JP2014141544A - Antioxidant composition for lubricant, and lubricant composition containing the same - Google Patents
Antioxidant composition for lubricant, and lubricant composition containing the same Download PDFInfo
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- JP2014141544A JP2014141544A JP2013009215A JP2013009215A JP2014141544A JP 2014141544 A JP2014141544 A JP 2014141544A JP 2013009215 A JP2013009215 A JP 2013009215A JP 2013009215 A JP2013009215 A JP 2013009215A JP 2014141544 A JP2014141544 A JP 2014141544A
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- antioxidant
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 43
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 33
- 239000000314 lubricant Substances 0.000 title abstract 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 64
- 239000010687 lubricating oil Substances 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 23
- 239000002199 base oil Substances 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 125000004185 ester group Chemical group 0.000 claims description 15
- 150000001721 carbon Chemical group 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 230000001050 lubricating effect Effects 0.000 claims description 8
- 125000001033 ether group Chemical group 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 150000002989 phenols Chemical class 0.000 abstract 1
- -1 isooctyl group Chemical group 0.000 description 155
- 150000002430 hydrocarbons Chemical group 0.000 description 31
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 239000003921 oil Substances 0.000 description 11
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 125000003342 alkenyl group Chemical group 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 239000002562 thickening agent Substances 0.000 description 9
- 239000002480 mineral oil Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 239000004519 grease Substances 0.000 description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 235000010446 mineral oil Nutrition 0.000 description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 6
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 5
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 4
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 4
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000006038 hexenyl group Chemical group 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 4
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 4
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000005504 styryl group Chemical group 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 4
- 125000005425 toluyl group Chemical group 0.000 description 4
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 4
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 125000005023 xylyl group Chemical group 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000003064 anti-oxidating effect Effects 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000004996 alkyl benzenes 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 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
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 2
- 239000010723 turbine oil Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- PUNFIBHMZSHFKF-KTKRTIGZSA-N (z)-henicos-12-ene-1,2,3-triol Chemical compound CCCCCCCC\C=C/CCCCCCCCC(O)C(O)CO PUNFIBHMZSHFKF-KTKRTIGZSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- XMKLTEGSALONPH-UHFFFAOYSA-N 1,2,4,5-tetrazinane-3,6-dione Chemical compound O=C1NNC(=O)NN1 XMKLTEGSALONPH-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- TWYIRJIBTNKLMI-UHFFFAOYSA-N 2-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC(C)=C(O)C(C(C)(C)C)=C1 TWYIRJIBTNKLMI-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- VKLOPQHLJNFYKK-UHFFFAOYSA-N 3-dodecylsulfanylpropanoic acid Chemical compound CCCCCCCCCCCCSCCC(O)=O VKLOPQHLJNFYKK-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Lubricants (AREA)
Abstract
Description
本発明は、少量の添加量で大きな効果が得られる潤滑油に適した酸化防止剤組成物、及び該酸化防止剤組成物を含有する潤滑油組成物に関する。 The present invention relates to an antioxidant composition suitable for a lubricating oil that can provide a great effect with a small addition amount, and a lubricating oil composition containing the antioxidant composition.
従来、潤滑油の酸化防止剤には、フェノール系酸化防止剤、アミン系酸化防止剤、硫黄系酸化防止剤、リン系酸化防止剤、及びこれらの組み合わせたものが使用されており、中でもフェノール系酸化防止剤とアミン系酸化防止剤を使用することが多い（例えば、特許文献１，２を参照）。しかしながら近年、エンジンの高性能化、燃費向上のための潤滑油の低粘度化等から、潤滑油への負荷が大きくなってきており、更なる潤滑油の酸化防止性能の向上が望まれている。 Conventionally, as antioxidants for lubricating oils, phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and combinations thereof are used. Antioxidants and amine-based antioxidants are often used (see, for example, Patent Documents 1 and 2). However, in recent years, the load on the lubricating oil has been increasing due to the higher performance of the engine and the lowering of the viscosity of the lubricating oil in order to improve fuel efficiency, and further improvement in the antioxidant performance of the lubricating oil is desired. .
潤滑油の酸価防止性能を向上させるためには、既存の酸化防止剤等の添加量を増量すればよいが、近年の潤滑油は既にかなりの量の酸化防止剤が添加されていることから、これ以上の添加は不溶解物が発生する場合やスラッジが生成する場合がある。また環境保護を理由とする潤滑油添加剤の配合規制等から、使用できる添加剤の種類や量が制限されていることもあり、添加量の増量による対応は困難であった。そこで新規の酸化防止剤や、様々な酸化防止剤を組み合わせて、今まで以上の酸化防止性能を引き出す試みがなされてきたが（例えば、特許文献３，４を参照）、市場からは更に長期間の使用に耐えうることができる酸化防止剤あるいは酸化防止剤組成物が要求されていた。 In order to improve the acid value prevention performance of the lubricating oil, it is only necessary to increase the amount of existing antioxidants, etc., but in recent years, a considerable amount of antioxidants have already been added to the lubricating oil. In addition, addition beyond this may cause insoluble matter or sludge. In addition, the type and amount of additives that can be used are limited due to blending regulations for lubricating oil additives for the purpose of environmental protection, and it has been difficult to respond by increasing the amount added. Therefore, attempts have been made to bring out antioxidation performance more than before by combining a new antioxidant and various antioxidants (see, for example, Patent Documents 3 and 4), but the market has a longer period of time. There has been a demand for an antioxidant or an antioxidant composition that can withstand the use of the composition.
従って、本発明が解決しようとする課題は、既存の酸化防止剤と比較して長期間の使用に耐えうることのできる潤滑油用の酸化防止剤組成物を提供することにある。 Therefore, the problem to be solved by the present invention is to provide an antioxidant composition for lubricating oil that can withstand long-term use as compared with existing antioxidants.
そこで本発明者等は鋭意検討し、長期間酸化防止性能が劣化しない潤滑油用の酸化防止剤組成物を見出し、本発明に至った。即ち、本発明は、下記の一般式（１）で表される化合物及び／又は一般式（２）で表される化合物（Ａ）、並びに一般式（３）で表される化合物及び／又は一般式（４）で表される化合物（Ｂ）を含有することを特徴とする潤滑油用酸化防止剤組成物である。 Thus, the present inventors have intensively studied and found an antioxidant composition for lubricating oil that does not deteriorate its antioxidant performance for a long period of time, and have reached the present invention. That is, the present invention relates to a compound represented by the following general formula (1) and / or a compound (A) represented by the general formula (2), and a compound represented by the general formula (3) and / or general It is an antioxidant composition for lubricating oils containing the compound (B) represented by Formula (4).
（式中、Ｒ１は水素原子又は炭素数１〜１８の炭化水素基を表し、Ｒ２及びＲ３はそれぞれ炭素数１〜８のアルキル基を表す。） (In the formula, R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, a R 2 and R 3 represents an alkyl group having 1 to 8 carbon atoms.)
（式中、Ｒ４は水素原子又は炭素数１〜８のアルキル基を表し、Ｒ５は炭素数１〜２０の炭化水素基、又は炭素数２〜２０の炭化水素基のいずれか１以上の炭素原子をエステル基又はエーテル基で置換した基を表し、Ｒ６は水素原子又は炭素数１〜４のアルキル基を表し、ｎは１〜６の数を表す。但しＲ４がアルキル基の場合、Ｒ４のベンゼン環と結合する炭素原子が４級炭素原子になることはない。） (In the formula, R 4 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R 5 is any one or more of a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 2 to 20 carbon atoms. Represents a group in which a carbon atom is substituted with an ester group or an ether group, R 6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents a number of 1 to 6. However, when R 4 is an alkyl group, , The carbon atom bonded to the benzene ring of R 4 is not a quaternary carbon atom.)
