EP1734103A1 - Composition d'huile de lubrification pour machines et équipements industriels - Google Patents

Composition d'huile de lubrification pour machines et équipements industriels Download PDF

Info

Publication number: EP1734103A1
Authority: EP; European Patent Office
Prior art keywords: group; component; carbon atoms; branched; amine
Prior art date: 2004-03-25
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 Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Withdrawn

Application number

EP05727597A

Other languages

German (de)

English (en)

Other versions

EP1734103A4 (fr

Inventor

Katsuya;c/o NIPPON OIL CORPORATION Chi TAKIGAWA

Yukiharu; c/o NIPPON OIL CORPORATION Chido BEPPU

Sinichi; c/o NIPPON OIL CORPORATION Ch MITSUMOTO

Masahiro;c/o NIPPON OIL CORPORATION Chidor HATA

Eiji; c/o NIPPON OIL CORPORATION Chidori AKIYAMA

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Eneos Corp

Original Assignee

Nippon Oil Corp

Priority date (The priority date 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 date listed.)

2004-03-25

Filing date

2005-03-25

Publication date

2006-12-20

2004-03-31 Priority claimed from JP2004108185A external-priority patent/JP2005290227A/ja

2004-03-31 Priority claimed from JP2004108503A external-priority patent/JP2005290235A/ja

2004-03-31 Priority claimed from JP2004106674A external-priority patent/JP2005290183A/ja

2004-03-31 Priority claimed from JP2004132155A external-priority patent/JP4582767B2/ja

2004-03-31 Priority claimed from JP2004108502A external-priority patent/JP4565612B2/ja

2004-03-31 Priority claimed from JP2004106670A external-priority patent/JP2005290182A/ja

2004-03-31 Priority claimed from JP2004108180A external-priority patent/JP4565611B2/ja

2004-03-31 Priority claimed from JP2004106664A external-priority patent/JP2005290181A/ja

2004-03-31 Priority claimed from JP2004108178A external-priority patent/JP4641381B2/ja

2005-03-25 Application filed by Nippon Oil Corp filed Critical Nippon Oil Corp

2006-12-20 Publication of EP1734103A1 publication Critical patent/EP1734103A1/fr

2009-05-06 Publication of EP1734103A4 publication Critical patent/EP1734103A4/fr

Status Withdrawn legal-status Critical Current

Links

239000000203 mixture Substances 0.000 title claims abstract description 386
239000010687 lubricating oil Substances 0.000 title claims abstract description 197
-1 carboxylic acid compound Chemical class 0.000 claims abstract description 384
150000002148 esters Chemical class 0.000 claims abstract description 196
239000002199 base oil Substances 0.000 claims abstract description 162
239000000654 additive Substances 0.000 claims abstract description 125
150000001875 compounds Chemical class 0.000 claims abstract description 112
239000002253 acid Substances 0.000 claims abstract description 69
239000003921 oil Substances 0.000 claims abstract description 68
229910052698 phosphorus Inorganic materials 0.000 claims abstract description 60
239000011574 phosphorus Substances 0.000 claims abstract description 59
OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 56
239000010720 hydraulic oil Substances 0.000 claims abstract description 50
239000012208 gear oil Substances 0.000 claims abstract description 43
239000002270 dispersing agent Substances 0.000 claims abstract description 39
239000002480 mineral oil Substances 0.000 claims abstract description 28
230000000996 additive effect Effects 0.000 claims abstract description 25
239000003925 fat Substances 0.000 claims abstract description 13
125000004432 carbon atom Chemical group C* 0.000 claims description 321
125000000217 alkyl group Chemical group 0.000 claims description 202
235000014113 dietary fatty acids Nutrition 0.000 claims description 77
229930195729 fatty acid Natural products 0.000 claims description 77
239000000194 fatty acid Substances 0.000 claims description 77
150000004665 fatty acids Chemical class 0.000 claims description 74
125000003342 alkenyl group Chemical group 0.000 claims description 59
150000005846 sugar alcohols Polymers 0.000 claims description 56
230000036961 partial effect Effects 0.000 claims description 46
230000032050 esterification Effects 0.000 claims description 38
238000005886 esterification reaction Methods 0.000 claims description 38
150000004671 saturated fatty acids Chemical class 0.000 claims description 28
235000021122 unsaturated fatty acids Nutrition 0.000 claims description 17
239000001257 hydrogen Substances 0.000 claims description 16
229910052739 hydrogen Inorganic materials 0.000 claims description 16
150000004670 unsaturated fatty acids Chemical class 0.000 claims description 15
125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
229910052784 alkaline earth metal Inorganic materials 0.000 claims description 11
229910052783 alkali metal Inorganic materials 0.000 claims description 10
150000001340 alkali metals Chemical class 0.000 claims description 10
150000007513 acids Chemical class 0.000 claims description 8
150000002431 hydrogen Chemical group 0.000 claims description 6
150000001735 carboxylic acids Chemical class 0.000 claims 1
150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 15
230000002349 favourable effect Effects 0.000 abstract 1
238000012360 testing method Methods 0.000 description 192
150000001412 amines Chemical class 0.000 description 157
238000005299 abrasion Methods 0.000 description 93
239000010802 sludge Substances 0.000 description 92
235000019198 oils Nutrition 0.000 description 64
PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 53
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 51
230000000694 effects Effects 0.000 description 51
RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 49
235000010354 butylated hydroxytoluene Nutrition 0.000 description 45
101000823778 Homo sapiens Y-box-binding protein 2 Proteins 0.000 description 43
238000013112 stability test Methods 0.000 description 41
229910052717 sulfur Inorganic materials 0.000 description 35
QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 33
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 33
125000004435 hydrogen atom Chemical group [H]* 0.000 description 33
230000003647 oxidation Effects 0.000 description 33
238000007254 oxidation reaction Methods 0.000 description 33
125000002947 alkylene group Chemical group 0.000 description 32
150000002430 hydrocarbons Chemical group 0.000 description 31
235000011187 glycerol Nutrition 0.000 description 30
125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 30
NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 29
239000011593 sulfur Substances 0.000 description 29
XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 28
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
125000003118 aryl group Chemical group 0.000 description 25
239000003054 catalyst Substances 0.000 description 24
AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 23
AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 23
229920001577 copolymer Polymers 0.000 description 23
238000011156 evaluation Methods 0.000 description 23
238000001556 precipitation Methods 0.000 description 23
LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 22
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 22
125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 22
NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 21
239000003963 antioxidant agent Substances 0.000 description 21
230000003078 antioxidant effect Effects 0.000 description 21
238000005096 rolling process Methods 0.000 description 21
VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 20
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 20
239000002904 solvent Substances 0.000 description 20
DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 19
239000002173 cutting fluid Substances 0.000 description 19
235000010446 mineral oil Nutrition 0.000 description 19
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 18
125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 18
239000004593 Epoxy Substances 0.000 description 17
125000002877 alkyl aryl group Chemical group 0.000 description 17
125000002958 pentadecyl 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])[H] 0.000 description 17
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 16
125000000753 cycloalkyl group Chemical group 0.000 description 16
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 16
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 16
ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 16
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 16
WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 16
QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 16
WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 15
LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 15
QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 15
239000005642 Oleic acid Substances 0.000 description 15
ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 15
239000003795 chemical substances by application Substances 0.000 description 15
QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 15
235000021313 oleic acid Nutrition 0.000 description 15
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 15
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 15
YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 14
125000003710 aryl alkyl group Chemical group 0.000 description 14
229910052742 iron Inorganic materials 0.000 description 14
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 14
125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 14
VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 13
RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
229910052802 copper Inorganic materials 0.000 description 13
239000010949 copper Substances 0.000 description 13
VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
235000011007 phosphoric acid Nutrition 0.000 description 13
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 13
238000003860 storage Methods 0.000 description 13
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 13
JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 12
TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 12
DIOYAVUHUXAUPX-ZHACJKMWSA-N 2-[methyl-[(e)-octadec-9-enoyl]amino]acetic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)N(C)CC(O)=O DIOYAVUHUXAUPX-ZHACJKMWSA-N 0.000 description 12
CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 12
FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 12
229910000147 aluminium phosphate Inorganic materials 0.000 description 12
125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 12
125000002960 margaryl 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])[H] 0.000 description 12
239000000178 monomer Substances 0.000 description 12
125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 12
238000010998 test method Methods 0.000 description 12
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 11
FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 11
235000011054 acetic acid Nutrition 0.000 description 11
125000001931 aliphatic group Chemical group 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 11
125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 11
235000019197 fats Nutrition 0.000 description 11
238000000034 method Methods 0.000 description 11
NGZUTZZGGAXKTO-UHFFFAOYSA-N nonyl 2-phenoxyacetate Chemical compound CCCCCCCCCOC(=O)COC1=CC=CC=C1 NGZUTZZGGAXKTO-UHFFFAOYSA-N 0.000 description 11
229920005862 polyol Polymers 0.000 description 11
125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 11
239000000600 sorbitol Substances 0.000 description 11
MGEQSWVPSCZGEK-UHFFFAOYSA-N 2,5-bis(nonyldisulfanyl)-1,3,4-thiadiazole Chemical compound CCCCCCCCCSSC1=NN=C(SSCCCCCCCCC)S1 MGEQSWVPSCZGEK-UHFFFAOYSA-N 0.000 description 10
238000010586 diagram Methods 0.000 description 10
SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 10
IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 10
HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 10
150000007519 polyprotic acids Polymers 0.000 description 10
IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 10
150000003839 salts Chemical class 0.000 description 10
MNZNJOQNLFEAKG-UHFFFAOYSA-N 2-morpholin-4-ylethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCN1CCOCC1 MNZNJOQNLFEAKG-UHFFFAOYSA-N 0.000 description 9
229910001018 Cast iron Inorganic materials 0.000 description 9
ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 9
150000001336 alkenes Chemical class 0.000 description 9
125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 9
125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 9
125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
150000001298 alcohols Chemical class 0.000 description 8
125000005119 alkyl cycloalkyl group Chemical group 0.000 description 8
150000001408 amides Chemical class 0.000 description 8
MIXQWVIPHYLBHL-UHFFFAOYSA-N benzamido 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ONC(=O)C1=CC=CC=C1 MIXQWVIPHYLBHL-UHFFFAOYSA-N 0.000 description 8
125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 8
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 8
229940105990 diglycerin Drugs 0.000 description 8
GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 8
POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 8
229910052751 metal Inorganic materials 0.000 description 8
239000002184 metal Substances 0.000 description 8
125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 8
OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 8
150000003014 phosphoric acid esters Chemical class 0.000 description 8
125000004434 sulfur atom Chemical group 0.000 description 8
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Classifications

- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
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- C10N2040/20—Metal working
- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling

Definitions

the present invention relates to a novel lubricative composition for industrial machinery and equipment, more specifically, to a lubricating oil composition with excellent lubricative characteristics such as the abrasion resistance, the extreme pressure property, the frictional property and the like, as well as excellent in characteristics required according to the use of industrial machinery and equipment, and even more specifically, to a gear oil composition, a lubricating oil composition for paper machines, a lubricating oil composition for slide guides and a hydraulic oil.
the gear oil composition is excellent in the sludge resistance and the extreme pressure property
the lubricating oil composition for paper machines is excellent in the sludge resistance and the extreme pressure property
the lubricating oil composition for slide guides is excellent in both aspects of the frictional property and the anti-stick-slip property
the hydraulic oil is excellent in all the sludge suppression property, the abrasion resistance and the frictional property.
Patent Document 1 JP-A No. 10-259394
Patent Document 2 JP-ANo. 9-208976
the conventional gear oil when used in the gear of the recent industrial machines, was not always sufficient in the sludge resistance and the extreme pressure property. That is, for the use required to have high extreme pressure property and abrasion resistance, a lubricating oil added with the extreme pressure agent such as zinc dialkyldithiophosphate is widely used, but even if these conventional extreme pressure agents are added in small amount, thermal load is increased and a great amount of sludge is generated, and there is tendency to lower thermal and oxidation stability. Therefore, it is difficult for the lubricating oil added with the sulfur-based extreme pressure agent to reach sufficient thermal and oxidation stability in the gear of the recent industrial machines. Meanwhile, the phosphorus-based extreme pressure agent has tendency not to generate sludge easily compared with the sulfur-based extreme pressure agent, but when the phosphorus-based extreme pressure agent is used alone, it is difficult to obtain high extreme pressure property in the gear oil level.
the extreme pressure agent such as zinc dialkyldithiophosphate
the anti-stick-slip property for example, using the lubricating oil composition which combined a sulfur compound or ester and fatty acid (e.g. see Patent Document 4 ( JP-A No. 57-67693 )), the lubricating oil composition which combined a sulfur compound and an amine salt of phosphorus compound (e.g., see Patent Document 5 ( JP-ANo. 51-74005 )), and the like are suggested.
Patent Document 4 JP-A No. 57-67693
Patent Document 5 JP-ANo. 51-74005
the frictional property for example, using the lubricating oil composition which combined acidic phosphoric acid ester or its alkyl ammonium salt, phosphorus acid, fatty acid and a straight-chained alkylamine (e.g., see Patent Document 6 (JP-ANo. 8-134488)), the lubricating oil composition for slide guides which used phosphorus compound (e.g. see Patent Document 7 ( JP-A No. 8-209175 )), the lubricating oil for operation machines which combined glycerin ether compounds and phosphoric acid esters or their amine salts (e.g. see Patent Document 8 ( JP-A No. 11-209775 )), and the like are suggested.
Patent Document 6 JP-ANo. 8-134488
Patent Document 7 JP-A No. 8-209175
Patent Document 8 JP-A No. 11-209775
the hydraulic system has became highly efficient, and in order to carry out high speed and highly precise control, a case for controlling the flow amount and direction of the hydraulic system by a valve such as a spool valve, and a case installing a servo valve has been increased.
the performance of such the spool valve or servo valve may be deteriorated to the great extent if sludge is generated in the hydraulic oil, thus the hydraulic oil used in the recent highly efficient system is strongly required to be a sludgeless hydraulic oil which does not generate sludge, in addition to have an excellent abrasive resistance.
a zinc-based abrasion resistant such as zinc dithiophosphate (ZnDTP)
ZnDTP zinc dithiophosphate
the abrasion resisting effect by using ZnDTP or the like may form rigid film such as iron phosphate on the surface of the metal, and by such film formation, the frictional index of the sliding part is increased, thus it is said to be not preferable in the viewpoint of energy-saving.
non-zinc-based hydraulic oil obtained by combining non-zinc-based abrasion resistant such as aromatic phosphoric ester, phosphorus acid ester and its amine salt, thiophosphate and ⁇ -dithiophosphorylated propionic acid compound is suggested instead of ZnDTP as a purpose to secure the sludge resistance and the abrasion resistance (e.g., see Patent Document 9 ( JP-A No. 10-67993 ), Patent Document 10 ( JP-A No. 11-217577 ) and Patent Document 11( JP-A No. 2002-265971 )).
Patent Document 9 JP-A No. 10-67993
Patent Document 10 JP-A No. 11-217577
Patent Document 11 JP-A No. 2002-265971
the first aspect of the present invention provides a lubricative composition for industrial machinery and equipment which comprises a base oil selected from mineral oils, fats and oils, synthetic oils and mixtures of two or more of them, and at least one additive selected from the following components (A) to (D):
the second aspect of the invention provides the lubricative composition in the first aspect of the invention as a gear oil composition, wherein at least one kind of the additive is selected from the component (A) to component (C).
the gear oil composition is excellent in the sludge resistance and the extreme pressure property.
the third aspect of the invention provides the lubricative composition in the first aspect of the invention as a lubricating oil composition for paper machines, wherein the additive is at least one selected from the component (A) to component (C).
the lubricating oil composition for paper machines is excellent in the sludge resistance and the extreme pressure property.
the fourth aspect of the invention provides the lubricative composition in the first aspect of the invention as a lubricating oil composition for slide guides, wherein the additive is at least one selected from the component (A) to component (C).
the lubricating oil composition for slide guides is excellent in both aspects of the frictional property and the anti-stick-slip property.
the fifth aspect of the invention provides the lubricative composition in the first aspect of the invention as a lubricating oil composition, wherein the additive comprises the phosphorus-containing carboxylic acid compound of the component (A-1) and the dispersant viscosity index improver of the component (B).
the sixth aspect of the invention provides the lubricative composition in the first aspect of the invention as a lubricating oil composition, wherein the additive comprises the thiophosphoric ester of the component (A-2) and the dispersant viscosity index improver of the component (B).
the seventh aspect of the invention provides the lubricative composition in the first aspect of the invention as a lubricating oil composition, wherein the additive comprises the ester oiliness improver of the component (D) which is an ester of a polyhydric alcohol and a fatty acid of monobasic acids.
the additive comprises the ester oiliness improver of the component (D) which is an ester of a polyhydric alcohol and a fatty acid of monobasic acids.
the eighth aspect of the invention provides the lubricative composition in the seventh aspect of the invention, wherein the ester oiliness improver of the component (D) which is an ester of a polyhydric alcohol and a fatty acid of monobasic acids is any one selected from the following esters of (D-1) to (D-3):
the ninth aspect of the invention provides the lubricative composition in the eighth aspect of the invention, wherein the lubricating oil composition is a hydraulic oil.
the hydraulic oil is excellent in all the sludge suppression property, the abrasion resistance and the frictional property.
a lubricative composition of the present invention at least one kind selected among mineral oils, fats and oils, and synthetic oils are used as a base oil.
examples of mineral oils may include paraffinic, naphthenic or the like mineral oil obtained by subjecting a lubricating oil distillate, which was obtained by the normal pressure distillation or the reduced pressure distillation of a crude oil, to suitably combined one kind or two or more kinds of refining means such as solvent deasphalting, solvent extraction, hydrogenolysis, solvent dewaxing, contact dewaxing, hydorefming, sulfuric acid washing, white clay treatment and the like.
a wax isomeric base oil a base oil prepared by the means of isomerization of GTL WAX (Gas-to-liquid Wax) can be also used.
examples of fats and oils include a tallow, a lard, a sunflower oil, a soybean oil, a canola oil, a rice bran oil, a coconut oil, a palm oil, palm kernel oil, or hydrogen additives thereof, and the like.
examples of synthetic oils include poly- ⁇ -olefm (ethylene-propylene copolymer, polybutene, 1-octene oligomer, 1-decene oligomer and hydrides thereof), alkyl benzene, alkyl naphthalene, monoester (butyl stearate, octyl laurate), diester (di-tridecyl glutarate, di-2-ethylhexyl adipate, di-isodecyladipate, di-tridecyl adipate, di-2-ethylhexyl sebacate, etc.), polyester (trimellitic acid ester, etc.), polyol ester (trimethylolpropane caprylate, trimethylolpropane peralgonate, pentaerythritol-2-ethyl hexanoate, pentaerythritol peralgonate, etc.), polyoxyalkylene glyco
mineral oils poly- ⁇ -olefm, polyol ester, polyoxyalkylene glycol are preferred.
the above-mentioned base oil may be used alone or in combination of two or more.
the kinematic viscosity of these base oils is arbitrary and not particularly limited, but the minimum value of the kinematic viscosity at 40°C in the aspect of pitch resistance is 10 mm 2 /s or higher, preferably 20 mm 2 /s or higher , more preferably 40 mm 2 /s or higher and most preferably 60 mm 2 /s or higher.
the maximum value thereof in the point of small friction loss by agitation resistance is 10000 mm 2 /s or less, preferably 5000 mm 2 /s or less and more preferably 1000 mm 2 /s or less.
the viscosity index of the base oil is also arbitrary, but in the point of inhibiting oil film degradation in high temperatures, the minimum value of the viscosity index is 80 or higher, preferably 90 or higher, and in general, the value is 500 or less.
the flow point is also arbitrary, but in the point of low temperature property, the flow point, in general, is preferably -5°C or lower and more preferably -15°C or lower.
At least one kind of additive selected from the components (A) to (D) is mixed with the base oil.
the component (A) is (A-1) a phosphorus-containing carboxylic acid compound, (A-2) a thiophosphoic acid ester or a mixture thereof.
the compound may have both carboxyl group and phosphorus atom in the same molecule, and its structure is not particularly limited. However, in the point of extreme pressure property and thermo-oxidative stability, phosphorylated carboxylic acid is preferred.
Examples of phosphorylated carboxylic acid include the compounds represented by the following formula (6). wherein R 5 and R 6 may be identical with or different from each other, and they are each independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, R 7 is an alkylene group having 1 to 20 carbon atoms, R 8 is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and X 1 , X 2 , X 3 and X 4 may be identical with or different from each other, and they are each independently an oxygen atom or a sulfur atom.
R 5 and R 6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group, an alkenyl group, a cycloalkyl group, a bicycloalkyl group, a tricycloalkyl group, an alkylcycloalkyl group, an alkylbicycloalkyl group, an alkyltricycloalkyl group, a cycloalkylalkyl group, a bicycloalkylalkyl group, a tricycloalkylalkyl group, an aryl group, an alkylaryl group, an arylalkyl group and the like.
R 5 and R 6 may be bonded to each other to form a divalent group represented by the following formula (7). Two bonds of the divalent group are bonded with X 1 and X 2 respectively.
R 9 and R 10 may be identical with or different from each other, and they are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and, both of R 9 and R 10 being a methyl group is preferred.
R 5 and R 6 an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, tricycloalkylalkyl group, an aryl group, an alkylaryl group, a divalent group represented by the formula (7) bonded with R 9 and R 10 are preferred, and an alkyl group is more preferred.
An alkyl group as R 5 and R 6 may be any one of straight-chained or branched, and the alkyl group having 1 to 18 carbon atoms is preferred.
Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, a 3-heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a h
Examples of the cycloalkyl group as R 5 and R 6 include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecyl group and the like.
a cycloalkyl group having 5 or 6 carbon atoms is preferred, and a cyclohexyl group is particularly preferred.
a cycloalkylmethyl group is preferred, a cycloalkylmethyl group having 6 or 7 carbon atoms is more preferred, and a cyclopentylmethyl group and a cyclohexylmethyl group are particularly preferred.
bicycloalkylalkyl group as R 5 and R 6 , a bicycloalkylmethyl group is preferred, a bicycloalkylmethyl group having 9 to 11 carbon atoms is more preferred, and a decalinylmethyl group is particularly preferred.
a tricycloalkylmethyl group is preferred, a tricycloalkylmethyl group having 9 to 15 carbon atoms is more preferred, and a group represented by the following formula (8) or (9) is particularly preferred.
Examples of the aryl group and the alkylaryl group as R 5 and R 6 include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a vinylphenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, an isopropylphenyl group, a tert-butylphenyl group, a di-tert-butylphenyl group, 2,6-di-tert-butyl-4-methylphenyl group and the like.
an aryl group and an alkylaryl group having 6 to 15 carbon atoms are preferred.
R 7 is an alkylene group having 1 to 20 carbon atoms.
the carbon numbers of such an alkylene group is preferably 1 to 10, more preferably 2 to 6, and even more preferably 3 to 4. Further, for such an alkylene group, a group represented by the following formula (10) is preferred.
R 11 , R 12 , R 13 and R 14 may be identical with or different from each other and are each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and the total carbon number of R 11 , R 12 , R 13 and R 14 is 6 or lower.
R 11 , R 12 , R 13 and R 14 may be identical with or different from each other and are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and the total carbon number of R 11 , R 12 , R 13 and R 14 is 5 or lower. More preferably, R 11 , R 12 , R 13 and R 14 may be identical with or different from each other and are each independently a hydrogen atom or a hydrocarbon group having 1 or 2 carbon atoms, and the total carbon number of R 11 , R 12 , R 13 and R 14 is 4 or lower.
R 11 , R 12 , R 13 and R 14 may be identical with or different from each other and are each independently a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and the total carbon number of R 11 , R 12 , R 13 and R 14 is 3 or lower. Most preferably, R 13 and R 14 are each independently a methyl group, and the remaining 3 groups are hydrogen atoms.
R 8 is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
Examples of such a hydrocarbon group include the hydrocarbon group exemplified in the description of R 5 and R 6 .
X 2 , X 3 , X 4 and X 5 may be identical or different from each other and are each independently an oxygen atom or a sulfur atom.
one or more among X 2 , X 3 , X 4 and X 5 is preferably a sulfur atom, two or more is more preferably a sulfur atom, and two among X 2 , X 3 , X 4 and X 5 being sulfur atoms and the remaining two being oxygen atoms is even more preferred.
any among X 2 , X 3 , X 4 and X 5 being a sulfur atom is arbitrary, but X 2 and X 3 being oxygen atoms and X 4 and X 5 being sulfur atoms is preferred.
⁇ -dithiophosphorylpropionic acid represented by the following formula (11) is preferably used.
R 5 and R 6 each independently have the same definition as R 5 and R 6 in the formula (6)
R 11 , R 12 , R 13 and R 14 each independently have the same definition as R 11 , R 12 , R 13 and R 14 in the formula (10).
(A-2) Thiophosphoric ester according to the invention is a compound represented by the following formula (12): wherein R 15 to R 17 may be identical with or different from each other and are each independently a hydrocarbon group having 1 to 24 carbon atoms.
Examples of the hydrocarbon group having 1 to 24 carbon atoms represented by R 15 to R 17 include an alkyl group, a cycloalkyl group, an alkenyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, an arylalkyl group and the like.
alkyl group examples include alkyl groups (wherein the alkyl group may be straight-chained or branched) such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group.
alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group
Examples of the cycloalkyl group include cycloalkyl groups having 5 to 7 carbon atoms such as a cyclopentyl group, a cyclohexyl group and a cycloheptyl group.
examples of the alkylcycloalkyl group include alkylcycloalkyl groups having 6 to 11 carbon atoms (wherein the substitution site of an alkyl group in the cycloalkyl group is arbitrary) such as a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a diethylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylethylcyclohexyl group, a diethylcyclohexyl group, a methylcycloheptyl group, a dimethylcycloheptyl group, a methylethy
alkenyl group examples include alkenyl groups (wherein the alkenyl group may be straight-chained or branched, and the position of the double bond is arbitrary) such as a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group and an octadecenyl group.
alkenyl groups such as a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group,
Examples of the aryl group include aryl groups such as a phenyl group, a naphthyl group.
examples of the alkylaryl group include alkylaryl groups having 7 to 18 carbon atoms (wherein the alkyl group may be straight-chained or branched, and the substitution site in the aryl group is arbitrary) such as a tolyl group, a xylyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, a nonylphenyl group, a decylphenyl group, an undecylphenyl group and a dodecylphenyl group.
arylalkyl group examples include arylalkyl groups having 7 to 12 carbon atoms (wherein the alkyl group may be straight-chained or branched) such as a benzyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group and a phenylhexyl group.
the hydrocarbon group having 1 to 24 carbon atoms represented by R 15 to R 17 is preferably an alkyl group, an aryl group and an alkylaryl group, and more preferably an alkyl group having 4 to 18 carbon atoms, an alkylaryl group having 7 to 24 carbon atoms and a phenyl group.
thiophosphoric ester represented by the formula (12) include tributyl phosphorothionate, tripentyl phosphorothionate, trihexyl phosphorothionate, triheptyl phosphorothionate, trioctyl phosphorothionate, trinonyl phosphorothionate, tridecyl phosphorothionate, triundecyl phosphorothionate, tridodecyl phosphorothionate, tri-tridecyl phosphorothionate, tritetradecyl phosphorothionate, tripentadecyl phosphorothionate, trihexadecyl phosphorothionate, triheptadecyl phosphorothionate, trioctadecyl phosphorothionate, trioleyl phosphorothionate, triphenyl phosphorothionate, tricresyl phosphorothionate, trixyleny
the (A-1) phosphorus-containing carboxylic acid compound or (A-2) thiophosphoric ester alone, or both of them in combination can be used.
the component (B) in the lubricative composition of the invention is a dispersant viscosity index improver.
the dispersant viscosity index improver an arbitrary compound used as a dispersant viscosity index improver of a lubricating oil can be used, but specific examples include a copolymer obtained by copolymerizing (B-1) a monomer of one kind or two or more kinds selected from compounds represented by the following formulas (13), (14) and (15) and (B-2) a nitrogen-containing monomer of one kind or two or more kinds selected from compounds represented by the following formulas (16) and (17), a hydride thereof, and the like.
Y 4 each independently, specific examples include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an anilino group a toluidino group a xylidino group an acetylamino group (CH 3 CONH-), a benzoylamino group a morpholino group a pyrrolyl group a pyrrolino group a pyridyl group a methylpyridyl group a pyrrolidinyl group a piperidinyl group a quinonyl group a pyrrolidonyl group a pyrrolidono group an imidazolino group a pyrazino group and the like.
Y 5 each independently, specific examples include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, an anilino group a toluidino group a xylidino group an acetylamino group (CH 3 CONH-), a benzoylamino group a morpholino group a pyrrolyl group a pyrrolino group a pyridyl group a methylpyridyl group a pyrrolidinyl group a piperidinyl group a quinonyl group a pyrrolidonyl group a pyrrolidono group an imidazolino group a pyrazino group and the like.
R 18 and R 20 are each independently a hydrogen atom or a methyl group
R 19 is an alkyl group having 1 to 18 carbon atoms
R 21 is a hydrocarbon group having 1 to 12 carbon atoms
Y 2 and Y 3 is each independently a hydrogen atom, a remaining group of alkylalcohol having 1 to 18 carbon atoms
-OR 25 R 25 is an alkyl group having 1 to 18 carbon atoms
a remaining group of monoalkylamine having 1 to 18 carbon atoms (-NHR 26 :
R 26 is an alkyl group having 1 to 18 carbon atoms, respectively.
alkyl group having 1 to 18 carbon atoms represented by R 19 , R 25 and R 26 each independently include alkyl groups (wherein the alkyl group may be straight-chained or branched) such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group.
alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a penty
R 21 include alkyl groups (wherein the alkyl group may be straight-chained or branched) such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group; alkenyl groups (wherein the alkenyl group may be straight-chained or branched) such as a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group and a dodecenyl group; cycloalkyl groups having 5 to 7 carbon atoms such as a cycloal
the monomer of the component (B-1) preferably include alkyl acrylate having 1 to 18 carbon atoms, alkyl methacrylate having 1 to 18 carbon atoms, olefm having 2 to 20 carbon atoms, styrene, methylstyrene, anhydrous maleic acid ester, anhydrous maleic acid amide, and mixtures thereof, and the like.
a monomer represented by the formula (13) for example, alkyl (meth)acrylate having 1 to 18 carbon atoms of the alkyl group is mentioned.
R 22 and R 24 in the formulas (16) and (17) as the component (B-2), are each independently a hydrogen atom or a methyl group, R 23 is an alkylene group having 2 to 18 carbon atoms, and a is an integer of 0 or 1.
Y 4 and Y 5 are each independently a nitrogen-containing organic group having 1 to 30 carbon atoms.
a group having a ring is preferred, and the group having an aliphatic ring than that having an aromatic ring as the ring is more preferred.
a group having a 6-membered ring is preferred in the point of the sludge resistance.
a group having an oxygen atom-containing ring is preferred in the point of the sludge resistance.
Y 4 and Y 5 a group having one nitrogen atom is preferred.
a morpholino group is most preferred in the point of the sludge resistnace.
R 23 include alkylene groups (wherein the alkylene group may be straight-chained or branched) such as an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group and an octadecylene.
alkylene groups such as an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decy
a monomer represented by the formula (16) is preferred in the point of the sludge resistance.
