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CN116601273A - Grease composition for constant velocity joints - Google Patents

Grease composition for constant velocity joints Download PDF

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Publication number
CN116601273A
CN116601273A CN202080107504.7A CN202080107504A CN116601273A CN 116601273 A CN116601273 A CN 116601273A CN 202080107504 A CN202080107504 A CN 202080107504A CN 116601273 A CN116601273 A CN 116601273A
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CN
China
Prior art keywords
mass
grease composition
composition
component
oil
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.)
Pending
Application number
CN202080107504.7A
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Chinese (zh)
Inventor
今野忠明
山口智彦
吉生·E
克里斯托夫·林德拉尔
约阿希姆·韦特
关富夫
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.)
GKN Driveline International GmbH
Kyodo Yushi Co Ltd
Original Assignee
GKN Driveline International GmbH
Kyodo Yushi Co Ltd
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Filing date
Publication date
Application filed by GKN Driveline International GmbH, Kyodo Yushi Co Ltd filed Critical GKN Driveline International GmbH
Publication of CN116601273A publication Critical patent/CN116601273A/en
Pending legal-status Critical Current

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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
    • 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
    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
    • 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
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M115/00—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof
    • C10M115/08—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof containing nitrogen
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/10—Thio derivatives
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/02—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic oxygen-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
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    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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    • C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
    • 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
    • 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
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
    • C10M2219/046—Overbased sulfonic acid salts
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    • 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
    • C10M2219/068—Thiocarbamate metal salts
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
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    • 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
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/76—Reduction of noise, shudder, or vibrations
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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    • 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

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

Abstract

根据本发明，提供一种等速万向节用润滑脂组合物，其包含：(a)基础油、(b)二脲系增稠剂、(c)二硫代氨基甲酸钼、(d)二硫代磷酸钼、(e)高碱性磺酸钙、(f)中性磺酸锌。本发明的组合物在高温下的耐久性和振动抑制方面优异。According to the present invention, there is provided a grease composition for constant velocity joints comprising: (a) base oil, (b) diurea thickener, (c) molybdenum dithiocarbamate, (d) Molybdenum dithiophosphate, (e) overbased calcium sulfonate, (f) neutral zinc sulfonate. The composition of the present invention is excellent in durability at high temperature and vibration suppression.

Description

Grease composition for constant velocity universal joint
Technical Field
The present invention relates to a grease composition for constant velocity joints.
Background
In automobiles, the environmental protection (CO reduction) is achieved from that of vehicles 2 ) In order to reduce weight and secure living space, FF vehicles are widely used, and Constant Velocity Joints (CVJ) which are essential for power transmission of FF vehicles are widely used.
In this CVJ type, since the telescopic constant velocity joint rotates in an angular state, the components inside the joint undergo complex rolling sliding motions with each other. At this time, a sliding resistance is generated in the axial direction due to friction of the internal components, and if the sliding resistance is large, vibration or sound may be caused.
With recent increases in the output of automobile engines, the lubrication conditions in the constant velocity universal joint shift to the high surface pressure side. As the lubrication condition increases, abrasion tends to occur in the constant velocity joint, and there is a problem that durability (peeling resistance) is lowered and vibration is deteriorated.
In addition, in the constant velocity universal joint, durability at high temperature is required to be ensured.
As grease excellent in vibration-suppressing performance, there has been proposed grease for constant velocity joints, which is obtained by mixing molybdenum dithiocarbamate and molybdenum dithiophosphate as additives to urea grease or by mixing zinc dithiophosphate with these organo molybdenum compounds (see patent document 1); a grease composition for constant velocity joints, which contains a base oil, a urea thickener, molybdenum dithiocarbamate, calcium sulfonate, and a phosphorothioate (see patent document 2). In addition, in recent years, further quietness has been demanded, and there has been proposed a grease composition for constant velocity joints, which contains a mixture of at least 1 of molybdenum dialkyldithiocarbamates and molybdenum dialkyldithiophosphates or molybdenum diaryldithiophosphates, and ashless zinc dithiocarbamates or zinc dithiocarbamates, in a grease comprising a base oil and a thickener of a urea compound (see patent document 3); a composition for constant velocity joints comprising a base oil, a diurea thickener, molybdenum sulfide dialkyldithiocarbamate, zinc sulfonate, a sulfur-phosphorus extreme pressure agent, and a vegetable oil or fat (see patent document 4).
