JP2011046903A - Power saving gear oil composition - Google Patents
Power saving gear oil composition Download PDFInfo
- Publication number
- JP2011046903A JP2011046903A JP2009199077A JP2009199077A JP2011046903A JP 2011046903 A JP2011046903 A JP 2011046903A JP 2009199077 A JP2009199077 A JP 2009199077A JP 2009199077 A JP2009199077 A JP 2009199077A JP 2011046903 A JP2011046903 A JP 2011046903A
- Authority
- JP
- Japan
- Prior art keywords
- group
- composition
- extreme pressure
- oil
- gear 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
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- 239000000203 mixture Substances 0.000 title claims abstract description 83
- 239000012208 gear oil Substances 0.000 title claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- 239000002199 base oil Substances 0.000 claims abstract description 45
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011593 sulfur Substances 0.000 claims abstract description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005977 Ethylene Substances 0.000 claims abstract description 24
- 150000001336 alkenes Chemical class 0.000 claims abstract description 24
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 24
- 239000003921 oil Substances 0.000 claims abstract description 24
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 238000004458 analytical method Methods 0.000 claims abstract description 5
- 229920013639 polyalphaolefin Polymers 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 11
- 230000001050 lubricating effect Effects 0.000 claims description 10
- 239000005078 molybdenum compound Substances 0.000 claims description 10
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000010687 lubricating oil Substances 0.000 abstract description 4
- -1 olefin hydrocarbons Chemical class 0.000 description 35
- 235000019198 oils Nutrition 0.000 description 20
- 239000000654 additive Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000003925 fat Substances 0.000 description 6
- 235000019197 fats Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 5
- 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 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Chemical class 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000005077 polysulfide Substances 0.000 description 5
- 229920001021 polysulfide Polymers 0.000 description 5
- 150000008117 polysulfides Polymers 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 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 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical class CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 125000005265 dialkylamine group Chemical group 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 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 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- ONJROLGQWMBXAP-UHFFFAOYSA-N 2-methyl-1-(2-methylpropyldisulfanyl)propane Chemical compound CC(C)CSSCC(C)C ONJROLGQWMBXAP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical class CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 2
- XYRMLECORMNZEY-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S XYRMLECORMNZEY-UHFFFAOYSA-B 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 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 2
- 239000010722 industrial gear oil Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000006078 metal deactivator Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- KHYKFSXXGRUKRE-UHFFFAOYSA-J molybdenum(4+) tetracarbamodithioate Chemical compound C(N)([S-])=S.[Mo+4].C(N)([S-])=S.C(N)([S-])=S.C(N)([S-])=S KHYKFSXXGRUKRE-UHFFFAOYSA-J 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000001117 oleyl 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])=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 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 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 2
- 239000000126 substance Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 150000005691 triesters Chemical class 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 235000019871 vegetable fat Nutrition 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000010698 whale oil Substances 0.000 description 2
- OGQVROWWFUXRST-FNORWQNLSA-N (3e)-hepta-1,3-diene Chemical compound CCC\C=C\C=C OGQVROWWFUXRST-FNORWQNLSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-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
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-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
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical class OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical class C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- MEESPVWIOBCLJW-KTKRTIGZSA-N [(z)-octadec-9-enyl] dihydrogen phosphate Chemical compound CCCCCCCC\C=C/CCCCCCCCOP(O)(O)=O MEESPVWIOBCLJW-KTKRTIGZSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
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- 239000002585 base Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- HWEQKSVYKBUIIK-UHFFFAOYSA-N cyclobuta-1,3-diene Chemical compound C1=CC=C1 HWEQKSVYKBUIIK-UHFFFAOYSA-N 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- DSGBMMNDXFQXBM-KTKRTIGZSA-N dihydroxy-[(z)-octadec-9-enoxy]-sulfanylidene-$l^{5}-phosphane Chemical compound CCCCCCCC\C=C/CCCCCCCCOP(O)(O)=S DSGBMMNDXFQXBM-KTKRTIGZSA-N 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
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Landscapes
- Lubricants (AREA)
Abstract
Description
本発明は、省電力型ギヤ油組成物に関する。 The present invention relates to a power-saving gear oil composition.
近年、地球規模での温暖化が進行し、温室効果ガスの一つである二酸化炭素排出量削減が急務となっている。わが国でも、２００６年にエネルギーの使用の合理化に関する法律、地球温暖化対策の推進に関する法律がそれぞれ改正施行され、工場、輸送事業者等はこれまで以上に電力消費量の削減が求められるようになってきた。 In recent years, global warming has progressed, and there is an urgent need to reduce carbon dioxide emissions, which is one of the greenhouse gases. In Japan, the Law Concerning the Rational Use of Energy and the Law Concerning the Promotion of Global Warming Countermeasures were revised and implemented in 2006, and factories, transporters, etc. are now required to reduce power consumption more than ever. I came.
電力消費量削減の一つの方法として、産業機械や輸送機械で使用される潤滑油側からの省電力化が図られている。そのような状況下、産業機械の軸受や歯車に用いられている工業用ギヤ油においても、省電力化が検討されており、例えば、摩擦調整剤である硫化オキシモリブデンジチオホスフェート、硫化オキシモリブデンジチオカーバメートなどの配合技術による対応が試みられている（例えば、特許文献１、２参照）。 As one method of reducing power consumption, power saving from the lubricating oil side used in industrial machines and transportation machines is being attempted. Under such circumstances, power savings are also being studied for industrial gear oils used in bearings and gears of industrial machinery. Attempts have been made to cope with blending techniques such as carbamate (see, for example, Patent Documents 1 and 2).
ところで、各種機械においては、通常運転時の他にも、起動時の電力消費量削減も求められており、これに対しては低温流動性の向上で対応している。ギヤ油においても同様に低温流動性の向上が必要とされている。
さらに、省電力化や低温流動性向上の際には、当然、ギヤ油としての基本性能である極圧性を十分に兼ね備えている必要もある。
By the way, various machines are required to reduce power consumption at the start-up in addition to during normal operation, and this is addressed by improving low-temperature fluidity. Similarly, improvement in low temperature fluidity is required for gear oil.
Furthermore, when saving power and improving low-temperature fluidity, it is naturally necessary to have sufficient extreme pressure, which is the basic performance of gear oil.
本発明は、省電力性、低温流動性に優れ、かつ、高荷重で運転される機械で、極圧性も良好なギヤ油組成物を提供することを目的とする。 An object of the present invention is to provide a gear oil composition that is excellent in power saving and low-temperature fluidity, is a machine that is operated under a high load, and has excellent extreme pressure.
本発明者は、上記課題を解決するために鋭意研究を行った結果、特定の％ＣＮ、及び％ＣＡを有する炭化水素系の潤滑油基油に特定のオレフィン系粘度指数向上剤を配合し、さらに、硫黄を含有する極圧剤を添加、混合することにより、特定の組成物とすることで、省電力性、低温流動性に優れ、かつ、良好な極圧性も示すギヤ油組成物が得られることを見出し、この知見に基づいて本発明を完成させるに至った。 As a result of diligent research to solve the above problems, the present inventor blends a specific olefinic viscosity index improver with a hydrocarbon-based lubricating base oil having a specific% CN and% CA, Furthermore, by adding and mixing an extreme pressure agent containing sulfur, a gear oil composition having excellent power saving, low temperature fluidity and good extreme pressure can be obtained by making a specific composition. Based on this finding, the present invention has been completed.
すなわち、本発明は、環分析による％ＣＮが１８以下で、かつ％ＣＡが１．０以下である炭化水素系潤滑油基油（ただし、ポリαオレフィン基油を除く。）に、エチレンとエチレン以外のモノマーとの共重合体からなるオレフィン系粘度指数向上剤及び硫黄を含有する極圧剤が配合された組成物であって、前記硫黄を含有する極圧剤の配合量が該組成物の全量に対して０．１〜１０質量％であり、かつ該組成物の４０℃における動粘度が５０〜３８０ｍｍ２／ｓ、さらに、１５℃における密度が０．８２５〜０．８４６ｇ／ｃｍ３であることを特徴とするギヤ油組成物を提供するものである。 That is, according to the present invention, ethylene and ethylene are added to a hydrocarbon-based lubricating base oil (excluding poly α-olefin base oil) having a% CN of 18 or less and a% CA of 1.0 or less by ring analysis. An olefin viscosity index improver comprising a copolymer with a monomer other than the above and a composition containing a sulfur-containing extreme pressure agent, wherein the amount of the sulfur-containing extreme pressure agent is a 0.1 to 10 mass% relative to the total amount, and kinematic viscosity at 40 ° C. of the composition 50~380mm 2 / s, further density at 15 ℃ is in 0.825~0.846g / cm 3 A gear oil composition is provided.
