US20080318819A1 - Grease composition and bearing - Google Patents

Grease composition and bearing Download PDF

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Publication number
US20080318819A1
US20080318819A1 US12/206,297 US20629708A US2008318819A1 US 20080318819 A1 US20080318819 A1 US 20080318819A1 US 20629708 A US20629708 A US 20629708A US 2008318819 A1 US2008318819 A1 US 2008318819A1
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Prior art keywords
grease composition
percent
mass
bearing
thickener
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US12/206,297
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Osamu SAITA
Yuji Onuki
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Kyodo Yushi Co Ltd
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Kyodo Yushi Co Ltd
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Assigned to KYODO YUSHI CO., LTD. reassignment KYODO YUSHI CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ONUKI, YUJI, SAITA, OSAMU
Publication of US20080318819A1 publication Critical patent/US20080318819A1/en
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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
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
    • C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/24—Aldehydes; Ketones
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
    • F16C33/30—Parts of ball or roller bearings
    • F16C33/66—Special parts or details in view of lubrication
    • F16C33/6603—Special parts or details in view of lubrication with grease as lubricant
    • F16C33/6633—Grease properties or compositions, e.g. rheological properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • 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
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/0406—Ethers; Acetals; Ortho-esters; Ortho-carbonates used as base material
    • 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
    • C10M2207/127—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 polycarboxylic
    • C10M2207/1276—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 polycarboxylic used as thickening agent
    • 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
    • C10M2207/128—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 containing hydroxy groups; Ethers thereof
    • C10M2207/1285—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 containing hydroxy groups; Ethers thereof used as thickening agents
    • 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
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • 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
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/289—Partial esters containing free hydroxy groups
    • 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
    • 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
    • C10M2215/18—Containing nitrogen-to-nitrogen bonds, e.g. hydrazine
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • 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
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • 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
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066—Thiocarbamic type compounds
    • 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
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • 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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C2300/00—Application independent of particular apparatuses
    • F16C2300/40—Application independent of particular apparatuses related to environment, i.e. operating conditions
    • F16C2300/54—Application independent of particular apparatuses related to environment, i.e. operating conditions high-temperature

Definitions

  • the present invention relates to a grease composition
  • a grease composition comprising a base oil, a thickener, and a specific antioxidant.
  • the present invention relates to a grease composition which is suitable for use in a ball bearing exposed to high temperatures and of which lubricant life is improved; and a bearing which encapsulates the grease composition therein.
  • the properties required for a grease composition to improve lubricant life thereof are thermo-oxidative stability and the like, and various proposals for improving the properties of the grease composition have hitherto been made.
  • An abrasive resistant extreme pressure composition with improved antioxidative property which composition comprises (a) methylenebis(di-n-butyldithiocarbamate) and (b) a diphenylamine derivative of tolutriazol or benzotriazol, wherein the ratio (a):(b) in percent by mass is in the range of about 4:1 to about 50:1; and a lubricant comprising the extreme pressure composition have been proposed (see, for example, Patent Document 2).
  • a lithium grease composition which comprises (a) a lubricating oil, (b) at least one compound selected from the group consisting of a lithium salt of C 12 -C 24 aliphatic monocarboxylic acid comprising at least one hydroxyl group, a dilithium salt of C 2 -C 12 aliphatic dicarboxylic acid, and a lithium salt of C 12 -C 24 aliphatic monocarboxylic acid, and (c) at least one compound selected from the group consisting of 3-(N-salicyloyl)amino-1,2,4-triazol and decamethylene-dicarboxylic acid-disalicyloylhydrazide, has been proposed (see, for example, Patent Document 3).
  • Patent Document 1 JP-B-03-31760
  • Patent Document 2 JP-T-2005-509732
  • Patent Document 3 Japanese Patent No. 2936084
  • An object of the present invention is to provide a grease composition which is suitable for a ball bearing exposed to high temperatures and exhibits stable lubricity for a prolonged period of time. That is, the object of the present invention is to provide a grease composition which is excellent in thermo-oxidative stability and lubricant life.
