WO2023182533A1 - Grease composition - Google Patents
Grease composition Download PDFInfo
- Publication number
- WO2023182533A1 WO2023182533A1 PCT/JP2023/012238 JP2023012238W WO2023182533A1 WO 2023182533 A1 WO2023182533 A1 WO 2023182533A1 JP 2023012238 W JP2023012238 W JP 2023012238W WO 2023182533 A1 WO2023182533 A1 WO 2023182533A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solid lubricant
- mass
- grease composition
- grease
- base oil
- Prior art date
Links
- 239000004519 grease Substances 0.000 title claims abstract description 71
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000007787 solid Substances 0.000 claims abstract description 53
- 239000000314 lubricant Substances 0.000 claims abstract description 45
- 239000002199 base oil Substances 0.000 claims abstract description 38
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 31
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000002562 thickening agent Substances 0.000 claims abstract description 20
- 150000002170 ethers Chemical class 0.000 claims abstract description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000292 calcium oxide Substances 0.000 claims abstract description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 6
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 6
- 229940078499 tricalcium phosphate Drugs 0.000 claims abstract description 6
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims abstract description 6
- 235000019731 tricalcium phosphate Nutrition 0.000 claims abstract description 6
- 239000003568 Sodium, potassium and calcium salts of fatty acids Substances 0.000 claims abstract description 5
- 235000010216 calcium carbonate Nutrition 0.000 claims abstract description 5
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 5
- 235000013969 calcium salts of fatty acid Nutrition 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- XMKLTEGSALONPH-UHFFFAOYSA-N 1,2,4,5-tetrazinane-3,6-dione Chemical compound O=C1NNC(=O)NN1 XMKLTEGSALONPH-UHFFFAOYSA-N 0.000 description 14
- 229910000831 Steel Inorganic materials 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 125000001931 aliphatic group Chemical group 0.000 description 11
- 239000003566 sealing material Substances 0.000 description 10
- 239000000344 soap Substances 0.000 description 10
- IHBLBMDDUQOYLA-UHFFFAOYSA-N 1-octadecyl-3-[4-[[4-(octadecylcarbamoylamino)phenyl]methyl]phenyl]urea Chemical compound C1=CC(NC(=O)NCCCCCCCCCCCCCCCCCC)=CC=C1CC1=CC=C(NC(=O)NCCCCCCCCCCCCCCCCCC)C=C1 IHBLBMDDUQOYLA-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229920002943 EPDM rubber Polymers 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 229920003052 natural elastomer Polymers 0.000 description 5
- 229920001194 natural rubber Polymers 0.000 description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 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 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 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 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- FPLIHVCWSXLMPX-UHFFFAOYSA-M lithium 12-hydroxystearate Chemical compound [Li+].CCCCCCC(O)CCCCCCCCCCC([O-])=O FPLIHVCWSXLMPX-UHFFFAOYSA-M 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- VIQSRHWJEKERKR-UHFFFAOYSA-L disodium;terephthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 VIQSRHWJEKERKR-UHFFFAOYSA-L 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 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 description 1
- 239000000178 monomer Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 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 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
- C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
- C10M107/34—Polyoxyalkylenes
-
- 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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
-
- 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
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/24—Compounds containing phosphorus, arsenic or antimony
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
-
- 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
- C10M147/00—Lubricating compositions characterised by the additive being a macromolecular compound containing halogen
- C10M147/02—Monomer containing carbon, hydrogen and halogen only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
Definitions
- This case relates to a grease composition that can be suitably used for mechanical parts that require peeling resistance, such as reduction gears and ball screws.
- Reactive anti-flake additives work by reacting on the metal surface to form a protective film.
- NBR nitrile rubber
- the sealing material may deteriorate due to low temperatures in winter or heat damage in tropical climates. Deterioration of the sealing material also occurs when the base oil contained in the grease that comes into contact with the sealing material causes the sealing material to swell. Therefore, if a mechanical component equipped with a sealing material is used for a long period of time, there is a risk that foreign matter may enter from the outside, leading to poor lubrication and shortening the life of the mechanical component.
- polyoxyalkylene or polyoxyalkylene derivatives are used as base oils that have excellent compatibility with rubber and can be applied to mechanical parts where EPDM or natural rubber is used for sealing members.
- a grease composition that can extend the life of mechanical parts by suppressing the occurrence of flaking of the mechanical parts even under high temperatures or high surface pressures.
- Non-reactive anti-peeling additives (solid lubricants) play a role by adhering to metal surfaces and preventing contact between metals, but they have greater anti-peeling properties than reactive anti-peeling additives. As a result, the resulting grease lacked versatility.
- the problem to be solved by the present invention is to improve the peeling resistance of a grease composition containing polyoxyalkylene or a polyoxyalkylene derivative as a base oil, even under high temperature or high surface pressure.
- the objective is to improve the anti-flamination properties without using anti-flake additives and to suppress thermal deterioration of the base oil.
- the present inventors solved the above-mentioned problem of improving peeling resistance by using a non-reactive solid lubricant. That is, the present invention provides the following grease composition. 1. A grease composition containing a base oil, a thickener, and an additive, The base oil is at least one selected from the group consisting of polyoxyalkylene, ether derivatives of polyoxyalkylene, and mixtures thereof, The additive contains polytetrafluoroethylene as the first solid lubricant, and at least one member selected from the group consisting of calcium carbonate, calcium oxide, tricalcium phosphate, and calcium salts of fatty acids as the second solid lubricant.
- the grease composition wherein the content of the second solid lubricant is 0.5% by mass or more based on the total mass of the composition.
- 2. 1. The grease composition according to item 1, wherein the content of the first solid lubricant is 0.5 to 20% by mass based on the total mass of the composition. 3.
- 3. The grease composition according to item 1 or 2 above, wherein the content of the second solid lubricant is 0.5 to 10% by mass based on the total mass of the composition. 4.
- 4. The grease composition according to any one of items 1 to 3 above, wherein the second solid lubricant is calcium carbonate. 5.
- the grease composition can be made to withstand even under high temperature or high surface pressure without using anti-flamination additives in the reaction system and without promoting the decomposition of polyoxyalkylene and/or ether derivatives of polyoxyalkylene. Peelability and heat resistance can be improved.
- the base oil used in the grease composition of the present invention is a polyoxyalkylene and/or an ether derivative of a polyoxyalkylene.
- Polyoxyalkylene and/or ether derivatives of polyoxyalkylene have low adverse effects on rubber, which is a sealing material.
- the polyoxyalkylene and/or the ether derivative of polyoxyalkylene is represented by the following formula (1).
- Polyoxyalkylene or its ether derivative means that R 1 and R 3 in formula (1) are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, or pentyl group. is an alkyl group having 1 to 6 carbon atoms such as hexyl group, R 2 is hydrogen or an alkyl group having 1 to 2 carbon atoms, and n is a compound having a number of 5 to 55.
- Polyoxyalkylene is a diol obtained by ring-opening polymerization of alkylene oxide such as ethylene oxide and propylene oxide.
- the ether derivative is a monoether in which either R 1 or R 3 is an alkyl group having one or more carbon atoms, or a diether in which both R 1 and R 3 are an alkyl group having one or more carbon atoms.
- polyoxyalkylene diols include polyoxyethylene, polyoxypropylene, poly(oxypropyleneoxyethylene), poly(oxybutyleneoxyethylene), poly(oxybutyleneoxypropylene), and poly(oxypentyleneoxyethylene).
- ether derivatives of polyoxyalkylene include polyoxypropylene monopropyl ether, polyoxypropylene monobutyl ether, polyoxybutylene monobutyl ether, polyoxyethylene oxypropylene monopropyl ether, polyoxyethylene oxypropylene monobutyl ether, polyoxy Examples include ethylene oxypropylene monopentyl ether.
- suitable base oils for the present invention are polyoxyalkylene in which R 2 is an alkyl group having 1 or more carbon atoms or its ether derivative, preferably polyoxypropylene monobutyl ether, and particularly preferably n is 10 to 10. 25, more particularly preferably polyoxypropylene monobutyl ether where n is 10 to 22.
- the base oil of the present invention may be a so-called biomass oil that is produced using biological resources derived from animals and plants as raw materials.
- the base oil of the present invention preferably has a kinematic viscosity of 2 to 100 mm 2 /s at 100°C. This provides excellent low temperature properties.
- the kinematic viscosity at 100° C. is more preferably 2 to 50 mm 2 /s, even more preferably 2 to 20 mm 2 /s, and particularly preferably 6 to 19 mm 2 /s.
- the base oil of the present invention preferably has a pour point of -10°C or lower. This provides excellent low temperature properties.
- the pour point is more preferably -20°C or lower, even more preferably -30°C or lower, particularly preferably -35°C or lower.
- the base oil of the present invention is a polyoxypropylene monomer having a kinematic viscosity of 6 to 19 mm 2 /s at 100°C, a pour point of -35°C or lower, and in which n is 10 to 22 in formula (1). Butyl ether is most preferred.
- the base oil content in the grease composition of the present invention is, for example, preferably 60 to 90% by mass, more preferably 60 to 80% by mass.
- the first solid lubricant in the present invention is polytetrafluoroethylene.
- the content of the first solid lubricant is preferably 0.5% by mass or more based on the total mass of the composition. This provides excellent peeling resistance. More preferably, it is 1% by mass or more. From the viewpoint of grease inflow, the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
- the second solid lubricant in the present invention is at least one selected from the group consisting of calcium carbonate, calcium oxide, tricalcium phosphate, and calcium salts of fatty acids.
- calcium carbonate is preferred from the viewpoint of peeling resistance.
- the fatty acid constituting the calcium salt of fatty acid is preferably a fatty acid having 1 to 22 carbon atoms, more preferably a fatty acid having 16 to 20 carbon atoms.
- the second solid lubricant is preferably larger in particle size than the first solid lubricant, PTFE, from the viewpoint of improving peeling resistance when used in combination.
- the content of the second solid lubricant is 0.5% by mass or more based on the total mass of the composition. This provides excellent peeling resistance.
- the content does not need to be the same as that of the first solid lubricant. More preferably, it is 1% by mass or more. From the viewpoint of grease inflow, the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less.
- the peeling resistance of the grease composition is particularly excellent. Therefore, from the viewpoint of peeling resistance, it is particularly preferable that calcium carbonate, which has a particle size larger than that of PTFE, be contained in an amount of 1 to 3 parts by mass per 10 parts by mass of PTFE.
- the total amount of the first solid lubricant and the second solid lubricant in the grease composition of the present invention is preferably 1 to 20% by mass, more preferably 5 to 15% by mass. It is preferable that the total amount of the first solid lubricant and the second solid lubricant be within this range, since the influence of grease inflow properties on performance is small.
- first and second solid lubricants of the present invention do not have polarity, even if they are included in polyoxyalkylene and/or ether derivatives of polyoxyalkylene, they will not be affected by the base oil and will have peeling resistance. can improve sex.
- the presence of polytetrafluoroethylene, which has a smaller particle size than the second solid lubricant, in the lubrication field provides excellent peeling resistance, while the second solid lubricant This makes it possible to stably supply the oil to the lubrication field, which is thought to significantly improve flaking resistance.
- the thickener for the grease of the present invention can be used without particular limitations. Specifically, soap-based thickeners such as Li soap and Li-complex soap, urea-based thickeners such as diurea, inorganic thickeners such as organic bentonite and silica, and sodium terephthalate are used. Examples include organic thickeners typified by . Among these, Li soap and diurea compounds are preferred. This is because these are practical thickeners because they have few drawbacks and are not expensive.
- Li-(12OH)St lithium 12-hydroxystearate
- Li-St lithium stearate
- Li-St lithium stearate
- Li complex soaps include complexes of lithium salts of aliphatic carboxylic acids such as stearic acid and 12-hydroxystearic acid and lithium salts of dibasic acids.
- dibasic acids include succinic acid, malonic acid, adipic acid, pimelic acid, azelaic acid, and sebacic acid.
- Azelaic acid and sebacic acid are preferred.
- a Li complex soap which is a mixture of a salt of azelaic acid and lithium hydroxide and a salt of 12-hydroxystearic acid and lithium hydroxide.
- a diurea compound is generally represented by the following formula (2).
- R 4 -NHCONH-R 5 -NHCONH-R 6 (2) (In the formula, R 4 and R 6 may be the same or different and represent a C6-30 alkyl group, a C5-8 cycloalkyl group, or a C6-10 aryl group, and R 5 is a C6-15 (Indicates a divalent aromatic hydrocarbon group.)
- Examples of diurea compounds include aliphatic diureas in which R 4 and R 6 are C6-30 alkyl groups which may be the same or different; one of R 4 and R 6 is a C5-8 cycloalkyl group, and the other is a C6-30 alkyl group; A cycloaliphatic diurea which is a -30 alkyl group, or an aromatic diurea where R 4 and R 6 are a C6-10 aryl group which may be the same or different from each other is preferred.
- the aliphatic diureas include aliphatic diureas in which both R 4 and R 6 are C8 alkyl groups, aliphatic diureas in which both R 4 and R 6 are C18 alkyl groups, and aliphatic diureas in which one of R 4 and R 6 is C8 alkyl groups. More preferred are aliphatic diureas in which one is an alkyl group and the other is a C18 alkyl group. Particularly preferred are aliphatic diureas in which one of R 4 and R 6 is a C8 alkyl group and the other is a C18 alkyl group.