（式中、Ｒ７及びＲ８はそれぞれ炭素数１〜２０の炭化水素基または炭素数３〜２０の炭化水素基のいずれか１以上の炭素原子をエステル基で置換した基を表す。） (In the formula, R 7 and R 8 each represents a group in which one or more carbon atoms of a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 3 to 20 carbon atoms are substituted with an ester group.)
（式中、Ｒ９〜Ｒ１１はそれぞれ炭素数１〜２０の炭化水素基表し、Ｒ１２は炭素原子又は炭素数１〜６の炭化水素基を表し、ｍは２〜６の数を表す。） (Wherein, R 9 to R 11 each represents a hydrocarbon group having 1 to 20 carbon atoms, R 12 represents a hydrocarbon group having 1 to 6 carbon atoms or carbon, m represents a number of 2-6. )
本発明の効果は、長期間使用しても酸価防止性能が劣化しない潤滑油用の酸化防止剤組成物を提供したことにある。 The effect of the present invention is to provide an antioxidant composition for lubricating oil that does not deteriorate the acid value prevention performance even when used for a long period of time.
本発明に使用できる化合物（Ａ）は、下記の一般式（１）及び一般式（２）で表すことができる。化合物（Ａ）としては、一般式（１）及び一般式（２）で表される化合物をそれぞれ単独で使用しても併用して使用してもよい。 The compound (A) that can be used in the present invention can be represented by the following general formula (1) and general formula (2). As the compound (A), the compounds represented by the general formula (1) and the general formula (2) may be used alone or in combination.
（式中、Ｒ１は水素原子又は炭素数１〜１８の炭化水素基を表し、Ｒ２及びＲ３はそれぞれ炭素数１〜８のアルキル基を表す。） (In the formula, R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, a R 2 and R 3 represents an alkyl group having 1 to 8 carbon atoms.)
（式中、Ｒ４は水素原子又は炭素数１〜８のアルキル基を表し、Ｒ５は炭素数１〜２０の炭化水素基、又は炭素数２〜２０の炭化水素基のいずれか１以上の炭素原子をエステル基又はエーテル基で置換した基を表し、Ｒ６は水素原子又は炭素数１〜４のアルキル基を表し、ｎは１〜６の数を表す。但しＲ４がアルキル基の場合、Ｒ４のベンゼン環と結合する炭素原子が４級炭素原子になることはない。） (In the formula, R 4 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R 5 is any one or more of a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 2 to 20 carbon atoms. Represents a group in which a carbon atom is substituted with an ester group or an ether group, R 6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents a number of 1 to 6. However, when R 4 is an alkyl group, , The carbon atom bonded to the benzene ring of R 4 is not a quaternary carbon atom.)
一般式（１）のＲ１は水素原子、炭素数１〜１８の炭化水素基又は炭素数１〜１８の炭化水素基のいずれか１つ以上の水素原子を水酸基に置換した基を表す。炭素数１〜１８の炭化水素基としては、アルキル基、アルケニル基、アリール基、シクロアルキル基及びこれらの組み合わせ、あるいは前述した基のいずれか１つ以上の水素原子を水酸基に置換した基が挙げられる。 R 1 in the general formula (1) represents a group obtained by substituting one or more hydrogen atoms of a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms with a hydroxyl group. Examples of the hydrocarbon group having 1 to 18 carbon atoms include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, and a combination thereof, or a group in which any one or more hydrogen atoms of the aforementioned groups are substituted with a hydroxyl group. It is done.
炭素数１〜１８のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ターシャリブチル基、ペンチル基、イソペンチル基、ヘキシル基、イソヘキシル基、ヘプチル基、イソヘプチル基、オクチル基、イソオクチル基、ノニル基、イソノニル基、デシル基、イソデシル基、ウンデシル基、イソウンデシル基、ドデシル基、イソドデシル基、トリデシル基、イソトリデシル基、テトラデシル基、イソテトラデシル基、ヘキサデシル基、イソヘキサデシル基、オクタデシル基、イソオクタデシル基が挙げられる。 Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, and a heptyl group. , Isoheptyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, isoundecyl group, dodecyl group, isododecyl group, tridecyl group, isotridecyl group, tetradecyl group, isotetradecyl group, hexadecyl group , Isohexadecyl group, octadecyl group, and isooctadecyl group.
アルケニル基としては、例えば、ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、イソブテニル基、ペンテニル基、イソペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基等が挙げられる。 Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, an isopentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, and an undecenyl group. , Dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group and the like.
アリール基としては、例えば、フェニル基、トルイル基、キシリル基、クメニル基、メシチル基、ベンジル基、フェネチル基、スチリル基、シンナミル基、ベンズヒドリル基、トリチル基、エチルフェニル基、プロピルフェニル基、ブチルフェニル基、ペンチルフェニル基、ヘキシルフェニル基、ヘプチルフェニル基、オクチルフェニル基、ノニルフェニル基、デシルフェニル基、ウンデシルフェニル基、ドデシルフェニル基、フェニルメチル基、フェニルエチル基、フェニルプロピル基、フェニルブチル基、フェニルペンチル基、フェニルヘキシル基、フェニルオクチル基、メチルフェニルメチル基、メチルフェニルエチル基、メチルフェニルプロピル基、スチレン化フェニル基、ｐ−クミルフェニル基、フェニルフェニル基、ベンジルフェニル基、α−ナフチル基、β−ナフチル基等が挙げられる。 As the aryl group, for example, phenyl group, toluyl group, xylyl group, cumenyl group, mesityl group, benzyl group, phenethyl group, styryl group, cinnamyl group, benzhydryl group, trityl group, ethylphenyl group, propylphenyl group, butylphenyl Group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, undecylphenyl group, dodecylphenyl group, phenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group , Phenylpentyl group, phenylhexyl group, phenyloctyl group, methylphenylmethyl group, methylphenylethyl group, methylphenylpropyl group, styrenated phenyl group, p-cumylphenyl group, phenylphenyl group, benzyl group Alkenyl groups, alpha-naphthyl, beta-naphthyl group.
シクロアルキル基、シクロアルケニル基としては、例えば、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、メチルシクロペンチル基、メチルシクロヘキシル基、メチルシクロヘプチル基、シクロペンテニル基、シクロヘキセニル基、シクロヘプテニル基、メチルシクロペンテニル基、メチルシクロヘキセニル基、メチルシクロヘプテニル基等が挙げられる。 Examples of the cycloalkyl group and the cycloalkenyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a methylcyclopentyl group, a methylcyclohexyl group, a methylcycloheptyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, and a methylcyclopentenyl group. , Methylcyclohexenyl group, methylcycloheptenyl group and the like.
また、上記のアルキル基、アルケニル基、アリール基、シクロアルキル基を組み合わせた基や、当該基のいずれか１つ以上の水素原子を水酸基に置換した基であってもよい。これらの基の中でも、炭素数１〜１２、好ましくは炭素数１〜８のアルキル基あるいはアリール基が好ましい。 Moreover, the group which combined the said alkyl group, the alkenyl group, the aryl group, and the cycloalkyl group, and the group which substituted the hydrogen atom of any one or more of the said group with the hydroxyl group may be sufficient. Among these groups, an alkyl group or an aryl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms is preferable.