Specific examples thereof include, dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methyl-5-vinyl pyridine, morpholinomethyl methacrylate, morpholinoethyl methacrylate, and mixtures thereof, and the like.
the dispersant viscosity index improver as the component (B) means a copolymer which has, as a comonomer, a nitrogen-containing monomer such as the component (B-2).
the dispersant viscosity index improver as the component (B) can be obtained by copolymerizing one kind or two or more kinds of monomer selected among the component (B-1) and one kind or two or more kinds of nitrogen-containing monomer selected among the component (B-2).
the copolymerization molar ratio of the component (B-1) and the component (B-2) is arbitrary, but, in general, about 80:20 to 95:5.
the copolymerization method such copolymers are generally obtained with ease by radical-solution polymerization of components (B-1) with components (B-2) in the presence of a polymerization initiator such as benzoyl peroxide.
a polymerization initiator such as benzoyl peroxide.
the number average molecular weight of the dispersant viscosity index improver as the component (B) is arbitrary, but, in general, the number average molecular weight of 1,000 to 1,500,000, and preferably 10,000 to 200,000 can be desirably used.
the component (C-1) is at least one kind of a compound represented by the following formulas (1) to (3) as mentioned above.
R 1 -CO-NR 2 -(CH 2 ) n -COOX 1 (1) wherein R 1 is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R 2 is an alkyl group having 1 to 4 carbon atoms, X 1 is hydrogen, an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 1 to 30 carbon atoms, and n is an integer of 1 to 4, [R 1 -CO-NR 2 -(CH 2 ) n -COO] m Y 1 (2) wherein R 1 is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R 2 is an alkyl group having 1 to 4 carbon atoms, Y 1 is an alkali metal or an alkali earth metal, n is an integer of 1
R 1 is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms.
the group is an alkyl group or an alkenyl group having 6 or more carbon atoms, preferably 7 or more carbon atoms, and more preferably 8 or more carbon atoms.
the group is an alkyl group or an alkenyl group having 30 or less carbon atoms, preferably 24 or less carbon atoms, and more preferably 20 or less carbon atoms.
alkyl group or the alkenyl group include alkyl groups (wherein the alkyl group may be straight-chained or branched) such as a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and an icosyl group; alkenyl groups (wherein the alkenyl group may be straight-chained or branched, and the position of the double bond is arbitrary) such as a hexenyl group, a heptenyl group, an octenyl group, a
R 2 is an alkyl group having 1 to 4 carbon atoms.
the group is an alkyl group having 4 or less carbon atoms, preferably 3 or less carbon atoms, and more preferably 2 or less carbon atoms.
n is an integer of 1 to 4. On the point of the storage stability, it is necessary that n is an integer of 4 or less, preferably 3 or less, and more preferably 2 or less.
X 1 is hydrogen, an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 1 to 30 carbon atoms.
X 1 represents an alkyl group or an alkenyl group, in the point of storage stability, it is necessary that the groups have 30 or less carbon atoms, preferably 20 or less carbon atoms, and more preferably 10 or less carbon atoms.
alkyl group or the alkenyl group include alkyl groups (wherein the alkyl group may be straight-chained or branched) such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group; alkenyl groups (wherein the alkenyl group may be straight-chained or branched, and the position of the double bond is arbitrary) such as an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group and a decenyl group; and the like.
an alkyl group is preferred.
X 1 in the point of improving the frictional property, improving persistent effect of the frictional property or the like, hydrogen, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 1 to 20 carbon atoms is preferred; hydrogen or an alkyl group having 1 to 20 carbon atoms is more preferred; and hydrogen or an alkyl group having 1 to 10 carbon atoms is even more preferred.
Y 1 is an alkali metal or an alkali earth metal, and specific examples include sodium, potassium, magnesium, calcium and the like. Among these, in the point of improving persistent effect of the frictional property, an alkali earth metal is preferred.
m is 1 when Y 1 is an alkali metal and 2 when Y 1 is an alkali earth metal.
Z is a residue having a hydroxyl group removed from a polyhydric alcohol with two or more valences.
the polyhydric alcohol include dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butandiol, 1,2-butandiol, neopentyl glycol, 1,6-hexandiol, 1,2-octandiol, 1,8-octandiol, isoprene glycol, 3-methyl-1,5-pentandiol, sorbite, catechol, resorcin, hydroxynone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F and dimmer diol; trihydric alcohols such as glycerin, 2-(hydroxymethyl)-1,3-propandiol, 1,2,3-butantriol, 1,2,3-pentantriol, 2-methyl-1,2,3-propantriol, 2-methyl-2,3,4-butantriol, 2-
m is an integer of 1 or more
m' is an integer of 0 or more
m + m' is the same as a valence number of Z. That is, among hydroxyl groups of the polyhydric alcohol of Z, all of them may be substituted or a part of them may be substituted.
the component (C-1) is at least a compound selected from the formulas (1) to (3), but in the point of improving persistent effect of the frictional property, at least a compound selected from the formulas (1) and (2).
at least a compound selected from the formulas (1) to (3) may be used alone or used in a mixture of two or more compounds.
N-oleoyl sarcosine may be mentioned, wherein R 1 is an alkenyl group having 17 carbon atoms, R 2 is a methyl group, X 1 is hydrogen and n is 1.
the component (C-2) is a compound represented by the following formula (4).
R 3 -CH 2 COOH (4) wherein R 3 is an alkyl group having 7 to 29 carbon atoms, an alkenyl group having 7 to 29 carbon atoms or a group represented by the formula (5).
R 4 -C 6 H 4 O- (5) wherein R 4 is an alkyl group having 1 to 20 carbon atoms or hydrogen.
R 3 is an alkyl group having 7 to 29 carbon atoms, an alkenyl group having 7 to 29 carbon atoms or a group represented by the formula (5).
R 3 represents an alkyl group
the alkyl group has 7 or more carbon atoms, and preferably 9 or more carbon atoms.
the alkyl group has 29 or less carbon atoms, preferably 22 or less carbon atoms, and more preferably 19 or less carbon atoms.
alkyl group examples include a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and the like (wherein the alkyl group may be straight-chained or branched).
R 3 represents an alkenyl group
the alkenyl group has 7 to 29 carbon atoms.
the alkenyl group has 7 or more carbon atoms, and preferably 9 or more carbon atoms.
the alkenyl group has 29 or less carbon atoms, preferably 22 or less carbon atoms, and more preferably 19 or less carbon atoms.
alkenyl group examples include a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group and the like (wherein the alkenyl group may be straight-chained or branched).
R 4 is an alkyl group having 1 to 20 carbon atoms or hydrogen.
R 4 is an alkyl group, in the point of the storage stability or the like, it is necessary that the alkyl group has 20 or less carbon atoms, preferably 19 or less carbon atoms, and more preferably 15 or less carbon atoms.
the alkyl group has 3 or more carbon atoms, and more preferably 5 or more carbon atoms.
R 4 is an alkyl group
its substitution site is arbitrary, but in the point of excelling in improving effect of the frictional property, the para position or the meta position is preferred, and the para position is more preferred.
R 3 may be an alkyl group having 7 to 29 carbon atoms, an alkenyl group having 7 to 29 carbon atoms or a group represented by the formula (5) as described above, but in the point of excelling in the frictional property or the like, a group represented by the formula (5) is preferred.
an ester oiliness improver as the component (D) is added.
the ester oiliness improver as the component (D) can be obtained by reacting alcohol with carboxylic acid.
an alcohol a monohydric alcohol as well as a polyhydric alcohol may be used.
a carboxylic acid a monobasic acid as well as a polybasic acid may be used.
the one having 1 to 24 carbon atoms preferably 1 to 12, and more preferably 1 to 8 can be used.
Such an alcohol may be straight-chained or branched, and may be saturated or unsaturated.
alcohol having 1 to 24 carbon atoms include methanol, ethanol, straight-chained or branched propanol, straight-chained or branched butanol, straight-chained or branched pentanol, straight-chained or branched hexanol, straight-chained or branched heptanol, straight-chained or branched octanol, straight-chained or branched nonanol, straight-chained or branched decanol, straight-chained or branched undecanol, straight-chained or branched dodecanol, straight-chained or branched tridecanol, straight-chained or branched tetradecanol, straight-chained or branched pentadecanol, straight-chained or branched hexadecanol, straight-chained or branched heptadecanol,
polyhydric alcohol composing the ester oiliness improver in general, 2 to 10, preferably 2 to 6 valent alcohol can be used.
specific examples of the polyhydric alcohol of 2 to 10 valences include dihydric alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol (3 to 15-meric ethylene glycol), propylene glycol, dipropylene glycol, polypropylene glycol (3 to 15-meric propylene glycol), 1,3-propandiol, 1,2-propandiol, 1,3-butandiol, 1,4-butandiol, 2-methyl-1,2-propandiol, 2-methyl-1,3-propandiol, 1,2-pentandiol, 1,3-pentandiol, 1,4-pentandiol, 1,5-pentandiol and neopentyl glycol; polyhydric alcohols such as glycerin, polyglycerin (2 to 8-meric glycerin, e.g., dig
polyhydric alcohols of 2 to 6 valences such as ethylene glycol, diethylene glycol, polyethylene glycol (3 to 10-meric ethylene glycol), propylene glycol, dipropylene glycol, polypropylene glycol (3 to 10-meric propylene glycol), 1,3-propandiol, 2-methyl-1,2-propandiol, 2-methyl-1,3-propandiol, neopentyl glycol, glycerin, diglycerin, triglycerin, trimethylol alkane (trimethylol ethane, trimethylol propane, trimethylol butane, etc.) and 2 to 4-mers thereof, pentaerythritol, dipentaerythritol, 1,2,4-butantriol, 1,3,5-pentantriol, 1,2,6-hexantriol, 1,2,3,4-butantetrol, sorbitol, sorbitan, sorbitol glycerin conden
ethylene glycol propylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitan and mixtures thereof, and glycerin is particularly preferred.
the alcohol composing the ester oiliness improver in the component (D) of the invention may be a monohydric alcohol or a polyhydric alcohol, as mentioned above. However, in the point of excelling in the frictional property, a polyhydric alcohol is preferred.
an aliphatic acid having 1 to 24 carbon atoms in general can be used as a monobasic acid.
Such the aliphatic acid may be straight-chained or branched, and may be saturated or unsaturated.
saturated aliphatic acids such as formic acid, acetic acid, propionic acid, straight-chained or branched butanoic acid, straight-chained or branched pentanoic acid, straight-chained or branched hexanoic acid, straight-chained or branched heptanoic acid, straight-chained or branched octanoic acid, straight-chained or branched nonanoic acid, straight-chained or branched decanoic acid, straight-chained or branched undecanoic acid, straight-chained or branched dodecanoic acid, straight-chained or branched tridecanoic acid, straight-chained or branched tetradecanoic acid, straight-chained or branched pentadecanoic acid, straight-chained or branched hexadecanoic acid, straight-chained or branched heptade
the dibasic acid may be a chain dibasic acid or a cyclic dibasic acid. In the case of the chain dibasic acid, it may be straight-chained or branched, and may be saturated or unsaturated.
chain dibasic acid a chain dibasic acid having 2 to 16 carbon atoms is preferred, and specific examples include ethane diacid, propane diacid, straight-chained or branched butane diacid, straight-chained or branched pentane diacid, straight-chained or branched hexane diacid, straight-chained or branched heptane diacid, straight-chained or branched octane diacid, straight-chained or branched nonane diacid, straight-chained or branched decane diacid, straight-chained or branched undecane diacid, straight-chained or branched dodecane diacid, straight-chained or branched tridecane diacid, straight-chained or branched tetradecane diacid, straight-chained or branched heptadecane diacid, straight-chain chain di
examples of the cyclic dibasic acid include 1,2-cyclohexane dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, aromatic dicarboxylic acid and the like. Among these, in the point of stability, chain dibasic acids are preferred.
the acid composing the ester oiliness improver may be a monobasic acid or a polybasic acid, as mentioned above. However, in the point of the frictional property, a monobasic acid is preferred.
the combination of alcohol and acid in the ester oiliness improver is arbitrary and not particularly limited, but, for example, the esters according to the following combinations (i) to (vii) can be mentioned.
Each ester of (ii) to (vii) above may be a complete ester which esterified all hydroxyl groups of polyhydric alcohol or carboxyl groups of polybasic acid, or a partial ester in which a part thereof remains as hydroxyl groups or carboxyl groups.
esters of (i) to (vii) above (ii) an ester of polyhydric alcohol and monobasic acid is preferred as the ester oiliness improver of the component (D). This ester is very high in the improving effect of the frictional property.
the esters of (ii) may be a complete ester in which all hydroxyl groups of polyhydric alcohol is esterified or a partial ester in which a part remains as hydroxyl groups.
the complete ester is preferred in the point of precipitation resistance and the partial ester is preferred in the point of the frictional property.
the partial ester is preferably a mixture of two or more kind of partial esters having different esterification degree, and more preferably a mixture of partial esters having the esterification degree of 1 and partial esters having the esterification degree of 2 or more in the point of the precipitation resistance, the abrasion resistance and the frictional property.
the esterification degree herein means the number of ester bonds in one molecule.
a partial ester having the esterification degree of 1 is sorbitan monoester
a partial ester having the esterification degree of 2 or more includes sorbitan diester and sorbitan triester.
the proportion of the partial ester having the esterification degree of 1 is preferably 10 to 70% by mole, and more preferably 20 to 50% by mole based on the total amount of both.
the proportion of the partial ester having the esterification degree of 2 or higher is preferably 30 to 70% by mole, and more preferably 50 to 80% by mole based on the total amount of both.
Monobasic acid constituting the esters of (ii) may be any one of a straight-chained fatty acid or branched fatty acid, but in the point of the frictional property, a straight-chained fatty acid is preferred, and in the point of the precipitation resistance, a branched fatty acid is preferred.
monobasic acid constituting the esters of (ii) may be any one of a saturated fatty acid or an unsaturated fatty acid, but in the point of the frictional property and abrasion resistance, a saturated fatty acid is preferred, and in the point of the precipitation resistance, an unsaturated fatty acid is preferred.
monobasic acid contains both saturated and unsaturated fatty acids the proportion of saturated fatty acids in the total of both fatty acids is preferably 60% by mole or higher, more preferably 75% by mole or higher, even more preferably 90% by mole or higher, and still more preferably 95% by mole or higher in the point of the friction property (i.e. reduction of the frictional index).
the number of carbon atoms in monobasic acid constituting ester of the (ii) is not particularly limited, but in the point of the precipitation resistance, a mixture of short-chained fatty acid having 1 to 4 carbon atoms, preferably 2 carbon atoms and long-chained fatty acid having 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms is preferably used. Further, when combining the short-chained fatty acid and the long-chained fatty acid, the proportion of the short-chained fatty acid in the total of both is preferably 50 to 80% by mole, more preferably 60 to 75% by mole, and even more preferably 65 to 70% by mole.
esters represented in the following (ii-1) to (ii-4) are preferably used in the point of achieving various characteristic such as the frictional property and the precipitation resistance in good balance.
the esters of (ii-1) are preferred in the point that both the frictional property and the precipitation resistance can be achieved in high degree.
the number of carbon atoms in the unsaturated fatty acid constituting the esters of (ii-1) is preferably 10 or higher, more preferably 12 or higher, and even more preferably 14 or higher in the point of further improving the frictional property. Further, the number of carbon atoms in the unsaturated fatty acid is preferably 28 or lower, more preferably 26 or lower and even more preferably 24 or lower in the point of the precipitation resistance.
esters include glycerin monoleate, sorbitan monoleate and the like.
esters of (ii-2) are preferred in the point of achieving all the frictional property, the precipitation resistance, the abrasion resistance and the rust resistance in good balance with high degree.
Further polyhydric alcohol constituting ester of the (ii-2) may be one kind or a mixture of two or more kinds, but when the polyhydric alcohol contains dihydric alcohol, it is preferable to further contain polyhydric alcohols of 3 or more valence.
the proportion of partial ester having the esterification degree of 1 is preferably 10 to 70% by mole, and more preferably 20 to 50 % by mole based on the total amount of partial ester having the esterification degree of 1 and partial ester having the esterification degree of 2 or more. Further, the proportion of partial ester having the esterification degree of 2 or more is preferably 30 to 70% by mole, and more preferably 50 to 80 % by mole based on the total amount of partial ester having the esterification degree of 1 and partial ester having the esterification degree of 2 or more.
esters of (ii-2) may further contain complete esters, but in the point of achieving all the frictional property, the precipitation resistance, the abrasion resistance and the rust resistance in good balance with high degree, the content of the complete ester is 10% by mole or lower, preferably 5% by mole or lower, and particularly preferably contains substantially no complete esters based on the esters of (ii-2).
Esters of (ii-3) are preferred in the point of achieving all the frictional property (i.e. reduction of the frictional index and energy-saving property), the precipitation resistance, the abrasion resistance and the rust resistance in good balance with high degree.
the proportion of the short-chained fatty acid in the total amount of the constituting fatty acids is preferably 60 to 80% by mole, more preferably 60 to 75% by mole, and even more preferably 65 to 70% by mole.
the proportion of the short-chained fatty acid is less than 50% by mole, there is tendency to lower the solubility to the base oil. Moreover, when the proportion of the short-chained fatty acid exceeds 80% by mole, there is tendency to lower the reduction effect of the friction. Further, in the point of further improving the frictional property (i.e. reduction of the frictional index), the proportion of the saturated fatty acid in the total amount of the constituting fatty acids is preferably 60% by mole or higher, more preferably 75% by mole or higher, even more preferably 90% by mole or higher, and still more preferably 95% by mole or higher. When the proportion of the saturated fatty acid is less than 60% by mole, there is tendency that the reduction effect of the friction becomes insufficient.
Esters of (ii-4) are preferred in the point of achieving all the frictional property, the precipitation resistance, the abrasion resistance and the rust resistance in good balance with high degree.
polyhydric alcohols constituting the esters of (ii-4) may be one kind or a mixture of two or more kinds, but when the polyhydric alcohol contains dihydric alcohol, it is preferable to further contain polyhydric alcohols of 3 or more valence.
the proportion of partial ester having the esterification degree of 1 is preferably 10 to 70% by mole, and more preferably 20 to 50 % by mole based on the total amount of partial ester having the esterification degree of 1 and partial ester having the esterification degree of 2 or more. Further, the proportion of partial ester having the esterification degree of 2 or more is preferably 30 to 70% by mole, and more preferably 50 to 80 % by mole based on the total amount of partial ester having the esterification degree of 1 and partial ester having the esterification degree of 2 or more.
esters of (ii-4) may further contain complete esters, but in the point of achieving all the frictional property, the precipitation resistance, the abrasion resistance and the rust resistance in good balance with high degree, the content of the complete ester is 10% by mole or lower, preferably 5% by mole or lower, and particularly preferably contains substantially no complete esters based on the esters of (ii-4).
esters of (ii-1) to (ii-4) in the point of having good balance of the frictional property, the precipitation resistance and the abrasion resistance, and excellent rust resistance, the esters of (ii-2), (ii-3) and (ii-4) are preferred as (D-1), (D-2) and (D-3) of the component (D), respectively. More preferably, esters of (D-1) are preferred.
the lubricative composition of the invention is specifically suitable as a lubricating oil composition. As more specific embodiment, it is suitable for a gear oil composition, a lubricating oil composition for paper machines, a lubricating oil composition for slide guides, a hydraulic oil, and the like.
Gear oil composition is more specifically a composition containing at least one kind of the component (A), the component (B) and the component (C) in the base oil.
the mixing ratio of the component (A), the component (B) and the component (C) concerning the gear oil composition is as in the following.
the content of a phosphorus-containing carboxylic acid compound as the component (A-1) in the gear oil composition of the invention is not particularly limited, but it is preferably 0.001 to 5% by weight, more preferably 0.002 to 3% by weight, and even more preferably 0.003 to 1% by weight based on the total amount of the composition.
the content of the phosphorus-containing carboxylic acid compound lower than the minimum value has tendency not to obtain sufficient lubricity.
the content exceeding the maximum value has tendency not to obtain appropriate improving effect of lubricity that meet with the content, and may have concerns of lowering thermal and oxidation stability or hydrolysis stability, thus not preferred.
the content of the compound (including ⁇ -dithiophosphorylated propionic acid represented by the formula (6)) whose R 4 is a hydrogen atom is preferably 0.001 to 0.1 % by weight, more preferably 0.002 to 0.08% by weight, even more preferably 0.003 to 0.07% by weight, much more preferably 0.004 to 0.06% by weight, and particularly preferably 0.005 to 0.05% by weight.
the content is less than 0.001
the content exceeds 0.1% by weight there may be a concern of lowering the thermal and oxidation stability.
the content of thiophosphoric ester (phosphorothionate) as the component (A-2) in the gear oil composition of the invention is not particularly limited, but usually the content is 0.001 to 10% by weight, preferably 0.005 to 5% by weight, and more preferably 0.01 to 3% by weight based on the total amount of the gear oil composition (based on the total amount of a base oil and all the combined additives).
