    Diethyl Malonate
    Dibutyl Malonate
    Dihexyl Malonate
    Dihexyl Sebacate
    Di-2-Ethylhexyl Sebacate 99.0 99.0
    Triester Tributyl Trimellitate
    Tetraester Pentaerythritol
    Glycol Tetraethylene Glycol
    Tripropylene Glycol
    Tetraethylene Glycol Dimethyl Ether
    Poly(Oxyethylene)Glycol
    Polypropylene Glycol Monobutyl Ether
    Poly (Oxypropylene, Oxybutylene)Glycol
    S-cont. cmd. Dibutyl Sulfoxide
    2,2'-Thiodiethanol
    P-cont. cmd. Trimethyl Phosphate
    N-cont. cmd. Formamide 1.0 0.1 1.0
    N-Methylformamide 0.1
    N-tert-Butylformamide 3.0
    Tetramethylurea 3.0
    Tetraethylurea
    General Antistatic Agent Poly (Oxyethylene)Alkylamine 3.0 3.0
    Glycerin Aliphatic Ester Monocaprylin
    Ionic Liquid (N-(Methoxyethyl)-1-Methylpyrrolidiniu m Bis(Trifluoromethylsulfonyl)Imide) 1.0 0.5 1.0
    Liquid Crystal 4-Cyano-4'-Pentylbiphenyl
    Mineral Oil P-Based Mineral Oil
    Synthetic Hydrocarbon PAO 99.9 99.9 97.0 97.0 97.0 99.5
    Ether ADE 99.0 97.0 99.0
    Alkyl Tetraphenyl Ether
    Pentaphenyl Ether
    Tetraphenyl Ether
    SP-cont. cmd. Alkylated Triphenyl Phosphorothioate
    NS-Based Compound Dimercaptothiadiazole Derivative
    MoDTC
    Fatty Acid Amine Salt Oleic Acid Dicycloamine Salt
    Number of Aromatic Carbon Atoms % - - - - - - - - - - -
    Specific Volume Resistivity Ω·cm - - - - - - - - - - -
    Dielectric Constant 500 MHz - - - - - - - - - - -
    Dielectric Constant 1 GHz - - - - - - - - - - -
    Hansen Parameter Polar Force δP - - - - - - - - - - -
    Amount of Hydrogen Generated % 0 0 0 0 0 0 0 0 0 0 0
    Table 10
    Comp. Ex. 1 Comp. Ex.2 Comp. Ex.3 Comp. Ex.4 Comp. Ex.5 Comp. Ex.6 Comp. Ex.7 Comp. Ex.8 Comp. Ex.9 Comp. Ex. 10
    Aromatic Hydrocarbon Compound Diphenylmethane
    Diphenylpropane
    Cis-1,2-Diphenylethylene
    Monoester Methyl Myristate 100
    Dimethyl Phthalate
    Dimethyl Maleate
    Dimethyl Malonate
    Dimethyl Succinate
    Dimethyl Glutarate
    Diester Dimethyl Adipate
    Dimethyl Suberate
    Dimethyl Sebacate
    Diethyl Malonate
    Dibutyl Malonate
    Dihexyl Malonate
    Dihexyl Sebacate 100
    Di-2-Ethylhexyl Sebacate 100
    Triester Tributyl Trimellitate 100
    Tetraester Pentaerythritol 100
    Glycol Tetraethylene Glycol
    Tripropylene Glycol
    Tetraethylene Glycol Dimethyl Ether
    Poly(Oxyethylene)Glycol
    Polypropylene Glycol Monobutyl Ether
    Poly(Oxypropylene, Oxybutylene)Glycol 100
    S-cont. cmd. Dibutyl Sulfoxide
    2,2'-Thiodiethanol
    P-cont. cmd. Trimethyl Phosphate
    N-cont. cmd. Formamide 0.05
    N-Methylformamide
    N-tert-Butylformamide
    Tetramethylurea
    Tetraethylurea
    General Antistatic Agent Poly(Oxyethylene)Alkylamine
    Glycerin Aliphatic Ester Monocaprylin
    Ionic Liquid (N-(Methoxyethyl)-1-Methylpyrrolidinium Bis(Trifluoromethylsulfonyl)Imide)
    Liquid Crystal 4-Cyano-4'-Pentylbiphenyl