Ｒ２及びＲ３は、それぞれ炭素数１〜８のアルキル基を表す。炭素数１〜８のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、イソペンチル基、ヘキシル基、イソヘキシル基、ヘプチル基、イソヘプチル基、オクチル基、イソオクチル基等が挙げられる。これらの中でも酸価防止性能が良好なことから炭素数１〜４のアルキル基が好ましく、メチル基、エチル基がより好ましく、メチル基が更に好ましい。 R 2 and R 3 each represent an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, and octyl. Group, isooctyl group and the like. Of these, an alkyl group having 1 to 4 carbon atoms is preferable due to good acid value prevention performance, a methyl group and an ethyl group are more preferable, and a methyl group is still more preferable.
一般式（１）で表される化合物は、公知の合成方法で得られることができ、また、当該化合物は市販されており、購入して使用することも可能である。この様な市販品としては、ヨシノックス（登録商標）ＢＢ（4,4'-ブチリデンビス（6-tert-ブチル-m-クレゾール））、ヨシノックス（登録商標）４２５（2,2'-メチレンビス（6-tert-ブチル-4-エチルフェノール））、ヨシノックス（登録商標）２２４６Ｒ（2,2'-メチリデンビス（6-tert-ブチル-メチルフェノール））（いずれも株式会社エーピーアイコーポレーション製）などが挙げられる。 The compound represented by the general formula (1) can be obtained by a known synthesis method, and the compound is commercially available and can be purchased and used. Such commercially available products include Yoshinox (registered trademark) BB (4,4′-butylidenebis (6-tert-butyl-m-cresol)), Yoshinox (registered trademark) 425 (2,2′-methylenebis (6- tert-butyl-4-ethylphenol)), Yoshinox (registered trademark) 2246R (2,2′-methylidenebis (6-tert-butyl-methylphenol)) (all manufactured by API Corporation) and the like.
一般式（２）のＲ４は、水素原子又は炭素数１〜８のアルキル基を表す。炭素数１〜８の直鎖アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、イソペンチル基、ヘキシル基、イソヘキシル基、ヘプチル基、イソヘプチル基、オクチル基、イソオクチル基等が挙げられる。これらの中でも酸化防止性能の相乗効果が大きいことから水素原子、メチル基、エチル基が好ましく、水素原子、メチル基がより好ましく、水素原子が更に好ましい。なお、Ｒ４はベンゼン環と結合する炭素原子が４級炭素原子になることはなく、例えば、ターシャリブチル基のような基はＲ４としては不適格である。 R 4 in the general formula (2) represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the linear alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group. Octyl group, isooctyl group and the like. Among these, a hydrogen atom, a methyl group, and an ethyl group are preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is still more preferable because the synergistic effect of antioxidant performance is great. In R 4, the carbon atom bonded to the benzene ring does not become a quaternary carbon atom. For example, a group such as a tertiary butyl group is ineligible as R 4 .
Ｒ５は炭素数１〜２０の炭化水素基、又は１以上のエステル基及び／又はエーテル基を含有する炭素数２〜２０の炭化水素基を表す。炭素数１〜２０の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、イソペンチル基、ヘキシル基、イソヘキシル基、ヘプチル基、イソヘプチル基、オクチル基、イソオクチル基、ノニル基、イソノニル基、デシル基、イソデシル基、ウンデシル基、イソウンデシル基、ドデシル基、イソドデシル基、トリデシル基、イソトリデシル基、テトラデシル基、イソテトラデシル基、ヘキサデシル基、イソヘキサデシル基、オクタデシル基、イソオクタデシル基、エイコシル基等のアルキル基；ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、イソブテニル基、ペンテニル基、イソペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基等のアルケニル基；フェニル基、トルイル基、キシリル基、クメニル基、メシチル基、ベンジル基、フェネチル基、スチリル基、シンナミル基、ベンズヒドリル基、トリチル基、エチルフェニル基、プロピルフェニル基、ブチルフェニル基、ペンチルフェニル基、ヘキシルフェニル基、ヘプチルフェニル基、オクチルフェニル基、ノニルフェニル基、デシルフェニル基、ウンデシルフェニル基、ドデシルフェニル基等のアリール基；シクロペンチル基、シクロヘキシル基、シクロヘプチル基、メチルシクロペンチル基、メチルシクロヘキシル基等のシクロアルキル基が挙げられる。上記の基は、一般式（２）のｎの値が１のときの基であり、ｎの値が２のときは、上記の基から任意の水素原子を１つ除いた基となり、ｎの値が３であれば上記の基から任意の水素原子を２つ取り除いた基となる。ｎの値は１〜６の数を表すが、酸化防止剤としての性能が良好なこと及び原料事情が良好なことから１〜４の数が好ましく、２又は３の数がより好ましい。 R 5 represents a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 2 to 20 carbon atoms containing one or more ester groups and / or ether groups. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, Octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, isoundecyl, dodecyl, isododecyl, tridecyl, isotridecyl, tetradecyl, isotetradecyl, hexadecyl, isohexadecyl Group, octadecyl group, isooctadecyl group, eicosyl group and the like alkyl group; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, isopentenyl group, hexenyl group, heptenyl group, octenyl group , Nonenyl , Decenyl group, undecenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group and other alkenyl groups; phenyl group, toluyl group, xylyl group, cumenyl group, mesityl group, benzyl group, phenethyl group, styryl group, cinnamyl group, Benzhydryl group, trityl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, undecylphenyl group, dodecylphenyl group Aryl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, methylcyclopentyl group, methylcyclohexyl group and the like. The above group is a group when the value of n in the general formula (2) is 1, and when the value of n is 2, the group is a group obtained by removing one arbitrary hydrogen atom from the above group. A value of 3 is a group obtained by removing two arbitrary hydrogen atoms from the above group. Although the value of n represents the number of 1-6, the number of 1-4 is preferable and the number of 2 or 3 is more preferable because the performance as an antioxidant is favorable and the raw material situation is favorable.
またＲ５は、炭素数２〜２０の炭化水素基のいずれかの部分を１以上のエステル基及び／又はエーテル基で置換した基であってもよい。当該基は、エステル基とエーテル基はどちらか一方のみを有するものでも、両方を有するものでも、あるいは複数個有するものであってもよい。 R 5 may be a group in which any part of the hydrocarbon group having 2 to 20 carbon atoms is substituted with one or more ester groups and / or ether groups. The group may have only one of the ester group and the ether group, may have both, or may have a plurality.
これらの中でも潤滑油への溶解性が良好なことから、炭素数２〜２０の炭化水素基のいずれかの部分をエステル基で置換した基であることが好ましく、炭素数２〜２０の炭化水素基のいずれかの部分を１以上のエステル基及びエーテル基で置換した基であることがより好ましい。 Among these, since solubility in lubricating oil is good, a group in which any part of a hydrocarbon group having 2 to 20 carbon atoms is substituted with an ester group is preferable, and a hydrocarbon having 2 to 20 carbon atoms It is more preferable that any part of the group is a group in which one or more ester groups and ether groups are substituted.
Ｒ６は水素原子又は炭素数１〜４のアルキル基を表す。炭素数１〜４のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ターシャリブチル基が挙げられる。 R 6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group.