また、本発明は、上記ギヤ油組成物において、前記オレフィン系粘度指数向上剤がエチレンと炭素数３〜３０のオレフィンとの共重合体であるギヤ油組成物を提供するものである。
また、本発明は、上記ギヤ油組成物において、前記硫黄を含有する極圧剤が硫化オレフィン及び硫黄−リン系極圧剤から選ばれる少なくとも1種以上であるギヤ油組成物を提供するものである。
また、本発明は、上記ギヤ油組成物において、さらにモリブデン化合物がモリブデン量換算で該組成物の全量に対して０．００１〜１．０質量％配合されているギヤ油組成物を提供するものである。
Moreover, this invention provides the gear oil composition whose said olefin type viscosity index improver is a copolymer of ethylene and a C3-C30 olefin in the said gear oil composition.
The present invention also provides a gear oil composition in which the sulfur-containing extreme pressure agent is at least one selected from sulfurized olefins and sulfur-phosphorus extreme pressure agents in the gear oil composition. is there.
The present invention also provides a gear oil composition in which 0.001 to 1.0% by mass of a molybdenum compound is added to the total amount of the composition in terms of molybdenum amount in the gear oil composition. It is.
本発明のギヤ油組成物は、特定の性状の炭化水素系潤滑油基油を用い、さらに特定のオレフィン系粘度指数向上剤及び特定量の硫黄を含有する極圧剤と組み合わせているため、省電力性、低温流動性に優れ、かつ、極圧性も良好である。 The gear oil composition of the present invention uses a hydrocarbon-based lubricating base oil having a specific property and is further combined with a specific olefinic viscosity index improver and an extreme pressure agent containing a specific amount of sulfur. Excellent power and low temperature fluidity, and excellent extreme pressure.
（基油）
本発明のギヤ油組成物に用いる炭化水素系潤滑油基油は、ＡＳＴＭ Ｄ３２３８環分析方法による％ＣＮが１８以下であり、好ましくは１６以下である。％ＣＮが１８を超えると、組成物の密度が高くなり、電力消費量が多くなる傾向にある。なお、％ＣＮはナフテンの含有量と相関するが、ナフテンが多いと電力消費量が多くなる傾向にあるため、より少ない方が好ましく、上記数値以下であれば下限値に限定はなく、ナフテンを実質的に含有しなくてもよい。
(Base oil)
The hydrocarbon-based lubricating base oil used in the gear oil composition of the present invention has a% CN of 18 or less, preferably 16 or less, according to ASTM D3238 ring analysis method. When% CN exceeds 18, the density of the composition tends to increase and the power consumption tends to increase. % CN correlates with the content of naphthene, but since there is a tendency that the power consumption increases when the amount of naphthene is large, the lower one is preferable. It does not need to contain substantially.
また、本発明のギヤ油組成物に用いる炭化水素系潤滑油基油は、ＡＳＴＭ Ｄ３２３８環分析方法による％ＣＡが１．０以下であり、好ましくは０．８以下であり、より好ましくは０．５以下である。％ＣＡが１．０を超えると、組成物の密度が高くなり、電力消費量が多くなる傾向にある。なお、％ＣＡは芳香族系炭化水素の含有量と相関するが、芳香族系炭化水素が多いと電力消費量が多くなる傾向にあるため、より少ない方が好ましく、上記数値以下であれば下限値に限定はなく、芳香族系炭化水素を実質的に含有しなくてもよい。 The hydrocarbon-based lubricating base oil used in the gear oil composition of the present invention has a% CA of 1.0 or less, preferably 0.8 or less, more preferably 0.8 or less according to ASTM D3238 ring analysis method. 5 or less. When% CA exceeds 1.0, the density of the composition tends to increase and the power consumption tends to increase. Note that% CA correlates with the content of aromatic hydrocarbons, but since there is a tendency for power consumption to increase when there are many aromatic hydrocarbons, the lower one is preferable. The value is not limited, and the aromatic hydrocarbon may not be substantially contained.
さらに、本発明のギヤ油組成物に用いる炭化水素系潤滑油基油は、本発明のギヤ油組成物の性状と組成に調整し易く、本発明の効果をより発揮するという観点から、ＪＩＳ Ｋ ２２４９に準拠の方法で測定される１５℃における密度が０．８２０〜０．８４０ｇ／ｃｍ３であることが好ましく、０．８２２〜０．８３７ｇ／ｃｍ３であることがより好ましい。 In addition, the hydrocarbon-based lubricating base oil used in the gear oil composition of the present invention is easily adjusted to the properties and composition of the gear oil composition of the present invention, and from the viewpoint that the effects of the present invention are more exerted, JIS K preferably density at 15 ℃ measured compliant way 2249 is 0.820~0.840g / cm 3, more preferably 0.822~0.837g / cm 3.
本発明で用いる炭化水素系潤滑油基油としては、鉱油系潤滑油基油であっても、メタン等の天然ガス等を原料としてフィッシャー−トロプシュ合成によって得られたワックスを原料として製造される基油等であってもよい。ただし、本発明で用いる炭化水素系潤滑油基油には、ポリαオレフィン基油は含まない。ここで、ポリαオレフィン基油とは、αオレフィンの重合体からなる基油である。 The hydrocarbon-based lubricant base oil used in the present invention is a base produced from a wax obtained by Fischer-Tropsch synthesis using a natural gas such as methane as a raw material, even if it is a mineral-based lubricant base oil. Oil etc. may be sufficient. However, the hydrocarbon-based lubricating base oil used in the present invention does not include a poly α-olefin base oil. Here, the poly α-olefin base oil is a base oil made of a polymer of α-olefin.
鉱油系潤滑油基油としては、例えば、原油の潤滑油留分を溶剤精製、水素化精製、水素化分解精製など適宜組合せた製造方法が挙げられる。この内、好ましいものとしては、以下の製造方法で製造されたものが挙げられる。まず、原油の常圧蒸留で得られたボトム油を減圧蒸留装置で処理する。そこで得られた減圧軽油を水素化処理および水素化分解を行い、その後、軽質分、燃料分を減圧ストリッパーで除去した残渣物を得る。この残渣物を減圧蒸留し、得られた潤滑油留分を水素化脱ロウ処理、安定化処理を行う。このようにして得られた基油が本発明の基油としては好ましい。 Examples of the mineral oil base oil include a production method in which crude oil lubricant fractions are appropriately combined, such as solvent refining, hydrorefining, and hydrocracking refining. Among these, what was manufactured with the following manufacturing methods is mentioned as a preferable thing. First, bottom oil obtained by atmospheric distillation of crude oil is treated with a vacuum distillation apparatus. The vacuum gas oil thus obtained is hydrotreated and hydrocracked, and then a residue obtained by removing light and fuel components with a vacuum stripper is obtained. This residue is distilled under reduced pressure, and the resulting lubricating oil fraction is subjected to hydrodewaxing treatment and stabilization treatment. The base oil thus obtained is preferred as the base oil of the present invention.
上記の炭化水素系潤滑油基油は、％ＣＮ及び％ＣＡが上記範囲である限り、１種を単独使用してもよいし、２種以上を併用してもよい。 As long as% CN and% CA are within the above ranges, one kind of the above hydrocarbon-based lubricating base oil may be used alone, or two or more kinds may be used in combination.
また、本発明のギヤ油組成物には、本発明の目的を害さない範囲内で、前記基油以外の他の基油を含んでもよいが、前記基油の含有割合は、全ての基油の合計量に対して７０質量％以上であることが好ましく、８０質量％以上であることがより好ましく、９０質量％以上であることがより好ましく、９５質量％以上であることが特に好ましい。
本発明のギヤ油組成物においては、全基油の配合量は、オレフィン系粘度指数向上剤、硫黄を含有する極圧剤や、必要に応じて添加されるモリブデン化合物やその他の添加剤の配合量と全基油の配合量の合計が１００質量％になるように調整されればよいが、組成物の全量に対して２０〜９５質量％が好ましく、２５〜９０質量％がより好ましく、３０〜９０質量％がさらに好ましく、３５〜９０質量％が特に好ましい。
Further, the gear oil composition of the present invention may contain a base oil other than the base oil as long as it does not impair the object of the present invention. The total amount is preferably 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
In the gear oil composition of the present invention, the blending amount of the total base oil is the blending of olefinic viscosity index improver, sulfur-containing extreme pressure agent, molybdenum compound added as necessary, and other additives. The total amount of the base oil and the total amount of the base oil may be adjusted so as to be 100% by mass, preferably 20 to 95% by mass, more preferably 25 to 90% by mass with respect to the total amount of the composition. -90 mass% is further more preferable, and 35-90 mass% is especially preferable.
本発明で用いる炭化水素系潤滑油基油の４０℃における動粘度は１０〜５０ｍｍ２／ｓであることが好ましく、１５〜４０ｍｍ２／ｓであることがより好ましい。この動粘度にすることで比較的密度の大きいオレフィン系粘度指数向上剤の添加量が少なくなり一層の省電力効果が得られる。 Preferably the kinematic viscosity at 40 ° C. hydrocarbon lubricating base oil used in the present invention is 10 to 50 mm 2 / s, more preferably 15 to 40 mm 2 / s. By using this kinematic viscosity, the amount of the olefin viscosity index improver having a relatively large density is reduced, and a further power saving effect can be obtained.
