WO2016158070A1 - 潤滑グリース組成物 - Google Patents
潤滑グリース組成物 Download PDFInfo
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- WO2016158070A1 WO2016158070A1 PCT/JP2016/054891 JP2016054891W WO2016158070A1 WO 2016158070 A1 WO2016158070 A1 WO 2016158070A1 JP 2016054891 W JP2016054891 W JP 2016054891W WO 2016158070 A1 WO2016158070 A1 WO 2016158070A1
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- WIPO (PCT)
- Prior art keywords
- grease composition
- lubricating grease
- resin
- acid
- base oil
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
- C10M117/02—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M147/00—Lubricating compositions characterised by the additive being a macromolecular compound containing halogen
- C10M147/02—Monomer containing carbon, hydrogen and halogen only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/02—Mixtures of base-materials and thickeners
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/06—Mixtures of thickeners and additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M117/00—Lubricating compositions characterised by the thickener being a non-macromolecular carboxylic acid or salt thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/022—Ethene
- C10M2205/0225—Ethene used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic 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
- C10M2205/0285—Organic 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/106—Carboxylix acids; Neutral salts thereof used as thickening agents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix 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
- C10M2207/1256—Carboxylix 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 used as thickening agent
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/102—Polyesters
- C10M2209/1023—Polyesters used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/06—Perfluoro polymers
- C10M2213/062—Polytetrafluoroethylene [PTFE]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
- C10M2215/065—Phenyl-Naphthyl amines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/02—Bearings
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Definitions
- the grease composition described in Patent Document 1 has a base oil kinematic viscosity at 40 ° C. of 500 to 1500 mm 2 / s, and the grease composition described in Patent Document 2 is 40 ° C. of the base oil.
- the kinematic viscosity is in the range of 400-2500 mm 2 / s, and all use high-viscosity base oils, so they have excellent lubricity and durability at the sliding part where the grease composition is applied.
- the starting friction coefficient static friction coefficient
- the lubricating grease composition for resin members according to the present invention is used to be supplied as a lubricant to at least the surface of the sliding portion of a resin member having a sliding portion with another member, particularly in a high load state.
- the resin member has characteristics that can realize a low starting friction coefficient on the surface of the contact portion of the resin member and excellent wear resistance.
- the base oil is a mixed oil of a poly- ⁇ -olefin having a kinematic viscosity of 18 to 50 mm 2 / s at 40 ° C. and an ethylene- ⁇ -olefin copolymer having a number average molecular weight of 40,000 to 200,000.
- the poly- ⁇ -olefin and the ethylene- ⁇ -olefin copolymer are both synthetic hydrocarbon oils.
- the base oil is other than synthetic hydrocarbon oil, for example, ester synthetic oil or ether synthetic oil.
- the base oil may be a mixed oil of poly- ⁇ -olefin and ethylene- ⁇ -olefin copolymer, and does not contain ester synthetic oil or ether synthetic oil. It is preferable to use only synthetic hydrocarbon oil.
- poly- ⁇ -olefin refers to a polymer obtained by homopolymerization or copolymerization of one or more monomers of ⁇ -olefin having 3 or more carbon atoms.
- the poly- ⁇ -olefin must have a kinematic viscosity at 40 ° C. in the range of 18 to 50 mm 2 / s. This is because if the kinematic viscosity at 40 ° C of poly- ⁇ -olefin is lower than 18 mm 2 / s, the wear resistance will deteriorate, and if it is higher than 50 mm 2 / s, the starting friction coefficient in a high load state will be reduced. Because it becomes high.
- the degree of polymerization of poly- ⁇ -olefin is not particularly limited, and includes what is usually called an oligomer. Further, poly- ⁇ -olefins may be used alone or in combination of two or more.
- the ethylene- ⁇ -olefin copolymer refers to a copolymer comprising ethylene and one or more ⁇ -olefins having 3 or more carbon atoms as constituent monomers.
- the number average molecular weight of the ethylene- ⁇ -olefin copolymer needs to be in the range of 40,000 to 200,000. This is because if the number average molecular weight of the ethylene- ⁇ -olefin copolymer is less than 40,000, the starting friction coefficient in a high load state increases, and if the number average molecular weight exceeds 200,000, the shear stability deteriorates. Because.
