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EP3269794A1 - Grease composition - Google Patents

Grease composition Download PDF

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Publication number
EP3269794A1
EP3269794A1 EP16761774.5A EP16761774A EP3269794A1 EP 3269794 A1 EP3269794 A1 EP 3269794A1 EP 16761774 A EP16761774 A EP 16761774A EP 3269794 A1 EP3269794 A1 EP 3269794A1
Authority
EP
European Patent Office
Prior art keywords
grease composition
hydroxycarboxylic acid
metal salt
acid metal
thickening agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP16761774.5A
Other languages
German (de)
French (fr)
Other versions
EP3269794A4 (en
EP3269794B1 (en
Inventor
Kazumi Sakai
Hisayuki Wada
Yusuke AYAME
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.)
Eneos Corp
Original Assignee
JXTG Nippon Oil and Energy Corp
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 JXTG Nippon Oil and Energy Corp filed Critical JXTG Nippon Oil and Energy Corp
Publication of EP3269794A1 publication Critical patent/EP3269794A1/en
Publication of EP3269794A4 publication Critical patent/EP3269794A4/en
Application granted granted Critical
Publication of EP3269794B1 publication Critical patent/EP3269794B1/en
Active legal-status Critical Current
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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/06Mixtures of thickeners and additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M129/26Carboxylic acids; Salts thereof
    • C10M129/28Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/38Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
    • C10M129/44Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms containing 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
    • 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
    • C10M2201/00Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06Metal compounds
    • C10M2201/061Carbides; Hydrides; Nitrides
    • 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
    • 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
    • C10M2207/1206Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms used as thickening agents
    • 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
    • C10M2207/1236Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic used as thickening agent
    • 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
    • C10M2207/128Carboxylix 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 containing hydroxy groups; Ethers 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
    • 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
    • C10M2207/128Carboxylix 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 containing hydroxy groups; Ethers thereof
    • C10M2207/1285Carboxylix 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 containing hydroxy groups; Ethers thereof used as thickening agents
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/283Esters of polyhydroxy compounds
    • C10M2207/2835Esters of polyhydroxy compounds used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/08Amides
    • 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
    • C10M2215/1026Ureas; Semicarbazides; Allophanates used as thickening 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
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/22Heterocyclic nitrogen compounds
    • C10M2215/221Six-membered rings containing nitrogen and carbon only
    • 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
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/04Groups 2 or 12
    • 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
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/02Bearings
    • 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
    • C10N2050/10Semi-solids; greasy