As a grease in which durability is also considered, a composition for constant velocity joints containing a base oil, a thickener, montan wax, zinc sulfonate, and molybdenum sulfide dialkyldithiocarbamate has been proposed (see patent document 5).
As described above, even the conventional grease composition for constant velocity joints exhibits excellent performance in vibration suppression, and durability is studied at normal temperature, but on the other hand, it is said that sufficient study is not necessarily performed in the problem of durability at high temperature.
Prior art literature
Patent literature
Patent document 1: japanese patent publication No. 5-79280
Patent document 2: japanese patent laid-open No. 11-172276
Patent document 3: japanese patent laid-open No. 2009-235416
Patent document 4: japanese patent laid-open No. 2011-37950
Patent document 5: international publication No. 2014/0954797
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object of the present invention is to provide a grease composition excellent in durability and vibration suppression properties even at high temperatures.
Means for solving the problems
1. A grease composition for constant velocity joints, comprising: (a) a base oil, (b) a diurea-based thickener, (c) molybdenum dithiocarbamate, (d) molybdenum dithiophosphate, (e) overbased calcium sulfonate, and (f) neutral zinc sulfonate.
2. The grease composition according to claim 1, wherein the content of the component (f) is 0.1 to 10% by mass based on the total mass of the composition.
3. The grease composition according to claim 1 or 2, wherein the content of the component (f) is 0.5 to 5% by mass based on the total mass of the composition.
4. A grease composition according to any one of claims 1 to 3, wherein the content of component (f) is 0.8 to 3 mass% based on the total mass of the composition.
5. The grease composition according to any one of claims 1 to 4, wherein the content of component (e) is 0.1 to 10% by mass based on the total mass of the composition.
6. The grease composition according to any one of claims 1 to 5, wherein the content of component (e) is 0.2 to 5% by mass based on the total mass of the composition.
7. The grease composition according to any one of claims 1 to 6, wherein the content of component (e) is 1.2 to 3.5% by mass based on the total mass of the composition.
8. The grease composition according to any one of claims 1 to 7, wherein component (b) is an aliphatic diurea thickener.
9. A constant velocity joint in which the grease composition according to any one of claims 1 to 8 is enclosed.
Effects of the invention
According to the present invention, a grease composition excellent in durability even at high temperatures and excellent in vibration suppression can be provided.
Detailed Description
(a) Base oil
The base oil that can be used in the composition of the present invention is not particularly limited, and mineral oil and/or synthetic oil can be used. Examples of the synthetic oil include synthetic hydrocarbon oils such as polyalphaolefins, and phenyl ether oils such as pentaphenyl ether, tetraphenyl ether, monoalkyl tetraphenyl ether, dialkyl tetraphenyl ether, and alkyl diphenyl ether; alkylbenzene oil; ester oils such as monoester oil, diester oil, polyol ester oil and aromatic ester oil; polyethylene glycol oil, silicone oil, fluorine oil, ionic liquid, and the like.
As the base oil of the present invention, mineral oil is preferably used from the viewpoint of cost. Base oils comprising mineral oil as a main component and synthetic oil mixed therein may also be used.
In the case where the base oil of the present invention is a mixed oil of a mineral oil and a synthetic oil, the mineral oil is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 90 to 100% by mass, based on the total mass of the base oil.
The base oils of the invention preferably have a kinematic viscosity at 100℃of from 5 to 30mm 2 And/s, more preferably 7 to 20mm 2 And/s. At less than 5mm 2 At/s, there is a tendency that an oil film is not formed in the constant velocity joint and durability becomes insufficient, and the thickness exceeds 30mm 2 At/s, durability tends to be lowered due to heat generation in the CVJ.
From the viewpoint of fluidity, the content of the base oil is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 80 to 100% by mass, based on the total mass of the composition.
(b) Diurea thickener
The diurea thickener that can be used in the present invention is represented by the following formula (1).
R 1 -NHCONH-R 2 -NHCONH-R 3 (1)
Wherein R is 2 Is a C6-15 2-valent aromatic hydrocarbon group as R 2 Toluene diisocyanate or diphenylmethane diisocyanate is preferred, and diphenylmethane diisocyanate is more preferred. R is R 1 R is R 3 The two groups may be the same or different and are a linear or branched alkyl group having 6 to 30 carbon atoms, an aryl group having 6 or 7 carbon atoms, or a cyclohexyl group.