- the blending ratio of the ethylene- ⁇ -olefin copolymer with respect to the entire lubricating grease composition is preferably in the range of 1.5 to 3.5% by mass. If the blending amount of the ethylene- ⁇ -olefin copolymer is less than 1.5% by mass, the base oil viscosity may not be increased to an appropriate range, and if it exceeds 3.5% by mass, the base oil viscosity is more than the appropriate range. It is because it may become too high.
- the base oil that is a mixed oil obtained by mixing the poly- ⁇ -olefin and the ethylene- ⁇ -olefin copolymer needs to have a kinematic viscosity at 40 ° C. of 80 to 200 mm 2 / s. It is. This is because if the kinematic viscosity at 40 ° C is lower than 80 mm 2 / s, the wear resistance deteriorates, and if the kinematic viscosity at 40 ° C is higher than 200 mm 2 / s, the coefficient of starting friction under high load conditions Because it becomes higher.
- thickener As the thickener in the lubricating grease composition of the present invention, it is necessary to use a lithium-based composite soap that is excellent in lubricity and compatibility with the resin member.
- the hydroxy fatty acid having 12 to 24 carbon atoms is not particularly limited, and examples thereof include 12-hydroxystearic acid, 12-hydroxylauric acid, 16-hydroxypalmitic acid and the like. Among these, 12-hydroxystearic acid is particularly preferable. Acid is preferred.
- aromatic carboxylic acid examples include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, salicylic acid, p-hydroxybenzoic acid and the like.
- adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylene dicarboxylic acid, decamethylene dicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedi Carboxylic acid, penta decane dicarboxylic acid, hexamethylene decanedicarboxylic acid, hepta-decane dicarboxylic acid, octadecane dicarboxylic acid, or the like is used.
- azelaic acid and sebacic acid are preferred.
- examples of the carboxylic acid monoamide include those in which one carboxyl group of the dicarboxylic acid is amidated.
- Preferable examples include those in which one carboxyl group of azelaic acid or sebacic acid is amidated.
- amines to be amidated include aliphatic primary amines such as butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, and behenylamine.
- lithium-based composite soap carboxylic acid and / or ester thereof and the above metal hydroxide may be added to the base oil and saponified in the base oil.
- the lithium composite soap preferably has a blending ratio of 8 to 14% by mass with respect to the entire lubricating grease composition. If the blending amount is less than 8% by mass, the required thickening effect may not be obtained. is there.
- Solid lubricant In the lubricating grease composition of the present invention, the solid lubricant is required to be a polytetrafluoroethylene (PTFE) resin in terms of low starting friction in a high load state.
- PTFE polytetrafluoroethylene
- the blending ratio of PTFE resin to the entire lubricating grease composition is preferably 4 to 12% by mass. If the blending ratio is less than 4% by mass, the starting friction coefficient in a high load state becomes high, and if it exceeds 12% by mass, the supply of the grease composition to the sliding portion of the resin member is insufficient. This is because the wear resistance deteriorates.
- the PTFE resin is preferably contained as a powder in the grease composition.
- PTFE resin powder those having a molecular weight of several hundreds of thousands at the maximum are usually used for lubricating applications, but the grease composition of the present invention has a number average molecular weight Mn (calculated from melting point Tm) of about 20,000 to 100,000, preferably about 20,000 to 80,000 are used. If a molecular weight other than this is used, the friction coefficient during sliding cannot be reduced, and the durability cannot be maintained.
- Such adjustment to the molecular weight is performed by a method by adjusting the addition amount of a chain transfer agent added during polymerization by a suspension polymerization method, an emulsion polymerization method, a solution polymerization method or the like, a method for reducing the molecular weight by radiation irradiation, or the like.
- the particle size of PTFE resin powder is 0.2 to 10 ⁇ m, preferably A material having a thickness of about 0.3 to 5 ⁇ m is used. If a particle size smaller than this is used, there will be a problem in durability. On the other hand, if a particle size larger than this is used, particles will not be supplied to the lubricated surface, so the effect of addition will be observed. It becomes impossible. Commercially available products can be used as they are for the PTFE resin powder having such molecular weight and particle size.
- the grease composition of the present invention is required to have a blendability in the range of 265 to 340 in terms of excellent lubricity in a high load state. If the penetration is less than 265, the starting friction coefficient in a high load state becomes high, and if it exceeds 340, the oil separation amount of the grease composition supplied to the sliding portion increases and wear resistance is reduced. Because it gets worse.