Definitions

  • the present invention relates to a grease composition capable of reducing an amount of wear in sliding parts.
  • Grease has been mainly used for slide bearings and rolling bearings (bearings), or for sliding surfaces where a lubricant film cannot easily remain attached because of moving contact surfaces.
  • grease is prepared by mixing a thickening agent, and, as required, additives, to a lubricant base oil.
  • Hydroxyfatty acid metal salts are used as thickening agents for grease (see, for example, PTL 3).
  • the hydroxyfatty acid metal salts used as thickening agents are mostly lithium 12-hydroxystearate, and an ⁇ - or ⁇ -hydroxyfatty acid metal salt is not used. It is also known that use of this type of compound as an grease additive results in a shorter life, though it improves antirust performance (for example, PTL 4).
  • the present invention was made under these circumstances, and it is an object of the present invention to provide a grease composition that is capable of reducing an amount of wear in sliding parts of various members of automobiles, electrical devices, and the like.
  • the present inventors diligently worked to achieve the foregoing object, and found that an amount of wear can be greatly reduced by the synergy between metal salts of specific hydroxycarboxylic acids and an amide compound.
  • the present invention was completed on the basis of this finding, and includes the following.
  • the grease composition of the present invention is highly effective at greatly reducing wear in sliding parts of various members of automobiles, electrical devices, and the like.
  • a lubricant base oil of the present invention may be a mineral or a synthetic lubricant base oil, as long as it is a lubricant base oil commonly used for grease.
  • the lubricant base oil has a kinetic viscosity at 40°C of preferably 1 to 500 mm 2 /s, more preferably 5 to 100 mm 2 /s.
  • a grease composition having desirable consistency can be prepared with ease when the kinetic viscosity at 40°C is 1 to 500 mm 2 /s.
  • a lubricant base oil of physical properties with a viscosity index of 90 or more, particularly 95 to 250, a pour point of -10°C or less, particularly -15 to -70°C, and a flash point of 150°C or more.
  • the lubricant base oil When containing a solid lubricant, the lubricant base oil preferably has a density of 0.75 to 0.95 g/cm 3 at a lubricant base oil temperature of 15°C.
  • the density is particularly preferably 0.8 to 0.9 g/cm 3 .
  • the mineral lubricant base oil may be a lubricant oil fraction obtained through purification of a distillate oil by various purification processes after distillation of a crude oil under ordinary pressure or under ordinary pressure and reduced pressure.
  • the purification processes include, for example, hydrorefining, solvent extraction, solvent dewaxing, hydrodewaxing, sulfuric acid washing, and clay treatment.
  • the base oil of the present invention can be obtained from a combination of these processes performed in appropriate order. A mixture of different refined oils of different qualities obtained by treating different crude oils or different distillate oils with a combination of different processes in different order is also useful. Regardless of the method, the base oil can be desirably used when the base oil quality is adjusted to satisfy the foregoing density.
  • the synthetic lubricant base oil uses preferably a base material having desirable hydrolytic stability.
  • base materials include polyolefins such as poly- ⁇ -olefins, polybutene, and a copolymer of two or more olefins; polyesters, polyalkylene glycols, alkylbenzenes, and alkylnaphthalenes.
  • Poly- ⁇ -olefins are preferred for availability, cost, viscosity characteristics, oxidation stability, and compatibility with system components. Further preferred for cost are poly- ⁇ -olefins made by polymerizing olefins such as 1-dodecene, and 1-decene.
  • ester-based base oils for example, such as a polyolester of a polyalcohol and a monovalent carboxylic acid, and a diester of a divalent carboxylic acid and an alcohol.
  • Preferred are polyolesters obtained from a polyalcohol selected from neopentyl glycol, trimethylolpropane, and pentaerythritol, and a fatty acid of 4 to 22 carbon atoms.
  • the fatty acid is particularly preferably a fatty acid of 12 to 20 carbon atoms, particularly an unsaturated fatty acid.
  • the lubricant base oil may use base oils other than the poly- ⁇ -olefinic base oil and the ester-based base oil. It is, however, preferable to contain 80 mass% or more, particularly 90 mass% or more of the poly- ⁇ -olefin or ester-based base oil with respect to the mass of the lubricant base oil.
  • the synthetic lubricant base oil may be used alone or as a mixture of two or more. It is also possible to use the synthetic lubricant base oil as a mixture with the mineral base oil.
  • the content of the lubricant base oil is preferably 50 to 95 mass%, particularly preferably 60 to 85 mass% with respect to the total amount of the grease composition.
  • a grease composition having desirable consistency can be prepared with ease when the lubricant base oil content is 50 to 95 mass%.
  • a thickening agent commonly used for grease may be used as the thickening agent of the present invention without causing trouble. It is, however, preferable to use a metal soap-based thickening agent, or a urea-based thickening agent.
  • the thickening agent may be used alone or as a mixture of two or more.
  • the thickening agent may be contained in any amount, as long as the desired consistency is obtained.
  • the thickening agent content is preferably 2 to 30 mass%, further preferably 5 to 20 mass% with respect to the total amount of the grease composition.
  • the metal soap-based thickening agent is a thickening agent of a carboxylic acid metal salt.
  • the carboxylic acid may be a derivative of carboxylic acids having a hydroxy group.
  • the carboxylic acids may be aliphatic carboxylic acids such as stearic acid, and azelaic acid, or aromatic carboxylic acids such as terephthalic acid.
  • Monovalent or divalent aliphatic carboxylic acids particularly aliphatic carboxylic acids of 6 to 20 carbon atoms are used. Particularly preferred for use are monovalent aliphatic carboxylic acids of 12 to 20 carbon atoms, and divalent aliphatic carboxylic acids of 6 to 14 carbon atoms.
