CN111065717A - 润滑剂组合物及封入有该润滑剂组合物的滚动轴承 - Google Patents
润滑剂组合物及封入有该润滑剂组合物的滚动轴承 Download PDFInfo
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- CN111065717A CN111065717A CN201880058772.7A CN201880058772A CN111065717A CN 111065717 A CN111065717 A CN 111065717A CN 201880058772 A CN201880058772 A CN 201880058772A CN 111065717 A CN111065717 A CN 111065717A
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- Prior art keywords
- acid
- lubricant composition
- grease
- additive
- tetramethyl
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 239000000314 lubricant Substances 0.000 title claims abstract description 40
- 238000005096 rolling process Methods 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- 239000000654 additive Substances 0.000 claims abstract description 44
- 239000002253 acid Substances 0.000 claims abstract description 42
- 150000003839 salts Chemical class 0.000 claims abstract description 35
- 230000000996 additive effect Effects 0.000 claims abstract description 33
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 20
- 239000000194 fatty acid Substances 0.000 claims abstract description 20
- 229930195729 fatty acid Natural products 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 14
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004519 grease Substances 0.000 abstract description 52
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 18
- 239000011737 fluorine Substances 0.000 abstract description 18
- 229910052731 fluorine Inorganic materials 0.000 abstract description 18
- 239000004202 carbamide Substances 0.000 abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 5
- -1 urea compound Chemical class 0.000 description 20
- 239000002199 base oil Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 10
- 239000002562 thickening agent Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229920013639 polyalphaolefin Polymers 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000002480 mineral oil Substances 0.000 description 5
- 235000010446 mineral oil Nutrition 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 235000010288 sodium nitrite Nutrition 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- OTCWVYFQGYOYJO-UHFFFAOYSA-N 1-o-methyl 10-o-(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound COC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 OTCWVYFQGYOYJO-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- KHAVLLBUVKBTBG-UHFFFAOYSA-N dec-9-enoic acid Chemical compound OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 3
