WO2024161460A1 - グリース組成物および転がり軸受 - Google Patents

グリース組成物および転がり軸受 Download PDF

Info

Publication number
WO2024161460A1
WO2024161460A1 PCT/JP2023/002875 JP2023002875W WO2024161460A1 WO 2024161460 A1 WO2024161460 A1 WO 2024161460A1 JP 2023002875 W JP2023002875 W JP 2023002875W WO 2024161460 A1 WO2024161460 A1 WO 2024161460A1
Authority
WO
WIPO (PCT)
Prior art keywords
grease composition
grease
zinc
carboxylic acid
bearing
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.)
Ceased
Application number
PCT/JP2023/002875
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
高原 加奈子 新谷
浩二 吉崎
智喬 中川
寛征 齊藤
一希 伊佐
沙耶 門脇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyodo Yushi Co Ltd
JTEKT Corp
Original Assignee
Kyodo Yushi Co Ltd
JTEKT 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 Kyodo Yushi Co Ltd, JTEKT Corp filed Critical Kyodo Yushi Co Ltd
Priority to CN202380092431.2A priority Critical patent/CN120584170A/zh
Priority to DE112023005706.0T priority patent/DE112023005706T5/de
Priority to JP2024574072A priority patent/JPWO2024161460A1/ja
Priority to PCT/JP2023/002875 priority patent/WO2024161460A1/ja
Publication of WO2024161460A1 publication Critical patent/WO2024161460A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/047—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M2207/126—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 monocarboxylic
    • 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
    • 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
    • C10M2215/10—Amides of carbonic or haloformic acids
    • C10M2215/102—Ureas; Semicarbazides; Allophanates
    • C10M2215/1026—Ureas; Semicarbazides; Allophanates used as thickening 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
    • C10M2217/00—Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04—Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/045—Polyureas; Polyurethanes
    • C10M2217/0453—Polyureas; Polyurethanes 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
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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—Form in which the lubricant is applied to the material being lubricated semi-solid; greasy