一般式（２）で表される化合物は、公知の合成方法で得られることができ、また、当該化合物は市販されており、購入して使用することも可能である。この様な市販品としては、アデカスタブ（登録商標）ＡＯ−３０（1,1,3-トリス(2-メチル-4-ヒドロキシ-5-tert-ブチルフェニル）ブタン）、アデカスタブ（登録商標）ＡＯ−４０（4,4'-ブチリデンビス(6-tert-ブチル-m-クレゾール））、アデカスタブ（登録商標）ＡＯ−７０（ビス[3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオン酸][エチレンビス(オキシエチレン)]）、アデカスタブ（登録商標）ＡＯ−８０（ビス[3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニルプロピオン酸](2,4,8,10-テトラオキサスピロ[5,5]ウンデカン-3,9-ジイル）ビス(2,2-ジメチル-2,1-エタンジイル)）（いずれも株式会社ＡＤＥＫＡ製）などが挙げられる。 The compound represented by the general formula (2) can be obtained by a known synthesis method, and the compound is commercially available and can be purchased and used. Examples of such commercially available products include ADK STAB (registered trademark) AO-30 (1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane), ADK STAB (registered trademark) AO- 40 (4,4′-butylidenebis (6-tert-butyl-m-cresol)), ADK STAB® AO-70 (bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl)] Propionic acid] [ethylenebis (oxyethylene)]), ADK STAB® AO-80 (bis [3- (3-tert-butyl-4-hydroxy-5-methylphenylpropionic acid)] (2,4,8 , 10-tetraoxaspiro [5,5] undecane-3,9-diyl) bis (2,2-dimethyl-2,1-ethanediyl)) (all manufactured by ADEKA Corporation).
化合物（Ａ）は一般式（１）及び一般式（２）で表される化合物を単独あるいは併用して使用することができるが、酸化防止性能が良好なことから一般式（２）で表される化合物が好ましい。 Compound (A) can be used alone or in combination with compounds represented by general formula (1) and general formula (2), but is represented by general formula (2) because of its good antioxidation performance. Are preferred.
本発明に使用できる化合物（Ｂ）は、下記の一般式（３）及び一般式（４）で表すことができる。化合物（Ｂ）としては、一般式（３）及び一般式（４）で表される化合物をそれぞれ単独で使用しても併用して使用してもよい。 The compound (B) that can be used in the present invention can be represented by the following general formula (3) and general formula (4). As the compound (B), the compounds represented by the general formula (3) and the general formula (4) may be used alone or in combination.
（式中、Ｒ７及びＲ８はそれぞれ炭素数１〜２０の炭化水素基または炭素数３〜２０の炭化水素基のいずれか１以上の炭素原子をエステル基で置換した基を表す。） (In the formula, R 7 and R 8 each represents a group in which one or more carbon atoms of a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 3 to 20 carbon atoms are substituted with an ester group.)
（式中、Ｒ９〜Ｒ１１はそれぞれ炭素数１〜２０の炭化水素基表し、Ｒ１２は炭素原子又は炭素数１〜６の炭化水素基を表し、ｍは２〜６の数を表す。） (Wherein, R 9 to R 11 each represents a hydrocarbon group having 1 to 20 carbon atoms, R 12 represents a hydrocarbon group having 1 to 6 carbon atoms or carbon, m represents a number of 2-6. )
一般式（３）のＲ７及びＲ８は、それぞれ炭素数１〜２０の炭化水素基または炭素数３〜２０の炭化水素基のいずれかの部分を１以上のエステル基で置換した基を表す。炭素数１〜２０の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、イソペンチル基、ヘキシル基、イソヘキシル基、ヘプチル基、イソヘプチル基、オクチル基、イソオクチル基、ノニル基、イソノニル基、デシル基、イソデシル基、ウンデシル基、イソウンデシル基、ドデシル基、イソドデシル基、トリデシル基、イソトリデシル基、テトラデシル基、イソテトラデシル基、ヘキサデシル基、イソヘキサデシル基、オクタデシル基、イソオクタデシル基、エイコシル基等のアルキル基；ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、イソブテニル基、ペンテニル基、イソペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基等のアルケニル基；フェニル基、トルイル基、キシリル基、クメニル基、メシチル基、ベンジル基、フェネチル基、スチリル基、シンナミル基、ベンズヒドリル基、トリチル基、エチルフェニル基、プロピルフェニル基、ブチルフェニル基、ペンチルフェニル基、ヘキシルフェニル基、ヘプチルフェニル基、オクチルフェニル基、ノニルフェニル基、デシルフェニル基、ウンデシルフェニル基、ドデシルフェニル基等のアリール基；シクロペンチル基、シクロヘキシル基、シクロヘプチル基、メチルシクロペンチル基、メチルシクロヘキシル基等のシクロアルキル基が挙げられる。また、上記に挙げた基の中の炭素数３〜２０の炭化水素基のいずれか１以上の炭素原子をエステル基で置換した基であってもよい。 R 7 and R 8 in the general formula (3) each represents a group in which any part of a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 3 to 20 carbon atoms is substituted with one or more ester groups. . Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, Octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, isoundecyl, dodecyl, isododecyl, tridecyl, isotridecyl, tetradecyl, isotetradecyl, hexadecyl, isohexadecyl Group, octadecyl group, isooctadecyl group, eicosyl group and the like alkyl group; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, isopentenyl group, hexenyl group, heptenyl group, octenyl group , Nonenyl , Decenyl group, undecenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group and other alkenyl groups; phenyl group, toluyl group, xylyl group, cumenyl group, mesityl group, benzyl group, phenethyl group, styryl group, cinnamyl group, Benzhydryl group, trityl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, undecylphenyl group, dodecylphenyl group Aryl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, methylcyclopentyl group, methylcyclohexyl group and the like. Moreover, the group which substituted any one or more carbon atom of the C3-C20 hydrocarbon group in the group quoted above by the ester group may be sufficient.
これらの基の中でも潤滑油への溶解性が良好なことから、炭素数３〜２０の炭化水素基のいずれかの部分を１以上のエステル基で置換した基が好ましく、炭素数８〜２０の炭化水素基のいずれかの部分を１以上のエステル基で置換した基がより好ましい。 Among these groups, a group in which any part of a hydrocarbon group having 3 to 20 carbon atoms is substituted with one or more ester groups is preferable because of its good solubility in lubricating oil, and it has 8 to 20 carbon atoms. A group in which any part of the hydrocarbon group is substituted with one or more ester groups is more preferable.
一般式（３）で表される化合物は、公知の合成方法で得られることができ、また、当該化合物は市販されており、購入して使用することも可能である。この様な市販品としては、アデカエコロイヤル（登録商標）ＡＩＮ−７００（3,3'-チオビスプロピオン酸ジトリデシル）（株式会社ＡＤＥＫＡ製）が挙げられる。 The compound represented by the general formula (3) can be obtained by a known synthesis method, and the compound is commercially available and can be purchased and used. Examples of such commercially available products include Adeka Eco Royal (registered trademark) AIN-700 (ditridecyl 3,3′-thiobispropionate) (manufactured by ADEKA Corporation).