- aliphatic diureas in which the ratio of the number of moles of the C8 alkyl group to the total number of moles of the C8 alkyl group and the C18 alkyl group is 30 to 70 mol %.
- an alicyclic aliphatic diurea in which one of R 4 and R 6 is a cyclohexyl group and the other is a C18 alkyl group is more preferable.
- an alicycloaliphatic diurea in which the ratio of the number of moles of the cyclohexyl group to the total number of moles of the cyclohexyl group and the C18 alkyl group is 30 to 90 mol%.
- an aromatic diurea an aromatic diurea in which both R 4 and R 6 are p-tolyl groups is particularly preferred.
- the content of the thickener in the grease composition of the present invention is, for example, preferably 4 to 25% by mass, more preferably 5 to 20% by mass.
- the grease has appropriate hardness and prevents leakage from lubricated parts, which is preferable.
- the grease composition of the present invention can optionally contain any additives commonly used in grease compositions. Examples include antioxidants, rust preventives, corrosion inhibitors, oiliness agents, viscosity index improvers, and the like. Preferably, it contains an antioxidant and/or a rust inhibitor.
- reactive additives i.e., additives that react at lubricated surfaces to produce components that degrade the base oil, such as molybdenum disulfide, amine phosphates, zinc dialkyldithiophosphates, and molybdenum dialkyldithiocarbamates
- antioxidants include amine-based, phenol-based, quinoline-based, and sulfur-based antioxidants, with amine-based and quinoline-based antioxidants being preferred.
- rust preventives include zinc-based, carboxylic acid-based, carboxylate-based, succinic acid-based, amine-based, sulfonate-based, and naphthenic acid-based. Amine type and naphthenic acid type are preferred. Mixtures of these are more preferred.
- corrosion inhibitors include thiadiazole, benzimidazole, and benzotriazole.
- oily agents include fatty acids, fatty acid esters, and phosphoric acid esters.
- the consistency of the grease composition of the present invention is adjusted depending on the intended use, but is preferably 235 to 370. By setting the consistency to 235 or more, a grease composition with excellent low-temperature properties can be obtained, and by setting the consistency to 370 or less, a grease composition with excellent adhesion to mechanical parts can be obtained.
- the term "penetration" refers to 60 times worked penetration. Consistency is JIS K2220 7. It can be measured according to
- the use of the grease composition of the present invention does not matter.
- rolling bearings, ball screws, linear guide bearings, reducers, injection molding machines, linear guides, machine tools, various gears, cams, constant velocity joints, journal bearings (sliding bearings), pistons, screws, ropes, chains, etc. can be mentioned.
- the heat resistance and flaking resistance required for reducers, ball screws, etc. are severe, and the grease composition of the present invention can satisfy such high demands.
- the type of sealing material provided in the mechanical parts is not particularly limited, and examples thereof include NBR, EPDM, natural rubber, and the like.
- Test grease composition in which the thickener is a diurea compound 1 mole of 4.4'-diphenylmethane diisocyanate was reacted with 2 moles of a predetermined amine in a base oil, and the mixture was cooled to obtain a base grease. Additives were added to the above base grease in the proportions shown in Table 1, additional base oil was added to give the amount of thickener in the proportions shown in Table 1, and the test grease was prepared by dispersing with a three-roll mill. A composition was prepared. The consistency of the test grease composition is 280.
- Test grease composition in which the thickener is lithium soap Lithium 12-hydroxystearate was added and stirred in base oil, and then heated to 230°C. Thereafter, the mixture was cooled to 100° C. or lower while stirring to obtain a base grease. Additives were blended into the above base grease in the proportions shown in Tables 1 and 2, additional base oil was added so that the amount of thickener was in the proportions shown in Tables 1 and 2, and the mixture was processed using a three-roll mill. Test grease compositions were prepared by dispersing. The consistency of the test grease composition is 280. The mass % of each component in each test grease composition is as shown in Tables 1 and 2.
- the kinematic viscosity of the base oil at 100°C is JIS K2220 23. Measured according to The pour point of the base oil was measured according to JIS K2269. The consistency of the grease composition is JIS K2220 7. Measured according to The grease composition obtained above was tested and evaluated by the method shown below.
- Test steel ball ⁇ 5/8in, Ra0.45 ⁇ m bearing steel ball (rotating ball) Steel ball for ⁇ 15mm bearing (driven ball)
- Test load 400kgf (6.5GPa)
- Rotation speed 1200rpm
- Evaluation criteria 150,000 times or more... ⁇ (pass) 100,000 times or more - less than 150,000 times... ⁇ (pass) 50,000 or more - less than 100,000 times... ⁇ (fail) Less than 50,000 times... ⁇ (fail) The results are shown in Tables 1 and 2.
- the first solid lubricant, polytetrafluoroethylene, and the second solid lubricant at least one selected from calcium carbonate, calcium oxide, tricalcium phosphate, and calcium salts of fatty acids, are used in combination.
- Examples 1 to 15 have superior peeling resistance compared to Comparative Examples 1 to 6, 9, and 10.
- Examples 1 to 15 have better heat resistance than Comparative Examples 7 to 10.
- the heat resistance of grease differs depending on the type of thickener, but the improvement in heat resistance in the examples was observed for both Li soap and urea-based thickener.
- the first solid additive and the second solid additive prescribed in the present application together as additives, it is possible to eliminate the need to use a flaking-resistant additive in the reaction system and without selecting a thickener. It is possible to improve the peeling resistance and heat resistance of grease even at high temperatures or high surface pressures.
Abstract
The present invention relates to a grease composition that contains a base oil, a thickener, and additives, the base oil being at least one type of base oil selected from the group that consists of polyoxyalkylenes, ether derivatives of polyoxyalkylenes, and mixtures of polyoxyalkylenes and ether derivatives of polyoxyalkylenes, and the additives including a first solid lubricant that is a polytetrafluoroethylene and a second solid lubricant that is at least one type of solid lubricant selected from the group that consists of calcium carbonate, calcium oxide, tricalcium phosphate, and calcium salts of fatty acids, the second solid lubricant content being at least 0.5 mass% of the total mass of the composition.
Description
本件は、減速機やボールねじ等、耐はく離性が求められる機械部品に好適に使用できるグリース組成物に関する。
This case relates to a grease composition that can be suitably used for mechanical parts that require peeling resistance, such as reduction gears and ball screws.
近年、機械部品は、軽量化のため小型化、高出力化が求められている。そのため、このような機械部品中の潤滑部に使用されるグリースも、高速化、高面圧化、使用温度範囲の高温側への拡大等、従来よりも厳しい使用環境への対応が求められている。特に、高温・高面圧下における部品において使用されるグリースの長寿命化は、重要な技術課題のひとつとなっている。
グリースの長寿命化は、機械部品のはく離を抑制することにより達成することができる。これまでに、グリース中に、アミンフォスフェート、ジアルキルジチオリン酸亜鉛、等の、いわゆる反応系の耐はく離添加剤を含ませることにより、グリースのはく離寿命を延ばすことができることが知られている（特許文献１）。反応系の耐はく離添加剤は、金属表面において反応して保護膜を形成することにより役割を果たす。
ところで、機械部品に使用されるシール材としては、耐油性、耐摩耗性、耐熱性、加工性、低価格等の理由により、ニトリルゴム（ＮＢＲ）が広く使用されている。しかし、冬季の低温や熱帯気候の熱害等によって、シール材が劣化してしまうことがある。シール材の劣化はまた、シール材に接触するグリースに含まれる基油が、シール材を膨潤させることによっても起こる。したがって、シール材を備えた機械部品を長期間使用すると、外部からの異物の浸入を許し、潤滑不良を誘発し、機械部品の寿命を低下させてしまうおそれがある。この問題への対策としては、シール材の選択と、グリースの基油の選択という２つの観点からのアプローチがなされてきた。すなわち、シール材として、ＮＢＲよりも耐熱性、耐寒性、耐候性、耐水性に優れるエチレンプロピレンゴム（ＥＰＤＭ）を使用すると、機械部品の寿命を延長できる。ＥＰＤＭや天然ゴムが潤滑部もしくはその周辺部材のシール材として使用される機械部品には、ポリオキシアルキレンまたはポリオキシアルキレン誘導体をグリースの基油とすることにより、ＥＰＤＭや天然ゴムの膨潤を抑制することができる（特許文献２）。 In recent years, mechanical parts have been required to be smaller in size and higher in output to reduce weight. Therefore, the grease used in the lubricating parts of such mechanical parts is required to be able to handle harsher operating environments than before, such as higher speeds, higher surface pressures, and an expanded operating temperature range to higher temperatures. There is. In particular, extending the lifespan of grease used in parts that are exposed to high temperatures and high surface pressures is an important technical issue.
Longer life of grease can be achieved by suppressing flaking of mechanical parts. It has been known that the flaking life of grease can be extended by incorporating so-called reactive flaking-resistant additives such as amine phosphate and zinc dialkyldithiophosphate into grease (patent Reference 1). Reactive anti-flake additives work by reacting on the metal surface to form a protective film.
By the way, nitrile rubber (NBR) is widely used as a sealing material for mechanical parts due to its oil resistance, abrasion resistance, heat resistance, workability, low cost, and other reasons. However, the sealing material may deteriorate due to low temperatures in winter or heat damage in tropical climates. Deterioration of the sealing material also occurs when the base oil contained in the grease that comes into contact with the sealing material causes the sealing material to swell. Therefore, if a mechanical component equipped with a sealing material is used for a long period of time, there is a risk that foreign matter may enter from the outside, leading to poor lubrication and shortening the life of the mechanical component. As a countermeasure to this problem, approaches have been taken from two viewpoints: selection of sealing material and selection of base oil for grease. That is, when ethylene propylene rubber (EPDM), which has better heat resistance, cold resistance, weather resistance, and water resistance than NBR, is used as a sealing material, the life of mechanical parts can be extended. For mechanical parts where EPDM or natural rubber is used as a sealant for lubricated parts or surrounding parts, use polyoxyalkylene or polyoxyalkylene derivatives as the base oil of the grease to suppress the swelling of EPDM or natural rubber. (Patent Document 2).
グリースの長寿命化は、機械部品のはく離を抑制することにより達成することができる。これまでに、グリース中に、アミンフォスフェート、ジアルキルジチオリン酸亜鉛、等の、いわゆる反応系の耐はく離添加剤を含ませることにより、グリースのはく離寿命を延ばすことができることが知られている（特許文献１）。反応系の耐はく離添加剤は、金属表面において反応して保護膜を形成することにより役割を果たす。
ところで、機械部品に使用されるシール材としては、耐油性、耐摩耗性、耐熱性、加工性、低価格等の理由により、ニトリルゴム（ＮＢＲ）が広く使用されている。しかし、冬季の低温や熱帯気候の熱害等によって、シール材が劣化してしまうことがある。シール材の劣化はまた、シール材に接触するグリースに含まれる基油が、シール材を膨潤させることによっても起こる。したがって、シール材を備えた機械部品を長期間使用すると、外部からの異物の浸入を許し、潤滑不良を誘発し、機械部品の寿命を低下させてしまうおそれがある。この問題への対策としては、シール材の選択と、グリースの基油の選択という２つの観点からのアプローチがなされてきた。すなわち、シール材として、ＮＢＲよりも耐熱性、耐寒性、耐候性、耐水性に優れるエチレンプロピレンゴム（ＥＰＤＭ）を使用すると、機械部品の寿命を延長できる。ＥＰＤＭや天然ゴムが潤滑部もしくはその周辺部材のシール材として使用される機械部品には、ポリオキシアルキレンまたはポリオキシアルキレン誘導体をグリースの基油とすることにより、ＥＰＤＭや天然ゴムの膨潤を抑制することができる（特許文献２）。 In recent years, mechanical parts have been required to be smaller in size and higher in output to reduce weight. Therefore, the grease used in the lubricating parts of such mechanical parts is required to be able to handle harsher operating environments than before, such as higher speeds, higher surface pressures, and an expanded operating temperature range to higher temperatures. There is. In particular, extending the lifespan of grease used in parts that are exposed to high temperatures and high surface pressures is an important technical issue.
Longer life of grease can be achieved by suppressing flaking of mechanical parts. It has been known that the flaking life of grease can be extended by incorporating so-called reactive flaking-resistant additives such as amine phosphate and zinc dialkyldithiophosphate into grease (patent Reference 1). Reactive anti-flake additives work by reacting on the metal surface to form a protective film.
By the way, nitrile rubber (NBR) is widely used as a sealing material for mechanical parts due to its oil resistance, abrasion resistance, heat resistance, workability, low cost, and other reasons. However, the sealing material may deteriorate due to low temperatures in winter or heat damage in tropical climates. Deterioration of the sealing material also occurs when the base oil contained in the grease that comes into contact with the sealing material causes the sealing material to swell. Therefore, if a mechanical component equipped with a sealing material is used for a long period of time, there is a risk that foreign matter may enter from the outside, leading to poor lubrication and shortening the life of the mechanical component. As a countermeasure to this problem, approaches have been taken from two viewpoints: selection of sealing material and selection of base oil for grease. That is, when ethylene propylene rubber (EPDM), which has better heat resistance, cold resistance, weather resistance, and water resistance than NBR, is used as a sealing material, the life of mechanical parts can be extended. For mechanical parts where EPDM or natural rubber is used as a sealant for lubricated parts or surrounding parts, use polyoxyalkylene or polyoxyalkylene derivatives as the base oil of the grease to suppress the swelling of EPDM or natural rubber. (Patent Document 2).