  • Another object of the present invention is to provide a bearing which encapsulates the grease composition.
  • the present inventors intensively studied in order to attain the above-described object to improve thermo-oxidative stability and lubricant life by using a base oil, a thickener, and a specific antioxidant; and preferably by further using a metal inactivator, thereby completing the grease composition which is suitable for a ball bearing exposed to high temperatures and exhibits stable lubricity for a prolonged period of time.
  • the present invention provides the following grease composition and a bearing.
  • a grease composition comprising (a) a base oil, (b) a thickener, (c) a compound having alkylthiocarbamoyl group of the general formula (1), and an amine-ketone condensate-based antioxidant.
  • R 1 , R 2 , R 3 , R 4 are independently C 1 -C 20 alkyl, and X is S, S—S, S—CH 2 —S, S—CH 2 CH 2 —S, or S—CH 2 CH 2 CH 2 —S) 2.
  • the grease composition according to the above-item 1 or 2 further comprising (e) a metal inactivator. 4.
  • the grease composition according to any one of the above-items 1 to 3 which comprises (a) 50 or more percent by mass of the base oil, (b) 1-30 percent by mass of the thickener, (c) 0.1-10 percent by mass of the compound having alkylthiocarbamoyl group of the general formula (1), and (d) 0.1-10 percent by mass of the amine-ketone condensate-based antioxidant based on the entire grease composition. 5.
  • the grease composition according to any one of the above-items 2 to 4 comprising (e) 0.1-10 percent by mass of the metal inactivator. 6.
  • the grease composition of the present invention is very useful in that it shows improved thermo-oxidative stability and lubricant life, and is suitable for use in a ball bearing exposed to high temperatures and exhibits stable lubricity for a prolonged period of time.
  • thermo-oxidative stability and lubricant life are improved, which is suitable for use in a ball bearing exposed to high temperatures and which exhibits stable lubricity for a prolonged period of time by using a specific antioxidant and a metal inactivator, which grease composition is encapsulated in the bearing together with a base oil.
  • the present invention is very useful.
  • the present invention was made based on the discovery that thermo-oxidative stability and lubricant life are drastically improved by using a specific antioxidant, or by further using a specific metal inactivator, more preferably by specifying the mixing ratio of these.
  • the reason why the grease composition of the present invention is excellent in lubricant life under the condition of high temperature is thought as follows. That is, the function of each component is well exhibited by using the antioxidant particularly selected or by further using a metal inactivator in the grease composition comprising a base oil and a thickener, and excellent thermo-oxidative stability, lubricity and lubricant life are given to the grease composition exposed to high temperatures also by virtue of the proper formulation of the grease composition.
  • the base oil used for the grease composition of the present invention is preferably one comprising at least one of the groups of mineral oils and/or synthetic oils.
  • the synthetic oil include ester synthetic oils typified by esters and polyol esters; synthetic hydrocarbon oils typified by poly( ⁇ -olefin) and polybutene; ether synthetic oils typified by alkyl diphenyl ethers and polypropyleneglycol; and silicone oils, fluorinated oils, and the like.
  • the synthetic oil is not restricted as long as it can be used in a lubricating oil and a grease composition.
  • the thickener used in the grease composition of the present invention is at least one selected from the group consisting of metal soap thickeners; urea thickeners typified by diurea; inorganic thickeners typified by organic clay and silica; organic thickeners typified by polytetrafluoroethylene and melamine cyanurate.
  • Preferred examples of the thickener are those selected from the group consisting of lithium soaps and lithium complex soaps, and most preferably lithium soaps, for example lithium stearate and lithium 12-hydroxystearate.
  • the antioxidant used in the grease composition of the present invention is (c) the compound (ATC) having the alkylthiocarbamoyl group of the general formula (1); and (d) the amine-ketone condensate-based antioxidant.
