WO2022113239A1 - Grease composition for constant-velocity joint - Google Patents
Grease composition for constant-velocity joint Download PDFInfo
- Publication number
- WO2022113239A1 WO2022113239A1 PCT/JP2020/044030 JP2020044030W WO2022113239A1 WO 2022113239 A1 WO2022113239 A1 WO 2022113239A1 JP 2020044030 W JP2020044030 W JP 2020044030W WO 2022113239 A1 WO2022113239 A1 WO 2022113239A1
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- Prior art keywords
- mass
- grease composition
- component
- composition
- grease
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 239000004519 grease Substances 0.000 title claims abstract description 48
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 claims abstract description 31
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 31
- 239000002199 base oil Substances 0.000 claims abstract description 20
- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 claims abstract description 16
- 239000002562 thickening agent Substances 0.000 claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011575 calcium Substances 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- XMKLTEGSALONPH-UHFFFAOYSA-N 1,2,4,5-tetrazinane-3,6-dione Chemical compound O=C1NNC(=O)NN1 XMKLTEGSALONPH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- -1 urea compound Chemical class 0.000 description 19
- 239000003921 oil Substances 0.000 description 17
- 235000019198 oils Nutrition 0.000 description 17
- 125000000217 alkyl group Chemical group 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 230000001629 suppression Effects 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 239000002480 mineral oil Substances 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- COGHWIKGZJHSAG-UHFFFAOYSA-L zinc;2,3-di(nonyl)naphthalene-1-sulfonate Chemical compound [Zn+2].C1=CC=C2C(S([O-])(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1.C1=CC=C2C(S([O-])(=O)=O)=C(CCCCCCCCC)C(CCCCCCCCC)=CC2=C1 COGHWIKGZJHSAG-UHFFFAOYSA-L 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- 235000010446 mineral oil Nutrition 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010696 ester oil Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- NCXUIEDQTCQZRK-UHFFFAOYSA-L disodium;decanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCCCCCC([O-])=O NCXUIEDQTCQZRK-UHFFFAOYSA-L 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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- C10M115/08—Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof containing nitrogen
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- 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
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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
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- 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
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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
- C10M141/02—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
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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
- C10M141/08—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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- 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
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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
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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—Overbasedsulfonic acid salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- 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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- 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
- C10N2030/76—Reduction of noise, shudder, or vibrations
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/02—Bearings
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- 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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Definitions
- the present invention relates to a grease composition for constant velocity joints.
- FF vehicles In automobiles, FF vehicles have become widespread in terms of weight reduction and securing of living space for the purpose of environmental measures (CO 2 reduction), and constant velocity joints (CVJs), which are indispensable for power transmission of FF vehicles, are widely used. It is used.
- CVJ type the plunging type constant velocity joint rotates in an angled state, so that the parts inside the joint perform complicated rolling and sliding motions. At this time, friction of internal parts causes slide resistance in the axial direction, and if this is large, it may cause vibration or noise.
- the lubrication conditions inside constant velocity joints have shifted to the high surface pressure side.
- a grease for constant velocity joints made by using molybdenum dithiocarbamate and molybdenum dithiophosphate additives in combination with urea grease, or by mixing these organic molybdenum compounds with zinc dithiophosphate (patented).
- a grease composition for a constant velocity joint containing a base oil, a urea-based thickener, molybdenum dithiocarbamate, calcium sulfonate, and thiophosphate has been proposed.
- molybdenum dialkyldithiocarbamate and molybdenum dialkyldithiophosphate or molybdenum dialkyldithiophosphate or grease composed of a base oil and a thickener of a urea compound is used as a grease.
- a grease composition for a constant velocity joint containing at least one of molybdenum diallyl dithiophosphate and a mixture with ashless dithiocarbamate or zinc dithiocarbamate see Patent Document 3
- a base oil, a diurea-based thickener, and sulfurization is used as a grease.
- a composition for a constant velocity joint containing molybdenum dialkyldithiocarbamate, zinc sulfonate, a sulfur-phosphorus extreme pressure agent, and a vegetable oil / fat has also been proposed (see Patent Document 4).
- a composition for a constant velocity joint containing a base oil, a thickener, a montan wax, a zinc sulfonate, and molybdenum dialkyldithiocarbamate sulfide has been proposed. (See Patent Document 5).
- Patent Document 5 As described above, even the grease compositions for constant velocity joints so far have exhibited excellent performance in vibration suppression, and durability has been studied at room temperature, but on the other hand, durability at high temperatures has been investigated. It cannot be said that sufficient consideration has been given to the issues.
- the component (b) is an aliphatic diurea-based thickener. 9. A constant velocity joint in which the grease composition according to any one of claims 1 to 8 is sealed.
- 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.
- the synthetic oil include synthetic hydrocarbon oils such as poly- ⁇ -olefins; phenyl ether oils such as pentaphenyl ethers, tetraphenyl ethers, monoalkyl tetraphenyl ethers, dialkyl tetraphenyl ethers and alkyl diphenyl ether oils; alkylbenzene oils; monoester oils, Examples thereof include ester oils such as diester oils, polyol ester oils and aromatic ester oils; polyglycol oils; silicone oils; fluorine oils; ionic liquids and the like.
- the base oil of the present invention it is preferable to use mineral oil from the viewpoint of cost.
- a base oil containing mineral oil as a main component and mixed with synthetic oil may be used.
- 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, based on the total mass of the base oil. , 90-100% by mass, more preferably.
- the kinematic viscosity of the base oil of the present invention at 100 ° C. is preferably 5 to 30 mm 2 / s, more preferably 7 to 20 mm 2 / s.
- the content of the base oil is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and 80 to 100% by mass, based on the total mass of the composition. Is more preferable.
- R 1 -NHCONH-R 2 -NHCONH-R 3 (1)
- R 2 is a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms, and as R 2 , tolylene diisocyanate or diphenylmethane diisocyanate is preferable, and diphenylmethane diisocyanate is more preferable.
- R 1 and R 3 may be the same or different from each other, 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.
- an aliphatic diurea compound in which both R 1 and R 3 are alkyl groups having 6 to 30 carbon atoms is preferable.
- the aliphatic diurea compound can be obtained by reacting diisocyanate with an aliphatic monoamine.
- an alicyclic aliphatic diurea compound in which one of R 1 and R 3 is an alkyl group having 6 to 30 carbon atoms and the other is a cyclohexyl group is preferable. Since the alicyclic aliphatic diurea compound is obtained by reacting diisocyanate with an alicyclic monoamine and an alicyclic monoamine, in reality, in addition to the alicyclic aliphatic diurea compound, an alicyclic aliphatic diurea compound and an alicyclic monoamine are used. It is a mixture containing a diurea compound.
- R 1 or R 3 is a cyclohexyl group
- the other is preferably a linear alkyl group having 8 or 18 carbon atoms.
- 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.
- an aliphatic diurea compound is preferable from the viewpoint of durability.
- a diurea compound in which any of R 1 and R 3 is an alkyl group having 8 to 30 carbon atoms and R 2 is a diphenylmethane diisocyanate is preferable.
- a diurea compound in which both R 1 and R 3 are linear alkyl groups having 8 or 18 carbon atoms and R 2 is diphenylmethane diisocyanate is preferable.