一般式（４）のＲ９〜Ｒ１１はそれぞれ炭素数１〜２０の炭化水素基表す。Ｒ９の場合、炭素数１〜２０の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、イソペンチル基、ヘキシル基、イソヘキシル基、ヘプチル基、イソヘプチル基、オクチル基、イソオクチル基、ノニル基、イソノニル基、デシル基、イソデシル基、ウンデシル基、イソウンデシル基、ドデシル基、イソドデシル基、トリデシル基、イソトリデシル基、テトラデシル基、イソテトラデシル基、ヘキサデシル基、イソヘキサデシル基、オクタデシル基、イソオクタデシル基、エイコシル基等のアルキル基；ビニル基、アリル基、プロペニル基、イソプロペニル基、ブテニル基、イソブテニル基、ペンテニル基、イソペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基等のアルケニル基；フェニル基、トルイル基、キシリル基、クメニル基、メシチル基、ベンジル基、フェネチル基、スチリル基、シンナミル基、ベンズヒドリル基、トリチル基、エチルフェニル基、プロピルフェニル基、ブチルフェニル基、ペンチルフェニル基、ヘキシルフェニル基、ヘプチルフェニル基、オクチルフェニル基、ノニルフェニル基、デシルフェニル基、ウンデシルフェニル基、ドデシルフェニル基等のアリール基；シクロペンチル基、シクロヘキシル基、シクロヘプチル基、メチルシクロペンチル基、メチルシクロヘキシル基等のシクロアルキル基が挙げられる。なお、Ｒ１０及びＲ１１は、上記の基から任意の水素原子を１つ取り除いた基となる。これらの中でも熱安定性が良好なことからアルキル基であることが好ましい。また、Ｒ９は潤滑油への溶解性が良好なことから、炭素数８〜２０のアルキル基が好ましく、炭素数１０〜１８のアルキル基がより好ましい。Ｒ１０及びＲ１１は、原料の入手が容易なこと、あるいは酸化防止剤としての性能が優れていることから、炭素数１〜１０のアルキレン基が好ましく、炭素数１〜６のアルキレン基がより好ましく、炭素数１〜４のアルキレン基が更に好ましい。 R < 9 > -R < 11 > of General formula (4) represents a C1-C20 hydrocarbon group, respectively. In the case of R 9 , as the hydrocarbon group having 1 to 20 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl Group, isoheptyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, isoundecyl group, dodecyl group, isododecyl group, tridecyl group, isotridecyl group, tetradecyl group, isotetradecyl group, hexadecyl Group, isohexadecyl group, octadecyl group, isooctadecyl group, eicosyl group and the like alkyl group; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, isopentenyl group, hexenyl group, Heptenyl group, octenyl Group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group and the like alkenyl group; phenyl group, toluyl group, xylyl group, cumenyl group, mesityl group, benzyl group, phenethyl group, styryl group Cinnamyl group, benzhydryl group, trityl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, undecylphenyl group And aryl groups such as dodecylphenyl group; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, methylcyclopentyl group, and methylcyclohexyl group. R 10 and R 11 are groups obtained by removing one arbitrary hydrogen atom from the above groups. Among these, an alkyl group is preferable because of good thermal stability. R 9 is preferably an alkyl group having 8 to 20 carbon atoms and more preferably an alkyl group having 10 to 18 carbon atoms because of its good solubility in lubricating oil. R 10 and R 11 are preferably an alkylene group having 1 to 10 carbon atoms and more preferably an alkylene group having 1 to 6 carbon atoms because the raw materials are easily available or the performance as an antioxidant is excellent. An alkylene group having 1 to 4 carbon atoms is more preferable.
Ｒ１２は炭素原子又は炭素数１〜６の炭化水素基を表す。こうした炭化水素基としては、例えば、メチレン基、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、イソブチレン基、ペンチレン基、イソペンチレン基、ヘキシレン基、イソヘキシレン基等のアルキレン基；ビニレン基、アリレン基、プロペニレン基、イソプロペニレン基、ブテニレン基、イソブテニレン基、ペンテニレン基、イソペンテニレン基、ヘキセニレン基等のアルケニレン基やフェニレン基が挙げられる。これらの基はｍの値が２のときの基であり、ｍの値が３のときは、これらの基から任意の水素原子を１つ取り除いた基となり、ｍの値が４のときは、これらの基から任意の水素原子を２つ取り除いた基となる。なお、ｍの値が４のときで且つ炭素数が１のとき、Ｒ１２は炭素原子になる。
ｍの値は２〜６の数であるが、酸化防止剤としての性能が良好なこと及び原料事情が良好なことから２〜４の数が好ましく、２又は４の数がより好ましい。
R 12 represents a carbon atom or a hydrocarbon group having 1 to 6 carbon atoms. Examples of such hydrocarbon groups include methylene groups, ethylene groups, propylene groups, isopropylene groups, butylene groups, isobutylene groups, pentylene groups, isopentylene groups, hexylene groups, and isohexylene groups; vinylene groups, arylene groups, Examples include an alkenylene group such as a propenylene group, an isopropenylene group, a butenylene group, an isobutenylene group, a pentenylene group, an isopentenylene group, and a hexenylene group, and a phenylene group. These groups are groups when the value of m is 2, when the value of m is 3, these groups are groups obtained by removing one arbitrary hydrogen atom, and when the value of m is 4, A group obtained by removing two arbitrary hydrogen atoms from these groups. When the value of m is 4 and the number of carbons is 1, R 12 is a carbon atom.
Although the value of m is a number of 2 to 6, the number of 2 to 4 is preferable and the number of 2 or 4 is more preferable because the performance as an antioxidant is good and the raw material situation is good.
一般式（４）で表される化合物は、公知の合成方法で得られることができ、また、当該化合物は市販されており、購入して使用することも可能である。この様な市販品としては、アデカエコロイヤル（登録商標）ＡＩＮ−７３０（ビス[3-(ドデシルチオ)プロピオン酸]2,2'-ビス[[3-(ドデシルチオ)-1-オキソプロピルオキシ]メチル]-1,3-プロパンジイル）（株式会社ＡＤＥＫＡ製）が挙げられる。 The compound represented by the general formula (4) can be obtained by a known synthesis method, and the compound is commercially available and can be purchased and used. Such commercial products include Adeka Eco Royal (registered trademark) AIN-730 (bis [3- (dodecylthio) propionic acid] 2,2′-bis [[3- (dodecylthio) -1-oxopropyloxy] methyl) ] -1,3-propanediyl) (manufactured by ADEKA Corporation).
化合物（Ｂ）は一般式（３）及び一般式（４）で表される化合物を単独あるいは併用して使用することができるが、酸化防止性能が良好なことから一般式（３）で表される化合物が好ましい。 As the compound (B), the compounds represented by the general formula (3) and the general formula (4) can be used singly or in combination, but are represented by the general formula (3) because of their good antioxidant performance. Are preferred.
化合物（Ａ）と化合物（Ｂ）は、任意の比で配合することで本発明の潤滑油用酸化防止剤組成物を得ることができる。しかしながら、一方の配合量が極端に少ないと、酸化防止剤の相乗効果が発揮できない場合があるため、質量比で（Ａ）／（Ｂ）＝１／１０〜１０／１で配合することが好ましく、（Ａ）／（Ｂ）＝１／４〜４／１で配合することがより好ましく、（Ａ）／（Ｂ）＝１／２〜２／１で配合することが更に好ましい。 The antioxidant composition for lubricating oil of the present invention can be obtained by blending the compound (A) and the compound (B) in an arbitrary ratio. However, since the synergistic effect of the antioxidant may not be exhibited when the blending amount of one is extremely small, it is preferable to blend at a mass ratio of (A) / (B) = 1/10 to 10/1. (A) / (B) = 1/4 to 4/1 is more preferable, and (A) / (B) = 1/2 to 2/1 is more preferable.
本発明の潤滑油組成物は、潤滑基油に本発明の潤滑油用酸化防止剤組成物を潤滑油組成物全量に対して０．１〜５質量％添加したものである。０．１質量％未満の場合は酸化防止剤としての機能が発揮できず、５質量％を超えると配合量に見合った効果が得られない場合やスラッジが発生する場合がある。 The lubricating oil composition of the present invention is obtained by adding 0.1 to 5% by mass of the antioxidant composition for lubricating oil of the present invention to a lubricating base oil with respect to the total amount of the lubricating oil composition. When the amount is less than 0.1% by mass, the function as an antioxidant cannot be exhibited. When the amount exceeds 5% by mass, an effect corresponding to the blending amount cannot be obtained or sludge may be generated.