- 239000010696 ester oil Substances 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- YWWVWXASSLXJHU-AATRIKPKSA-N (9E)-tetradecenoic acid Chemical compound CCCC\C=C\CCCCCCCC(O)=O YWWVWXASSLXJHU-AATRIKPKSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 description 2
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- MOABYHZDQQELLG-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCC MOABYHZDQQELLG-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010692 aromatic oil Substances 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 150000004659 dithiocarbamates Chemical class 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- NWPIOULNZLJZHU-UHFFFAOYSA-N (1,2,2,6,6-pentamethylpiperidin-4-yl) 2-methylprop-2-enoate Chemical compound CN1C(C)(C)CC(OC(=O)C(C)=C)CC1(C)C NWPIOULNZLJZHU-UHFFFAOYSA-N 0.000 description 1
- YSSBODGKHOXDDC-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 YSSBODGKHOXDDC-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- XMKLTEGSALONPH-UHFFFAOYSA-N 1,2,4,5-tetrazinane-3,6-dione Chemical compound O=C1NNC(=O)NN1 XMKLTEGSALONPH-UHFFFAOYSA-N 0.000 description 1
- QDNPLNOHUNPYHZ-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethyl-4-propoxypiperidine Chemical compound CCCOC1CC(C)(C)N(O)C(C)(C)C1 QDNPLNOHUNPYHZ-UHFFFAOYSA-N 0.000 description 1
- CSGAUKGQUCHWDP-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1O CSGAUKGQUCHWDP-UHFFFAOYSA-N 0.000 description 1
- NEJCZFWLACPLGJ-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-ol;propanoic acid Chemical compound CCC(O)=O.CC1(C)CC(O)CC(C)(C)N1O NEJCZFWLACPLGJ-UHFFFAOYSA-N 0.000 description 1
- KRNWYBIEWUXCOB-UHFFFAOYSA-N 1-hydroxy-4-methoxy-2,2,6,6-tetramethylpiperidine Chemical compound COC1CC(C)(C)N(O)C(C)(C)C1 KRNWYBIEWUXCOB-UHFFFAOYSA-N 0.000 description 1
- VWLLHDWJGQYFRO-UHFFFAOYSA-N 11-methyldodecanoic acid phosphoric acid Chemical compound OP(O)(O)=O.CC(C)CCCCCCCCCC(O)=O VWLLHDWJGQYFRO-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 description 1
- RXKWXQVRFBMHCY-UHFFFAOYSA-N 2,3-diethylbenzoic acid Chemical compound CCC1=CC=CC(C(O)=O)=C1CC RXKWXQVRFBMHCY-UHFFFAOYSA-N 0.000 description 1