the gear oil composition of the invention can be obtained by (A-1) the phosphorus-containing carboxylic acid compound or (A-2) the thiophosphoric ester alone, or in combination of both.
the maximum value of the content of the dispersant viscosity index improver as an arbitrary component (B) in the gear oil composition of the invention is 10% by weight, preferably 5% by weight, and more preferably 2% by weight based on the total amount of the composition.
the minimum value of the content of the dispersant viscosity index improver is 0.01 % by weight, preferably 0.05% by weight, and more preferably 0.1 % by weight based on the total amount of the composition.
the maximum value of the content of the component (C-1) as an arbitrary component in the gear oil composition of the invention is 5% by weight, preferably 2% by weight, and more preferably 1% by weight based on the total amount of the composition.
the minimum value of the content of the component (C-1) is 0.001% by weight, preferably 0.003% by weight, and more preferably 0.005% by weight based on the total amount of the composition.
the content of the component (C-1) is less than 0.001% by weight, the improving effect of the frictional property cannot be seen, thus not preferred.
the content of the component (C-2), when combining in the gear oil composition of the invention, is arbitrary, but since there may be a concern of lowering the sludge resistance when a great amount is combined, the content is 5% by weight or lower, preferably 1% by weight or lower, and more preferably 0.5% by weight or lower based on the total amount of the composition. On the other hand, in the point of exhibiting sufficient improving effect of the frictional property, the content is 0.001 % by weight or higher, preferably 0.003% by weight or higher, and more preferably 0.005% by weight or higher based on the total amount of the composition.
the lubricative composition of the invention is specifically suitable as a lubricating oil composition for paper machines.
Lubricating oil composition for paper machines is more specifically a composition containing at least one kind of the component (A), the component (B) and the component (C) in the base oil.
the mixing ratio of the component (A), the component (B) and the component (C) concerning the lubricating oil composition for paper machines is as in the following.
the content of (A-1) a phosphorus-containing carboxylic acid compound in the lubricating oil composition for paper machines of the invention is not particularly limited, but it is preferably 0.001 to 5% by weight, more preferably 0.002 to 3% by weight, and even more preferably 0.003 to 1% by weight based on the total amount of the composition.
the content of a phosphorus-containing carboxylic acid compound lower than the minimum value has tendency not to obtain sufficient lubricity.
the content exceeding the maximum value has tendency not to obtain appropriate improving effect of lubricity that meet with the content, and may have concerns of lowering thermal and oxidation stability or hydrolysis stability, thus not preferred.
the content of the compound (including ⁇ -dithiophosphorylated propionic acid represented by the formula (6)) whose R 4 is a hydrogen atom is preferably 0.001 to 0.1% by weight, more preferably 0.002 to 0.08% by weight, even more preferably 0.003 to 0.07% by weight, much more preferably 0.004 to 0.06% by weight, and particularly preferably 0.005 to 0.05% by weight.
the content is less than 0.001
the content exceeds 0.1 % by weight there may be a concern of lowering the thermal and oxidation stability.
the content of thiophosphoric ester (phosphorothionate) as the component (A-2) is not particularly limited, but usually the content is 0.001 to 10% by weight, preferably 0.005 to 5% by weight, and more preferably 0.01 to 3% by weight based on the total amount of the lubricating oil composition for paper machines (based on the total amount of a base oil and all the combined additives).
the lubricating oil composition for paper machines of the invention can be obtained by (A-1) the phosphorus-containing carboxylic acid compound or (A-2) the phosphorothionate alone, or in combination of both.
the maximum value of the content of the component (B), the dispersant viscosity index improver, as an arbitrary component in the lubricating oil composition for paper machines of the invention is 10% by weight, preferably 5% by weight, and more preferably 2% by weight based on the total amount of the composition.
the minimum value of the content of the component (B) is 0.01% by weight, preferably 0.05% by weight, and more preferably 0.1 % by weight based on the total amount of the composition.
the maximum value of the content of the component (C-1) as an arbitrary component in the lubricating oil composition for paper machines of the invention is 5% by weight, preferably 2% by weight, and more preferably 1% by weight based on the total amount of the composition.
the minimum value of the content of the component (C-1) is 0.001% by weight, preferably 0.003% by weight, and more preferably 0.005% by weight based on the total amount of the composition.
the content of the component (C-1) is less than 0.001% by weight, the improving effect of the frictional property cannot be seen, thus not preferred.
the content of the component (C-2), when combining in the lubricating oil composition for paper machines of the invention, is arbitrary, but since there may be a concern of lowering the sludge resistance when a great amount is combined, the content is 5% by weight or lower, preferably 1% by weight or lower, and more preferably 0.5% by weight or lower based on the total amount of the composition. On the other hand, in the point of exhibiting sufficient improving effect of the frictional property, the content is 0.001% by weight or higher, preferably 0.003% by weight or higher, and more preferably 0.005% by weight or higher based on the total amount of the composition.
the lubricative composition of the invention is specifically suitable as a lubricating oil composition for slide guides.
Lubricating oil composition for slide guides is more specifically a composition containing at least one kind of the component (A), the component (B) and the component (C) in the base oil.
the mixing ratio of the component (A), the component (B) and the component (C) concerning the lubricating oil composition for slide guides is as in the following.
the content of (A-1) a phosphorus-containing carboxylic acid compound in the lubricating oil composition for slide guides of the invention is not particularly limited, but it is preferably 0.001 to 5% by weight, more preferably 0.002 to 3% by weight, and even more preferably 0.003 to 1% by weight based on the total amount of the lubricating oil composition for slide guides.
the content of a phosphorus-containing carboxylic acid compound lower than the minimum value has tendency not to obtain sufficient low frictional property and anti-stick-slip property.
the content exceeding the maximum value has tendency not to obtain low frictional property and anti-stick-slip property that meet with the content, and may have concerns of lowering thermal and oxidation stability or hydrolysis stability, thus not preferred.
the content of the compound (including ⁇ -dithiophosphorylated propionic acid represented by the formula (6)) whose R 4 is a hydrogen atom is preferably 0.001 to 0.1% by weight, more preferably 0.002 to 0.08% by weight, even more preferably 0.003 to 0.07% by weight, much more preferably 0.004 to 0.06% by weight, and particularly preferably 0.005 to 0.05% by weight.
the content When the content is less than 0.001, there may be a concern of having insufficient improving effect of low frictional property and anti-stick-slip property, and on the other hand, when the content exceeds 0.1 % by weight, there may be a concern of lowering the thermal and oxidation stability.
the content of thiophosphoric ester (phosphorothionate) as the component (A-2) is not particularly limited, but usually the content is 0.001 to 10% by weight, preferably 0.005 to 5% by weight, and more preferably 0.01 to 3% by weight based on the total amount of the lubricating oil composition for slide guides (based on the total amount of a base oil and all the combined additives).
the lubricating oil composition for slide guides of the invention can be obtained by (A-1) the phosphorus-containing carboxylic acid compound or (A-2) the thiophosphoric ester alone, or in combination of both.
the maximum value of the content of the component (B), the dispersant viscosity index improver, as an arbitrary component in the lubricating oil composition for slide guides of the invention is 10% by weight, preferably 5% by weight, and more preferably 2% by weight based on the total amount of the composition.
the minimum value of the content of the component (B) is 0.01% by weight, preferably 0.05% by weight, and more preferably 0.1% by weight based on the total amount of the composition.
the maximum value of the content of the component (C-1) as an arbitrary component in the lubricating oil composition for slide guides of the invention is 5% by weight, preferably 2% by weight, and more preferably 1% by weight based on the total amount of the composition.
the content exceeds 5% by weight, further improvement in the frictional property that meet with the content cannot be seen, and lowering of the storage stability is generated, thus not preferred.
the minimum value of the content of the component (C-1) is 0.001% by weight, preferably 0.003% by weight, and more preferably 0.005% by weight based on the total amount of the composition.
the content of the component (C-1) is less than 0.001% by weight, the improving effect of the frictional property cannot be seen, thus not preferred.
the content of the component (C-2), when combining in the lubricating oil composition for slide guides of the invention, is arbitrary, but since there may be a concern of lowering the sludge resistance when a great amount is combined, the content is 5% by weight or lower, preferably 1% by weight or lower, and more preferably 0.5% by weight or lower based on the total amount of the composition. On the other hand, in the point of exhibiting sufficient improving effect of the frictional property, the content is 0.001 % by weight or higher, preferably 0.003% by weight or higher, and more preferably 0.005% by weight or higher based on the total amount of the composition.
the lubricative composition of the invention is specifically suitable as a hydraulic oil.
Hydraulic oil composition is more specifically a composition containing at least one kind of the component (A) and the component (B) in the base oil. Further, hydraulic oil composition is even more specifically a composition containing the component (D) in the base oil.
the mixing ratio of the component (A), the component (B) and the component (D) concerning the hydraulic oil composition is as in the following.
the content of (A-1) a phosphorus-containing carboxylic acid compound in the hydraulic oil of the invention is not particularly limited, but it is preferably 0.001 to 1% by weight, and more preferably 0.002 to 0.5% by weight based on the total amount of the composition.
the content of a phosphorus-containing carboxylic acid compound lower than the minimum value has tendency to be insufficient in improving effect of abrasion resistance and frictional property.
the content exceeding the maximum value has tendency to lower sludge resistance.
the content of the compound (including ⁇ -dithiophosphorylated propionic acid represented by the formula (6)) whose R 4 is a hydrogen atom is preferably 0.001 to 0.1% by weight, more preferably 0.002 to 0.08% by weight, even more preferably 0.003 to 0.07% by weight, much more preferably 0.004 to 0.06% by weight, and particularly preferably 0.005 to 0.05% by weight.
the content is less than 0.001, there is tendency to be insufficient in improving effect of abrasion resistance and frictional property, and on the other hand, when the content exceeds 0.1 % by weight, there is tendency to lower sludge resistance.
the content of the component (A-2) in the hydraulic oil of the invention is preferably 5% by weight or lower, more preferably 2% by weight or lower, and even more preferably 1.5% by weight or lower based on the total amount of the composition.
the content of the component (A-2) is preferably 0.005% by weight or higher, more preferably 0.01 % by weight or higher, and even more preferably 0.05% by weight or higher based on the total amount of the composition.
the content is lower than 0.005% by weight, there is tendency to be insufficient in the abrasion resistance.
the hydraulic oil of the invention can be obtained by (A-1) the phosphorus-containing carboxylic acid compound or (A-2) the thiophosphoric ester alone, or in combination of both.
the content of (B) the dispersant viscosity index improver in the hydraulic oil of the invention is preferably 10% by weight or lower, more preferably 5% by weight or lower, and even more preferably 2% by weight or lower based on the total amount of the composition.
the content of (B) the dispersant viscosity index improver in the hydraulic oil is preferably 0.01% by weight or higher, more preferably 0.05% by weight or higher, and even more preferably 0.1 % by weight or higher based on the total amount of the composition.
the content is less than 0.01 % by weight, there is tendency to lower the sludge resistance, the abrasion resistance and the frictional property.
the content of (D) an ester oiliness improver in the hydraulic oil of the invention is arbitrary, but in the point of excelling in the friction reducing effect, the content is preferably 0.01% by weight or higher, more preferably 0.05% by weight or higher, and even more preferably 0.1 % by weight or higher based on the total amount of the composition. Further, the content, in the point of precipitation resistance, is preferably 10% by weight or lower, more preferably 7.5% by weight or lower, and even more preferably 5% by weight or lower based on the total amount of the composition.
the hydraulic oil composition is a composition containing the component (A) and component (B) in the base oil
a sulfur-based abrasion resistant or a phosphorus-based abrasion resistant when used, there may be a concern of increasing the friction index or worsening the sludge resistance; thus, the content of the sulfur-based abrasion resistant or the phosphorus-based abrasion resistant is 5% by weight or lower, preferably 1% by weight or lower, more preferably 0.5% by weight or lower based on the total amount of the composition, and it is the most preferable that no such abrasion resistant is contained therein.
the hydraulic oil composition is, more specifically, a composition containing the component (D) in the base oil, but in this case, when a sulfur-based abrasion resistant is used, there may be a concern of increasing the friction index or worsening the sludge resistance; thus, the content of the sulfur-based abrasion resistant is 5% by weight or lower, preferably 1% by weight or lower, more preferably 0.5% by weight or lower based on the total amount of the composition, and it is the most preferable that no such abrasion resistant is contained therein.
the sulfur-based extreme pressure agent is preferably used as an arbitrary component (E) in the point of improving the extreme pressure property.
sulfur-based extreme pressure agent examples include sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, sulfurized olefins, dihydrocarbyl (poly)sulfides, thiadiazole compounds, alkylthiocarbamoyl compounds, thiocarbamate compounds, thioterpene compounds, dialkyl thiodipropionate compounds, sulfurized mineral oils, zinc dithiophosphate compounds, zinc dithicarbamate compounds, molybdenum dithiophosphate compounds, molybdenum dithicarbamate and the like. These sulfur-based extreme pressure agents may be used alone or in a mixture of two or more.
Sulfurized fats and oils are obtained by reacting sulfur or a sulfur-containing compound with fat and oil (lard oil, whale oil, plant oil, fish oil, etc.).
the content of the sulfur is not particularly limited, but generally 5 to 30% by weight is preferred. Specific examples thereof include, sulfurized lard, sulfurized seed oil, sulfurized castor oil, sulfurized soybean oil, sulfurized rice bran oil, and mixtures thereof, and the like.
sulfurized fatty acids include sulfurized oleic acid and the like
sulfurized esters include the ones obtained by sulfurizing unsaturated fatty acid esters and mixtures thereof obtained by reacting unsaturated fatty acids (including oleic acid, linoleic acid or fatty acids extracted from the animal and plant fats and oils) and various alcohols, with an arbitrary method.
sulfurized esters include sulfurized oleic acid methyl or sulfurized rice bran fatty acid octyl, and mixtures thereof, and the like.
sulfurized olefins examples include compounds represented by the following formula (18).
R 27 -S a -R 28 (18) wherein R 27 is an alkenyl group having 2 to 15 carbon atoms, R 28 is an alkyl group or an alkenyl group having 2 to 15 carbon atoms, and a is an integer of 1 to 8.
dihydrocarbyl (poly)sulfide is a compound represented by the following formula (19).
R 29 and R 30 are an alkyl group, they may be referred to as alkyl sulfide.
R 29 and R 30 include straight-chained or branched alkyl groups such as an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a straight-chained or branched pentyl group, a straight-chained or branched hexyl group, a straight-chained or branched heptyl group, a straight-chained or branched octyl group, a straight-chained or branched nonyl group, a straight-chained or branched decyl group, a straight-chained or branched undecyl group, a straight-chained or branched dodecyl group, a straight-chained or branched tridecyl group, a straight-chained or branched te
R 29 and R 30 in the formula (19) are preferably an alkyl group having 3 to 18 carbon atoms derived from propylene, 1-butene or isobutylene, an aryl group, an alkylaryl group or an arylalkyl group having 6 to 8 carbon atoms.
alkyl groups such as a branched hexyl group (including all branched isomers) derived from an isopropyl group or a propylene dimer, a branched nonyl group (including all branched isomers) derived from a propylene trimer, a branched dodecyl group (including all branched isomers) derived from a propylene tetramer, a branched pentadecyl group (including all branched isomers) derived from a propylene pentamer, a branched octadecyl group (including all branched isomers) derived from a propylene hexamer, a branched octyl group (including all branched isomers) derived from a sec-butyl group, a tert-butyl group or a 1-butene dimer, a branched octyl groups such as
R 29 and R 30 in the formula (19) are each independently preferably a branched alkyl group having 3 to 18 carbon atoms derived from ethylene or propylene, and particularly preferably a branched alkyl group having 6 to 15 carbon atoms derived from ethylene or propylene.
dihydrocarbyl (poly)sulfide examples include dibenzyl polysulfide, various dinonyl polysulfides, various didodecyl polysulfides, various dibutyl polysulfides, various dioctyl polysulfides, diphenyl polysulfide, dicyclohexyl polysulfide, and mixtures thereof, and the like.
thiadiazole compounds include 1,3,4-thiadiazole represented by the following formula (20), 1,2,4-thiadiazole compounds represented by the following formula (21) and 1,4,5-thiadiazole compounds represented by the following formula (22).
R 31 and R 32 may be identical with or different from each other and are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and c and d may be identical with or different from each other and are each independently an integer of 0 to 8.
thiadiazole compound examples include 2,5-bis(n-hexyldithio)-1,3,4-thiadiazole, 2,5-bis(n-octyldithio)-1,3,4-thiadiazole, 2,5-bis(n-nonyldithio)-1,3,4-thiadiazole, 2,5-bis(1,1,3,3-tetramethylbutyldithio)-1,3,4-thiadiazole, 3,5-bis(n-hexyldithio)-1,2,4-thiadiazole, 3,5-bis(n-octyldithio)-1,2,4-thiadiazole, 3,5-bis(n-nonyldithio)-1,2,4-thiadiazole, 3,5-bis(1,1,3,3-tetramethylbutyldithio)-1,2,4-thiadiazole, 4,5-bis(n-hexyldithio)-1,2,3-thiadiazole, 4,5
alkylthiocarbamoyl compounds include compounds represented by the following formula (23). wherein R 33 to R 36 may be identical with or different from each other and are each independently an alkyl group having 1 to 20 carbon atoms, and e is an integer of 1 to 8.
alkylthiocarbamoyl compounds include bis(dimethyl thiocarbamoyl)monosulfide, bis(dibutyl thiocarbamoyl)monosulfide, bis(dimethyl thiocarbamoyl)disulfide, bis(dibutyl thiocarbamoyl)disulfide, bis(diamyl thiocarbamoyl)disulfide, bis(dioctyl thiocarbamoyl)disulfide, and mixtures thereof, and the like.
alkylcarbamate compounds include compounds represented by the following formula (24). wherein R 37 to R 40 may be identical with or different from each other and are each independently an alkyl group having 1 to 20 carbon atoms, and R 41 is an alkyl group having 1 to 10 carbon atoms.
alkylcarbamate compounds include methylene bis(dibutyl dithiocarbamate), methylene bis[di(2-ethylhexyl)dithiocarbamate] and the like.
examples of thioterpene compounds include reactants of phosphorus pentasulfide and pinene, and examples of dialkyl thiodipropionate compounds include dilauryl thiodipropionate, distearyl thiodipropionate, and mixtures thereof, and the like.
Sulfurized mineral oil means what dissolved a simple sulfur in mineral oil.
mineral oil used for the sulfurized mineral oil concerning the invention is not particularly limited, but specifically include paraffinic, naphthenic or the like mineral oil obtained by subjecting a lubricating oil distillate, which was obtained by the normal pressure distillation or the reduced pressure distillation of a crude oil, to suitably combined refining treatment such as solvent deasphalting, solvent extraction, hydrogenolysis, solvent dewaxing, contact dewaxing, hydorefining, sulfuric acid washing, white clay treatment and the like.
any form of clusters, powders, melt liquid and the like may be used, but if a simple sulfur of powder or melt liquid form is used dissolution to a base oil can be effectively carried out, thus preferred.
a melt liquid simple sulfur is mixed with the same liquid, it has an advantage that the dissolution operation can be carried out in very short time.
the mixture must be handled in the temperature higher than or equal to the melting point of the simple sulfur, thus special equipments such as a heating equipment or the like are necessary, and since handling is done in high temperature atmosphere, danger is accompanied, and the like, thereby the handling is not necessarily easy.
the powdered simple sulfur is easily handled due to the cheap price, and since the time needed for the dissolution is sufficiently short, thus particularly preferred.
the content of sulfur in sulfurized mineral oil concerning the invention is not particularly limited, but it is preferably 0.05 to 1.0% by weight, and more preferably 0.1 to 0.5% by weight based on the total amount of sulfurized mineral oil.
Zinc dithiophosphate compounds, zinc dithiocarbamate compounds, molybdenum dithiophosphate compounds and molybdenum dithiocarbamate compounds are referred to as the compounds represented by the following formulas (25) to (28), respectively.
R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 and R 57 may be identical with or different from each other and are each independently a hydrocarbon group having 1 or more carbon atoms, and X 6 and X 7 are each independently an oxygen atom or a sulfur atom.