このような事情のもと、優れたゴムへの適合性を有することでシール部材にＥＰＤＭや天然ゴムが使用される機械部品にも適用できる基油として、ポリオキシアルキレンまたはポリオキシアルキレン誘導体を含有するグリース組成物について、高温または高面圧下でも機械部品のはく離の発生を抑制することにより、機械部品の寿命を延長させることができるグリース組成物が求められている。
ポリオキシアルキレン又はポリオキシアルキレン誘導体を基油とするグリースに、反応系の耐はく離添加剤を含ませることにより、ＥＰＤＭや天然ゴムの膨潤と、機械部品のはく離は抑制できる。しかし、このグリースを高温下で使用すると、前記反応系の耐はく離添加剤が金属表面において反応膜を形成する際に生成する酸成分により、ポリオキシアルキレン又はポリオキシアルキレン誘導体の分解が促進されてしまうという問題があった。
また、反応系の耐はく離添加剤は、ポリアルファオレフィンなど極性をもたない基油中では、はく離抑制効果を有効に発揮する。しかし、ポリオキシアルキレン又はポリオキシアルキレン誘導体の様に極性をもつ場合、基油中に分散して潤滑場に吸着しにくくなってしまい、はく離抑制効果が得られにくいという問題もあった。
反応系の耐はく離添加剤に代えて、ポリテトラフルオロエチレン（ＰＴＦＥ）やメラミンシアヌレートなどの固体潤滑剤、すなわち非反応系の耐はく離添加剤を使用すると、基油の分解は抑制できる。非反応系の耐はく離添加剤（固体潤滑剤）は、金属表面に接着し、金属間の接触を妨げることにより役割を果たすが、反応系の耐はく離添加剤と比較して耐はく離性が大きく劣るため、得られるグリースは汎用性に欠けるものであった。
このような技術の流れにおいて、本発明が解決しようとする課題は、ポリオキシアルキレン又はポリオキシアルキレン誘導体を基油とするグリース組成物の耐はく離性を、高温または高面圧下でも、反応系の耐はく離添加剤を使用せずに向上させ、かつ基油の熱劣化を抑制することである。 Under these circumstances, polyoxyalkylene or polyoxyalkylene derivatives are used as base oils that have excellent compatibility with rubber and can be applied to mechanical parts where EPDM or natural rubber is used for sealing members. There is a need for a grease composition that can extend the life of mechanical parts by suppressing the occurrence of flaking of the mechanical parts even under high temperatures or high surface pressures.
By including a reactive anti-peeling additive in a grease containing polyoxyalkylene or a polyoxyalkylene derivative as a base oil, swelling of EPDM or natural rubber and peeling of mechanical parts can be suppressed. However, when this grease is used at high temperatures, the decomposition of the polyoxyalkylene or polyoxyalkylene derivative is accelerated by the acid component generated when the anti-flamination additive in the reaction system forms a reaction film on the metal surface. There was a problem with putting it away.
In addition, the anti-peeling additive in the reactive system effectively exhibits a peeling-inhibiting effect in non-polar base oils such as polyalphaolefins. However, when polyoxyalkylene or polyoxyalkylene derivatives have polarity, they are dispersed in the base oil and become difficult to adsorb to the lubricating field, resulting in a problem that it is difficult to obtain a peeling suppressing effect.
If a solid lubricant such as polytetrafluoroethylene (PTFE) or melamine cyanurate, that is, a non-reactive anti-peeling additive is used instead of a reactive anti-peeling additive, decomposition of the base oil can be suppressed. Non-reactive anti-peeling additives (solid lubricants) play a role by adhering to metal surfaces and preventing contact between metals, but they have greater anti-peeling properties than reactive anti-peeling additives. As a result, the resulting grease lacked versatility.
In this technological trend, the problem to be solved by the present invention is to improve the peeling resistance of a grease composition containing polyoxyalkylene or a polyoxyalkylene derivative as a base oil, even under high temperature or high surface pressure. The objective is to improve the anti-flamination properties without using anti-flake additives and to suppress thermal deterioration of the base oil.
ポリオキシアルキレン又はポリオキシアルキレン誘導体を基油とするグリースに、反応系の耐はく離添加剤を含ませることにより、ＥＰＤＭや天然ゴムの膨潤と、機械部品のはく離は抑制できる。しかし、このグリースを高温下で使用すると、前記反応系の耐はく離添加剤が金属表面において反応膜を形成する際に生成する酸成分により、ポリオキシアルキレン又はポリオキシアルキレン誘導体の分解が促進されてしまうという問題があった。
また、反応系の耐はく離添加剤は、ポリアルファオレフィンなど極性をもたない基油中では、はく離抑制効果を有効に発揮する。しかし、ポリオキシアルキレン又はポリオキシアルキレン誘導体の様に極性をもつ場合、基油中に分散して潤滑場に吸着しにくくなってしまい、はく離抑制効果が得られにくいという問題もあった。
反応系の耐はく離添加剤に代えて、ポリテトラフルオロエチレン（ＰＴＦＥ）やメラミンシアヌレートなどの固体潤滑剤、すなわち非反応系の耐はく離添加剤を使用すると、基油の分解は抑制できる。非反応系の耐はく離添加剤（固体潤滑剤）は、金属表面に接着し、金属間の接触を妨げることにより役割を果たすが、反応系の耐はく離添加剤と比較して耐はく離性が大きく劣るため、得られるグリースは汎用性に欠けるものであった。
このような技術の流れにおいて、本発明が解決しようとする課題は、ポリオキシアルキレン又はポリオキシアルキレン誘導体を基油とするグリース組成物の耐はく離性を、高温または高面圧下でも、反応系の耐はく離添加剤を使用せずに向上させ、かつ基油の熱劣化を抑制することである。 Under these circumstances, polyoxyalkylene or polyoxyalkylene derivatives are used as base oils that have excellent compatibility with rubber and can be applied to mechanical parts where EPDM or natural rubber is used for sealing members. There is a need for a grease composition that can extend the life of mechanical parts by suppressing the occurrence of flaking of the mechanical parts even under high temperatures or high surface pressures.
By including a reactive anti-peeling additive in a grease containing polyoxyalkylene or a polyoxyalkylene derivative as a base oil, swelling of EPDM or natural rubber and peeling of mechanical parts can be suppressed. However, when this grease is used at high temperatures, the decomposition of the polyoxyalkylene or polyoxyalkylene derivative is accelerated by the acid component generated when the anti-flamination additive in the reaction system forms a reaction film on the metal surface. There was a problem with putting it away.
In addition, the anti-peeling additive in the reactive system effectively exhibits a peeling-inhibiting effect in non-polar base oils such as polyalphaolefins. However, when polyoxyalkylene or polyoxyalkylene derivatives have polarity, they are dispersed in the base oil and become difficult to adsorb to the lubricating field, resulting in a problem that it is difficult to obtain a peeling suppressing effect.
If a solid lubricant such as polytetrafluoroethylene (PTFE) or melamine cyanurate, that is, a non-reactive anti-peeling additive is used instead of a reactive anti-peeling additive, decomposition of the base oil can be suppressed. Non-reactive anti-peeling additives (solid lubricants) play a role by adhering to metal surfaces and preventing contact between metals, but they have greater anti-peeling properties than reactive anti-peeling additives. As a result, the resulting grease lacked versatility.
In this technological trend, the problem to be solved by the present invention is to improve the peeling resistance of a grease composition containing polyoxyalkylene or a polyoxyalkylene derivative as a base oil, even under high temperature or high surface pressure. The objective is to improve the anti-flamination properties without using anti-flake additives and to suppress thermal deterioration of the base oil.
本発明者らは、上記耐はく離性の向上の課題を、非反応系の固体潤滑剤を併用することにより解決した。すなわち、本発明により、以下のグリース組成物を提供する。
１．基油、増ちょう剤、添加剤を含有するグリース組成物であって、
基油が、ポリオキシアルキレン、ポリオキシアルキレンのエーテル誘導体及びこれらの混合物からなる群から選ばれる少なくとも１種であり、
添加剤が、第１の固体潤滑剤としてポリテトラフルオロエチレン、および第２の固体潤滑剤として、炭酸カルシウム、酸化カルシウム、リン酸三カルシウム及び脂肪酸のカルシウム塩からなる群から選ばれる少なくとも１種を含み、第２の固体潤滑剤の含有量が、組成物の全質量を基準として０．５質量％以上である、前記グリース組成物。
２．第１の固体潤滑剤の含有量が、組成物の全質量を基準にして、０．５～２０質量％である前記１項記載のグリース組成物。
３．第２の固体潤滑剤の含有量が、組成物の全質量を基準にして、０．５～１０質量％である前記１又は２項記載のグリース組成物。
４．第２の固体潤滑剤が炭酸カルシウムである前記１～３のいずれか１項記載のグリース組成物。
５．第１の固体潤滑剤１０質量％に対して、第２の固体潤滑剤を１～３質量％となる割合で、第１及び第２の固体潤滑剤を含む、前記１～４のいずれか１項記載のグリース組成物。
６．前記１～５のいずれか１項記載のグリース組成物を適用した機械部品。 The present inventors solved the above-mentioned problem of improving peeling resistance by using a non-reactive solid lubricant. That is, the present invention provides the following grease composition.
1. A grease composition containing a base oil, a thickener, and an additive,
The base oil is at least one selected from the group consisting of polyoxyalkylene, ether derivatives of polyoxyalkylene, and mixtures thereof,
The additive contains polytetrafluoroethylene as the first solid lubricant, and at least one member selected from the group consisting of calcium carbonate, calcium oxide, tricalcium phosphate, and calcium salts of fatty acids as the second solid lubricant. The grease composition, wherein the content of the second solid lubricant is 0.5% by mass or more based on the total mass of the composition.
2. 1. The grease composition according to item 1, wherein the content of the first solid lubricant is 0.5 to 20% by mass based on the total mass of the composition.
3. 3. The grease composition according to item 1 or 2 above, wherein the content of the second solid lubricant is 0.5 to 10% by mass based on the total mass of the composition.
4. 4. The grease composition according to any one of items 1 to 3 above, wherein the second solid lubricant is calcium carbonate.
5. Any one of 1 to 4 above, comprising the first and second solid lubricants at a ratio of 1 to 3% by mass of the second solid lubricant to 10% by mass of the first solid lubricant. Grease composition as described in .
6. A mechanical part to which the grease composition according to any one of items 1 to 5 is applied.
１．基油、増ちょう剤、添加剤を含有するグリース組成物であって、
基油が、ポリオキシアルキレン、ポリオキシアルキレンのエーテル誘導体及びこれらの混合物からなる群から選ばれる少なくとも１種であり、
添加剤が、第１の固体潤滑剤としてポリテトラフルオロエチレン、および第２の固体潤滑剤として、炭酸カルシウム、酸化カルシウム、リン酸三カルシウム及び脂肪酸のカルシウム塩からなる群から選ばれる少なくとも１種を含み、第２の固体潤滑剤の含有量が、組成物の全質量を基準として０．５質量％以上である、前記グリース組成物。
２．第１の固体潤滑剤の含有量が、組成物の全質量を基準にして、０．５～２０質量％である前記１項記載のグリース組成物。
３．第２の固体潤滑剤の含有量が、組成物の全質量を基準にして、０．５～１０質量％である前記１又は２項記載のグリース組成物。
４．第２の固体潤滑剤が炭酸カルシウムである前記１～３のいずれか１項記載のグリース組成物。
５．第１の固体潤滑剤１０質量％に対して、第２の固体潤滑剤を１～３質量％となる割合で、第１及び第２の固体潤滑剤を含む、前記１～４のいずれか１項記載のグリース組成物。
６．前記１～５のいずれか１項記載のグリース組成物を適用した機械部品。 The present inventors solved the above-mentioned problem of improving peeling resistance by using a non-reactive solid lubricant. That is, the present invention provides the following grease composition.
1. A grease composition containing a base oil, a thickener, and an additive,
The base oil is at least one selected from the group consisting of polyoxyalkylene, ether derivatives of polyoxyalkylene, and mixtures thereof,
The additive contains polytetrafluoroethylene as the first solid lubricant, and at least one member selected from the group consisting of calcium carbonate, calcium oxide, tricalcium phosphate, and calcium salts of fatty acids as the second solid lubricant. The grease composition, wherein the content of the second solid lubricant is 0.5% by mass or more based on the total mass of the composition.
2. 1. The grease composition according to item 1, wherein the content of the first solid lubricant is 0.5 to 20% by mass based on the total mass of the composition.
3. 3. The grease composition according to item 1 or 2 above, wherein the content of the second solid lubricant is 0.5 to 10% by mass based on the total mass of the composition.
4. 4. The grease composition according to any one of items 1 to 3 above, wherein the second solid lubricant is calcium carbonate.
5. Any one of 1 to 4 above, comprising the first and second solid lubricants at a ratio of 1 to 3% by mass of the second solid lubricant to 10% by mass of the first solid lubricant. Grease composition as described in .