  • Monovalent aliphatic carboxylic acids having one hydroxyl group are preferred.
  • the metal may be an alkali metal such as lithium and sodium, an alkali earth metal such as calcium, or an amphoteric metal such as aluminum. Preferred are alkali metals, particularly lithium.
  • Metal salts of ⁇ - or ⁇ -hydroxyfatty acids are not preferred as thickening agents because of poor thickening capability.
  • the thickening agent may be added in the form of a metal soap, or as a metal-soap thickening agent by separately adding the carboxylic acid and a metal source (e.g., a metal salt, a metal salt hydroxide), and causing these to react at the time of grease production.
  • a metal source e.g., a metal salt, a metal salt hydroxide
  • the carboxylic acid metal salt may be used alone or as a mixture of two or more.
  • a mixture of lithium 12-hydroxystearate and lithium azelate is particularly preferred.
  • the urea-based thickening agent may be, for example, a diurea compound obtained by a reaction of a diisocyanate and a monoamine, or a polyurea compound obtained by a reaction of a diisocyanate with a monoamine or a diamine.
  • Diisocyanates are compounds in which two of the hydrogen atoms of the hydrocarbon are substituted with isocyanate groups.
  • Preferred examples of the diisocyanates include phenylene diisocyanate, tolylene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, octadecane diisocyanate, decane diisocyanate, and hexane diisocyanate.
  • the hydrocarbon may be a non-cyclic hydrocarbon or a cyclic hydrocarbon, or an aromatic hydrocarbon, an alicyclic hydrocarbon, or an aliphatic hydrocarbon.
  • the hydrocarbon is an aromatic hydrocarbon.
  • the hydrocarbon has preferably 4 to 20 carbon atoms, particularly 8 to 18 carbon atoms.
  • Monoamines are compounds in which one of the hydrogen atoms of the ammonia is substituted with a hydrocarbon group.
  • Preferred examples of the monoamines include octylamine, dodecylamine, hexadecylamine, stearylamine, oleylamine, aniline, p-toluidine, and cyclohexylamine.
  • Diamines are compounds in which two of the hydrogen atoms of the ammonia are substituted with hydrocarbon groups.
  • the diamines include ethylenediamine, propanediamine, butanediamine, hexanediamine, octanediamine, phenylenediamine, tolylenediamine, xylenediamine, and diaminodiphenylmethane.
  • the hydrocarbon groups of the monoamines and diamines may be non-cyclic hydrocarbon groups or cyclic hydrocarbon groups, or aromatic hydrocarbon groups, alicyclic hydrocarbon groups, or aliphatic hydrocarbon groups.
  • the monoamines and diamines contain aliphatic hydrocarbon groups.
  • the monoamines and diamines have preferably 2 to 20 carbon atoms, particularly preferably 4 to 18 carbon atoms.
  • the present invention contains at least one of an ⁇ -hydroxycarboxylic acid metal salt, and an ⁇ -hydroxycarboxylic acid metal salt. It is preferable to contain both an ⁇ -hydroxycarboxylic acid metal salt, and an ⁇ -hydroxycarboxylic acid metal salt, though only one of these may be contained.
  • the metallic element forming the salt is preferably an alkali metal or an alkali earth metal, particularly preferably calcium or barium.
  • the total content of the hydroxycarboxylic acid metal salts is 0.1 to 2 mass%, preferably 0.2 to 1 mass% with respect to the total amount of the grease composition. The wear reducing effect will not be obtained when the total content of the hydroxycarboxylic acid metal salts is less than 0.1 mass%, whereas the hydroxycarboxylic acid metal salt may inhibit the effects of other components when the content is above 2 mass%.
  • the ⁇ - and ⁇ -hydroxycarboxylic acids are preferably monovalent, more preferably monovalent acids of 8 to 24 carbon atoms.
  • the monovalent ⁇ -hydroxycarboxylic acid is represented by R 1 -CH(-OH)-COOH, and the ⁇ -hydroxycarboxylic acid is represented by HO-CH 2 -R 2 -COOH.
  • R 1 is preferably an alkyl group of 1 to 38 carbon atoms, or an alkenyl group of 2 to 38 carbon atoms, more preferably an alkyl group of 6 to 22 carbon atoms, or an alkenyl group of 6 to 22 carbon atoms.
  • R 2 is preferably an alkylene group of 1 to 38 carbon atoms, or an alkenylene group of 2 to 38 carbon atoms, more preferably an alkylene group of 6 to 22 carbon atoms, or an alkenylene group of 6 to 22 carbon atoms.
  • the present invention further contains metal salts of hydroxycarboxylic acids other than ⁇ - and ⁇ -hydroxycarboxylic acids, or metal salts of carboxylic acids containing no hydroxyl group.
  • carboxylic acid metal salts include alkali metal salts or alkali earth metals, preferably calcium or barium salts of ⁇ - and ⁇ -hydroxycarboxylic acids in which the hydroxyl group is substituted at different positions from the foregoing ⁇ - and ⁇ -hydroxycarboxylic acids, or in which two or more hydroxyl groups are substituted, and alkali metal salts or alkali earth metals, preferably calcium or barium salts of carboxylic acids that do not have a substitution of the hydroxyl group.
  • the hydroxycarboxylic acids, and the carboxylic acids may be obtained by chemical synthesis. It is, however, preferable to use a lanolin fatty acid - an acid obtained through purification (e.g., hydrolysis) of a wax-like substance adhering to sheep hairs - as a raw material of these acids.
  • a lanolin fatty acid an acid obtained through purification (e.g., hydrolysis) of a wax-like substance adhering to sheep hairs -
  • the ⁇ - and ⁇ -hydroxycarboxylic acids, and other preferred carboxylic acids may be separately used. It is, however, preferable to prepare the lanolin fatty acid directly into a metal salt, without separating these acids.
  • the present invention further contains an amide compound.
  • the amide compound which is a compound having at least one amide group (-NH-CO-), may be a compound containing one amide group (monoamide), or a compound containing two amide groups (bisamide).
  • amide compound a compound having at least one amide group (monoamide), or a compound containing two amide groups (bisamide).
  • saturated aliphatic monoamides, or saturated aliphatic bisamides are used.
  • the saturated aliphatic bisamides are most preferred for their advantages including desirable heat resistance, and the ability to reduce the frictional resistance at a sliding part even with a relatively small amount.