使用できる潤滑基油は公知の潤滑基油であればいずれも使用することができ、例えば、ポリ−α−オレフィン、エチレン−α−オレフィン共重合体、ポリブテン、アルキルベンゼン、アルキルナフタレン、ポリアルキレングリコール、ポリフェニルエーテル、アルキル置換ジフェニルエーテル、ポリオールエステル、二塩基酸エステル、炭酸エステル、ＧＴＬ等の合成油；パラフィン系鉱油、ナフテン系鉱油あるいはこれらを精製した精製鉱油類等が挙げられる。これらの基油はそれぞれ単独で用いてもよく、混合物で用いてもよい。これらの基油の中でも、基油としての性能が高く、エンジン等の機械に悪影響を与えないことから、ポリ−α−オレフィン、エチレン−α−オレフィン共重合体、ポリブテン、アルキルベンゼン、アルキルナフタレン、パラフィン系鉱油、ナフテン系鉱油、ＧＴＬが好ましく、ポリ−α−オレフィン、パラフィン系鉱油、ナフテン系鉱油、ＧＴＬがより好ましい。また、粘度指数が１００以上の基油を使用するのが好ましく、粘度指数が１００以上のポリ−α−オレフィン、ＧＴＬ、精製鉱油の使用がより好ましい。 Any lubricating base oil can be used as long as it is a known lubricating base oil, such as poly-α-olefin, ethylene-α-olefin copolymer, polybutene, alkylbenzene, alkylnaphthalene, polyalkylene glycol, Synthetic oils such as polyphenyl ether, alkyl-substituted diphenyl ether, polyol ester, dibasic acid ester, carbonate ester, and GTL; paraffinic mineral oil, naphthenic mineral oil, and refined mineral oils obtained by purifying them are listed. These base oils may be used alone or in a mixture. Among these base oils, the performance as a base oil is high and does not adversely affect machines such as engines. Therefore, poly-α-olefin, ethylene-α-olefin copolymer, polybutene, alkylbenzene, alkylnaphthalene, paraffin Mineral oil, naphthenic mineral oil, and GTL are preferable, and poly-α-olefin, paraffinic mineral oil, naphthenic mineral oil, and GTL are more preferable. Further, it is preferable to use a base oil having a viscosity index of 100 or more, and more preferable to use poly-α-olefin, GTL, or refined mineral oil having a viscosity index of 100 or more.
本発明の潤滑油組成物はグリースとして使用することもできる。グリースは、潤滑基油及び本発明の潤滑油用酸化防止剤組成物を含有する本発明の潤滑油組成物に増ちょう剤を更に添加することで得ることができる。増ちょう剤としては、アルミニウム、バリウム、カルシウム、リチウム、ナトリウム等の石鹸増ちょう剤、複合リチウム、複合カルシウム、複合アルミニウム等のコンプレックス石鹸増ちょう剤、ウレア、ジウレア、トリウレア、テトラウレア、アリールウレア、テレフタラメート等の有機非石鹸増ちょう剤、ベントナイト、シリカエアロゲル等の無機非石鹸増ちょう剤等が用いられるが、これらの増ちょう剤は単独で用いてもよく、また２種以上を組み合わせても良い。増ちょう剤の量は特に限定されるものではないが、潤滑基油と増ちょう剤からなる基グリースに対して通常３〜４０質量％、好ましくは５〜２０質量％添加すればよい。 The lubricating oil composition of the present invention can also be used as a grease. The grease can be obtained by further adding a thickener to the lubricating oil composition of the present invention containing the lubricating base oil and the antioxidant composition for lubricating oil of the present invention. Thickeners include soap thickeners such as aluminum, barium, calcium, lithium and sodium, complex soap thickeners such as complex lithium, complex calcium and complex aluminum, urea, diurea, triurea, tetraurea, arylurea, terephthalate Organic non-soap thickeners such as taramate and inorganic non-soap thickeners such as bentonite and silica aerogel are used. These thickeners may be used alone or in combination of two or more. good. The amount of the thickener is not particularly limited, but is usually 3 to 40% by mass, preferably 5 to 20% by mass based on the base grease composed of the lubricating base oil and the thickener.
本発明の潤滑油組成物は、公知の潤滑油添加剤の添加を拒むものではなく、使用目的に応じて、摩擦低減剤、極圧剤、油性向上剤、清浄剤、分散剤、粘度指数向上剤、流動点降下剤、防錆剤、腐食防止剤、消泡剤などを本発明の効果を損なわない範囲で添加してもよい。 The lubricating oil composition of the present invention does not refuse the addition of known lubricating oil additives, and depending on the intended use, friction reducer, extreme pressure agent, oiliness improver, detergent, dispersant, viscosity index improvement An agent, a pour point depressant, a rust inhibitor, a corrosion inhibitor, an antifoaming agent, and the like may be added as long as the effects of the present invention are not impaired.
摩擦低減剤としては、例えば、硫化オキシモリブデンジチオカルバメート、硫化オキシモリブデンジチオフォスフェート等の有機モリブデン化合物が挙げられる。これら摩擦低減剤の好ましい配合量は、基油に対してモリブデン含量で３０〜２０００質量ｐｐｍ、より好ましくは５０〜１０００質量ｐｐｍである。ただし、リン原子はエンジンの触媒に悪影響を与えるので、リン原子を含有している硫化オキシモリブデンジチオフォスフェートより、硫化オキシモリブデンジチオカルバメートの使用が好ましく、炭素数８〜１３のアルキル基を持つ硫化オキシモリブデンジチオカルバメートの使用がより好ましい。 Examples of the friction reducing agent include organic molybdenum compounds such as sulfurized oxymolybdenum dithiocarbamate and sulfurized oxymolybdenum dithiophosphate. A preferable blending amount of these friction reducing agents is 30 to 2000 ppm by mass, more preferably 50 to 1000 ppm by mass with respect to the base oil. However, since phosphorus atoms adversely affect the catalyst of the engine, it is preferable to use sulfurized oxymolybdenum dithiocarbamate rather than sulfurized oxymolybdenum dithiophosphate containing phosphorus atoms. The use of molybdenum dithiocarbamate is more preferred.
極圧剤としては、例えば、硫化油脂、オレフィンポリスルフィド、ジベンジルスルフィド等の硫黄系添加剤；モノオクチルフォスフェート、トリブチルフォスフェート、トリフェニルフォスファイト、トリブチルフォスファイト、チオリン酸エステル等のリン系化合物；チオリン酸金属塩、チオカルバミン酸金属塩、酸性リン酸エステル金属塩、亜鉛ジチオホスフェート等の有機金属化合物などが挙げられる。これら極圧剤の好ましい配合量は、基油に対して０．０１〜２質量％、より好ましくは０．０５〜１質量％である。なお、亜鉛ジチオホスフェートは磨耗防止剤としての機能や酸化防止剤としての機能も併せ持つ。 Examples of extreme pressure agents include sulfur-based additives such as sulfurized fats and oils, olefin polysulfides, and dibenzyl sulfide; phosphorus-based compounds such as monooctyl phosphate, tributyl phosphate, triphenyl phosphite, tributyl phosphite, and thiophosphate A metal salt of thiophosphate, a metal salt of thiocarbamate, an acid phosphate metal salt, an organic metal compound such as zinc dithiophosphate, and the like. A preferable blending amount of these extreme pressure agents is 0.01 to 2% by mass, more preferably 0.05 to 1% by mass with respect to the base oil. Zinc dithiophosphate also has a function as an antiwear agent and a function as an antioxidant.