（オレフィン系粘度指数向上剤）
本発明の作動油組成物に用いるオレフィン系粘度指数向上剤は、エチレンとエチレン以外のモノマーからなる共重合体である。
エチレンと共重合体を形成するエチレン以外のモノマーとしては、例えば、オレフィン系炭化水素、ジエン系炭化水素、ビニル芳香族炭化水素等が挙げられる。これらのエチレン以外のモノマーの炭素数は、好ましくは３〜３０であり、より好ましくは３〜２５であり、さらに好ましくは３〜１５であり、特に好ましくは３〜８であり、最も好ましくは３〜５である。エチレン以外のモノマーの炭素数が３０以下とすることで、粘度指数向上剤の分子量を比較的低く抑えることができ、耐せん断安定性を向上させることができるため好ましい。
(Olefin viscosity index improver)
The olefin viscosity index improver used in the hydraulic oil composition of the present invention is a copolymer composed of ethylene and a monomer other than ethylene.
Examples of monomers other than ethylene that form a copolymer with ethylene include olefin hydrocarbons, diene hydrocarbons, vinyl aromatic hydrocarbons, and the like. The number of carbon atoms of these monomers other than ethylene is preferably 3 to 30, more preferably 3 to 25, still more preferably 3 to 15, particularly preferably 3 to 8, and most preferably 3. ~ 5. It is preferable that the number of carbon atoms of the monomer other than ethylene is 30 or less because the molecular weight of the viscosity index improver can be kept relatively low and shear stability can be improved.
エチレン以外のモノマーとして用いられるオレフィン系炭化水素としては、直鎖であっても環状であっても良く、分岐があっても良い。オレフィン系炭化水素の具体例としては、プロピレン、ｎ−ブテン、ｉ−ブチレン、シクロブテン、ｎ−ペンテン、ｉ−ペンテン、シクロペンテン、ｎ−へキセン、ｉ−へキセン、ｎ−へプテン、ｉ−へプテン等が挙げられる。
エチレン以外のモノマーとして用いられるジエン系炭化水素は、鎖状であっても、環状であってもよく、分岐鎖があってもよい。ジエン系炭化水素の具体例としては、ブタジエン、シクロブタジエン、ペンタジエン、シクロペンタジエン、ヘキサジエン、ヘプタジエン等が挙げられる。
The olefinic hydrocarbon used as a monomer other than ethylene may be linear, cyclic, or branched. Specific examples of the olefinic hydrocarbon include propylene, n-butene, i-butylene, cyclobutene, n-pentene, i-pentene, cyclopentene, n-hexene, i-hexene, n-heptene, and i-to. Puten and the like.
The diene hydrocarbon used as a monomer other than ethylene may be a chain, a ring, or a branched chain. Specific examples of the diene hydrocarbon include butadiene, cyclobutadiene, pentadiene, cyclopentadiene, hexadiene, heptadiene and the like.
エチレン以外のモノマーとして用いられるビニル芳香族炭化水素としては、スチレン、ジビニルベンゼン等が挙げられる。
これらエチレン以外のモノマーの内、好ましいものはオレフィン系炭化水素であり、特に好ましいものは炭素数３〜５のオレフィン系炭化水素である。
オレフィン系粘度指数向上剤はエチレンとエチレン以外のモノマーを重合して合成するが、エチレン以外のモノマーは１種類であってもよいし、２種類以上であってもよい。
Examples of vinyl aromatic hydrocarbons used as monomers other than ethylene include styrene and divinylbenzene.
Among these monomers other than ethylene, preferred are olefinic hydrocarbons, and particularly preferred are olefinic hydrocarbons having 3 to 5 carbon atoms.
The olefin-based viscosity index improver is synthesized by polymerizing monomers other than ethylene and ethylene. However, the number of monomers other than ethylene may be one, or two or more.
エチレンとエチレン以外のモノマーのモル比は特に制限されないが、好ましくは８０：２０〜２０:８０であり、より好ましくは７０：３０〜３０：７０であり、さらに好ましくは６５：３５〜３５：６５である。
オレフィン系粘度指数向上剤は、規則的交互重合体、ランダム重合体、ブロック重合体またはグラフト重合体のいずれであってもよい。
オレフィン系粘度指数向上剤の好ましい重量平均分子量は１，０００〜１５０，０００であり、より好ましくは１，２００〜１００，０００であり、さらに好ましくは１，５００〜５５，０００であり、特に好ましくは３，０００〜３０，０００であり、最も好ましくは５，０００〜２５，０００である。重量平均分子量を１，０００以上とすることで、添加量を抑えることができる。重量平均分子量が１５０，０００以下とすることで、せん断下における粘度低下を抑制しやすい傾向にある。なお、重量平均分子量はゲル浸透クロマトグラフィーで測定され、ポリスチレン換算による値である。
The molar ratio of ethylene and a monomer other than ethylene is not particularly limited, but is preferably 80:20 to 20:80, more preferably 70:30 to 30:70, and still more preferably 65:35 to 35:65. It is.
The olefin viscosity index improver may be a regular alternating polymer, a random polymer, a block polymer, or a graft polymer.
The preferred weight average molecular weight of the olefin viscosity index improver is 1,000 to 150,000, more preferably 1,200 to 100,000, still more preferably 1,500 to 55,000, and particularly preferably. Is from 3,000 to 30,000, most preferably from 5,000 to 25,000. By setting the weight average molecular weight to 1,000 or more, the amount added can be suppressed. By setting the weight average molecular weight to 150,000 or less, viscosity reduction under shear tends to be suppressed. The weight average molecular weight is measured by gel permeation chromatography and is a value in terms of polystyrene.
オレフィン系粘度指数向上剤は、本発明の目的が損なわれないかぎり、分散型、非分散型のいずれであってもよい（モノマー由来の極性基を有するものを分散型、極性基を有さないものを非分散型という）。すなわち、エチレン以外のモノマー分子として窒素原子含有化合物やアルキルエステル類が用いられている分散型であってもよい。このような窒素原子含有化合物の具体例としては、アルキル-ビニルピリジン、Ｎ−ビニルピロリドン、ビニルイミダゾール等が挙げられる。また、アルキルエステル類の具体例として、ポリアルキレングリコールエステル、マレイン酸エステル、フマル酸エステル等が挙げられる。これらは１種でも、２種以上でも用いることができる。 As long as the object of the present invention is not impaired, the olefin viscosity index improver may be either a dispersion type or a non-dispersion type (one having a monomer-derived polar group is a dispersion type and does not have a polar group) Things are called non-dispersive). That is, a dispersion type in which nitrogen atom-containing compounds and alkyl esters are used as monomer molecules other than ethylene may be used. Specific examples of such nitrogen atom-containing compounds include alkyl-vinyl pyridine, N-vinyl pyrrolidone, vinyl imidazole and the like. Specific examples of alkyl esters include polyalkylene glycol esters, maleic acid esters, and fumaric acid esters. These can be used alone or in combination of two or more.
ただし、オレフィン系粘度指数向上剤中の分散基を有するモノマーとそれ以外のモノマーのモル比は、分散基のモル比が２５を超えると、基油とオレフィン系粘度指数向上剤の混合物のトラクション係数が高くなり、電力消費量が多くなる傾向がある。そのため、分散基を有するモノマーとそれ以外のモノマーのモル比は、好ましくは０：１００〜２５：７５であり、より好ましくは０：１００〜１０：９０である。 However, when the molar ratio of the monomer having a dispersing group in the olefinic viscosity index improver and the other monomer exceeds 25, the traction coefficient of the mixture of the base oil and the olefinic viscosity index improving agent Tends to increase and power consumption tends to increase. Therefore, the molar ratio of the monomer having a dispersing group and the other monomer is preferably 0: 100 to 25:75, and more preferably 0: 100 to 10:90.
オレフィン系粘度指数向上剤の配合量は、ギヤ油組成物の全量に対して好ましくは１〜６０質量％であり、より好ましくは３〜５５質量％であり、さらに好ましくは５〜４５質量％である。配合量の下限値を１質量％以上とすることで、省電力効果を得やすい傾向にある。一方、オレフィン系粘度指数向上剤は比較的密度が高いため、配合量を６０質量%以下とすることで本発明で規定する１５℃における密度の範囲内に調整しやすく、省電力効果を得やすい傾向にある。 The blending amount of the olefin-based viscosity index improver is preferably 1 to 60% by mass, more preferably 3 to 55% by mass, and further preferably 5 to 45% by mass with respect to the total amount of the gear oil composition. is there. By setting the lower limit of the amount to be 1% by mass or more, it tends to easily obtain a power saving effect. On the other hand, since the olefin viscosity index improver has a relatively high density, it is easy to adjust the blending amount to 60% by mass or less within the density range at 15 ° C. defined in the present invention, and to easily obtain a power saving effect. There is a tendency.