  • the saturated aliphatic monoamides are amide compounds of a saturated aliphatic monoamine and a saturated aliphatic monocarboxylic acid.
  • the saturated aliphatic bisamides may be amide compounds of a saturated aliphatic diamine and a saturated aliphatic monocarboxylic acid, or amide compounds of a saturated aliphatic dicarboxylic acid and a saturated aliphatic monoamine.
  • a preferred saturated aliphatic amide compound has a melting point of 100 to 170°C, and a molecular weight of 298 to 876.
  • the saturated aliphatic monoamides are represented by the following general formula (1).
  • the saturated aliphatic bisamides are represented by the following general formulae (2) and (3).
  • R 11 -CO-NH-R 12 ... (1)
  • R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 each independently represent a saturated aliphatic hydrocarbon group of 5 to 25 carbon atoms.
  • R 12 may be hydrogen.
  • a 1 and A 2 represent divalent saturated aliphatic hydrocarbon groups of 1 to 10 carbon atoms, and are preferably divalent saturated chain hydrocarbon groups of 1 to 4 carbon atoms.
  • saturated aliphatic monoamides include lauramide, palmitamide, stearamide, and behenamide.
  • Preferred examples of the saturated aliphatic bisamides represented by formula (2) include ethylene bis(stearamide), ethylene bis(isostearamide), ethylene bis(lauramide), and methylene bis(lauramide).
  • Preferred examples of the saturated aliphatic bisamides represented by formula (3) include N,N'-bisstearylsebacamide.
  • the bisamides are preferably amide compounds in which R 13 , R 14 , R 15 , and R 16 in formulae (2) and (3) are each independently a saturated chain hydrocarbon group of 12 to 20 carbon atoms.
  • the amide compounds may be used alone or in a combination of two or more in any proportions.
  • the content of the amide compound is preferably 1 to 30 mass%, more preferably 5 to 20 mass% with respect to the total amount of the grease composition.
  • the amide compound when thermofused in the presence of the lubricant base oil, produces a state in which the lubricant base oil is held in the amide compound forming a three-dimensional network structure. This further lowers the coefficient of friction at a sliding part than when the amide compound is simply dispersed or mixed in the grease.
  • the present invention further contains a solid lubricant component.
  • the solid lubricant component may be, for example, melamine cyanurate, molybdenum disulfide, boron nitride, graphite, mica, fluororesin, fluorinated graphite, or a molybdenum organic compound commonly used for lubricants.
  • the content of the solid lubricant component is preferably 0.1 to 10 mass%, more preferably 0.2 to 5 mass% with respect to the total amount of the grease composition.
  • boron nitride or melamine cyanurate as the solid lubricant component.
  • a hexagonal, atmospheric-phase boron nitride (h-BN) powder of a particle size suited for the intended purpose may be appropriately selected and used.
  • the solid lubricant component has a particle diameter of preferably 1 to 10 ⁇ m.
  • Additives commonly used for lubricant oils and greases may be appropriately added, as required, to the grease composition of the present invention, in addition to the foregoing components.
  • additives include cleaners, dispersants, antiwear agents, viscosity index improvers, antioxidants, extreme-pressure agents, anti-rusting agents, and corrosion inhibitors.
  • the grease composition of the present invention is preferably used at sliding parts, preferably for lubrication of various sliding members, for example, between metal parts, metal and resin parts, and resin parts.
  • the sliding member resin may be a natural resin or a synthetic resin.
  • synthetic resins are general-purpose plastics (e.g., polyethylene, polystyrene, polypropylene, and polyvinyl chloride), and engineering plastics. Engineering plastics are particularly preferred in terms of heat resistance, and mechanical strength.
  • synthetic resins include polyamide resins, polyacetal resins, polycarbonate resins, polysulfone resins, polyphenylene sulfide resins, polyamideimide resins, polyetheretherketone resins, phenolic resins, polyester resins, and epoxy resins.
  • the grease composition is particularly preferred for lubrication of polyamide resins, and polyoxymethylene resins.
  • Examples of the applicable areas of the grease composition of the present invention include transport machinery such as automobiles, railway, and aircraft; industrial machines such as machine tools; home electrical appliances such as washing machines, refrigerators, and vacuum cleaners; and precision machines such as watches and cameras.
  • the grease composition has use for, for example, bearings, gears, sliding surfaces, belts, joints, and cams used for these machines.
  • the grease composition is particularly useful for improving the abrasion resistance of gears (e.g., spur wheels, helical gears, crossed helical gears, hypoid gears, worm gears, and wheel gears) exposed to a high-surface-pressure sliding environment.
  • gears e.g., spur wheels, helical gears, crossed helical gears, hypoid gears, worm gears, and wheel gears
  • Each component was put in a container in the amounts (mass%) shown in Tables 1 and 2, and heated to 150°C (a temperature equal to or greater than the melting point of the amide compound). The mixture was then stirred with a magnetic stirrer, and cooled to room temperature. The product was subjected to a dispersion process under applied pressure using rollers (three rolls) to prepare a grease composition.
  • the amount of wear was considerably smaller in the grease compositions of Examples that contained at least one of the ⁇ -hydroxycarboxylic acid metal salt and the ⁇ -hydroxycarboxylic acid metal salt with the thickening agent and the amide compound. On the other hand, there was no large reduction in the amount of wear when the hydroxycarboxylic acid metal salts were not contained, even when simple carboxylates, or a phosphite ester (a known anti-wear agent) were added (Comparative Examples 1 to 7).
  • the grease composition of the present invention can greatly reduce an amount of wear in sliding members, and is useful for lubrication of sliding parts of various members of automobiles, electrical devices, and the like.