    Mineral Oil P-Based Mineral Oil 100
    Synthetic Hydrocarbon PAO 100 99.95
    Ether ADE 100
    Alkyl Tetraphenyl Ether
    Pentaphenyl Ether
    Tetraphenyl Ether
    SP-cont. cmd. Alkylated Triphenyl Phosphorothioate
    NS-Based Compound Dimercaptothiadiazole Derivative
    MoDTC
    Fatty Acid Amine Salt Oleic Acid Dicycloamine Salt
    Number of Aromatic Carbon Atoms % 0 0 0 0 0 0 0 0 35 -
    Specific Volume Resistivity Ω·cm 7.9E+10 2.2E+11 2.4E+12 2.7E+10 2.8E+13 2.1E+11 5.7E+14 4.3E+13 7.7E+14 -
    Dielectric Constant 500 MHz 4.0 - 4.2 - 3.5 3.5 2.7 2.7 2.8 -
    Dielectric Constant 1 GHz 4.1 - 3.9 - 3.5 3.5 2.8 2.8 2.9 -
    Hansen Parameter Polar Force δP 2.7 3.0 2.1 6.8 2.1 8.1 - 1.0 25.0 -
    Amount of Hydrogen Generated % 105 95 100 77 88 101 106 100 93 100
  • The suppliers and trade names of the compounds used in Examples and Comparative Examples are presented below.
    Tetraester : Ester of pentaerythritol with carboxylic acid (manufactured by Kao Corporation under the trade name of "KAOLUBE 279")
    Glycol : Poly(oxyethylene)glycol (manufactured by NOF Corporation under the trade name of "PEG #200")
    : Polypropylene glycol monobutyl ether (manufactured by NOF Corporation under the trade name of "UNILUBE MB-19")
    : Poly(oxypropylene, oxybutylene)glycol monodecyl ether (manufactured by Dow Chemical Company under the trade name of "OSP-68")
    Antistatic Agent : Poly(oxyethylene)laurylamine (manufactured by Nippon Nyukazai Co., Ltd. under the trade name of "Newcol LA-407")
    : Glycerin aliphatic ester monocaprylin (manufactured by Riken Vitamin Co., Ltd. under the trade name of "Poem M-100")
    Ionic Liquid : N-(Methoxyethyl)-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (manufactured by Merck)
    Liquid Crystal : 4-Cyano-4'-pentylbiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd. under the trade name of "5CB")
    Mineral Oil : P-based mineral oil (manufactured by JX Energy under the trade name of "Super Oil K-100")
    Synthetic Hydrocarbon : PAO8 (kinematic viscosity at 40°C is 45 mm2/s)
    Ether Oil : ADE (manufactured by MORESCO under the trade name of "LB-100")
    : Alkyl tetraphenyl ether (manufactured by MORESCO under the trade name of "s-3101")
    : Pentaphenyl ether (manufactured by MORESCO under the trade name of "s-3105")
    : Tetraphenyl ether (manufactured by MORESCO under the trade name of "s-3103")
    SP-Based Compound : Alkylated triphenyl phosphorothionate (manufactured by BASF Japan under the trade name of "IRGALUBE 211")
    NS-Based Compound : Dimercaptothiadiazole derivative (manufactured by The Elco Corporation under the trade name of "Elco 461")
    : MoDTC (manufactured by ADEKA Corporation under the trade name of "SAKURA-LUBE 525")
    Fatty Acid Amine Salt : Oleic acid dicycloamine salt (manufactured by Albess Co., Ltd. under the trade name of "NONRUST Z-1000")