- PYHYPLDLZPFMJN-UHFFFAOYSA-N 2-(2,2,6,6-tetramethylpiperidin-4-yl)octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)C1CC(C)(C)NC(C)(C)C1 PYHYPLDLZPFMJN-UHFFFAOYSA-N 0.000 description 1
- XKZGIJICHCVXFV-UHFFFAOYSA-N 2-ethylhexyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCC(CC)CCCC)OC1=CC=CC=C1 XKZGIJICHCVXFV-UHFFFAOYSA-N 0.000 description 1
- YLHTWBSSXRGRNF-UHFFFAOYSA-N 2-ethylpentadecanoic acid Chemical compound CCCCCCCCCCCCCC(CC)C(O)=O YLHTWBSSXRGRNF-UHFFFAOYSA-N 0.000 description 1
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- JVAKNQLSBYBCSZ-VAWYXSNFSA-N 2-methyl-2-dodecenoic acid Chemical compound CCCCCCCCC\C=C(/C)C(O)=O JVAKNQLSBYBCSZ-VAWYXSNFSA-N 0.000 description 1
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- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- UFYABLZSCAJYAX-UHFFFAOYSA-N 3-(1-hydroxypropan-2-yloxy)-1,1,1,2-tetraphenylpropan-2-ol;phosphorous acid Chemical compound OP(O)O.C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C(O)(COC(CO)C)C1=CC=CC=C1 UFYABLZSCAJYAX-UHFFFAOYSA-N 0.000 description 1
- LMFRDZYWEWGVPW-UHFFFAOYSA-N 4,6-dimethyloctanoic acid Chemical compound CCC(C)CC(C)CCC(O)=O LMFRDZYWEWGVPW-UHFFFAOYSA-N 0.000 description 1
- YKVAWSVTEWXJGJ-UHFFFAOYSA-N 4-chloro-2-methylsulfanylthieno[3,2-d]pyrimidine Chemical compound CSC1=NC(Cl)=C2SC=CC2=N1 YKVAWSVTEWXJGJ-UHFFFAOYSA-N 0.000 description 1
- AHPXMHKEFQCGBY-UHFFFAOYSA-N 4-ethoxy-1-hydroxy-2,2,6,6-tetramethylpiperidine Chemical compound CCOC1CC(C)(C)N(O)C(C)(C)C1 AHPXMHKEFQCGBY-UHFFFAOYSA-N 0.000 description 1
- VGTGKCFPAUECEZ-UHFFFAOYSA-N 4-ethoxy-2,2,6,6-tetramethylpiperidine Chemical compound CCOC1CC(C)(C)NC(C)(C)C1 VGTGKCFPAUECEZ-UHFFFAOYSA-N 0.000 description 1
- RWWGPCWSFFOXJN-UHFFFAOYSA-N 4-methoxy-2,2,6,6-tetramethylpiperidine Chemical compound COC1CC(C)(C)NC(C)(C)C1 RWWGPCWSFFOXJN-UHFFFAOYSA-N 0.000 description 1
- ZRIMDWRLVGDUBW-UHFFFAOYSA-N 5-hydroxy-2-methylpent-2-enoic acid phosphoric acid Chemical compound P(=O)(O)(O)O.OCCC=C(C(=O)O)C ZRIMDWRLVGDUBW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- YWWVWXASSLXJHU-UHFFFAOYSA-N 9E-tetradecenoic acid Natural products CCCCC=CCCCCCCCC(O)=O YWWVWXASSLXJHU-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
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Images
Classifications
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/30—Parts of ball or roller bearings