hydrocarbon group represented by R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 , R 50 , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 and R 57 include alkyl groups such as a methyl group, an ethyl group, a propyl group (including all branched isomers), a butyl group (including all branched isomers), a pentyl group (including all branched isomers), a hexyl group (including all branched isomers), a heptyl group (including all branched isomers), an octyl group (including all branched isomers), a nonyl group (including all branched isomers), a decyl group (including all branched isomers), an undecyl group (including all branched isomers), a dodecyl group (
the content of a sulfur-based extreme pressure agent as the component (E) in the lubricative composition of the invention is arbitrary, but in the point of improving the extreme pressure property of the obtained lubricative composition, the minimum value of the content is preferably 0.01% by weight or higher, more preferably 0.05% by weight or higher, and even more preferably 0.1 % by weight or higher based on the total amount of the composition.
the maximum value of the content of the sulfur-based extreme pressure agent in the point that an effect to the extent that meet with the added amount is not acquired even if more than such the amount is combined, is preferably 10% by weight or lower, more preferably 5% by weight or lower, even more preferably 3% by weight or lower, and most preferably 1% by weight or lower based on the total amount of the composition.
the component (F) in the lubricative composition of the invention is an arbitrary component in the point of the sludge resistance, but combining an epoxy compound is possible.
epoxy compounds include the following compounds:
phenylglycidyl ether-type epoxy compounds include phenylglycidyl ether or alkylphenylglycidyl ether.
alkylphenylglycidyl ether the one having 1 to 3 alkyl groups having 1 to 13 carbon atoms can be mentioned, and among these, the one having one alkyl group having 4 to 10 carbon atoms is preferred.
Examples thereof include n-butylphenylglycidyl ether, i-butylphenylglycidyl ether, sec-butylphenylglycidyl ether, tert-butylphenylglycidyl ether, pentylphenylglycidyl ether, hexylphenylglycidyl ether, heptylphenylglycidyl ether, octylphenylglycidyl ether, nonylphenylglycidyl ether, decylphenylglycidyl ether and the like.
alkylglycidyl ether-type epoxy compounds include decylglycidyl ether, undecylglycidyl ether, dodecyl glycidyl ether, tridecylglycidyl ether, tetradecylglycidyl ether, 2-ethylhexylglycidyl ether, neopentylglycol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkyleneglycol monoglycidyl ether, polyalkyleneglycol diglycidyl ether and the like.
(3) glycidyl ester-type epoxy compounds include the compounds represented by the following formula (29): wherein R 58 is a hydrocarbon group having 1 to 18 carbon atoms.
R 58 is a hydrocarbon group having 1 to 18 carbon atoms, and examples of such the hydrocarbon group include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an alkylcycloalkyl group having 6 to 18 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, an arylalkyl group having 7 to 18 carbon atoms and the like.
an alkyl group having 5 to 15 carbon atoms an alkyenyl group having 2 to 15 carbon atoms and an alkylphenyl group having a phenyl group and an alkyl group having 1 to 4 carbon atoms are preferred.
glycidyl ester-type epoxy compounds include glycidyl-2,2-dimethyl octanoate, glycidyl benzoate, glycidyl-tert-butyl benzoate, glycidyl arylate, glycidyl methacrylate and the like.
(4) aryloxirane compounds include 1,2-epoxystyrene, alkyl-1,2-epoxystyrene and the like.
alkyloxirane compounds include 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,1,2-epoxyoctadecane, 2-epoxynonadecane, 1,2-epoxyicosaen and the like.
Examples of (6) alicyclic epoxy compounds include the compound in which carbon atoms constituting the epoxy group directly constitutes the alicyclic ring, such as the compounds represented by the following formula (30):
alicyclic epoxy compounds include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, expoxo-2,3-epoxy norbomene, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 2-(7-oxabicyclo[4.1.0]hepto-3-yl)-spiro(1,3-dioxane-5,3'-[7]oxabicyclo[4.1.0]heptane, 4-(1'-methylepoxyethyl)-1,2-epoxy-2-methylcyclohexane, 4-epoxyethyl-1,2-epoxycyclohexane and the like.
epoxidized fatty acid monoester examples include esters of epoxidized fatty acid having 12 to 20 carbon atoms and alcohol having 1 to 8 carbon atoms, phenol or alkylphenol, and the like. Particularly, butyl epoxystearate, hexyl epoxystearate, benzyl epoxystearate, cyclohexyl epoxystearate, methoxyethyl epoxystearate, octyl epoxystearate, phenyl epoxystearate and butylphenyl ester epoxystearate are preferably used.
(8) epoxidized plant oil include an epoxy compound of plant oils such as soybean oil, linseed oil and cottonseed oil.
the combined amount is not particularly limited, but usually, the content of the epoxy compound combined therein is preferably 0.1 to 5.0% by weight, and more preferably 0.2 to 2.0% by weight based on the total amount of the lubricative composition (based on the total amount of base oil and all combined additives).
the component (G), in the point of oxidation stability in the lubricative composition of the invention, is an arbitrary component, but it may be (G-A) a phenol-based antioxidant, (G-B) an amine-based antioxidant or an antioxidant containing both of them.
an arbitrary phenol-based compound used as an antioxidant of a lubricating oil can be used without any particular limitation, but for example, an alkylphenol compounds of one kind or two or more kinds selected from the compound represented by the following formula (31) or the formula (32) are preferably mentioned.
R 59 is al alkyl group having 1 to 4 carbon atoms
R 60 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
R 61 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a group represented by the following formula (31-i) or a group represented by the following formula (31-ii).
R 62 is an alkylene group having 1 to 6 carbon atoms
R 63 is an alkyl group or akenyl group having 1 to 24 carbon atoms
R 64 is an alkylene group having 1 to 6 carbon atoms
R 65 is an alkyl group having 1 to 4 carbon atoms
R 66 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R 67 and R 71 are each independently an alkyl group having 1 to 4 carbon atoms
R 68 and R 72 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
R 69 and R 70 are each independently an alkylene group having 1 to 6 carbon atoms
X 8 is an alkylene group having 1 to 18 carbon atoms or a group represented by the following formula (32-i).
R 59 examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like, but in the point of excelling in the oxidation stability, a tert-butyl group is preferred.
examples of R 60 include a hydrogen atom or an alkyl group having 1 to 4 carbon atoms as described above, but in the point of excelling in the oxidation stability, a methyl group or a tert-butyl group is preferred.
R 61 when R 61 is an alkyl group having 1 to 4 carbon atoms, specific examples of R 61 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like, but in the point of excelling in the oxidation stability, a methyl group or an ethyl group is preferred.
alkylphenol compound represented by the formula (31) particularly preferred example of the compound when R 61 is an alkyl group having 1 to 4 carbon atoms is 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol, and mixtures thereof, and the like.
an alkylene group having 1 to 6 carbon atoms represented by R 62 in the formula (31-i) may be straight-chained or branched, and specific examples thereof include a methylene group, a methylmethylene group, an ethylene group (a dimethylene group), an ethylmethylene group, a propylene group(a methylethylene group), a trimethylene group, a straight-chained or branched butylenes group, a straight-chained or branched pentylene group, a straight-chained or branched hexylene group and the like.
R 62 is more preferably an akylene group having 1 to 2 carbon atoms, and specific examples thereof include a methylene group, a methylmethylene group, an ethylene group (dimethylene group) and the like.
an alkyl group or alkenyl group having 1 to 24 carbon atoms represented by R 63 in the formula (31-i) may be straight-chained or branched, and specific examples thereof include alkyl groups (wherein the alkyl group may be straight-chained or branched) such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosy
an alkyl group having 4 to 18 carbon atoms is preferred, and specific examples include alkyl groups (wherein the alkyl group may be straight-chained or branched) such as a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group, a straight-chained or branched alkyl group having 6 to 12 carbon atoms is more preferred, and a branched alkyl group having 6 to 12 carbon atoms is
R 62 in the formula (31-i) is an alkylene group having 1 to 2 carbon atoms and R 63 is a straight-chained or branched alkyl group having 6 to 12 carbon atoms
R 62 in the formula (31-i) is an alkylene group having 1 to 2 carbon atoms and R 63 is a branched alkyl group having 6 to 12 carbon atoms.
more preferred examples include n-hexyl (3-methyl-5-tert-butyl-4-hydroxyphenyl)acetate, isohexyl (3-methyl-5-tert-butyl-4-hydroxyphenyl)acetate, n-heptyl (3-methyl-5-tert-butyl-4-hydroxyphenyl)acetate, isoheptyl (3-methyl-5-tert-butyl-4-hydroxyphenyl)acetate, n-octyl (3-methyl-5-tert-butyl-4-hydroxyphenyl)acetate, isooctyl (3-methyl-5-tert-butyl-4-hydroxyphenyl)acetate, 2-ethylhexyl (3-methyl-5-tert-butyl-4-hydroxyphenyl)acetate, n-nonyl (3-methyl-5-tert-butyl-4-hydroxyphenyl)acetate, isononyl (3-methyl-5-tert-butyl-4-hydroxyphenyl)acetate
R 61 in the formula (31) is a group represented by the formula (31-ii)
R 64 in the formula (31-ii) is an alkylene group having 1 to 6 carbon atoms.
Such the alkylene group may be straight-chained or branched, and specific examples include various alkylene groups as exemplified for R 63 in the above.
R 64 is more preferably an alkylene group having 1 to 3 carbon atoms, and specific examples include a methylene group, a methylmethylene group, an ethylene group (a dimethylene group), an ethylmethylene group, a propylene group (a methylethylene group), a trimethylene group and the like.
R 65 in the formula (31-ii) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like, but in the point of excelling in the oxidation stability, a tert-butyl group is preferred.
examples of R 66 include a hydrogen atom or an alkyl group having 1 to 4 carbon atoms as described above, but in the point of excelling in the oxidation stability, a methyl group or a tert-butyl group is preferred.
alkylphenol compounds represented by the formula (31) as the compound when R 61 is a group represented by the formula (31-ii), preferred specific examples include bis(3,5-di-tert-butyl-4-hydroxyphenyl)methane, 1,1-bis(3,5-di-tert-butyl-4-hydroxyphenyl)ethane, 1,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)ethane, 1,1-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 1,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 1,3-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, and mixtures thereof, and the like.
R 67 and R 71 are each independently an alkyl group having 1 to 4 carbon atoms, and specifically they are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like, but in the point of excelling in the oxidation stability, a tert-butyl group is preferred.
examples of R 68 and R 72 include, each independently, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms as described above, but in the point of excelling in the oxidation stability, a methyl group or a tert-butyl group is preferred.
an alkylene group having 1 to 6 carbon atoms representing R 69 and R 70 may be straight-chained or branched, and specific examples include, each independently, various alkylene groups described above for R 62 .
R 69 and R 70 are each independently and more preferably, an alkylene group having 1 to 2 carbon atoms, and specific examples include a methylene group, a methylmethylene group, an ethylene group (a diemtylene group) and the like.
an alkylene group having 1 to 18 carbon atoms representing X 8 include a methylene group, a methylmethylene group, an ethylene group (a dimethylene group), an ethylmethylene group, a propylene group (a methylethylene group), a trimethylene group, a butylenes group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, an octadecylene group and the like (wherein the alkylene group may be straight-chained or branched).
an alkylene group having 1 to 6 carbon atoms specifically for example, a methylene group, a methylmethylene group, an ethylene group (a dimethylene group), an ethylmethylene group, a propylene group (a methylethylene group), a trimethylene group, a butylenes group, a pentylene group, a hexylene group and the like (wherein the alkylene group may be straight-chained or branched), are more preferred; and a straight-chained alkylene group having 2 to 6 carbon atoms such as an ethylene group (a dimethylene group), a trimethylene group, a straight-chained butylene group(a tetramethylene group), a straight-chained pentylene group (a pentamethylene group), and a straight-chained hexylene group (a hexamethylene group), are particularly preferred.
alkylphenol compounds represented by the formula (1) specifically for example, a methylene group, a
an alkylene group having 1 to 6 carbon atoms represented by R 73 and R 74 in the formula (32-i) may be straight-chained or branched, and specific examples include, each independently, various alkylene groups described above for R 62 .
R 73 and R 74 are each independently and more preferably, an alkylene group having 1 to 3 carbon atoms, and specific examples include a methylene group, a methylmethylene group, an ethylene group (a dimethylene group), an ethylmethylene group, a propylene group (a methylethylene group), a trimethylene group and the like.
alkylphenols represented by the formula (32) particularly preferred compound when X 8 is a group represented by the formula (32-i), is the compound represented by the following formula (34).
a compound selected from alkylphenol compounds represented by the formula (31) and the formula (32) may be used alone, or a mixture of two or more compounds selected from the alkylphenol compounds may be used in an arbitrary mixing ratio.
the maximum value of the component (G-A) in the lubricative composition of the invention is 3% by weight, preferably 2% by weight, and more preferably 1% by weight based on the total amount of the composition.
the content exceeds 3% by weight further improvement in the oxidation stability and sludge resisting effect that meet with the content cannot be seen, and the solubility to the base oil may be lowered, thus not preferred.
the minimum value of the content of the component (G-A) is 0.01 % by weight, preferably 0.1% by weight, and more preferably 0.2% by weight based on the total amount of the composition.
the content of the component (G-A) is less than 0.01 % by weight, its addition effect cannot be seen, and there may be a concern of worsening the oxidation stability of the gear oil composition or sludge resisting effect, thus not preferred.
an amine-based antioxidant which can be added as an arbitrary component in the component (G) an arbitrary amine-based compound used as an antioxidant of the lubricating oil can be used without any particular limitation, but for example, it is preferably one kind or two or more kinds of aromatic amine selected from (N-p-alkyl)phenyl- ⁇ -naphthyl amine represented by the following formula (35) or p,p'-dialkyldiphenyl amine represented by the formula (36).
R 75 is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms.
R 76 and R 77 are each independently an alkyl group having 1 to 16 carbon atoms.
R 75 is a hydrogen atom or a straight-chained or branched alkyl group having 1 to 16 carbon atoms.
R 75 exceeds 16 the proportion of the functional group occupied in a molecule becomes small, and there may be a concern of weakening the oxidation resisting ability.
an alkyl group in R 75 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group and the like (wherein the alkyl group may be straight-chained or branched).
R 75 is an alkyl group
a branched alkyl group having 8 to 16 carbon atoms is preferred
a branched alkyl group having 8 to 16 carbon atoms derived from an olefm oligomer having 3 or 4 carbon atoms is more preferred, in the point of excelling in solubility of its oxidized product to the base oil.
specific examples of olefm having 3 or 4 carbon atoms include propylene, 1-butene, 2-butene and isobutylene, but in the point of excelling in solubility of its oxidized product to the base oil, propylene or isobutylene is preferred.
R 75 is particularly preferably a hydrogen molecule or a branched octyl group derived from an isobutylene dimer, a branched nonyl group derived from a propylene trimer, a branched dodecyl group derived from an isobutylene trimer, a branched dodecyl group derived from a propylene tetramer or a branched pentadecyl group derived from a propylene pentamer, and particularly preferably a hydrogen molecule or a branched octyl group derived from an isobutylene dimer, a branched dodecyl group derived from an isobutylene trimer, a branched dodecyl group derived from a propylene te
N-p-alkylphenyl- ⁇ -naphthyl amine whose R 75 is an alkyl group
the commercially available N-p-alkylphenyl- ⁇ -naphthyl amine may be used. Further, it can be easily synthesized by reacting phenyl- ⁇ -naphthyl amine with a halogenated alkyl compound having 1 to 16 carbon atoms and an olefin having 2 to 16 carbon atoms, or an olefin oligomer having 2 to 16 carbon atoms with phenyl- ⁇ -naphthyl amine using a Fiedel-Craft catalyst.
Fiedel-Craft catalyst including metal halides such as aluminum chloride, zinc chloride and iron chloride; acidic catalysts such as sulfuric acid, phosphoric acid, phosphorus pentoxide, boron fluoride, acid earth and activated earth; and the like can be used.
R 76 and R 77 are each independently an alkyl group having 1 to 16 carbon atoms.
R 76 and R 77 are a hydrogen atom, there may be a concern of sedimenting as sludge by its oxidized products, on the contrary, when the number of carbon atoms exceeds 16, the proportion of the functional group occupied in a molecule becomes small, and there may be a concern of weakening the oxidation resisting ability.
R 76 and R 77 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group and the like (wherein the alkyl group may be straight-chained or branched).
R 76 and R 77 are preferably a branched alkyl group having 3 to 16 carbon atoms, and more preferably a branched alkyl group having 3 to 16 carbon atoms derived from olefin having 3 or 4 carbon atoms or its oligomer, in the point of excelling in solubility of its oxidized product to the base oil.
specific examples of olefin having 3 or 4 carbon atoms include propylene, 1-butene, 2-butene and isobutylene, but in the point of excelling in solubility of its oxidized product to the base oil of the lubricating oil, propylene or isobutylene is preferred.
R 76 and R 77 are particularly preferably an isopropyl group derived from propylene, a tert-butyl group derived from isobutylene, a branched hexyl group derived from a propylene dimer, a branched octyl group derived from an isobutylene dimer, a branched nonyl group derived from a propylene trimer, a branched dodecyl group derived from an isobutylene trimer, a branched dodecyl group derived from a propylene tetramer or a branched pentadecyl group derived from a propylene pentamer, and particularly preferably a tert-butyl group derived from isobutylene, a branched hexyl group
p,p'-dialkyldiphenyl amine represented by the formula (36) the commercially available one may be used. Further, in the same manner as for N-p-alkylphenyl- ⁇ -naphthyl amine represented by the formula (35), it can be easily synthesized by reacting diphenyl amine with a halogenated alkyl compound having 1 to 16 carbon atoms and an olefin having 2 to 16 carbon atoms, or olefin having 2 to 16 carbon atoms or its oligomer with diphenyl amine using a Fiedel-Craft catalyst.
Fiedel-Craft catalyst including metal halides and acidic catalysts exemplified in the synthesis of N-p-alkylphenyl- ⁇ -naphthyl amine
component (G-B) as an arbitrary component of the invention, a compound selected from aromatic amines represented by the formula (35) and the formula(36) may be used alone, or a mixture of two or more compounds selected from the aromatic amines may be used in an arbitrary mixing ratio.
the maximum value of (G-B) amine-based antioxidant in the lubricative composition of the invention is 3% by weight, preferably 2% by weight, and more preferably 1% by weight based on the total amount of the composition.
the minimum value of the content of (G-B) amine-based antioxidant is 0.01 % by weight, preferably 0.1 % by weight, and more preferably 0.2% by weight based on the total amount of the composition.
Component (H) Phosphorus-based compound
(H) a phosphorus-based compound as the component (H) may be contained for the improvement of the extreme pressure property of the lubricative composition of the invention.
phosphorus-based compound contained herein examples include phosphoric acid esters such as phosphoric acid monoester, phosphoric acid diester and phosphoric acid triester; phosphorus acid esters such as phosphorus acid monoester, phosphorus acid diester and phosphorus acid triester; salts of these phosphoric acid esters or phosphorus acid esters; and mixtures thereof; and the like.
the phosphoric acid esters and phosphorous acid esters described above are generally a compound containing a hydrocarbon having 2 to 30 carbon atoms, and preferably 3 to 20 carbon atoms.
hydrocarbon atoms having 2 to 30 carbon atoms include alkyl groups (wherein the alkyl group may be straight-chained or branched) such as an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group and an octadecyl group; alkenyl groups (wherein the alkenyl group may be straight-chained or branched, and the position of the double bond is arbitrary) such as a butenyl group, a pentenyl group,
phosphoric acid monoalkyl esters such as monopropyl phosphate, monobutyl phosphate, monopentyl phosphate, monohexyl phosphate, monoheptyl phosphate and monooctyl phosphate; phosphoric acid mono(alkyl)aryl esters such as monophenyl phosphate and monocresyl phosphate; phosphoric acid dialkyl esters (the alkyl group may be straight-chained or branched) such as dipropyl phosphate, dibutyl phosphate, dipentylphosphate, dihexyl phosphate, diheptyl phosphate and dioctyl phosphate; phosphoric acid di(alkyl)aryl esters such as diphenyl phosphate and dicresyl phosphate
salts of phosphoric acid esters or phosphorus acid esters include salts obtained by reacting nitrogen-containing compound such as amine compounds having only ammonium, a hydrocarbon group having 1 to 8 carbon atoms or a hydrocarbon group having a hydroxyl group in the molecule to phosphoric acid monoester, phosphoric acid diester, phosphorus acid monoester, phosphorus acid diesterester and the like, and then neutralizing a part or all the remaining acidic hydrogen.
nitrogen-containing compound such as amine compounds having only ammonium, a hydrocarbon group having 1 to 8 carbon atoms or a hydrocarbon group having a hydroxyl group in the molecule
nitrogen-containing compound examples include ammonia; alkyl amines (the alkyl group may be straight-chained or branched) such as monomethyl amine, monoethyl amine, monopropyl amine, monobutyl amine, monopentyl amine, monohexyl amine, monoheptyl amine, monooctyl amine, dimethyl amine, methylethyl amine, diethyl amine, methylpropyl amine, ethylpropyl amine, dipropyl amine, methylbutyl amine, ethylbutyl amine, propylbutyl amine, dibutyl amine, dipentyl amine, dihexyl amine, diheptyl amine and dioctyl amine; alkanol amines (the alkanol group may be straight-chained or branched) such as monomethanol amine, monoethanol amine, monopropyl
the phosphorus-based compound which may be contained as the component (H) may used a compound selected from the above-described phosphoric acid esters, phosphorus acid esters or salts thereof alone, or a mixture of two or more compounds selected therefrom may be used in an arbitrary mixing ratio.