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  • Chemical & Material Sciences (AREA)
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  • Lubricants (AREA)

Abstract

Provided herein is a grease composition capable of reducing an amount of wear in sliding parts of various members of automobiles, electrical devices, and the like. The grease composition includes a lubricant base oil, a thickening agent, an amide compound, and at least one of an α-hydroxycarboxylic acid metal salt, and an ω-hydroxycarboxylic acid metal salt. The hydroxycarboxylic acid metal salts are contained in a total content of 0.1 to 2 mass% with respect to the total amount of the grease composition.

Description

    Technical Field
  • The present invention relates to a grease composition capable of reducing an amount of wear in sliding parts.
  • Background Art
  • Grease has been mainly used for slide bearings and rolling bearings (bearings), or for sliding surfaces where a lubricant film cannot easily remain attached because of moving contact surfaces. Typically, grease is prepared by mixing a thickening agent, and, as required, additives, to a lubricant base oil.
  • With the advancement in machine technology such as in automobiles and electrical devices, these devices are used in increasing severe operating conditions as the trend for downsizing and lighting, higher output, and longer life continues to grow. This has increased the demand for higher performance, for example, lubricity, in greases used for these devices.
  • Various options are proposed for the base oil, thickening agent, and additives to improve grease lubricity. For example, it has been proposed to add an amide compound and a solid lubricant to improve grease lubricity, for example, such as abrasion resistance (see PTL 1, and PTL 2). However, a grease having better lubricity is needed.
  • Hydroxyfatty acid metal salts are used as thickening agents for grease (see, for example, PTL 3). However, the hydroxyfatty acid metal salts used as thickening agents are mostly lithium 12-hydroxystearate, and an α- or ω-hydroxyfatty acid metal salt is not used. It is also known that use of this type of compound as an grease additive results in a shorter life, though it improves antirust performance (for example, PTL 4).
  • Citation List Patent Literature
    • PTL 1: JP-A-2013-181154
    • PTL 2: JP-A-2013-181156
    • PTL 3: WO2012/141222
    • PTL 4: JP-B-7-000796
    Summary of Invention Technical Problem
  • The present invention was made under these circumstances, and it is an object of the present invention to provide a grease composition that is capable of reducing an amount of wear in sliding parts of various members of automobiles, electrical devices, and the like.
  • Solution to Problem
  • The present inventors diligently worked to achieve the foregoing object, and found that an amount of wear can be greatly reduced by the synergy between metal salts of specific hydroxycarboxylic acids and an amide compound. The present invention was completed on the basis of this finding, and includes the following.
    1. (1) A grease composition comprising:
      • a lubricant base oil;
      • a thickening agent;
      • an amide compound; and
      • at least one of an α-hydroxycarboxylic acid metal salt, and an ω-hydroxycarboxylic acid metal salt,
      • wherein the hydroxycarboxylic acid metal salts are contained in a total content of 0.1 to 2 mass% with respect to a total amount of the grease composition.
    2. (2) The grease composition according to item (1), wherein the hydroxycarboxylic acid metal salt is an alkali metal salt, or an alkali earth metal salt.
    3. (3) The grease composition according to item (2), wherein the hydroxycarboxylic acid metal salt is a calcium salt, or a barium salt.
    4. (4) The grease composition according to any one of items (1) to (3), wherein the hydroxycarboxylic acid is a monovalent hydroxycarboxylic acid of 8 to 24 carbon atoms.
    5. (5) The grease composition according to any one of items (1) to (4), wherein the thickening agent contains at least one of a urea-based thickening agent, and a metal soap-based thickening agent.
    6. (6) The grease composition according to any one of items (1) to (5), which further comprises a solid lubricant component.
    7. (7) A lubrication method comprising using the grease composition of any one of items (1) to (6) at a sliding part.
    Advantageous Effects of Invention
  • The grease composition of the present invention is highly effective at greatly reducing wear in sliding parts of various members of automobiles, electrical devices, and the like.
  • Description of Embodiments Lubricant Base Oil
  • A lubricant base oil of the present invention may be a mineral or a synthetic lubricant base oil, as long as it is a lubricant base oil commonly used for grease. The lubricant base oil has a kinetic viscosity at 40°C of preferably 1 to 500 mm2/s, more preferably 5 to 100 mm2/s. A grease composition having desirable consistency can be prepared with ease when the kinetic viscosity at 40°C is 1 to 500 mm2/s. In order to prepare a grease having excellent lubricity, it is preferable to use a lubricant base oil of physical properties with a viscosity index of 90 or more, particularly 95 to 250, a pour point of -10°C or less, particularly -15 to -70°C, and a flash point of 150°C or more.
  • When containing a solid lubricant, the lubricant base oil preferably has a density of 0.75 to 0.95 g/cm3 at a lubricant base oil temperature of 15°C. The density is particularly preferably 0.8 to 0.9 g/cm3.
  • The mineral lubricant base oil may be a lubricant oil fraction obtained through purification of a distillate oil by various purification processes after distillation of a crude oil under ordinary pressure or under ordinary pressure and reduced pressure. The purification processes include, for example, hydrorefining, solvent extraction, solvent dewaxing, hydrodewaxing, sulfuric acid washing, and clay treatment. The base oil of the present invention can be obtained from a combination of these processes performed in appropriate order. A mixture of different refined oils of different qualities obtained by treating different crude oils or different distillate oils with a combination of different processes in different order is also useful. Regardless of the method, the base oil can be desirably used when the base oil quality is adjusted to satisfy the foregoing density.
  • The synthetic lubricant base oil uses preferably a base material having desirable hydrolytic stability. Examples of such base materials include polyolefins such as poly-α-olefins, polybutene, and a copolymer of two or more olefins; polyesters, polyalkylene glycols, alkylbenzenes, and alkylnaphthalenes. Poly-α-olefins are preferred for availability, cost, viscosity characteristics, oxidation stability, and compatibility with system components. Further preferred for cost are poly-α-olefins made by polymerizing olefins such as 1-dodecene, and 1-decene.
  • Also preferred as the synthetic lubricant base oil are ester-based base oils, for example, such as a polyolester of a polyalcohol and a monovalent carboxylic acid, and a diester of a divalent carboxylic acid and an alcohol. Preferred are polyolesters obtained from a polyalcohol selected from neopentyl glycol, trimethylolpropane, and pentaerythritol, and a fatty acid of 4 to 22 carbon atoms. The fatty acid is particularly preferably a fatty acid of 12 to 20 carbon atoms, particularly an unsaturated fatty acid.
  • The lubricant base oil may use base oils other than the poly-α-olefinic base oil and the ester-based base oil. It is, however, preferable to contain 80 mass% or more, particularly 90 mass% or more of the poly-α-olefin or ester-based base oil with respect to the mass of the lubricant base oil.
  • The synthetic lubricant base oil may be used alone or as a mixture of two or more. It is also possible to use the synthetic lubricant base oil as a mixture with the mineral base oil.
  • The content of the lubricant base oil is preferably 50 to 95 mass%, particularly preferably 60 to 85 mass% with respect to the total amount of the grease composition. A grease composition having desirable consistency can be prepared with ease when the lubricant base oil content is 50 to 95 mass%.