  • Specific examples of the compound (ATC) having an alkylthiocarbamoyl group of the general formula (1) include methylenebis(di-n-butyldithiocarbamate), bis(dimethylcarbamoyl)monosulfide, bis(dimethylcarbamoyl)disulfide, bis(dibutylcarbamoyl)disulfide, bis(diamylcarbamoyl)disulfide, bis(dioctylcarbamoyl)disulfide, and the like.
  • Examples of (d) the amine-ketone condensate-based antioxidant include TMDQ (2,2,4-trimethyl-1,2-dihydroquinoline polymer) of the formula (2) designated by JIS K6220-3 code, ETMDQ (6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline) of the formula (3), ADPAL (the reaction mixture of diphenylamine and acetone), and the like.
  • n is an integer of 1 to 10, preferably 1 to 6, most preferably 2 to 3.
  • ETMDQ 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline
  • the grease composition of the present invention preferably comprises a metal inactivator.
  • the metal inactivator include oxalic acid derivatives, salicylic acid derivatives, hydrazine derivatives and the like. Especially, examples thereof include 3-(N-salicyloyl)amino-1,2,4-triazol of the formula (4), decamethylenecarboxylic acid disalicyloylhydrazide (MCSH) of the formula (5), N,N-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine of the formula (6), isophthalic acid bis(2-phenoxypropionylhydrazide), N-formyl-N′-salicyloylhydrazine, 2,2-oxamidebis-[ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], oxalyl-bis-benzylidene-hydrazide
  • the grease composition of the present invention comprises (a) 50 or more percent by mass, preferably 60 or more percent by mass of the base oil, (b) 1-30 percent by mass, preferably 5-20 percent by mass of the thickener, (c) 0.1-10 percent by mass, preferably 0.5-5 percent by mass of the compound having alkylthiocarbamoyl group of the general formula (1), and (d) 0.1-10 percent by mass, preferably 0.5-5 percent by mass of the amine-ketone condensate-based antioxidant based on the entire grease composition.
  • 0.1-10 percent by mass, preferably 0.5-5 percent by mass of the metal inactivator may be added.
  • the present invention also provides a bearing which encapsulates the above-described grease composition.
  • the ether oil (alkyl diphenyl ether: kinematic viscosity 40° C. 100 mm 2 /s, 100° C. 12.5 mm 2 /s), the ester oil (pentaerythritol ester: kinematic viscosity 40° C. 102 mm 2 /s, 100° C. 12.9 mm 2 /S), and 1:1 mixture thereof were used as the base oil.
  • the test was carried out according to the method based on ASTM D 3336. The test was conducted at 150° C., and lubricant life is expressed in terms of hour (h).
  • An SPCC steel plate sizing 60 ⁇ 80 ⁇ 1 mm is coated with a grease having a thickness of 2 mm, and the total acid value is measured after the prescribed time (500 h) passed at the prescribed temperature (160° C.).
  • Comparative Example 4 having the same composition as in Example 1 except that the component (d) was not contained, the change in acid value was larger, thermo-oxidative stability was poorer, and bearing-lubrication life was shorter.
  • Comparative Example 5 having the same composition as in Example 1 except that the component (c) was not contained, the change in acid value was larger, thermo-oxidative stability was poorer, and bearing-lubrication life was shorter.
  • Comparative Example 1 having the same composition as in Example 2 except that the conventional amine antioxidant was contained instead of components (c) and (d), the change in acid value was larger, thermo-oxidative stability was poorer, and bearing-lubrication life was shorter.

Abstract

A grease composition which is suitable for a ball bearing exposed to high temperatures and exhibits stable lubricity for a prolonged period of time, and a bearing which encapsulates the grease composition are provided.
A grease composition comprising (a) a base oil, (b) a thickener, (c) a compound having alkylthiocarbamoyl group of the general formula (1), and an amine-ketone condensate-based antioxidant. A grease composition further comprising (e) a metal inactivator.
Figure US20080318819A1-20081225-C00001
(wherein R1, R2, R3, R4 are independently C1-C20 alkyl, and X is S, S—S, S—CH2—S, S—CH2CH2—S, or S—CH2CH2CH2—S)

Description

    TECHNICAL FIELD
  • The present invention relates to a grease composition comprising a base oil, a thickener, and a specific antioxidant. Particularly, the present invention relates to a grease composition which is suitable for use in a ball bearing exposed to high temperatures and of which lubricant life is improved; and a bearing which encapsulates the grease composition therein.