- the consistency of the grease composition of the present invention is preferably 250 to 400, more preferably 280 to 370, and even more preferably 310 to 340.
- concentration refers to a 60-time mixing consistency. Consistency is JIS K2220 7. Can be measured according to.
- the content of the thickener is preferably 10% by mass or less, preferably 5 to 10% by mass, based on the total mass of the composition so that the consistency of the grease composition can be set in the above range. More preferably, it is more preferably 6 to 7% by mass.
- Molybdenum dithiocarbamate that can be used in the present invention is a general term for organometallic load-bearing additives whose metal group is molybdenum, and is generally widely used as an extreme pressure additive.
- a preferred 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)
- R 4 and R 5 may be the same or different from each other, and independently represent a linear or branched alkyl group having 1 to 24 carbon atoms, preferably 3 to 18 carbon atoms, and m is 0 to 3.
- Molybdenum dithiocarbamate includes oil-soluble molybdenum dithiocarbamate (that is, liquid at room temperature (about 25 ° C.)) and non-oil-soluble molybdenum dithiocarbamate (that is, solid at room temperature). Any of the molybdenum dithiocarbamate of the present invention can be used, but the combination of the oil-soluble molybdenum dithiocarbamate and the non-oil-soluble molybdenum dithiocarbamate is excellent in durability, heat generation suppression in CVJ, and vibration suppression. Therefore, it is preferable.
- the content of the component (b) in the grease composition of the present invention is preferably 0.1 to 10% by mass, preferably 0.5 to 5%, based on the total mass of the composition from the viewpoint of vibration suppression. It is more preferably by mass%, and even more preferably 1 to 3% by mass.
- the mass ratio of the oil-soluble molybdenum dithiocarbamate to the non-oil-soluble molybdenum dithiocarbamate is preferably 4: 6 to 10: 0. It is preferable to use it in a ratio of 6: 4 to 8: 2 because it is excellent in vibration suppression.
- (D) Molybdenum dithiophosphate (MoDTP) Preferred examples of the molybdenum dithiophosphate used in the present invention include those represented by the following formula (3).
- the content of the component (d) in the grease composition of the present invention is preferably 0.1% by mass or more, preferably 0.1 to 5% by mass, based on the total mass of the composition. %, More preferably 0.2 to 2% by mass.
- the hyperbasic calcium sulfonate used in the present invention is a calcium sulfonate having a base value of 200 mgKOH / g or more. From the viewpoint of durability, the base value is preferably 300 mgKOH / g or more, and more preferably 300 to 500 mgKOH / g. In the present invention, the base value is a value measured according to JIS K 2501. As the component (e), a calcium salt of a sulfonic acid having an organic group which is a lipophilic group can be used.
- organic sulfonic acid examples include petroleum sulfonic acid obtained by sulfonated aromatic hydrocarbon component in lubricating oil distillate, synthetic sulfonic acid such as dinonylnaphthalene sulfonic acid and heavy alkylbenzene sulfonic acid. Be done.
- component (e) calcium sulfonate, which is overbasic due to calcium carbonate, is preferable.
- an alkyl aromatic calcium sulfonate containing calcium carbonate is preferred.
- the content of the component (e) in the grease composition of the present invention is preferably 0.1 to 10% by mass, preferably 0.2 to 5% by mass, based on the total mass of the composition. It is more preferably by mass%, and even more preferably 1.2 to 3.5% by mass.
- the neutral zinc sulfonate used in the present invention has a base value of 10 mgKOH / g or less.
- the sulfonic acid constituting the zinc sulfonate is the same as that described for the component (e).
- As the neutral zinc sulfonate zinc dinonylnaphthalenesulfonate is preferable.
- the content of neutral zinc sulfonate in the grease composition of the present invention is preferably 0.1 to 10% by mass, preferably 0.5 to 5% by mass, based on the total mass of the composition. It is more preferably by mass%, and even more preferably 0.8 to 3% by mass.
- the heat resistance is excellent. Therefore, it is preferable.
- the grease composition of the present invention may contain additives usually used for grease, if necessary.
- 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 amine-based, phenol-based, quinoline-based, sulfur-based, and zinc dithiophosphate antioxidants; zinc-based, carboxylic acid-based, and carboxylate-based (particularly sodium sebacate and azeline).
- Dibasic acid salts such as sodium acid and sodium sverate), amine-based rust preventives; abrasion resistant agents such as sulfide oils and fats, sulphide olefins, phosphate esters, phosphite esters, acid phosphate ester amine salts; fatty acids , Fatty agents such as fatty acid esters and phosphate esters; solid lubricants such as graphite, polytetrafluoroethylene (PTFE) and zinc oxide.
- an antioxidant an amine-based antioxidant is preferable, and alkyldiphenylamine is more preferable.
- the content of the antioxidant is preferably 0.1% by mass or more, more preferably 0.1 to 2% by mass, and 0.2 to 1% by mass based on the total mass of the composition. % Is more preferable.
- the composition of the present invention includes (A) Base oil (b) Diurea-based thickener (c) Molybdenum dithiocarbamate (d) Molybdenum dithiophosphate (e) Perbasic calcium sulfonate (f) Neutral zinc sulfonate (g) It consists only of an antioxidant. Is preferable.
- the content of each component at this time is 80 to 100% by mass in (a), 6 to 7% by mass in (b), and 1 to 3% by mass in (c), based on the total mass of the composition.
- (D) is 0.2 to 2% by mass
- (e) is 0.5 to 3% by mass
- (f) is 0.8 to 3% by mass
- (g) is 0.2 to 1% by mass. Is preferable.
- composition of the present invention also (A) Base oil (b) Fat group diurea-based thickener (c) Molybdenum dithiocarbamate (d) Molybdenum dithiophosphate (e) Fluorobasic calcium sulfonate (f) containing calcium carbonate and having a base value of 300 mgKOH / g or more. It preferably contains a neutral zinc sulfonate (g) amine-based antioxidant.
- the content of each component at this time is 80 to 100% by mass in (a), 6 to 7% by mass in (b), and 1 to 3% by mass in (c), based on the total mass of the composition.
- D) is 0.2 to 2% by mass
- (e) is 0.5 to 3% by mass
- (f) is 0.8 to 3% by mass
- (g) is 0.2 to 1% by mass. Is preferable.
- composition of the present invention also (A) Base oil (b) In the above formula (1), any of R 1 and R 3 is a linear alkyl group having 8 carbon atoms, and R 2 is a diphenylmethane diisocyanate, which is an aliphatic diurea-based thickener ( c) Mixture of oil-soluble molybdenum dithiocarbamate and non-oil-soluble molybdenum dithiocarbamate (d) Molybdenum dithiophosphate (e) Alkyl aromatic calcium sulfonate (f) base value containing calcium carbonate and having a base value of 300 to 500 mgKOH / g It is preferable to contain dinonylnaphthalene sulfonate zinc (g) alkyldiphenylamine of 10 mgKOH / g or less.
- each component at this time is 80 to 100% by mass in (a), 6 to 7% by mass in (b), and 1 to 3% by mass in (c), based on the total mass of the composition.
- (D) is 0.2 to 2% by mass
- (e) is 0.5 to 3% by mass
- (f) is 0.8 to 3% by mass
- (g) is 0.2 to 1% by mass. Is preferable.