Definitions

  • the present disclosure relates to a grease composition and a rolling bearing.
  • Bearings for automobile engine auxiliaries and electrical equipment include mainly bearings for electromagnetic clutches, bearings for alternators, bearings for idler pulleys, etc.
  • Grease compositions are used for these bearings.
  • Grease compositions used in these bearings are required to have a long bearing lubrication life and excellent resistance to white layer peeling in high temperature environments.
  • Patent Document 1 proposes a grease composition containing a base oil, a thickener, a rust inhibitor, and zinc dialkyldithiophosphate. Since this grease composition contains zinc dialkyldithiophosphate, when the grease composition is used in a rolling bearing, a reaction film is formed by the zinc dialkyldithiophosphate, and the reaction film can suppress the occurrence of white layer peeling in the rolling bearing.
  • the grease composition of the present disclosure includes a base oil, a thickener, a zinc dialkyldithiophosphate, a rust inhibitor, and a carboxylic acid.
  • the rust inhibitor includes four types of agents: calcium sulfonate, zinc carboxylate, ester additives, and zinc sulfonate.
  • the number of carboxy groups of the carboxylic acid is 1 or more and 7 ⁇ 10 ⁇ 6 or less per gram of the grease composition excluding the carboxylic acid.
  • the rolling bearing of the present disclosure includes an inner ring, an outer ring, rolling elements, and grease,
  • the grease comprises the grease composition of the present disclosure.
  • the grease composition of the present disclosure is likely to exhibit the effect of suppressing the occurrence of white layer peeling.
  • the rolling bearing of the present disclosure is less susceptible to white layer peeling and has a long life.
  • FIG. 1 is a cross-sectional view showing a ball bearing as an example of a rolling bearing according to the present disclosure.
  • a grease composition according to one embodiment of the present disclosure includes a base oil, a thickener, a zinc dialkyldithiophosphate, a rust inhibitor, and a carboxylic acid
  • the rust inhibitor includes four types of agents: calcium sulfonate, zinc carboxylate, ester additives, and zinc sulfonate.
  • the number of carboxy groups of the carboxylic acid is 1 or more and 7 ⁇ 10 ⁇ 6 or less per gram of the grease composition excluding the carboxylic acid.
  • the grease composition of (1) above contains zinc dialkyldithiophosphate and has 1 or more and 7 ⁇ 10 mol or less of carboxyl groups of the carboxylic acid per gram of the grease composition excluding the carboxylic acid, and therefore can reliably suppress the occurrence of white layer peeling.
  • the grease composition of (1) above contains a rust inhibitor
  • the rust inhibitors include four types: calcium sulfonate, zinc carboxylate, ester-based additives, and zinc sulfonate.
  • the rolling bearing packed with the grease made of the grease composition is prevented from rusting without impairing the white layer peeling resistance, and therefore the rolling bearing can be suitably used as a bearing used in a water-exposed environment, such as a bearing for an electromagnetic clutch or a bearing for an idler pulley.
  • the grease composition according to (1) further comprises an antioxidant,
  • the preferred antioxidants include naphthylamines.
  • the base oil preferably contains an alkyl diphenyl ether.
  • the thickener preferably contains diurea.
  • a rolling bearing according to one embodiment of the present disclosure includes an inner ring, an outer ring, rolling elements, and grease,
  • the grease comprises any one of the grease compositions (1) to (4) above.
  • the rolling bearing is provided with grease made of the grease composition, and therefore is less susceptible to white layer peeling and has a long life.
  • the rolling bearing according to the embodiment of the present disclosure is a ball bearing packed with grease made of the grease composition according to the embodiment of the present disclosure.
  • FIG. 1 is a cross-sectional view showing a ball bearing according to one embodiment of the present disclosure.
  • the ball bearing 1 comprises an inner ring 2, an outer ring 3 provided radially outward of the inner ring 2, a plurality of balls 4 as rolling elements provided between the inner ring 2 and the outer ring 3, and an annular cage 5 that holds the balls 4.
  • the ball bearing 1 also comprises seals 6 on each of a first side and a second side in the axial direction.
  • grease G made of the grease composition according to an embodiment of the present disclosure is sealed in the annular region 7 between the inner ring 2 and the outer ring 3.