6. A mechanical part to which the grease composition according to any one of items 1 to 5 is applied.
本発明により、高温または高面圧下でも、反応系の耐はく離添加剤を使用しなくても、ポリオキシアルキレン及び／又はポリオキシアルキレンのエーテル誘導体の分解を促進せずに、グリース組成物の耐はく離性及び耐熱性を向上させることができる。
According to the present invention, the grease composition can be made to withstand even under high temperature or high surface pressure without using anti-flamination additives in the reaction system and without promoting the decomposition of polyoxyalkylene and/or ether derivatives of polyoxyalkylene. Peelability and heat resistance can be improved.
＜基油＞
本発明のグリース組成物に使用される基油は、ポリオキシアルキレン及び／又はポリオキシアルキレンのエーテル誘導体である。ポリオキシアルキレン及び／又はポリオキシアルキレンのエーテル誘導体は、シール材であるゴムに対する悪影響が低い。ポリオキシアルキレン及び／又はポリオキシアルキレンのエーテル誘導体は、下記式（１）で表される。 <Base oil>
The base oil used in the grease composition of the present invention is a polyoxyalkylene and/or an ether derivative of a polyoxyalkylene. Polyoxyalkylene and/or ether derivatives of polyoxyalkylene have low adverse effects on rubber, which is a sealing material. The polyoxyalkylene and/or the ether derivative of polyoxyalkylene is represented by the following formula (1).
本発明のグリース組成物に使用される基油は、ポリオキシアルキレン及び／又はポリオキシアルキレンのエーテル誘導体である。ポリオキシアルキレン及び／又はポリオキシアルキレンのエーテル誘導体は、シール材であるゴムに対する悪影響が低い。ポリオキシアルキレン及び／又はポリオキシアルキレンのエーテル誘導体は、下記式（１）で表される。 <Base oil>
The base oil used in the grease composition of the present invention is a polyoxyalkylene and/or an ether derivative of a polyoxyalkylene. Polyoxyalkylene and/or ether derivatives of polyoxyalkylene have low adverse effects on rubber, which is a sealing material. The polyoxyalkylene and/or the ether derivative of polyoxyalkylene is represented by the following formula (1).
ポリオキシアルキレンまたはそのエーテル誘導体とは、式（１）中のＲ1およびＲ3が、それぞれ独立して、水素またはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、ヘキシル基等の炭素数１～６のアルキル基であり、Ｒ2は水素あるいは炭素数１～２のアルキル基であり、ｎが５～５５の数を表わす化合物である。
ポリオキシアルキレンは、エチレンオキサイド、プロピレンオキサイド等のアルキレンオキサイドを開環重合させたジオールである。そのエーテル誘導体は、Ｒ1，Ｒ3のどちらか一方が炭素数１以上のアルキル基であるモノエーテルであるか、またはＲ1，Ｒ3共に炭素数１以上のアルキル基であるジエーテルである。 Polyoxyalkylene or its ether derivative means that R 1 and R 3 in formula (1) are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, or pentyl group. is an alkyl group having 1 to 6 carbon atoms such as hexyl group, R 2 is hydrogen or an alkyl group having 1 to 2 carbon atoms, and n is a compound having a number of 5 to 55.
Polyoxyalkylene is a diol obtained by ring-opening polymerization of alkylene oxide such as ethylene oxide and propylene oxide. The ether derivative is a monoether in which either R 1 or R 3 is an alkyl group having one or more carbon atoms, or a diether in which both R 1 and R 3 are an alkyl group having one or more carbon atoms.
ポリオキシアルキレンは、エチレンオキサイド、プロピレンオキサイド等のアルキレンオキサイドを開環重合させたジオールである。そのエーテル誘導体は、Ｒ1，Ｒ3のどちらか一方が炭素数１以上のアルキル基であるモノエーテルであるか、またはＲ1，Ｒ3共に炭素数１以上のアルキル基であるジエーテルである。 Polyoxyalkylene or its ether derivative means that R 1 and R 3 in formula (1) are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, or pentyl group. is an alkyl group having 1 to 6 carbon atoms such as hexyl group, R 2 is hydrogen or an alkyl group having 1 to 2 carbon atoms, and n is a compound having a number of 5 to 55.
Polyoxyalkylene is a diol obtained by ring-opening polymerization of alkylene oxide such as ethylene oxide and propylene oxide. The ether derivative is a monoether in which either R 1 or R 3 is an alkyl group having one or more carbon atoms, or a diether in which both R 1 and R 3 are an alkyl group having one or more carbon atoms.
ポリオキシアルキレンジオールの具体例としては、ポリオキシエチレン、ポリオキシプロピレン、ポリ（オキシプロピレンオキシエチレン）、ポリ（オキシブチレンオキシエチレン）、ポリ（オキシブチレンオキシプロピレン）、ポリ（オキシペンチレンオキシエチレン）、ポリ（オキシペンチレンオキシプロピレン）があげられる。
ポリオキシアルキレンのエーテル誘導体の具体例としては、ポリオキシプロピレンモノプロピルエーテル、ポリオキシプロピレンモノブチルエーテル、ポリオキシブチレンモノブチルエーテル、ポリオキシエチレンオキシプロピレンモノプロピルエーテル、ポリオキシエチレンオキシプロピレンモノブチルエーテル、ポリオキシエチレンオキシプロピレンモノペンチルエーテルがあげられる。
尚、このうちポリオキシエチレン、ポリ（オキシプロピレンオキシエチレン）とそのエーテル誘導体は水溶性であるため、これらを基油としたグリースは耐水性に劣る。この為、本発明の基油として適切なのは、Ｒ2が炭素数１以上のアルキル基のポリオキシアルキレンまたはそのエーテル誘導体であり、好ましくはポリオキシプロピレンモノブチルエーテルであり、特に好ましくはｎが１０～２５であるポリオキシプロピレンモノブチルエーテルであり、さらに特に好ましくはｎが１０～２２であるポリオキシプロピレンモノブチルエーテルである。
本発明の基油は、動植物などから生まれた生物資源を原料として製造される、所謂バイオマス油でもよい。 Specific examples of polyoxyalkylene diols include polyoxyethylene, polyoxypropylene, poly(oxypropyleneoxyethylene), poly(oxybutyleneoxyethylene), poly(oxybutyleneoxypropylene), and poly(oxypentyleneoxyethylene). , poly(oxypentylene oxypropylene).
Specific examples of ether derivatives of polyoxyalkylene include polyoxypropylene monopropyl ether, polyoxypropylene monobutyl ether, polyoxybutylene monobutyl ether, polyoxyethylene oxypropylene monopropyl ether, polyoxyethylene oxypropylene monobutyl ether, polyoxy Examples include ethylene oxypropylene monopentyl ether.
Note that among these, polyoxyethylene, poly(oxypropyleneoxyethylene), and their ether derivatives are water-soluble, so greases using these as base oils have poor water resistance. Therefore, suitable base oils for the present invention are polyoxyalkylene in which R 2 is an alkyl group having 1 or more carbon atoms or its ether derivative, preferably polyoxypropylene monobutyl ether, and particularly preferably n is 10 to 10. 25, more particularly preferably polyoxypropylene monobutyl ether where n is 10 to 22.
The base oil of the present invention may be a so-called biomass oil that is produced using biological resources derived from animals and plants as raw materials.
ポリオキシアルキレンのエーテル誘導体の具体例としては、ポリオキシプロピレンモノプロピルエーテル、ポリオキシプロピレンモノブチルエーテル、ポリオキシブチレンモノブチルエーテル、ポリオキシエチレンオキシプロピレンモノプロピルエーテル、ポリオキシエチレンオキシプロピレンモノブチルエーテル、ポリオキシエチレンオキシプロピレンモノペンチルエーテルがあげられる。
尚、このうちポリオキシエチレン、ポリ（オキシプロピレンオキシエチレン）とそのエーテル誘導体は水溶性であるため、これらを基油としたグリースは耐水性に劣る。この為、本発明の基油として適切なのは、Ｒ2が炭素数１以上のアルキル基のポリオキシアルキレンまたはそのエーテル誘導体であり、好ましくはポリオキシプロピレンモノブチルエーテルであり、特に好ましくはｎが１０～２５であるポリオキシプロピレンモノブチルエーテルであり、さらに特に好ましくはｎが１０～２２であるポリオキシプロピレンモノブチルエーテルである。
本発明の基油は、動植物などから生まれた生物資源を原料として製造される、所謂バイオマス油でもよい。 Specific examples of polyoxyalkylene diols include polyoxyethylene, polyoxypropylene, poly(oxypropyleneoxyethylene), poly(oxybutyleneoxyethylene), poly(oxybutyleneoxypropylene), and poly(oxypentyleneoxyethylene). , poly(oxypentylene oxypropylene).
Specific examples of ether derivatives of polyoxyalkylene include polyoxypropylene monopropyl ether, polyoxypropylene monobutyl ether, polyoxybutylene monobutyl ether, polyoxyethylene oxypropylene monopropyl ether, polyoxyethylene oxypropylene monobutyl ether, polyoxy Examples include ethylene oxypropylene monopentyl ether.
Note that among these, polyoxyethylene, poly(oxypropyleneoxyethylene), and their ether derivatives are water-soluble, so greases using these as base oils have poor water resistance. Therefore, suitable base oils for the present invention are polyoxyalkylene in which R 2 is an alkyl group having 1 or more carbon atoms or its ether derivative, preferably polyoxypropylene monobutyl ether, and particularly preferably n is 10 to 10. 25, more particularly preferably polyoxypropylene monobutyl ether where n is 10 to 22.
The base oil of the present invention may be a so-called biomass oil that is produced using biological resources derived from animals and plants as raw materials.
本発明の基油は、１００℃における動粘度が２～１００mm2/sであるのが好ましい。これにより、低温性に優れる。１００℃における動粘度は２～５０mm2/sであるのがより好ましく、２～２０mm2/sであるのがさらに好ましく、６～１９mm2/sであるのが特に好ましい。
本発明の基油は、流動点が－１０℃以下であるのが好ましい。これにより、低温性に優れる。流動点は、－２０℃以下であるのがより好ましく、－３０℃以下であるのがさらに好ましく、－３５℃以下であるのが特に好ましい。
本発明の基油としては、１００℃における動粘度が６～１９mm2/sであり、流動点が－３５℃以下である、式（１）中、ｎが１０～２２であるポリオキシプロピレンモノブチルエーテルが最も好ましい。
本発明のグリース組成物における基油の含有量は、例えば、６０～９０質量％であるのが好ましく、６０～８０質量％であるのがより好ましい。 The base oil of the present invention preferably has a kinematic viscosity of 2 to 100 mm 2 /s at 100°C. This provides excellent low temperature properties. The kinematic viscosity at 100° C. is more preferably 2 to 50 mm 2 /s, even more preferably 2 to 20 mm 2 /s, and particularly preferably 6 to 19 mm 2 /s.
The base oil of the present invention preferably has a pour point of -10°C or lower. This provides excellent low temperature properties. The pour point is more preferably -20°C or lower, even more preferably -30°C or lower, particularly preferably -35°C or lower.
The base oil of the present invention is a polyoxypropylene monomer having a kinematic viscosity of 6 to 19 mm 2 /s at 100°C, a pour point of -35°C or lower, and in which n is 10 to 22 in formula (1). Butyl ether is most preferred.
The base oil content in the grease composition of the present invention is, for example, preferably 60 to 90% by mass, more preferably 60 to 80% by mass.
本発明の基油は、流動点が－１０℃以下であるのが好ましい。これにより、低温性に優れる。流動点は、－２０℃以下であるのがより好ましく、－３０℃以下であるのがさらに好ましく、－３５℃以下であるのが特に好ましい。
本発明の基油としては、１００℃における動粘度が６～１９mm2/sであり、流動点が－３５℃以下である、式（１）中、ｎが１０～２２であるポリオキシプロピレンモノブチルエーテルが最も好ましい。
本発明のグリース組成物における基油の含有量は、例えば、６０～９０質量％であるのが好ましく、６０～８０質量％であるのがより好ましい。 The base oil of the present invention preferably has a kinematic viscosity of 2 to 100 mm 2 /s at 100°C. This provides excellent low temperature properties. The kinematic viscosity at 100° C. is more preferably 2 to 50 mm 2 /s, even more preferably 2 to 20 mm 2 /s, and particularly preferably 6 to 19 mm 2 /s.
The base oil of the present invention preferably has a pour point of -10°C or lower. This provides excellent low temperature properties. The pour point is more preferably -20°C or lower, even more preferably -30°C or lower, particularly preferably -35°C or lower.
The base oil of the present invention is a polyoxypropylene monomer having a kinematic viscosity of 6 to 19 mm 2 /s at 100°C, a pour point of -35°C or lower, and in which n is 10 to 22 in formula (1). Butyl ether is most preferred.
The base oil content in the grease composition of the present invention is, for example, preferably 60 to 90% by mass, more preferably 60 to 80% by mass.
＜固体潤滑剤＞
本発明における第１の固体潤滑剤は、ポリテトラフルオロエチレンである。
第１の固体潤滑剤の含有量は、組成物の全質量を基準として、０．５質量％以上であるのが好ましい。これにより、耐はく離性に優れる。１質量％以上であるのがより好ましい。上限は、グリースの流入性の観点から、２０質量％以下であるのが好ましく、１５質量％以下であるのがより好ましい。 <Solid lubricant>
The first solid lubricant in the present invention is polytetrafluoroethylene.