- the grease composition of the present invention is applied to constant velocity joints.
- a plunging type constant velocity joint particularly a tripod type constant velocity joint, a double offset type constant velocity joint, and particularly to an inboard side constant velocity joint because it is excellent in durability and vibration suppression.
- the components used for preparing 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- ⁇ -olefin (kinematic viscosity at 100 ° C: 12.0 mm 2 / s) ⁇ Additives> -MoDTC (non-oil soluble): Molybdenum dithiocarbamate (ADEKA Sakuralube 600, made by ADEKA) -MoDTC (non-oil soluble): molybdenum dithiocarbamate (Mollyvan A, manufactured by Vanderbilt, used in Comparative Example 5) -MoDTC (oil-soluble): Molybdenum dithiocarbamate (ADEKA Sakuralube 525, manufactured by ADEKA) -MoDTP: Molybdenum dithiophosphate (ADEKA Sakura Lube 300, made
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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
Description
このCVJの形式の中でプランジング型等速ジョイントは、角度の付いた状態で回転するためにジョイント内部の部品同士が複雑なころがりすべり運動を行う。この時内部部品の摩擦により軸方向にスライド抵抗を生じ、これが大きいと振動や音の原因となる場合がある。
近年の自動車のエンジンの高出力化にともない、等速ジョイント内部における潤滑条件は高面圧側にシフトしている。潤滑条件が高面圧になるほど、等速ジョイント内部においては摩耗が発生しやすい傾向にあり、それによって耐久性(耐フレーキング性)の低下や振動の悪化という問題を引き起こす場合がある。
また、係る等速ジョイントにおいては、高温での耐久性を確保することも求められてきた。 In automobiles, FF vehicles have become widespread in terms of weight reduction and securing of living space for the purpose of environmental measures (CO 2 reduction), and constant velocity joints (CVJs), which are indispensable for power transmission of FF vehicles, are widely used. It is used.
In this CVJ type, the plunging type constant velocity joint rotates in an angled state, so that the parts inside the joint perform complicated rolling and sliding motions. At this time, friction of internal parts causes slide resistance in the axial direction, and if this is large, it may cause vibration or noise.
With the increase in output of automobile engines in recent years, the lubrication conditions inside constant velocity joints have shifted to the high surface pressure side. The higher the lubrication condition, the more likely it is that wear will occur inside the constant velocity joint, which may cause problems such as deterioration of durability (flaking resistance) and deterioration of vibration.
Further, it has been required to ensure durability at high temperatures in such constant velocity joints.
耐久性も考慮したグリースとしては、基油、増ちょう剤、モンタンワックス、亜鉛スルホネート、及び硫化ジアルキルジチオカルバミン酸モリブデンを含有する等速ジョイント用組成物が提案されている。(特許文献5参照)。
このように、これまでの等速ジョイント用グリース組成物でも振動抑制においては優れた性能を発揮しており、耐久性も常温においては検討されてきたが、しかし一方で、高温での耐久性の課題においては必ずしも十分な検討がされてきたとはいえない。 As a grease with excellent vibration suppression performance, a grease for constant velocity joints made by using molybdenum dithiocarbamate and molybdenum dithiophosphate additives in combination with urea grease, or by mixing these organic molybdenum compounds with zinc dithiophosphate (patented). A grease composition for a constant velocity joint containing a base oil, a urea-based thickener, molybdenum dithiocarbamate, calcium sulfonate, and thiophosphate has been proposed. (Refer to Patent Document 2) Further, since further quietness is required in recent years, molybdenum dialkyldithiocarbamate and molybdenum dialkyldithiophosphate or molybdenum dialkyldithiophosphate or grease composed of a base oil and a thickener of a urea compound is used as a grease. A grease composition for a constant velocity joint containing at least one of molybdenum diallyl dithiophosphate and a mixture with ashless dithiocarbamate or zinc dithiocarbamate (see Patent Document 3), a base oil, a diurea-based thickener, and sulfurization. A composition for a constant velocity joint containing molybdenum dialkyldithiocarbamate, zinc sulfonate, a sulfur-phosphorus extreme pressure agent, and a vegetable oil / fat has also been proposed (see Patent Document 4).
As a grease in consideration of durability, a composition for a constant velocity joint containing a base oil, a thickener, a montan wax, a zinc sulfonate, and molybdenum dialkyldithiocarbamate sulfide has been proposed. (See Patent Document 5).
As described above, even the grease compositions for constant velocity joints so far have exhibited excellent performance in vibration suppression, and durability has been studied at room temperature, but on the other hand, durability at high temperatures has been investigated. It cannot be said that sufficient consideration has been given to the issues.
(b)ジウレア系増ちょう剤
(c)モリブデンジチオカルバメート
(d)モリブデンジチオホスフェート
(e)過塩基性カルシウムスルホネート
(f)中性亜鉛スルホネート
を含む、等速ジョイント用グリース組成物。
2.成分(f)の含有量が、組成物の全質量を基準として、0.1~10質量%である、請求項1記載のグリース組成物。
3.成分(f)の含有量が、組成物の全質量を基準として、0.5~5質量%である、請求項1又は2記載のグリース組成物。
4.成分(f)の含有量が、組成物の全質量を基準として、0.8~3質量%である、請求項1~3のいずれか1項記載のグリース組成物。
5.成分(e)の含有量が、組成物の全質量を基準として、0.1~10質量%である、請求項1~4のいずれか1項記載のグリース組成物。
6.成分(e)の含有量が、組成物の全質量を基準として、0.2~5質量%である、請求項1~5のいずれか1項記載のグリース組成物。
7.成分(e)の含有量が、組成物の全質量を基準として、1.2~3.5質量%である、請求項1~6のいずれか1項記載のグリース組成物。
8.成分(b)が、脂肪族ジウレア系増ちょう剤である、請求項1~7のいずれか1項記載のグリース組成物。
9.請求項1~8のいずれか1項記載のグリース組成物を封入した等速ジョイント。 1. 1. (A) Base oil (b) Diurea-based thickener (c) Molybdenum dithiocarbamate (d) Molybdenum dithiophosphate (e) Perbasic calcium sulfonate (f) Neutral zinc sulfonate-containing grease composition for constant velocity joints ..
2. 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. 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. 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. 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. 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. 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. The grease composition according to any one of claims 1 to 7, wherein the component (b) is an aliphatic diurea-based thickener.