さらに、オレフィン系粘度指数向上剤の配合量は、組成物の動粘度によってより好ましい範囲が異なる。例えば、各ＩＳＯ粘度グレードを参考に動粘度を分けた場合、オレフィン系粘度指数向上剤の配合量の範囲は下表のようにすることが好ましい。なお、下記表１はＩＳＯ粘度グレードをベースに４０℃における動粘度の範囲を設定しているため、表１中の動粘度の範囲はＩＳＯで規定されている動粘度の範囲そのものではない。ちなみに、ＩＳＯ粘度グレードで規定されている４０℃における動粘度は、ＶＧ６８は６１．２〜７４．８ｍｍ２／ｓ、ＶＧ１００は９０〜１１０ｍｍ２／ｓ、ＶＧ１５０は１３５〜１６５ｍｍ２／ｓ、ＶＧ２２０は１９８〜２４２ｍｍ２／ｓ、ＶＧ３２０は２８８〜３５２ｍｍ２／ｓである。 Furthermore, the blending amount of the olefin-based viscosity index improver has a more preferable range depending on the kinematic viscosity of the composition. For example, when the kinematic viscosity is divided with reference to each ISO viscosity grade, the range of the blending amount of the olefin viscosity index improver is preferably as shown in the following table. In Table 1, since the kinematic viscosity range at 40 ° C. is set based on the ISO viscosity grade, the kinematic viscosity range in Table 1 is not the kinematic viscosity range itself defined by ISO. By the way, the kinematic viscosity at 40 ° C. specified by the ISO viscosity grade is as follows: VG68 is 61.2-74.8 mm 2 / s, VG100 is 90-110 mm 2 / s, VG150 is 135-165 mm 2 / s, and VG220 is 198-242mm < 2 > / s, VG320 is 288-352mm < 2 > / s.
（硫黄を含有する極圧剤）
本発明のギヤ油組成物は、極圧剤として、硫黄を含有する極圧剤を含有する。
この硫黄を含有する極圧剤としては、例えば、硫黄系極圧剤や硫黄−リン系極圧剤が挙げられ、耐摩耗性の観点から、硫黄系極圧剤のうちの硫化オレフィンや硫黄−リン系極圧剤を配合することが好ましい。
(Extreme pressure agent containing sulfur)
The gear oil composition of the present invention contains an extreme pressure agent containing sulfur as the extreme pressure agent.
Examples of the extreme pressure agent containing sulfur include a sulfur-based extreme pressure agent and a sulfur-phosphorus extreme pressure agent. From the viewpoint of wear resistance, sulfurized olefins and sulfur- It is preferable to mix a phosphorus extreme pressure agent.
（ｉ）硫黄系極圧剤
硫黄系極圧剤としては、炭化水素硫化物、硫化油脂、硫化エステル等が挙げられる。
上記炭化水素硫化物としては、一般式（１）又は一般式（２）で表される炭化水素硫化物が挙げられる。
(I) Sulfur-based extreme pressure agent Examples of the sulfur-based extreme pressure agent include hydrocarbon sulfides, sulfurized fats and oils, and sulfurized esters.
As said hydrocarbon sulfide, the hydrocarbon sulfide represented by General formula (1) or General formula (2) is mentioned.
一般式（１）及び一般式（２）中、Ｒ１は、１価の炭化水素基（例えば、炭素数２〜２０個の直鎖もしくは分岐の飽和もしくは不飽和の脂肪族炭化水素基（例えば、アルキル基又はアルケニル基）、又は炭素数６〜２６の芳香族炭化水素基）を表し、Ｒ２は、２価の炭化水素基（例えば、炭素数２〜２０の直鎖もしくは分岐の飽和もしくは不飽和の脂肪族炭化水素基、又は炭素数６〜２６の芳香族炭化水素基）を表す。 In General Formula (1) and General Formula (2), R 1 is a monovalent hydrocarbon group (for example, a linear or branched saturated or unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms (for example, , An alkyl group or an alkenyl group), or an aromatic hydrocarbon group having 6 to 26 carbon atoms), and R 2 is a divalent hydrocarbon group (for example, linear or branched saturated or 2 to 20 carbon atoms) An unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 6 to 26 carbon atoms).
また、一般式（１）及び一般式（２）中、ｂは１以上の整数で、繰り返し単位中において各々のｂは同じでも異なっていてもよく、ｃは０又は１以上の整数を表す。
Ｒ１で表される１価の炭化水素基の具体例としては、エチル基、プロピル基、ブチル基、ノニル基、ドデシル基、プロペニル基、ブテニル基、フェニル基、トリル基、へキシルフェニル基、ベンジル基などが挙げられる。
Ｒ２で表される２価の炭化水素基の具体例としては、エチレン基、プロピレン基、ブチレン基、フェニレン基などが挙げられる。
Moreover, in general formula (1) and general formula (2), b is an integer greater than or equal to 1, and each b may be the same or different in a repeating unit, and c represents 0 or an integer greater than or equal to 1.
Specific examples of the monovalent hydrocarbon group represented by R 1 include ethyl group, propyl group, butyl group, nonyl group, dodecyl group, propenyl group, butenyl group, phenyl group, tolyl group, hexylphenyl group, A benzyl group etc. are mentioned.
Specific examples of the divalent hydrocarbon group represented by R 2 include an ethylene group, a propylene group, a butylene group, and a phenylene group.
これら炭化水素硫化物の具体的な化合物例としては、（１）ジイソブチルジサルファイド、ジオクチルポリサルファイド、ジ−ｔｅｒｔ−ブチルポリサルファイド、ジ−ｔｅｒｔ−ノニルポリサルファイド、ジベンジルポリサルファイドなどのポリサルファイド化合物、（２）ポリイソブチレン、テルペン類などのオレフィン類を、硫黄などの硫化物で硫化した硫化オレフィン類、（３）イソブチレンと硫黄との反応生成物で、一般式（３）、一般式（４）の化学式を有するものと推測される化合物などが挙げられる。 Specific examples of these hydrocarbon sulfides include (1) polysulfide compounds such as diisobutyl disulfide, dioctyl polysulfide, di-tert-butyl polysulfide, di-tert-nonyl polysulfide, dibenzyl polysulfide, and the like. Sulfurized olefins obtained by sulfurizing olefins such as isobutylene and terpenes with sulfides such as sulfur, and (3) reaction products of isobutylene and sulfur, which have chemical formulas of general formula (3) and general formula (4). Examples of such compounds are envisioned.
一般式（４）中、ｂ及びｃは、一般式（２）におけるｂ及びｃと同じである。
上記硫化油脂としては、油脂と硫黄の反応生成物が挙げられる。
ここで、油脂としては、ラード、牛脂、鯨油、パーム油、ヤシ油、ナタネ油などの動植物油脂が挙げられる。
硫化エステルは、油脂と各種アルコールとの反応により得られる脂肪酸エステルを硫化することにより得られ、化学構造そのものは明確でない。油脂としてラード、牛脂、鯨油、パーム油、ヤシ油、ナタネ油などの動植物油脂などが挙げられる。
In general formula (4), b and c are the same as b and c in general formula (2).
Examples of the sulfurized fats and oils include reaction products of fats and sulfur.
Here, as fats and oils, animal and vegetable fats and oils such as lard, beef tallow, whale oil, palm oil, coconut oil, rapeseed oil and the like can be mentioned.
The sulfurized ester is obtained by sulfurizing a fatty acid ester obtained by a reaction between fats and oils and various alcohols, and the chemical structure itself is not clear. Examples of the fats and oils include animal and vegetable fats and oils such as lard, beef tallow, whale oil, palm oil, coconut oil and rapeseed oil.
（ｉｉ）硫黄−リン系極圧剤
硫黄−リン系極圧剤としては、上記の硫黄系極圧剤とリン系極圧剤とを組みあわせて配合したものや、硫黄−リン系化合物が挙げられる。
硫黄系極圧剤と組み合わせるリン系極圧剤としては、ホスフェート、ホスファイト、及びこれらの誘導体が挙げられる。ホスフェート、ホスファイトは、モノ、ジ、トリエステルのいずれでもよく、そのアルコール残基としては、ブチル、オクチル、ラウリル、ステアリル、オレイル基などの炭素数４〜３０のアルキル基、フェニル基などの炭素数６〜３０のアリール基、メチルフェニル、オクチルフェニル基などの炭素数７〜３０のアルキル置換アリール基などが挙げられる。上記リン系極圧剤の具体的化合物の例としては、トリブチルホスフェート、モノオレイルホスフェート、ジオクチルホスフェート、ジオレイルホスファイト、ジフェニルホスファイト、トリクレジルホスファイトなどが挙げられる。これらの誘導体としては、上記モノエステルすなわちアシッドホスフェートやアシッドホスファイトのアミン塩があり、例えばステアリルアミン塩、オレイルアミン塩、ココナッツアミン塩などが挙げられる。
(Ii) Sulfur-phosphorus extreme pressure agent Examples of the sulfur-phosphorus extreme pressure agent include those prepared by combining the above sulfur extreme pressure agent and phosphorus extreme pressure agent, and sulfur-phosphorus compounds. It is done.