The content of the first solid lubricant is preferably 0.5% by mass or more based on the total mass of the composition. This provides excellent peeling resistance. More preferably, it is 1% by mass or more. From the viewpoint of grease inflow, the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
本発明における第１の固体潤滑剤は、ポリテトラフルオロエチレンである。
第１の固体潤滑剤の含有量は、組成物の全質量を基準として、０．５質量％以上であるのが好ましい。これにより、耐はく離性に優れる。１質量％以上であるのがより好ましい。上限は、グリースの流入性の観点から、２０質量％以下であるのが好ましく、１５質量％以下であるのがより好ましい。 <Solid lubricant>
The first solid lubricant in the present invention is polytetrafluoroethylene.
The content of the first solid lubricant is preferably 0.5% by mass or more based on the total mass of the composition. This provides excellent peeling resistance. More preferably, it is 1% by mass or more. From the viewpoint of grease inflow, the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less.
本発明における第２の固体潤滑剤は、炭酸カルシウム、酸化カルシウム、リン酸三カルシウム及び脂肪酸のカルシウム塩からなる群から選ばれる少なくとも１種である。このうち、耐はく離性の観点から、炭酸カルシウムが好ましい。脂肪酸のカルシウム塩を構成する脂肪酸としては、炭素数１～２２の脂肪酸が好ましく、炭素数１６～２０の脂肪酸がより好ましい。
第２の固体潤滑剤は、併用による耐はく離性向上効果の観点から、第１の固体潤滑剤であるＰＴＦＥの粒径よりも大きいものが好ましい。 The second solid lubricant in the present invention is at least one selected from the group consisting of calcium carbonate, calcium oxide, tricalcium phosphate, and calcium salts of fatty acids. Among these, calcium carbonate is preferred from the viewpoint of peeling resistance. The fatty acid constituting the calcium salt of fatty acid is preferably a fatty acid having 1 to 22 carbon atoms, more preferably a fatty acid having 16 to 20 carbon atoms.
The second solid lubricant is preferably larger in particle size than the first solid lubricant, PTFE, from the viewpoint of improving peeling resistance when used in combination.
第２の固体潤滑剤は、併用による耐はく離性向上効果の観点から、第１の固体潤滑剤であるＰＴＦＥの粒径よりも大きいものが好ましい。 The second solid lubricant in the present invention is at least one selected from the group consisting of calcium carbonate, calcium oxide, tricalcium phosphate, and calcium salts of fatty acids. Among these, calcium carbonate is preferred from the viewpoint of peeling resistance. The fatty acid constituting the calcium salt of fatty acid is preferably a fatty acid having 1 to 22 carbon atoms, more preferably a fatty acid having 16 to 20 carbon atoms.
The second solid lubricant is preferably larger in particle size than the first solid lubricant, PTFE, from the viewpoint of improving peeling resistance when used in combination.
第２の固体潤滑剤の含有量は、組成物の全質量を基準として、０．５質量％以上である。これにより、耐はく離性に優れる。第１の固体潤滑剤の含有量と同じである必要は無い。１質量％以上であるのがより好ましい。上限は、グリースの流入性の観点から、１０質量％以下であるのが好ましく、５質量％以下であるのがより好ましい。
第２の固体潤滑剤の種類を問わず、ＰＴＦＥ１０質量部に対して、１～３質量部の量の第２の固体潤滑剤を含ませると、グリース組成物の耐はく離性が特に優れる。したがって、耐はく離性の観点からは、ＰＴＦＥ１０質量部に対して、ＰＴＦＥよりも粒子径の大きい炭酸カルシウムが１～３質量部となる割合で含むのがとりわけ好ましい。 The content of the second solid lubricant is 0.5% by mass or more based on the total mass of the composition. This provides excellent peeling resistance. The content does not need to be the same as that of the first solid lubricant. More preferably, it is 1% by mass or more. From the viewpoint of grease inflow, the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less.
Regardless of the type of the second solid lubricant, when the second solid lubricant is included in an amount of 1 to 3 parts by mass based on 10 parts by mass of PTFE, the peeling resistance of the grease composition is particularly excellent. Therefore, from the viewpoint of peeling resistance, it is particularly preferable that calcium carbonate, which has a particle size larger than that of PTFE, be contained in an amount of 1 to 3 parts by mass per 10 parts by mass of PTFE.
第２の固体潤滑剤の種類を問わず、ＰＴＦＥ１０質量部に対して、１～３質量部の量の第２の固体潤滑剤を含ませると、グリース組成物の耐はく離性が特に優れる。したがって、耐はく離性の観点からは、ＰＴＦＥ１０質量部に対して、ＰＴＦＥよりも粒子径の大きい炭酸カルシウムが１～３質量部となる割合で含むのがとりわけ好ましい。 The content of the second solid lubricant is 0.5% by mass or more based on the total mass of the composition. This provides excellent peeling resistance. The content does not need to be the same as that of the first solid lubricant. More preferably, it is 1% by mass or more. From the viewpoint of grease inflow, the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less.
Regardless of the type of the second solid lubricant, when the second solid lubricant is included in an amount of 1 to 3 parts by mass based on 10 parts by mass of PTFE, the peeling resistance of the grease composition is particularly excellent. Therefore, from the viewpoint of peeling resistance, it is particularly preferable that calcium carbonate, which has a particle size larger than that of PTFE, be contained in an amount of 1 to 3 parts by mass per 10 parts by mass of PTFE.
本発明のグリース組成物における第１の固体潤滑剤及び第２固体潤滑剤の総量は、１～２０質量％であるのが好ましく、５～１５質量％であるのがより好ましい。第１の固体潤滑剤及び第２の固体潤滑剤の総量がこのような範囲にあると、グリースの流入性による性能への影響が小さいので好ましい。
The total amount of the first solid lubricant and the second solid lubricant in the grease composition of the present invention is preferably 1 to 20% by mass, more preferably 5 to 15% by mass. It is preferable that the total amount of the first solid lubricant and the second solid lubricant be within this range, since the influence of grease inflow properties on performance is small.
本発明の第１及び第２の固体潤滑剤は、極性をもたないことから、ポリオキシアルキレン及び／又はポリオキシアルキレンのエーテル誘導体に含ませても、基油の影響を受けることなく耐はく離性を向上させることができる。
如何なる理論にも拘束されるものではないが、第２の固体潤滑剤よりも粒子径の小さいポリテトラフルオロエチレンが潤滑場に介在することで、耐はく離性に優れる一方、第２の固体潤滑剤を安定して潤滑場へ供給することが可能となり、耐はく離性を著しく向上させていると考えられる。 Since the first and second solid lubricants of the present invention do not have polarity, even if they are included in polyoxyalkylene and/or ether derivatives of polyoxyalkylene, they will not be affected by the base oil and will have peeling resistance. can improve sex.
Without being bound by any theory, the presence of polytetrafluoroethylene, which has a smaller particle size than the second solid lubricant, in the lubrication field provides excellent peeling resistance, while the second solid lubricant This makes it possible to stably supply the oil to the lubrication field, which is thought to significantly improve flaking resistance.
如何なる理論にも拘束されるものではないが、第２の固体潤滑剤よりも粒子径の小さいポリテトラフルオロエチレンが潤滑場に介在することで、耐はく離性に優れる一方、第２の固体潤滑剤を安定して潤滑場へ供給することが可能となり、耐はく離性を著しく向上させていると考えられる。 Since the first and second solid lubricants of the present invention do not have polarity, even if they are included in polyoxyalkylene and/or ether derivatives of polyoxyalkylene, they will not be affected by the base oil and will have peeling resistance. can improve sex.
Without being bound by any theory, the presence of polytetrafluoroethylene, which has a smaller particle size than the second solid lubricant, in the lubrication field provides excellent peeling resistance, while the second solid lubricant This makes it possible to stably supply the oil to the lubrication field, which is thought to significantly improve flaking resistance.
＜増ちょう剤＞
本発明のグリースの増ちょう剤としては、特に制限無く用いることができる。具体的には、Ｌｉ石けんやＬｉコンプレックス石けんに代表される石けん系増ちょう剤、ジウレアに代表されるウレア系増ちょう剤、有機化ベントナイトやシリカに代表される無機系増ちょう剤、ナトリウムテレフタラートに代表される有機系増ちょう剤などが挙げられる。
このうち、Ｌｉ石けん及びジウレア化合物が好ましい。これらは、欠点が少なく、かつ高価でないため、実用性のある増ちょう剤であるからである。 <Thickener>
The thickener for the grease of the present invention can be used without particular limitations. Specifically, soap-based thickeners such as Li soap and Li-complex soap, urea-based thickeners such as diurea, inorganic thickeners such as organic bentonite and silica, and sodium terephthalate are used. Examples include organic thickeners typified by .
Among these, Li soap and diurea compounds are preferred. This is because these are practical thickeners because they have few drawbacks and are not expensive.
本発明のグリースの増ちょう剤としては、特に制限無く用いることができる。具体的には、Ｌｉ石けんやＬｉコンプレックス石けんに代表される石けん系増ちょう剤、ジウレアに代表されるウレア系増ちょう剤、有機化ベントナイトやシリカに代表される無機系増ちょう剤、ナトリウムテレフタラートに代表される有機系増ちょう剤などが挙げられる。
このうち、Ｌｉ石けん及びジウレア化合物が好ましい。これらは、欠点が少なく、かつ高価でないため、実用性のある増ちょう剤であるからである。 <Thickener>
The thickener for the grease of the present invention can be used without particular limitations. Specifically, soap-based thickeners such as Li soap and Li-complex soap, urea-based thickeners such as diurea, inorganic thickeners such as organic bentonite and silica, and sodium terephthalate are used. Examples include organic thickeners typified by .
Among these, Li soap and diurea compounds are preferred. This is because these are practical thickeners because they have few drawbacks and are not expensive.
Ｌｉ石けんとしては、１２－ヒドロキシステアリン酸リチウム（Ｌｉ－（１２ＯＨ）Ｓｔ）又はステアリン酸リチウム（Ｌｉ－Ｓｔ）が好ましい。これらは潤滑性に優れる。
Ｌｉコンプレックス石けんは、ステアリン酸や１２－ヒドロキシステアリン酸等の脂肪族カルボン酸のリチウム塩と二塩基酸リチウム塩とのコンプレックス等が挙げられる。二塩基酸としては、コハク酸、マロン酸、アジピン酸、ピメリン酸、アゼライン酸、セバシン酸等が挙げられる。アゼライン酸、セバシン酸が好ましい。特に、アゼライン酸と水酸化リチウムとの塩と、１２－ヒドロキシステアリン酸と水酸化リチウムとの塩との混合物であるＬｉコンプレックス石けんが好ましい。 As the Li soap, lithium 12-hydroxystearate (Li-(12OH)St) or lithium stearate (Li-St) is preferable. These have excellent lubricity.
Li complex soaps include complexes of lithium salts of aliphatic carboxylic acids such as stearic acid and 12-hydroxystearic acid and lithium salts of dibasic acids. Examples of dibasic acids include succinic acid, malonic acid, adipic acid, pimelic acid, azelaic acid, and sebacic acid. Azelaic acid and sebacic acid are preferred. Particularly preferred is a Li complex soap which is a mixture of a salt of azelaic acid and lithium hydroxide and a salt of 12-hydroxystearic acid and lithium hydroxide.
Ｌｉコンプレックス石けんは、ステアリン酸や１２－ヒドロキシステアリン酸等の脂肪族カルボン酸のリチウム塩と二塩基酸リチウム塩とのコンプレックス等が挙げられる。二塩基酸としては、コハク酸、マロン酸、アジピン酸、ピメリン酸、アゼライン酸、セバシン酸等が挙げられる。アゼライン酸、セバシン酸が好ましい。特に、アゼライン酸と水酸化リチウムとの塩と、１２－ヒドロキシステアリン酸と水酸化リチウムとの塩との混合物であるＬｉコンプレックス石けんが好ましい。 As the Li soap, lithium 12-hydroxystearate (Li-(12OH)St) or lithium stearate (Li-St) is preferable. These have excellent lubricity.
Li complex soaps include complexes of lithium salts of aliphatic carboxylic acids such as stearic acid and 12-hydroxystearic acid and lithium salts of dibasic acids. Examples of dibasic acids include succinic acid, malonic acid, adipic acid, pimelic acid, azelaic acid, and sebacic acid. Azelaic acid and sebacic acid are preferred. Particularly preferred is a Li complex soap which is a mixture of a salt of azelaic acid and lithium hydroxide and a salt of 12-hydroxystearic acid and lithium hydroxide.
ジウレア化合物は、一般的に、下記式（２）で表される。
Ｒ4－ＮＨＣＯＮＨ－Ｒ5－ＮＨＣＯＮＨ－Ｒ6 （２）
（式中、Ｒ4及びＲ6は、互いに同一でも異なっていてもよく、Ｃ６－３０アルキル基、Ｃ５－８シクロアルキル基、又はＣ６－１０アリール基を示し、Ｒ5は、Ｃ６－１５の２価の芳香族炭化水素基を示す。）
ジウレア化合物としては、Ｒ4及びＲ6が互いに同一でも異なっていてもよいＣ６－３０アルキル基である脂肪族ジウレア、Ｒ4及びＲ6の一方がＣ５－８シクロアルキル基であり、他方がＣ６－３０アルキル基である脂環式脂肪族ジウレア、又はＲ4及びＲ6が互いに同一でも異なっていてもよいＣ６－１０アリール基である芳香族ジウレアが好ましい。 A diurea compound is generally represented by the following formula (2).