As the diurea compound of formula (1), R is preferable 1 And R is 3 Aliphatic diurea compounds each of which is an alkyl group having 6 to 30 carbon atoms. The aliphatic diurea compound can be obtained by reacting a diisocyanate with an aliphatic monoamine.
In addition, R is also preferable as the diurea compound of formula (1) 1 And R is 3 Any one of which is an alkyl group having 6 to 30 carbon atoms and the other of which is a cyclohexyl groupAlicyclic aliphatic diurea compounds. Since the alicyclic aliphatic diurea compound is obtained by reacting a diisocyanate with an alicyclic monoamine and an aliphatic monoamine, it is actually a mixture containing an aliphatic diurea compound and an alicyclic diurea compound in addition to the alicyclic aliphatic diurea compound.
R 1 And R is 3 When any one of the groups is a cyclohexyl group, the other group is preferably a linear alkyl group having 8 or 18 carbon atoms. In this case, the ratio of the cyclohexyl group to the total of the cyclohexyl group and the alkyl group is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, from the viewpoint of fluidity.
As the thickener of the present invention, an aliphatic diurea compound is preferable from the viewpoint of durability.
R in formula (1) is particularly preferred 1 And R is 3 Are all alkyl groups having 8 to 30 carbon atoms, R 2 A diurea compound which is diphenylmethane diisocyanate.
R in formula (1) is particularly preferred 1 And R is 3 Straight-chain alkyl groups each having 8 or 18 carbon atoms, R 2 A diurea compound which is diphenylmethane diisocyanate.
The grease composition of the present invention preferably has a consistency of 250 to 400, more preferably 280 to 370, and still more preferably 310 to 340. In this specification, the term "consistency" means a 60-time mixed consistency. The consistency can be measured in accordance with JIS K2220.7.
The content of the thickener is preferably 10 mass% or less, more preferably 5 to 10 mass%, and still more preferably 6 to 7 mass% based on the total mass of the composition, so that the consistency of the grease composition can be set to the above range.
(c) Molybdenum dithiocarbamate (MoDTC)
Molybdenum dithiocarbamates that can be used in the present invention are a generic term for molybdenum-based substances in organometallic-based load-resistant additives and are generally widely used as extreme pressure additives. A preferable example of molybdenum dithiocarbamate can be represented by the following formula (2).
[R 4 R 5 N-CS-S] 2 -Mo 2 O m S n (2)
Wherein R is 4 And R is 5 Each of which may be the same or different, independently represents a linear or branched alkyl group having 1 to 24 carbon atoms, preferably 3 to 18 carbon atoms, m is 0 to 3, n is 4 to 1, and m+n=4.
Molybdenum dithiocarbamates exist in both oil-soluble molybdenum dithiocarbamates (i.e., liquid at room temperature (about 25 ℃) and non-oil-soluble molybdenum dithiocarbamates (i.e., solid at room temperature). The molybdenum dithiocarbamate of the present invention can be used as a combination of oil-soluble molybdenum dithiocarbamate and non-oil-soluble molybdenum dithiocarbamate, but is preferable because of excellent durability and heat generation suppression and vibration suppression in CVJ.
The content of the component (b) in the grease composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and even more preferably 1 to 3% by mass, based on the total mass of the composition, from the viewpoint of vibration suppression. In the case where the oil-soluble molybdenum dithiocarbamate and the non-oil-soluble molybdenum dithiocarbamate are included, the use of the oil-soluble molybdenum dithiocarbamate and the non-oil-soluble molybdenum dithiocarbamate in a mass ratio of preferably 4:6 to 10:0, more preferably 6:4 to 8:2 is preferable because vibration suppression is excellent.
(d) Molybdenum dithiophosphate (MoDTP)
Preferable examples of the molybdenum dithiophosphate used in the present invention include those represented by the following formula (3).
[(R 6 O)(R 7 O)PS-S] 2 Mo 2 O m S n
(wherein R is 6 R is R 7 Each independently represents an alkyl group having 1 to 24 carbon atoms or an aryl group having 6 to 30 carbon atoms, m is 0 to 3, n is 4 to 1, and m+n=4. )
From the viewpoint of durability, the content of the component (d) in the grease composition of the present invention is preferably 0.1 mass% or more, more preferably 0.1 to 5 mass%, and still more preferably 0.2 to 2 mass% based on the total mass of the composition.