  • Thickening Agent
  • A thickening agent commonly used for grease may be used as the thickening agent of the present invention without causing trouble. It is, however, preferable to use a metal soap-based thickening agent, or a urea-based thickening agent. The thickening agent may be used alone or as a mixture of two or more. The thickening agent may be contained in any amount, as long as the desired consistency is obtained. For example, the thickening agent content is preferably 2 to 30 mass%, further preferably 5 to 20 mass% with respect to the total amount of the grease composition.
  • The metal soap-based thickening agent is a thickening agent of a carboxylic acid metal salt. The carboxylic acid may be a derivative of carboxylic acids having a hydroxy group.
  • The carboxylic acids may be aliphatic carboxylic acids such as stearic acid, and azelaic acid, or aromatic carboxylic acids such as terephthalic acid. Monovalent or divalent aliphatic carboxylic acids, particularly aliphatic carboxylic acids of 6 to 20 carbon atoms are used. Particularly preferred for use are monovalent aliphatic carboxylic acids of 12 to 20 carbon atoms, and divalent aliphatic carboxylic acids of 6 to 14 carbon atoms. Monovalent aliphatic carboxylic acids having one hydroxyl group are preferred.
  • The metal may be an alkali metal such as lithium and sodium, an alkali earth metal such as calcium, or an amphoteric metal such as aluminum. Preferred are alkali metals, particularly lithium.
  • Metal salts of α- or ω-hydroxyfatty acids are not preferred as thickening agents because of poor thickening capability.
  • The thickening agent may be added in the form of a metal soap, or as a metal-soap thickening agent by separately adding the carboxylic acid and a metal source (e.g., a metal salt, a metal salt hydroxide), and causing these to react at the time of grease production.
  • The carboxylic acid metal salt may be used alone or as a mixture of two or more. For example, a mixture of lithium 12-hydroxystearate and lithium azelate is particularly preferred.
  • The urea-based thickening agent may be, for example, a diurea compound obtained by a reaction of a diisocyanate and a monoamine, or a polyurea compound obtained by a reaction of a diisocyanate with a monoamine or a diamine.
  • Diisocyanates are compounds in which two of the hydrogen atoms of the hydrocarbon are substituted with isocyanate groups. Preferred examples of the diisocyanates include phenylene diisocyanate, tolylene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, octadecane diisocyanate, decane diisocyanate, and hexane diisocyanate. The hydrocarbon may be a non-cyclic hydrocarbon or a cyclic hydrocarbon, or an aromatic hydrocarbon, an alicyclic hydrocarbon, or an aliphatic hydrocarbon. Preferably, the hydrocarbon is an aromatic hydrocarbon. The hydrocarbon has preferably 4 to 20 carbon atoms, particularly 8 to 18 carbon atoms.
  • Monoamines are compounds in which one of the hydrogen atoms of the ammonia is substituted with a hydrocarbon group. Preferred examples of the monoamines include octylamine, dodecylamine, hexadecylamine, stearylamine, oleylamine, aniline, p-toluidine, and cyclohexylamine. Diamines are compounds in which two of the hydrogen atoms of the ammonia are substituted with hydrocarbon groups. Preferred examples of the diamines include ethylenediamine, propanediamine, butanediamine, hexanediamine, octanediamine, phenylenediamine, tolylenediamine, xylenediamine, and diaminodiphenylmethane. The hydrocarbon groups of the monoamines and diamines may be non-cyclic hydrocarbon groups or cyclic hydrocarbon groups, or aromatic hydrocarbon groups, alicyclic hydrocarbon groups, or aliphatic hydrocarbon groups. Preferably, the monoamines and diamines contain aliphatic hydrocarbon groups. The monoamines and diamines have preferably 2 to 20 carbon atoms, particularly preferably 4 to 18 carbon atoms.
  • Hydroxycarboxylic Acid Metal Salt
  • The present invention contains at least one of an α-hydroxycarboxylic acid metal salt, and an ω-hydroxycarboxylic acid metal salt. It is preferable to contain both an α-hydroxycarboxylic acid metal salt, and an ω-hydroxycarboxylic acid metal salt, though only one of these may be contained. The metallic element forming the salt is preferably an alkali metal or an alkali earth metal, particularly preferably calcium or barium. The total content of the hydroxycarboxylic acid metal salts is 0.1 to 2 mass%, preferably 0.2 to 1 mass% with respect to the total amount of the grease composition. The wear reducing effect will not be obtained when the total content of the hydroxycarboxylic acid metal salts is less than 0.1 mass%, whereas the hydroxycarboxylic acid metal salt may inhibit the effects of other components when the content is above 2 mass%.
  • In the present invention, the α- and ω-hydroxycarboxylic acids are preferably monovalent, more preferably monovalent acids of 8 to 24 carbon atoms. The monovalent α-hydroxycarboxylic acid is represented by R1-CH(-OH)-COOH, and the ω-hydroxycarboxylic acid is represented by HO-CH2-R2-COOH. In the present invention, R1 is preferably an alkyl group of 1 to 38 carbon atoms, or an alkenyl group of 2 to 38 carbon atoms, more preferably an alkyl group of 6 to 22 carbon atoms, or an alkenyl group of 6 to 22 carbon atoms. R2 is preferably an alkylene group of 1 to 38 carbon atoms, or an alkenylene group of 2 to 38 carbon atoms, more preferably an alkylene group of 6 to 22 carbon atoms, or an alkenylene group of 6 to 22 carbon atoms.
  • Preferably, the present invention further contains metal salts of hydroxycarboxylic acids other than α- and ω-hydroxycarboxylic acids, or metal salts of carboxylic acids containing no hydroxyl group. Preferred examples of such carboxylic acid metal salts include alkali metal salts or alkali earth metals, preferably calcium or barium salts of α- and ω-hydroxycarboxylic acids in which the hydroxyl group is substituted at different positions from the foregoing α- and ω-hydroxycarboxylic acids, or in which two or more hydroxyl groups are substituted, and alkali metal salts or alkali earth metals, preferably calcium or barium salts of carboxylic acids that do not have a substitution of the hydroxyl group.
  • The hydroxycarboxylic acids, and the carboxylic acids may be obtained by chemical synthesis. It is, however, preferable to use a lanolin fatty acid - an acid obtained through purification (e.g., hydrolysis) of a wax-like substance adhering to sheep hairs - as a raw material of these acids. When using a lanolin fatty acid as a raw material, the α- and α-hydroxycarboxylic acids, and other preferred carboxylic acids may be separately used. It is, however, preferable to prepare the lanolin fatty acid directly into a metal salt, without separating these acids.
  • Amide Compound
  • The present invention further contains an amide compound. The amide compound, which is a compound having at least one amide group (-NH-CO-), may be a compound containing one amide group (monoamide), or a compound containing two amide groups (bisamide). Preferably, saturated aliphatic monoamides, or saturated aliphatic bisamides are used.
  • The saturated aliphatic bisamides are most preferred for their advantages including desirable heat resistance, and the ability to reduce the frictional resistance at a sliding part even with a relatively small amount.
  • The saturated aliphatic monoamides are amide compounds of a saturated aliphatic monoamine and a saturated aliphatic monocarboxylic acid. The saturated aliphatic bisamides may be amide compounds of a saturated aliphatic diamine and a saturated aliphatic monocarboxylic acid, or amide compounds of a saturated aliphatic dicarboxylic acid and a saturated aliphatic monoamine.
  • A preferred saturated aliphatic amide compound has a melting point of 100 to 170°C, and a molecular weight of 298 to 876.
  • The saturated aliphatic monoamides are represented by the following general formula (1). The saturated aliphatic bisamides are represented by the following general formulae (2) and (3).