R 4 -NHCONH-R 5 -NHCONH-R 6 (2)
(In the formula, R 4 and R 6 may be the same or different and represent a C6-30 alkyl group, a C5-8 cycloalkyl group, or a C6-10 aryl group, and R 5 is a C6-15 (Indicates a divalent aromatic hydrocarbon group.)
Examples of diurea compounds include aliphatic diureas in which R 4 and R 6 are C6-30 alkyl groups which may be the same or different; one of R 4 and R 6 is a C5-8 cycloalkyl group, and the other is a C6-30 alkyl group; A cycloaliphatic diurea which is a -30 alkyl group, or an aromatic diurea where R 4 and R 6 are a C6-10 aryl group which may be the same or different from each other is preferred.
Ｒ4－ＮＨＣＯＮＨ－Ｒ5－ＮＨＣＯＮＨ－Ｒ6 （２）
（式中、Ｒ4及びＲ6は、互いに同一でも異なっていてもよく、Ｃ６－３０アルキル基、Ｃ５－８シクロアルキル基、又はＣ６－１０アリール基を示し、Ｒ5は、Ｃ６－１５の２価の芳香族炭化水素基を示す。）
ジウレア化合物としては、Ｒ4及びＲ6が互いに同一でも異なっていてもよいＣ６－３０アルキル基である脂肪族ジウレア、Ｒ4及びＲ6の一方がＣ５－８シクロアルキル基であり、他方がＣ６－３０アルキル基である脂環式脂肪族ジウレア、又はＲ4及びＲ6が互いに同一でも異なっていてもよいＣ６－１０アリール基である芳香族ジウレアが好ましい。 A diurea compound is generally represented by the following formula (2).
R 4 -NHCONH-R 5 -NHCONH-R 6 (2)
(In the formula, R 4 and R 6 may be the same or different and represent a C6-30 alkyl group, a C5-8 cycloalkyl group, or a C6-10 aryl group, and R 5 is a C6-15 (Indicates a divalent aromatic hydrocarbon group.)
Examples of diurea compounds include aliphatic diureas in which R 4 and R 6 are C6-30 alkyl groups which may be the same or different; one of R 4 and R 6 is a C5-8 cycloalkyl group, and the other is a C6-30 alkyl group; A cycloaliphatic diurea which is a -30 alkyl group, or an aromatic diurea where R 4 and R 6 are a C6-10 aryl group which may be the same or different from each other is preferred.
脂肪族ジウレアとしては、Ｒ4及びＲ6の両方がＣ８アルキル基である脂肪族ジウレア、Ｒ4及びＲ6の両方がＣ１８アルキル基である脂肪族ジウレア、及びＲ4及びＲ6の一方がＣ８アルキル基であり、他方がＣ１８アルキル基である脂肪族ジウレアがより好ましい。Ｒ4及びＲ6の一方がＣ８アルキル基であり、他方がＣ１８アルキル基である脂肪族ジウレアが特に好ましい。Ｃ８アルキル基とＣ１８アルキル基の総モル数に対するＣ８アルキル基のモル数の割合が、３０～７０モル％である脂肪族ジウレアがさらに特に好ましい。
脂環式脂肪族ジウレアとしては、Ｒ4及びＲ6の一方がシクロヘキシル基であり、他方がＣ１８アルキル基である脂環式脂肪族ジウレアがより好ましい。シクロヘキシル基とＣ１８アルキル基の総モル数に対するシクロヘキシル基のモル数の割合が、３０～９０モル％であるである脂環式脂肪族ジウレアが特に好ましい。
芳香族ジウレアとしては、Ｒ4及びＲ6がいずれもｐ-トルイル基である芳香族ジウレアが特に好ましい。 The aliphatic diureas include aliphatic diureas in which both R 4 and R 6 are C8 alkyl groups, aliphatic diureas in which both R 4 and R 6 are C18 alkyl groups, and aliphatic diureas in which one of R 4 and R 6 is C8 alkyl groups. More preferred are aliphatic diureas in which one is an alkyl group and the other is a C18 alkyl group. Particularly preferred are aliphatic diureas in which one of R 4 and R 6 is a C8 alkyl group and the other is a C18 alkyl group. More particularly preferred are aliphatic diureas in which the ratio of the number of moles of the C8 alkyl group to the total number of moles of the C8 alkyl group and the C18 alkyl group is 30 to 70 mol %.
As the alicyclic aliphatic diurea, an alicyclic aliphatic diurea in which one of R 4 and R 6 is a cyclohexyl group and the other is a C18 alkyl group is more preferable. Particularly preferred is an alicycloaliphatic diurea in which the ratio of the number of moles of the cyclohexyl group to the total number of moles of the cyclohexyl group and the C18 alkyl group is 30 to 90 mol%.
As the aromatic diurea, an aromatic diurea in which both R 4 and R 6 are p-tolyl groups is particularly preferred.
脂環式脂肪族ジウレアとしては、Ｒ4及びＲ6の一方がシクロヘキシル基であり、他方がＣ１８アルキル基である脂環式脂肪族ジウレアがより好ましい。シクロヘキシル基とＣ１８アルキル基の総モル数に対するシクロヘキシル基のモル数の割合が、３０～９０モル％であるである脂環式脂肪族ジウレアが特に好ましい。
芳香族ジウレアとしては、Ｒ4及びＲ6がいずれもｐ-トルイル基である芳香族ジウレアが特に好ましい。 The aliphatic diureas include aliphatic diureas in which both R 4 and R 6 are C8 alkyl groups, aliphatic diureas in which both R 4 and R 6 are C18 alkyl groups, and aliphatic diureas in which one of R 4 and R 6 is C8 alkyl groups. More preferred are aliphatic diureas in which one is an alkyl group and the other is a C18 alkyl group. Particularly preferred are aliphatic diureas in which one of R 4 and R 6 is a C8 alkyl group and the other is a C18 alkyl group. More particularly preferred are aliphatic diureas in which the ratio of the number of moles of the C8 alkyl group to the total number of moles of the C8 alkyl group and the C18 alkyl group is 30 to 70 mol %.
As the alicyclic aliphatic diurea, an alicyclic aliphatic diurea in which one of R 4 and R 6 is a cyclohexyl group and the other is a C18 alkyl group is more preferable. Particularly preferred is an alicycloaliphatic diurea in which the ratio of the number of moles of the cyclohexyl group to the total number of moles of the cyclohexyl group and the C18 alkyl group is 30 to 90 mol%.
As the aromatic diurea, an aromatic diurea in which both R 4 and R 6 are p-tolyl groups is particularly preferred.
本発明のグリース組成物における増ちょう剤の含有量は、例えば、４～２５質量％であるのが好ましく、５～２０質量％であるのがより好ましい。増ちょう剤の含有量がこのような範囲にあると、グリースが適度な硬さを有し、潤滑部からの漏洩を防止するので好ましい。
The content of the thickener in the grease composition of the present invention is, for example, preferably 4 to 25% by mass, more preferably 5 to 20% by mass. When the content of the thickener is within this range, the grease has appropriate hardness and prevents leakage from lubricated parts, which is preferable.
＜その他の添加剤＞
本発明のグリース組成物には、一般にグリース組成物に使用される任意の添加剤を必要に応じて含ませることができる。例えば、酸化防止剤、防錆剤、腐食防止剤、油性剤、粘度指数向上剤などが挙げられる。酸化防止剤及び／又は防錆剤を含むのが好ましい。しかし、反応系の添加剤（すなわち、潤滑表面で反応して、基油を分解する成分を生成する添加剤、例えば、二硫化モリブデン、アミンフォスフェート、ジアルキルジチオリン酸亜鉛、ジアルキルジチオカルバミン酸モリブデン）を含まないのが好ましい。
酸化防止剤としては、アミン系、フェノール系、キノリン系、硫黄系等が挙げられるが、アミン系、キノリン系酸化防止剤が好ましい。
防錆剤としては、亜鉛系、カルボン酸系、カルボン酸塩系、コハク酸系、アミン系、スルホン酸塩系、ナフテン酸系が挙げられる。アミン系、ナフテン酸系が好ましい。これらの混合物がさらに好ましい。
腐食防止剤としては、チアジアゾール系、ベンゾイミダゾール系、ベンゾトリアゾール系が挙げられる。
油性剤としては、脂肪酸、脂肪酸エステル、リン酸エステルが挙げられる。
本発明のグリース組成物がその他の添加剤を含む場合、その含有量は、グリース組成物の全量を基準として、通常０．５～１０質量％、好ましくは０．５～５質量％である。 <Other additives>
The grease composition of the present invention can optionally contain any additives commonly used in grease compositions. Examples include antioxidants, rust preventives, corrosion inhibitors, oiliness agents, viscosity index improvers, and the like. Preferably, it contains an antioxidant and/or a rust inhibitor. However, reactive additives (i.e., additives that react at lubricated surfaces to produce components that degrade the base oil, such as molybdenum disulfide, amine phosphates, zinc dialkyldithiophosphates, and molybdenum dialkyldithiocarbamates) It is preferable not to include it.
Examples of antioxidants include amine-based, phenol-based, quinoline-based, and sulfur-based antioxidants, with amine-based and quinoline-based antioxidants being preferred.
Examples of rust preventives include zinc-based, carboxylic acid-based, carboxylate-based, succinic acid-based, amine-based, sulfonate-based, and naphthenic acid-based. Amine type and naphthenic acid type are preferred. Mixtures of these are more preferred.
Examples of corrosion inhibitors include thiadiazole, benzimidazole, and benzotriazole.
Examples of oily agents include fatty acids, fatty acid esters, and phosphoric acid esters.
When the grease composition of the present invention contains other additives, the content thereof is usually 0.5 to 10% by mass, preferably 0.5 to 5% by mass, based on the total amount of the grease composition.
本発明のグリース組成物には、一般にグリース組成物に使用される任意の添加剤を必要に応じて含ませることができる。例えば、酸化防止剤、防錆剤、腐食防止剤、油性剤、粘度指数向上剤などが挙げられる。酸化防止剤及び／又は防錆剤を含むのが好ましい。しかし、反応系の添加剤（すなわち、潤滑表面で反応して、基油を分解する成分を生成する添加剤、例えば、二硫化モリブデン、アミンフォスフェート、ジアルキルジチオリン酸亜鉛、ジアルキルジチオカルバミン酸モリブデン）を含まないのが好ましい。
酸化防止剤としては、アミン系、フェノール系、キノリン系、硫黄系等が挙げられるが、アミン系、キノリン系酸化防止剤が好ましい。
防錆剤としては、亜鉛系、カルボン酸系、カルボン酸塩系、コハク酸系、アミン系、スルホン酸塩系、ナフテン酸系が挙げられる。アミン系、ナフテン酸系が好ましい。これらの混合物がさらに好ましい。
腐食防止剤としては、チアジアゾール系、ベンゾイミダゾール系、ベンゾトリアゾール系が挙げられる。
油性剤としては、脂肪酸、脂肪酸エステル、リン酸エステルが挙げられる。
本発明のグリース組成物がその他の添加剤を含む場合、その含有量は、グリース組成物の全量を基準として、通常０．５～１０質量％、好ましくは０．５～５質量％である。 <Other additives>
The grease composition of the present invention can optionally contain any additives commonly used in grease compositions. Examples include antioxidants, rust preventives, corrosion inhibitors, oiliness agents, viscosity index improvers, and the like. Preferably, it contains an antioxidant and/or a rust inhibitor. However, reactive additives (i.e., additives that react at lubricated surfaces to produce components that degrade the base oil, such as molybdenum disulfide, amine phosphates, zinc dialkyldithiophosphates, and molybdenum dialkyldithiocarbamates) It is preferable not to include it.
Examples of antioxidants include amine-based, phenol-based, quinoline-based, and sulfur-based antioxidants, with amine-based and quinoline-based antioxidants being preferred.
Examples of rust preventives include zinc-based, carboxylic acid-based, carboxylate-based, succinic acid-based, amine-based, sulfonate-based, and naphthenic acid-based. Amine type and naphthenic acid type are preferred. Mixtures of these are more preferred.
Examples of corrosion inhibitors include thiadiazole, benzimidazole, and benzotriazole.
Examples of oily agents include fatty acids, fatty acid esters, and phosphoric acid esters.
When the grease composition of the present invention contains other additives, the content thereof is usually 0.5 to 10% by mass, preferably 0.5 to 5% by mass, based on the total amount of the grease composition.