9. A constant velocity joint in which the grease composition according to any one of claims 1 to 8 is sealed.
本発明の組成物に使用出来る基油は特に限定されず、鉱油及び/又は合成油を使用することができる。合成油としては、ポリαオレフィン等の合成炭化水素油;ペンタフェニルエーテル、テトラフェニルエーテル、モノアルキルテトラフェニルエーテル、ジアルキルテトラフェニルエーテル及びアルキルジフェニルエーテル油等のフェニルエーテル油;アルキルベンゼン油;モノエステル油、ジエステル油、ポリオールエステル油及び芳香族エステル油等のエステル油;ポリグリコール油;シリコーン油;フッ素油;イオン液体等が挙げられる。
本発明の基油としては、コストの点から、鉱物油を用いるのが好ましい。鉱物油を主成分とし、これに合成油を混合した基油を用いてもよい。
本発明の基油が鉱油と合成油との混合油の場合、基油の全質量を基準として、鉱油が50~100質量%であるのが好ましく、70~100質量%であるのがより好ましく、90~100質量%であるのがさらに好ましい。
本発明の基油の100℃における動粘度は、好ましくは5~30mm2/sであり、より好ましくは7~20mm2/sである。5mm2/s未満では、等速ジョイント内で油膜を形成せず耐久性が不充分となる傾向があり、30mm2/sを超えるとCVJ内の発熱のため耐久性が低下する傾向がある。
基油の含有量は、流動性の観点から、組成物の全質量を基準として、50~100質量%であるのが好ましく、70~100質量%であるのがより好ましく、80~100質量%であるのがさらに好ましい。 (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 poly-α-olefins; phenyl ether oils such as pentaphenyl ethers, tetraphenyl ethers, monoalkyl tetraphenyl ethers, dialkyl tetraphenyl ethers and alkyl diphenyl ether oils; alkylbenzene oils; monoester oils, Examples thereof include ester oils such as diester oils, polyol ester oils and aromatic ester oils; polyglycol oils; silicone oils; fluorine oils; ionic liquids and the like.
As the base oil of the present invention, it is preferable to use mineral oil from the viewpoint of cost. A base oil containing mineral oil as a main component and mixed with synthetic oil may be used.
When 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, based on the total mass of the base oil. , 90-100% by mass, more preferably.
The kinematic viscosity of the base oil of the present invention at 100 ° C. is preferably 5 to 30 mm 2 / s, more preferably 7 to 20 mm 2 / s. If it is less than 5 mm 2 / s, an oil film is not formed in the constant velocity joint and the durability tends to be insufficient, and if it exceeds 30 mm 2 / s, the durability tends to decrease 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 80 to 100% by mass, based on the total mass of the composition. Is more preferable.
本発明で用いることができるジウレア系増ちょう剤は、下記式(1)で表わされる。
R1-NHCONH-R2-NHCONH-R3 (1)
式中、R2は炭素数6~15の2価の芳香族炭化水素基であり、R2としては、トリレンジイソシアネート又はジフェニルメタンジイソシアネートが好ましく、ジフェニルメタンジイソシアネートがより好ましい。R1及びR3は、互いに同一でも異なっていてもよく、炭素数6~30の直鎖又は分岐アルキル基、炭素数6又は7のアリール基、又はシクロヘキシル基である。
式(1)のジウレア化合物としては、R1及びR3のいずれもが、炭素数6~30のアルキル基である脂肪族ジウレア化合物が好ましい。脂肪族ジウレア化合物は、ジイソシアネートと脂肪族モノアミンとを反応させることにより得ることができる。 (B) Diurea-based thickener The diurea-based 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)
In the formula, R 2 is a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms, and as R 2 , tolylene diisocyanate or diphenylmethane diisocyanate is preferable, and diphenylmethane diisocyanate is more preferable. R 1 and R 3 may be the same or different from each other, 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 the formula (1), an aliphatic diurea compound in which both R 1 and R 3 are alkyl groups having 6 to 30 carbon atoms is preferable. The aliphatic diurea compound can be obtained by reacting diisocyanate with an aliphatic monoamine.
R1及びR3のいずれかがシクロヘキシル基の場合、もう一方は炭素数8又は18の直鎖アルキル基であるのが好ましい。このとき、シクロヘキシル基とアルキル基の合計に占めるシクロヘキシル基の比率は、流動性の観点から、70~100モル%であるのが好ましく、80~100モル%であるのがより好ましい。 As the diurea compound of the formula (1), an alicyclic aliphatic diurea compound in which one of R 1 and R 3 is an alkyl group having 6 to 30 carbon atoms and the other is a cyclohexyl group is preferable. Since the alicyclic aliphatic diurea compound is obtained by reacting diisocyanate with an alicyclic monoamine and an alicyclic monoamine, in reality, in addition to the alicyclic aliphatic diurea compound, an alicyclic aliphatic diurea compound and an alicyclic monoamine are used. It is a mixture containing a diurea compound.
When either R 1 or R 3 is a cyclohexyl group, the other is preferably a linear alkyl group having 8 or 18 carbon atoms. At this time, 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.
特に、式(1)中、R1及びR3のいずれかもが炭素数8~30のアルキル基であり、R2がジフェニルメタンジイソシアネートであるジウレア化合物が好ましい。
とりわけ、式(1)中、R1及びR3のいずれもが炭素数8または18の直鎖アルキル基であり、R2がジフェニルメタンジイソシアネートであるジウレア化合物が好ましい。 As the thickener of the present invention, an aliphatic diurea compound is preferable from the viewpoint of durability.
In particular, in the formula (1), a diurea compound in which any of R 1 and R 3 is an alkyl group having 8 to 30 carbon atoms and R 2 is a diphenylmethane diisocyanate is preferable.
In particular, in the formula (1), a diurea compound in which both R 1 and R 3 are linear alkyl groups having 8 or 18 carbon atoms and R 2 is diphenylmethane diisocyanate is preferable.
増ちょう剤の含有量は、グリース組成物のちょう度を上記範囲に設定できるよう、組成物の全質量を基準として、10質量%以下であるのが好ましく、5~10質量%であるのがより好ましく、6~7質量%であるのがさらに好ましい。 The consistency of the grease composition of the present invention is preferably 250 to 400, more preferably 280 to 370, and even more preferably 310 to 340. In addition, in this specification, the term "concentration" refers to a 60-time mixing consistency. Consistency is JIS K2220 7. Can be measured according to.
The content of the thickener is preferably 10% by mass or less, preferably 5 to 10% by mass, based on the total mass of the composition so that the consistency of the grease composition can be set in the above range. More preferably, it is more preferably 6 to 7% by mass.
本発明において用いることのできるモリブデンジチオカルバメートは、有機金属系耐荷重添加剤のうち、金属基がモリブデンであるものの総称であり、一般に極圧添加剤として広く用いられている。モリブデンジチオカーバメートの好ましい例は、下記の式(2)で表すことができる。
[R4R5N-CS-S]2-Mo2OmSn (2)
式中、R4及びR5は、互いに同一でも異なっていてもよく、それぞれ独立して、炭素数1~24、好ましくは3~18の直鎖又は分岐アルキル基を表し、mは0~3、nは4~1、m+n=4である。
モリブデンジチオカルバメートには、油溶性モリブデンジチオカルバメート(すなわち、室温(約25℃)で液体)と非油溶性モリブデンジチオカルバメート(すなわち、室温で固体)とが存在する。本発明のモリブデンジチオカルバメートとしてはいずれも使用することができるが、油溶性モリブデンジチオカルバメートと、非油溶性モリブデンジチオカルバメートとの組合せであると、耐久性及びCVJ内の発熱抑制及び振動抑制に優れるので好ましい。
本発明のグリース組成物における成分(b)の含有量は、振動抑制の観点から、組成物の全質量を基準にして、0.1~10質量%であるのが好ましく、0.5~5質量%であるのがより好ましく、1~3質量%であるのがさらに好ましい。なお、油溶性モリブデンジチオカルバメートと、非油溶性モリブデンジチオカルバメートとを含む場合、油溶性モリブデンジチオカルバメートと、非油溶性モリブデンジチオカルバメートとの質量比が、好ましくは4:6~10:0、より好ましくは6:4~8:2となる割合で用いると、振動抑制に優れるので好ましい。 (C) Molybdenum dithiocarbamate (MoDTC)
Molybdenum dithiocarbamate that can be used in the present invention is a general term for organometallic load-bearing additives whose metal group is molybdenum, and is generally widely used as an extreme pressure additive. A preferred 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)
In the formula, R 4 and R 5 may be the same or different from each other, and independently represent a linear or branched alkyl group having 1 to 24 carbon atoms, preferably 3 to 18 carbon atoms, and m is 0 to 3. , N is 4 to 1, m + n = 4.