- F16C33/66—Special parts or details in view of lubrication
- F16C33/6603—Special parts or details in view of lubrication with grease as lubricant
- F16C33/6633—Grease properties or compositions, e.g. rheological properties
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/06—Mixtures of thickeners and additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/12—Thio-acids; Thiocyanates; Derivatives thereof
- C10M135/14—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond
- C10M135/18—Thio-acids; Thiocyanates; Derivatives thereof having a carbon-to-sulfur double bond thiocarbamic type, e.g. containing the groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
-
- 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
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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- 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
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/30—Parts of ball or roller bearings
- F16C33/66—Special parts or details in view of lubrication
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
- C10M2201/082—Inorganic acids or salts thereof containing nitrogen
- C10M2201/083—Inorganic acids or salts thereof containing nitrogen nitrites
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Abstract
本发明的滚动轴承通过润滑剂组合物被润滑,所述润滑剂组合物含有脂肪酸金属盐、二硫代氨基甲酸金属盐、磷系添加剂以及碱性添加剂,并且总酸值为3.7mgKOH/g以上,能够实现耐微振磨损性能的进一步提高,并且即使在氟系润滑脂侵入使用了脲系润滑脂的轴承内的环境下使用时也能够抑制耐微振磨损性的降低。
Description
技术领域
本发明涉及含有特定添加剂的润滑剂组合物、以及通过润滑剂组合物进行了润滑的滚动轴承。
背景技术
如AC伺服电动机用轴承、轮毂用轴承、HDD(硬盘驱动)的枢轴用轴承等那样支撑支持轴的滚动轴承进行轻微往复运动的情况、或受到轻微往复运动的情况下,轴承的滚动体表面、滚动面会产生微振磨损,会产生轴承转矩的增大、以损伤部为起点的剥离等各种不良状况。
作为微振磨损磨耗对策,如例如专利文献1所记载,也进行了将陶瓷球用于滚动体。然而,陶瓷球与通常所使用的钢球相比,成本高。
因此,也进行了通过润滑所使用的润滑剂组合物来提高耐微振磨损性。例如,专利文献2中记载了添加有无机的镁微粒和硬脂酸镁的润滑脂组合物。此外,专利文献3中记载了添加有选自由脂肪酸的铝盐、镁盐、锌盐和钙盐组成的组中的一种或多种的润滑脂组合物。
为了同样地提高耐微振磨损性,如例如专利文献4所记载,还广泛使用了添加有磷系添加剂的脲系润滑脂。
现有技术文献
专利文献
专利文献1:日本特开2005-188726号公报
专利文献2:日本特开2007-023015号公报
专利文献3:日本特开2006-169386号公报
专利文献4:日本特开2008-88386号公报
发明内容
发明所要解决的课题
然而,根据用途,有时在氟系润滑脂侵入使用了脲系润滑脂的轴承内的环境下使用轴承。而且,如专利文献4所示,为了提高耐微振磨损性而使脲系润滑脂所包含的磷系添加剂与通常配合于氟系润滑脂中的亚硝酸钠发生反应时,会生成硝酸,导致耐微振磨损性降低。
进一步提高耐微振磨损性的要求强烈,本发明的目的在于,实现耐微振磨损性能的进一步提高,并且即使在氟系润滑脂侵入使用了脲系润滑脂的轴承内的环境下使用时也抑制耐微振磨损性的降低。
用于解决课题的方法
为了解决上述课题,本发明人发现:由脂肪酸金属盐和二硫代氨基甲酸金属盐带来的优异的耐微振磨损性能够通过利用磷系添加剂将润滑剂组合物的酸值提高至某一定值以上而进一步提高,并且碱性添加剂作为中和与氟系润滑脂混合使用时所生成的硝酸并且抑制润滑剂组合物的酸值降低的添加剂是有效的,由此完成本发明。即,本发明提供下述润滑剂组合物以及滚动轴承。