〔ちょう度〕
本発明のグリース組成物のちょう度は、使用目的に合わせて調整されるが、好ましくは２３５～３７０である。ちょう度を２３５以上に設定することにより、低温性に優れたグリース組成物を得ることが出来、３７０以下にすることにより、機械部品への付着性に優れたグリース組成物を得ることが出来る。なお、本明細書において、用語「ちょう度」は、６０回混和ちょう度を指す。ちょう度は、ＪＩＳ Ｋ２２２０ ７．に従って測定することができる。 [Consistency]
The consistency of the grease composition of the present invention is adjusted depending on the intended use, but is preferably 235 to 370. By setting the consistency to 235 or more, a grease composition with excellent low-temperature properties can be obtained, and by setting the consistency to 370 or less, a grease composition with excellent adhesion to mechanical parts can be obtained. In addition, in this specification, the term "penetration" refers to 60 times worked penetration. Consistency is JIS K2220 7. It can be measured according to
本発明のグリース組成物のちょう度は、使用目的に合わせて調整されるが、好ましくは２３５～３７０である。ちょう度を２３５以上に設定することにより、低温性に優れたグリース組成物を得ることが出来、３７０以下にすることにより、機械部品への付着性に優れたグリース組成物を得ることが出来る。なお、本明細書において、用語「ちょう度」は、６０回混和ちょう度を指す。ちょう度は、ＪＩＳ Ｋ２２２０ ７．に従って測定することができる。 [Consistency]
The consistency of the grease composition of the present invention is adjusted depending on the intended use, but is preferably 235 to 370. By setting the consistency to 235 or more, a grease composition with excellent low-temperature properties can be obtained, and by setting the consistency to 370 or less, a grease composition with excellent adhesion to mechanical parts can be obtained. In addition, in this specification, the term "penetration" refers to 60 times worked penetration. Consistency is JIS K2220 7. It can be measured according to
本発明のグリース組成物の用途、すなわちグリース組成物が塗布される機械部品の種類は問わない。例えば、転がり軸受、ボールねじ、直動案内軸受、減速機、射出成型機、リニアガイド、工作機械、各種ギア、カム、等速ジョイント、ジャーナル軸受（滑り軸受）、ピストン、ねじ、ロープ、チェーンなどが挙げられる。なかでも、減速機やボールねじ等は、求められる耐熱性及び耐はく離性のレベルが厳しいが、本発明のグリース組成物は、そのような高い要求も満足し得る。
機械部品に備えられるシール材の種類は特に限定されず、例えば、ＮＢＲ，ＥＰＤＭ，天然ゴム等があげられる。 The use of the grease composition of the present invention, that is, the type of mechanical parts to which the grease composition is applied, does not matter. For example, rolling bearings, ball screws, linear guide bearings, reducers, injection molding machines, linear guides, machine tools, various gears, cams, constant velocity joints, journal bearings (sliding bearings), pistons, screws, ropes, chains, etc. can be mentioned. Among these, the heat resistance and flaking resistance required for reducers, ball screws, etc. are severe, and the grease composition of the present invention can satisfy such high demands.
The type of sealing material provided in the mechanical parts is not particularly limited, and examples thereof include NBR, EPDM, natural rubber, and the like.
機械部品に備えられるシール材の種類は特に限定されず、例えば、ＮＢＲ，ＥＰＤＭ，天然ゴム等があげられる。 The use of the grease composition of the present invention, that is, the type of mechanical parts to which the grease composition is applied, does not matter. For example, rolling bearings, ball screws, linear guide bearings, reducers, injection molding machines, linear guides, machine tools, various gears, cams, constant velocity joints, journal bearings (sliding bearings), pistons, screws, ropes, chains, etc. can be mentioned. Among these, the heat resistance and flaking resistance required for reducers, ball screws, etc. are severe, and the grease composition of the present invention can satisfy such high demands.
The type of sealing material provided in the mechanical parts is not particularly limited, and examples thereof include NBR, EPDM, natural rubber, and the like.
実施例及び比較例のグリース組成物を、以下の成分を用いて調製した。
＜基油＞
・ＰＰＧ：ポリオキシプロピレンモノブチルエーテル（製品名「ユニルーブＭＢ－７」、日油株式会社製、プロピレンオキシド付加モル数１２、平均分子量７００、４０℃における動粘度：３２．８ｍｍ2／ｓ、１００℃における動粘度：６．７ｍｍ2／ｓ、流動点：－４７．５℃）
＜増ちょう剤＞
・リチウム石けん：１２－ヒドロキシステアリン酸リチウム
・脂肪族ジウレア：ジフェニルメタンジイソシアネートと、オクチルアミン及びステアリルアミンとの反応物（オクチルアミンとステアリルアミンとのモル比は５：５）
・脂環式脂肪族ジウレア：ジフェニルメタンジイソシアネートと、シクロヘキシルアミン及びステアリルアミンとの反応物（シクロヘキセンとステアリルアミンとのモル比は７：１）
・芳香族ジウレア：ジフェニルメタンジイソシアネートとｐ－トルイジンとの反応物
＜第１及び第２の固体潤滑剤＞
・ＰＴＦＥ：ポリテトラフルオロエチレン（固体）
・炭酸カルシウム（固体）・酸化カルシウム（固体）
・リン酸三カルシウム（固体）
・ステアリン酸カルシウム（固体）
・ＭｏＤＴＣ：ジチオカルバミン酸モリブデン（液体）
・ＭｏＳ2：二硫化モリブデン（固体）
・ＺｎＤＴＰ：ジチオリン酸亜鉛（液体）
・アミンフォスフェート（液体）
なお、ＭｏＤＴＣ、ＭｏＳ2、ＺｎＤＴＰ及びアミンフォスフェートは、比較用の、反応系の耐はく離添加剤である。
＜その他の添加剤＞
・酸化防止剤：２，２，４－トリメチル－１，２－ジヒドロキノリン重合体
・防錆剤 Grease compositions of Examples and Comparative Examples were prepared using the following ingredients.
<Base oil>
・PPG: Polyoxypropylene monobutyl ether (product name "Unilube MB-7", manufactured by NOF Corporation, number of moles of propylene oxide added 12, average molecular weight 700, kinematic viscosity at 40°C: 32.8 mm 2 /s, 100°C kinematic viscosity: 6.7 mm 2 /s, pour point: -47.5°C)
<Thickener>
・Lithium soap: Lithium 12-hydroxystearate ・Aliphatic diurea: Reaction product of diphenylmethane diisocyanate and octylamine and stearylamine (molar ratio of octylamine and stearylamine is 5:5)
・Alicycloaliphatic diurea: reaction product of diphenylmethane diisocyanate, cyclohexylamine and stearylamine (molar ratio of cyclohexene and stearylamine is 7:1)
・Aromatic diurea: reaction product of diphenylmethane diisocyanate and p-toluidine <first and second solid lubricants>
・PTFE: Polytetrafluoroethylene (solid)
・Calcium carbonate (solid) ・Calcium oxide (solid)
・Tricalcium phosphate (solid)
・Calcium stearate (solid)
・MoDTC: Molybdenum dithiocarbamate (liquid)
・MoS 2 : Molybdenum disulfide (solid)
・ZnDTP: Zinc dithiophosphate (liquid)
・Amine phosphate (liquid)
Note that MoDTC, MoS 2 , ZnDTP, and amine phosphate are anti-peeling additives in the reaction system for comparison.
<Other additives>
・Antioxidant: 2,2,4-trimethyl-1,2-dihydroquinoline polymer ・Rust inhibitor
＜基油＞
・ＰＰＧ：ポリオキシプロピレンモノブチルエーテル（製品名「ユニルーブＭＢ－７」、日油株式会社製、プロピレンオキシド付加モル数１２、平均分子量７００、４０℃における動粘度：３２．８ｍｍ2／ｓ、１００℃における動粘度：６．７ｍｍ2／ｓ、流動点：－４７．５℃）
＜増ちょう剤＞
・リチウム石けん：１２－ヒドロキシステアリン酸リチウム
・脂肪族ジウレア：ジフェニルメタンジイソシアネートと、オクチルアミン及びステアリルアミンとの反応物（オクチルアミンとステアリルアミンとのモル比は５：５）
・脂環式脂肪族ジウレア：ジフェニルメタンジイソシアネートと、シクロヘキシルアミン及びステアリルアミンとの反応物（シクロヘキセンとステアリルアミンとのモル比は７：１）
・芳香族ジウレア：ジフェニルメタンジイソシアネートとｐ－トルイジンとの反応物
＜第１及び第２の固体潤滑剤＞
・ＰＴＦＥ：ポリテトラフルオロエチレン（固体）
・炭酸カルシウム（固体）・酸化カルシウム（固体）
・リン酸三カルシウム（固体）
・ステアリン酸カルシウム（固体）
・ＭｏＤＴＣ：ジチオカルバミン酸モリブデン（液体）
・ＭｏＳ2：二硫化モリブデン（固体）
・ＺｎＤＴＰ：ジチオリン酸亜鉛（液体）
・アミンフォスフェート（液体）
なお、ＭｏＤＴＣ、ＭｏＳ2、ＺｎＤＴＰ及びアミンフォスフェートは、比較用の、反応系の耐はく離添加剤である。
＜その他の添加剤＞
・酸化防止剤：２，２，４－トリメチル－１，２－ジヒドロキノリン重合体
・防錆剤 Grease compositions of Examples and Comparative Examples were prepared using the following ingredients.
<Base oil>
・PPG: Polyoxypropylene monobutyl ether (product name "Unilube MB-7", manufactured by NOF Corporation, number of moles of propylene oxide added 12, average molecular weight 700, kinematic viscosity at 40°C: 32.8 mm 2 /s, 100°C kinematic viscosity: 6.7 mm 2 /s, pour point: -47.5°C)
<Thickener>
・Lithium soap: Lithium 12-hydroxystearate ・Aliphatic diurea: Reaction product of diphenylmethane diisocyanate and octylamine and stearylamine (molar ratio of octylamine and stearylamine is 5:5)
・Alicycloaliphatic diurea: reaction product of diphenylmethane diisocyanate, cyclohexylamine and stearylamine (molar ratio of cyclohexene and stearylamine is 7:1)
・Aromatic diurea: reaction product of diphenylmethane diisocyanate and p-toluidine <first and second solid lubricants>
・PTFE: Polytetrafluoroethylene (solid)
・Calcium carbonate (solid) ・Calcium oxide (solid)
・Tricalcium phosphate (solid)
・Calcium stearate (solid)
・MoDTC: Molybdenum dithiocarbamate (liquid)
・MoS 2 : Molybdenum disulfide (solid)
・ZnDTP: Zinc dithiophosphate (liquid)
・Amine phosphate (liquid)
Note that MoDTC, MoS 2 , ZnDTP, and amine phosphate are anti-peeling additives in the reaction system for comparison.
<Other additives>
・Antioxidant: 2,2,4-trimethyl-1,2-dihydroquinoline polymer ・Rust inhibitor
＜試験グリース＞
調製例１ 増ちょう剤がジウレア化合物である試験グリース組成物
基油中で、4.4'－ジフェニルメタンジイソシアネート１モルに対し、所定のアミン２モルの比率で反応させ、冷却してベースグリースとした。
上記ベースグリースに、添加剤を、表１に示す割合で配合し、表１に示す割合の増ちょう剤量になるように追加の基油を添加し、３本ロールミルで分散することにより試験グリース組成物を調製した。試験グリース組成物のちょう度は２８０である。 <Test grease>
Preparation Example 1 Test grease composition in which the thickener is a diurea compound 1 mole of 4.4'-diphenylmethane diisocyanate was reacted with 2 moles of a predetermined amine in a base oil, and the mixture was cooled to obtain a base grease.
Additives were added to the above base grease in the proportions shown in Table 1, additional base oil was added to give the amount of thickener in the proportions shown in Table 1, and the test grease was prepared by dispersing with a three-roll mill. A composition was prepared. The consistency of the test grease composition is 280.
調製例１ 増ちょう剤がジウレア化合物である試験グリース組成物
基油中で、4.4'－ジフェニルメタンジイソシアネート１モルに対し、所定のアミン２モルの比率で反応させ、冷却してベースグリースとした。
上記ベースグリースに、添加剤を、表１に示す割合で配合し、表１に示す割合の増ちょう剤量になるように追加の基油を添加し、３本ロールミルで分散することにより試験グリース組成物を調製した。試験グリース組成物のちょう度は２８０である。 <Test grease>
Preparation Example 1 Test grease composition in which the thickener is a diurea compound 1 mole of 4.4'-diphenylmethane diisocyanate was reacted with 2 moles of a predetermined amine in a base oil, and the mixture was cooled to obtain a base grease.
Additives were added to the above base grease in the proportions shown in Table 1, additional base oil was added to give the amount of thickener in the proportions shown in Table 1, and the test grease was prepared by dispersing with a three-roll mill. A composition was prepared. The consistency of the test grease composition is 280.
調製例２ 増ちょう剤がリチウム石けんである試験グリース組成物
基油中で、１２－ヒドロキシステアリン酸リチウムを添加攪拌し、その後２３０℃まで加熱した。その後、攪拌しながら１００℃以下まで冷却し、ベースグリースとした。
上記ベースグリースに、添加剤を、表１及び表２に示す割合で配合し、表１及び表２に示す割合の増ちょう剤量になるように追加の基油を添加し、３本ロールミルで分散することにより試験グリース組成物を調製した。試験グリース組成物のちょう度は２８０である。
各試験グリース組成物中の各成分の質量％は表１及び表２に示したとおりである。
なお、基油の１００℃における動粘度は、ＪＩＳ Ｋ２２２０ ２３．に従って測定した。基油の流動点は、ＪＩＳ Ｋ２２６９に従って測定した。グリース組成物のちょう度は、ＪＩＳ Ｋ２２２０ ７．に従って測定した。
上で得られたグリース組成物を、以下に示す方法で試験し、評価した。 Preparation Example 2 Test grease composition in which the thickener is lithium soap Lithium 12-hydroxystearate was added and stirred in base oil, and then heated to 230°C. Thereafter, the mixture was cooled to 100° C. or lower while stirring to obtain a base grease.