Molybdenum dithiocarbamate includes oil-soluble molybdenum dithiocarbamate (that is, liquid at room temperature (about 25 ° C.)) and non-oil-soluble molybdenum dithiocarbamate (that is, solid at room temperature). Any of the molybdenum dithiocarbamate of the present invention can be used, but the combination of the oil-soluble molybdenum dithiocarbamate and the non-oil-soluble molybdenum dithiocarbamate is excellent in durability, heat generation suppression in CVJ, and vibration suppression. Therefore, it is preferable.
The content of the component (b) in the grease composition of the present invention is preferably 0.1 to 10% by mass, preferably 0.5 to 5%, based on the total mass of the composition from the viewpoint of vibration suppression. It is more preferably by mass%, and even more preferably 1 to 3% by mass. When the oil-soluble molybdenum dithiocarbamate and the non-oil-soluble molybdenum dithiocarbamate are contained, the mass ratio of the oil-soluble molybdenum dithiocarbamate to the non-oil-soluble molybdenum dithiocarbamate is preferably 4: 6 to 10: 0. It is preferable to use it in a ratio of 6: 4 to 8: 2 because it is excellent in vibration suppression.
本発明に使用するモリブデンジチオホスフェートの好ましい例としては下記の式(3)で表されるものが挙げられる。
[(R6O)(R7O)PS-S]2Mo2OmSn
(式中、R6及びR7はそれぞれ独立して、炭素数1~24のアルキル基又は炭素数6~30のアリール基であり、mは0~3、nは4~1であり、m+n=4である。)
本発明のグリース組成物における成分(d)の含有量は、耐久性の観点から、組成物の全質量を基準にして、0.1質量%以上であるのが好ましく、0.1~5質量%であるのがより好ましく、0.2~2質量%であるのがさらに好ましい。 (D) Molybdenum dithiophosphate (MoDTP)
Preferred 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
(In the formula, R 6 and R 7 are independently alkyl groups having 1 to 24 carbon atoms or aryl groups having 6 to 30 carbon atoms, m is 0 to 3, n is 4-1 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% by mass or more, preferably 0.1 to 5% by mass, based on the total mass of the composition. %, More preferably 0.2 to 2% by mass.
本発明において用いる過塩基性カルシウムスルホネートは、塩基価が200mgKOH/g以上のカルシウムスルホネートである。塩基価は、耐久性の観点から、300mgKOH/g以上であるのが好ましく、300~500mgKOH/gであるのがより好ましい。なお、本発明において、塩基価は、JIS K 2501に準拠して測定した値である。
成分(e)としては、親油基である有機基を有するスルホン酸のカルシウム塩を使用することができる。このような有機スルホン酸としては、潤滑油留分中の芳香族炭化水素成分のスルホン化によって得られる石油スルホン酸、ジノニルナフタレンスルホン酸や重質アルキルベンゼンスルホン酸のような合成スルホン酸等が挙げられる。成分(e)としては、炭酸カルシウムにより過塩基性とされているカルシウムスルホネートが好ましい。とりわけ、炭酸カルシウムを含むアルキル芳香族スルホン酸カルシウムが好ましい。
本発明のグリース組成物における成分(e)の含有量は、耐久性の観点から、組成物の全質量を基準にして、0.1~10質量%であるのが好ましく、0.2~5質量%であるのがより好ましく、1.2~3.5質量%であるのがさらに好ましい。 (E) Hyperbasic calcium sulfonate The hyperbasic calcium sulfonate used in the present invention is a calcium sulfonate having a base value of 200 mgKOH / g or more. From the viewpoint of durability, the base value is preferably 300 mgKOH / g or more, and more preferably 300 to 500 mgKOH / g. In the present invention, the base value is a value measured according to JIS K 2501.
As the component (e), a calcium salt of a sulfonic acid having an organic group which is a lipophilic group can be used. Examples of such organic sulfonic acid include petroleum sulfonic acid obtained by sulfonated aromatic hydrocarbon component in lubricating oil distillate, synthetic sulfonic acid such as dinonylnaphthalene sulfonic acid and heavy alkylbenzene sulfonic acid. Be done. As the component (e), calcium sulfonate, which is overbasic due to calcium carbonate, is preferable. In particular, an alkyl aromatic calcium sulfonate containing calcium carbonate is 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% by mass, preferably 0.2 to 5% by mass, based on the total mass of the composition. It is more preferably by mass%, and even more preferably 1.2 to 3.5% by mass.
本発明において用いる中性亜鉛スルホネートは、塩基価が10mgKOH/g以下である。
亜鉛スルホネートを構成するスルホン酸は、成分(e)について述べたのと同様である。
中性亜鉛スルホネートとしては、ジノニルナフタレンスルホン酸亜鉛が好ましい。
本発明のグリース組成物における中性亜鉛スルホネートの含有量は、耐久性の観点から、組成物の全質量を基準にして、0.1~10質量%であるのが好ましく、0.5~5質量%であるのがより好ましく、0.8~3質量%であるのがさらに好ましい。 (F) Neutral zinc sulfonate The neutral zinc sulfonate used in the present invention has a base value of 10 mgKOH / g or less.
The sulfonic acid constituting the zinc sulfonate is the same as that described for the component (e).
As the neutral zinc sulfonate, zinc dinonylnaphthalenesulfonate 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% by mass, preferably 0.5 to 5% by mass, based on the total mass of the composition. It is more preferably by mass%, and even more preferably 0.8 to 3% by mass.
成分(e)と成分(f)との質量比が、(e):(f)=9:1~1:9であると、耐久性に優れるので好ましい。(e):(f)=8:2~3:7がより好ましく、(e):(f)=7:3~4:6がさらに好ましい。特に、成分(e)と成分(f)との合計が、組成物の全質量を基準にして、1~3質量%であり、成分(e)と成分(f)との質量比が、(e):(f)=7:3~4:6のとき、耐久性と耐熱性とに優れるので好ましい。 When 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, the heat resistance is excellent. Therefore, it is preferable.
When the mass ratio of the component (e) to the component (f) is (e) :( f) = 9: 1 to 1: 9, it is preferable because the durability is excellent. (E): (f) = 8: 2 to 3: 7 is more preferable, and (e): (f) = 7: 3 to 4: 6 is even more preferable. In particular, the total of the component (e) and the component (f) is 1 to 3% by mass with respect to the total mass of the composition, and the mass ratio of the component (e) to the component (f) is ( e): When (f) = 7: 3 to 4: 6, it is preferable because it is excellent in durability and heat resistance.