            R11-CO-NH-R12 ...     (1)

            R13-CO-NH-A1-NH-CO-R14 ...     (2)

            R15-NH-CO-A2CO-NH-R16 ...     (3)

  • In the formulae, R11, R12, R13, R14, R15, and R16 each independently represent a saturated aliphatic hydrocarbon group of 5 to 25 carbon atoms. In general formula (1), R12 may be hydrogen. A1 and A2 represent divalent saturated aliphatic hydrocarbon groups of 1 to 10 carbon atoms, and are preferably divalent saturated chain hydrocarbon groups of 1 to 4 carbon atoms.
  • Specifically, preferred examples of the saturated aliphatic monoamides include lauramide, palmitamide, stearamide, and behenamide.
  • Preferred examples of the saturated aliphatic bisamides represented by formula (2) include ethylene bis(stearamide), ethylene bis(isostearamide), ethylene bis(lauramide), and methylene bis(lauramide). Preferred examples of the saturated aliphatic bisamides represented by formula (3) include N,N'-bisstearylsebacamide.
  • The bisamides are preferably amide compounds in which R13, R14, R15, and R16 in formulae (2) and (3) are each independently a saturated chain hydrocarbon group of 12 to 20 carbon atoms.
  • The amide compounds may be used alone or in a combination of two or more in any proportions. The content of the amide compound is preferably 1 to 30 mass%, more preferably 5 to 20 mass% with respect to the total amount of the grease composition.
  • It is to be noted here that the amide compound, when thermofused in the presence of the lubricant base oil, produces a state in which the lubricant base oil is held in the amide compound forming a three-dimensional network structure. This further lowers the coefficient of friction at a sliding part than when the amide compound is simply dispersed or mixed in the grease.
  • Solid Lubricant Component
  • Preferably, the present invention further contains a solid lubricant component.
  • The solid lubricant component may be, for example, melamine cyanurate, molybdenum disulfide, boron nitride, graphite, mica, fluororesin, fluorinated graphite, or a molybdenum organic compound commonly used for lubricants. The content of the solid lubricant component is preferably 0.1 to 10 mass%, more preferably 0.2 to 5 mass% with respect to the total amount of the grease composition.
  • In the present invention, it is more preferable to use boron nitride or melamine cyanurate as the solid lubricant component. Particularly preferably, a hexagonal, atmospheric-phase boron nitride (h-BN) powder of a particle size suited for the intended purpose may be appropriately selected and used. The solid lubricant component has a particle diameter of preferably 1 to 10 µm.
  • Other Additives
  • Additives commonly used for lubricant oils and greases may be appropriately added, as required, to the grease composition of the present invention, in addition to the foregoing components. Examples of such additives include cleaners, dispersants, antiwear agents, viscosity index improvers, antioxidants, extreme-pressure agents, anti-rusting agents, and corrosion inhibitors.
  • Subject of Lubrication
  • The grease composition of the present invention is preferably used at sliding parts, preferably for lubrication of various sliding members, for example, between metal parts, metal and resin parts, and resin parts.
  • The sliding member resin may be a natural resin or a synthetic resin. Preferred as synthetic resins are general-purpose plastics (e.g., polyethylene, polystyrene, polypropylene, and polyvinyl chloride), and engineering plastics. Engineering plastics are particularly preferred in terms of heat resistance, and mechanical strength. Examples of synthetic resins include polyamide resins, polyacetal resins, polycarbonate resins, polysulfone resins, polyphenylene sulfide resins, polyamideimide resins, polyetheretherketone resins, phenolic resins, polyester resins, and epoxy resins. The grease composition is particularly preferred for lubrication of polyamide resins, and polyoxymethylene resins.
  • Examples of the applicable areas of the grease composition of the present invention include transport machinery such as automobiles, railway, and aircraft; industrial machines such as machine tools; home electrical appliances such as washing machines, refrigerators, and vacuum cleaners; and precision machines such as watches and cameras. The grease composition has use for, for example, bearings, gears, sliding surfaces, belts, joints, and cams used for these machines. The grease composition is particularly useful for improving the abrasion resistance of gears (e.g., spur wheels, helical gears, crossed helical gears, hypoid gears, worm gears, and wheel gears) exposed to a high-surface-pressure sliding environment.
  • Examples
  • The present invention is described below using Examples representing implementations of the present invention. The present invention, however, is not limited to the following implementations.
  • Preparation Method
  • Each component was put in a container in the amounts (mass%) shown in Tables 1 and 2, and heated to 150°C (a temperature equal to or greater than the melting point of the amide compound). The mixture was then stirred with a magnetic stirrer, and cooled to room temperature. The product was subjected to a dispersion process under applied pressure using rollers (three rolls) to prepare a grease composition.
  • The components used are as follows.
    1. 1. Lubricant base oil:
      1. (1) Poly-α-olefin (Durasyn 170 available from INEOS)
        • Kinetic viscosity at 40°C: 68 mm2/s
        • Density at 15°C: 0.83 g/cm3
        • Viscosity index: 133
        • Pour point: -45°C
        • Flash point: 250°C
      2. (2) Polyolester (an ester of trimethylolpropane and an oleic acid of 18 carbon atoms)
        • Kinetic viscosity at 40°C: 46 mm2/s
        • Density at 15°C: 0.92 g/cm3
        • Viscosity index: 146
        • Pour point: -32.5°C
        • Flash point: 310°C
    2. 2. Thickening agent:
      1. (1) Urea-based thickening agent
        Alicyclic diurea of cyclohexylamine and methylene diphenyl diisocyanate
      2. (2) Lithium-based thickening agent
        A lithium salt of a mixed acid of 12-hydroxystearic acid and azelaic acid
    3. 3. Solid lubricant component:
      1. (1) Boron nitride
        • Hexagonal boron nitride having an average particle size of 2 µm as measured by laser diffractometry (2) Melamine cyanurate (MCA)
        • Melamine cyanurate having an average particle size of 1 µm as measured by laser diffractometry
    4. 4. Amide compound:
      1. (1) Ethylene bis(stearamide) (guaranteed reagent)
      2. (2) Ethylene bis(lauramide) (guaranteed reagent)
    5. 5. Carboxylic acid metal salt
      1. (1) Barium lanolate
        • Content of α-hydroxycarboxylate: 30 mass%
        • Content of ω-hydroxycarboxylate: 5 mass%
        • Content of hydroxycarboxylates other than α- and ω-hydroxycarboxylates: 1 mass%
        • Content of carboxylate having no hydroxyl group: 40 mass%
        • Number of carbon atoms in hydroxycarboxylic acid: 8 to 24
        • Number of carbon atoms in carboxylic acid having no hydroxyl group: 8 to 24
      2. (2) Calcium lanolate
        • Content of α-hydroxycarboxylate: 30 mass%
        • Content of ω-hydroxycarboxylate: 5 mass%
        • Content of hydroxycarboxylates other than α- and ω-hydroxycarboxylates: 1 mass%
        • Content of carboxylate having no hydroxyl group: 40 mass%
        • Number of carbon atoms in hydroxycarboxylic acid: 8 to 24
        • Number of carbon atoms in carboxylic acid having no hydroxyl group: 8 to 24
    Evaluation of Amount of Wear
  • Evaluation was made according to the ASTM D 3233 test method for measurement of load bearing properties of lubricant oil, using a Falex friction tester. In this test, a resin (polyamide resin (PA66)) pin was held between two steel (SUJ-2) V blocks, and a sample was charged into a sample container. A 55-MPa load was applied with the rotational axis held stationary, and the lubricant oil was tested for load bearing properties at an oil temperature of 120°C under a rotation speed of 360 rpm. The amount of wear was measured by measuring the reduction of the pin weight after 10 minutes. The results are presented in Tables 1 and 2.
  • Evaluation Result
  • The amount of wear was considerably smaller in the grease compositions of Examples that contained at least one of the α-hydroxycarboxylic acid metal salt and the ω-hydroxycarboxylic acid metal salt with the thickening agent and the amide compound. On the other hand, there was no large reduction in the amount of wear when the hydroxycarboxylic acid metal salts were not contained, even when simple carboxylates, or a phosphite ester (a known anti-wear agent) were added (Comparative Examples 1 to 7). [Table 1]
    Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6
    Lubricant base oil Poly-α-olefin Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance
    Thickener Urea-based thickener 10 10 10 10 10 10 10 10 10 10
    Amide compound Ethylene bis-stearylamide 15 15 15 15 15 15 15 15 15 15
    Solid lubricants Boron nitride 1.0 1.0 1.0 - 1.0 1.0 1.0 1.0 1.0 1.0
    Carboxylic acid metal salt Barium lanolate 1.0 2.0 - 2.0 - - - - - -
    Calcium lanolate - - 1.0 - - - - - - -
    Content of α-hydroxycarboxylic acid metal salt and ω-hydroxycarboxylic acid metal salt 0.35 0.70 0.35 0.70 - - - - - -
    Other additive compounds Oleylamide - - - - - 1.0 - - - -
    Aluminum stearate - - - - - - 1.0 - - -
    Zinc naphthenate - - - - - - - 1.0 - -
    naphtenate Phosphite ester - - - - - - - - 1.0 -
    Phosphate - - - - - - - - - 1.0
    Evaluation results Worked penetration 324 308 321 330 315 293 306 316 330 328
    Amount of wear (mg) 0.5 0.6 0.8 0.8 1.3 0.9 1.0 1.0 0.9 1.2
    [Table 2]
    Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative Example 7
    Lubricant base oil Poly-α-olefin Balance Balance Balance Balance - Balance Balance
    Polyolester - - - - Balance - -
    Thickener Litium-based thickener 10 10 10 10 10 10 10
    Amide compound Ethylene bis-stearylamide 15 15 - 15 15 15 -
    Ethylene bis-laurylamide - - 15 - - - -
    Solid lubricants Boron nitride - 2.0 2.0 - 2.0 2.0 -
    MCA - - - 2.0 - - -
    Carboxylic acid metal salt Barium lanolate 1.0 1.0 1.0 1.0 1.0 - -
    Calcium lanolate - - - - - 1.0 -
    Content of α-hydroxycarboxylic acid metal salt and ω-hydroxycarboxylic acid metal salt 0.35 0.35 0.35 0.35 0.35 0.35 -
    Evaluation results Worked penetration 320 280 300 274 298 280 300
    Amount of wear (mg) 1.2 0.8 1.0 1.0 1.0 1.0 1.6
  • Industrial Applicability
  • The grease composition of the present invention can greatly reduce an amount of wear in sliding members, and is useful for lubrication of sliding parts of various members of automobiles, electrical devices, and the like.