Additives were blended into the above base grease in the proportions shown in Tables 1 and 2, additional base oil was added so that the amount of thickener was in the proportions shown in Tables 1 and 2, and the mixture was processed using a three-roll mill. Test grease compositions were prepared by dispersing. The consistency of the test grease composition is 280.
The mass % of each component in each test grease composition is as shown in Tables 1 and 2.
Note that the kinematic viscosity of the base oil at 100°C is JIS K2220 23. Measured according to The pour point of the base oil was measured according to JIS K2269. The consistency of the grease composition is JIS K2220 7. Measured according to
The grease composition obtained above was tested and evaluated by the method shown below.
基油中で、１２－ヒドロキシステアリン酸リチウムを添加攪拌し、その後２３０℃まで加熱した。その後、攪拌しながら１００℃以下まで冷却し、ベースグリースとした。
上記ベースグリースに、添加剤を、表１及び表２に示す割合で配合し、表１及び表２に示す割合の増ちょう剤量になるように追加の基油を添加し、３本ロールミルで分散することにより試験グリース組成物を調製した。試験グリース組成物のちょう度は２８０である。
各試験グリース組成物中の各成分の質量％は表１及び表２に示したとおりである。
なお、基油の１００℃における動粘度は、ＪＩＳ Ｋ２２２０ ２３．に従って測定した。基油の流動点は、ＪＩＳ Ｋ２２６９に従って測定した。グリース組成物のちょう度は、ＪＩＳ Ｋ２２２０ ７．に従って測定した。
上で得られたグリース組成物を、以下に示す方法で試験し、評価した。 Preparation Example 2 Test grease composition in which the thickener is lithium soap Lithium 12-hydroxystearate was added and stirred in base oil, and then heated to 230°C. Thereafter, the mixture was cooled to 100° C. or lower while stirring to obtain a base grease.
Additives were blended into the above base grease in the proportions shown in Tables 1 and 2, additional base oil was added so that the amount of thickener was in the proportions shown in Tables 1 and 2, and the mixture was processed using a three-roll mill. Test grease compositions were prepared by dispersing. The consistency of the test grease composition is 280.
The mass % of each component in each test grease composition is as shown in Tables 1 and 2.
Note that the kinematic viscosity of the base oil at 100°C is JIS K2220 23. Measured according to The pour point of the base oil was measured according to JIS K2269. The consistency of the grease composition is JIS K2220 7. Measured according to
The grease composition obtained above was tested and evaluated by the method shown below.
＜試験方法＞
・高温薄膜試験による耐熱性の評価
下記鋼板にグリースを塗布し、規定温度の恒温槽内に規定時間静置後、ゲル浸透クロマトグラフィー分析を実施し、基油の分解の発生有無を確認する。
［試験条件］
鋼板 ：ＳＰＣＣ－ＳＤ ８０ｍｍ×６０ｍｍ×１ｍｍ
温度 ：１２０℃
時間 ：１１５２ｈ
塗布厚 ：２ｍｍ
ＧＰＣ測定溶媒 ：クロロホルム
ＧＰＣ検出器 ：ＲＩ検出器
［評価基準］
基油の分解なし・・・〇（合格）
基油の分解あり・・・×（不合格） <Test method>
・Evaluation of heat resistance by high-temperature thin film test Apply grease to the following steel plate, leave it in a constant temperature bath at a specified temperature for a specified period of time, and then perform gel permeation chromatography analysis to confirm whether or not base oil decomposition occurs.
[Test condition]
Steel plate: SPCC-SD 80mm x 60mm x 1mm
Temperature: 120℃
Time: 1152h
Coating thickness: 2mm
GPC measurement solvent: Chloroform GPC detector: RI detector [Evaluation criteria]
No decomposition of base oil...〇 (passed)
Base oil decomposed...× (fail)
・高温薄膜試験による耐熱性の評価
下記鋼板にグリースを塗布し、規定温度の恒温槽内に規定時間静置後、ゲル浸透クロマトグラフィー分析を実施し、基油の分解の発生有無を確認する。
［試験条件］
鋼板 ：ＳＰＣＣ－ＳＤ ８０ｍｍ×６０ｍｍ×１ｍｍ
温度 ：１２０℃
時間 ：１１５２ｈ
塗布厚 ：２ｍｍ
ＧＰＣ測定溶媒 ：クロロホルム
ＧＰＣ検出器 ：ＲＩ検出器
［評価基準］
基油の分解なし・・・〇（合格）
基油の分解あり・・・×（不合格） <Test method>
・Evaluation of heat resistance by high-temperature thin film test Apply grease to the following steel plate, leave it in a constant temperature bath at a specified temperature for a specified period of time, and then perform gel permeation chromatography analysis to confirm whether or not base oil decomposition occurs.
[Test condition]
Steel plate: SPCC-SD 80mm x 60mm x 1mm
Temperature: 120℃
Time: 1152h
Coating thickness: 2mm
GPC measurement solvent: Chloroform GPC detector: RI detector [Evaluation criteria]
No decomposition of base oil...〇 (passed)
Base oil decomposed...× (fail)
・転がり４球試験による耐はく離性の評価 φ１５ｍｍの軸受鋼球を３個用意し、内径４０ｍｍ、
高さ１４ｍｍの円筒状容器内に配置し、試験グリースを約２０ｇ満たす。この３個の鋼球の上に、φ５/８インチの軸受用鋼球１個を接触させ、所定の回転数で回転させると、下側の３個の鋼球は自転しながら公転する。これを鋼球表面にはく離が生じるまで連続回転させる。
※はく離は、最も面圧の高い球―球間に生じる。
※寿命は、はく離が生じた時点の上鋼球の下鋼球に対する接触回数とする。寿命により耐剥離性を評価した。
［試験条件］
試験鋼球：φ５/８ｉｎ、Ｒａ０．４５μｍ軸受用鋼球（回転球）
φ１５ｍｍ軸受用鋼球（従動球）
試験荷重：４００ｋｇｆ（６．５ＧＰａ）
回転速度：１２００ｒｐｍ
評価基準：１５００００回以上・・・◎（合格）
１０００００回以上～１５００００回未満・・・○（合格）
５００００以上～１０００００回未満・・・△（不合格）
５００００回未満・・・×（不合格）
結果を表１及び表２に示す。 ・Evaluation of peeling resistance by rolling 4-ball test Prepare three bearing steel balls of φ15 mm, inner diameter of 40 mm,
Placed in a cylindrical container with a height of 14 mm and filled with approximately 20 g of test grease. When one steel ball for a bearing with a diameter of 5/8 inch is brought into contact with these three steel balls and rotated at a predetermined rotation speed, the lower three steel balls revolve while rotating on their own axis. This is continuously rotated until peeling occurs on the surface of the steel ball.
*Peeling occurs between balls with the highest surface pressure.
*Life is defined as the number of times the upper steel ball contacts the lower steel ball at the time of peeling. Peeling resistance was evaluated based on life.
[Test condition]
Test steel ball: φ5/8in, Ra0.45μm bearing steel ball (rotating ball)
Steel ball for φ15mm bearing (driven ball)
Test load: 400kgf (6.5GPa)
Rotation speed: 1200rpm
Evaluation criteria: 150,000 times or more...◎ (pass)
100,000 times or more - less than 150,000 times...○ (pass)
50,000 or more - less than 100,000 times...△ (fail)
Less than 50,000 times...× (fail)
The results are shown in Tables 1 and 2.
高さ１４ｍｍの円筒状容器内に配置し、試験グリースを約２０ｇ満たす。この３個の鋼球の上に、φ５/８インチの軸受用鋼球１個を接触させ、所定の回転数で回転させると、下側の３個の鋼球は自転しながら公転する。これを鋼球表面にはく離が生じるまで連続回転させる。
※はく離は、最も面圧の高い球―球間に生じる。
※寿命は、はく離が生じた時点の上鋼球の下鋼球に対する接触回数とする。寿命により耐剥離性を評価した。
［試験条件］
試験鋼球：φ５/８ｉｎ、Ｒａ０．４５μｍ軸受用鋼球（回転球）
φ１５ｍｍ軸受用鋼球（従動球）
試験荷重：４００ｋｇｆ（６．５ＧＰａ）
回転速度：１２００ｒｐｍ
評価基準：１５００００回以上・・・◎（合格）
１０００００回以上～１５００００回未満・・・○（合格）
５００００以上～１０００００回未満・・・△（不合格）
５００００回未満・・・×（不合格）
結果を表１及び表２に示す。 ・Evaluation of peeling resistance by rolling 4-ball test Prepare three bearing steel balls of φ15 mm, inner diameter of 40 mm,
Placed in a cylindrical container with a height of 14 mm and filled with approximately 20 g of test grease. When one steel ball for a bearing with a diameter of 5/8 inch is brought into contact with these three steel balls and rotated at a predetermined rotation speed, the lower three steel balls revolve while rotating on their own axis. This is continuously rotated until peeling occurs on the surface of the steel ball.
*Peeling occurs between balls with the highest surface pressure.
*Life is defined as the number of times the upper steel ball contacts the lower steel ball at the time of peeling. Peeling resistance was evaluated based on life.
[Test condition]
Test steel ball: φ5/8in, Ra0.45μm bearing steel ball (rotating ball)
Steel ball for φ15mm bearing (driven ball)
Test load: 400kgf (6.5GPa)
Rotation speed: 1200rpm
Evaluation criteria: 150,000 times or more...◎ (pass)
100,000 times or more - less than 150,000 times...○ (pass)
50,000 or more - less than 100,000 times...△ (fail)
Less than 50,000 times...× (fail)
The results are shown in Tables 1 and 2.
添加剤として、第１の固体潤滑剤であるポリテトラフルオロエチレンと、第２の固体潤滑剤である炭酸カルシウム、酸化カルシウム、リン酸三カルシウム、脂肪酸のカルシウム塩から選ばれる少なくとも１種とを併用した実施例１～１５は、比較例１～６、９、１０に比べ、耐はく離性に優れる。実施例１～１５は、比較例７～１０に比べ、耐熱性に優れる。一般的に、増ちょう剤の種類によりグリースの耐熱性は異なるが、実施例における耐熱性の改善は、Ｌｉ石けん、ウレア系増ちょう剤の両者ともに認められる。したがって、添加剤として、本願所定の第１の固体添加剤と第２の固体添加剤とを併用することにより、反応系の耐はく離添加剤を使用しなくても、増ちょう剤を選ばずに、高温又は高面圧下でも、グリースの耐はく離性及び耐熱性を向上させることが可能である。
As an additive, the first solid lubricant, polytetrafluoroethylene, and the second solid lubricant, at least one selected from calcium carbonate, calcium oxide, tricalcium phosphate, and calcium salts of fatty acids, are used in combination. Examples 1 to 15 have superior peeling resistance compared to Comparative Examples 1 to 6, 9, and 10. Examples 1 to 15 have better heat resistance than Comparative Examples 7 to 10. Generally, the heat resistance of grease differs depending on the type of thickener, but the improvement in heat resistance in the examples was observed for both Li soap and urea-based thickener. Therefore, by using the first solid additive and the second solid additive prescribed in the present application together as additives, it is possible to eliminate the need to use a flaking-resistant additive in the reaction system and without selecting a thickener. It is possible to improve the peeling resistance and heat resistance of grease even at high temperatures or high surface pressures.
Claims (6)
- 基油、増ちょう剤、添加剤を含有するグリース組成物であって、
基油が、ポリオキシアルキレン、ポリオキシアルキレンのエーテル誘導体及びこれらの混合物からなる群から選ばれる少なくとも１種であり、
添加剤が、第１の固体潤滑剤としてポリテトラフルオロエチレン、および第２の固体潤滑剤として、炭酸カルシウム、酸化カルシウム、リン酸三カルシウム及び脂肪酸のカルシウム塩からなる群から選ばれる少なくとも１種を含み、第２の固体潤滑剤の含有量が、組成物の全質量を基準として０．５質量％以上である、前記グリース組成物。 A grease composition containing a base oil, a thickener, and an additive,
The base oil is at least one selected from the group consisting of polyoxyalkylene, ether derivatives of polyoxyalkylene, and mixtures thereof,
The additive contains polytetrafluoroethylene as the first solid lubricant, and at least one member selected from the group consisting of calcium carbonate, calcium oxide, tricalcium phosphate, and calcium salts of fatty acids as the second solid lubricant. The grease composition, wherein the content of the second solid lubricant is 0.5% by mass or more based on the total mass of the composition. - 第１の固体潤滑剤の含有量が、組成物の全質量を基準にして、０．５～２０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 first solid lubricant is 0.5 to 20% by mass based on the total mass of the composition.
- 第２の固体潤滑剤の含有量が、組成物の全質量を基準にして、０．５～１０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 second solid lubricant is 0.5 to 10% by mass based on the total mass of the composition.
- 第２の固体潤滑剤が炭酸カルシウムである請求項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 second solid lubricant is calcium carbonate.
- 第１の固体潤滑剤１０質量％に対して、第２の固体潤滑剤を１～３質量％となる割合で、第１及び第２の固体潤滑剤を含む、請求項１～４のいずれか１項記載のグリース組成物。 Any one of claims 1 to 4, wherein the first and second solid lubricants are contained in a ratio of 1 to 3% by mass of the second solid lubricant to 10% by mass of the first solid lubricant. The grease composition according to item 1.
- 請求項１～５のいずれか１項記載のグリース組成物を適用した機械部品。 A mechanical component to which the grease composition according to any one of claims 1 to 5 is applied.
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