  • the inner ring 2 has an inner raceway 21 on its outer periphery along which the balls 4 roll.
  • the outer ring 3 has an outer raceway 31 on its inner periphery along which the balls 4 roll.
  • a plurality of balls 4 are interposed between the inner raceway surface 21 and the outer raceway surface 31 and roll on these inner raceway surface 21 and outer raceway surface 31.
  • Grease G enclosed in region 7 is present at the contact points between balls 4 and inner raceway surface 21 of inner ring 2, and at the contact points between balls 4 and outer raceway surface 31 of outer ring 3.
  • Grease G is enclosed so as to occupy 20 to 40% by volume of the space surrounded by inner ring 2, outer ring 3, and seal 6, excluding balls 4 and cage 5.
  • the seal 6 is an annular member including an annular metal ring 6a and an elastic member 6b fixed to the metal ring 6a.
  • the radially outer portion of the seal 6 is fixed to the outer ring 3, and the lip tip of the radially inner portion of the seal 6 is attached so as to be in sliding contact with the inner ring 2.
  • the seal 6 prevents the enclosed grease G from leaking to the outside.
  • the ball bearing 1 thus configured is filled with grease G, which is made of a grease composition according to an embodiment of the present disclosure, which will be described later. Therefore, the ball bearing 1 filled with grease G is less likely to experience white layer peeling.
  • the grease composition constituting grease G is a grease composition according to an embodiment of the present disclosure, and contains a base oil, a thickener, a zinc dialkyldithiophosphate, a rust inhibitor, and a carboxylic acid.
  • the number of carboxy groups of the carboxylic acid contained in the grease composition is 1 to 7 ⁇ 10 mol per 1 g of the grease composition excluding the carboxylic acid. Therefore, by filling a bearing with grease G consisting of the grease composition, the bearing can reliably enjoy the effect of suppressing white layer peeling.
  • the zinc dialkyldithiophosphate is an extreme pressure agent.
  • the zinc dialkyldithiophosphate forms a reaction film on the raceway surfaces of the inner and outer rings during rotation of the bearing, thereby preventing the white layer from peeling off.
  • a grease composition containing a carboxylic acid together with zinc dialkyldithiophosphate the formation of a reaction film by zinc dialkyldithiophosphate can be inhibited. It was believed that the formation of a reaction film by zinc dialkyldithiophosphate is inhibited by the carboxyl group of the carboxylic acid adhering to the raceway surfaces of the inner and outer rings, etc.
  • the grease composition contains a carboxylic acid, but the number of carboxy groups of the carboxylic acid is 1 or more and 7 ⁇ 10 ⁇ 6 mol or less per gram of the grease composition excluding the carboxylic acid. Therefore, the grease composition can suppress the occurrence of white layer peeling, even though it contains a carboxylic acid together with a zinc dialkyldithiophosphate. In contrast, when the carboxy group of the carboxylic acid exceeds 7 ⁇ 10 -6 mol per 1 g of the grease composition excluding the carboxylic acid, the grease composition becomes difficult to suppress the occurrence of white layer peeling, despite the inclusion of zinc dialkyldithiophosphate.
  • the amount (number) of carboxyl groups of the carboxylic acid contained in the grease composition can be measured using liquid chromatography mass spectrometry (LC-MS).
  • the carboxylic acid is not particularly limited, and is an organic acid having at least one carboxy group.
  • Examples of the carboxylic acid include saturated fatty acids, unsaturated fatty acids, hydroxy acids, and aromatic carboxylic acids.
  • the carboxylic acid is not limited to a monocarboxylic acid, but may be a polycarboxylic acid such as a dicarboxylic acid, tricarboxylic acid, or tetracarboxylic acid having a plurality of carboxy groups in one molecule.
  • the base oil examples include ether oils such as alkyldiphenyl ether (ADE), ester oils, poly- ⁇ -olefins (PAO), polyalkylene glycols, fluorine oils, and silicone oils.
  • ether oils such as alkyldiphenyl ether (ADE), ester oils, poly- ⁇ -olefins (PAO), polyalkylene glycols, fluorine oils, and silicone oils.
  • the preferred base oil is alkyl diphenyl ether (ADE), because the use of alkyl diphenyl ether (ADE) as the base oil of the grease composition is suitable for providing a grease composition with excellent white layer peeling resistance.
  • ADE alkyl diphenyl ether