    • BACKGROUND ART
  • The properties required for a grease composition to improve lubricant life thereof are thermo-oxidative stability and the like, and various proposals for improving the properties of the grease composition have hitherto been made.
  • Improved lubricants in fatigue life have been proposed, in which a compound having alkylthiocarbamoyl group and a molybdenum compound are added to a lubricant base material, or an ester compound is further added thereto, thereby improving fatigue life (see, for example, Patent Document 1). An abrasive resistant extreme pressure composition with improved antioxidative property, which composition comprises (a) methylenebis(di-n-butyldithiocarbamate) and (b) a diphenylamine derivative of tolutriazol or benzotriazol, wherein the ratio (a):(b) in percent by mass is in the range of about 4:1 to about 50:1; and a lubricant comprising the extreme pressure composition have been proposed (see, for example, Patent Document 2). Additionally, a lithium grease composition which comprises (a) a lubricating oil, (b) at least one compound selected from the group consisting of a lithium salt of C12-C24 aliphatic monocarboxylic acid comprising at least one hydroxyl group, a dilithium salt of C2-C12 aliphatic dicarboxylic acid, and a lithium salt of C12-C24 aliphatic monocarboxylic acid, and (c) at least one compound selected from the group consisting of 3-(N-salicyloyl)amino-1,2,4-triazol and decamethylene-dicarboxylic acid-disalicyloylhydrazide, has been proposed (see, for example, Patent Document 3).
  • However, even if the grease composition using these additives is employed in a roll bearing exposed to high temperatures, thermo-oxidative stability and lubricant life are insufficient, and a grease composition satisfying users has not been obtained at present.
  • Patent Document 1: JP-B-03-31760
  • Patent Document 2: JP-T-2005-509732
  • Patent Document 3: Japanese Patent No. 2936084
    • DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
  • An object of the present invention is to provide a grease composition which is suitable for a ball bearing exposed to high temperatures and exhibits stable lubricity for a prolonged period of time. That is, the object of the present invention is to provide a grease composition which is excellent in thermo-oxidative stability and lubricant life.
  • Another object of the present invention is to provide a bearing which encapsulates the grease composition.
    • Means for Solving the Problems
  • The present inventors intensively studied in order to attain the above-described object to improve thermo-oxidative stability and lubricant life by using a base oil, a thickener, and a specific antioxidant; and preferably by further using a metal inactivator, thereby completing the grease composition which is suitable for a ball bearing exposed to high temperatures and exhibits stable lubricity for a prolonged period of time.
  • The present invention provides the following grease composition and a bearing.
  • 1. A grease composition comprising (a) a base oil, (b) a thickener, (c) a compound having alkylthiocarbamoyl group of the general formula (1), and an amine-ketone condensate-based antioxidant.
  • Figure US20080318819A1-20081225-C00002
  • (wherein R1, R2, R3, R4 are independently C1-C20 alkyl, and X is S, S—S, S—CH2—S, S—CH2CH2—S, or S—CH2CH2CH2—S)
    2. The grease composition according to the above-item 1, wherein the thickener is at least one selected from the group consisting of lithium soaps and lithium complex soaps.
    3. The grease composition according to the above-item 1 or 2, further comprising (e) a metal inactivator.
    4. The grease composition according to any one of the above-items 1 to 3, which comprises (a) 50 or more percent by mass of the base oil, (b) 1-30 percent by mass of the thickener, (c) 0.1-10 percent by mass of the compound having alkylthiocarbamoyl group of the general formula (1), and (d) 0.1-10 percent by mass of the amine-ketone condensate-based antioxidant based on the entire grease composition.
    5. The grease composition according to any one of the above-items 2 to 4, comprising (e) 0.1-10 percent by mass of the metal inactivator.