Claims (7)

  1. A grease composition comprising:
    a lubricant base oil;
    a thickening agent;
    an amide compound; and
    at least one of an α-hydroxycarboxylic acid metal salt, and an ω-hydroxycarboxylic acid metal salt,
    wherein the hydroxycarboxylic acid metal salts are contained in a total content of 0.1 to 2 mass% with respect to a total amount of the grease composition.
  2. The grease composition according to claim 1, wherein the hydroxycarboxylic acid metal salt is an alkali metal salt, or an alkali earth metal salt.
  3. The grease composition according to claim 2, wherein the hydroxycarboxylic acid metal salt is a calcium salt, or a barium salt.
  4. The grease composition according to any one of claims 1 to 3, wherein the hydroxycarboxylic acid is a monovalent hydroxycarboxylic acid of 8 to 24 carbon atoms.
  5. The grease composition according to any one of claims 1 to 4, wherein the thickening agent contains at least one of a urea-based thickening agent, and a metal soap-based thickening agent.
  6. The grease composition according to any one of claims 1 to 5, which further comprises a solid lubricant component.
  7. A lubrication method comprising using the grease composition of any one of claims 1 to 6 at a sliding part.
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JP7339214B2 (en) 2020-07-20 2023-09-05 トヨタ自動車株式会社 sliding member
JP7290611B2 (en) * 2020-07-20 2023-06-13 トヨタ自動車株式会社 Automobile sliding member
JP7290612B2 (en) 2020-07-20 2023-06-13 トヨタ自動車株式会社 sliding member
JP7558033B2 (en) 2020-11-06 2024-09-30 カヤバ株式会社 Grease composition and method for lubricating sliding parts using said grease composition

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JP6511128B2 (en) 2019-05-15
US20180057768A1 (en) 2018-03-01
EP3269794A4 (en) 2018-08-01
WO2016143807A1 (en) 2016-09-15
CN107406800A (en) 2017-11-28
CN107406800B (en) 2021-06-01
JPWO2016143807A1 (en) 2017-12-21
EP3269794B1 (en) 2021-07-28

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