- antioxidants In addition to the antioxidants, rust inhibitors, extreme pressure agents, oil agents, viscosity index improvers, and the like that have been added to conventional greases within the range that does not affect the effects of the present invention, these additives can be added as necessary.
- antioxidants examples include phenolic antioxidants such as 2,6-ditertiarybutyl-4-methylphenol and 4,4′-methylenebis (2,6-ditertiarybutylphenol), alkyldiphenylamine, Examples include amine-based antioxidants such as phenylamine, phenyl- ⁇ -naphthylamine, phenothiazine, alkylated phenyl- ⁇ -naphthylamine, and alkylated phenothiazine. In addition, phosphorus antioxidants, sulfur antioxidants, and the like are also used.
- Examples of the rust preventive include Ca salt or Na salt of aromatic sulfonic acid or saturated aliphatic dicarboxylic acid, fatty acid, fatty acid amine, alkyl sulfonic acid metal salt, alkyl sulfonic acid amine salt, oxidized paraffin, polyoxyalkyl ether and the like. Can be mentioned.
- extreme pressure agents include phosphorus compounds such as phosphate esters, phosphite esters, phosphate ester amine salts, sulfur compounds such as sulfides and disulfides, dialkyldithiophosphate metal salts (excluding zinc salts), Examples thereof include sulfur compound metal salts such as dialkyldithiocarbamate metal salts, chlorine compounds such as chlorinated paraffin and chlorinated diphenyl, and organometallic compounds such as molybdenum dialkyldithiocarbamate (MoDTP).
- phosphorus compounds such as phosphate esters, phosphite esters, phosphate ester amine salts
- sulfur compounds such as sulfides and disulfides
- dialkyldithiophosphate metal salts dialkyldithiophosphate metal salts (excluding zinc salts)
- sulfur compound metal salts such as dialkyldithiocarbamate metal salts, chlorine compounds such as chlorinated paraffin and chlorin
- viscosity index improver examples include polymethacrylate, ethylene-propylene copolymer, polyisobutylene, polyalkylstyrene, styrene-isoprene hydrogenated copolymer, and the like.
- composition is prepared by a method in which a predetermined amount of each of the above components is added and sufficiently kneaded with a three-roll or high-pressure homogenizer.
- the amount of each component constituting the blended thickener is 63.5% by mass of 12-hydroxystearic acid, 19.0% by mass of azelaic acid, and 17.5% by mass of lithium hydroxide with respect to the total amount of the thickener.