    6. A bearing which encapsulates the grease composition according to any one of the above-items 1 to 5.
    • EFFECTS OF THE INVENTION
  • The grease composition of the present invention is very useful in that it shows improved thermo-oxidative stability and lubricant life, and is suitable for use in a ball bearing exposed to high temperatures and exhibits stable lubricity for a prolonged period of time.
  • A satisfactory proposal has not been made on a grease composition of which thermo-oxidative stability and lubricant life are improved, which is suitable for use in a ball bearing exposed to high temperatures and which exhibits stable lubricity for a prolonged period of time by using a specific antioxidant and a metal inactivator, which grease composition is encapsulated in the bearing together with a base oil. Thus, the present invention is very useful.
  • The present invention was made based on the discovery that thermo-oxidative stability and lubricant life are drastically improved by using a specific antioxidant, or by further using a specific metal inactivator, more preferably by specifying the mixing ratio of these.
  • The reason why the grease composition of the present invention is excellent in lubricant life under the condition of high temperature is thought as follows. That is, the function of each component is well exhibited by using the antioxidant particularly selected or by further using a metal inactivator in the grease composition comprising a base oil and a thickener, and excellent thermo-oxidative stability, lubricity and lubricant life are given to the grease composition exposed to high temperatures also by virtue of the proper formulation of the grease composition.
    • BEST MODE FOR CARRYING OUT THE INVENTION
  • The present invention will be explained in detail below.
  • The base oil used for the grease composition of the present invention is preferably one comprising at least one of the groups of mineral oils and/or synthetic oils. Examples of the synthetic oil include ester synthetic oils typified by esters and polyol esters; synthetic hydrocarbon oils typified by poly(α-olefin) and polybutene; ether synthetic oils typified by alkyl diphenyl ethers and polypropyleneglycol; and silicone oils, fluorinated oils, and the like. The synthetic oil is not restricted as long as it can be used in a lubricating oil and a grease composition.
  • The thickener used in the grease composition of the present invention is at least one selected from the group consisting of metal soap thickeners; urea thickeners typified by diurea; inorganic thickeners typified by organic clay and silica; organic thickeners typified by polytetrafluoroethylene and melamine cyanurate. Preferred examples of the thickener are those selected from the group consisting of lithium soaps and lithium complex soaps, and most preferably lithium soaps, for example lithium stearate and lithium 12-hydroxystearate.
  • The antioxidant used in the grease composition of the present invention is (c) the compound (ATC) having the alkylthiocarbamoyl group of the general formula (1); and (d) the amine-ketone condensate-based antioxidant.
  • Specific examples of the compound (ATC) having an alkylthiocarbamoyl group of the general formula (1) include methylenebis(di-n-butyldithiocarbamate), bis(dimethylcarbamoyl)monosulfide, bis(dimethylcarbamoyl)disulfide, bis(dibutylcarbamoyl)disulfide, bis(diamylcarbamoyl)disulfide, bis(dioctylcarbamoyl)disulfide, and the like.
  • Examples of (d) the amine-ketone condensate-based antioxidant include TMDQ (2,2,4-trimethyl-1,2-dihydroquinoline polymer) of the formula (2) designated by JIS K6220-3 code, ETMDQ (6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline) of the formula (3), ADPAL (the reaction mixture of diphenylamine and acetone), and the like.
  • TMDQ; 2,2,4-trimethyl-1,2-dihydroquinoline polymer
  • Figure US20080318819A1-20081225-C00003
  • wherein n is an integer of 1 to 10, preferably 1 to 6, most preferably 2 to 3.
    ETMDQ; 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline
  • Figure US20080318819A1-20081225-C00004
  • The grease composition of the present invention preferably comprises a metal inactivator. Examples of the metal inactivator include oxalic acid derivatives, salicylic acid derivatives, hydrazine derivatives and the like. Especially, examples thereof include 3-(N-salicyloyl)amino-1,2,4-triazol of the formula (4), decamethylenecarboxylic acid disalicyloylhydrazide (MCSH) of the formula (5), N,N-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine of the formula (6), isophthalic acid bis(2-phenoxypropionylhydrazide), N-formyl-N′-salicyloylhydrazine, 2,2-oxamidebis-[ethyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], oxalyl-bis-benzylidene-hydrazide and the like.