Claims (5)

  1. Use as an anti-flaking agent of at least one selected from the group consisting of
    (A) a compound having a specific volume resistivity of 1.0 × 1010 Ω·cm or less, wherein the compound (A) is a diester selected from the group consisting of dimethyl phthalate, dimethyl maleate, diethyl malonate, dibutyl malonate, and dihexyl malonate.
  2. Lubricant composition comprising a diester selected from the group consisting of dimethyl maleate, dibutyl malonate, and dihexyl malonate and at least one conventional base oil selected from the group consisting of mineral oils and synthetic oils.
  3. The lubricant composition according to claim 2, wherein the base oil is at least one selected from the group consisting of mineral oils, synthetic hydrocarbon oils, and ether oils.
  4. The lubricant composition according to any one of claims 2 to 3, wherein a content of the compound exceeds 0.1% by mass based on a total mass of the composition.
  5. The lubricant composition according to any one of claims 2 to 4, further comprising a thickener.
EP19206606.6A 2018-11-06 2019-11-06 Anti-flaking agent and lubricant composition comprising the same Active EP3666860B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2018/041151 WO2020095359A1 (en) 2018-11-06 2018-11-06 Anti-strip agent and lubricant composition containing same

Publications (2)

Publication Number Publication Date
EP3666860A1 EP3666860A1 (en) 2020-06-17
EP3666860B1 true EP3666860B1 (en) 2025-06-25

Family

ID=68887192

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19206606.6A Active EP3666860B1 (en) 2018-11-06 2019-11-06 Anti-flaking agent and lubricant composition comprising the same

Country Status (4)

Country Link
EP (1) EP3666860B1 (en)
JP (2) JP2020076099A (en)
CN (1) CN111139117B (en)
WO (1) WO2020095359A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022034883A1 (en) 2020-08-12 2022-02-17 株式会社ジェイテクト Grease composition, and rolling bearings
AU2021336726A1 (en) * 2020-09-07 2023-04-06 Basf Se Polyalkylene glycol for reducing white etching cracks

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5462683A (en) * 1991-03-07 1995-10-31 Nippon Oil Co., Ltd. Grease composition for constant velocity joint
EP1516911A1 (en) * 2002-06-28 2005-03-23 Nippon Oil Corporation Lubricating oil additive, lubricating oil composition containing the same, and process for producing the same
EP2003187A9 (en) * 2006-03-29 2009-02-11 Kyodo Yushi Co., Ltd. Lubricant composition
US20150057203A1 (en) * 2012-03-23 2015-02-26 Idemitsu Kosan Co., Ltd. Lubricating oil composition and device using same
CN106281620A (en) * 2016-08-17 2017-01-04 吴江华威特种油有限公司 A kind of thin-layer rust-preventative oil and preparation method thereof
CN107312589A (en) * 2017-05-30 2017-11-03 刘秀梅 A kind of alloy bearing soap base grease