Phosphorus extreme pressure agents combined with sulfur extreme pressure agents include phosphates, phosphites, and derivatives thereof. The phosphate and phosphite may be any of mono, di and triester, and the alcohol residue thereof is an alkyl group having 4 to 30 carbon atoms such as butyl, octyl, lauryl, stearyl or oleyl group, carbon such as phenyl group, etc. Examples include an aryl group having 6 to 30 carbon atoms, an alkyl-substituted aryl group having 7 to 30 carbon atoms such as methylphenyl and octylphenyl groups. Specific examples of the phosphorus extreme pressure agent include tributyl phosphate, monooleyl phosphate, dioctyl phosphate, dioleyl phosphite, diphenyl phosphite, tricresyl phosphite and the like. Examples of these derivatives include the above monoesters, ie, acid phosphates and amine salts of acid phosphites, and examples thereof include stearylamine salts, oleylamine salts, and coconutamine salts.
硫黄−リン系化合物としては、チオホスファイト、チオホスフェート及びこれらの誘導体が挙げられる。チオホスファイトは、モノ、ジ、トリチオホスファイトのいずれでもよい。チオホスフェートは、モノ、ジ、トリ、テトラチオホスフェートのいずれでもよい。またチオホスファイト、チオホスフェートは、モノ、ジ、トリエステルのいずれでもよく、そのアルコール残基としては、ブチル、オクチル、ラウリル、ステアリル、オレイル基などの炭素数４〜３０のアルキル基、フェニル基などの炭素数６〜３０のアリール基、メチルフェニル、オクチルフェニル基などの炭素数７〜３０のアルキル置換アリール基などが挙げられる。 Examples of the sulfur-phosphorus compound include thiophosphite, thiophosphate, and derivatives thereof. The thiophosphite may be mono, di, or trithiophosphite. The thiophosphate may be mono, di, tri, or tetrathiophosphate. Thiophosphite and thiophosphate may be mono-, di- or triester, and the alcohol residue thereof is an alkyl group having 4 to 30 carbon atoms such as butyl, octyl, lauryl, stearyl or oleyl group, or phenyl group. And aryl groups having 6 to 30 carbon atoms such as alkyl substituted aryl groups having 7 to 30 carbon atoms such as methylphenyl and octylphenyl groups.
硫黄−リン系化合物の具体例としては、トリブチルチオホスフェート、モノオレイルチオホスフェート、ジオクチルチオホスフェート、トリクレジルチオホスフェートなどが挙げられる。これらのアミン塩としては、ステアリルアミン塩、オレイルアミン塩、ココナッツアミン塩などが挙げられる。チオホスファイト及びチオホスフェートの誘導体としては、上記アシッドチオホスファイト及びアシッドチオホスフェートとのアミン塩、金属塩、脂肪酸との反応物等が挙げられ、下記一般式（５）で表されるジチオリン酸エステル系化合物等も用いることができる。 Specific examples of the sulfur-phosphorus compound include tributyl thiophosphate, monooleyl thiophosphate, dioctyl thiophosphate, tricresyl thiophosphate, and the like. Examples of these amine salts include stearylamine salts, oleylamine salts, and coconut amine salts. Examples of thiophosphite and thiophosphate derivatives include amine salts, metal salts, and reaction products with fatty acids with the above acid thiophosphites and acid thiophosphates, and dithiophosphoric acids represented by the following general formula (5) An ester compound or the like can also be used.
上記一般式（５）において、Ｒ３、Ｒ４は、炭素数３〜１８の直鎖または分岐鎖の飽和または不飽和の脂肪族炭化水素基、環状炭化水素基を表し、同一であっても異なっていてもよい。具体的には、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ペンチル基、ヘキシル基、オクチル基、２−エチルへキシル基、ノニル基、ドデシル基、プロペニル基、ブテニル基、フェニル基、ヘキシルフェニル基などがある。 In the general formula (5), R 3 and R 4 each represent a linear or branched saturated or unsaturated aliphatic hydrocarbon group or cyclic hydrocarbon group having 3 to 18 carbon atoms, and may be the same. May be different. Specifically, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, nonyl group, dodecyl group, propenyl group, butenyl group, phenyl Group, hexylphenyl group and the like.
Ｒ５は炭素数１〜６の直鎖または分岐鎖のアルキレン基を表し、具体的には、メチレン基、エチレン基、プロピレン基、ブチレン基、アミレン基、へキシレン基があり、好ましくはエチレン基、プロピレン基、ブチレン基である。
Ｒ６は水素原子または炭素数１〜１８の直鎖または分岐鎖の飽和または不飽和の脂肪族炭化水素基、環状炭化水素基を表す。具体的には、水素原子、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ペンチル基、ヘキシル基、オクチル基、２−エチルへキシル基、ノニル基、ドデシル基、プロペニル基、ブテニル基、フェニル基、ヘキシルフェニル基などがある。好ましい例として、Ｒ５がプロピレン基でＲ６が水素原子のものが挙げられる。
R 5 represents a linear or branched alkylene group having 1 to 6 carbon atoms, and specifically includes a methylene group, an ethylene group, a propylene group, a butylene group, an amylene group, and a hexylene group, preferably an ethylene group. , Propylene group, butylene group.
R 6 represents a hydrogen atom or a linear or branched, saturated or unsaturated aliphatic hydrocarbon group or cyclic hydrocarbon group having 1 to 18 carbon atoms. Specifically, hydrogen atom, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, nonyl group, dodecyl group, propenyl group, butenyl Group, phenyl group, hexylphenyl group and the like. Preferable examples include those in which R 5 is a propylene group and R 6 is a hydrogen atom.
上記の硫黄を含有する極圧剤の含有量は、本発明のギヤ油組成物の全量に対し、０．１〜１０質量％であることが必要である。この含有量は、より好ましくは０．１〜８質量％であり、さらに好ましくは０．２〜５質量％であり、特に好ましくは０．５〜３質量％である。含有量が０．１質量％未満であると、ギヤ油組成物として求められる極圧性能を得にくくなる傾向にあり、１０質量％を超えても添加量に見合った効果が得られない。
上記の硫黄を含有する極圧剤は、１種単独または２種以上を組み合わせて用いることができる。
The content of the extreme pressure agent containing sulfur needs to be 0.1 to 10% by mass with respect to the total amount of the gear oil composition of the present invention. This content is more preferably 0.1 to 8% by mass, further preferably 0.2 to 5% by mass, and particularly preferably 0.5 to 3% by mass. If the content is less than 0.1% by mass, the extreme pressure performance required as a gear oil composition tends to be difficult to obtain, and even if it exceeds 10% by mass, an effect commensurate with the added amount cannot be obtained.
The above-mentioned extreme pressure agent containing sulfur can be used singly or in combination of two or more.
（モリブデン化合物）
本発明のギヤ油組成物は、さらにモリブデン化合物をギヤ組成物の全量に対しモリブデン量換算で０．００１〜１．０質量％含有させることで、さらに省電力効果を高めることができる。モリブデン化合物のモリブデン量換算の含有量は、好ましくは０．００５〜０．３質量％であり、より好ましくは０．０１〜０．２質量％である。
上記モリブデン化合物としては、モリブデン酸アミン、モリブデンジチオホスフェート、モリブデンジチオカーバメートなどが挙げられる。
(Molybdenum compound)
The gear oil composition of the present invention can further enhance the power saving effect by further containing 0.001 to 1.0% by mass of a molybdenum compound in terms of molybdenum based on the total amount of the gear composition. The molybdenum compound content of the molybdenum compound is preferably 0.005 to 0.3% by mass, more preferably 0.01 to 0.2% by mass.
Examples of the molybdenum compound include amine molybdate, molybdenum dithiophosphate, molybdenum dithiocarbamate, and the like.
モリブデン酸アミンとしては、三酸化モリブデン、モリブデン酸、又はそのアルカリ塩を還元剤にて還元後、アミン類と反応させて得ることができる。ここで用いられるアミン類としては第一級アミン、第二級アミン、第三級アミンのいずれであってもよく、その一例として、第一級アミンとしては炭素数４〜２４のアルキル基を有するモノアルキルアミン等、第二級アミンとしては炭素数１〜２４のアルキル基を有するジアルキルアミン等、第三級アミンとしては炭素数１〜２４のアルキル基を有するトリアルキルアミン等を挙げることができる。このうち、生成物の油溶性の点で特に好ましいアミンは、第二級アミンであり、炭素数６〜２４のアルキル基を有するジアルキルアミンが好ましい。ジアルキルアミンにおけるアルキル基の炭素数は、８〜２０がより好ましく、１０〜１６がさらに好ましい。 The amine molybdate can be obtained by reducing molybdenum trioxide, molybdic acid, or an alkali salt thereof with a reducing agent and then reacting with amines. The amines used here may be any of primary amines, secondary amines, and tertiary amines. As an example, primary amines have an alkyl group having 4 to 24 carbon atoms. Examples of secondary amines include monoalkylamines, dialkylamines having an alkyl group having 1 to 24 carbon atoms, and tertiary amines include trialkylamines having an alkyl group having 1 to 24 carbon atoms. . Among these, a particularly preferable amine in terms of oil solubility of the product is a secondary amine, and a dialkylamine having an alkyl group having 6 to 24 carbon atoms is preferable. As for carbon number of the alkyl group in dialkylamine, 8-20 are more preferable, and 10-16 are more preferable.