このような添加剤としては、例えば、アミン系、フェノール系、キノリン系、硫黄系、ジチオリン酸亜鉛等の酸化防止剤;亜鉛系、カルボン酸系、カルボン酸塩系(特に、セバシン酸ナトリウム、アゼライン酸ナトリウム、スベリン酸ナトリウムなどの二塩基酸塩)、アミン系等の防錆剤;硫化油脂、硫化オレフィン、リン酸エステル、亜リン酸エステル、酸性リン酸エステルアミン塩等の耐摩耗剤;脂肪酸、脂肪酸エステル、リン酸エステル等の油性剤;グラファイト、ポリテトラフルオロエチレン(PTFE)、酸化亜鉛等の固体潤滑剤があげられる。
耐熱性の観点から、酸化防止剤を含むのが好ましい。
酸化防止剤としては、アミン系酸化防止剤が好ましく、アルキルジフェニルアミンがより好ましい。酸化防止剤の含有量は、組成物の全質量を基準にして、0.1質量%以上であるのが好ましく、0.1~2質量%であるのがより好ましく、0.2~1質量%であるのがさらに好ましい。 The grease composition of the present invention may contain additives usually used for grease, if necessary. 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 amine-based, phenol-based, quinoline-based, sulfur-based, and zinc dithiophosphate antioxidants; zinc-based, carboxylic acid-based, and carboxylate-based (particularly sodium sebacate and azeline). Dibasic acid salts such as sodium acid and sodium sverate), amine-based rust preventives; abrasion resistant agents such as sulfide oils and fats, sulphide olefins, phosphate esters, phosphite esters, acid phosphate ester amine salts; fatty acids , Fatty agents such as fatty acid esters and phosphate esters; solid lubricants such as graphite, polytetrafluoroethylene (PTFE) and zinc oxide.
From the viewpoint of heat resistance, it is preferable to contain an antioxidant.
As the antioxidant, an amine-based antioxidant is preferable, and alkyldiphenylamine is more preferable. The content of the antioxidant is preferably 0.1% by mass or more, more preferably 0.1 to 2% by mass, and 0.2 to 1% by mass based on the total mass of the composition. % Is more preferable.
(a)基油
(b)ジウレア系増ちょう剤
(c)モリブデンジチオカルバメート
(d)モリブデンジチオホスフェート
(e)過塩基性カルシウムスルホネート
(f)中性亜鉛スルホネート
(g)酸化防止剤
のみからなるのが好ましい。
このときの各成分の含有量は、組成物の全質量を基準にして、(a)が80~100質量%、(b)が6~7質量%、(c)が1~3質量%、(d)が0.2~2質量%、(e)が0.5~3質量%、(f)が0.8~3質量%、(g)が0.2~1質量%であるのが好ましい。 The composition of the present invention includes
(A) Base oil (b) Diurea-based thickener (c) Molybdenum dithiocarbamate (d) Molybdenum dithiophosphate (e) Perbasic calcium sulfonate (f) Neutral zinc sulfonate (g) It consists only of an antioxidant. Is preferable.
The content of each component at this time is 80 to 100% by mass in (a), 6 to 7% by mass in (b), and 1 to 3% by mass in (c), based on the total mass of the composition. (D) is 0.2 to 2% by mass, (e) is 0.5 to 3% by mass, (f) is 0.8 to 3% by mass, and (g) is 0.2 to 1% by mass. Is preferable.
(a)基油
(b)脂肪族ジウレア系増ちょう剤
(c)モリブデンジチオカルバメート
(d)モリブデンジチオホスフェート
(e)炭酸カルシウムを含む、塩基価300mgKOH/g以上の過塩基性カルシウムスルホネート
(f)中性亜鉛スルホネート
(g)アミン系酸化防止剤
を含むのが好ましい。
このときの各成分の含有量は、組成物の全質量を基準にして、(a)が80~100質量%、(b)が6~7質量%、(c)が1~3質量%、(d)が0.2~2質量%、(e)が0.5~3質量%、(f)が0.8~3質量%、(g)が0.2~1質量%であるのが好ましい。 The composition of the present invention also
(A) Base oil (b) Fat group diurea-based thickener (c) Molybdenum dithiocarbamate (d) Molybdenum dithiophosphate (e) Fluorobasic calcium sulfonate (f) containing calcium carbonate and having a base value of 300 mgKOH / g or more. It preferably contains a neutral zinc sulfonate (g) amine-based antioxidant.
The content of each component at this time is 80 to 100% by mass in (a), 6 to 7% by mass in (b), and 1 to 3% by mass in (c), based on the total mass of the composition. (D) is 0.2 to 2% by mass, (e) is 0.5 to 3% by mass, (f) is 0.8 to 3% by mass, and (g) is 0.2 to 1% by mass. Is preferable.
(a)基油
(b)前記式(1)中、R1及びR3のいずれかもが炭素数8の直鎖アルキル基であり、R2がジフェニルメタンジイソシアネートである脂肪族ジウレア系増ちょう剤
(c)油溶性モリブデンジチオカルバメートと非油溶性モリブデンジチオカルバメートとの混合物
(d)モリブデンジチオホスフェート
(e)炭酸カルシウムを含む、塩基価300~500mgKOH/gのアルキル芳香族スルホン酸カルシウム
(f)塩基価10mgKOH/g以下のジノニルナフタレンスルホン酸亜鉛
(g)アルキルジフェニルアミン
を含むのが好ましい。
このときの各成分の含有量は、組成物の全質量を基準にして、(a)が80~100質量%、(b)が6~7質量%、(c)が1~3質量%、(d)が0.2~2質量%、(e)が0.5~3質量%、(f)が0.8~3質量%、(g)が0.2~1質量%であるのが好ましい。 The composition of the present invention also
(A) Base oil (b) In the above formula (1), any of R 1 and R 3 is a linear alkyl group having 8 carbon atoms, and R 2 is a diphenylmethane diisocyanate, which is an aliphatic diurea-based thickener ( c) Mixture of oil-soluble molybdenum dithiocarbamate and non-oil-soluble molybdenum dithiocarbamate (d) Molybdenum dithiophosphate (e) Alkyl aromatic calcium sulfonate (f) base value containing calcium carbonate and having a base value of 300 to 500 mgKOH / g It is preferable to contain dinonylnaphthalene sulfonate zinc (g) alkyldiphenylamine of 10 mgKOH / g or less.
The content of each component at this time is 80 to 100% by mass in (a), 6 to 7% by mass in (b), and 1 to 3% by mass in (c), based on the total mass of the composition. (D) is 0.2 to 2% by mass, (e) is 0.5 to 3% by mass, (f) is 0.8 to 3% by mass, and (g) is 0.2 to 1% by mass. Is preferable.
基油中で、4’,4-ジフェニルメタンジイソシアネート1モルと、オクチルアミン2モルとを反応させ、昇温、冷却した後、表1又は表2に示す割合で添加剤を配合し、3本ロールミルで混練し、混和ちょう度315のグリース組成物を製造した。なお、表1及び表2中の数値は、特に記載のない限り、グリース組成物の全質量を基準とする質量%を表す。
〔2〕比較例5のグリース組成物の製造
特許第6470851号の実施例C4の記載に即し、比較例5のグリース組成物を調製した。 [1] Production of Grease Compositions of Examples 1 to 7 and Comparative Examples 1 to 4 In the base oil, 1 mol of 4', 4-diphenylmethane diisocyanate was reacted with 2 mol of octylamine, and the temperature was raised and cooled. After that, the additives were blended in the proportions shown in Table 1 or Table 2 and kneaded with a three-roll mill to produce a grease composition having an mixing consistency of 315. Unless otherwise specified, the numerical values in Tables 1 and 2 represent mass% based on the total mass of the grease composition.