  • a conventionally known alkyl diphenyl ether used as a base oil for grease for rolling bearings can be used.
  • the alkyl diphenyl ether preferably has a base oil kinematic viscosity of 60 to 200 mm 2 /s at 40° C.
  • the grease composition is suitable for use at high temperatures.
  • the base oil kinematic viscosity (40°C) is less than 60 mm2 /s, the use of the grease composition may cause seizure at high temperatures, and if the base oil kinematic viscosity (40°C) is more than 200 mm2 /s, the use of the grease composition may cause an increase in starting torque at low temperatures.
  • the base oil kinematic viscosity (40° C.) is more preferably 80 to 120 mm 2 /s.
  • the kinematic viscosity of the base oil is a value in accordance with JIS K 2283.
  • a preferred thickener is diurea.
  • a preferred diurea is a diurea represented by the following formula (1): R 1 -NHCONH-R 2 -NHCONH-R 3 ...(1)
  • R 1 and R 3 are each independently an alkyl group represented by -C n H 2n+1 (n is an integer of 8 to 18) or an alicyclic group represented by R 4 -C 6 H 10 - (R 4 is hydrogen, a 2-methyl group, a 3-methyl group, or a 4-methyl group), and R 2 is -(CH 2 ) 6 -, -C 6 H 3 (CH 3 )-, or -C 6 H 4 -CH 2 -C 6 H 4 -.)
  • R 2 is -C 6 H 3 (CH 3 )-
  • a preferred diisocyanate has a methyl group at position 1 and phenylene groups bonded at positions 2,4 or 2,6
  • R 2 is -C 6 H 4 -CH 2 -C 6 H 4 -
  • a preferred diisocyanate has both phenylene groups bonded at para positions.
  • Preferred R 1 and R 3 are —C 18 H 37 and —C 6 H 11 (cyclohexyl group).
  • Preferred R 2 is —C 6 H 4 —CH 2 —C 6 H 4 —.
  • the thickener may consist of one diurea
  • the preferred thickener is a mixture of two or more diureas.
  • the preferred mixture is A mixture of an aliphatic diurea in which R 1 and R 3 in the above formula (1) are both the above alkyl group and an alicyclic diurea in which R 1 and R 3 in the above formula (1) are both the above alicyclic group, or
  • the diurea is a mixture of an alicyclic aliphatic diurea in which one of R 1 and R 3 in the above formula (1) is the above alkyl group and the other is the above alicyclic group, and an aliphatic diurea in which R 1 and R 3 in the above formula (1) are both the above alkyl group and/or an alicyclic diurea in which R 1 and R 3 in the above formula (1) are both the above alicyclic group.
  • diurea in which the functional groups of R1 and R3 are a mixture of an alkyl group and an alicyclic group, is suitable as a thickener for a grease composition that can achieve both high levels of seizure resistance and leakage resistance.
  • the diurea represented by the above formula (1) is a product formed by the reaction of an amine compound with a diisocyanate compound.
  • the amine compound is an aliphatic amine and/or an alicyclic amine.
  • the aliphatic amine is an aliphatic amine having 8 to 18 carbon atoms, and specific examples thereof are selected from octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, and the like.
  • the alicyclic amine is selected from cyclohexylamine, 1-amino-2-methylcyclohexane, 1-amino-3-methylcyclohexane, and 1-amino-4-methylcyclohexane.
  • the diisocyanate compound is selected from hexamethylene diisocyanate (HDI), 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), a mixture of 2,4-TDI and 2,6-TDI, and 4,4'-diphenylmethane diisocyanate (MDI).
  • HDI hexamethylene diisocyanate
  • 2,4-TDI 2,4-toluene diisocyanate
  • 2,6-TDI 2,6-toluene diisocyanate
  • MDI 4,4'-diphenylmethane diisocyanate
  • the amine compound and the diisocyanate compound can be reacted under various conditions.
  • the preferred reaction is in the base oil, since this gives a diurea compound with high uniform dispersibility as a thickener.
  • the reaction between the amine compound and the diisocyanate compound may be carried out by adding a base oil having the diisocyanate compound dissolved therein to a base oil having the amine compound dissolved therein, or by adding a base oil having the amine compound dissolved therein to a base oil having the diisocyanate compound dissolved therein.
  • the temperature and time for the reaction between the amine compound and the diisocyanate compound are not particularly limited, and conditions similar to those usually employed in this type of reaction may be employed.
  • the preferred reaction temperature is from 25°C to 110°C.
  • the preferred reaction time is 0.5 to 2.0 hours from the viewpoints of completing the reaction between the amine compound and the diisocyanate compound and of shortening the production time to efficiently produce the grease.