(e) Overbased calcium sulfonates
The overbased calcium sulfonate used in the present invention is a calcium sulfonate having a base number of 200mgKOH/g or more. From the viewpoint of durability, the base number is preferably 300mgKOH/g or more, more preferably 300 to 500mgKOH/g. In the present invention, the base number is a value measured in accordance with JIS K2501.
As component (e), a calcium salt of a sulfonic acid having an organic group as a lipophilic group can be used. Examples of such organic sulfonic acids include petroleum sulfonic acid obtained by sulfonation of aromatic hydrocarbon components in a lubricating oil fraction, synthetic sulfonic acids such as dinonylnaphthalene sulfonic acid and heavy alkylbenzenesulfonic acid, and the like. As component (e), calcium sulfonate which becomes highly alkaline by calcium carbonate is preferable. Calcium carbonate-containing calcium alkyl aromatic sulfonate is particularly preferred.
From the viewpoint of durability, the content of the component (e) in the grease composition of the present invention is preferably 0.1 to 10 mass%, more preferably 0.2 to 5 mass%, and even more preferably 1.2 to 3.5 mass% based on the total mass of the composition.
(f) Neutral zinc sulfonate
The neutral zinc sulfonate used in the present invention has a base number of 10mgKOH/g or less.
The sulfonic acid constituting the zinc sulfonate is the same as the sulfonic acid described for the component (e).
As neutral zinc sulfonate, zinc dinonyl naphthalene sulfonate is preferable.
From the viewpoint of durability, the content of neutral zinc sulfonate in the grease composition of the present invention is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, and even more preferably 0.8 to 3 mass%, based on the total mass of the composition.
The total of the component (e) and the component (f) is preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass, based on the total mass of the composition, and therefore, the heat resistance is excellent.
When the mass ratio of the component (e) to the component (f) is (e): (f) =9:1 to 1:9, the durability is excellent, and thus it is preferable. More preferably, (e): (f) =8:2 to 3:7, and still more preferably, (e): (f) =7:3 to 4:6. In particular, when the total of the component (e) and the component (f) is 1 to 3% by mass based on the total mass of the composition and the mass ratio of the component (e) to the component (f) is (e): f) =7:3 to 4:6, the durability and heat resistance are excellent, and thus, the composition is preferable.
The grease composition of the present invention may contain additives commonly used in greases, as required. The content of these additives is usually 0.1 to 5% by mass, preferably 0.5 to 3% by mass, based on the total amount of the grease composition.
Examples of such additives include antioxidants such as amine-based, phenol-based, quinoline-based, sulfur-based, and zinc dithiophosphate; rust inhibitors such as zinc-based, carboxylic acid-based (in particular, dibasic acid salts such as sodium sebacate, sodium azelate, sodium suberate) and amine-based; wear-resistant agents such as vulcanized grease, vulcanized olefin, phosphate, phosphite, acid-type phosphate amine salt and the like; oily agents such as fatty acids, fatty acid esters, and phosphoric acid esters; solid lubricants such as graphite, polytetrafluoroethylene (PTFE), zinc oxide, and the like.
From the viewpoint of heat resistance, it is preferable to contain an antioxidant.
As the antioxidant, an amine-based antioxidant is preferable, and an alkyldiphenylamine is more preferable. The content of the antioxidant is preferably 0.1 mass% or more, more preferably 0.1 to 2 mass%, and still more preferably 0.2 to 1 mass%, based on the total mass of the composition.
The composition of the present invention preferably comprises only (a) a base oil, (b) a diurea thickener, (c) molybdenum dithiocarbamate, (d) molybdenum dithiophosphate, (e) overbased calcium sulfonate, (f) neutral zinc sulfonate, and (g) an antioxidant.
In this case, the content of each component is preferably (a) 80 to 100% by mass, (b) 6 to 7% by mass, (c) 1 to 3% by mass, (d) 0.2 to 2% by mass, (e) 0.5 to 3% by mass, (f) 0.8 to 3% by mass, and (g) 0.2 to 1% by mass based on the total mass of the composition.
The composition of the present invention preferably further contains (a) a base oil, (b) an aliphatic diurea thickener, (c) molybdenum dithiocarbamate, (d) molybdenum dithiophosphate, (e) a highly basic calcium sulfonate having a base number of 300mgKOH/g or more, which contains calcium carbonate, (f) a neutral zinc sulfonate, and (g) an amine antioxidant.