モリブデンジチオカーバメートとしては一般式（６）の構造を有する化合物が挙げられる。 Examples of molybdenum dithiocarbamate include compounds having the structure of general formula (6).
（式中、Ｒ７〜Ｒ１０は炭素数６〜１８の炭化水素基であり、それぞれ同一であってもよいし、異なってもよい。Ｘ及びＹは、硫黄原子又は酸素原子を示す。）
(In formula, R < 7 > -R < 10 > is a C6-C18 hydrocarbon group, and may be the same respectively, and may differ. X and Y show a sulfur atom or an oxygen atom.)
モリブデンジチオホスフェートとしては、一般式（７）の構造を有する化合物が挙げられる。 Examples of molybdenum dithiophosphate include compounds having the structure of general formula (7).
上記モリブデン化合物の中で、最も好ましいものはモリブデン酸アミンである。
Of the molybdenum compounds, the most preferred is an amine molybdate.
（その他添加剤）
本発明のギヤ油組成物には、本発明の目的が損なわれない範囲で、必要に応じて各種公知の添加剤を配合することができる。例えば酸化防止剤、油性剤、清浄分散剤、さび止め剤、金属不活性化剤、流動点降下剤、泡消剤、抗乳化剤等が挙げられる。
酸化防止剤としては、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール等のフェノール系酸化防止剤、アルキル化ジフェニルアミン、アルキル化フェニル−α−ナフチルアミン等のアミン系酸化防止剤、ホスホン酸エステル等のリン系酸化防止剤等が挙げられる。
(Other additives)
In the gear oil composition of the present invention, various known additives can be blended as necessary within a range that does not impair the object of the present invention. For example, an antioxidant, an oily agent, a detergent / dispersant, a rust inhibitor, a metal deactivator, a pour point depressant, a defoamer, a demulsifier, and the like can be mentioned.
Antioxidants include phenol-based antioxidants such as 2,6-di-tert-butyl-p-cresol, amine-based antioxidants such as alkylated diphenylamine and alkylated phenyl-α-naphthylamine, phosphonic acid esters, etc. And phosphorus-based antioxidants.
油性剤としては、オレイン酸、ステアリン酸等の高級脂肪酸、オレイルアルコール等の高級アルコール、オレイルアミン等のアミン、ブチルステアレート等のエステルが挙げられる。
清浄分散剤としては、アルケニルコハク酸イミド、アルケニルコハク酸エステル等の無灰系清浄分散剤、アルカリ土類金属系清浄分散剤が挙げられる。
さび止め剤としては、カルボン酸、金属セッケン、カルボン酸アミン塩、スルホン酸の金属塩、多価アルコールの部分エステル等が挙げられる。
Examples of the oily agent include higher fatty acids such as oleic acid and stearic acid, higher alcohols such as oleyl alcohol, amines such as oleylamine, and esters such as butyl stearate.
Examples of the cleaning dispersant include ashless cleaning dispersants such as alkenyl succinimides and alkenyl succinic esters, and alkaline earth metal cleaning dispersants.
Examples of the rust inhibitor include carboxylic acid, metal soap, carboxylic acid amine salt, sulfonic acid metal salt, and partial ester of polyhydric alcohol.
金属不活性化剤としては、ベンゾトリアゾ−ルおよびその誘導体、アルキルコハク酸誘導体が挙げられる。
流動点降下剤としては、ポリアルキルメタクリレート、ポリブテン、ポリアルキルスチレン、ポリビニルアセテート、ポリアルキルアクリレート等が挙げられる。
消泡剤としては、シリコーン油やエステル系消泡剤等が挙げられる。
抗乳化剤としては、アニオン系界面活性剤、カチオン系界面活性剤、非イオン系界面活性剤等の抗乳化剤が挙げられる。
これら添加剤は、１種を単独使用してもよいし、２種以上を併用してもよい。
Examples of metal deactivators include benzotriazole and derivatives thereof, and alkyl succinic acid derivatives.
Examples of the pour point depressant include polyalkyl methacrylate, polybutene, polyalkyl styrene, polyvinyl acetate, polyalkyl acrylate and the like.
Examples of antifoaming agents include silicone oil and ester-based antifoaming agents.
Examples of the demulsifier include demulsifiers such as an anionic surfactant, a cationic surfactant, and a nonionic surfactant.
These additives may be used alone or in combination of two or more.
（ギヤ油組成物の性状）
本発明のギヤ油組成物の４０℃における動粘度は、ＪＩＳ Ｋ２２８３動粘度試験方法(４０℃)において、５０〜３８０ｍｍ２／ｓである。
(Properties of gear oil composition)
The kinematic viscosity at 40 ° C. of the gear oil composition of the present invention is 50 to 380 mm 2 / s in the JIS K2283 kinematic viscosity test method (40 ° C.).
また、本発明のギヤ油組成物が省電力効果を発揮するためには、組成物の１５℃における密度は、ＪＩＳ Ｋ ２２４９に準拠の方法で測定される値が０．８２５〜０．８４６ｇ／ｃｍ３であることが肝要であり、０．８２５〜０．８４４ｇ／ｃｍ３であることが好ましい。１５℃における密度が上記の上限値を超えるとギヤ歯面の攪拌抵抗が大きくなり、十分な省電力効果が得られない。一方、組成物の１５℃における密度は低ければ低いほどよいが、１５℃における密度は使用する基油やオレフィン系粘度指数向上剤の性状や配合量の影響を受けるため、これを勘案した場合、実質的な１５℃密度の下限値は０．８２５ｇ／ｃｍ３、より実質的な下限値は０．８２７ｇ／ｃｍ３である。
さらに、組成物の１５℃における密度は、組成物の動粘度によってより好ましい範囲が異なる。例えば、各ＩＳＯ粘度グレードを参考に動粘度を分けた場合、好ましい１５℃における密度の範囲は下表のようになる。
In order for the gear oil composition of the present invention to exhibit a power saving effect, the density of the composition at 15 ° C. is 0.825 to 0.846 g / value measured by a method according to JIS K 2249. it is is important is cm 3, and is preferably 0.825~0.844g / cm 3. When the density at 15 ° C. exceeds the above upper limit value, the stirring resistance of the gear tooth surface increases, and a sufficient power saving effect cannot be obtained. On the other hand, the lower the density at 15 ° C. of the composition, the better. However, since the density at 15 ° C. is affected by the properties and blending amounts of the base oil and olefin viscosity index improver used, The practical lower limit of the 15 ° C. density is 0.825 g / cm 3 , and the more substantial lower limit is 0.827 g / cm 3 .
Furthermore, the density at 15 ° C. of the composition has a more preferable range depending on the kinematic viscosity of the composition. For example, when kinematic viscosities are divided with reference to each ISO viscosity grade, the preferred density range at 15 ° C. is as shown in the table below.
本発明のギヤ油組成物の粘度指数は、ＪＩＳ Ｋ２２８３動粘度試験方法において、好ましくは１００以上であり、より好ましくは１１０以上、さらに好ましくは１２０以上、特に好ましくは１３０以上である。粘度指数が低すぎると低温粘度が高くなり、低温始動時の電力消費量が多くなる傾向がある。 The gear oil composition of the present invention has a viscosity index of preferably 100 or more, more preferably 110 or more, still more preferably 120 or more, and particularly preferably 130 or more in the JIS K2283 kinematic viscosity test method. If the viscosity index is too low, the low-temperature viscosity tends to be high, and the power consumption during low-temperature starting tends to increase.
（用途）
本発明のギヤ油組成物は、種々の用途において使用することが可能である。例えば、産業機械の軸受や歯車、金属加工、特に好ましくは圧延機、搬送用ベルトコンベア、発電所のタービン、建設機械、工作機械、船舶等に用いることができる。
(Use)
The gear oil composition of the present invention can be used in various applications. For example, it can be used for bearings and gears of industrial machines, metal processing, particularly preferably rolling mills, conveyor belt conveyors, turbines of power plants, construction machines, machine tools, ships and the like.
次に、本発明を実施例によりさらに具体的に説明する。なお、本発明は、これらの例によって何ら制限されるものではない。
各実施例、比較例において、基油及び組成物の評価方法は、以下の方法により行った。
（評価方法）
ギヤ油組成物の密度、粘度指数、極圧性、省電力効果について、下記の評価方法により評価した。
＜密度＞
密度はＪＩＳ Ｋ ２２４９密度試験方法により測定した。
＜粘度指数＞
粘度指数はＪＩＳ Ｋ２２８３動粘度試験方法により測定した。
Next, the present invention will be described more specifically with reference to examples. In addition, this invention is not restrict | limited at all by these examples.
In each of the examples and comparative examples, the base oil and the composition were evaluated by the following methods.
(Evaluation methods)
The density, viscosity index, extreme pressure property, and power saving effect of the gear oil composition were evaluated by the following evaluation methods.
<Density>
The density was measured by the JIS K 2249 density test method.
<Viscosity index>
The viscosity index was measured by the JIS K2283 kinematic viscosity test method.