[2] Production of Grease Composition of Comparative Example 5 The grease composition of Comparative Example 5 was prepared in accordance with the description of Example C4 of Japanese Patent No. 6470851.
<基油>
・鉱油(100℃における動粘度:12.4mm2/s)
・鉱油+合成油:ポリ-α-オレフィン(100℃における動粘度:12・0mm2/s)
<添加剤>
・MoDTC(非油溶性):モリブデンジチオカルバメート(アデカ サクラルーブ 600、ADEKA製)
・MoDTC(非油溶性):モリブデンジチオカルバメート(Molyvan A、Vanderbilt製、比較例5で使用)
・MoDTC(油溶性):モリブデンジチオカルバメート(アデカ サクラルーブ525、ADEKA製)
・MoDTP:モリブデンジチオホスフェート(アデカ サクラルーブ300、ADEKA製)
・MoDTP:モリブデンジチオホスフェート(Molyvan L、Vanderbilt製、比較例5で使用)
・Caスルホネート(過塩基性):アルキル芳香族スルホン酸のカルシウム塩((LUBRIZOL 5283C、ザ・ルーブリゾール・コーポレーション製、塩基価375mgKOH/g)
・Znスルホネート(中性):ジノニルナフタレンスルホン酸亜鉛(NA-SUL ZS、KING INDUSTRIES製、塩基価5mgKOH/g)
・酸化防止剤 The components used for preparing 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-α-olefin (kinematic viscosity at 100 ° C: 12.0 mm 2 / s)
<Additives>
-MoDTC (non-oil soluble): Molybdenum dithiocarbamate (ADEKA Sakuralube 600, made by ADEKA)
-MoDTC (non-oil soluble): molybdenum dithiocarbamate (Mollyvan A, manufactured by Vanderbilt, used in Comparative Example 5)
-MoDTC (oil-soluble): Molybdenum dithiocarbamate (ADEKA Sakuralube 525, manufactured by ADEKA)
-MoDTP: Molybdenum dithiophosphate (ADEKA Sakura Lube 300, made by ADEKA)
-MoDTP: Molybdenum dithiophosphate (Mollyvan L, manufactured by Vanderbilt, used in Comparative Example 5)
-Ca sulfonate (hyperbasic): Calcium salt of alkyl aromatic sulfonic acid ((LUBRIZOL 5283C, manufactured by The Lubrizol Corporation, base value 375 mgKOH / g))
Zn sulfonate (neutral): Zinc dinonylnaphthalene sulfonate (NA-SUL ZS, manufactured by KING INDUSTRIES, base value 5 mgKOH / g)
·Antioxidant
(1)SRV試験(高負荷)
[試験条件]
試験速度:11.9mm/s(周波数:3.3Hz、ストローク:1.8mm)
試験温度:90℃
荷重:5.5GPa
試験片:ボール(直径17.5mm、SUJ-2)/プレート(SUJ-2、表面粗さRz0.5μm)
[評価基準]
◎(合格):摩擦係数0.08以下
〇(合格):摩擦係数0.08超、0.10以下
△(合格):摩擦係数0.10超、0.12以下
×(不合格):焼付き発生又は摩擦係数0.12超 [2] Evaluation of durability (1) SRV test (high load)
[Test conditions]
Test speed: 11.9 mm / s (frequency: 3.3 Hz, stroke: 1.8 mm)
Test temperature: 90 ° C
Load: 5.5 GPa
Specimen: Ball (diameter 17.5 mm, SUJ-2) / plate (SUJ-2, surface roughness Rz 0.5 μm)
[Evaluation criteria]
◎ (Pass): Friction coefficient 0.08 or less 〇 (Pass): Friction coefficient over 0.08, 0.10 or less △ (Pass): Friction coefficient over 0.10, 0.12 or less × (Fail): Burn Occurrence or friction coefficient over 0.12
[試験条件]
試験速度:2.0mm/s(周波数:3.3Hz、ストローク:0.3mm)
試験温度:95℃
荷重:2.1GPa
試験片:ボール(直径17.5mm、SUJ-2)/プレート(SUJ-2、表面粗さRz5μm)
[評価基準]
〇(合格):摩擦係数0.10以下
△(合格):摩擦係数0.10超、0.14以下
×(不合格):焼付き発生又は摩擦係数0.14超 (2) SRV test (low load)
[Test conditions]
Test speed: 2.0 mm / s (frequency: 3.3 Hz, stroke: 0.3 mm)
Test temperature: 95 ° C
Load: 2.1 GPa
Specimen: Ball (diameter 17.5 mm, SUJ-2) / plate (SUJ-2, surface roughness Rz 5 μm)
[Evaluation criteria]
〇 (Pass): Friction coefficient 0.10 or less △ (Pass): Friction coefficient over 0.10, 0.14 or less × (Fail): Seizure occurrence or friction coefficient over 0.14
(1)TE77試験
TE77試験機は、すべり条件下における振動摩擦摩耗試験機である。等速ジョイントを起振源とした振動と、TE77試験機で測定した振動条件下での摩擦係数には関係があることが報告されている(特開2010-065194号公報)。そこで、TE77試験機を用い、等速ジョイントにおける振動抑制を評価した。
[試験条件]
試験速度:16mm/s(周波数:10Hz、ストローク:0.8mm)
試験温度:40℃
荷重:1.2GPa
試験片:ボール(直径17.5mm、SUJ-2)/プレート(SCM)
[評価基準]
〇(合格):摩擦係数0.07以下
△(合格):摩擦係数0.07超、0.10以下
×(不合格):摩擦係数0.10超 [2] Evaluation of vibration suppression (1) TE77 test The TE77 tester is a vibration friction wear tester under slip conditions. It has been reported that there is a relationship between the vibration caused by the constant velocity joint and the friction coefficient under the vibration conditions measured by the TE77 tester (Japanese Patent Laid-Open No. 2010-065194). Therefore, a TE77 tester was used to evaluate the vibration suppression in the constant velocity joint.
[Test conditions]
Test speed: 16 mm / s (frequency: 10 Hz, stroke: 0.8 mm)
Test temperature: 40 ° C
Load: 1.2 GPa
Specimen: Ball (17.5 mm in diameter, SUJ-2) / Plate (SCM)
[Evaluation criteria]
〇 (Pass): Friction coefficient 0.07 or less △ (Pass): Friction coefficient over 0.07, 0.10 or less × (Fail): Friction coefficient over 0.10
〇(合格):上記試験結果のいずれも合格
×(不合格):上記試験結果の一以上が不合格
結果を表1および表2に示す。 [Comprehensive evaluation]
〇 (Pass): All of the above test results passed × (Failed): One or more of the above test results failed The results are shown in Tables 1 and 2.