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57108196A (en) * 1980-12-17 1982-07-06 Tokai Rika Co Ltd Lubricating grease
JP2878749B2 (en) 1990-01-16 1999-04-05 エヌティエヌ株式会社 Grease-filled rolling bearings for alternators
JPH03250094A (en) 1990-02-28 1991-11-07 Ntn Corp Grease-filled gearing for electrical equipment and auxiliary machinery of vehicle
JP3519417B2 (en) * 1991-10-04 2004-04-12 協同油脂株式会社 Grease composition for bearings with excellent low starting torque for high temperature, high speed and high load application
JP2557597B2 (en) 1992-01-22 1996-11-27 エヌティエヌ株式会社 Rolling bearing with grease for alternator
JP2002130301A (en) 2000-10-17 2002-05-09 Nsk Ltd Rolling bearing
FR2832160B1 (en) * 2001-11-15 2005-01-14 Atofina PROCESS FOR WORKING OR FORMING METALS IN THE PRESENCE OF AQUEOUS LUBRICANTS BASED ON METHANESULFONIC ACID (AMS) OR AMS WATER SOLUBLE SALT
KR101302940B1 (en) * 2003-04-02 2013-09-06 이데미쓰 고산 가부시키가이샤 Conductive lubricant composition
JP2004359848A (en) * 2003-06-05 2004-12-24 Nsk Ltd Grease composition and rolling device using the same
JP5038719B2 (en) * 2004-10-18 2012-10-03 日本精工株式会社 Water-resistant grease composition for wheel-supporting rolling bearing and wheel-supporting rolling bearing
CN101107347B (en) * 2005-01-24 2011-08-17 日本精工株式会社 Grease composition for hub unit bearing, and hub unit bearing for vehicles
JP5074687B2 (en) * 2005-07-15 2012-11-14 出光興産株式会社 Oil-impregnated bearing lubricant
US8153568B2 (en) * 2005-09-28 2012-04-10 Ntn Corporation Water-resistant grease and water-resistant-grease-enclosed rolling bearing and hub
JP4942321B2 (en) * 2005-09-28 2012-05-30 Ntn株式会社 Hub bearing
JP4885534B2 (en) * 2005-12-20 2012-02-29 出光興産株式会社 Refrigerator oil composition, compressor for refrigeration machine and refrigeration apparatus using the same
JP2007211220A (en) * 2006-02-13 2007-08-23 Nsk Ltd Rolling bearing for automotive electrical equipment and automotive electrical equipment using the same
JP2007217609A (en) * 2006-02-17 2007-08-30 Nsk Ltd Grease composition and bearing
JP2007231987A (en) * 2006-02-27 2007-09-13 Nsk Ltd Rolling device, and air compressor and turbocharger using the same
JP5005931B2 (en) * 2006-03-03 2012-08-22 Ntn株式会社 Rolling bearings for automotive electrical equipment and accessories
JP2008127404A (en) * 2006-11-16 2008-06-05 Ntn Corp Rolling bearing
JP2009173750A (en) * 2008-01-23 2009-08-06 Kyodo Yushi Co Ltd Lubricant composition and machine member
JP5467723B2 (en) * 2008-01-23 2014-04-09 協同油脂株式会社 Lubricant composition and machine member
JP5616613B2 (en) * 2009-02-27 2014-10-29 Ntn株式会社 Grease composition, grease-filled bearing, and universal joint for propeller shaft
JP5557179B2 (en) * 2009-05-14 2014-07-23 協同油脂株式会社 Grease composition and bearing
JP5214649B2 (en) * 2010-02-26 2013-06-19 協同油脂株式会社 Grease composition for hub unit bearing using angular ball bearing and hub unit bearing
JP5657462B2 (en) * 2011-04-21 2015-01-21 日本グリース株式会社 Grease composition
JP5738712B2 (en) * 2011-08-03 2015-06-24 協同油脂株式会社 Grease composition
JP5850718B2 (en) * 2011-11-25 2016-02-03 日本グリース株式会社 Grease composition and bearing
JP6093991B2 (en) * 2013-02-04 2017-03-15 協同油脂株式会社 Grease composition
JP6193619B2 (en) * 2013-05-22 2017-09-06 Ntn株式会社 Rolling bearing
EP3023657B1 (en) * 2013-07-19 2018-08-22 NTN Corporation Rolling bearing
CN105492582B (en) * 2013-08-02 2018-05-25 协同油脂株式会社 grease composition
CA2952066A1 (en) * 2014-06-18 2015-12-23 The Lubrizol Corporation Motorcycle engine lubricant
JP6646379B2 (en) * 2015-08-10 2020-02-14 Ntn株式会社 Grease composition and grease-filled rolling bearing
CN107460025A (en) * 2017-08-31 2017-12-12 东莞安默琳机械制造技术有限公司 A kind of micro-lubricating cutting oil of machining titanium alloy and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5462683A (en) * 1991-03-07 1995-10-31 Nippon Oil Co., Ltd. Grease composition for constant velocity joint
EP1516911A1 (en) * 2002-06-28 2005-03-23 Nippon Oil Corporation Lubricating oil additive, lubricating oil composition containing the same, and process for producing the same
EP2003187A9 (en) * 2006-03-29 2009-02-11 Kyodo Yushi Co., Ltd. Lubricant composition
US20150057203A1 (en) * 2012-03-23 2015-02-26 Idemitsu Kosan Co., Ltd. Lubricating oil composition and device using same
CN106281620A (en) * 2016-08-17 2017-01-04 吴江华威特种油有限公司 A kind of thin-layer rust-preventative oil and preparation method thereof
CN107312589A (en) * 2017-05-30 2017-11-03 刘秀梅 A kind of alloy bearing soap base grease