＜極圧性＞
極圧性を耐荷重試験で評価した。耐荷重試験はＦＺＧギヤ試験機を用い、ドイツ工業規格（ＤＩＮ）のＤＩＮ５１３５４−２に準拠した。具体的には、規格に沿った荷重をギヤに負荷したのち、ギヤ回転速度１，４４０ｒｐｍで２１，７００回転に達するまで試験を行う。ここまでを１ステージとする。以下、荷重ステージを段階的に上昇させ、各ステージ終了時におけるピニオンの１６歯面における摩耗傷（スカッフィング、スコーリング）の合計面積を測定し、２０ｍｍ２未満を合格とした。各表に記載した「ＦＺＧギヤ試験不合格ステージ」は不合格となった最終ステージである（例えば、ＦＺＧギヤ試験不合格ステージが１１のものは、１０ステージまでは合格で、１１ステージ目で不合格となったことを示す。）。したがって、ＦＺＧギヤ試験合格ステージの数値が大きい程、極圧性は高い。なお、試験は１２ステージまで実施し、１２ステージ目を合格したものは１２＋として示した。
<Extreme pressure>
Extreme pressure was evaluated by a load bearing test. The load resistance test was based on German Industrial Standard (DIN) DIN 51354-2 using an FZG gear tester. Specifically, after applying a load conforming to the standard to the gear, the test is performed until the speed reaches 21,700 at a gear rotation speed of 1,440 rpm. This is one stage. Hereinafter, the load stage was raised stepwise, and the total area of wear scratches (scuffing, scoring) on the 16 tooth surfaces of the pinion at the end of each stage was measured, and less than 20 mm 2 was accepted. The "FZG gear test failure stage" described in each table is the final stage that has failed (for example, those with 11 FZG gear test failure stages are acceptable up to 10 stages, and not at the 11th stage. Indicates that it passed.) Therefore, the higher the numerical value of the FZG gear test pass stage, the higher the extreme pressure property. The test was conducted up to 12 stages, and those that passed the 12th stage were shown as 12+.
＜省電力効果＞
ＡＳＴＭ Ｄ ５１８２に規定されるＦＺＧ試験において、５０℃、１４５０ｒｐｍ、３ステージにおける消費電力をＪＩＳ Ｋ ２２１９に規定する工業用２種のギヤ油（実施例１〜６、比較例１〜６ではコスモギヤＳＥ６８、実施例７〜１２、比較例７〜１２ではコスモギヤＳＥ１００、実施例１３〜１８、比較例１３〜１８ではコスモギヤＳＥ１５０、実施例１９〜２４、比較例１９〜２４ではコスモギヤＳＥ２２０、実施例２５〜３０、比較例２５〜３０ではコスモギヤＳＥ３２０）の消費電力と比較し、下記の基準で評価した。
◎：省電力効果３％以上
○：省電力効果２％以上〜３％未満
△：省電力効果１％以上〜２％未満
×：省電力効果１％未満
<Power saving effect>
In the FZG test specified in ASTM D 5182, two types of industrial gear oils that specify the power consumption in 3 stages at 50 ° C., 1450 rpm (Examples 1 to 6 and Cosmo Gear SE68 in Comparative Examples 1 to 6). In Examples 7-12 and Comparative Examples 7-12, Cosmo Gear SE100, Examples 13-18, Cosmo Gear SE150 in Comparative Examples 13-18, Examples 19-24, Cosmo Gear SE220, Examples 25-25 in Comparative Examples 19-24. 30 and Comparative Examples 25 to 30 were compared with the power consumption of Cosmo Gear SE320) and evaluated according to the following criteria.
◎: Power saving effect 3% or more ○: Power saving effect 2% or more to less than 3% △: Power saving effect 1% or more to less than 2% ×: Power saving effect less than 1%
各実施例、比較例において組成物の調製に用いた基油、添加剤成分は次のとおりである。
（Ａ）基油
各実施例、比較例において組成物の調製に用いた基油の製造方法と性状を下記に記載する。
なお、４０℃動粘度はＪＩＳ Ｋ２２８３動粘度試験方法で測定した。
The base oil and additive components used in the preparation of the compositions in each Example and Comparative Example are as follows.
(A) Base oil The production method and properties of the base oil used for preparing the compositions in each Example and Comparative Example are described below.
In addition, 40 degreeC kinematic viscosity was measured by the JISK2283 kinematic viscosity test method.
（１）水素化分解油
原油の常圧蒸留で得られたボトム油を減圧蒸留装置で処理し、そこで得られた減圧軽油を水素化処理および水素化分解を行った。その後、軽質分、燃料分を減圧ストリッパーで除去した残渣物を得た。残渣物を減圧蒸留し、得られた潤滑油留分の水素化脱ロウ処理、安定化処理を行った。
以下に、基油（Ａ−１）及び（Ａ−２）の性状を示す。
(1) Hydrocracked oil Bottom oil obtained by atmospheric distillation of crude oil was treated with a vacuum distillation apparatus, and the vacuum gas oil obtained there was hydrotreated and hydrocracked. Then, the residue which removed the light part and the fuel part with the vacuum stripper was obtained. The residue was distilled under reduced pressure, and the resulting lubricating oil fraction was subjected to hydrodewaxing treatment and stabilization treatment.
The properties of the base oils (A-1) and (A-2) are shown below.
（Ａ−１）水素化分解油
４０℃動粘度：３４．７ｍｍ２／ｓ、１５℃における密度：０．８３５、
％ＣＮ：１５、 ％ＣＡ：０．１以下
（Ａ−２）水素化分解油
４０℃動粘度：１７．９ｍｍ２／ｓ、１５℃における密度：０．８２４、
％ＣＮ：１２、％ＣＡ：０．１以下
(A-1) Hydrocracked oil 40 ° C. kinematic viscosity: 34.7 mm 2 / s, density at 15 ° C .: 0.835,
% CN: 15,% CA: 0.1 or less (A-2) Hydrocracked oil 40 ° C. Kinematic viscosity: 17.9 mm 2 / s, Density at 15 ° C .: 0.824
% CN: 12,% CA: 0.1 or less
（２）水素化精製油
原油を常圧蒸留し、分留後の残油を減圧下で分留、得られた留出油をフルフラール溶剤抽出法によってパラフィンリッチラフィネートを精製した。つづいてそのラフィネートをベンゾケトンによる溶剤脱ロウ処理し、得られた脱ロウ油の高圧水素化処理を行った。
（Ａ−３）水素化精製油
４０℃動粘度：３１ｍｍ２／ｓ、１５℃における密度：０．８６０、
％ＣＮ：２９．８、％ＣＡ:０．４
(2) Hydrorefined crude oil was subjected to atmospheric distillation, the residual oil after fractional distillation was fractionated under reduced pressure, and the resulting distillate oil was purified to paraffin-rich raffinate by a furfural solvent extraction method. Subsequently, the raffinate was subjected to solvent dewaxing treatment with benzoketone, and the resulting dewaxed oil was subjected to high-pressure hydrogenation treatment.
(A-3) Hydrorefined oil 40 ° C. kinematic viscosity: 31 mm 2 / s, density at 15 ° C .: 0.860,
% CN: 29.8,% CA: 0.4
（３）精製鉱油
原油を常圧蒸留し、分留後の残油を減圧下で分留、得られた留出油をフルフラール溶剤抽出法によってパラフィンリッチラフィネートを精製した。つづいてそのラフィネートをベンゾケトンによる溶剤脱ロウ処理をした。以下に、得られた基油（Ａ−４）及び（Ａ−５）の性状を示す。
（Ａ−４）精製鉱油
４０℃動粘度：３３ｍｍ２／ｓ、１５℃における密度：０．８６６
％ＣＮ：２８．０、％ＣＡ：３．６
（Ａ−５）精製鉱油
４０℃動粘度：１００ｍｍ２／ｓ、１５℃における密度：０．８８５
％ＣＮ：２４．４、％ＣＡ：７．７
(3) Refined mineral oil crude oil was subjected to atmospheric distillation, the residual oil after fractional distillation was fractionated under reduced pressure, and the resulting distillate oil was purified to paraffin-rich raffinate by a furfural solvent extraction method. Subsequently, the raffinate was subjected to solvent dewaxing treatment with benzoketone. The properties of the obtained base oils (A-4) and (A-5) are shown below.