    • 3-(N-salicyloyl)amino-1,2,4-triazol
  • Figure US20080318819A1-20081225-C00005
  • MCSH; decamethylenecarboxylic acid disalicyloylhydrazide
  • Figure US20080318819A1-20081225-C00006
    • N,N-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine
  • Figure US20080318819A1-20081225-C00007
  • The grease composition of the present invention comprises (a) 50 or more percent by mass, preferably 60 or more percent by mass of the base oil, (b) 1-30 percent by mass, preferably 5-20 percent by mass of the thickener, (c) 0.1-10 percent by mass, preferably 0.5-5 percent by mass of the compound having alkylthiocarbamoyl group of the general formula (1), and (d) 0.1-10 percent by mass, preferably 0.5-5 percent by mass of the amine-ketone condensate-based antioxidant based on the entire grease composition. To the mixture of (a)-(d), 0.1-10 percent by mass, preferably 0.5-5 percent by mass of the metal inactivator may be added.
  • The present invention also provides a bearing which encapsulates the above-described grease composition.
  • The present invention will be further described in detail below by way of Examples, however, the present invention is not restricted to the following Examples. Any modification without departing from the spirit of the invention is within the scope of the present invention.
    • EXAMPLES 1. Test Greases
  • The grease compositions of Examples 1 to 8 and Comparative Examples 1 to 5 were prepared according to the formulation shown in Tables 1 and 2. The amount of each component is based on percent by mass.
    • 2. Method for Preparing Grease
  • Into 467.5 g of the base oil, 82.5 g of 12-hydroxystearic acid was added, and the resulting mixture was heated to the temperature (80-90° C.) at which the mixture became a clear liquid. To this mixture, a solution prepared by adding 11.9 g of lithium hydroxide monohydrate to 60 g of water and heating the obtained mixture to dissolve the solute, was added. The saponification of 12-hydroxystearic acid was carried out under vigorous stirring to obtain lithium 12-hydroxystearate. To the obtained mixture, 26 g of azelaic acid was then added, and stirring was continued until the mixture became a uniform solution. To this mixture, a solution prepared by adding 11.9 g of lithium hydroxide monohydrate to 60 g of water and heating the obtained mixture to dissolve the solute, was added. The saponification of azelaic acid was carried out under vigorous stirring. The saponification was terminated after confirming that the absorption of the unreacted fatty acid was not found by infrared spectroscopic analysis at about 60 minutes after the start of the reaction. In the subsequent heating step, the contents were slowly heated to 200° C. When the temperature of the contents reached 200° C., 400.2 g of the residual base oil was added the contents, followed by cooling them to room temperature. Lithium complex grease was obtained by mixing the contents using a three-roll mill twice. The amount of the final product was 1000 g.
  • The ether oil (alkyl diphenyl ether: kinematic viscosity 40° C. 100 mm2/s, 100° C. 12.5 mm2/s), the ester oil (pentaerythritol ester: kinematic viscosity 40° C. 102 mm2/s, 100° C. 12.9 mm2/S), and 1:1 mixture thereof were used as the base oil.
    • 3. Analytical Method and Evaluation Test Method Bearing-Lubrication Life Test
  • The test was carried out according to the method based on ASTM D 3336. The test was conducted at 150° C., and lubricant life is expressed in terms of hour (h).
    • Thin Film Test at High Temperature
  • An SPCC steel plate sizing 60×80×1 mm is coated with a grease having a thickness of 2 mm, and the total acid value is measured after the prescribed time (500 h) passed at the prescribed temperature (160° C.).
    • 4. Results of Evaluation Test
  • The test results of the grease compositions of Examples 1 to 6 and Comparative Examples 1 to 5 are shown in Tables 1 and 2.