  • the content of the thickener is 5.00 to 30.00 mass % based on the total mass of the grease composition. If the content of the thickener is too low, grease leakage may occur during use of the bearing, whereas if the content of the thickener is too high, seizure may occur in the bearing using the grease composition.
  • the content of the thickener is more preferably 10.00 to 20.00 mass % relative to the total mass % of the grease composition.
  • ZnDTP zinc dialkyldithiophosphate
  • ZnDTP zinc dialkyldithiophosphate
  • Specific examples of the ZnDTP include compounds represented by the following formula (2).
  • R 5 to R 8 are each independently any one of a primary alkyl group, a secondary alkyl group, and an aryl group.
  • the above ZnDTP is preferably a ZnDTP represented by the above formula (2) in which R 5 to R 8 are each independently a primary alkyl group or a secondary alkyl group having 3 to 8 carbon atoms.
  • a single type of ZnDTP in which R 5 to R 8 are each independently a primary alkyl group or a secondary alkyl group having 3 to 8 carbon atoms may be used alone, or a mixture of ZnDTPs containing multiple types of ZnDTPs having different carbon numbers may be used.
  • the content of the ZnDTP is 2.00 to 14.00 mass % based on the total mass of the grease composition.
  • the ZnDTP content is less than 2.00% by mass, the grease composition cannot ensure sufficient resistance to white layer peeling, whereas when the ZnDTP content is more than 14.00% by mass, the resistance to white layer peeling is not significantly improved compared to when the ZnDTP content is 14.00% by mass.
  • the grease composition further contains a rust inhibitor.
  • the rust inhibitor includes calcium sulfonate, zinc carboxylate, ester additive, and zinc sulfonate.
  • a dense adsorption film is easily formed by the rust inhibitor on the raceway surface of the inner and outer rings and on the surface of the rolling element when the rolling bearing is not rotating, such as when the rolling bearing is stored or stopped.
  • the dense adsorption film by the rust inhibitor is not easily maintained on the raceway surface of the inner and outer rings and on the surface of the rolling element, so that the adsorption film by the rust inhibitor does not easily inhibit the formation of a reaction film of ZnDTP when the bearing is rotating. Therefore, by using a grease composition containing the above-mentioned rust inhibitor, it is possible to achieve both good resistance to white layer peeling and good rust prevention properties for rolling bearings.
  • the calcium sulfonate is not particularly limited as long as it can be used as a rust inhibitor when blended in a grease composition.
  • Specific examples of the calcium sulfonate include calcium sulfonate represented by the following formula (3). [R 9 -SO 3 ] 2 Ca...(3) (In formula (3), R 9 is an alkyl group, an alkenyl group, an alkylnaphthyl group, a dialkylnaphthyl group, an alkylphenyl group, or a high-boiling petroleum fraction, and the alkyl and alkenyl are both linear or branched and have 2 to 22 carbon atoms.)
  • R9 is an alkylphenyl group in which the alkyl group in R9 has 6 to 18 carbon atoms. More preferred R9 is an alkylphenyl group in which the alkyl group has 8 to 18 carbon atoms. Particularly preferred R9 is an alkylphenyl group in which the alkyl group has 10 to 18 carbon atoms.
  • a preferred compound represented by formula (3) is an overbased calcium sulfonate having a base number (in accordance with JIS K 2501) of 50 to 500 mg KOH/g. A more preferred compound is an overbased calcium sulfonate having a base number of 300 to 500 mg KOH/g. The overbased calcium sulfonate contains calcium sulfonate and calcium carbonate.
  • the content of calcium sulfonate is preferably 0.10 to 10.00 mass % based on the total mass of the grease composition.
  • a grease composition having a calcium sulfonate content in this range is suitable for achieving both rust prevention and white layer peeling resistance.
  • a more preferable content of the calcium sulfonate is 0.30 to 4.00 mass % relative to the total mass of the grease composition, from the viewpoint that a grease composition containing this calcium sulfonate is more suitable for achieving both rust prevention properties and white layer peeling resistance.
  • the zinc carboxylate is not particularly limited as long as it can be used as a rust inhibitor when blended in a grease composition.
  • Specific examples of the zinc carboxylate include zinc naphthenate, zinc rosinate, zinc neodecanoate, zinc octoate, zinc stearate, and zinc laurate.
  • the preferred zinc carboxylate is zinc naphthenate.
  • the content of the zinc carboxylate is preferably 0.10 to 10.00 mass % based on the total mass of the grease composition.