(1)一种润滑剂组合物,其特征在于,含有脂肪酸金属盐、二硫代氨基甲酸金属盐、磷系添加剂以及碱性添加剂,并且总酸值为3.7mgKOH/g以上。
(2)根据上述(1)所述的润滑剂组合物,其特征在于,pH为8.6以上。
(3)一种滚动轴承,其特征在于,通过上述(1)或(2)所述的润滑剂组合物被润滑。
发明效果
根据本发明的润滑剂组合物,可获得由脂肪酸金属盐和二硫代氨基甲酸金属盐带来的优异的耐微振磨损性,并且进一步利用磷系添加剂将总酸值提高至一定以上而实现了耐微振磨损性的进一步提高。此外,通过利用碱性添加剂将氟系润滑脂混合使用时所生成的硝酸进行中和并且抑制润滑剂组合物的总酸值降低,从而能够维持由脂肪酸金属盐和二硫代氨基甲酸金属盐、进一步磷系添加剂带来的耐微振磨损性的提高效果。因此,如果将该润滑剂组合物应用于滚动轴承,则滚动体不需要使用昂贵的陶瓷球,可获得虽然便宜但具有优异的耐微振磨损性且长寿命的滚动轴承。
附图说明
图1为预备试验1中获得的、表示胺的含量与总酸值或pH的关系的图表。
图2为预备试验2中获得的、表示比较例1~3的损伤比的图表。
图3为实施例中获得的、表示胺的含量与损伤比的关系的图表。
具体实施方式
以下,关于本发明进行详细说明。
〔润滑剂组合物〕
本发明的润滑剂组合物通过含有脂肪酸金属盐和二硫代氨基甲酸金属盐,从而利用磷系添加剂将润滑剂组合物的酸值提高至某一定以上而使耐微振磨损性提高。进一步并用碱性添加剂,将氟系润滑脂混合使用时所产生的硝酸进行中和的同时抑制润滑剂组合物的酸值降低。
需要说明的是,润滑剂组合物的形态没有限制,可以是在润滑油中添加有这4种添加剂的润滑油组合物,也可以采用在包含基油和增稠剂的基础润滑脂中添加有这4种添加剂的润滑脂组合物。
润滑油以及润滑脂组合物的基油也没有限制,可以使用矿物油、合成油。作为矿物油,可举出石蜡系矿物油、环烷系矿物油,特别优选为将减压蒸馏、油剂脱沥青、溶剂提取、氢化分解、溶剂脱蜡、硫酸清洗、白土精制、氢化精制等适当组合而精制的矿物油。作为合成油,可举出烃系油、芳香族系油、酯系油、醚系油。作为烃系油,可举出正链烷烃、异链烷烃、聚丁烯、聚异丁烯、1-癸烯低聚物、1-癸烯与乙烯低聚物等聚α-烯烃或它们的氢化物。作为芳香族系油,可举出单烷基苯、二烷基苯等烷基苯、单烷基萘、二烷基萘等烷基萘等。作为酯系油,可举出癸二酸二丁酯、癸二酸二-2-乙基己酯、己二酸二辛酯、己二酸二异癸酯、己二酸二(十三烷基)酯、戊二酸二(十三烷基)酯、乙酰基蓖麻酸甲酯等二酯油、偏苯三酸三辛酯、偏苯三酸十三烷基酯、均苯四酸四辛酯等芳香族酯油、三羟甲基丙烷辛酸酯、三羟甲基丙烷壬酸酯、季戊四醇-2-乙基己酸酯、季戊四醇壬酸酯等多元醇酯油、作为多元醇与二元酸/一元酸的混合脂肪酸的低聚酯的复合酯油等。作为醚系油,可举出聚乙二醇、聚丙二醇、聚乙二醇单醚、聚丙二醇单醚等聚二醇、单烷基三苯基醚、烷基二苯基醚、二烷基二苯基醚、五苯基醚、四苯基醚、单烷基四苯基醚、二烷基四苯基醚等苯基醚油等。它们可以分别单独使用,也可以将两种以上混合使用。
其中,优选合成油,更优选聚α-烯烃(PAO)、酯油。此外,在重视耐微振磨损性等耐磨耗性的情况下,优选PAO。
此外,考虑到低温直至高温的流动性,上述油在40℃时的运动粘度优选为5~400mm2/s,更优选为10~100mm2/s。在将两种以上的油混合使用的情况下,以成为该运动粘度的方式进行调整。
另外,在润滑脂组合物的情况下,增稠剂使用脲化合物或金属皂。作为脲化合物,有脂肪族脲化合物、脂环式脲化合物、芳香族脲化合物,都没有限制,二脲、三脲、四脲和聚脲均可以。作为金属皂,可举出将Li、Na、Ba、Ca等作为金属种的金属皂或复合金属皂等。此外,增稠剂量只要能够将基油保持为凝胶状就没有限制,相对于基油和增稠剂的合计量优选为5~50质量%。在增稠剂量小于5质量%时,由于润滑脂组合物会泄漏,因此并不优选,如果超过50质量%,则易于产生润滑脂组合物的压送性变差等其他问题。
此外,润滑脂组合物的混合稠度优选为150~400,如果超过400,则润滑脂组合物会由于离心力而飞散以至于污染外部,小于150时,润滑脂组合物的压送性变差。
(脂肪酸金属盐)
作为脂肪酸金属盐,例如优选由碳原子数4~18的饱和或不饱和的脂肪酸或羟基脂肪酸与选自由铝、镁、银、镉、铜、铁、镍、钡、锂、钾、钠、锌和钙组成的组中的金属所形成的金属盐。作为脂肪酸,作为直链饱和酸,有己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、12-羟基硬脂酸等,作为支链饱和酸,可举出4,6-二甲基辛酸、2-甲基十一烷酸、2-甲基十四烷酸、2-乙基十五烷酸等。作为不饱和酸,可举出3-辛烯酸、2-癸烯酸、9-癸烯酸(caproleic acid)、肉豆蔻脑酸(myristoleic acid)、2-甲基-2-十二碳烯酸、油酸、反油酸、亚油酸、亚麻酸、蓖麻油酸等。脂肪酸金属盐可以将它们单独使用,也可以将两种以上混合使用。特别优选将硬脂酸的铜盐、铁盐、锌盐或镁盐的4种混合添加。
脂肪酸金属盐的含量优选为润滑剂组合物总量的0.001~15质量%,更优选为0.001~10质量%。在含量小于0.001质量%时,不能充分地获得耐微振磨损性的提高效果。此外,即使含量超过15质量%,也只是效果饱和。
(二硫代氨基甲酸金属盐)
作为二硫代氨基甲酸金属盐,例如优选下述通式(I)所示的化合物。
[化1]
式中,M为金属,可举出例如铝、镁、铜、铁、镍、钡、锂、钾、钠、锌、钼,特别是优选锌。n为与金属的价数相对应的整数。R1、R2为碳原子数2~18的伯烷基、仲烷基、芳基或烷基芳基,R1和R2彼此可以相同也可以不同。这些二硫代氨基甲酸金属盐可以单独使用,也可以将多种混合使用。
此外,在润滑剂组合物为润滑脂组合物的情况下,认为二硫代氨基甲酸金属盐具有强化增稠剂而有助于提高耐微振磨损性的效果。
二硫代氨基甲酸金属盐的含量优选为润滑剂组合物总量的0.001~15质量%,更优选为0.001~10质量%。含量小于0.001质量%时,不能充分地获得耐微振磨损性的提高效果。此外,即使含量超过15质量%,也只是效果饱和。
(磷系添加剂)
润滑剂组合物优选总酸值高达某一定以上,特别是如果含有二硫代氨基甲酸金属盐并成为3.7mgKOH/g以上,则脂肪酸金属盐会完全溶解于润滑剂组合物的基油。如果润滑剂组合物的总酸值低,则脂肪酸金属盐不溶解于基油而以粉末(固体)的状态进行分散。而且,该粉末在接触区域内作为异物而行动,成为磨料磨耗的原因,会引起微振磨损磨耗。
因此,为了提高润滑剂组合物的总酸值而使用磷系添加剂。如果该磷系添加剂少,则润滑剂组合物的总酸值的上升小,不能充分地获得耐微振磨损性的进一步提高效果。磷系添加剂的含量越多,则润滑剂组合物的总酸值变得越高,如果含量为1质量%以上,则表现出耐微振磨损性的进一步提高效果,特别是如果含量成为2质量%以上,则能够使总酸值为脂肪酸金属盐完全溶解于基油的3.7mgKOH/g以上。即,磷系添加剂的含量为1质量%以上,优选为2质量%以上。
作为磷系添加剂,如果考虑添加至润滑剂组合物时的稳定性、润滑性能等,则优选磷酸酯和亚磷酸酯,可以将下述所列举的物质分别单独使用或混合使用。
作为磷酸酯,可举出例如烷基(C12、C14、C16、C18)酸式磷酸酯、异十三烷基酸式磷酸酯、油基酸式磷酸酯、二十四烷基酸式磷酸酯、乙二醇酸式磷酸酯、2-羟基甲基甲基丙烯酸酯酸式磷酸酯、二丁基磷酸酯、双(2-乙基己基)磷酸酯、二乙基苄基磷酸酯、三苯基膦、单乙基磷酸酯、单正丁基磷酸酯、单正辛基磷酸酯、单正月桂基磷酸酯、单(2-羟基乙基甲基丙烯酸酯)磷酸酯等,特别优选异十三烷基酸式磷酸酯和单正丁基磷酸酯。
作为亚磷酸酯,可举出三苯基亚磷酸酯、三壬基苯基亚磷酸酯、三甲苯基亚磷酸酯、三乙基亚磷酸酯、三(2-乙基己基)亚磷酸酯、十三烷基亚磷酸酯、三月桂基亚磷酸酯、三(十三烷基)亚磷酸酯、三油基亚磷酸酯、二苯基单(2-乙基己基)亚磷酸酯、二苯基单癸基亚磷酸酯、二苯基单(十三烷基)亚磷酸酯、三月桂基三硫代亚磷酸酯、二乙基卤代亚磷酸酯、双(2-乙基己基)氢亚磷酸酯、二月桂基氢亚磷酸酯、二油基氢亚磷酸酯、二苯基氢亚磷酸酯、四苯基双丙二醇亚磷酸酯、四苯基(四(十三烷基))季戊四醇四亚磷酸酯与邻苯二甲酸双(2-乙基己基)酯的混合物、四(C12~C15烷基)-4,4’-亚异丙基二苯基亚磷酸酯、双(十三烷基)季戊四醇二亚磷酸酯与双(壬基苯基)季戊四醇二亚磷酸酯的混合物、双(癸基)季戊四醇二亚磷酸酯、双(十三烷基)季戊四醇二亚磷酸酯、三硬脂基亚磷酸酯、二硬脂基季戊四醇二亚磷酸酯、三(2,4-二叔丁基苯基)亚磷酸酯、氢化双酚A-季戊四醇亚磷酸酯聚合物、氢化双酚A亚磷酸酯等。
需要说明的是,润滑剂组合物的总酸值可以基于JIS K 2501;2003,中和点设为pH12,利用电位滴定法进行测定。
(碱性添加剂)
如上所述,通过添加上述3种添加剂并且优选使总酸值为3.7mgKOH/g以上,能够使耐微振磨损性大幅提高。但是,有时根据用途将氟系润滑脂混合使用,在该情况下,即使添加上述3种添加剂并且使总酸值为3.7mgKOH/g以上,也得不到目标的耐微振磨损性的提高效果。具体而言,通常配合于氟系润滑脂中的亚硝酸钠与磷系添加剂反应而产生硝酸,使耐微振磨损性降低。也可考虑添加中和剂,但酸值会降低至小于3.7mgKOH/g,使耐微振磨损性降低。因此,为了在将所产生的硝酸中和的同时不使总酸值降低,并用碱性添加剂。
作为碱性添加剂,可举出金属系磺酸盐、胺等。具体而言,作为金属系磺酸盐,可举出磺酸钙、磺酸钡、磺酸钠等。作为胺,优选受阻胺,具体而言,可以适合地使用双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、四(1,2,2,6,6-五甲基-4-哌啶基)丁烷-1,2,3,4-四甲酸酯、四(2,2,6,6-四甲基-4-哌啶基)丁烷-1,2,3,4-四甲酸酯、双(1-十一烷氧基-2,2,6,6-四甲基哌啶-4-基)碳酸酯、1,2,2,6,6-五甲基-4-哌啶基甲基丙烯酸酯、2,2,6,6-四甲基-4-哌啶基甲基丙烯酸酯、2,2,6,6-四甲基-哌啶-4-基-十六烷酸酯、2,2,6,6-四甲基-哌啶-4-基-十八烷酸酯、甲基(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、N,N’,N”,N”’-四(4,6-双(丁基-(N-甲基-2,2,6,6-四甲基哌啶-4-基)氨基)三嗪-2-基)-4、7-二氮杂癸烷-1,10-二胺、聚(4-羟基-2,2,6,6-四甲基-1-哌啶乙醇-alt-1,4-丁二酸)、聚[[6-(1,1,3,3-四甲基丁基)氨基]-均三嗪-2,4-二基]-[(2,2,6,6-四甲基-4-哌啶基)亚氨基]-六亚甲基-[(2,2,6,6-四甲基-4-哌啶基)亚氨基]]、4-羟基-2,2,6,6-四甲基哌啶、4-甲氧基-2,2,6,6-四甲基哌啶、4-乙氧基-2,2,6,6-四甲基哌啶、4-丙氧基-2,2,6,6-四甲基哌啶、1-羟基-2,2,6,6-四甲基-4-羟基哌啶、1-羟基-2,2,6,6-四甲基-4-甲氧基哌啶、1-羟基-2,2,6,6-四甲基-4-乙氧基哌啶、1-羟基-2,2,6,6-四甲基-4-丙氧基哌啶、双(1-羟基-2,2,6,6-四甲基哌啶-4-基)癸二酸酯、1-氧基-2,2,6,6-四甲基哌啶、1-氧基-2,2,6,6-四甲基-4-羟基哌啶、1-氧基-2,2,6,6-四甲基-4-羟基哌啶乙酸酯、1-氧基-2,2,6,6-四甲基-4-羟基哌啶丙酸酯、1-氧基-2,2,6,6-四甲基-4-羟基哌啶丁酸酯、1-氧基-2,2,6,6-四甲基-4-羟基哌啶戊酸酯、1-氧基-2,2,6,6-四甲基-4-羟基哌啶己酸酯、1-氧基-2,2,6,6-四甲基-4-羟基哌啶庚酸酯、1-氧基-2,2,6,6-四甲基-4-羟基哌啶辛酸酯、1-氧基-2,2,6,6-四甲基-4-羟基哌啶壬酸酯、1-氧基-2,2,6,6-四甲基-4-羟基哌啶癸酸酯、1-氧基-2,2,6,6-四甲基-4-羟基哌啶十一烷酸酯、1-氧基-2,2,6,6-四甲基-4-羟基哌啶十二烷酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)丙二酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)丁二酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)戊二酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)己二酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)庚二酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)辛二酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)壬二酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)癸二酸酯、双(1-氧基-2,2,6,6-四甲基哌啶-4-基)十二烷二酸酯、1-氧基-2,2,6,6-四甲基-4-甲氧基哌啶、1-氧基-2,2,6,6-四甲基-4-乙氧基哌啶、1-氧基-2,2,6,6-四甲基-4-丙氧基哌啶和它们的混合物等。特别优选双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、甲基(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯,进一步优选将双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯与甲基(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯混合使用。
为了稳定地获得其效果,这些碱性添加剂优选添加润滑剂组合物总量的1质量%以上。但是,如果过量地添加,则效果饱和,其他成分的含量变少,对润滑性等带来不良影响,因此设为20质量%以下。
(其他添加剂)
润滑剂组合物中,为了进一步提高各种性能,可以添加各种添加剂。例如,可以将酚系、硫系等的抗氧化剂、防锈剂、油性提高剂、金属减活剂等分别单独添加,或适当组合而添加。需要说明的是,这些添加剂的添加量只要为不损害本发明目的的范围,就没有特别限制。
需要说明的是,氟系润滑脂没有限制,作为添加剂,也可以添加亚硝酸钠。
(滚动轴承)
本发明的润滑剂组合物能够用于各种用途,对于耐微振磨损性的提高具有效果,例如对于滚动轴承的应用是有效果的。作为滚动轴承的润滑方式,可以从外部将润滑剂组合物连续或间歇地供给至滚动轴承,也可以封入至滚动轴承来使用。通过上述润滑剂组合物,本发明的滚动轴承被赋予了优异的耐微振磨损性能。
而且,滚动轴承的内轮、外轮和滚动体都可以采用轴承钢等金属制。以往也进行了滚动体使用陶瓷球作为微振磨损对策,但由于陶瓷球昂贵,因此通过使滚动体成为金属制,能够提供便宜的滚动轴承。
需要说明的是,滚动轴承的种类也没有限制,带有保持器的滚子轴承、总球轴承、总滚子轴承等也能够适用。此外,滚动面可以为单列也可以为多列。
特别适合于氟系润滑脂侵入那样的轴承。
实施例
以下举出实施例和比较例来进一步说明本发明,但本发明不受此任何的限制。
(预备试验1)
如表1所示,将PAO(48mm/s@40℃)设为基油,将脲化合物(在MDI(二苯基甲烷二异氰酸酯)中,以环己胺:硬脂胺=7:3反应而得的产物)设为增稠剂,进一步将作为脂肪酸金属盐的硬脂酸的Cu盐、Fe盐、Zn盐和Mg盐的混合物、作为二硫代氨基甲酸金属盐的ZnDTC、以及作为磷系添加剂的异十三烷基酸式磷酸酯以表中记载的量添加以调制基础润滑脂。然后,在该基础润滑脂中,将作为碱性添加剂的胺(双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯与甲基(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯的混合物)在0~3质量%的范围内变化地添加,制成试验润滑脂。需要说明的是,使增稠剂量固定为15质量%,使余量为基油量,并使合计为100质量%。此外,将混合稠度调整至240。然后,按照JIS K 2501:2003(中和点pH12)来测定各试验润滑脂的总酸值,使用市售的pH计来测定pH。
[表1]
将结果示于表1,并图表化而示于图1中。如上所述,如果总酸值为3.7mg/g以上,则能够将硬脂酸金属盐完全溶解于基油中,耐微振磨损性变得特别良好。此外,如后述的实施例1~7和比较例1所示,优选使pH为8.6以上。而且,如果参照图1,则即使增加胺的添加量也能够在试验润滑脂的总酸值维持于3.7mgKOH/g以上的状态下提高pH,特别是如果为1质量%以上,则能够将pH提高至8.6以上。
(预备试验2)
如表2所示,将PAO(48mm/s@40℃)设为基油,将脲化合物(与预备试验1相同)设为增稠剂,进一步以表中记载的量添加硬脂酸的Cu盐、Fe盐、Zn盐、Mg盐的混合物、ZnDTC和异十三烷基酸式磷酸酯,从而调制试验润滑脂。然后,在内径25mm、外径52mm、高度18mm的单式推力球轴承(标牌;51305)中封入试验润滑脂1.0g,实施将振幅比(=振幅/接触圆直径)设为2.0时的微振磨损试验。其中,为了准确地测定损伤部的最大高度Ry,下座圈使用实施了抛光的圆盘试验片,使用日本精工株式会社制微振磨损试验机,按照下述条件进行微振磨损试验。即,在作为下座圈的圆盘试验片上载置推力球轴承的球和上座圈,在封入有试验润滑脂的状态下,一边从圆盘试验片侧加载负荷一边使上座圈轻微摇动。然后,使用干涉显微镜来测定试验后的圆盘试验片中的损伤痕迹的最大高度Ry,将损伤的程度以损伤比(=试验后的Ry/试验前的Ry)来评价。损伤比越接近1,则意味着损伤越少。此外,将试验润滑脂的总酸值按照JIS K 2501:2003(中和点pH12)进行测定。
<试验条件>
·最大面压:3.2GPa
·最大摇动速度:20mm/s
·摇动次数:500000次
·振幅比:2.0
[表2]
将结果示于表2,并图表化而示于图2中,如No.10那样可知,通过包含脂肪酸金属盐、二硫代氨基甲酸金属盐以及磷系添加剂这3种并且使总酸值成为3.7mgKOH/g以上,可获得优异的耐微振磨损性。此外可知,为了使总酸值为3.7mgKOH/g以上,只要使磷系添加剂为2质量%以上即可。需要说明的是,总酸值为3.7mgKOH/g的No.10的脂肪酸金属盐全部溶解了,与此相对,2.0mgKOH/g的No.9的脂肪酸金属盐没有完全溶解。
(实施例1~7和比较例1)
根据上述预备试验1和预备试验2的结果,以表3所示的组成调制出基础润滑脂。需要说明的是,基油和增稠剂、各种添加剂使用与预备试验1和预备试验2相同的种类。而且,在各基础润滑脂中混合氟系润滑脂(含有亚硝酸钠)来调制试验润滑脂。试验润滑脂中的氟系润滑脂的比例相对于基础润滑脂固定为5质量%。而且,与预备试验1和预备试验2同样地操作,测定试验润滑脂的总酸值和pH,进一步与预备试验2同样地操作,测定损伤比(其中,振动次数为10000次)。
[表3]
将结果示于表3,并将实施例1、实施例2、实施例4、实施例7和比较例1的胺含量与损伤比的关系图表化而示于图3中。需要说明的是,图中的点附近的数值表示pH。
比较例1的试验润滑脂是在预备试验2的No.10的试验润滑脂中混合有氟系润滑脂而成的,但损伤比变大。此外,比较例1的试验润滑脂的pH变小,认为这是因为作为基础润滑脂所包含的磷系添加剂的异十三烷基酸式磷酸酯与氟系润滑脂的亚硝酸钠发生反应而生成了硝酸。与此相对,实施例1~7的试验润滑脂中,生成的硝酸被胺(碱性添加剂)中和,pH成为7以上,与此相伴,损伤比也变小。特别是pH优选为8.6以上,作为胺的添加量,优选为1质量%以上。
这样,在氟系润滑脂侵入那样的情况下,可以通过添加碱性添加剂来提高耐微振磨损性。
对本发明详细并参照特定的实施方式进行了说明,但可以不脱离本发明的精神和范围地施加各种变更、修正,这对于本领域技术人员而言是明确的。
本申请基于2017年12月25日申请的日本专利申请(日本特愿2017-247912),其内容作为参照被并入本文中。
产业可利用性
对于进行AC伺服电动机用轴承、轮毂用轴承、HDD(硬盘驱动)的枢轴用轴承等的轻微往复运动、或受到轻微往复运动的滚动轴承而言,抑制微振磨损磨耗。
Claims (3)
1.一种润滑剂组合物,其特征在于,含有脂肪酸金属盐、二硫代氨基甲酸金属盐、磷系添加剂以及碱性添加剂,并且总酸值为3.7mgKOH/g以上。
2.根据权利要求1所述的润滑剂组合物,其特征在于,pH为8.6以上。
3.一种滚动轴承,其特征在于,通过权利要求1或2所述的润滑剂组合物被润滑。
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EP3733821A1 (en) | 2020-11-04 |
EP3733821B1 (en) | 2023-08-30 |
KR20200100591A (ko) | 2020-08-26 |
JP6610841B1 (ja) | 2019-11-27 |
WO2019131561A1 (ja) | 2019-07-04 |
US11767488B2 (en) | 2023-09-26 |
US20200248096A1 (en) | 2020-08-06 |
KR102583520B1 (ko) | 2023-09-26 |
JPWO2019131561A1 (ja) | 2019-12-26 |
CN111065717B (zh) | 2024-02-20 |
EP3733821A4 (en) | 2021-02-24 |
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