(A-4) Refined mineral oil 40 ° C. kinematic viscosity: 33 mm 2 / s, density at 15 ° C .: 0.866
% CN: 28.0,% CA: 3.6
(A-5) Refined mineral oil 40 ° C. kinematic viscosity: 100 mm 2 / s, density at 15 ° C .: 0.885
% CN: 24.4,% CA: 7.7
（Ｂ）粘度指数向上剤
（Ｂ−１） 重量平均分子量が１６，０００、エチレン/プロピレンのモル比が５３：４７であるエチレン/プロピレン共重合体
（Ｂ−２） 重量平均分子量が１０，０００、エチレン/プロピレンのモル比が５３：４７であるエチレン/プロピレン共重合体
（Ｂ−３） 重量平均分子量が２２，０００であるポリメタクリレート
重量平均分子量はゲル浸透クロマトグラフィーにて測定、ポリスチレン換算にて算出した。ゲル浸透クロマトグラフィーはカラムにＳｈｏｄｅｘ ＧＰＣ ＬＦ−８０４を３本、移動層にＴＨＦ、検出器に示差屈折検出器を用いた。
(B) Viscosity index improver (B-1) Ethylene / propylene copolymer (B-2) having a weight average molecular weight of 16,000 and an ethylene / propylene molar ratio of 53:47 The weight average molecular weight is 10,000. An ethylene / propylene copolymer (B-3) having a molar ratio of ethylene / propylene of 53:47 and a polymethacrylate weight average molecular weight of 22,000 is measured by gel permeation chromatography and converted to polystyrene. Calculated. In gel permeation chromatography, three Shodex GPC LF-804 were used for the column, THF was used for the moving layer, and a differential refraction detector was used for the detector.
（Ｃ）極圧剤
（Ｃ−１） 硫化オレフィン（硫黄含有量１９質量％）
（Ｃ−２） アシッドホスフェートのアミン塩
（Ｃ―３） β−ジチオホスホリル化プロピオン酸（一般式（５）の、Ｒ３とＲ４がイソブチル基、Ｒ５がプロピレン基、Ｒ６が水素原子であるもの）
（Ｃ−４） 硫化エステル
（Ｄ）モリブデン化合物
（Ｄ−１） Ｍｏ酸アミン（Ｍｏ量：４．４質量％、モリブデン酸のジトリデシルアミンとの反応物）
(C) Extreme pressure agent (C-1) Sulfurized olefin (sulfur content 19% by mass)
(C-2) Amine salt of acid phosphate (C-3) β-dithiophosphorylated propionic acid (in formula (5), R 3 and R 4 are isobutyl groups, R 5 is a propylene group, R 6 is a hydrogen atom That is)
(C-4) Sulfurized ester (D) Molybdenum compound (D-1) Mo acid amine (Mo content: 4.4% by mass, reaction product of molybdic acid with ditridecylamine)
ＶＧ６８相当の実施例
（実施例１〜６）
基油に粘度指数向上剤、硫黄を含有する極圧剤、その他の添加剤を表３の上段に示す割合（質量％）で配合し、ギヤ油組成物を調製した。それらのギヤ油組成物の各種性能を評価し、その結果を表３の下段に示す。
（比較例１〜６）
基油に粘度指数向上剤、極圧剤、その他の添加剤を表４の上段に示す割合（質量％）で配合し、ギヤ油組成物を調製した。それらのギヤ油組成物の各種性能を評価し、その結果を表４の下段に示す。
Examples corresponding to VG68 (Examples 1 to 6)
A gear oil composition was prepared by blending the base oil with a viscosity index improver, an extreme pressure agent containing sulfur, and other additives in the proportions (mass%) shown in the upper part of Table 3. Various performances of these gear oil compositions were evaluated, and the results are shown in the lower part of Table 3.
(Comparative Examples 1-6)
A gear oil composition was prepared by blending a base oil with a viscosity index improver, an extreme pressure agent, and other additives in the proportions (mass%) shown in the upper part of Table 4. Various performances of these gear oil compositions were evaluated, and the results are shown in the lower part of Table 4.
ＶＧ１００相当の実施例
（実施例７〜１２）
基油に粘度指数向上剤、硫黄を含有する極圧剤、その他の添加剤を表５の上段に示す割合（質量％）で配合し、ギヤ油組成物を調製した。それらのギヤ油組成物の各種性能を評価し、その結果を表５の下段に示す。
（比較例７〜１２）
基油に粘度指数向上剤、極圧剤、その他の添加剤を表６の上段に示す割合（質量％）で配合し、ギヤ油組成物を調製した。それらのギヤ油組成物の各種性能を評価し、その結果を表６の下段に示す。
Examples corresponding to VG100 (Examples 7 to 12)
A gear oil composition was prepared by blending a base oil with a viscosity index improver, an extreme pressure agent containing sulfur, and other additives in the proportions (mass%) shown in the upper part of Table 5. Various performances of these gear oil compositions were evaluated, and the results are shown in the lower part of Table 5.
(Comparative Examples 7-12)
A gear oil composition was prepared by blending the base oil with a viscosity index improver, an extreme pressure agent, and other additives in the proportions (mass%) shown in the upper part of Table 6. Various performances of these gear oil compositions were evaluated, and the results are shown in the lower part of Table 6.
ＶＧ１５０相当の実施例
（実施例１３〜１８）
基油に粘度指数向上剤、硫黄を含有する極圧剤、その他の添加剤を表７の上段に示す割合（質量％）で配合し、ギヤ油組成物を調製した。それらのギヤ油組成物の各種性能を評価し、その結果を表７の下段に示す。
（比較例１３〜１８）
基油に粘度指数向上剤、極圧剤、その他の添加剤を表８の上段に示す割合（質量％）で配合し、ギヤ油組成物を調製した。それらのギヤ油組成物の各種性能を評価し、その結果を表８の下段に示す。
Examples corresponding to VG150 (Examples 13 to 18)
A gear oil composition was prepared by blending the base oil with a viscosity index improver, an extreme pressure agent containing sulfur, and other additives in the proportions (mass%) shown in the upper part of Table 7. Various performances of these gear oil compositions were evaluated, and the results are shown in the lower part of Table 7.
(Comparative Examples 13-18)
A gear oil composition was prepared by blending the base oil with a viscosity index improver, an extreme pressure agent, and other additives in the proportions (mass%) shown in the upper part of Table 8. Various performances of these gear oil compositions were evaluated, and the results are shown in the lower part of Table 8.
ＶＧ２２０相当の実施例
（実施例１９〜２４）
基油に粘度指数向上剤、硫黄を含有する極圧剤、その他の添加剤を表９の上段に示す割合（質量％）で配合し、ギヤ油組成物を調製した。それらのギヤ油組成物の各種性能を評価し、その結果を表９の下段に示す。
（比較例１９〜２４）
基油に粘度指数向上剤、極圧剤、その他の添加剤を表１０の上段に示す割合（質量％）で配合し、ギヤ油組成物を調製した。それらのギヤ油組成物の各種性能を評価し、その結果を表１０の下段に示す。
Examples corresponding to VG220 (Examples 19 to 24)
A gear oil composition was prepared by blending the base oil with a viscosity index improver, an extreme pressure agent containing sulfur, and other additives in the proportions (mass%) shown in the upper part of Table 9. Various performances of these gear oil compositions were evaluated, and the results are shown in the lower part of Table 9.
(Comparative Examples 19-24)
A gear oil composition was prepared by blending the base oil with a viscosity index improver, an extreme pressure agent, and other additives in the proportion (mass%) shown in the upper part of Table 10. Various performances of these gear oil compositions were evaluated, and the results are shown in the lower part of Table 10.
ＶＧ３２０相当の実施例
（実施例２５〜３０）
基油に粘度指数向上剤、硫黄を含有する極圧剤、その他の添加剤を表１１の上段に示す割合（質量％）で配合し、ギヤ油組成物を調製した。それらのギヤ油組成物の各種性能を評価し、その結果を表１１の下段に示す。
（比較例２５〜３０）
基油に粘度指数向上剤、極圧剤、その他の添加剤を表１２の上段に示す割合（質量％）で配合し、ギヤ油組成物を調製した。それらのギヤ油組成物の各種性能を評価し、その結果を表１２の下段に示す。
Examples corresponding to VG320 (Examples 25 to 30)
A gear oil composition was prepared by blending the base oil with a viscosity index improver, an extreme pressure agent containing sulfur, and other additives in the proportions (mass%) shown in the upper part of Table 11. Various performances of these gear oil compositions were evaluated, and the results are shown in the lower part of Table 11.
(Comparative Examples 25-30)
A gear oil composition was prepared by blending a base oil with a viscosity index improver, an extreme pressure agent, and other additives in the proportions (mass%) shown in the upper part of Table 12. Various performances of these gear oil compositions were evaluated, and the results are shown in the lower part of Table 12.
本発明のギヤ油組成物は、ギヤ油を必要とする種々の機械に使用でき、特に、高荷重で運転される機械に好適に使用できる。その機械の具体例としては、産業機械の軸受け歯車、金属加工、特に好ましくは圧延機、搬送用ベルトコンベア、発電所のタービン、建設機械、工作機械、船舶等が挙げられる。 The gear oil composition of the present invention can be used for various machines that require gear oil, and can be particularly suitably used for machines that are operated under high loads. Specific examples of such machines include bearing gears for industrial machines, metal processing, particularly preferably rolling mills, conveyor belt conveyors, power plant turbines, construction machines, machine tools, ships, and the like.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014103426A1 (en) * | 2012-12-28 | 2014-07-03 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition |
| JP2017171768A (en) * | 2016-03-23 | 2017-09-28 | 出光興産株式会社 | Lubricant composition, and lubrication method |
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| US10883064B2 (en) | 2016-03-23 | 2021-01-05 | Idemitsu Kosan Co., Ltd. | Lubricant oil composition and lubrication method |
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