  • a grease composition having a zinc carboxylate content in this range is suitable for achieving both rust prevention and white layer peeling resistance.
  • a more preferable content of the zinc carboxylate is 0.10 to 1.00 mass % relative to the total mass of the grease composition, from the viewpoint that a grease composition containing this zinc carboxylate is more suitable for achieving both rust prevention properties and white layer peeling resistance.
  • the ester-based additive is not particularly limited as long as it can be used as a rust inhibitor when blended with the grease composition.
  • Specific examples of the ester-based additives include sorbitan monooleate, sorbitan trioleate, and alkenyl succinate esters.
  • the preferred ester additive is sorbitan trioleate.
  • the content of the ester-based additive is preferably 0.10 to 3.00 mass % based on the total mass of the grease composition.
  • a grease composition having an ester-based additive content in this range is suitable for achieving both rust prevention and white layer peeling resistance.
  • a more preferable content of the ester-based additive is 0.50 to 2.00 mass % relative to the total mass of the grease composition, from the viewpoint that a grease composition containing this ester-based additive is more suitable for achieving both rust prevention properties and white layer peeling resistance.
  • the rust inhibitor may further contain zinc sulfonate.
  • the zinc sulfonate is not particularly limited as long as it can be used as a rust inhibitor when blended in a grease composition.
  • Specific examples of the zinc sulfonate include zinc sulfonate represented by the following formula (4). [R 10 -SO 3 ] 2 Zn... (4)
  • R 10 is an alkyl group, an alkenyl group, an alkylnaphthyl group, a dialkylnaphthyl group, or an alkylphenyl group, and the alkyl and alkenyl are both linear or branched and have 2 to 22 carbon atoms.
  • the preferred zinc sulfonate is a zinc alkylnaphthalene sulfonate.
  • the content of the zinc sulfonate is preferably 0.20 to 10.00 mass % based on the total mass of the grease composition.
  • a grease composition having a zinc sulfonate content in this range is suitable for achieving both rust prevention and white layer peeling resistance.
  • a more preferable content of the zinc sulfonate is 0.50 to 3.00 mass % relative to the total mass of the grease composition, from the viewpoint that a grease composition containing this zinc sulfonate is more suitable for achieving both rust prevention properties and white layer peeling resistance.
  • the preferred upper limit of the content of the rust inhibitor is 15.00 mass% based on the total mass of the grease composition. If the total content of the rust inhibitor exceeds 15.00 mass%, the grease composition containing this rust inhibitor may inhibit the formation of a reaction film that suppresses the peeling of the white layer.
  • the total amount of the rust inhibitor and the extreme pressure agent is preferably 15.00 mass% or less relative to the total mass of the grease composition.
  • the above-mentioned grease composition preferably further contains an antioxidant.
  • the antioxidant is not particularly limited, and any known antioxidant can be used.
  • the antioxidant is preferably an amine-based antioxidant, and more preferably naphthylamine.
  • a grease composition using naphthylamine as the antioxidant has particularly good anti-seizure properties at high temperatures.
  • naphthylamine examples include 1-naphthylamine, phenyl-1-naphthylamine, N-naphthyl-(1,1,3,3-tetramethylbutylphenyl)-1-amine, alkylphenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine, phenyl-2-naphthylamine, and N-[4-(1,1,3,3-tetramethylbutyl)phenyl]-1-naphthylamine.
  • the content of the antioxidant is preferably 0.50 to 5.00 mass % based on the total mass of the grease composition.
  • the antioxidant does not sufficiently suppress the oxidation of the grease composition, whereas when the content of the antioxidant is more than 5.00 mass %, the antioxidant cannot significantly improve the effect of suppressing the oxidation of the grease composition compared to when the content of the antioxidant is 5.00 mass %.
  • the above grease composition may further contain appropriate amounts of additives such as anti-wear agents, dyes, color stabilizers, thickeners, structural stabilizers, metal deactivators, and viscosity index improvers, within the scope of the present disclosure.
  • additives such as anti-wear agents, dyes, color stabilizers, thickeners, structural stabilizers, metal deactivators, and viscosity index improvers, within the scope of the present disclosure.
