JP5663765B2 - Dibasic acid ester compound and lubricating base oil composition containing the compound - Google Patents
Dibasic acid ester compound and lubricating base oil composition containing the compound Download PDFInfo
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- JP5663765B2 JP5663765B2 JP2010200949A JP2010200949A JP5663765B2 JP 5663765 B2 JP5663765 B2 JP 5663765B2 JP 2010200949 A JP2010200949 A JP 2010200949A JP 2010200949 A JP2010200949 A JP 2010200949A JP 5663765 B2 JP5663765 B2 JP 5663765B2
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- 150000001875 compounds Chemical class 0.000 title claims description 75
- 239000000203 mixture Substances 0.000 title claims description 41
- 230000001050 lubricating effect Effects 0.000 title claims description 26
- 239000002199 base oil Substances 0.000 title claims description 18
- -1 ester compound Chemical class 0.000 title description 32
- 239000002253 acid Substances 0.000 title description 6
- 239000012530 fluid Substances 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 3
- 238000005461 lubrication Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 4
- 239000000047 product Substances 0.000 description 29
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 18
- 239000003921 oil Substances 0.000 description 16
- 238000004817 gas chromatography Methods 0.000 description 15
- 239000010687 lubricating oil Substances 0.000 description 14
- 239000000706 filtrate Substances 0.000 description 11
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000009835 boiling Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 239000000314 lubricant Substances 0.000 description 8
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
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- 239000013078 crystal Substances 0.000 description 5
- 230000010354 integration Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000010721 machine oil Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
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- 238000001228 spectrum Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 238000013461 design Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012208 gear oil Substances 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000010720 hydraulic oil Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- UCJDJEMUDBTURE-UHFFFAOYSA-N 2-ethylhexyl 4-(2-ethylhexoxy)butanoate Chemical compound CCCCC(CC)COCCCC(=O)OCC(CC)CCCC UCJDJEMUDBTURE-UHFFFAOYSA-N 0.000 description 1
- QZESEQBMSFFHRY-UHFFFAOYSA-N 2-methylheptan-1-ol Chemical compound CCCCCC(C)CO QZESEQBMSFFHRY-UHFFFAOYSA-N 0.000 description 1
- LCFKURIJYIJNRU-UHFFFAOYSA-N 2-methylhexan-1-ol Chemical compound CCCCC(C)CO LCFKURIJYIJNRU-UHFFFAOYSA-N 0.000 description 1
- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- PCWGTDULNUVNBN-UHFFFAOYSA-N 4-methylpentan-1-ol Chemical compound CC(C)CCCO PCWGTDULNUVNBN-UHFFFAOYSA-N 0.000 description 1
- BXEJOKIIZFHEMK-UHFFFAOYSA-N 5-methyloxolan-2-one Chemical compound CC1CCC(=O)O1.CC1CCC(=O)O1 BXEJOKIIZFHEMK-UHFFFAOYSA-N 0.000 description 1
- QZTGFVZFZYKIPX-UHFFFAOYSA-N 6-methyloxan-2-one Chemical compound CC1CCCC(=O)O1.CC1CCCC(=O)O1 QZTGFVZFZYKIPX-UHFFFAOYSA-N 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 1