  • TABLE 1
    Example Example Example Example Example Example Example Example
    1 2 3 4 5 6 7 8
    (a)ether oil 41.75 41.5 40.25 40.0 39.5 38.5 83.5 —
    (a)ester oil 41.75 41.5 40.25 40.0 39.5 38.5 — 83.5
    (b)thickener 13.0 13.0 13.0 13.0 13.0 13.0 13.0 13.0
    (c)ATC*1 0.5 0.5 0.5 1.0 1.0 2.0 0.5 0.5
    (d)TMDQ 2.0 2.0 4.0 4.0 4.0 5.0 2.0 2.0
    (e)MCSH — 0.5 1.0 — 1.0 2.0 — —
    Amine — — — — — — — —
    antioxidant*2
    Phenol 1.0 1.0 1.0 2.0 2.0 1.0 1.0 1.0
    antioxidant*3
    Bearing- 1310 2750 1530 1780 2370 2260 1220 1190
    lubrication
    life (150° C.)h
    Evaluation ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘
    results
    Total acid 0.04 0.05 0.05 0.04 0.07 0.06 0.06 0.05
    value before
    thin film test
    at high
    temperature
    (mgKOH/g)
    Total acid .019 0.15 0.18 0.16 0.12 0.15 0.17 0.18
    value after
    thin film test
    at high
    temperature
    (mgKOH/g)
    Change in 0.15 0.10 0.13 0.12 0.05 0.09 0.11 0.13
    acid value
    (mgKOH/g)
    Evaluation ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘
    results on
    change in
    acid value
    Total ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘
    evaluation
    *1ATC: methylenebis(di-n-butyldithiocarbamate)
    *2Amine antioxidant: N-phenyl-1,1,3,3-tetramethylbutylnaphthalene-1-amine
    *3Phenol antioxidant: pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate
  • TABLE 2
    Comparative Comparative Comparative Comparative Comparative
    Example 1 Example 2 Example 3 Example 4 Example 5
    (a)ether oil 41.75 — 84.0 42.75 42.0
    (a)ester oil 41.75 84.0 — 42.75 42.0
    (b)thickener 13.0 13.0 13.0 13.0 13.0
    (c)ATC*1 — — — 0.5 —
    (d)TMDQ — — — — 2.0
    (e)MCSH 0.5 — — — —
    Amine 2.0 2.0 2.0
    antioxidant*2
    Phenol 1.0 1.0 1.0 1.0 1.0
    antioxidant*3
    Bearing- 860 590 410 630 780
    lubrication life
    (150° C.) h
    Evaluation x x x x x
    results
    Total acid 0.05 0.06 0.06 0.06 0.05
    value before
    thin film test at
    high
    temperature
    (mgKOH/g)
    Total acid 1.90 2.20 10.6 1.26 0.68
    value after thin
    film test at
    high
    temperature
    (mgKOH/g)
    Change in acid 1.85 2.14 10.54 1.20 0.63
    value
    (mgKOH/g)
    Evaluation x x x x x
    results on
    change in acid
    value
    Total x x x x x
    evaluation
    • Evaluation Criteria
  • Change in acid value (mgKOH/g) o: 0.02 or less, x; over 0.20
    Bearing-lubrication life o: pass, over 1000 h, x: fail, 1000 or less
    • Total Evaluation
  • o: Both of change in acid value and bearing-lubrication life passed the criteria (O).
  • x: Change in Acid Value and/or bearing-lubrication life failed(x).
    • Test Results
  • The grease compositions of Examples 1, 4, 7 and 8 comprising components (a)-(d), and Examples 2, 3, 5 and 6 comprising components (a)-(e) showed smaller changes in acid value, and were excellent in thermo-oxidative stability. All the grease compositions attained criteria of bearing-lubrication life, and passed the criteria of the total evaluation.
  • On the other hand, in Comparative Example 4 having the same composition as in Example 1 except that the component (d) was not contained, the change in acid value was larger, thermo-oxidative stability was poorer, and bearing-lubrication life was shorter.