  • the grease composition of the present disclosure can be used in places where grease lubrication is required, and is preferably used as a grease for rolling bearings, particularly for rolling bearings that require resistance to white layer peeling. Therefore, the grease made of the above grease composition is preferably used as a grease to be filled into bearings for electromagnetic clutches, bearings for alternators, bearings for idler pulleys, and the like.
  • the grease composition is produced, for example, by first preparing a mixture of a base oil and a thickener, then adding the ZnDTP and the like to the resulting mixture, and stirring the mixture with a triple roll mill to disperse the components.
  • the invention of the present disclosure is not limited to the above-described embodiment and can be implemented in other embodiments.
  • the rolling bearing according to the embodiment of the present disclosure is not limited to a ball bearing packed with the grease composition according to the embodiment of the present disclosure.
  • the rolling bearing may be any other rolling bearing, such as a needle roller bearing, a cylindrical roller bearing, or a tapered roller bearing, in which something other than balls is used as the rolling element, so long as the rolling bearing is packed with the grease composition according to the embodiment of the present disclosure.
  • Rust inhibitor A calcium sulfonate: Product name: BRYTON C-400C (manufactured by CHEMTURA CORPORATION, contains 26% by weight of calcium sulfonate as the active ingredient)
  • Rust inhibitor B zinc carboxylate: Product name DAILUBE Z-310 (manufactured by DIC Corporation, contains 20% by weight of zinc naphthenate as the active ingredient)
  • Rust inhibitor C (ester-based additive): Product name: Nonion OP-85R (manufactured by NOF Corporation, containing 100% by weight of sorbitan trioleate as the active ingredient)
  • Rust inhibitor D zinc sulfonate
  • Product name NA-SUL ZS-HT manufactured by KING INDUSTRIES, contains 35% by weight of zinc sulfonate as the active ingredient
  • Zinc dialkyldithiophosphate A Product name: LUBRIZOL 1395 (manufactured by Lubrizol Japan, containing 84% by weight of zinc dialkyldithiophosphate as the active ingredient)
  • Zinc dialkyldithiophosphate B Product name: LUBRIZOL 677A (manufactured by Lubrizol Japan, containing 93% by weight of zinc dialkyldithiophosphate as the active ingredient)
  • ⁇ Carboxylic acid Oleic acid
  • Solution B was prepared by mixing a diisocyanate compound, which is a thickener raw material, in an amount to give a thickener content of 23.00% by mass with half the amount of ADE prepared so that the base oil content was 77.00% by mass, and heating the mixture to 70 to 80°C to dissolve it.
  • the solution A was gradually added to the solution B in a stirred state.
  • the mixture of solution A and solution B was held at 100 to 110°C for 30 minutes to react and generate a product. Thereafter, the product generated by the reaction of the mixture of solution A and solution B was heated to 160 to 180°C and then cooled to become a mixture of base oil and thickener.
  • the mixture of base oil and thickener had a base oil content of 77.00 mass% and a thickener content of 23.00 mass%.
  • the worked penetration (60W) of the base grease was measured using a method in accordance with JIS K 2220-7.
  • the worked penetration of the above base grease was 255.
  • Example 1 To 1 g of the base grease, 5.8 ⁇ 10 ⁇ 6 mol of oleic acid was added, mixed using a mixer, and further dispersed using a three-roll mill to obtain a grease composition.
  • Example 2 To 1 g of the base grease, 6.9 ⁇ 10 ⁇ 6 mol of oleic acid was added, mixed using a mixer, and further dispersed using a three-roll mill to obtain a grease composition.
  • the thickness of the reaction film formed on the surface of the bearing balls and derived from zinc dialkyldithiophosphate was measured using an X-ray photoelectron spectroscopy (XPS) analyzer under the following conditions and evaluated according to the following criteria. Table 1 shows the results.
  • the X-ray photoelectron spectrometer used was a VersaProbe III manufactured by ULVAC-PHI.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
PCT/JP2023/002875 2023-01-30 2023-01-30 グリース組成物および転がり軸受 Ceased WO2024161460A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202380092431.2A CN120584170A (zh) 2023-01-30 2023-01-30 润滑脂组合物和滚动轴承
DE112023005706.0T DE112023005706T5 (de) 2023-01-30 2023-01-30 Schmiermittelzusammensetzung und wälzlager
JP2024574072A JPWO2024161460A1 (https=) 2023-01-30 2023-01-30
PCT/JP2023/002875 WO2024161460A1 (ja) 2023-01-30 2023-01-30 グリース組成物および転がり軸受