- UUNBFTCKFYBASS-UHFFFAOYSA-N C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC Chemical compound C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC UUNBFTCKFYBASS-UHFFFAOYSA-N 0.000 description 1
- POEXNBXOLDYCPY-UHFFFAOYSA-N CCC1CCC(=O)O1.CCC1CCC(=O)O1 Chemical compound CCC1CCC(=O)O1.CCC1CCC(=O)O1 POEXNBXOLDYCPY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- WXUJYKFINNMZHH-UHFFFAOYSA-N O(CCCC(=O)OCC(CCCC)CC)CCCC(=O)OCC(CCCC)CC Chemical compound O(CCCC(=O)OCC(CCCC)CC)CCCC(=O)OCC(CCCC)CC WXUJYKFINNMZHH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YVNYRZGQMJTPLA-UHFFFAOYSA-N O=C1CCCCCO1.O=C1CCCCCO1 Chemical compound O=C1CCCCCO1.O=C1CCCCCO1 YVNYRZGQMJTPLA-UHFFFAOYSA-N 0.000 description 1
- SCMOHRVGZDLFNM-UHFFFAOYSA-N O=C1CCCCO1.O=C1CCCCO1 Chemical compound O=C1CCCCO1.O=C1CCCCO1 SCMOHRVGZDLFNM-UHFFFAOYSA-N 0.000 description 1
- PKVGKJDLLALEMP-UHFFFAOYSA-N O=C1CCCO1.O=C1CCCO1 Chemical compound O=C1CCCO1.O=C1CCCO1 PKVGKJDLLALEMP-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 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 1
- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 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 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid group Chemical group C(CCCCC)(=O)O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 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 1
- 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 1
- 230000003287 optical effect Effects 0.000 description 1
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
Description
本発明は新規２塩基酸エステル化合物および該化合物と新規ポリエステルとを含む潤滑油基油組成物に関する。 The present invention relates to a novel dibasic acid ester compound and a lubricating base oil composition comprising the compound and a novel polyester.
潤滑油の合成基油としては、モノエステル、ジエステルやポリオールエステル等のエステル類、ポリアルキレングリコール類、ポリ−α−オレフィン類、シリコーン油、アルキルジフェニルエーテル類などが知られている。そのなかでもジエステル系の化合物は、低温特性や潤滑性、耐熱性、粘度その他の特性において、性能のバランスが良いことが知られている。そのため種々の潤滑油、例えば軸受油、グリース、ギア油、エンジン油、自動変速機油、冷凍機用潤滑油等の基油として用いられている（例えば非特許文献１）。ジエステル化合物としては、直鎖の２塩基酸のアルコールエステルが一般的で、例えばジオクチルアジペート、ジオクチルアゼレート、ジオクチルセバケート（ＤＯＳ）などが用いられている。なかでもＤＯＳは潤滑油基油として最も主要なものの１つである。また直鎖の２塩基酸の炭素鎖の一部をイオウ原子で置換したジエステル系の化合物が軸受用潤滑剤として有用であることも知られている（例えば特許文献１）。しかし、直鎖の２塩基酸の炭素鎖の一部を酸素原子で置換したジエステル系化合物の潤滑剤への適用は知られていない。 Known synthetic base oils for lubricating oils include esters such as monoesters, diesters and polyol esters, polyalkylene glycols, poly-α-olefins, silicone oils and alkyldiphenyl ethers. Among them, diester compounds are known to have a good balance of performance in terms of low temperature characteristics, lubricity, heat resistance, viscosity and other characteristics. For this reason, it is used as a base oil for various lubricating oils such as bearing oil, grease, gear oil, engine oil, automatic transmission oil, and refrigerator lubricating oil (for example, Non-Patent Document 1). As the diester compound, a linear dibasic acid alcohol ester is generally used. For example, dioctyl adipate, dioctyl azelate, dioctyl sebacate (DOS) and the like are used. Among them, DOS is one of the most important lubricant base oils. It is also known that a diester compound in which a part of the carbon chain of a linear dibasic acid is substituted with a sulfur atom is useful as a bearing lubricant (for example, Patent Document 1). However, application of a diester compound in which a part of the carbon chain of a straight chain dibasic acid is substituted with an oxygen atom to a lubricant is not known.
近年の産業分野の多様化及び高度化に伴う、自動車並びに、映像・音響機器、パソコン等の小型・軽量化、大容量化及び情報処理の高速化の進歩には目覚しいものがある。これらの電子機器には、各種の回転装置、例えば、ＦＤ、ＭＯ、ｚｉｐ、ミニディスク、コンパクトディスク（ＣＤ）、ＤＶＤ、ハードディスク等の磁気ディスクや光ディスクを駆動する回転装置が使用されており、これら電子機器の小型・軽量化、大容量化及び高速化には回転装置に不可欠な軸受の改良が大きく寄与している。そして、潤滑流体を介して対向するスリーブと回転軸とからなる流体軸受は、ボールベアリングを持たないため、小型・軽量化に好適であり、しかも静寂性、経済性等に優れており、情報・通信、オーディオ・ビジュアル機器やカーナビゲーション等にその用途を広げてきている。上記諸機器の適用状況に関しても、機器の大衆化により過酷な環境での使用が拡大している。特に車に搭載して用いられるカーナビゲーション等の機器は、自動車の使用環境を考慮すると、寒冷地から炎天下までの使用に耐えるものでなければならない。従って、車載機器に用いられる流体軸受油に使用される潤滑流体は、−５０〜１５０℃といった広い温度範囲で問題なく使用できるものであることが要求される。また、近年ではモバイル機器への利用を考慮して、特に低温領域での粘度が低く、しかも高温下での蒸発減量が少ない新規潤滑流体の開発が強く望まれている。 With the diversification and sophistication of industrial fields in recent years, there have been remarkable advances in the miniaturization and weight reduction of automobiles, video / audio equipment, personal computers, etc., increase in capacity and speed of information processing. These electronic devices use various rotating devices such as rotating devices that drive magnetic disks and optical disks such as FD, MO, zip, mini disk, compact disk (CD), DVD, hard disk, etc. Improvements in bearings, which are indispensable for rotating devices, have greatly contributed to the reduction in size, weight, capacity, and speed of electronic equipment. A fluid bearing consisting of a sleeve and a rotating shaft that face each other via a lubricating fluid does not have a ball bearing, so it is suitable for miniaturization and weight reduction, and is excellent in quietness, economy, etc. Its application has been expanded to communications, audio / visual equipment and car navigation. Regarding the application status of the above devices, the use in harsh environments is expanding due to the popularization of the devices. In particular, a device such as a car navigation system used in a car must be able to withstand use from a cold region to a hot sun in consideration of the use environment of the car. Therefore, it is required that the lubricating fluid used for the fluid bearing oil used in the in-vehicle device can be used without any problem in a wide temperature range of −50 to 150 ° C. In recent years, in consideration of use in mobile devices, development of a new lubricating fluid that has a low viscosity particularly in a low temperature region and a low evaporation loss at a high temperature is strongly desired.
従来、この用途の基油として各種ジエステルの物理的混合物が適用されており、分枝ＤＯＳが一定の評価を得ている。しかし、省エネ・環境対応の観点から更なる低粘度化の強い要求(４０℃動粘度が一桁)が出されている。 Conventionally, a physical mixture of various diesters has been applied as a base oil for this application, and branching DOS has obtained a certain evaluation. However, there is a strong demand for further lowering the viscosity (40 ° C kinematic viscosity is one digit) from the viewpoint of energy saving and environmental friendliness.
潤滑油を上記した種々の用途に適用する場合、その用途や使用環境によって求められる性能、特性はそれぞれ異なっている。従って、潤滑油を設計する場合は、その求められる特性に応じて基油の選定や種々の添加剤、たとえば油性向上剤、粘度指数向上剤、酸化防止剤、さび止め剤等との組合せを勘案して設計するのが通常である。そのため潤滑油基油として従来使用されている化合物と異なる特性を持つ化合物があれば選択の幅が広がり、それぞれの用途、使用環境に最適な潤滑油の設計を行うことができる。また種々の添加剤と組合せたときに、性能の向上効果（以下添加剤効果という）が著しいことも潤滑油基油として重要な特性である。 When the lubricating oil is applied to the various uses described above, the required performance and characteristics vary depending on the use and usage environment. Therefore, when designing a lubricating oil, take into account the selection of base oil and combinations with various additives such as oiliness improvers, viscosity index improvers, antioxidants, rust inhibitors, etc. according to the required properties. It is usual to design. Therefore, if there is a compound having characteristics different from those conventionally used as a lubricating base oil, the range of selection is widened, and the optimum lubricating oil can be designed for each application and use environment. In addition, when combined with various additives, a remarkable performance improvement effect (hereinafter referred to as additive effect) is also an important characteristic as a lubricating base oil.
本発明の課題は、種々の潤滑油の基油として従来の化合物とは異なった特性を有するとともに、前記の諸々要望に応え得る添加剤効果に優れた新規化合物または組成物を提供することにある。 An object of the present invention is to provide a novel compound or composition excellent in additive effect that has characteristics different from those of conventional compounds as a base oil of various lubricating oils and can meet the above-mentioned various needs. .
本発明は以下の化合物および組成物を提供する。
１．式（１）で表される化合物
Ｒ１ＯＣＯ−Ａ−Ｏ−Ａ−ＣＯＯＲ２ （１）
ここで、Ｒ１およびＲ２は、同一又は異なって炭素数６〜１０の直鎖または分岐のアルキル基であり、Ａは同一又は異なって炭素数３〜５の直鎖または分岐のアルキレン基である。
２．式（２）で表される化合物
Ｒ１−Ｏ−（Ａ−ＣＯＯ−）ｎ−Ｒ２ （２）
ここで、ｎは、１以上の整数をあらわし、Ｒ１およびＲ２は、同一又は異なって炭素数６〜１０の直鎖または分岐のアルキル基であり、Ａは同一又は異なって、炭素数３〜５の直鎖または分岐のアルキレン基である。
３．式（１）で表される化合物及び／又は式（２）で表される化合物を含有する組成物
Ｒ１ＯＣＯ−Ａ−Ｏ−Ａ−ＣＯＯＲ２ （１）
Ｒ１−Ｏ−（Ａ−ＣＯＯ−）ｎ−Ｒ２ （２）
ここで、ｎは、１以上の整数をあらわし、Ｒ１およびＲ２は、同一又は異なって炭素数６〜１０の直鎖または分岐のアルキル基であり、Ａは同一又は異なって、炭素数３〜５の直鎖または分岐のアルキレン基である。
４．式（１）で表される化合物及び／又は式（２）で表される化合物を含有する軸受用潤滑流体
Ｒ１ＯＣＯ−Ａ−Ｏ−Ａ−ＣＯＯＲ２ （１）
Ｒ１−Ｏ−（Ａ−ＣＯＯ−）ｎ−Ｒ２ （２）
ここで、ｎは、１以上の整数をあらわし、Ｒ１およびＲ２は、同一又は異なって炭素数６〜１０の直鎖または分岐のアルキル基であり、Ａは同一又は異なって、炭素数３〜５の直鎖または分岐のアルキレン基である。
５．流体軸受を上記に記載の軸受用潤滑流体を用いて潤滑することを特徴とする流体軸受の潤滑方法。
The present invention provides the following compounds and compositions.
1. Compound represented by formula (1) R 1 OCO-AO-A-COOR 2 (1)
Here, R 1 and R 2 are the same or different and are linear or branched alkyl groups having 6 to 10 carbon atoms, and A is the same or different and is a linear or branched alkylene group having 3 to 5 carbon atoms. is there.
2. Compound represented by formula (2) R 1 —O— (A—COO—) n—R 2 (2)
Here, n represents an integer of 1 or more, R 1 and R 2 are the same or different and are linear or branched alkyl groups having 6 to 10 carbon atoms, and A is the same or different and has 3 carbon atoms. -5 linear or branched alkylene groups.
3. A composition comprising a compound represented by the formula (1) and / or a compound represented by the formula (2): R 1 OCO-A-O-A-COOR 2 (1)
R < 1 > -O- (A-COO-) n-R < 2 > (2)
Here, n represents an integer of 1 or more, R 1 and R 2 are the same or different and are linear or branched alkyl groups having 6 to 10 carbon atoms, and A is the same or different and has 3 carbon atoms. -5 linear or branched alkylene groups.