the maximum value of the content of the phosphorus-based compound (the component (H)) in the lubricative composition of the invention is 10% by weight, preferably 5% by weight, and more preferably 3% by weight based on the total amount of the composition.
the minimum value of the content of the phosphorus-based compound is 0.01% by weight, preferably 0.05% by weight, and more preferably 0.1% by weight based on the total amount of the composition.
an oiliness improver as the component (I) can be added to the lubricative composition of the invention in the point of improving the frictional property.
oiliness improver examples include an ester oiliness improver, an alcohol oiliness improver, a carboxylic acid oiliness improver, an ether oiliness improver, an amine oiliness improver, an amide oiliness improver and the like.
the compounds given as the component (D) can be exemplified.
the number of carbon atoms in the alcohol oiliness improver is preferably 6 or higher, more preferably 8 or higher, and most preferably 10 or higher in the point of improving the frictional property. Moreover, in case of too many number of carbon atoms, there may be a concern of easy precipitation, thus the number of carbon atoms is preferably 24 or less, more preferably 20 or less, and most preferably 18 or less.
the carboxylic acid oiliness improver may be mono basic acid or polybasic acid.
the carboxylic acid for example, monobasic acids and polybasic acids exemplified in the description of ester oiliness improver can be mentioned.
monobasic acids are preferred in the point of improving the frictional property.
the number of carbon atoms in the carboxylic acid oiliness improver is preferably 6 or higher, more preferably 8 or higher, and most preferably 10 or higher in the point of improving the frictional property.
the number of carbon atoms is preferably 24 or less, more preferably 20 or less, and most preferably 18 or less.
an ether compound of an aliphatic polyhydric alcohol having 3 to 6 valences an ether compound of bimolecular condensate or termolecular condensate of an aliphatic polyhydric alcohol having 3 to 6 valences and the like are mentioned.
R 78 to R 102 may be identical with or different from each other and are each independently a hydrogen atom, a straight-chained or branched alkyl group, aryl group or aralkyl group having 1 to 18 carbon atoms, or a glycol ether remaining group represented by -(R a O) n -R b (wherein R a is an alkylene group having 2 to 6 carbon atoms, R b is an alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, and n is an integer of 1 to 10).
ether compound of an aliphatic polyhydric alcohol having 3 to 6 valences include glycerin, trimethylol propane, erythritol, pentaerythritol, arabitol, sorbitol, mannitol and the like.
R 77 to R 101 in the formulas (37) to (42) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, a phenyl group, a benzyl group and the like.
the ether compound also include partial ether compound whose part of R 77 to R 101 is a hydrogen atom.
the same kind or different kind condensates from the compound represented by the formulas (37) to (42) are mentioned.
the ether compounds of bimolecular condensate or termolecular condensate of alcohol represented by the formula (37) are represented by the formulas (43) and (44), respectively.
the ether compounds of bimolecular condensate or termolecular condensate of alcohol represented by the formula (39) are represented by the formulas (45) and (46), respectively.
R 78 to R 80 and R 88 to R 91 have the same definition as R 77 to R 79 of the formula (37) and R 88 to R 91 of the formula (40), respectively.
bimolecular condensate and termolecular condensate of an aliphatic polyhydric alcohol having 3 to 6 valences include diglycerin, ditrimethylolpropane, dipentaerythritol, disorbitol, triglycerin, tritrimethylolpropane, tripentaerythritol, trisorbitol and the like.
ether oiliness improver represented by the formulas (37) to (46) include glycerin trihexyl ether, glycerin dimethyloctyl triether, glycerin di(methyloxyisopropylene)dodecyl triether, glycerin diphenyloctyl triether, glycerin di(phenyloxyisopropylene)dodecyl triether, trimethylolpropane trihexyl ether, trimethylolpropane dimethyloctyl triether, trimethylolpropane di(methyloxyisopropylene)dodecyl triether, pentaerythritol tetrahexyl ether, pentaerythritol trimethyloctyl tetraether, pentaerythritol tri(methyloxyisopropylene)dodecyl tetraether, sorbitol hexapropyl
glycerin diphenyloctyl triether trimethylolpropane di(methyloxyisopropylene)dodecyl triether, pentaerythritol tetrahexyl ether, sorbitol hexapropyl ether, diglycerin dimethyldioctyl tetraether, triglycerin tetra(methyloxyisopropylene)decyl pentaether, dipentaerythritol hexapropyl ether, tripentaerythritol pentamethyloctyl hexaether are preferred.
oiliness improver as the component (I) which can be used in the lubricative composition of the invention, additionally, (I-1) an amine oiliness improver, (I-2) an amide oiliness improver and the like are mentioned.
Examples of (I-1) the amine oiliness improver include monoamine, polyamine, alkanol amine, but among these, monoamine is preferred in the point of improving the frictional property.
monoamine examples include alkyl amines such as monomethyl amine, dimethyl amine, trimethyl amine, monoethyl amine, diethyl amine, triethyl amine, monopropyl amine (including all isomers), dipropyl amine (including all isomers), tripropyl amine (including all isomers), monobutyl amine (including all isomers), dibutyl amine (including all isomers), tributyl amine (including all isomers), monopentyl amine (including all isomers), dipentyl amine (including all isomers), tripentyl amine (including all isomers), monohexyl amine (including all isomers), dihexyl amine (including all isomers), monoheptyl amine (including all isomers), diheptyl amine (including all isomers), monooctyl amine (including all isomers), dioctyl amine (including all isomers
alkyl amines in the point of improving the frictional property, alkyl amines, monoamines having an alkyl group and an alkenyl group, monoamines having an alkyl group and a cycloalkyl group, cycloalkyl amines and alkylcycloalkyl amines are particularly preferred, and alkyl amines and monoamines having an alkyl group and an alkenyl group are more preferred.
the number of carbon atoms in monoamine is not particularly limited, but it is preferably 8 or higher, and more preferably 12 or higher in the point of the rust resistance. Moreover, in the point of improving the frictional property, it is preferably 24 or lower, and more preferably 18 or lower.
the number of hydrocarbon groups bonded to a nitrogen atom in monoamine is not particularly limited, but it is preferably 1 to 2 hydrocarbon groups, and more preferably 1 hydrocarbon group in the point of improving the frictional property.
an amide oiliness improver amides obtained by reacting a fatty acid having 6 to 30 carbon atoms or its acidic salt with ammonia, or a nitrogen-containing compound such as an amine compound containing only a hydrocarbon group having 1 to 8 carbon atoms or a hydrocarbon group having a hydroxyl group in the molecule are mentioned.
the fatty acid may be straight-chained or branched, and may be saturated fatty acid or unsaturated fatty acid. Further, the number of carbon atoms is 6 to 30, and preferably 9 to 24.
fatty acid examples include saturated fatty acids (wherein the saturated fatty acid may be straight-chained or branched) such as heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, henicosanoic acid, docosanoic acid, tricosanoic acid tetracosanoic acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid and triacontanoic group; unsaturated fatty acids (wherein the saturated
straight-chained fatty acids of straight-chained fatty acids derived from lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and various fats and oils (such as coconut oil fatty acid, etc.) or a mixture of straight-chained fatty acids and brached fatty acids synthesized by an oxo method or the like are preferably used.
nitrogen-containing compound reacted with the fatty acids include ammonia; alkyl amines (the alkyl group may be straight-chained or branched) such as monomethyl amine, monoethyl amine, monopropyl amine, monobutyl amine, monopentyl amine, monohexyl amine, monoheptyl amine, monooctyl amine, dimethyl amine, methylethyl amine, diethyl amine, methylpropyl amine, ethylpropyl amine, dipropyl amine, methylbutyl amine, ethylbutyl amine, propylbutyl amine, dibutyl amine, dipentyl amine, dihexyl amine, diheptyl amine and dioctyl amine; alkanol amines (the alkanol group may be straight-chained or branched) such as monomethanol amine,
fatty acid amide including lauric acid amide, lauric acid diethanol amide, lauric acid monopropanol amide, myristic acid amide, myristic acid diethanol amide, myristic acid monopropanol amide, palmitic acid amide, palmitic acid diethanol amide, palmitic acid monopropanol amide, stearic acid amide, stearic acid diethanol amide, stearic acid monopropanol amide, oleic acid amide, oleic acid diethanol amide, oleic acid monopropanol amide, coconut oil fatty acid amide, coconut oil fatty acid diethanol amide, coconut oil fatty acid monopropanol amide, synthetic mixture fatty acid amide having 12 to 13 carbon atoms, synthetic mixture fatty acid diethanol amide having 12 to 13 carbon atoms, synthetic mixture fatty acid monopropanol amide having 12 to 13 carbon atoms, and mixtures thereof and the like, are preferably used.
polyhydric alcohol partial esters and aliphatic amides are preferred in the point of improving effect on the frictional property.
the content of the oiliness improver as the component (I) in the lubricative composition is arbitrary, but in the point of excelling in the improving effect of the frictional property, it is preferably 0.01 % by weight or higher, more preferably 0.05% by weight or higher, and even more preferably 0.1% by weight or higher based on the total amount of the lubricative composition. Further, the content, in the point of the precipitation resistance, is preferably 10% by weight or lower, more preferably 7.5% by weight or lower, and even more preferably 5% by weight or lower based on the total amount of the composition.
Component(J) Tiazole and/or its derivatives
triazole and/or its derivatives represented by the formula (47) as the composition (J) can be added to the lubricative composition of the invention in the point of improving thermal and oxidation stability.
the two dotted lines are the same or different substituents substituted to the triazole ring and are preferably each independently a hydrocarbon group, and they can be bonded to each other to form a ring group, for example, to form a condensed benzene ring.
Preferred compound as triazole and/or its derivatives is benzotriazole and/or its derivatives.
benzotriazole examples include a compound represented by the following formula (48).
examples of the benzotriazole derivatives include alkylbenzotriazole represented by the following formula (49) and (alkyl)aminoalkylbenzotriazole represented by the formula (50).
R 103 is a straight-chained or branched alkyl group having 1 to 4 carbon atoms and preferably a methyl group or an ethyl group, and x is a number of 1 to 3, and preferably 1 or 2.
R 103 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like.
alkylbenzotriazole represented by the formula (49) a compound, wherein R 103 is a methyl group or an ethyl group, and x is 1 or 2, is preferred, and examples include methylbenzotriazole (tolyltriazole), dimethylbenzotriazole, ethylbenzotriazole, ethylmethylbenzotriazole, diethylbenzotriazole or mixtures thereof, and the like.
R 104 is a straight-chained or branched alkyl group having 1 to 4 carbon atoms and preferably a methyl group or an ethyl group;
R 105 is a methylene group or an ethylene group;
R 106 and R 107 may be identical with or different from each other and are each independently a hydrogen atom or a straight-chained or branched alkyl group having 1 to 18 carbon atoms and preferably a straight-chained or branched alkyl group having 1 to 12 carbon atoms; and y is a number of 0 to 3 and preferably 0 or 1.
R 103 examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like.
R 106 and R 107 include, each independently, a hydrogen atom and alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a straight-chained or branched pentyl group, a straight-chained or branched hexyl group, a straight-chained or branched heptyl group, a straight-chained or branched octyl group, a straight-chained or branched nonyl group, a straight-chained or branched decyl group, a straight-chained or branched undecyl group, a straight-chained or branched dodecyl group, a straight-chained or branched tridecyl group, a straight-chainl
dialkylaminoalkylbenzotriazole As (alkyl)aminobenzotriazole represented by the formula (50), dialkylaminoalkylbenzotriazole, dialkylaminoalkyltriazole or mixtures thereof are preferably used in the point of excelling particularly the oxidation resistance, wherein R 104 is a methyl group, y is 0 or 1, R 105 is a methylene group or an ethylene group, and R 106 and R 107 are a straight-chained or branched alkyl group having 1 to 12 carbon atoms.
dialkylaminoalkylbenzotriazole examples include dimethylaminomethylbenzotriazole, diethylaminomethylbenzotriazole, di(straight-chained or branched)propylaminomethylbenzotriazole, di(straight-chained or branched)butylaminomethylbenzotriazole, di(straight-chained or branched)pentylaminomethylbenzotriazole, di(straight-chained or branched)hexylaminomethylbenzotriazole, di(straight-chained or branched)heptylaminomethylbenzotriazole, di(straight-chained or branched)octylaminomethylbenzotriazole, di(straight-chained or branched)nonylaminomethylbenzotrizole, di(straight-chained or branched)decylaminomethylbenzotriazole, di(straight-chain-
the content of triazole and its derivatives as the composition (J), which is an arbitary component in the lubricative composition, is arbitrary, but it is preferably 0.001% by weight or higher, and more preferably 0.005% by weight or higher based on the total amount of the composition.
the content is less than 0.001 % by weight, there may be a concern of becoming insufficient in the improving effect of the thermal and oxidation stability by containing triazole and/or its derivatives.
the content of triazole and/or its derivatives is preferably 1.0% by weight or lower, and more preferably 0.5% by weight or lower based on the total amount of the composition. When the content exceeds 1.0% by weight, the thermal and oxidation stability that meet with the content cannot be obtained, and there may be a concern of becoming disadvantageous economically.
various additives such as a rust inhibitor, a metal deactivator, a viscosity index improver or detergent additive in addition to the dispersant viscosity index improver of the component (B), a pour-point depressant and an defoaming agent can be contained alone or in combination of a plurality of kinds in the lubricative composition of the invention.
the rust inhibitor include metal soaps such as fatty acid metal salt, lanoline fatty acid metal salt and oxidized wax metal salt; polyhydric alcohol partial esters such as sorbitan fatty acid ester; esters such as lanoine fatty acid ester; sulfonates such as calcium sulfonate and barium sulfonate; oxidized wax; amines; phosphoric acids; phosphoric acid salts; and the like.
one kind or two or more kinds of compound arbitrarily selected from these rust inhibitors can be contained in an arbitrary amount, but in general, the content is preferably 0.01 to 1% by weight based on the total amount of the lubricative composition.
the metal deactivator include imidazole compounds other than the benzotriazole compound mentioned as the component (J).
one kind or two or more kinds of compound arbitrarily selected from these metal deactivators can be contained in an arbitrary amount, but in general, the content is preferably 0.001 to 1% by weight based on the total amount of the lubricative composition.
viscosity index improver in addition to the dispersant viscosity index improver of the component (B) include nondispersant viscosity index improvers such as a copolymer of one kind or two or more kinds of monomers selected from various methacrylic acid esters, or its hydrides, an ethylene- ⁇ -olefin compolymer (examples of ⁇ -olefin include propylene, 1-butene, 1-pentene and the like) or its hydrides, polyisobutylene or its hydrides, a styrene-diene hydrogenated copolymer or polyalkylstyrene, and the like.
nondispersant viscosity index improvers such as a copolymer of one kind or two or more kinds of monomers selected from various methacrylic acid esters, or its hydrides, an ethylene- ⁇ -olefin compolymer (examples of ⁇ -olefin include propylene, 1-
examples of the detergent additive in addition to the dispersant viscosity index improver of the component (B) include alkenyl succinic acid imide, sulfonate, salicylate, phenate and the like.
One kind or two or more kinds of compound arbitrarily selected from these viscosity index improvers or detergent additives can be contained in an arbitrary amount, but in general, the content is preferably 0.01 to 10% by weight based on the total amount of the lubricative composition.
the pour-point depressant include a copolymer of one kind or two or more kinds of monomers selected from various acrylic acid esters or methacrylic acid esters or its hydrides.
One kind or two or more kinds of compound arbitrarily selected from these pour-point depressants can be contained in an arbitrary amount, but in general, the content is preferably 0.01 to 5% by weight based on the total amount of the lubricative composition.
the defoaming agent examples include silicones such as dimehtylsilicone and fluorosilicone.
one kind or two or more kinds of compound arbitrarily selected from these defoaming agents can be contained in an arbitrary amount, but in general, the content is preferably 0.0001 to 0.05% by weight based on the total amount of the lubricative composition.
This Example is an embodiment related to the gear oil formed by combining the component (C-1), the component (C-2) or a mixture thereof into the base oil.
Tested base oils the kind of additives added thereto and their amounts are listed below. Further, the test methods carried out on each combined lubricating oil composition is also listed below. The obtained test results are presented in Tables 1 to 3.
the oil temperature of the gear box was measured after 120 minutes by operating under the rotation number of 6000 rpm, the oil amount of 1250 ml and the load of 80 1b.
the gear oil composition of this embodiment is excellent in energy-saving. Therefore, the oil composition copes with the gear equipment used for various industrial machines with high efficiency and low cost and also keeps up with the tendency for high-speed and high-output as the gear oil, thus more energy-saving operation is possible.
This Example is an embodiment related to the gear oil formed by combining the dispersant viscosity index improver of the component (B) into the base oil.
test methods carried out on each combined lubricating oil composition is also listed below.
the oil temperature of the gear box was measured after 120 minutes by operating under the rotation number of 6000 rpm, the oil amount of 1250 ml and the load of 80 lb.
the antiemulsifying property was measured at 82°C.
NPA nonyl phenoxyacetate
the gear oil composition of this embodiment is excellent in the sludge resistance and water dissolubility. Therefore, the oil composition corresponds to the gear equipment used for various industrial machines with high efficiency and low cost and also to the tendency for high-speed and high-output as the gear oil, thus tolerant in higher temperature and tolerant in operation under higher load is possible.
This Example is an embodiment related to the gear oil formed by combining the phosphorus-containing carboxylic acid compound of the component (A-1), thiophosphic acid ester (A-2), or mixtures thereof into the base oil.
Tested base oils the kind of additives added thereto and their amounts are listed below. Further, the test methods carried out on each combined lubricating oil composition is also listed below. The obtained test results are presented in Tables 1 to 5.
the sludge resisting effect of the lubricating oil was evaluated. That is, to a 50 ml-beaker, 45 g of the lubricating oil in Table was fed, and a copper and iron catalyst was added thereto. The mixture was left to stand in an air constant-temperature bath at 140°C for 240 hours, and then the amount of sludge in the sample oil was measured. The amount of sludge generated was determined by diluting the tested lubricating oil with n-hexane, passing through a membrane filter of 0.8 ⁇ m, and measuring the weight of the collected substance. Further, for the copper and iron catalyst, the catalyst used in the test for oxidation stability of the turbine oil (JIS K2514) that has been cut 8 times (length: about 3.5 cm) was used.
the oil temperature of the gear box was measured after 120 minutes by operating under the rotation number of 6000 rpm, the oil amount of 1250 ml and the load of 80 lb.
the gear oil composition of this embodiment is excellent in the sludge resistance and extreme pressure property. Therefore, the oil composition corresponds to the gear equipment used for various industrial machines with high efficiency and low cost and also to the tendency for high-speed and high-output as the gear oil, thus tolerant in higher temperature and tolerant in operation under higher load is possible.
This Example is an embodiment related to the lubricating oil composition for paper machines formed by combining the component (C-1), the component (C-2), or mixtures thereof into the base oil.
Tested base oils the kind of additives added thereto and their amounts are listed below. Further, the test methods carried out on each combined lubricating oil composition is also listed below. The obtained test results are presented in Tables 1 to 3.
the sludge resisting effect of the lubricating oil was evaluated. That is, to a 50 ml-beaker, 45 g of the lubricating oil in Table was fed, and a copper and iron catalyst was added thereto. The mixture was left to stand in an air constant-temperature bath at 150°C for 120 hours, and then the amount of sludge in the sample oil was measured. The amount of sludge generated was determined by diluting the tested lubricating oil with n-hexane, passing through a membrane filter of 0.8 ⁇ m, and measuring the weight of the collected substance. Further, for the copper and iron catalyst, the catalyst used in the test for oxidation stability of the turbine oil (JIS K2514) that has been cut 8 times (length: about 3.5 cm) was used.
the lubricating oil composition for paper machines of this embodiment is excellent in the heat resistance, the abrasion resistance and the anticorrosion property at the same time. Therefore, the lubricating oil composition for paper machines is capable of corresponding to the recently developed paper machines.
Table 1 Example 1 2 3 4 5 Base oil 1 99.19 98.17 98.99 99.15 98.85 2 - - - - - 3 - - - - - - - Additives C-1 component C-1-1 - C-1-1 C-1-1-1 0.01 0.01 0.02 0.02 C-2 component - C-2-1 - C-2-1 C-2-1 0.03 0.03 0.03 0.03 E component - - E1 - E1 0.2 0.3 DBPC 0.5 0.5 0.5 0.5 0.5 0.5 Amine 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
This Example is an embodiment related to the lubricating oil composition for paper machines formed by combining the dispersant viscosity index improver of the component (B) into the base oil.
Tested base oils the kind of additives added thereto and their amounts are listed below. Further, the test methods carried out on each combined lubricating oil composition is also listed below. The obtained test results are presented in Tables 1 to 3.