  • In Comparative Example 5 having the same composition as in Example 1 except that the component (c) was not contained, the change in acid value was larger, thermo-oxidative stability was poorer, and bearing-lubrication life was shorter.
  • In Comparative Example 1 having the same composition as in Example 2 except that the conventional amine antioxidant was contained instead of components (c) and (d), the change in acid value was larger, thermo-oxidative stability was poorer, and bearing-lubrication life was shorter.
  • In Comparative Example 2 in which the ester oil was used as the base oil and the conventional amine antioxidant was contained instead of components (c)-(e), the change in acid value was larger, thermo-oxidative stability was poorer, and bearing-lubrication life was shorter.
  • In Comparative Example 3 in which the ether oil was used as the base oil and the conventional amine antioxidant was contained instead of components (c)-(e), the change in acid value was larger, thermo-oxidative stability was poorer, and bearing-lubrication life was shortest.

Claims (9)

1. A grease composition comprising (a) a base oil, (b) a thickener, (c) a compound having alkylthiocarbamoyl group of the general formula (1), and an amine-ketone condensate-based antioxidant.
Figure US20080318819A1-20081225-C00008
(wherein R1, R2, R3, R4 are independently C1-C20 alkyl, and X is S, S—S, S—CH2—S, S—CH2CH2—S, or S—CH2CH2CH2—S)
2. The grease composition according to claim 1, wherein said thickener is at least one selected from the group consisting of lithium soaps and lithium complex soaps.
3. The grease composition according to claim 1, further comprising (e) a metal inactivator.
4. The grease composition according to claim 2, further comprising (e) a metal inactivator.
5. The grease composition according to claim 1, which comprises (a) 50 or more percent by mass of said base oil, (b) 1-30 percent by mass of said thickener, (c) 0.1-10 percent by mass of said compound having alkylthiocarbamoyl group of the general formula (1), and (d) 0.1-10 percent by mass of said amine-ketone condensate-based antioxidant based on the entire grease composition.
6. The grease composition according to claim 2, which comprises (a) 50 or more percent by mass of said base oil, (b) 1-30 percent by mass of said thickener, (c) 0.1-10 percent by mass of said compound having alkylthiocarbamoyl group of the general formula (1), and (d) 0.1-10 percent by mass of said amine-ketone condensate-based antioxidant based on the entire grease composition.
7. The grease composition according to claim 5, comprising (e) 0.1-10 percent by mass of said metal inactivator.
8. The grease composition according to claim 6, comprising (e) 0.1-10 percent by mass of said metal inactivator.
9. A bearing comprising said grease composition according to claim 1 encapsulated therein.
US12/206,297 2006-03-08 2008-09-08 Grease composition and bearing Abandoned US20080318819A1 (en)

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US20140038865A1 (en) * 2010-11-05 2014-02-06 Nok Klueber Co., Ltd. Lubricant composition
US20140336090A1 (en) * 2012-01-18 2014-11-13 Kyodo Yushi Co., Ltd. Grease composition and bearing
US8969269B2 (en) * 2011-06-24 2015-03-03 Chevron U.S.A. Inc. Lubricating grease composition
US20180230396A1 (en) * 2015-08-10 2018-08-16 Ntn Corporation Grease composition and grease-sealed rolling bearing
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JP5411457B2 (en) * 2008-06-16 2014-02-12 昭和シェル石油株式会社 Lubricant composition
WO2013037456A1 (en) * 2011-09-15 2013-03-21 Klüber Lubrication München Se & Co. Kg High-temperature grease
JP2016014087A (en) * 2014-07-01 2016-01-28 Ntn株式会社 Lubricant composition and lubricant composition sealed bearing
JP6097414B2 (en) * 2016-01-13 2017-03-15 協同油脂株式会社 Grease composition and bearing
JP7328663B2 (en) * 2018-07-31 2023-08-17 株式会社ハーベス Grease composition, multi-base oil grease composition, lubricant composition, polypropylene resin member

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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SAITA, OSAMU;ONUKI, YUJI;REEL/FRAME:021496/0193

Effective date: 20080901

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION