EP2341121A1 - Lubricating grease composition and manufacturing method therefor - Google Patents
Lubricating grease composition and manufacturing method therefor Download PDFInfo
- Publication number
- EP2341121A1 EP2341121A1 EP09820564A EP09820564A EP2341121A1 EP 2341121 A1 EP2341121 A1 EP 2341121A1 EP 09820564 A EP09820564 A EP 09820564A EP 09820564 A EP09820564 A EP 09820564A EP 2341121 A1 EP2341121 A1 EP 2341121A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluorine
- base oil
- grease
- acid
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004519 grease Substances 0.000 title claims abstract description 107
- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 230000001050 lubricating effect Effects 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000011737 fluorine Substances 0.000 claims abstract description 100
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 100
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 98
- 239000002199 base oil Substances 0.000 claims abstract description 80
- 239000000344 soap Substances 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 239000002562 thickening agent Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 20
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004898 kneading Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract 5
- 239000003921 oil Substances 0.000 claims description 45
- 229910052788 barium Inorganic materials 0.000 claims description 14
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims 1
- 229910001863 barium hydroxide Inorganic materials 0.000 claims 1
- -1 unsaturated aliphatic monocarboxylic acid lithium salts Chemical class 0.000 description 35
- 238000005299 abrasion Methods 0.000 description 27
- 229910052744 lithium Inorganic materials 0.000 description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 18
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 16
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 8
- 150000004696 coordination complex Chemical class 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 8
- 239000010702 perfluoropolyether Substances 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 150000002763 monocarboxylic acids Chemical class 0.000 description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 229920013639 polyalphaolefin Polymers 0.000 description 6
- 231100000241 scar Toxicity 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- 238000003682 fluorination reaction Methods 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 238000007539 photo-oxidation reaction Methods 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000013011 mating Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- QBHXHSCLADKAGG-UHFFFAOYSA-N 10-(octadecylamino)-10-oxodecanoic acid Chemical compound C(CCCCCCCCCCCCCCCCC)NC(CCCCCCCCC(=O)O)=O QBHXHSCLADKAGG-UHFFFAOYSA-N 0.000 description 2
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 description 2
- RZUDZAJRBFRQLS-UHFFFAOYSA-N 2-dodecylpropanedioic acid Chemical compound CCCCCCCCCCCCC(C(O)=O)C(O)=O RZUDZAJRBFRQLS-UHFFFAOYSA-N 0.000 description 2
- BTBJCTWMARHHQD-UHFFFAOYSA-N 2-heptadecylpropanedioic acid Chemical compound CCCCCCCCCCCCCCCCCC(C(O)=O)C(O)=O BTBJCTWMARHHQD-UHFFFAOYSA-N 0.000 description 2
- MVDKKZZVTWHVMC-UHFFFAOYSA-N 2-hexadecylpropanedioic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)C(O)=O MVDKKZZVTWHVMC-UHFFFAOYSA-N 0.000 description 2
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 description 2
- SMTKGALBDOEZCA-UHFFFAOYSA-N 2-tetradecylpropanedioic acid Chemical compound CCCCCCCCCCCCCCC(C(O)=O)C(O)=O SMTKGALBDOEZCA-UHFFFAOYSA-N 0.000 description 2
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 2
- 239000005069 Extreme pressure additive Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
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- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
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- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
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- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 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
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
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- 239000012170 montan wax Substances 0.000 description 1
- MJCJUDJQDGGKOX-UHFFFAOYSA-N n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC MJCJUDJQDGGKOX-UHFFFAOYSA-N 0.000 description 1
- NQYKSVOHDVVDOR-UHFFFAOYSA-N n-hexadecylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCC NQYKSVOHDVVDOR-UHFFFAOYSA-N 0.000 description 1
- HKUFIYBZNQSHQS-UHFFFAOYSA-N n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- HSUGDXPUFCVGES-UHFFFAOYSA-N n-tetradecyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCNCCCCCCCCCCCCCC HSUGDXPUFCVGES-UHFFFAOYSA-N 0.000 description 1
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- 239000012860 organic pigment Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
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- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 239000004711 α-olefin Substances 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
- 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
- C10M169/02—Mixtures of base-materials and thickeners
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/0206—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/0406—Ethers; Acetals; Ortho-esters; Ortho-carbonates used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
- C10M2207/1236—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic used as thickening agent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
- C10M2207/1276—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic used as thickening agent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
- C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/06—Perfluoro polymers
- C10M2213/0606—Perfluoro polymers used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2213/06—Perfluoro polymers
- C10M2213/062—Polytetrafluoroethylene [PTFE]
- C10M2213/0626—Polytetrafluoroethylene [PTFE] used as thickening agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/08—Amides
- C10M2215/0813—Amides used as thickening agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/68—Shear stability
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/02—Bearings
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/17—Electric or magnetic purposes for electric contacts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2070/00—Specific manufacturing methods for lubricant compositions
Definitions
- the present invention relates to a lubricating grease composition and a method for producing the same. More particularly, the present invention relates to a lubricating grease composition comprising a base oil mixture of a non-fluorine-based base oil and a fluorine-based base oil, which are incompatible with each other; and a method for producing the composition.
- Conventional fluorine-based greases comprise a perfluoropolyether oil as a base oil, a homopolymer of tetrafluoroethylene [PTFE], a copolymer of tetrafluoroethylene and hexafluoropropene [HFP], or the like as a thickener, and small amounts of additives, such as rust inhibitors. They are used under severe conditions requiring, for example, low-temperature characteristics, high-temperature durability, oxidation stability, and chemical resistance.
- PTFE tetrafluoroethylene
- HFP hexafluoropropene
- the base oil and thickener both contain fluorine, and thus have such problems as high cost; poor compatibility with materials to be lubricated, such as resins, metals, rubber, etc.; failure to form oil films necessary for lubrication under high-load conditions, causing abrasion, and resulting in increased friction coefficients, so that the torque transmission efficiency is lowered; and poor rust prevention and corrosion resistance.
- lubricating grease compositions comprising a base oil mixture of a non-fluorine-based base oil and a fluorine-based base oil are as follows:
- Patent Document 2 discloses a ball-and-roller bearing for an electromagnetic clutch and an idler pulley, the bearing being filled with a grease mixture of a fluorine-based grease comprising a perfluoropolyether oil as a base oil and PTFE as a thickener, and a grease other than fluorine-based grease.
- the ball-and-roller bearing has a longer seizure life at a high temperature exceeding 180°C and enhanced resistance to rust.
- Hydrocarbon-based and ester-based oils, etc. are used as the base oil for non-fluorine-based grease, and lithium, sodium, barium, calcium, and other metal complex soaps are used as metal complex soap thickeners.
- Patent Document 2 disclose a method for producing a lithium complex soap thickener by a two-step saponification reaction comprising saponifying 12-hydroxystearic acid and lithium hydroxide, and then adding dibasic acid and lithium hydroxide, followed by saponification.
- Patent Document 3 discloses a grease mixture, using for a ball-and-roller bearing, comprising a metal complex soap-based grease and a fluorine-based grease at a specific ratio, the metal complex soap-based grease containing 8 to 35 mass% of thickener, and the fluorine-based grease containing a perfluoropolyether oil as a base oil and 15 to 42.5 mass% of PTFE as a thickener, wherein the total amount of the thickeners is 20 to 30 mass%.
- Hydrocarbon-based and ester-based oils, etc. are used as the base oil for non-fluorine-based grease, and lithium, sodium, barium, calcium, and other metal complex soaps are used as metal complex soap thickeners.
- Patent Document 3 disclose a method for producing a lithium complex soap thickener by a two-step saponification reaction comprising saponifying 12-hydroxystearic acid and lithium hydroxide, and then adding dibasic acid and lithium hydroxide, followed by saponification.
- Patent Document 4 discloses a ball-and-roller bearing for a fuel cell in which a fluorine-based grease comprising a fluorine oil as a base oil and a fluororesin as a thickener, and a grease other than fluorine-based grease are enclosed; and a pressure-feeder for a fuel cell system providing the ball-and-roller bearing.
- Patent Document 4 merely indicates that hydrocarbon-based and ester-based oils, etc. are used as the base oil for non-fluorine-based grease, and that lithium, sodium, barium, calcium, and other metal complex soaps are used as metal complex soap thickeners.
- Patent Document 5 discloses a lubricating grease composition comprising a straight-chain perfluoropolyether oil, a synthetic lubricating oil other than the straight-chain perfluoropolyether oil, and a thickener, wherein lithium soaps or lithium complex soaps, such as saturated or unsaturated aliphatic monocarboxylic acid lithium salts or aliphatic dicarboxylic acid lithium salts, are used.
- lithium soaps or lithium complex soaps such as saturated or unsaturated aliphatic monocarboxylic acid lithium salts or aliphatic dicarboxylic acid lithium salts
- Patent Document 6 which was also filed by the present applicant, discloses a lubricating grease composition comprising a perfluoropolyether oil, and, as a thickener, at least one selected from an aliphatic dicarboxylic acid metal salt, a monoamide monocarboxylic acid metal salt, and a monoester carboxylic acid metal salt.
- the lubricating grease composition reportedly has excellent abrasion resistance to mating materials, leakage resistance, washing properties, etc., and satisfies the cost requirements.
- the monoamide carboxylic acid metal salts used in Patent Document 6 are obtained as amide and metal salt of the each dicarboxylic group of dicarboxylic acids. It is reported that primary, secondary, or unsaturated aliphatic amines are used as amines to be amidated, and Li, Na, K, Ca, Ba, Mg, Cu, Fe, Co, Zn, Al, and other salts are used as metal salts.
- An object of the present invention is to provide a lubricating grease composition prepared by adding a metal soap-based thickener to a fluorine-based base oil, the composition having improved abrasion resistance and ensuring cost reduction; and a method for producing the composition.
- a lubricating grease composition comprising a fluororesin powder and a complex metal soap thickener of aliphatic dicarboxylic acid and monoamide monocarboxylic acid contained in a base oil mixture of a non-fluorine-based base oil and a fluorine-based base oil, which are incompatible with each other.
- the lubricating grease composition can be produced by kneading a non-fluorine-based grease and a fluorine-based grease preferably using a three-roll mill; the non-fluorine-based grease being prepared by stirring a non-fluorine-based base oil, aliphatic dicarboxylic acid, and monoamide monocarboxylic acid under heating, and adding metal hydroxide thereto to form a complex metal soap in the non-fluorine-based base oil; and the fluorine-based grease being prepared from a fluorine-based base oil and a fluororesin powder.
- a complex metal soap a complex barium metal soap is preferably used.
- the lubricating grease composition of the present invention has excellent abrasion resistance, load resistance, heat resistance (degree of oil separation), and shear stability (consistency change). Particularly, compared with the lubricating grease composition disclosed in Patent Document 6, the lubricating grease composition of the present invention has improved abrasion resistance and ensures cost reduction.
- the lubricating grease composition (perfluoropolyether oil: 80 wt.%, lithium azelate: 15 wt.%, and PTFE: 5 wt.%) of Example 15 of Patent Document 6 has a abrasion scar diameter of 0.9 mm.
- the non-fluorine-based base oil is at least one of, for example, synthetic hydrocarbon oils such as poly- ⁇ -olefin, ethylene- ⁇ -olefin oligomer, polybutene or hydrogenates thereof, alkyl benzene, and alkyl naphthalene; ether-based synthetic oils such as polyalkylene glycol, polyphenyl ether, and alkyl-substituted diphenyl ether; ester-based synthetic oils such as trimellitic acid ester, pyromellitic acid ester, neopentyl glycol ester, trimethylolpropane ester, pentaerythritol ester, and dipentaerythritol ester; synthetic oils such as polyol ester, aromatic polycarboxylic acid ester, aliphatic dibasic acid ester, phosphoric acid ester, phosphorous acid ester, and carbonic acid ester; paraffinic mineral oil, naphthenic mineral oil or purified
- non-fluorine-based base oils those having a kinematic viscosity at 40°C (according to JIS K2283 corresponding to ASTM D445) of about 5 to 1,500 mm 2 /sec., preferably about 10 to 500 mm 2 /sec., are generally used.
- Non-fluorine-based base oils having a kinematic viscosity of less than this range are largely evaporated, and do not comply with the requirements for the standard of JIS ball-and-roller bearing grease, class 3 specified as heat-resistant grease (i.e., the amount of evaporation is 1.5% or less).
- non-fluorine-based base oils having a kinematic viscosity of more than this range have a pour point (according to JIS K2283) of 10°C or more; bearings cannot be rotated by an ordinary method at the time of low-temperature starting; and they must be heated to make them usable.
- a pour point according to JIS K2283
- fluorine-based base oils those having a kinematic viscosity at 40°C (according to JIS K2283) of about 10 to 1,500 mm 2 /sec., preferably about 20 to 500 mm 2 /sec., are generally used. More specifically, those represented by the general formula: RfO(CF 2 O) x (C 2 F 4 O) y (C 3 F 6 O) z Rf are used. Specific examples thereof include those represented by the following general formulae (1) to (4), and one represented by the general formula (5).
- Rf is perfluoromethyl, perfluoroethyl, perfluoropropyl, or other perfluoro lower alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms.
- the non-fluorine-based base oil and fluorine-based base oil are used in such a proportion that the former base oil is generally used at a ratio of about 5 to 95 wt.%, preferably about 10 to 90 wt.%, with respect to about 95 to 5 wt.%, preferably about 90 to 10 wt.%, of the latter base oil.
- the proportion of the non-fluorine-based base oil is less than this range, load resistance increases, while abrasion resistance, heat resistance, shear stability, etc. decrease. Conversely, when the proportion is higher than this range, abrasion resistance increases, while heat resistance, load resistance, shear stability, etc. decrease.
- the complex metal soap used as a thickener is formed as a complex metal soap of aliphatic dicarboxylic acid and monoamide monocarboxylic acid.
- the formation of the complex metal soap is carried out during preparation of the lubricating grease composition, as described later.
- saturated or unsaturated dicarboxylic acids having 2 to 20 carbon atoms are used.
- saturated dicarboxylic acids include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylenedicarboxylic acid, decamethylenedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, heptadecanedicarboxylic acid, octadecanedicarboxylic acid, etc.
- adipic acid Preferably used are adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylenedicarboxylic acid, decamethylenedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, heptadecanedicarboxylic acid, octadecanedicarboxylic acid, etc.
- unsaturated dicarboxylic acids examples include maleic acid, fumaric acid, 2-methylenesuccinic acid, 2-ethylenesuccinic acid, 2-methyleneglutaric acid, and other alkenyl succinic acids. These saturated or unsaturated dicarboxylic acids are used singly or in combination of two or more.
- Monoamide monocarboxylic acids are obtained by amidation of the monocarboxylic groups of the above dicarboxylic acids.
- amines to be amidated include aliphatic primary amines, such as butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, and behenylamine; aliphatic secondary amines, such as dipropylamine, diisopropylamine, dibutylamine, diamylamine, dilaurylamine, monomethyl laurylamine, distearylamine, monomethyl stearylamine, dimyristylamine, and dipalmitylamine; aliphatic unsaturated amines, such as allylamine, diallylamine, oleylamine, and dioleylamine; alicyclic amines, such as cycl
- Preferably used are hexylamine, heptylamine, octylamine, nonylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, behenylamine, dibutylamine, diamylamine, monomethyl laurylamine, monomethyl stearylamine, oleylamine, etc.
- aliphatic dicarboxylic acids and monoamide monocarboxylic acids are used to form complex metal soaps together with lithium, sodium, potassium, calcium, barium, magnesium, copper, iron, cobalt, zinc, aluminum, and other metals; complex barium soaps are preferred.
- examples of the fluororesin powder include PTFE powder, HFP powder, perfluoroalkylene resin powder, etc.
- the fluororesin powder generally has an average primary particle size of about 500 ⁇ m or less, preferably about 0.1 to 30 ⁇ m.
- tetrafluoroethylene is subjected to emulsion polymerization, suspension polymerization, solution polymerization, or like method to produce polytetrafluoroethylene, and the resulting polytetrafluoroethylene is treated by pyrolysis, degradation by electron-beam irradiation, physical pulverization, or like method, so that the number average molecular weight Mn is about 1,000 to 1,000,000.
- the copolymerization of tetrafluoroethylene and hexafluoropropene and the reduction of molecular weight are carried out in the same manner as with polytetrafluoroethylene, so that the number average molecular weight Mn is about 1,000 to 600,000.
- the molecular weight can be controlled by a chain transfer agent during copolymerization reaction.
- the lubricating grease composition of the present invention can be prepared by mixing two kinds of greases, i.e., a non-fluorine-based grease that is a complex metal soap thickener-containing non-fluorine-based base oil, and a fluorine-based grease that is a fluororesin powder-containing fluorine-based base oil.
- the lubricating grease composition of the present invention can also be prepared by adding a fluorine-based base oil and fluororesin to the non-fluorine-based grease prepared in the above manner, and mixing them in a mixing kettle, followed by kneading with a three-roll mill.
- the non-fluorine-based base oil is used in an amount of about 5 to 90 wt.%, preferably about 10 to 80 wt.%, in the base grease;
- the fluorine-based base oil which is used together with the non-fluorine-based base oil at the above-described ratio, is used in an amount of about 5 to 90 wt.%, preferably about 10 to 80 wt.%, in the base grease;
- the complex metal soap is used in an amount of about 1.5 to 30 wt.%, preferably about 5 to 25 wt.%, in the base grease;
- the fluororesin powder is used in an amount of about 0.1 to 50 wt.%, preferably about 5 to 35 wt.%, in the base grease.
- the lubricating grease composition may contain, if necessary, antioxidants, rust inhibitors, corrosion inhibitors, extreme pressure additives, oiliness agents, solid lubricants, and other additives used in conventional lubricants.
- antioxidants include phenol-based antioxidants, such as 2,6-di-tert-butyl-4-methylphenol and 4,4'-methylenebis(2,6-di-tert-butylphenol); amine-based antioxidants, such as alkyl diphenylamine having a C 4 -C 20 alkyl group, triphenylamine, phenyl- ⁇ -naphthylamine, alkylated phenyl- ⁇ -naphthylamine, phenothiazine, and alkylated phenothiazine; phosphoric acid-based antioxidants, sulfur-based antioxidants, and the like.
- rust inhibitors include fatty acids, fatty acid metal salts, fatty acid amines, alkylsulfonic acid metal salts, alkylsulfonic acid amine salts, oxided paraffin, polyoxyethylene alkyl ethers, and the like.
- corrosion inhibitors include benzotriazole, benzoimidazole, thiadiazole, and the like.
- extreme pressure additives include phosphorus-based compounds, such as phosphoric acid esters, phosphorous acid esters, and phosphoric acid ester amine salts; sulfur-based compounds, such as sulfides and disulfides; sulfur-based compound metal salts, such as dialkyldithiophosphoric acid metal salts and dialkyldithiocarbamic acid metal salts; chlorine-based compounds, such as chlorinated paraffin and chlorinated diphenyl; and the like.
- phosphorus-based compounds such as phosphoric acid esters, phosphorous acid esters, and phosphoric acid ester amine salts
- sulfur-based compounds such as sulfides and disulfides
- sulfur-based compound metal salts such as dialkyldithiophosphoric acid metal salts and dialkyldithiocarbamic acid metal salts
- chlorine-based compounds such as chlorinated paraffin and chlorinated diphenyl; and the like.
- oiliness agents include fatty acids or esters thereof, higher alcohols, polyhydric alcohols or esters thereof, aliphatic esters, aliphatic amines, fatty acid monoglycerides, montan wax, amide-based wax, and the like.
- oiliness agents include fatty acids or esters thereof, higher alcohols, polyhydric alcohols or esters thereof, aliphatic esters, aliphatic amines, fatty acid monoglycerides, montan wax, amide-based wax, and the like.
- other solid lubricants include molybdenum disulfide, graphite, boron nitride, silane nitride, melamine cyanurate, and the like. Such other solid lubricants have an average primary particle size of 30 ⁇ m or less, preferably 0.1 to 20 ⁇ m.
- thickeners that have generally been used as thickeners, such as silica, clay, graphite, zinc oxide, urea compounds, polyethylene, polypropylene, polyamide, organic pigments, metal soaps, etc., can be suitably added.
- a barium complex soap of sebacic acid and sebacic acid monostearylamide accounting for 30 wt.% of the base grease as a thickener, was synthesized by the process (a-1) described above.
- amine-based antioxidant NA-LUBE AO-120, a product of King Industries, Inc.; alkyl diphenylamine
- a lithium soap of 12-hydroxystearic acid accounting for 10 wt.% of the base grease as a thickener, was synthesized.
- 2 wt.% of amine-based antioxidant NA-LUBE AO-120 was added, and the mixture was kneaded twice by a three-roll mill, thereby producing a grease D.
- a lithium complex soap of azelaic acid and 12-hydroxystearic acid accounting for 20 wt.% of the base grease as a thickener, was synthesized.
- 3 wt.% of oiliness agent trimethylolpropane alkyl ester; 40°C viscosity: 30 mm 2 /sec.
- 2 wt.% of amine-based antioxidant NA-LUBE AO-120
- a fluorine-based base oil (40°C viscosity: 230 mm 2 /sec.) having a molecular structure represented by the general formula: RfO[CF(CF 3 )CF 2 O] m Rf was mixed with a PTFE powder (average particle diameter: 0.3 ⁇ m) in an amount accounting for 32 wt.% of the base grease. The mixture was kneaded twice by a three-roll mill, thereby producing a grease I.
- a fluorine-based base oil (40°C viscosity: 230 mm 2 /sec.) having a molecular structure represented by the general formula: RfO[CF(CF 3 )CF 2 O] m Rf was mixed with a PTFE powder (average particle diameter: 0.3 ⁇ m) in an amount accounting for 18 wt.% of the base grease. The mixture was kneaded twice by a three-roll mill, thereby producing a grease II.
- a fluorine-based base oil (40°C viscosity: 85 mm 2 /sec.) having a molecular structure represented by the general formula: RfO(CF 2 CF 2 O) m (CF 2 O) n Rf was mixed with a PTFE powder (average particle diameter: 0.3 ⁇ m) in an amount accounting for 27 wt.% of the base grease. The mixture was kneaded twice by a three-roll mill, thereby producing a grease III.
- One or two kinds of the non-fluorine-based greases A to E and the fluorine-based greases I and II prepared in the above Reference Examples were mixed at predetermined weight ratios. Each of the resulting mixtures was sufficiently stirred in a mixing kettle, and then kneaded twice by a three-roll mill, thereby producing lubricating grease compositions.
- the produced lubricating grease compositions were measured for the following items:
- the lubricating grease composition of the present invention which has excellent characteristics as described above, i.e., excellent heat resistance, shear stability, abrasion resistance to mating materials, and load resistance, as well as satisfies the cost requirements, can be suitably used to lubricate and protect the contact portion between individual sliding parts of ball-and-roller bearings, sliding bearings, sintering bearings, gears, valves, cocks, oil seals, electric contacts, etc.
- the lubricating grease composition can be suitably applied in various parts of various devices, machines, and apparatuses listed below.
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Abstract
Description
- The present invention relates to a lubricating grease composition and a method for producing the same. More particularly, the present invention relates to a lubricating grease composition comprising a base oil mixture of a non-fluorine-based base oil and a fluorine-based base oil, which are incompatible with each other; and a method for producing the composition.
- Conventional fluorine-based greases comprise a perfluoropolyether oil as a base oil, a homopolymer of tetrafluoroethylene [PTFE], a copolymer of tetrafluoroethylene and hexafluoropropene [HFP], or the like as a thickener, and small amounts of additives, such as rust inhibitors. They are used under severe conditions requiring, for example, low-temperature characteristics, high-temperature durability, oxidation stability, and chemical resistance.
- However, the base oil and thickener both contain fluorine, and thus have such problems as high cost; poor compatibility with materials to be lubricated, such as resins, metals, rubber, etc.; failure to form oil films necessary for lubrication under high-load conditions, causing abrasion, and resulting in increased friction coefficients, so that the torque transmission efficiency is lowered; and poor rust prevention and corrosion resistance.
- In order to solve these problems, it has been proposed to use a fluorine-based base oil in combination with a non-fluorine-based base oil (e.g., hydrocarbon-based oil) to form a lubricating grease composition, which is thus less expensive and has excellent abrasion resistance to mating materials.
- Examples of lubricating grease compositions comprising a base oil mixture of a non-fluorine-based base oil and a fluorine-based base oil are as follows:
- (1) Patent Document 1 discloses a grease comprising a hydrogenated mineral oil and/or synthetic lubricating oil, a fluoropolyether oil, and an organic or inorganic thickening agent, wherein the weight ratio of the lubricating oil and the fluoropolyether oil to the thickening agent is 97:3 to 80:20, and the weight ratio of the lubricating oil to the fluoropolyether oil is 95:5 to 60:40. The grease is evaluated for abrasion resistance, load resistance, and bearing durability. In the Examples of Patent Document 1, an ester oil mixed with an aliphatic lithium complex soap (a lithium complex soap of azelaic acid and 12-hydroxystearic acid) is used.
- (2) Patent Document 2 discloses a ball-and-roller bearing for an electromagnetic clutch and an idler pulley, the bearing being filled with a grease mixture of a fluorine-based grease comprising a perfluoropolyether oil as a base oil and PTFE as a thickener, and a grease other than fluorine-based grease. The ball-and-roller bearing has a longer seizure life at a high temperature exceeding 180°C and enhanced resistance to rust. Hydrocarbon-based and ester-based oils, etc. are used as the base oil for non-fluorine-based grease, and lithium, sodium, barium, calcium, and other metal complex soaps are used as metal complex soap thickeners. The Examples of Patent Document 2 disclose a method for producing a lithium complex soap thickener by a two-step saponification reaction comprising saponifying 12-hydroxystearic acid and lithium hydroxide, and then adding dibasic acid and lithium hydroxide, followed by saponification.
- (3) Patent Document 3 discloses a grease mixture, using for a ball-and-roller bearing, comprising a metal complex soap-based grease and a fluorine-based grease at a specific ratio, the metal complex soap-based grease containing 8 to 35 mass% of thickener, and the fluorine-based grease containing a perfluoropolyether oil as a base oil and 15 to 42.5 mass% of PTFE as a thickener, wherein the total amount of the thickeners is 20 to 30 mass%. Hydrocarbon-based and ester-based oils, etc. are used as the base oil for non-fluorine-based grease, and lithium, sodium, barium, calcium, and other metal complex soaps are used as metal complex soap thickeners. The Examples of Patent Document 3 disclose a method for producing a lithium complex soap thickener by a two-step saponification reaction comprising saponifying 12-hydroxystearic acid and lithium hydroxide, and then adding dibasic acid and lithium hydroxide, followed by saponification.
- (4) Patent Document 4 discloses a ball-and-roller bearing for a fuel cell in which a fluorine-based grease comprising a fluorine oil as a base oil and a fluororesin as a thickener, and a grease other than fluorine-based grease are enclosed; and a pressure-feeder for a fuel cell system providing the ball-and-roller bearing. Patent Document 4 merely indicates that hydrocarbon-based and ester-based oils, etc. are used as the base oil for non-fluorine-based grease, and that lithium, sodium, barium, calcium, and other metal complex soaps are used as metal complex soap thickeners.
- (5) Patent Document 5, which was filed by the present applicant, discloses a lubricating grease composition comprising a straight-chain perfluoropolyether oil, a synthetic lubricating oil other than the straight-chain perfluoropolyether oil, and a thickener, wherein lithium soaps or lithium complex soaps, such as saturated or unsaturated aliphatic monocarboxylic acid lithium salts or aliphatic dicarboxylic acid lithium salts, are used.
- (6) Patent Document 6, which was also filed by the present applicant, discloses a lubricating grease composition comprising a perfluoropolyether oil, and, as a thickener, at least one selected from an aliphatic dicarboxylic acid metal salt, a monoamide monocarboxylic acid metal salt, and a monoester carboxylic acid metal salt. The lubricating grease composition reportedly has excellent abrasion resistance to mating materials, leakage resistance, washing properties, etc., and satisfies the cost requirements.
- The monoamide carboxylic acid metal salts used in Patent Document 6 are obtained as amide and metal salt of the each dicarboxylic group of dicarboxylic acids. It is reported that primary, secondary, or unsaturated aliphatic amines are used as amines to be amidated, and Li, Na, K, Ca, Ba, Mg, Cu, Fe, Co, Zn, Al, and other salts are used as metal salts.
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- Patent Document 1 :
JP-A-7-268370 - Patent Document 2 :
JP-A-2003-239997 - Patent Document 3 :
JP-A-2004-028326 - Patent Document 4 :
JP-A-2004-190688 - Patent Document 5 :
JP-A-2003-096480 - Patent Document 6 :
JP-A-2001-354986 - An object of the present invention is to provide a lubricating grease composition prepared by adding a metal soap-based thickener to a fluorine-based base oil, the composition having improved abrasion resistance and ensuring cost reduction; and a method for producing the composition.
- The above object of the present invention can be achieved by a lubricating grease composition comprising a fluororesin powder and a complex metal soap thickener of aliphatic dicarboxylic acid and monoamide monocarboxylic acid contained in a base oil mixture of a non-fluorine-based base oil and a fluorine-based base oil, which are incompatible with each other. The lubricating grease composition can be produced by kneading a non-fluorine-based grease and a fluorine-based grease preferably using a three-roll mill; the non-fluorine-based grease being prepared by stirring a non-fluorine-based base oil, aliphatic dicarboxylic acid, and monoamide monocarboxylic acid under heating, and adding metal hydroxide thereto to form a complex metal soap in the non-fluorine-based base oil; and the fluorine-based grease being prepared from a fluorine-based base oil and a fluororesin powder. As a complex metal soap, a complex barium metal soap is preferably used.
- The lubricating grease composition of the present invention has excellent abrasion resistance, load resistance, heat resistance (degree of oil separation), and shear stability (consistency change). Particularly, compared with the lubricating grease composition disclosed in Patent Document 6, the lubricating grease composition of the present invention has improved abrasion resistance and ensures cost reduction.
- More specifically, in abrasion scar diameter measurement using the Shell four-ball test, the lubricating grease composition (perfluoropolyether oil: 80 wt.%, lithium azelate: 15 wt.%, and PTFE: 5 wt.%) of Example 15 of Patent Document 6 has a abrasion scar diameter of 0.9 mm. This value is inferior to the abrasion scar diameter (0.6 mm) of grease compositions of Comparative Examples 2 and 3 of the present specification, described later (poly-α-olefin oil containing a 12-hydroxystearic acid lithium soap or a lithium complex soap of azelaic acid and 12-hydroxystearic acid: 80 wt.%, and PTFE-containing perfluoropolyether oil: 20 wit.%). In contrast, grease compositions of Examples of the present invention have a abrasion scar diameter of 0.4 to 0.8 mm, showing further improved abrasion resistance. Additionally, the expensive fluorine-based base oil is partially substituted by the non-fluorine-based base oil, leading to effective cost reduction.
- Mutual incompatibility between the non-fluorine-based base oil and the fluorine-based base oil means that a homogeneous base oil mixture cannot be formed by simply mixing these two base oils.
- The non-fluorine-based base oil is at least one of, for example, synthetic hydrocarbon oils such as poly-α-olefin, ethylene-α-olefin oligomer, polybutene or hydrogenates thereof, alkyl benzene, and alkyl naphthalene; ether-based synthetic oils such as polyalkylene glycol, polyphenyl ether, and alkyl-substituted diphenyl ether; ester-based synthetic oils such as trimellitic acid ester, pyromellitic acid ester, neopentyl glycol ester, trimethylolpropane ester, pentaerythritol ester, and dipentaerythritol ester; synthetic oils such as polyol ester, aromatic polycarboxylic acid ester, aliphatic dibasic acid ester, phosphoric acid ester, phosphorous acid ester, and carbonic acid ester; paraffinic mineral oil, naphthenic mineral oil or purified mineral oils thereof, etc. Preferably, synthetic hydrocarbon oils or ether-based synthetic oils are used.
- As such non-fluorine-based base oils, those having a kinematic viscosity at 40°C (according to JIS K2283 corresponding to ASTM D445) of about 5 to 1,500 mm2/sec., preferably about 10 to 500 mm2/sec., are generally used. Non-fluorine-based base oils having a kinematic viscosity of less than this range are largely evaporated, and do not comply with the requirements for the standard of JIS ball-and-roller bearing grease, class 3 specified as heat-resistant grease (i.e., the amount of evaporation is 1.5% or less). Conversely, non-fluorine-based base oils having a kinematic viscosity of more than this range have a pour point (according to JIS K2283) of 10°C or more; bearings cannot be rotated by an ordinary method at the time of low-temperature starting; and they must be heated to make them usable. Thus, such non-fluorine-based base oils cannot suitably be used in general greases.
- As fluorine-based base oils, those having a kinematic viscosity at 40°C (according to JIS K2283) of about 10 to 1,500 mm2/sec., preferably about 20 to 500 mm2/sec., are generally used. More specifically, those represented by the general formula:
RfO(CF2O)x(C2F4O)y(C3F6O)zRf
are used. Specific examples thereof include those represented by the following general formulae (1) to (4), and one represented by the general formula (5). Rf is perfluoromethyl, perfluoroethyl, perfluoropropyl, or other perfluoro lower alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms.
(1) RfO(CF2CF2O)m(CF2O)nRf
wherein m+n is 3 to 200, m:n is 10:90 to 90:10, and CF2CF2O group and CF2O group are randomly bonded to the main chain. This can be obtained by complete fluorination of a precursor produced by photooxidation polymerization of tetrafluoroethylene.
(2) RfO[CF(CF3)CF2O)]m(CF2O)nRf
wherein m+n is 3 to 200, m:n is 10:90 to 90:10, and CF(CF3)CF2O group and CF2O group are randomly bonded to the main chain. This can be obtained by complete fluorination of a precursor produced by photooxidation polymerization of hexafluoropropylene.
(3) RfO[CF(CF3)CF2O]p(CF2CF2O)q(CF2O)rRf
wherein p+q+r is 3 to 200, q and r may be 0, (q+r)/p is 0 to 2, and CF(CF3)CF2O, CF2CF2O group and CF2O group are randomly bonded to the main chain. This can be obtained by complete fluorination of a precursor produced by photooxidation polymerization of hexafluoropropylene and tetrafluoroethylene.
(4) RfO[CF(CF3)CF2O]s(CF2CF2O)tRf
wherein s+t is 2 to 200, t may be 0, t/s is 0 to 2, and CF(CF3)CF2O group and CF2CF2O group are randomly bonded to the main chain. This can be obtained by complete fluorination of a precursor produced by photooxidation polymerization of hexafluoropropylene and tetrafluoroethylene. Alternatively, it can be obtained by anionic polymerization of hexafluoropropylene oxide or tetrafluoroethylene oxide in the presence of a cesium fluoride catalyst, and then by fluorine gas treatment of the obtained acid fluoride compound having a terminal -CF(CF3)COF group.
(5) F(CF2CF2CF2O)2-100C2F5
This can be obtained by anionic polymerization of 2,2,3,3-tetrafluorooxetane in the presence of a cesium fluoride catalyst, and then by fluorine gas treatment of the obtained fluorine-containing polyether (CH2CF2CF2O)n under UV irradiation at about 160 to 300°C. - The non-fluorine-based base oil and fluorine-based base oil are used in such a proportion that the former base oil is generally used at a ratio of about 5 to 95 wt.%, preferably about 10 to 90 wt.%, with respect to about 95 to 5 wt.%, preferably about 90 to 10 wt.%, of the latter base oil. When the proportion of the non-fluorine-based base oil is less than this range, load resistance increases, while abrasion resistance, heat resistance, shear stability, etc. decrease. Conversely, when the proportion is higher than this range, abrasion resistance increases, while heat resistance, load resistance, shear stability, etc. decrease.
- The complex metal soap used as a thickener is formed as a complex metal soap of aliphatic dicarboxylic acid and monoamide monocarboxylic acid. The formation of the complex metal soap is carried out during preparation of the lubricating grease composition, as described later.
- As aliphatic dicarboxylic acids, saturated or unsaturated dicarboxylic acids having 2 to 20 carbon atoms are used. Examples of saturated dicarboxylic acids include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylenedicarboxylic acid, decamethylenedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, heptadecanedicarboxylic acid, octadecanedicarboxylic acid, etc. Preferably used are adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonamethylenedicarboxylic acid, decamethylenedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, heptadecanedicarboxylic acid, octadecanedicarboxylic acid, etc. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, 2-methylenesuccinic acid, 2-ethylenesuccinic acid, 2-methyleneglutaric acid, and other alkenyl succinic acids. These saturated or unsaturated dicarboxylic acids are used singly or in combination of two or more.
- Monoamide monocarboxylic acids are obtained by amidation of the monocarboxylic groups of the above dicarboxylic acids. Examples of amines to be amidated include aliphatic primary amines, such as butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, and behenylamine; aliphatic secondary amines, such as dipropylamine, diisopropylamine, dibutylamine, diamylamine, dilaurylamine, monomethyl laurylamine, distearylamine, monomethyl stearylamine, dimyristylamine, and dipalmitylamine; aliphatic unsaturated amines, such as allylamine, diallylamine, oleylamine, and dioleylamine; alicyclic amines, such as cyclopropylamine, cyclobutylamine, cyclopentylamine, and cyclohexylamine; aromatic amines, such as aniline, methylaniline, ethylaniline, benzylamine, dibenzylamine, diphenylamine, and α-naphthylamine; and the like. Preferably used are hexylamine, heptylamine, octylamine, nonylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, behenylamine, dibutylamine, diamylamine, monomethyl laurylamine, monomethyl stearylamine, oleylamine, etc.
- These aliphatic dicarboxylic acids and monoamide monocarboxylic acids are used to form complex metal soaps together with lithium, sodium, potassium, calcium, barium, magnesium, copper, iron, cobalt, zinc, aluminum, and other metals; complex barium soaps are preferred.
- Moreover, examples of the fluororesin powder include PTFE powder, HFP powder, perfluoroalkylene resin powder, etc. The fluororesin powder generally has an average primary particle size of about 500 µm or less, preferably about 0.1 to 30 µm.
- As for usable PTFE (polytetrafluoroethylene), tetrafluoroethylene is subjected to emulsion polymerization, suspension polymerization, solution polymerization, or like method to produce polytetrafluoroethylene, and the resulting polytetrafluoroethylene is treated by pyrolysis, degradation by electron-beam irradiation, physical pulverization, or like method, so that the number average molecular weight Mn is about 1,000 to 1,000,000. Moreover, as for usable HFP powders, the copolymerization of tetrafluoroethylene and hexafluoropropene and the reduction of molecular weight are carried out in the same manner as with polytetrafluoroethylene, so that the number average molecular weight Mn is about 1,000 to 600,000. The molecular weight can be controlled by a chain transfer agent during copolymerization reaction.
- The formation of the complex metal soap and the preparation of the lubricating grease composition are carried out as follows.
- (a-1) A non-fluorine-based base oil, aliphatic dicarboxylic acid, and monoamide monocarboxylic acid are placed in a reaction kettle that allows stirring under heating, and the mixture is stirred while heating to about 80 to 180°C, at which stirring is possible, the reaction is efficiently promoted, and the base oil does not deteriorate. To the mixture, metal hydroxide is added to form a complex metal soap in the non-fluorine-based base oil. After cooling, a predetermined amount of amine-based antioxidant, etc. is added thereto, and the mixture is kneaded through a three-roll mill or a high-pressure homogenizer, thereby preparing a non-fluorine-based grease. Prior to kneading, non-fluorine-based base oils other than the non-fluorine-based base oil initially used may be added.
- (a-2) A fluorine-based base oil and a fluororesin powder are mixed in a mixing kettle, and the mixture is then kneaded through a three-roll mill or a high-pressure homogenizer, thereby preparing a fluorine-based grease.
- (a-3) These two kinds of greases are mixed in a mixing kettle, preferably kneaded by a three-roll mill, thereby preparing a lubricating grease composition. Generally, a hydraulic three-roll mill is used for kneading.
- That is, the lubricating grease composition of the present invention can be prepared by mixing two kinds of greases, i.e., a non-fluorine-based grease that is a complex metal soap thickener-containing non-fluorine-based base oil, and a fluorine-based grease that is a fluororesin powder-containing fluorine-based base oil.
- (b) The lubricating grease composition of the present invention can also be prepared by adding a fluorine-based base oil and fluororesin to the non-fluorine-based grease prepared in the above manner, and mixing them in a mixing kettle, followed by kneading with a three-roll mill.
- In the lubricating grease composition (base grease) comprising the above essential components, the non-fluorine-based base oil is used in an amount of about 5 to 90 wt.%, preferably about 10 to 80 wt.%, in the base grease; the fluorine-based base oil, which is used together with the non-fluorine-based base oil at the above-described ratio, is used in an amount of about 5 to 90 wt.%, preferably about 10 to 80 wt.%, in the base grease; the complex metal soap is used in an amount of about 1.5 to 30 wt.%, preferably about 5 to 25 wt.%, in the base grease; and the fluororesin powder is used in an amount of about 0.1 to 50 wt.%, preferably about 5 to 35 wt.%, in the base grease.
- Compounding of each component in the proportion described above has the following effects:
- Non-fluorine-based base oil: thickeners having little or no compatibility with the fluorine-based base oil can be added, thereby resulting in increased abrasion resistance, lower friction coefficient, and improved rust prevention and corrosion inhibition effect.
- Fluorine-based base oil: heat resistance is improved.
- Complex metal soap: abrasion resistance is improved.
- Fluororesin powder: the compatibility between the fluorine-based base oil and the complex metal soap increases.
- The lubricating grease composition may contain, if necessary, antioxidants, rust inhibitors, corrosion inhibitors, extreme pressure additives, oiliness agents, solid lubricants, and other additives used in conventional lubricants. Examples of antioxidants include phenol-based antioxidants, such as 2,6-di-tert-butyl-4-methylphenol and 4,4'-methylenebis(2,6-di-tert-butylphenol); amine-based antioxidants, such as alkyl diphenylamine having a C4-C20 alkyl group, triphenylamine, phenyl-α-naphthylamine, alkylated phenyl-α-naphthylamine, phenothiazine, and alkylated phenothiazine; phosphoric acid-based antioxidants, sulfur-based antioxidants, and the like.
- Examples of rust inhibitors include fatty acids, fatty acid metal salts, fatty acid amines, alkylsulfonic acid metal salts, alkylsulfonic acid amine salts, oxided paraffin, polyoxyethylene alkyl ethers, and the like. Examples of corrosion inhibitors include benzotriazole, benzoimidazole, thiadiazole, and the like.
- Examples of extreme pressure additives include phosphorus-based compounds, such as phosphoric acid esters, phosphorous acid esters, and phosphoric acid ester amine salts; sulfur-based compounds, such as sulfides and disulfides; sulfur-based compound metal salts, such as dialkyldithiophosphoric acid metal salts and dialkyldithiocarbamic acid metal salts; chlorine-based compounds, such as chlorinated paraffin and chlorinated diphenyl; and the like.
- Examples of oiliness agents include fatty acids or esters thereof, higher alcohols, polyhydric alcohols or esters thereof, aliphatic esters, aliphatic amines, fatty acid monoglycerides, montan wax, amide-based wax, and the like. Examples of other solid lubricants include molybdenum disulfide, graphite, boron nitride, silane nitride, melamine cyanurate, and the like. Such other solid lubricants have an average primary particle size of 30 µm or less, preferably 0.1 to 20 µm.
- Additionally, other thickeners that have generally been used as thickeners, such as silica, clay, graphite, zinc oxide, urea compounds, polyethylene, polypropylene, polyamide, organic pigments, metal soaps, etc., can be suitably added.
- The following describes the present invention with reference to Examples.
- In a poly-α-olefin oil (40°C viscosity: 30 mm2/sec.), a barium complex soap of sebacic acid and sebacic acid monostearylamide, accounting for 30 wt.% of the base grease as a thickener, was synthesized by the process (a-1) described above. To the barium complex soap, 2 wt.% of amine-based antioxidant (NA-LUBE AO-120, a product of King Industries, Inc.; alkyl diphenylamine) was added, and the mixture was kneaded twice by a three-roll mill, thereby producing a grease A.
- In a poly-α-olefin oil (40°C viscosity: 46 mm2/sec.), a barium complex soap of azelaic acid and azelaic acid monooctylamide, accounting for 25 wt.% of the base grease as a thickener, was synthesized by the process (a-1) described above. To the barium complex soap, 3 wt.% of oiliness agent (trimethylolpropane alkyl ester; 40°C viscosity: 30 mm2/sec.) and 2 wt.% of amine-based antioxidant (NA-LUBE AO-120) were added, and the mixture was kneaded twice by a three-roll mill, thereby producing a grease B.
- In a diphenyl ether oil (40°C viscosity: 100 mm2/sec.), a barium complex soap of sebacic acid and sebacic acid monostearylamide, accounting for 30 wt.% of the base grease as a thickener, was synthesized by the process (a-1) described above. To the barium complex soap, 2 wt.% of amine-based antioxidant (NA-LUBE AO-120) was added, and the mixture was kneaded twice by a three-roll mill, thereby producing a grease C.
- In a poly-α-olefin oil (40°C viscosity: 30 mm2/sec.), a lithium soap of 12-hydroxystearic acid, accounting for 10 wt.% of the base grease as a thickener, was synthesized. To the lithium soap, 2 wt.% of amine-based antioxidant (NA-LUBE AO-120) was added, and the mixture was kneaded twice by a three-roll mill, thereby producing a grease D.
- In a poly-α-olefin oil (40°C viscosity: 46 mm2/sec.), a lithium complex soap of azelaic acid and 12-hydroxystearic acid, accounting for 20 wt.% of the base grease as a thickener, was synthesized. To the lithium complex soap, 3 wt.% of oiliness agent (trimethylolpropane alkyl ester; 40°C viscosity: 30 mm2/sec.) and 2 wt.% of amine-based antioxidant (NA-LUBE AO-120) were added, and the mixture was kneaded twice by a three-roll mill, thereby producing a grease E.
- A fluorine-based base oil (40°C viscosity: 230 mm2/sec.) having a molecular structure represented by the general formula: RfO[CF(CF3)CF2O]mRf was mixed with a PTFE powder (average particle diameter: 0.3 µm) in an amount accounting for 32 wt.% of the base grease. The mixture was kneaded twice by a three-roll mill, thereby producing a grease I.
- A fluorine-based base oil (40°C viscosity: 230 mm2/sec.) having a molecular structure represented by the general formula: RfO[CF(CF3)CF2O]mRf was mixed with a PTFE powder (average particle diameter: 0.3 µm) in an amount accounting for 18 wt.% of the base grease. The mixture was kneaded twice by a three-roll mill, thereby producing a grease II.
- A fluorine-based base oil (40°C viscosity: 85 mm2/sec.) having a molecular structure represented by the general formula: RfO(CF2CF2O)m(CF2O)nRf was mixed with a PTFE powder (average particle diameter: 0.3 µm) in an amount accounting for 27 wt.% of the base grease. The mixture was kneaded twice by a three-roll mill, thereby producing a grease III.
- One or two kinds of the non-fluorine-based greases A to E and the fluorine-based greases I and II prepared in the above Reference Examples were mixed at predetermined weight ratios. Each of the resulting mixtures was sufficiently stirred in a mixing kettle, and then kneaded twice by a three-roll mill, thereby producing lubricating grease compositions.
- The produced lubricating grease compositions were measured for the following items:
- Abrasion resistance: Shell four-ball test, according to ASTM D2266
Temperature: 75°C
Number of rotations: 1,200 rpm
Load: 392 N
Time: 60 minutes
The abrasion scar diameter after the test was measured
(Smaller values indicate better abrasion resistance) - Load resistance (four-ball test): Soda type, according to JIS K2519
Step pressurization method
Number of rotations: 750 rpm
Temperature: room temperature
(Larger values indicate better load resistance) - Heat resistance (oil separation degree): according to JIS K2220.11
corresponding to ASTM D6184
The degree of oil separation after 24 hours at a temperature of 180°C was measured
(Smaller values indicate better heat resistance) - Shear stability (consistency change): Shell roll test, according to ASTM 1831
Temperature: 80°C
Number of rotations: 165 rpm
Time: 24 hours
Consistency changes before and after the test were measured
(Smaller values indicate better shear stability) - The following table shows the measurement results.
Table Ex. Comp. Ex. 1 2 3 4 5 6 1 2 3 4 5 [Grease] A (wt.%) 80 60 60 20 - - 100 - - - - B (wt.%) - - - - 80 - - - - - C (wt.%) - - - - - 50 - - - - - D (wt.%) - - - - - - - 80 - - - E (wt.%) - - - - - - - - 80 - - I (wt.%) 20 40 - 80 20 - - 20 20 100 - II (wt.%) - - - - - 50 - - - - - III (wt.%) - - 40 - - - - - - - 100 [Measurement Item] Abrasion scar diameter (mm) 0.4 0.5 0.5 0.7 0.5 0.6 0.4 0.6 0.6 1.0 1.1 Load resistance (MPa) 0.784 0.833 0.784 0.980 0.735 0.784 0.637 0.294 0.441 0.980 0.980 Oil separation degree (wt.%) 1.1 0.9 0.8 0.5 1.5 1.5 2.4 5.2 3.0 5.5 5.0 Consistency 44 38 35 30 45 35 50 76 69 30 30 change (-) - The above results demonstrate that the greases obtained in the Examples of the present invention are obviously superior in load resistance, oil separation degree, and consistency change to the greases of Comparative Examples 2 and 3 prepared using, as a thickening agent, a lithium soap of 12-hydroxystearic acid or a lithium complex soap of azelaic acid and 12-hydroxystearic acid.
- The lubricating grease composition of the present invention, which has excellent characteristics as described above, i.e., excellent heat resistance, shear stability, abrasion resistance to mating materials, and load resistance, as well as satisfies the cost requirements, can be suitably used to lubricate and protect the contact portion between individual sliding parts of ball-and-roller bearings, sliding bearings, sintering bearings, gears, valves, cocks, oil seals, electric contacts, etc.
- More specifically, the lubricating grease composition can be suitably applied in various parts of various devices, machines, and apparatuses listed below.
- Automobiles: ball-and-roller bearings, sliding bearings, or gear parts of electric radiator fan motors, fan couplings, electronically controlled EGR, electronically controlled throttle valves, alternators, idler pulleys, electric brakes, hub units, water pumps, power windows, wipers, electric power steering systems, etc., to which heat resistance and shear stability are required;
electric contact parts of control switches for automatic transmissions, lever control switches, push switches, etc., to which heat resistance, shear stability, and abrasion resistance are required;
rubber sealing parts of X ring parts of viscous couplings, O rings of exhaust brakes, etc., to which heat resistance and shear stability are required; and
ball-and-roller bearings, sliding bearings, gears, sliding parts, etc., of headlights, sheets, ABSs, door locks, door hinges, clutch boosters, two-divided flywheels, window regulators, ball joints, clutch boosters, etc. - Office appliances: ball-and-roller bearings, sliding bearings, sliding parts or gear parts of resin films, etc., of fixing rolls, fixing belts, etc., of copying machines, laser beam printers, etc., to which heat resistance and abrasion resistance are required
- Resin manufacturing apparatuses: ball-and-roller bearings, sliding bearings, pins, oil seals, gears, etc., of film tenters, film laminators, Banbury mixers, etc., to which heat resistance and load resistance are required
- Paper making devices: ball-and-roller bearings, sliding bearings, pins, oil seals, gears, etc., of corrugate machines etc., to which heat resistance and abrasion resistance are required
- Timber processing devices: ball-and-roller bearings, sliding bearings, pins, oil seals, gears, etc., of conch presses etc., to which heat resistance and abrasion resistance are required
- Machines for food products: ball-and-roller bearings etc. of linear guides of bread-baking machines, ovens, etc., to which heat resistance and abrasion resistance are required
- Ball-and-roller bearings, sliding bearings, etc., in spindles, servomotors, etc., of machine tools, to which a low friction coefficient is required
- Sliding parts etc. of hinges of mobile phones, to which shear stability and abrasion resistance are required
- Ball-and-roller bearings and gears in vacuum pumps of semiconductor manufacturing apparatuses, liquid crystal manufacturing apparatuses, electron microscopes, etc; and ball-and-roller bearings etc. in breakers of power controlling device
- Household electrical/information appliances: ball-and-roller bearings, sliding bearings, oil seals, etc., in cooling fans for personal computers, vacuum cleaners, washing machines, etc
Claims (13)
- A lubricating grease composition comprising a complex metal soap thickener of aliphatic dicarboxylic acid and monoamide monocarboxylic acid, and a fluororesin powder contained in a base oil mixture of a non-fluorine-based base oil and a fluorine-based base oil, which are incompatible with each other.
- The lubricating grease composition according to claim 1, which comprises a mixture of two kinds of greases, one grease comprising a complex metal soap thickener of aliphatic dicarboxylic acid and monoamide monocarboxylic acid contained in a non-fluorine-based base oil, and the other grease comprising a fluororesin powder contained in a fluorine-based base oil.
- The lubricating grease composition according to claim 1, wherein the non-fluorine-based base oil is a synthetic hydrocarbon oil or an ether-based synthetic oil.
- The lubricating grease composition according to claim 2, wherein the non-fluorine-based base oil is a synthetic hydrocarbon oil or an ether-based synthetic oil.
- The lubricating grease composition according to claim 1, wherein the complex metal soap is a barium complex soap.
- The lubricating grease composition according to claim 2, wherein the complex metal soap is a barium complex soap.
- The lubricating grease composition according to claim 1, wherein the fluorine-based base oil is used at a ratio of 95 to 5 wt.% with respect to 5 to 95 wt.% of the non-fluorine-based base oil.
- The lubricating grease composition according to claim 1, wherein the fluorine-based base oil is used at a ratio of 90 to 10 wt.% with respect to 10 to 90 wt.% of the non-fluorine-based base oil.
- A method for producing a lubricating grease composition, the method comprises by kneading a non-fluorine-based grease and a fluorine-based grease;
the non-fluorine-based grease being prepared by stirring a non-fluorine-based base oil, aliphatic dicarboxylic acid, and monoamide monocarboxylic acid under heating, and adding metal hydroxide thereto to form a complex metal soap in the non-fluorine-based base oil; and
the fluorine-based grease being prepared from a fluorine-based base oil and a fluororesin powder. - The method for producing a lubricating grease composition according to claim 9, wherein the non-fluorine-based grease and the fluorine-based grease are each prepared by kneading through a three-roll mill or a high-pressure homogenizer.
- The method for producing a lubricating grease composition according to claim 9, wherein the non-fluorine-based grease and the fluorine-based grease are kneaded by a three-roll mill.
- The method for producing a lubricating grease composition according to claim 9, wherein a synthetic hydrocarbon oil or an ether-based synthetic oil is used as the non-fluorine-based base oil.
- The method for producing a lubricating grease composition according to claim 9, wherein barium hydroxide is used as the metal hydroxide.
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JP2008268115 | 2008-10-17 | ||
PCT/JP2009/067698 WO2010044386A1 (en) | 2008-10-17 | 2009-10-13 | Lubricating grease composition and manufacturing method therefor |
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US (1) | US20110218128A1 (en) |
EP (1) | EP2341121B1 (en) |
JP (1) | JP5310732B2 (en) |
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EP2824167A4 (en) * | 2012-03-05 | 2015-09-23 | Jx Nippon Oil & Energy Corp | Grease composition |
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GB0220581D0 (en) | 2002-09-04 | 2002-10-09 | Novartis Ag | Organic Compound |
JP5429285B2 (en) * | 2009-10-13 | 2014-02-26 | Nokクリューバー株式会社 | Lubricating grease composition for reciprocating sliding and manufacturing method thereof |
FI125317B (en) * | 2010-05-20 | 2015-08-31 | Kone Corp | Metal rope, lift provided with a metal rope and use of a lubricant for lubricating a metal rope |
EP2626406A1 (en) * | 2012-02-13 | 2013-08-14 | Prosimet S.p.A. | Lubricating composition for continuous casting processes |
US20140256605A1 (en) * | 2013-03-08 | 2014-09-11 | Elevance Renewable Sciences, Inc. | Natural oil based grease compositions and processes for making such compositions |
EP3094712B1 (en) * | 2014-01-15 | 2019-06-12 | Elevance Renewable Sciences, Inc. | Natural oil derivative based thickener components used in grease compositions |
CN104119985A (en) * | 2014-07-01 | 2014-10-29 | 上海亚杜润滑材料股份有限公司 | Novel mechanical lubricant |
GB201419439D0 (en) * | 2014-10-31 | 2014-12-17 | Skf Ab | Grease compositions |
US9732301B2 (en) | 2014-11-05 | 2017-08-15 | Infineum International Limited | Power transmitting fluids with improved materials compatibility |
JP6753699B2 (en) * | 2016-05-27 | 2020-09-09 | ミネベアミツミ株式会社 | Rolling bearing |
DE112017003959B4 (en) * | 2016-08-08 | 2024-01-18 | Nok Klueber Co., Ltd. | Grease composition and its use |
JP2018090783A (en) * | 2016-11-30 | 2018-06-14 | ミネベアミツミ株式会社 | Grease composition and rolling bearing |
JP6868467B2 (en) * | 2017-05-26 | 2021-05-12 | Nokクリューバー株式会社 | Lubricant composition |
JP7029972B2 (en) * | 2018-02-07 | 2022-03-04 | Nokクリューバー株式会社 | Lubricating grease composition, clutches and power window motors |
JP6755905B2 (en) * | 2018-07-27 | 2020-09-16 | ミネベアミツミ株式会社 | Grease composition for resin lubrication and resin sliding member |
JP7188235B2 (en) | 2019-03-29 | 2022-12-13 | 株式会社オートネットワーク技術研究所 | Lubricants, electrical contacts, connector terminals, and wire harnesses |
DE102020112993A1 (en) * | 2020-05-13 | 2021-11-18 | Klüber Lubrication München Se & Co. Kg | Lithium complex hybrid grease |
CN114395118A (en) * | 2021-12-31 | 2022-04-26 | 西安近代化学研究所 | Terpolymer perfluoropolyether and preparation method thereof |
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JP3816118B2 (en) * | 1993-12-01 | 2006-08-30 | アウシモント、ソチエタ、ペル、アツィオーニ | Hydrogenated mineral or synthetic greases with improved properties |
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JP4048758B2 (en) * | 2001-07-18 | 2008-02-20 | Nokクリューバー株式会社 | Lubricating grease composition |
JP2003239997A (en) * | 2002-02-18 | 2003-08-27 | Nsk Ltd | Rolling bearing for electromagnetic clutch, compressor, and idler pulley |
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2009
- 2009-10-13 JP JP2010533891A patent/JP5310732B2/en active Active
- 2009-10-13 EP EP09820564.4A patent/EP2341121B1/en active Active
- 2009-10-13 US US13/124,753 patent/US20110218128A1/en not_active Abandoned
- 2009-10-13 WO PCT/JP2009/067698 patent/WO2010044386A1/en active Application Filing
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EP2824167A4 (en) * | 2012-03-05 | 2015-09-23 | Jx Nippon Oil & Energy Corp | Grease composition |
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WO2010044386A1 (en) | 2010-04-22 |
EP2341121B1 (en) | 2015-05-27 |
US20110218128A1 (en) | 2011-09-08 |
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CN102186958B (en) | 2013-11-06 |
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JPWO2010044386A1 (en) | 2012-03-15 |
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