the sludge resisting effect of the lubricating oil was evaluated. That is, to a 50 ml-beaker, 45 g of the lubricating oil in Table was fed, and a copper and iron catalyst was added thereto. The mixture was left to stand in an air constant-temperature bath at 150°C for 120 hours, and then the amount of sludge in the sample oil was measured. The amount of sludge generated was determined by diluting the tested lubricating oil with n-hexane, passing through a membrane filter of 0.8 ⁇ m, and measuring the weight of the collected substance. Further, for the copper and iron catalyst, the catalyst used in the test for oxidation stability of the turbine oil (JIS K2514) that has been cut 8 times (length: about 3.5 cm) was used.
the lubricating oil composition for paper machines of this embodiment is excellent in the heat resistance, the abrasion resistance and the anticorrosion property at the same time. Therefore, the lubricating oil composition for paper machines is capable of corresponding to the recently developed paper machines.
Table 1 Example 1 2 3 4 5 Base oil 1 96.1 98.5 99.09 98.97 98.89 2 - - - - - 3 - - - - - B: dispersant polymer B1 B2 B1 B1 B1 0.1 0.2 0.1 0.2 0.1 C-1: sarcosine - - C-1-1 - C-1-1 0.01 0.01 C-2: NPA - - - C-2-1 - 0.03
E sulfur-based extreme pressure additives - - - - E1 0.2 DBPC 0.5 0.5 0.5 0.5 0.5 Amine 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Other additives TCP OAP - - - 3.
This Example is an embodiment related to the lubricating oil composition for paper machines formed by combining the phosphorus-containing carboxylic acid compound of the component (A-1), thiophosphic acid ester (A-2), or mixtures thereof into the base oil.
Tested base oils the kind of additives added thereto and their amounts are listed below. Further, the test methods carried out on each combined lubricating oil composition is also listed below. The obtained test results are presented in Tables 1 to 5.
the sludge resisting effect of the lubricating oil was evaluated. That is, to a 50 ml-beaker, 45 g of the lubricating oil in Table was fed, and a copper and iron catalyst was added thereto. The mixture was left to stand in an air constant-temperature bath at 150°C for 120 hours, and then the amount of sludge in the sample oil was measured. The amount of sludge generated was determined by diluting the tested lubricating oil with n-hexane, passing through a membrane filter of 0.8 ⁇ m, and measuring the weight of the collected substance. Further, for the copper and iron catalyst, the catalyst used in the test for oxidation stability of the turbine oil (JIS K2514) that has been cut 8 times (length: about 3.5 cm) was used.
test For the rust resistance test, the test specified in "Testing Method of Anticorrosion Properties of Lubricating Oil" of JIS K 2510, that was modified to evaluate anticorrosion property of the lubricating oil for paper machine, was carried out.
the modified point is that usually when evaluating the lubricating oil, distilled water or artificial salt water is used, but in the case of evaluating the lubricating oil for paper machines, artificial white water is used instead, and the test time was 2 hours.
the lubricating oil composition for paper machines of this embodiment is excellent in the heat resistance, the abrasion resistance and the anticorrosion property at the same time. Therefore, the lubricating oil composition for paper machines is capable of corresponding to the recently developed paper machines.
Table 1 Example 1 2 3 4 5 Base oil 1 99.18 99.0 99.0 99.0 98.9 2 - - - - - - 3 - - - - - - - Additives A-1 component A-1-1 A-1-2 - A-1-2 A-1-2 0.02 0.2 0.1 0.2 A-2 component - - A-2-1 A-2-1 - 0.2 0.2 B component - - - - - B 1 0.1 C-1 component - - - - - C-2 component - - - - - - E component - - - - - - DBPC 0.5 0.5 0.5 0.5 0.5 Amine 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
This Example is an embodiment related to the lubricating oil composition for slide guides formed by combining the component (C-1), the component (C-2), or mixtures thereof into the base oil.
the embodiment will be further described by way of Examples.
Tested base oils the kind of additives added thereto and their amounts are listed below. Further, the test methods carried out on each combined lubricating oil composition is also listed below. The obtained test results are presented in Tables 1 to 3.
Fig. 1 is a simplified block diagram illustrating the frictional index measuring system used in the frictional property evaluation test.
a table 1 and a rolling jig 4 connected by introducing a load cell 5 is arranged on a bed 6, and a heavyweight 9 as a substituted of a working tool is further arranged on the table 1.
the table 1 and the bed 6 are all made of cast iron.
the rolling jig 4 has a bearing part, whereto an A/C servmotor 2 is connected by introducing a lead screw 3. By driving the lead screw 3 by the A/C servmotor 2, the rolling jig 4 can be reciprocated in the axial direction (the arrow direction in Fig. 1) of the lead screw 3.
the load cell 5 is connected with a computer 7 and the computer 7 and the A/C servmotor 2 are individually connected with a control board 8 electrically, thereby controlling the reciprocating movement of the rolling jig 4 and measuring the load between the table 1 and the rolling jig 4 can be carried out.
the lubricating oil composition is dropped on the surface of the bed 6, the surface pressure between the table 1 and the bed 6 is adjusted to 200 kPa by the selection of the table heavyweight 9, and then the rolling jig 4 is reciprocated with the screw speed of 60 mm/min and the screw length of 750 mm.
the frictional index of each lubricating oil composition is presented in Tables 1 to 3.
Fig. 2 is a simplified block diagram illustrating the anti-stick-slip property evaluation apparatus (TE-77 tester manufactured by PLINT & PARTNERS LTD.).
the apparatus illustrated in Fig. 2 is an apparatus in which a lower test piece 12, an upper test piece 11 and an elastic body 10 are laminated on the supporting die 110 in this order, and the test pieces 11 and 12 are slided by reciprocally moving (sliding movement) the elastic body 10 along the surface of the supporting die 110 while imposing the test pieces 11 and 12 together with a specific load. During such sliding, the frictional index between the test pieces 11 and 12 can be determined by measuring the load added to the test pieces 11 and 12 using a load detector 13.
Fig. 3 is a graph showing an example of the correlation between the frictional index obtained by the operation and time. ⁇ in Fig. 3 represents the amplitude of the frictional index.
⁇ when each lubricating oil composition was indroduced between the test pieces 11 and 12, was measured based on the method illustrated in the publication (Proceedings of Japanese Society of Tribologist Tribology conference, Tokyo 1999-5 D17), except that the test pieces and the conditions were modified for the lubricating oil for slide guides evaluation. Specifically, the test was carried out using JIS G 4051 S45C as the test pieces 11, 12 and chloroprene rubber as the elastic body 10, and with the average sliding speed of 0.3 mm/s and under the load of 250 N. The obtained results are presented in Tables 1 to 3.
the lubricating oil composition for slide guides of this embodiment is excellent in both the frictional property and the anti-stick-slip property.
Table 1 Example 1 2 3 4 5 Base oil 1 99.69 99.67 99.49 99.65 99.35 2 - - - - - 3 - - - - - - - Additives C-1 component C-1-1 - C-1-1 C-1-1 C-1-1 0.01 0.01 0.02 0.02 C-2 component - C-2-1 - C-2-1 C-2-1 0.03 0.03 0.03 0.03 E component - - E1 - E1 0.2 0.3 DBPC 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Amine 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Other additives - - - - - - - Frictional index 0.109 0.110 0.112 0.106 0.109 Anti-stick-slip property ( ⁇ ) 0.009 0.010 0.008 0.008 0.007 Table 2
Example 6 Base oil 1
This Example is an embodiment related to the lubricating oil composition for slide guides formed by combining the dispersant viscosity index improver of the component (B) into the base oil.
the embodiment will be further described by way of Examples.
test methods carried out on each combined lubricative composition is also listed below.
Fig. 1 is a simplified block diagram illustrating the frictional index measuring system used in the frictional property evaluation test.
a table 1 and a rolling jig 4 connected by introducing a load cell 5 is arranged on a bed 6, and a heavyweight 9 as a substituted of a working tool is further arranged on the table 1.
the table 1 and the bed 6 are all made of cast iron.
the rolling jig 4 has a bearing part, whereto an A/C servmotor 2 is connected by introducing a lead screw 3. By driving the lead screw 3 by the A/C servmotor 2, the rolling jig 4 can be reciprocated in the axial direction (the arrow direction in Fig. 1) of the lead screw 3.
the load cell 5 is connected with a computer 7 and the computer 7 and the A/C servmotor 2 are individually connected with a control board 8 electrically, thereby controlling the reciprocating movement of the rolling jig 4 and measuring the load between the table 1 and the rolling jig 4 can be carried out.
the lubricating oil composition is dropped on the surface of the bed 6, the surface pressure between the table 1 and the bed 6 is adjusted to 200 kPa by the selection of the table heavyweight 9, and then the rolling jig 4 is reciprocated with the screw speed of 60 mm/min and the screw length of 750 mm.
the frictional index of each lubricating oil composition is presented in Tables 1 to 4.
Fig. 2 is a simplified block diagram illustrating the anti-stick-slip property evaluation apparatus (TE-77 tester manufactured by PLINT & PARTNERS LTD.).
the apparatus illustrated in Fig. 2 is an apparatus in which a lower test piece 12, an upper test piece 11 and an elastic body 10 are laminated on the supporting die 110 in this order, and the test pieces 11 and 12 are slided by reciprocally moving (sliding movement) the elastic body 10 along the surface of the supporting die 110 while imposing the test pieces 11 and 12 together with a specific load. During such sliding, the frictional index between the test pieces 11 and 12 can be determined by measuring the load added to the test pieces 11 and 12 using a load detector 13.
Fig. 3 is a graph showing an example of the correlation between the frictional index obtained by the operation and time. ⁇ in Fig. 3 represents the amplitude of the frictional index.
⁇ when each lubricating oil composition was indroduced between the test pieces 11 and 12, was measured based on the method illustrated in the publication (Proceedings of Japanese Society of Tribologist Tribology conference, Tokyo 1999-5 D 17), except that the test pieces and the conditions were modified for the lubricating oil for slide guides evaluation. Specifically, the test was carried out using JIS G 4051 S45C as the test pieces 11, 12 and chloroprene rubber as the elastic body 10, and with the average sliding speed of 0.3 mm/s and under the load of 250 N. The obtained results are presented in Tables 1 to 4.
Fig. 4 is an illustration showing an example of the separation appearance in the mess cylinder 15 when a specific time was passed after vibration.
separated each layer was designated as the foam layer (F layer) 16, the oil layer (O layer) 17, the cream layer (C layer) 18, the elmusion layer (E layer) 19 in the order closest from the stopper 14, and the volume of each layer was measured.
the obtained results are presented in Tables 1 and 2.
the shown values in Tables represent the volume of F layer-O layer-C layer-E layer, for example, "0-20-0-80" means that F layer is 0 ml, O layer is 20 ml, C layer is 0 ml and E layer is 80 ml.
shorter time for the volume of C layer to become small or 0 ml means that the dissolubility is good.
the lubricating oil composition for slide guides of this embodiment is satisfied in all the frictional property, the anti-stick-slip property and the dissolubility with water-soluble cutting fluid.
Table 1 Example 1 2 3 4 5 Base oil 1 99.4 99.4 99.39 99.37 99.19 2 - - - - - 3 - - - - - - B component B1 B2 B1 B2 B1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 C1 component - - C-1-1 - C-1-1 0.01 0.01 C-2 component - - - C-2-1 - 0.03 E component - - - - E1 0.2 DBPC 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Amine 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Other additives - - - - - - Frictional index 0.117 0.116 0.101 0.105 0.110 Anti-stick-slip property ( ⁇ )
This Example is an embodiment related to the lubricating oil composition for slide guides formed by combining the phosphorus-containing carboxylic acid compound of the component (A-1), thiophosphic acid ester (A-2), or mixtures thereof into the base oil.
the embodiment will be further described by way of Examples.
Tested base oils the kind of additives added thereto and their amounts are listed below. Further, the test methods carried out on each combined lubricating oil composition is also listed below. The obtained test results are presented in Tables 1 to 5.
Fig. 1 is a simplified block diagram illustrating the frictional index measuring system used in the frictional property evaluation test.
a table 1 and a rolling jig 4 connected by introducing a load cell 5 is arranged on a bed 6, and a heavyweight 9 as a substituted of a working tool is further arranged on the table 1.
the table 1 and the bed 6 are all made of cast iron.
the rolling jig 4 has a bearing part, whereto an A/C servmotor 2 is connected by introducing a lead screw 3. By driving the lead screw 3 by the A/C servmotor 2, the rolling jig 4 can be reciprocated in the axial direction (the arrow direction in Fig. 1) of the lead screw 3.
the load cell 5 is connected with a computer 7 and the computer 7 and the A/C servmotor 2 are individually connected with a control board 8 electrically, thereby controlling the reciprocating movement of the rolling jig 4 and measuring the load between the table 1 and the rolling jig 4 can be carried out.
the lubricating oil composition is dropped on the surface of the bed 6, the surface pressure between the table 1 and the bed 6 is adjusted to 200 kPa by the selection of the table heavyweight 9, and then the rolling jig 4 is reciprocated with the screw speed of 60 mm/min and the screw length of 750 mm.
the frictional index of each lubricating oil composition is presented in Tables 1 to 5.
Fig. 2 is a simplified block diagram illustrating the anti-stick-slip property evaluation apparatus (TE-77 tester manufactured by PLINT & PARTNERS LTD.).
the apparatus illustrated in Fig. 2 is an apparatus in which a lower test piece 12, an upper test piece 11 and an elastic body 10 are laminated on the supporting die 110 in this order, and the test pieces 11 and 12 are slided by reciprocally moving (sliding movement) the elastic body 10 along the surface of the supporting die 110 while imposing the test pieces 11 and 12 together with a specific load. During such sliding, the frictional index between the test pieces 11 and 12 can be determined by measuring the load added to the test pieces 11 and 12 using a load detector 13.
Fig. 3 is a graph showing an example of the correlation between the frictional index obtained by the operation and time. ⁇ in Fig. 3 represents the amplitude of the frictional index.
⁇ when each lubricating oil composition was indroduced between the test pieces 11 and 12, was measured based on the method illustrated in the publication (Proceedings of Japanese Society of Tribologist Tribology conference, Tokyo 1999-5 D 17), except that the test pieces and the conditions were modified for the lubricating oil for slide guides evaluation. Specifically, the test was carried out using JIS G 4051 S45C as the test pieces 11, 12 and chloroprene rubber as the elastic body 10, and with the average sliding speed of 0.3 mm/s and under the load of 250 N. The obtained results are presented in Tables 1 to 5.
Fig. 4 is an illustration showing an example of the separation appearance in the mess cylinder 15 when a specific time was passed after vibration.
separated each layer was designated as the foam layer (F layer) 16, the oil layer (O layer) 17, the cream layer (C layer) 18, the elmusion layer (E layer) 19 in the order closest from the stopper 14, and the volume of each layer was measured.
the obtained results are presented in Tables 1 and 2.
the shown values in Tables represent the volume of F layer-O layer-C layer-E layer, for example, "0-20-0-80" means that F layer is 0 ml, O layer is 20 ml, C layer is 0 ml and E layer is 80 ml.
shorter time for the volume of C layer to become small or 0 ml means that the dissolubility is good.
the lubricating oil composition for slide guides of this embodiment is excellent in both the frictional property and the anti-stick-slip property Table 1
Example 1 2 3 4 5 Base oil 1 99.68 99.5 99.5 99.5 99.4 2 - - - - - - 3 - - - - - - Additives
This Example is an embodiment related to the hydraulic oil formed by combining thiophosphoric ester of the component (A-2) and the dispersant viscosity index improver of the component (B) into the base oil.
the embodiment will be further described by way of Examples.
SRV test was carried out and the frictional property was evaluated. More specifically, as shown in Fig. 5, to the point contact area of a disc 1 and a ball 2 arranged on the upper surface of the disc, the test oil was coated. While adding load in the vertically downward direction (the arrow A in Fig. 5) to the ball 2, the ball 2 was reciprocated relative to the linear direction (the arrow B in Fig. 5) on the upper surface of the disc 1. The frictional index at this time was measured by a load cell (not shown) mounted on a disc 1 supportor (not shown). The disc 1 of SPCC product with the diameter of 25 mm and the thickness of 8 mm was used.
the ball 2 of SPCC product with the diameter of 10 mm was used. Furthermore, the load added to the ball 2 was 1,200 N, the amplitude of the ball 2 was 1 mm, the frequency was 50Hz and the temperature was 80°C. The obtained results are presented in Tables 1 to 3.
the lubricating oil composition of this embodiment may achieve all the sludge resistance, the abrasion resistance and the frictional property in good balance with high degree, and further excellent in the water dissolubility. Therefore, the lubricating oil composition useful for improving credibility of hydraulic systems and achieving energy-saving from using the lubricating oil of this embodiment as a hydraulic oil was provided.
Example 6 the lubricating oil compositions having the formulation presented in Table 4 were prepared using the base oils and additives above, and the ester oiliness improver listed below, respectively.
This Example is an embodiment related to the hydraulic oil formed by combining phosphorus-containing carboxylic acid of the component (A-1) and the dispersant viscosity index improver of the component (B) into the base oil.
the embodiment will be further described by way of Examples.
SRV test was carried out and the frictional property was evaluated. More specifically, as shown in Fig. 5, to the point contact area of a disc 1 and a ball 2 arranged on the upper surface of the disc, the test oil was coated. While adding load in the vertically downward direction (the arrow A in Fig. 5) to the ball 2, the ball 2 was reciprocated relative to the linear direction (the arrow B in Fig. 5) on the upper surface of the disc 1. The frictional index at this time was measured by a load cell (not shown) mounted on a disc 1 supportor (not shown). The disc 1 of SPCC product with the diameter of 25 mm and the thickness of 8 mm was used.
the ball 2 of SPCC product with the diameter of 10 mm was used. Furthermore, the load added to the ball 2 was 1,200 N, the amplitude of the ball 2 was 1 mm, the frequency was 50Hz and the temperature was 80°C. The obtained results are presented in Tables 1 to 3.
the lubricating oil composition of this embodiment may achieve all the sludge resistance, the abrasion resistance and the frictional property in good balance with high degree, and further excellent in the water dissolubility. Therefore, the lubricating oil composition useful for improving credibility of hydraulic systems and achieving energy-saving from using the lubricating oil of this embodiment as a hydraulic oil was provided.
Example 6 the lubricating oil compositions having the formulation presented in Table 4 were prepared using the base oils and additives above, and the ester oiliness improver listed below, respectively.
This Example is an embodiment related to the hydraulic oil formed by combining ester oiliness improver of the component (D) into the base oil.
the embodiment will be further described by way of Examples.
SRV test was carried out and the frictional property was evaluated. More specifically, as shown in Fig. 5, to the point contact area of a disc 1 and a ball 2 arranged on the upper surface of the disc, the test oil was coated. While adding load in the vertically downward direction (the arrow A in Fig. 5) to the ball 2, the ball 2 was reciprocated relative to the linear direction (the arrow B in Fig. 5) on the upper surface of the disc 1. The frictional index at this time was measured by a load cell (not shown) mounted on a disc 1 supportor (not shown). The disc 1 of SUJ2 product with the diameter of 25 mm and the thickness of 8 mm was used.
the ball 2 of SUJ2 product with the diameter of 10 mm was used. Furthermore, the load added to the ball 2 was 1,200 N, the amplitude of the ball 2 was 1 mm, the frequency was 50Hz and the temperature was 80°C. The obtained results are presented in Tables 1 and 2.
the lubricating oil composition of this embodiment may achieve all the sludge resistance, the abrasion resistance and the precipitation resistance in good balance with high degree. Therefore, the lubricating oil composition useful for improving credibility of hydraulic systems and achieving energy-saving from using the lubricating oil of this embodiment as a hydraulic oil was provided.
Example 1 2 3 4 Base oil 1 97.80 - 97.90 97.67 2 - 98.30 - - D1 0.20 - - D2 - 0.20 - - D3 - - 0.30 0.30 A-1-1 - - - 0.03 H1 1.00 - 0.60 1.00 A-2-1 - 0.50 0.20 - G-A-1 0.50 0.50 0.50 0.50 G-B-1 0.20 0.20 0.20 0.20 K1 0.30 0.30 0.30 0.30 Amount of sludge (mg/45g) in the thermal stability test 10 days 1.8 1.3 0.110 1.3 20 days 5.2 6.5 8.4 5.3 SRV (frictional index) 0.108 0.108 0.110 0.106 Abrasion resistance (abrasion amount[mg]) 10.2 9.3 8.4 4.8 Low temperature storage stability (precipitation) None None None None None None Table 2 Example 1 2 3 4 Base oil 1 97.70 - - - 2 - 98.20 97.70
the composition of the present invention is used for lubricative composition for industrial machinery and equipment, which comprises a base oil selected from mineral oils, fats and oils, synthetic oils and mixtures of two or more of them, and at least one additive selected from the component (A), the component (B) or the component (C).
a base oil selected from mineral oils, fats and oils, synthetic oils and mixtures of two or more of them
at least one additive selected from the component (A), the component (B) or the component (C).
Such lubricative composition for industrial machinery and equipment is used as a gear oil composition, a lubricating oil composition for paper machines or a lubricating oil composition for slide guides.
the lubricative composition for industrial machinery and equipment comprises a base oil selected from mineral oils, fats and oils, synthetic oils and mixtures of two or more of them, and is combined therewith (A-1) a phosphorus-containing carboxylic acid compound and/or (A-2) a thiophosphoric ester as the component (A), and the dispersant viscosity index improver of the component (B), or instead combined therewith an ester oiliness improver as the component (D).
a base oil selected from mineral oils, fats and oils, synthetic oils and mixtures of two or more of them, and is combined therewith (A-1) a phosphorus-containing carboxylic acid compound and/or (A-2) a thiophosphoric ester as the component (A), and the dispersant viscosity index improver of the component (B), or instead combined therewith an ester oiliness improver as the component (D).
Such lubricative composition for industrial machinery and equipment is used as a lubricating oil, and particularly a hydraulic oil

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Chemical & Material Sciences (AREA)
Chemical Kinetics & Catalysis (AREA)
General Chemical & Material Sciences (AREA)
Oil, Petroleum & Natural Gas (AREA)
Organic Chemistry (AREA)
Lubricants (AREA)

EP05727597A 2004-03-25 2005-03-25 Composition d'huile de lubrification pour machines et équipements industriels Withdrawn EP1734103A4 (fr)

Applications Claiming Priority (12)

Application Number	Priority Date	Filing Date	Title
JP2004090240		2004-03-25
JP2004090218		2004-03-25
JP2004108503A JP2005290235A (ja)	2004-03-31	2004-03-31	すべり案内面用潤滑油組成物
JP2004106674A JP2005290183A (ja)	2004-03-31	2004-03-31	ギヤ油組成物
JP2004132155A JP4582767B2 (ja)	2004-03-31	2004-03-31	すべり案内面用潤滑油組成物
JP2004108185A JP2005290227A (ja)	2004-03-31	2004-03-31	抄紙機用潤滑油組成物
JP2004108502A JP4565612B2 (ja)	2004-03-31	2004-03-31	すべり案内面用潤滑油組成物
JP2004106670A JP2005290182A (ja)	2004-03-31	2004-03-31	ギヤ油組成物
JP2004108180A JP4565611B2 (ja)	2004-03-31	2004-03-31	抄紙機用潤滑油組成物
JP2004106664A JP2005290181A (ja)	2004-03-31	2004-03-31	ギヤ油組成物
JP2004108178A JP4641381B2 (ja)	2004-03-31	2004-03-31	抄紙機用潤滑油組成物
PCT/JP2005/006410 WO2005093020A1 (fr)	2004-03-25	2005-03-25	Composition d’huile de lubrification pour machines et équipements industriels

Publications (2)

Publication Number	Publication Date
EP1734103A1 true EP1734103A1 (fr)	2006-12-20
EP1734103A4 EP1734103A4 (fr)	2009-05-06

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US9499763B2 (en)	2012-12-21	2016-11-22	Afton Chemical Corporation	Additive compositions with plural friction modifiers
EP2746373A3 (fr) *	2012-12-21	2014-09-10	Afton Chemical Corporation	Modificateurs de frottement pour une utilisation dans des compositions d'huile lubrifiante
EP2746374A3 (fr) *	2012-12-21	2014-09-10	Afton Chemical Corporation	Compositions d'additif avec un modificateur de frottement et un détergent
EP2746371A1 (fr) *	2012-12-21	2014-06-25	Afton Chemical Corporation	Compositions d'additif avec un modificateur de frottement et un sel métallique de dithio phosphate de dialkyle
US9249371B2 (en)	2012-12-21	2016-02-02	Afton Chemical Corporation	Additive compositions with a friction modifier and a dispersant
EP2746372A1 (fr) *	2012-12-21	2014-06-25	Afton Chemical Corporation	Compositions d'additif avec plusieurs modificateurs de frottement
US9550955B2 (en)	2012-12-21	2017-01-24	Afton Chemical Corporation	Friction modifiers for lubricating oils
US9499762B2 (en)	2012-12-21	2016-11-22	Afton Chemical Corporation	Additive compositions with a friction modifier and a detergent
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Also Published As

Publication number	Publication date
US20080058235A1 (en)	2008-03-06
WO2005093020A1 (fr)	2005-10-06
EP1734103A4 (fr)	2009-05-06

Publication	Publication Date	Title
EP1734103A1 (fr)	2006-12-20	Composition d'huile de lubrification pour machines et équipements industriels
JP5502356B2 (ja)	2014-05-28	ギヤ油組成物
JP5595999B2 (ja)	2014-09-24	潤滑油組成物
EP2960321B1 (fr)	2018-01-10	Composition d'huile de graissage pour transmissions
EP2261309A1 (fr)	2010-12-15	Composition lubrifiante
EP1835013A1 (fr)	2007-09-19	Formule d'huile lubrifiante
JP5337598B2 (ja)	2013-11-06	ギヤ油組成物
WO2010064347A1 (fr)	2010-06-10	Composition d’huile hydraulique ignifuge
JP4878441B2 (ja)	2012-02-15	潤滑油組成物
JP2005290181A (ja)	2005-10-20	ギヤ油組成物
JP4863634B2 (ja)	2012-01-25	潤滑油組成物
JP2024540315A (ja)	2024-10-31	潤滑油組成物
JP2005060527A (ja)	2005-03-10	油圧作動油組成物及び油圧作動システムの作動方法
JP2005307202A (ja)	2005-11-04	潤滑油組成物
JP5406886B2 (ja)	2014-02-05	潤滑油組成物および油圧作動油
JP4565611B2 (ja)	2010-10-20	抄紙機用潤滑油組成物
JP2006265494A (ja)	2006-10-05	潤滑油組成物
JP4641381B2 (ja)	2011-03-02	抄紙機用潤滑油組成物
WO2005093021A1 (fr)	2005-10-06	Composition d'huile lubrifiante
JP2005060526A (ja)	2005-03-10	油圧作動油組成物及び油圧作動システムの作動方法
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