In this case, the content of each component is preferably (a) 80 to 100% by mass, (b) 6 to 7% by mass, (c) 1 to 3% by mass, (d) 0.2 to 2% by mass, (e) 0.5 to 3% by mass, (f) 0.8 to 3% by mass, and (g) 0.2 to 1% by mass based on the total mass of the composition.
The composition of the present invention preferably further comprises (a) a base oil, (b) R in the above formula (1) 1 And R is 3 Are each a linear alkyl group having 8 carbon atoms and R 2 An aliphatic diurea thickener which is diphenylmethane diisocyanate, (c) a mixture of oil-soluble molybdenum dithiocarbamate and non-oil-soluble molybdenum dithiocarbamate, (d) molybdenum dithiophosphate, (e) an alkyl aromatic calcium sulfonate having a base number of 300 to 500mgKOH/g containing calcium carbonate, (f) zinc dinonylnaphthalene sulfonate having a base number of 10mgKOH/g or less, and (g) an alkyl diphenylamine.
In this case, the content of each component is preferably (a) 80 to 100% by mass, (b) 6 to 7% by mass, (c) 1 to 3% by mass, (d) 0.2 to 2% by mass, (e) 0.5 to 3% by mass, (f) 0.8 to 3% by mass, and (g) 0.2 to 1% by mass based on the total mass of the composition.
The grease composition of the present invention is suitable for use in constant velocity joints. Among them, the application to a telescopic constant velocity universal joint, particularly a tripod constant velocity universal joint, a double-effect compensation constant velocity universal joint, and particularly an inner disk constant velocity universal joint is preferable because of excellent durability and vibration suppression.
Examples
Production of grease compositions of examples 1 to 7 and comparative examples 1 to 4
After reacting 1 mol of 4', 4-diphenylmethane diisocyanate with 2 mol of octylamine in base oil and heating and cooling, additives were blended in the proportions shown in table 1 or table 2, and kneaded by a 3-roll mill to prepare a grease composition having a mixed consistency 315. The numerical values in tables 1 and 2 represent mass% based on the total mass of the grease composition unless otherwise specified.
Production of grease composition of comparative example 5
The grease composition of comparative example 5 was prepared according to the description of example C4 of japanese patent No. 6470851.
The components used in the preparation of the grease composition are as follows.
< base oil >)
Mineral oil (kinematic viscosity at 100 ℃ C.: 12.4 mm) 2 /s)
Mineral oil + synthetic oil: poly-alpha-olefins (kinematic viscosity at 100 ℃ C.: 12.0 mm) 2 /s)
< additive >)
MoDTC (non-oil soluble): molybdenum dithiocarbamate (manufactured by ADEKASAKURALUBE 600, manufactured by ADEKA)
MoDTC (non-oil soluble): molybdenum dithiocarbamate (Molyvan A, vanderbilt, comparative example 5)
MoDTC (oil-soluble): molybdenum dithiocarbamate (manufactured by ADEKA SAKURALUBE 525, manufactured by ADEKA)
MoDTP: molybdenum dithiophosphate (manufactured by ADEKASAKURALUBE 300, manufactured by ADEKA)
MoDTP: molybdenum dithiophosphate (Molyvan L, vanderbilt, comparative example 5)
Calcium sulfonate (overbased): calcium salt of alkyl aromatic sulfonic acid ((LUBRIZOL 5283C, the product of the-Lubrizol Corporation, base number 375 mgKOH/g)
Zinc sulfonate (neutral): zinc dinonylnaphthalene sulfonate (NA-SUL ZS, manufactured by KING INDUSTRIES, base number 5 mgKOH/g)
Antioxidant(s)
Evaluation of durability
(1) SRV test (high load)
Test conditions
Test speed: 11.9mm/s (frequency: 3.3Hz, stroke: 1.8 mm)
Test temperature: 90 DEG C
Load: 5.5GPa
Test piece: ball (diameter 17.5mm, SUJ-2)/plate (SUJ-2, surface roughness Rz0.5 μm)
[ evaluation criterion ]
Excellent (acceptable): friction coefficient of less than 0.08
(qualified): the friction coefficient exceeds 0.08 and is less than 0.10
Delta (pass): the friction coefficient exceeds 0.10 and is less than 0.12
X (reject): occurrence of seizing or friction coefficient exceeding 0.12
(2) SRV test (Low load)
Test conditions
Test speed: 2.0mm/s (frequency: 3.3Hz, stroke: 0.3 mm)
Test temperature: 95 DEG C
Load: 2.1GPa
Test piece: ball (diameter 17.5mm, SUJ-2)/plate (SUJ-2, surface roughness Rz5 μm)
[ evaluation criterion ]
(qualified): friction coefficient of 0.10 or less
Delta (pass): the friction coefficient exceeds 0.10 and is less than 0.14
X (reject): occurrence of seizing or friction coefficient exceeding 0.14
Evaluation of vibration suppression
(1) TE77 test
The TE77 tester is a vibratory frictional wear tester under sliding conditions. It is reported that vibration using a constant velocity universal joint as a vibration source has a relationship with a friction coefficient under vibration conditions measured by a TE77 tester (japanese patent application laid-open No. 2010-065194). Therefore, vibration suppression in the constant velocity universal joint was evaluated using a TE77 tester.