油性向上剤としては、例えば、オレイルアルコール、ステアリルアルコール等の高級アルコール類；オレイン酸、ステアリン酸等の脂肪酸類；オレイルグリセリンエステル、ステリルグリセリンエステル、ラウリルグリセリンエステル等のエステル類；ラウリルアミド、オレイルアミド、ステアリルアミド等のアミド類；ラウリルアミン、オレイルアミン、ステアリルアミン等のアミン類；ラウリルグリセリンエーテル、オレイルグリセリンエーテル等のエーテル類が挙げられる。これら油性向上剤の好ましい配合量は、基油に対して０．１〜５質量％、より好ましくは０．２〜３質量％である。 Examples of oiliness improvers include higher alcohols such as oleyl alcohol and stearyl alcohol; fatty acids such as oleic acid and stearic acid; esters such as oleyl glycerin ester, steryl glycerin ester and lauryl glycerin ester; lauryl amide and oleyl Amides such as amide and stearylamide; amines such as laurylamine, oleylamine and stearylamine; ethers such as laurylglycerol ether and oleylglycerol ether. The preferable compounding quantity of these oiliness improvers is 0.1-5 mass% with respect to base oil, More preferably, it is 0.2-3 mass%.
清浄剤としては、例えば、カルシウム、マグネシウム、バリウムなどのスルフォネート、フェネート、サリシレート、フォスフェート及びこれらの過塩基性塩が挙げられる。これらの中でも過塩基性塩が好ましく、過塩基性塩の中でもＴＢＮ（トータルベーシックナンバー）が３０〜５００ｍｇＫＯＨ／ｇのものがより好ましい。更に、リン及び硫黄原子のないサリシレート系の清浄剤が好ましい。これらの清浄剤の好ましい配合量は、基油に対して０．５〜１０質量％、より好ましくは１〜８質量％である。 Examples of the detergent include sulfonates such as calcium, magnesium, and barium, phenates, salicylates, phosphates, and overbased salts thereof. Among these, overbased salts are preferable, and among the overbased salts, those having a TBN (total basic number) of 30 to 500 mgKOH / g are more preferable. Furthermore, salicylate-based detergents having no phosphorus and sulfur atoms are preferred. The preferable compounding quantity of these detergents is 0.5-10 mass% with respect to base oil, More preferably, it is 1-8 mass%.
分散剤としては、例えば、重量平均分子量約５００〜３０００のアルキル基またはアルケニル基が付加されたコハク酸イミド、コハク酸エステル、ベンジルアミン又はこれらのホウ素変性物等が挙げられる。これらの分散剤の好ましい配合量は、基油に対して０．５〜１０質量％、より好ましくは１〜８質量％である。 Examples of the dispersant include succinimide, succinate ester, benzylamine, and boron-modified products thereof to which an alkyl group or alkenyl group having a weight average molecular weight of about 500 to 3000 is added. The preferable compounding quantity of these dispersing agents is 0.5-10 mass% with respect to base oil, More preferably, it is 1-8 mass%.
粘度指数向上剤としては、例えば、ポリ（Ｃ１〜１８）アルキルメタクリレート、（Ｃ１〜１８）アルキルアクリレート／（Ｃ１〜１８）アルキルメタクリレート共重合体、ジエチルアミノエチルメタクリレート／（Ｃ１〜１８）アルキルメタクリレート共重合体、エチレン／（Ｃ１〜１８）アルキルメタクリレート共重合体、ポリイソブチレン、ポリアルキルスチレン、エチレン／プロピレン共重合体、スチレン／マレイン酸エステル共重合体、スチレン／イソプレン水素化共重合体等が挙げられる。あるいは、分散性能を付与した分散型もしくは多機能型粘度指数向上剤を用いてもよい。平均分子量は１０，０００〜１，５００，０００程度である。これらの粘度指数向上剤の好ましい配合量は、基油に対して０．１〜２０質量％。より好ましくは０．３〜１５質量％である。 Examples of the viscosity index improver include poly (C1-18) alkyl methacrylate, (C1-18) alkyl acrylate / (C1-18) alkyl methacrylate copolymer, diethylaminoethyl methacrylate / (C1-18) alkyl methacrylate copolymer. Polymers, ethylene / (C1-18) alkyl methacrylate copolymers, polyisobutylene, polyalkylstyrene, ethylene / propylene copolymers, styrene / maleic ester copolymers, styrene / isoprene hydrogenated copolymers, and the like. . Alternatively, a dispersion type or multifunctional viscosity index improver imparted with a dispersion performance may be used. The average molecular weight is about 10,000 to 1,500,000. A preferable blending amount of these viscosity index improvers is 0.1 to 20% by mass with respect to the base oil. More preferably, it is 0.3-15 mass%.
流動点降下剤としては、例えば、ポリアルキルメタクリレート、ポリアルキルアクリレート、ポリアルキルスチレン、ポリビニルアセテート等が挙げられ、重量平均分子量は１０００〜１００，０００である。これらの流動点降下剤の好ましい配合量は、基油に対して０．００５〜３質量％、より好ましくは０．０１〜２質量％である。 Examples of the pour point depressant include polyalkyl methacrylate, polyalkyl acrylate, polyalkyl styrene, polyvinyl acetate and the like, and the weight average molecular weight is 1000 to 100,000. A preferable blending amount of these pour point depressants is 0.005 to 3% by mass, more preferably 0.01 to 2% by mass with respect to the base oil.
防錆剤としては、例えば、亜硝酸ナトリウム、酸化パラフィンワックスカルシウム塩、酸化パラフィンワックスマグネシウム塩、牛脂脂肪酸アルカリ金属塩、アルカリ土類金属塩又はアミン塩、アルケニルコハク酸又はアルケニルコハク酸ハーフエステル（アルケニル基の分子量は１００〜３００程度）、ソルビタンモノエステル、ノニルフェノールエトキシレート、ラノリン脂肪酸カルシウム塩等が挙げられる。これらの防錆剤の好ましい配合量は、基油に対して０．０１〜３質量％、より好ましくは０．０２〜２質量％である。 Examples of the rust preventive include sodium nitrite, oxidized paraffin wax calcium salt, oxidized paraffin wax magnesium salt, beef tallow fatty acid alkali metal salt, alkaline earth metal salt or amine salt, alkenyl succinic acid or alkenyl succinic acid half ester (alkenyl The molecular weight of the group is about 100 to 300), sorbitan monoester, nonylphenol ethoxylate, lanolin fatty acid calcium salt and the like. The preferable compounding quantity of these rust preventives is 0.01-3 mass% with respect to base oil, More preferably, it is 0.02-2 mass%.
腐食防止剤としては、例えば、ベンゾトリアゾール、ベンゾイミダゾール、ベンゾチアゾール、テトラアルキルチウラムジサルファイド等が挙げられる。これら腐食防止剤の好ましい配合量は、基油に対して０．０１〜３質量％、より好ましくは０．０２〜２質量％である。 Examples of the corrosion inhibitor include benzotriazole, benzimidazole, benzothiazole, tetraalkylthiuram disulfide and the like. The preferable compounding quantity of these corrosion inhibitors is 0.01-3 mass% with respect to base oil, More preferably, it is 0.02-2 mass%.