Also Published As

Publication number Publication date
JP2020076099A (en) 2020-05-21
CN111139117B (en) 2023-03-24
JP2024052955A (en) 2024-04-12
WO2020095359A1 (en) 2020-05-14
JP7787214B2 (en) 2025-12-16
EP3666860A1 (en) 2020-06-17
CN111139117A (en) 2020-05-12

Similar Documents

Publication Publication Date Title
KR101216353B1 (en) lubricating grease composition
EP2489721B1 (en) Use of a grease composition for bearing of wind power generator
EP2003187B1 (en) Use in lubricant compositions
JP5321587B2 (en) Conductive grease
EP3029132B1 (en) Grease composition
EP3702435B1 (en) Method for producing a lubricating oil composition
JP7787214B2 (en) Anti-peeling agent and lubricant composition containing same
JP2012097827A (en) Rolling bearing
JP4784092B2 (en) Lubricating grease composition
EP4198111B1 (en) Lubricant composition including carbon nanotubes
EP2597141B1 (en) Grease composition and bearing
CN111876218B (en) Conductive bearing lubricating grease composition and preparation method thereof
JP4613530B2 (en) Lubricating grease composition
JP2008223902A (en) Rolling device and inverter control motor
KR20170138781A (en) Conductive grease composition
JP2003097571A (en) Rolling bearing
JP2008196526A (en) Rolling device and alternator
Kabir et al. Influence of Carbon Nanoparticles on Electrically Induced Wear of Grease‐Lubricated Steels
JP5267074B2 (en) Rolling bearing unit for forward / reverse rotation motor
JP2004292693A (en) Conductive grease composition and rolling device
KR20260064730A (en) Conductive composition comprising perfluoropolyether oil and carbon nanotubes
JP2025065621A (en) Conductive composition comprising silicone oil and carbon nanotubes
Kürten et al. Conductive lubricants to prevent hydrogen assisted rolling contact fatigue
WO2025079613A1 (en) Conductive composition containing perfluoropolyether oil and carbon nanotubes
KR20260064731A (en) Conductive composition comprising silicone oil and carbon nanotubes

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

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

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

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

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: 20201215

RBV Designated contracting states (corrected)

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

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: 20231214

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: 20240927

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

Free format text: ORIGINAL CODE: EPIDOSDIGR1

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

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTC Intention to grant announced (deleted)
INTG Intention to grant announced

Effective date: 20250131

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

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

Free format text: CASE NUMBER: APP_22546/2025

Effective date: 20250513

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: 602019071481

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

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

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: 20250625

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

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

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: 20250925

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: 20250926

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

Ref country code: BG

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

Effective date: 20250625

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

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: 20250625

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: 20250925

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

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: 20250625

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20250625

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250625

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

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: 20251027

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1806450

Country of ref document: AT

Kind code of ref document: T

Effective date: 20250625

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

Ref country code: IS

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

Effective date: 20251025

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

Ref country code: DE

Payment date: 20251119

Year of fee payment: 7

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

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: 20250625

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: 20250625

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

Ref country code: FR

Payment date: 20251126

Year of fee payment: 7

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

Ref country code: CZ

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

Effective date: 20250625

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

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: 20250625

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

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: 20250625

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

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: 20250625

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

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: 20250625

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

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: 20250625

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

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: 20250625

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: 20250625

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

REG Reference to a national code

Ref country code: CH

Ref legal event code: L10

Free format text: ST27 STATUS EVENT CODE: U-0-0-L10-L00 (AS PROVIDED BY THE NATIONAL OFFICE)

Effective date: 20260507