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2023/002875 WO2024161460A1 (ja) 2023-01-30 2023-01-30 グリース組成物および転がり軸受

Publications (1)

Publication Number Publication Date
WO2024161460A1 true WO2024161460A1 (ja) 2024-08-08

Family

ID=92146089

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/002875 Ceased WO2024161460A1 (ja) 2023-01-30 2023-01-30 グリース組成物および転がり軸受

Country Status (4)

Country Link
JP (1) JPWO2024161460A1 (https=)
CN (1) CN120584170A (https=)
DE (1) DE112023005706T5 (https=)
WO (1) WO2024161460A1 (https=)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003062657A1 (fr) * 2002-01-21 2003-07-31 Nsk Ltd. Palier de roulement
JP2003342593A (ja) * 2002-05-29 2003-12-03 Nsk Ltd グリース組成物及び転がり軸受
JP2004224823A (ja) * 2003-01-20 2004-08-12 Nsk Ltd グリース組成物及び転動装置
WO2006001309A1 (ja) * 2004-06-23 2006-01-05 Nsk Ltd. 一方向クラッチ内蔵型回転伝達装置
JP2007112920A (ja) * 2005-10-21 2007-05-10 Nsk Ltd グリース組成物、並びにパワステポンプ用転がり軸受及び過給機用転がり軸受
JP2008088386A (ja) * 2006-10-05 2008-04-17 Nsk Ltd グリース組成物及び車両用ハブユニット軸受
JP2014084442A (ja) * 2012-10-26 2014-05-12 Kyodo Yushi Co Ltd グリース組成物
WO2022009841A1 (ja) * 2020-07-06 2022-01-13 株式会社ジェイテクト グリース組成物および転がり軸受

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003062657A1 (fr) * 2002-01-21 2003-07-31 Nsk Ltd. Palier de roulement
JP2003342593A (ja) * 2002-05-29 2003-12-03 Nsk Ltd グリース組成物及び転がり軸受
JP2004224823A (ja) * 2003-01-20 2004-08-12 Nsk Ltd グリース組成物及び転動装置
WO2006001309A1 (ja) * 2004-06-23 2006-01-05 Nsk Ltd. 一方向クラッチ内蔵型回転伝達装置
JP2007112920A (ja) * 2005-10-21 2007-05-10 Nsk Ltd グリース組成物、並びにパワステポンプ用転がり軸受及び過給機用転がり軸受
JP2008088386A (ja) * 2006-10-05 2008-04-17 Nsk Ltd グリース組成物及び車両用ハブユニット軸受
JP2014084442A (ja) * 2012-10-26 2014-05-12 Kyodo Yushi Co Ltd グリース組成物
WO2022009841A1 (ja) * 2020-07-06 2022-01-13 株式会社ジェイテクト グリース組成物および転がり軸受

Also Published As

Publication number Publication date
JPWO2024161460A1 (https=) 2024-08-08
DE112023005706T5 (de) 2025-11-13
CN120584170A (zh) 2025-09-02

Similar Documents

Publication Publication Date Title
EP2540813B1 (en) Grease composition for hub unit bearing equipped with angular contact ball bearing, and hub unit bearing
US6919301B2 (en) Grease composition and rolling apparatus
WO2005080536A1 (ja) グリース組成物及び転動装置
JP2013035882A (ja) グリース組成物
JP2021046557A (ja) グリース組成物を用いた転がり軸受
JPWO2004061058A1 (ja) 自動車電装補機用グリース組成物及び前記グリース組成物を封入した転がり軸受
EP2687584A1 (en) Grease composition
JP7522594B2 (ja) グリース組成物および転がり軸受
JP2018090783A (ja) グリース組成物および転がり軸受
JP7434953B2 (ja) グリース組成物および転がり軸受
JP2004224823A (ja) グリース組成物及び転動装置
WO2024161460A1 (ja) グリース組成物および転がり軸受
JP6480785B2 (ja) グリース組成物
JP2004339448A (ja) グリース組成物、転がり軸受、及び電動モータ
WO2018101432A1 (ja) グリース組成物および転がり軸受
EP4403615B1 (en) Grease composition for vehicular hub unit bearings
JP2006077967A (ja) 一方向クラッチ内蔵型回転伝達装置
TW202441086A (zh) 滾動軸承
JP2008286230A (ja) モータ用転がり軸受
JP7435003B2 (ja) グリース組成物および転がり軸受
WO2022210531A1 (ja) 密封型転がり軸受
JP2021123691A (ja) 潤滑グリース組成物
JP5267074B2 (ja) 正逆回転モータ用転がり軸受ユニット
JP2008285574A (ja) ころ軸受
JP2015229705A (ja) グリース組成物及び転がり軸受

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23919605

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2024574072

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2024574072

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 202380092431.2

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 112023005706

Country of ref document: DE

WWP Wipo information: published in national office

Ref document number: 202380092431.2

Country of ref document: CN

122 Ep: pct application non-entry in european phase

Ref document number: 23919605

Country of ref document: EP

Kind code of ref document: A1