消泡剤としては、例えば、ポリジメチルシリコーン、トリフルオロプロピルメチルシリコーン、コロイダルシリカ、ポリアルキルアクリレート、ポリアルキルメタクリレート、アルコールエトキシ／プロポキシレート、脂肪酸エトキシ／プロポキシレート、ソルビタン部分脂肪酸エステル等が挙げられる。これらの消泡剤の好ましい配合量は、基油に対して０．００１〜０．１質量％、より好ましくは０．００１〜０．０１質量％である。 Examples of the antifoaming agent include polydimethyl silicone, trifluoropropylmethyl silicone, colloidal silica, polyalkyl acrylate, polyalkyl methacrylate, alcohol ethoxy / propoxylate, fatty acid ethoxy / propoxylate, sorbitan partial fatty acid ester and the like. The preferable compounding quantity of these antifoaming agents is 0.001-0.1 mass% with respect to base oil, More preferably, it is 0.001-0.01 mass%.
本発明の潤滑油組成物及びグリース組成物は、潤滑の用途であればいずれにも使用することができ、例えば、エンジン油、ギヤー油、タービン油、作動油、難燃性作動液、冷凍機油、コンプレッサー油、真空ポンプ油、軸受油、絶縁油、しゅう動面油、ロックドリル油、金属加工油、塑性加工油、熱処理油、軸受グリース、等の潤滑油に使用することができる。これらの中でも、使用環境が厳しく、高い酸化防止性能を求められるエンジン油やタービン油で好適に使用することができ、グリースにおいては、大きな負荷がかかって高温になりやすい自動車用の軸受グリースとして好適に使用することができる。 The lubricating oil composition and grease composition of the present invention can be used for any lubricating application, such as engine oil, gear oil, turbine oil, hydraulic oil, flame retardant hydraulic fluid, refrigerator oil. , Compressor oil, vacuum pump oil, bearing oil, insulating oil, sliding surface oil, rock drill oil, metal working oil, plastic working oil, heat treatment oil, bearing grease, and the like. Among these, it can be suitably used in engine oil and turbine oil, which are used in harsh environments and require high anti-oxidation performance. Grease is suitable as a bearing grease for automobiles that are subject to large loads and are likely to become hot. Can be used for
以下本発明を実施例により、具体的に説明する。
＜試験に使用した試験化合物＞
化合物１（ヨシノックス２２４６Ｒ：株式会社エーピーアイコーポレーション製）
Hereinafter, the present invention will be specifically described by way of examples.
<Test compounds used in the test>
Compound 1 (Yoshinox 2246R: manufactured by API Corporation)
化合物２（アデカスタブＡＯ−３０：株式会社ＡＤＥＫＡ製） Compound 2 (ADK STAB AO-30: manufactured by ADEKA Corporation)
化合物３（アデカスタブＡＯ−８０：株式会社ＡＤＥＫＡ製） Compound 3 (ADK STAB AO-80: manufactured by ADEKA Corporation)
化合物４（アデカエコロイヤルＡＩＮ−７００：株式会社ＡＤＥＫＡ製） Compound 4 (Adeka Eco Royal AIN-700: manufactured by ADEKA Corporation)
化合物５（アデカエコロイヤルＡＩＮ−７３０：株式会社ＡＤＥＫＡ製） Compound 5 (Adeka Eco Royal AIN-730: manufactured by ADEKA Corporation)
化合物６ Compound 6
化合物７ Compound 7
化合物８ Compound 8
＜試験方法＞
ＪＩＳ Ｋ−２５１４の方法に準拠して行った。具体的には、圧力計を備えた容量１００ｍｌの耐圧ボンベの中に、試料５０ｇ、水５ｇ、及び触媒として直径１．６ｍｍの銅線３ｍをコンパクトに丸めたものを入れ、密封した後ボンベ内の圧力が６２０ｋＰａになるまで酸素を圧入する。このボンベを１５０℃の恒温槽内で、３０℃の角度を保持したまま毎分１００回転で回転させる。最初、ボンベ内の圧力は温度がかかることで増加していくが、酸化劣化が始まると酸素を吸収してボンベ内の圧力は低下する。圧力を経時で測定し、圧力が最高になったときから１７５ｋＰａに低下するまでの時間を求め、これを酸化劣化の誘導期間とした。誘導期間が長いほど酸化防止性能が良好な試料である。なお、試料は下記の表１〜表３の配合に従って基油に試験化合物を添加して作成した。試験結果も表１〜表３に記載してある。
<Test method>
This was performed according to the method of JIS K-2514. Specifically, in a pressure-resistant cylinder having a capacity of 100 ml equipped with a pressure gauge, 50 g of a sample, 5 g of water, and a compactly rolled copper wire having a diameter of 1.6 mm as a catalyst are placed in a cylinder. Oxygen is injected until the pressure reaches 620 kPa. The cylinder is rotated at 100 revolutions per minute while maintaining a 30 ° C. angle in a 150 ° C. constant temperature bath. Initially, the pressure in the cylinder increases as the temperature is applied, but when oxidative deterioration starts, oxygen is absorbed and the pressure in the cylinder decreases. The pressure was measured over time, the time from when the pressure reached the maximum until the pressure decreased to 175 kPa was determined, and this was used as the induction period for oxidative degradation. The longer the induction period, the better the antioxidant performance. The sample was prepared by adding the test compound to the base oil according to the formulation shown in Tables 1 to 3 below. Test results are also described in Tables 1 to 3.
＜試験結果の解析＞
配合１〜配合１１は化合物１〜８それぞれ単品についての酸化防止性能である。また、配合１２〜配合１７は本発明品であり、配合１８〜配合２８は比較品である。
配合１２〜２８は化合物１〜８を組み合わせた配合になっており、配合１２〜２８の酸化防止の効果が、それぞれの配合に使用している化合物１〜８が持つ酸化防止の効果を足したものより大きくなっていれば相乗効果があると判断できる。具体的な解析結果を表４及び表５に記載した。なお、相乗効果率が１００％を超えると相乗効果があると判断することができる。
<Analysis of test results>
Formulations 1 to 11 are antioxidant performances for each of the compounds 1 to 8. Formulations 12 to 17 are products of the present invention, and Formulations 18 to 28 are comparative products.
Formulations 12-28 are a combination of compounds 1-8, and the antioxidant effect of Formulations 12-28 added the antioxidant effect of compounds 1-8 used in each formulation. If it is larger than the one, it can be judged that there is a synergy effect. Specific analysis results are shown in Tables 4 and 5. It can be determined that there is a synergistic effect when the synergistic effect rate exceeds 100%.
Claims (4)
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| JPS4944982A (en) * | 1972-09-05 | 1974-04-27 | ||
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| JPS5819394A (en) * | 1981-07-28 | 1983-02-04 | Sumitomo Chem Co Ltd | Liquid antioxidant for lubricating oil |
| JPS5859293A (en) * | 1981-10-02 | 1983-04-08 | Sumitomo Chem Co Ltd | Liquid antioxidant for lubricating oil |
| JPH07197071A (en) * | 1993-12-29 | 1995-08-01 | Mitsubishi Cable Ind Ltd | Lubricant composition |
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| JPH09194868A (en) * | 1996-01-16 | 1997-07-29 | Nippon Oil Co Ltd | Lubricating oil composition |
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| JPS4944982A (en) * | 1972-09-05 | 1974-04-27 | ||
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| JPS5819394A (en) * | 1981-07-28 | 1983-02-04 | Sumitomo Chem Co Ltd | Liquid antioxidant for lubricating oil |
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