Claims (9)
- (a)基油
(b)ジウレア系増ちょう剤
(c)モリブデンジチオカルバメート
(d)モリブデンジチオホスフェート
(e)過塩基性カルシウムスルホネート
(f)中性亜鉛スルホネート
を含む、等速ジョイント用グリース組成物。 (A) Base oil (b) Diurea-based thickener (c) Molybdenum dithiocarbamate (d) Molybdenum dithiophosphate (e) Perbasic calcium sulfonate (f) Neutral zinc sulfonate-containing grease composition for constant velocity joints .. - 成分(f)の含有量が、組成物の全質量を基準として、0.1~10質量%である、請求項1記載のグリース組成物。 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.
- 成分(f)の含有量が、組成物の全質量を基準として、0.5~5質量%である、請求項1又は2記載のグリース組成物。 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.
- 成分(f)の含有量が、組成物の全質量を基準として、0.8~3質量%である、請求項1~3のいずれか1項記載のグリース組成物。 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.
- 成分(e)の含有量が、組成物の全質量を基準として、0.1~10質量%である、請求項1~4のいずれか1項記載のグリース組成物。 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.
- 成分(e)の含有量が、組成物の全質量を基準として、0.2~5質量%である、請求項1~5のいずれか1項記載のグリース組成物。 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.
- 成分(e)の含有量が、組成物の全質量を基準として、1.2~3.5質量%である、請求項1~6のいずれか1項記載のグリース組成物。 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.
- 成分(b)が、脂肪族ジウレア系増ちょう剤である、請求項1~7のいずれか1項記載のグリース組成物。 The grease composition according to any one of claims 1 to 7, wherein the component (b) is an aliphatic diurea-based thickener.
- 請求項1~8のいずれか1項記載のグリース組成物を封入した等速ジョイント。 A constant velocity joint in which the grease composition according to any one of claims 1 to 8 is sealed.
Priority Applications (6)
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US18/252,723 US20230416633A1 (en) | 2020-11-26 | 2020-11-26 | Grease composition for constant-velocity joints |
CN202080107504.7A CN116601273A (en) | 2020-11-26 | 2020-11-26 | Grease composition for constant velocity universal joint |
KR1020237013863A KR20230110495A (en) | 2020-11-26 | 2020-11-26 | Grease composition for constant velocity joints |
EP20963504.4A EP4253507A4 (en) | 2020-11-26 | 2020-11-26 | Grease composition for constant-velocity joint |
JP2022564910A JPWO2022113239A1 (en) | 2020-11-26 | 2020-11-26 | |
PCT/JP2020/044030 WO2022113239A1 (en) | 2020-11-26 | 2020-11-26 | Grease composition for constant-velocity joint |
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PCT/JP2020/044030 WO2022113239A1 (en) | 2020-11-26 | 2020-11-26 | Grease composition for constant-velocity joint |
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US (1) | US20230416633A1 (en) |
EP (1) | EP4253507A4 (en) |
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JPH0579280B2 (en) | 1986-01-16 | 1993-11-01 | Ntn Toyo Bearing Co Ltd | |
JPH11172276A (en) | 1997-12-10 | 1999-06-29 | Kyodo Yushi Co Ltd | Grease composition for constant-velocity joint |
JP2004108403A (en) * | 2002-09-13 | 2004-04-08 | Koyo Seiko Co Ltd | Rolling bearing |
WO2006049280A1 (en) * | 2004-11-08 | 2006-05-11 | Thk Co., Ltd. | Grease composition conforming to vibration and guide employing the same |
JP2007302761A (en) * | 2006-05-10 | 2007-11-22 | Showa Shell Sekiyu Kk | Grease composition for constant velocity joint |
JP2009235416A (en) | 2009-06-19 | 2009-10-15 | Showa Shell Sekiyu Kk | Grease composition for constant velocity joint |
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JP2011037950A (en) | 2009-08-07 | 2011-02-24 | Kyodo Yushi Co Ltd | Grease composition for constant velocity joint and constant velocity joint |
JP2017115104A (en) * | 2015-12-25 | 2017-06-29 | 協同油脂株式会社 | Lubricant composition for speed reducer and speed reducer |
JP6470851B2 (en) | 2015-03-31 | 2019-02-13 | ゲーカーエン ドライブライン インターナショナル ゲゼルシャフト ミト ベシュレンクテル ハフツングGkn Driveline International Gmbh | Grease composition for constant velocity joints |
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JPH0579280A (en) | 1991-09-19 | 1993-03-30 | Kajima Corp | Tail clearance measuring device for shieled excavating machine |
CN104822811B (en) | 2012-10-05 | 2019-03-01 | 协同油脂株式会社 | Lubricant composition |
JP5641487B2 (en) * | 2012-12-21 | 2014-12-17 | 協同油脂株式会社 | Grease composition |
JP5807833B1 (en) * | 2015-05-16 | 2015-11-10 | 有限会社タービュランス・リミテッド | Lubricating oil additive and lubricating oil composition |
-
2020
- 2020-11-26 EP EP20963504.4A patent/EP4253507A4/en active Pending
- 2020-11-26 JP JP2022564910A patent/JPWO2022113239A1/ja active Pending
- 2020-11-26 KR KR1020237013863A patent/KR20230110495A/en unknown
- 2020-11-26 WO PCT/JP2020/044030 patent/WO2022113239A1/en active Application Filing
- 2020-11-26 CN CN202080107504.7A patent/CN116601273A/en active Pending
- 2020-11-26 US US18/252,723 patent/US20230416633A1/en active Pending
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JPH0579280B2 (en) | 1986-01-16 | 1993-11-01 | Ntn Toyo Bearing Co Ltd | |
JPH11172276A (en) | 1997-12-10 | 1999-06-29 | Kyodo Yushi Co Ltd | Grease composition for constant-velocity joint |
JP2004108403A (en) * | 2002-09-13 | 2004-04-08 | Koyo Seiko Co Ltd | Rolling bearing |
WO2006049280A1 (en) * | 2004-11-08 | 2006-05-11 | Thk Co., Ltd. | Grease composition conforming to vibration and guide employing the same |
JP2007302761A (en) * | 2006-05-10 | 2007-11-22 | Showa Shell Sekiyu Kk | Grease composition for constant velocity joint |
JP2010065194A (en) | 2008-09-12 | 2010-03-25 | Kyodo Yushi Co Ltd | Grease composition for constant velocity joint and constant velocity joint |
JP2009235416A (en) | 2009-06-19 | 2009-10-15 | Showa Shell Sekiyu Kk | Grease composition for constant velocity joint |
JP2011037950A (en) | 2009-08-07 | 2011-02-24 | Kyodo Yushi Co Ltd | Grease composition for constant velocity joint and constant velocity joint |
JP6470851B2 (en) | 2015-03-31 | 2019-02-13 | ゲーカーエン ドライブライン インターナショナル ゲゼルシャフト ミト ベシュレンクテル ハフツングGkn Driveline International Gmbh | Grease composition for constant velocity joints |
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Title |
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See also references of EP4253507A4 |
Also Published As
Publication number | Publication date |
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EP4253507A1 (en) | 2023-10-04 |
CN116601273A (en) | 2023-08-15 |
US20230416633A1 (en) | 2023-12-28 |
JPWO2022113239A1 (en) | 2022-06-02 |
EP4253507A4 (en) | 2024-04-17 |
KR20230110495A (en) | 2023-07-24 |
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