4). Lubricating fluid for bearings containing a compound represented by the formula (1) and / or a compound represented by the formula (2) R 1 OCO-AO-A-COOR 2 (1)
R < 1 > -O- (A-COO-) n-R < 2 > (2)
Here, n represents an integer of 1 or more, R 1 and R 2 are the same or different and are linear or branched alkyl groups having 6 to 10 carbon atoms, and A is the same or different and has 3 carbon atoms. -5 linear or branched alkylene groups.
5. A fluid bearing lubrication method comprising lubricating a fluid bearing using the bearing lubricating fluid described above.
本発明の化合物は、炭素鎖中に酸素原子を有することから、分子鎖の柔軟性が増加することで、特に低温および常温での低粘度が期待できる。軸受油等の使用環境から上記の低温特性に優れることが、重要である。 Since the compound of the present invention has an oxygen atom in the carbon chain, it can be expected to have a low viscosity at a low temperature and a normal temperature by increasing the flexibility of the molecular chain. It is important to be excellent in the above-mentioned low temperature characteristics from the usage environment such as bearing oil.
本発明の化合物および組成物は、低温および常温で比較的低い粘度を有する。これは、分子内に酸素原子を含むためと考えられる。また潤滑性においても従来のジエステル系化合物と同等であり、酸化防止剤による蒸発量低減効果（添加剤効果）も期待できる。本発明は、従来の化合物にない特性と添加剤効果を有する化合物及び組成物を提供する。 The compounds and compositions of the present invention have a relatively low viscosity at low and normal temperatures. This is presumably because the molecule contains oxygen atoms. In addition, the lubricity is equivalent to that of conventional diester compounds, and the effect of reducing the evaporation amount (additive effect) by the antioxidant can be expected. The present invention provides compounds and compositions having properties and additive effects not found in conventional compounds.
本発明は式（１）で表される化合物を提供する。
また本発明は式（２）で表される化合物を提供する。
更に、本発明は式（１）で表される化合物及び／又は式（２）で表される化合物を含有する組成物を提供する。
Ｒ１ＯＣＯ−Ａ−Ｏ−Ａ−ＣＯＯＲ２ （１）
Ｒ１−Ｏ−（Ａ−ＣＯＯ−）ｎ−Ｒ２ （２）
ここで、Ｒ１およびＲ２は、同一又は異なって炭素数６〜１０の直鎖または分岐のアルキル基であり、Ａは同一又は異なって炭素数３〜５の直鎖または分岐のアルキレン基であり、ｎは、１以上の整数を表す。
炭素数６〜１０の直鎖または分岐のアルキル基としては、例えばヘキシル、イソヘキシル、エチルヘキシル、ヘプチル、イソヘプチル、オクチル、ノニル、デシル、イソデシル等を挙げることができる。なかでも２−エチルヘキシルまたはｎ−オクチル基が好ましく、Ｒ１、Ｒ２が同一であっても異なっていてもよい。
The present invention provides a compound represented by the formula (1).
The present invention also provides a compound represented by formula (2).
Furthermore, this invention provides the composition containing the compound represented by the compound represented by Formula (1), and / or Formula (2).
R 1 OCO-A-O-A-COOR 2 (1)
R < 1 > -O- (A-COO-) n-R < 2 > (2)
Here, R 1 and R 2 are the same or different and are linear or branched alkyl groups having 6 to 10 carbon atoms, and A is the same or different and is a linear or branched alkylene group having 3 to 5 carbon atoms. Yes, n represents an integer of 1 or more.
Examples of the linear or branched alkyl group having 6 to 10 carbon atoms include hexyl, isohexyl, ethylhexyl, heptyl, isoheptyl, octyl, nonyl, decyl, isodecyl and the like. Among them, 2-ethylhexyl or n-octyl group is preferable, and R 1 and R 2 may be the same or different.