- Thickener A Li-Comp shown below was used.
- the lubricating grease composition contained in was prepared.
- the amount of each component constituting the blended thickener is 27.5% by mass of sebacic acid, 41.5% by mass of carboxylic acid monostearylamide, and 31% by mass of barium hydroxide with respect to the total amount of the thickener.
- Thickener B (Ba-Comp) shown below was used.
- Thickener A Li-Comp (Lithium Composite Soap)
- Thickener B Ba-Comp (barium complex soap)
- Thickener C Li-OHST (lithium soap)
- PTFE resin powder (TLP-10F-1 manufactured by Mitsui & DuPont Fluorochemicals)
- Rust preventive Calcium sulfonate (NA SUL CA 1089 manufactured by KING)
- Antioxidant Phenylnaphthylamine (VANLUBE 81 manufactured by Sanyo Chemical Industries)
- Extreme pressure agent zinc dialkyldithiophosphate (C 12 straight chain alkyl group) (ADEKA Corporation Ade Kakikurufu Bu Z-112)
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- General Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
Description
本発明において、基油は、40℃での動粘度が18~50mm2/sのポリ-α-オレフィンと、数平均分子量が40,000~200,000のエチレン-α-オレフィン共重合体との混合油に限定するとともに、基油の40℃での動粘度を80~200mm2/sに限定することが必要である。ポリ-α-オレフィンとエチレン-α-オレフィン共重合体とは、いずれも合成炭化水素油であり、基油として、合成炭化水素油以外、例えばエステル系合成油やエーテル系合成油を用いた場合、樹脂部材に対し悪影響を与えるおそれがあるため、基油を、ポリ-α-オレフィンとエチレン-α-オレフィン共重合体との混合油とし、エステル系合成油やエーテル系合成油を含有させず、合成炭化水素油だけで構成することが好ましい。
本発明の潤滑グリース組成物における増ちょう剤としては、樹脂部材に対し潤滑性や相性に優れているリチウム系複合石けんを用いることが必要である。
本発明の潤滑グリース組成物において、固体潤滑剤は、ポリテトラフルオロエチレン(PTFE)樹脂であることが高負荷状態での起動摩擦が低い点で必要である。
(1)潤滑グリース組成物の調製方法
潤滑グリース組成物の調製方法は、以下の方法で行なった。
(i)増ちょう剤としてリチウム複合石けん(Li-Comp)を用いた場合
まず、基油と12-ヒドロキシステアリン酸(増ちょう剤成分)と水酸化リチウム(増ちょう剤成分)を、混合攪拌釜に所定量配合し、約80~130℃で加熱攪拌しけん化反応を行なった。更にアゼライン酸(増ちょう剤成分)を所定量配合し、約80~200℃で加熱攪拌し、そこに水酸化リチウム(増ちょう剤成分)をさらに加えてけん化反応を行い、その後冷却してゲル状物質を生成した。この生成したゲル状物質に、PTFE粉末等の各種添加剤を加え攪拌した後、ロールミルもしくは高圧ホモジナイザに通すことにより、以下に示す各成分を、表1及び表2で示す配合量(質量%)で含有する潤滑グリース組成物を調整した。なお、配合した増ちょう剤を構成する各成分の量は、増ちょう剤の全量に対し、12-ヒドロキシステアリン酸が63.5質量%、アゼライン酸が19.0質量%、水酸化リチウムが17.5質量%であり、下記に示す増ちょう剤A(Li-Comp)を用いた。
まず、基油とセバシン酸(増ちょう剤成分)およびカルボン酸モノステアリルアミド(増ちょう剤成分)を混合攪拌釜に所定量配合し、約80~200℃で加熱攪拌し、そこに水酸化バリウム(増ちょう剤成分)を加えてけん化反応を行い、その後冷却してゲル状物質を生成した。この生成したゲル状物質に、PTFE粉末等の各種添加剤を加え攪拌した後、ロールミルもしくは高圧ホモジナイザーに通すことにより、以下に示す各成分を、表1及び表2で示す配合量(重量%)で含有する潤滑グリース組成物を調整した。なお、配合した増ちょう剤を構成する各成分の量は、増ちょう剤の全量に対し、セバシン酸が27.5質量%、カルボン酸モノステアリルアミドが41.5質量%、水酸化バリウムが31質量%であり、下記に示す増ちょう剤B(Ba-Comp)を用いた。