[ test conditions ]
Test speed: test temperature of 16mm/s (frequency: 10Hz, stroke: 0.8 mm): 40 DEG C
Load: 1.2GPa
Test piece: ball (diameter 17.5mm, SUJ-2)/plate (SCM) [ evaluation criterion ]
(qualified): friction coefficient of 0.07 or less
Delta (pass): the friction coefficient exceeds 0.07 and is less than 0.10
X (reject): coefficient of friction exceeding 0.10
[ comprehensive evaluation ]
(qualified): the test results are all qualified
X (reject): one or more failed test results are shown in tables 1 and 2.
TABLE 1
TABLE 2

Claims (9)

1.一种等速万向节用润滑脂组合物，其包含：(a)基础油、(b)二脲系增稠剂、(c)二硫代氨基甲酸钼、(d)二硫代磷酸钼、(e)高碱性磺酸钙、(f)中性磺酸锌。1. A grease composition for constant velocity joints, comprising: (a) base oil, (b) diurea thickener, (c) molybdenum dithiocarbamate, (d) dithiocarbamate Molybdenum phosphate, (e) overbased calcium sulfonate, (f) neutral zinc sulfonate. 2.根据权利要求1所述的润滑脂组合物，其中，以组合物的总质量为基准，成分(f)的含量为0.1～10质量％。2. The grease composition according to claim 1, wherein the content of the component (f) is 0.1 to 10% by mass based on the total mass of the composition. 3.根据权利要求1或2所述的润滑脂组合物，其中，以组合物的总质量为基准，成分(f)的含量为0.5～5质量％。3. The grease composition according to claim 1 or 2, wherein the content of the component (f) is 0.5 to 5% by mass based on the total mass of the composition. 4.根据权利要求1～3中任一项所述的润滑脂组合物，其中，以组合物的总质量为基准，成分(f)的含量为0.8～3质量％。4. The grease composition according to any one of claims 1 to 3, wherein the content of the component (f) is 0.8 to 3% by mass based on the total mass of the composition. 5.根据权利要求1～4中任一项所述的润滑脂组合物，其中，以组合物的总质量为基准，成分(e)的含量为0.1～10质量％。5. The grease composition according to any one of claims 1 to 4, wherein the content of the component (e) is 0.1 to 10% by mass based on the total mass of the composition. 6.根据权利要求1～5中任一项所述的润滑脂组合物，其中，以组合物的总质量为基准，成分(e)的含量为0.2～5质量％。6. The grease composition according to any one of claims 1 to 5, wherein the content of the component (e) is 0.2 to 5% by mass based on the total mass of the composition. 7.根据权利要求1～6中任一项所述的润滑脂组合物，其中，以组合物的总质量为基准，成分(e)的含量为1.2～3.5质量％。7. The grease composition according to any one of claims 1 to 6, wherein the content of the component (e) is 1.2 to 3.5% by mass based on the total mass of the composition. 8.根据权利要求1～7中任一项所述的润滑脂组合物，其中，成分(b)为脂肪族二脲系增稠剂。8. The grease composition according to any one of claims 1 to 7, wherein component (b) is an aliphatic diurea thickener. 9.一种等速万向节，其封入有权利要求1～8中任一项所述的润滑脂组合物。9. A constant velocity joint filled with the grease composition according to any one of claims 1 to 8.
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