まず、基油と12-ヒドロキシステアリン酸(増ちょう剤成分)と水酸化リチウム(増ちょう剤成分)を、混合攪拌釜に所定量配合し、約80~130℃で加熱攪拌しけん化反応を行ない、溶融温度まで加熱攪拌した後、冷却してゲル状物質を生成した。生成したゲル状物質に、PTFE粉末等の各種添加剤を加え攪拌した後、ロールミルもしくは高圧ホモジナイザに通すことにより、以下に示す各成分を、表1及び表2で示す配合量(重量%)で含有する潤滑グリース組成物を調整した。なお、配合した増ちょう剤を構成する各成分の量は、増ちょう剤の全量に対し、12-ヒドロキシステアリン酸が88質量%、水酸化リチウムが12質量%であり、下記に示す増ちょう剤C(Li-OHST)を用いた。
ポリ-α-オレフィンB:40℃動粘度30mm2/s(イネオスオリゴマーズジャパン社製 DURASYN 166)
ポリ-α-オレフィンC:40℃動粘度46mm2/s(イネオスオリゴマーズジャパン社製 DURASYN 168)
ポリ-α-オレフィンD:40℃動粘度5mm2/s(イネオスオリゴマーズジャパン社製 DURASYN 162)
ポリ-α-オレフィンE:40℃動粘度68mm2/s(イネオスオリゴマーズジャパン社製 DURASYN 168)
ポリ-α-オレフィンF:40℃動粘度400mm2/s(イネオスオリゴマーズジャパン社製 DURASYN174)
ポリオールエステル:40℃動粘度20mm2/s(日油社製 ユニスターH-334R)
エチレン-α-オレフィン共重合体A:数平均分子量68000、重量平均分子量147000(昭和ワニス社製L6Z-25)
エチレン-α-オレフィン共重合体B:数平均分子量7700、重量平均分子量14400(三井化学社製 ルーカントHC-2000)
増ちょう剤A:Li-Comp(リチウム複合石けん)
増ちょう剤B:Ba-Comp(バリウム複合石けん)
増ちょう剤C:Li-OHST(リチウム石けん)
PTFE樹脂粉末:(三井・デュポン フロロケミカル社製 TLP-10F-1)
防錆剤:カルシウムスルホネート(KING社製 NA SUL CA 1089)
酸化防止剤:フェニルナフチルアミン(三洋化成工業社製 VANLUBE 81)
極圧剤:ジアルキルジチオリン酸亜鉛(C12直鎖アルキル基)(ADEKA社製 アテ゛カキクルーフ゛Z-112)
(2-1)基油粘度
基油粘度は、JIS K2283:2000に準拠して測定した。
混和ちょう度は、それぞれJIS K2220.7:2013に準拠して測定した。
起動摩擦試験は、ピンオンディスク型試験機を用い、ポリアミド(PA)66樹脂材料製のディスク上にグリース組成物を塗布し、上から金属(S45C炭素鋼)製のシリンダ(φ10mm×10mm)を横置きにし、一定荷重(98N)、接触平均面圧にして46MPaで押し付けた状態で5mm/sの速度で回転摺動させて行い、回転摺動させたときの金属製シリンダと樹脂製ディスクとの間で発生する起動時の摩擦力を測定し、この摩擦力から起動摩擦係数(静摩擦係数)を算出した。なお、試験温度は100℃とし、試験時間は5秒とした。本発明では、起動摩擦係数の数値は、0.100以下である場合を合格レベルとし、0.100超えの場合を不合格とした。
耐摩耗試験は、ピンオンディスク型試験機を用い、ポリアミド(PA)66樹脂材料製のディスク上にグリース組成物を塗布し、上から金属(S45C炭素鋼)製のシリンダ(φ10mm×10mm)を横置きにし、一定荷重(98N)、接触平均面圧にして46MPaで押し付けた状態で、1m/sの速度で、一定時間、正-逆回転摺動させて行い、回転摺動後の樹脂製ディスクの摩耗深さ(μm)を測定し、耐摩耗性を評価した。なお、試験温度は100℃とし、試験時間は2時間(正回転:5秒、逆回転:5秒)とした。本発明では、摩耗深さの数値は、1.80μm以下である場合を合格レベルとし、1.80μm超えの場合を不合格とした。
樹脂部材(樹脂製ディスク)に各潤滑グリース組成物を塗布したときの起動摩擦係数と摩耗深さに関する評価結果を、表1および表2に示す。
Claims (4)
- 他の部材との摺動部をもつ樹脂部材の少なくとも前記摺動部の表面に、潤滑剤として供給されるのに使用される樹脂部材用潤滑グリース組成物であって、
40℃での動粘度が18~50mm2/sのポリ-α-オレフィンと、数平均分子量が40,000~200,000のエチレン-α-オレフィン共重合体との混合油である基油と、
増ちょう剤としてのリチウム系複合石けんと、
潤滑グリース組成物全体に対する配合比率が4~12質量%である、固体潤滑剤としてのポリテトラフルオロエチレン樹脂と
を含有し、
前記基油は、40℃での動粘度が80~200mm2/sであり、
前記潤滑グリース組成物の混和ちょう度が265~340の範囲であることを特徴とする樹脂部材用潤滑グリース組成物。 - 前記エチレン-α-オレフィン共重合体は、潤滑グリース組成物全体に対する配合比率が1.5~3.5質量%の範囲である請求項1に記載の樹脂部材用潤滑グリース組成物。
- 前記樹脂部材の材質がポリアミド樹脂である請求項1または2に記載の樹脂部材用潤滑グリース組成物。
- 前記他の部材が金属部材である請求項1、2または3に記載の樹脂部材用潤滑グリース組成物。
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US11174450B2 (en) | 2018-07-27 | 2021-11-16 | Minebea Mitsumi Inc. | Grease composition for resin lubrication and sliding member having sliding surface made of resin |
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