直鎖の基Ａとしては、
−ＣＨ２ＣＨ２ＣＨ２−
−ＣＨ２ＣＨ２ＣＨ２ＣＨ２−
−ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２−
が例示できる。直鎖の基としては、低温における粘度の点から、−ＣＨ２ＣＨ２ＣＨ２−が好ましい。
また、分岐の基Ａとしては、
酸素側 ―ＣＨ（ＣＨ３）ＣＨ２ＣＨ２− カルボニル側
酸素側 ―ＣＨ（ＣＨ２ＣＨ３）ＣＨ２ＣＨ２− カルボニル側
酸素側 ―ＣＨ（ＣＨ３）ＣＨ２ＣＨ２ＣＨ２− カルボニル側
が例示できる。
As the linear group A,
-CH 2 CH 2 CH 2 -
-CH 2 CH 2 CH 2 CH 2 -
-CH 2 CH 2 CH 2 CH 2 CH 2 -
Can be illustrated. As the linear group, —CH 2 CH 2 CH 2 — is preferable from the viewpoint of viscosity at low temperature.
As the branched group A,
Oxygen side —CH (CH 3 ) CH 2 CH 2 —Carbonyl side
The oxygen side —CH (CH 2 CH 3 ) CH 2 CH 2 —carbonyl side The oxygen side —CH (CH 3 ) CH 2 CH 2 CH 2 —carbonyl side can be exemplified.
本発明の化合物および組成物は、例えば以下のようにして製造することができる。
即ち、式（３）で表されるラクトン化合物と、Ｒ１−ＯＨおよび／またはＲ２−ＯＨで示されるアルコールとを開環カップリング反応させることにより、式（１）と式（２）を含む混合物を得る。さらに、前記混合物から、式（２）の化合物をエステル交換・留去することにより、式（１）の化合物を得る。
The compound and composition of this invention can be manufactured as follows, for example.
That is, the lactone compound represented by the formula (3) and the alcohol represented by R 1 —OH and / or R 2 —OH are subjected to a ring-opening coupling reaction to thereby convert the formula (1) and the formula (2). A mixture containing is obtained. Further, the compound of formula (1) is obtained by transesterifying and distilling off the compound of formula (2) from the mixture.
式（３）で表される、ラクトン化合物としては、以下を例示することができる。
γ−ブチロラクトン（テトラヒドロフラン−２−オン）、γ−バレロラクトン（５−メチルテトラヒドロフラン−２−オン）、γ−カプロラクトン（５−エチルテトラヒドロフラン−２−オン）、δ−バレロラクトン（テトラヒドロピラン−２−オン）、δ−カプロラクトン（６−メチルテトラヒドロピラン−２−オン）、ε−カプロラクトン（オキセパン−２−オン）などが好適に用いられる。アルキル置換基を有しないラクトンを用いると上記式（１）および（２）においてＡとして、直鎖のアルキレン基を導入でき、アルキル置換基を有するラクトンを用いるとＡとして分岐のアルキレン基を導入できる。
The following can be illustrated as a lactone compound represented by Formula (3).
γ-butyrolactone (tetrahydrofuran-2-one), γ-valerolactone (5-methyltetrahydrofuran-2-one), γ-caprolactone (5-ethyltetrahydrofuran-2-one), δ-valerolactone (tetrahydropyran-2-one) ON), δ-caprolactone (6-methyltetrahydropyran-2-one), ε-caprolactone (oxepan-2-one) and the like are preferably used. When a lactone having no alkyl substituent is used, a linear alkylene group can be introduced as A in the above formulas (1) and (2), and when a lactone having an alkyl substituent is used, a branched alkylene group can be introduced as A. .
アルコールとしては、炭素数６〜１０の直鎖または分岐のアルキルアルコールを用いることができる。例えば、ｎ−ヘキサノール、イソヘキサノール、２−メチルヘキサノール、ｎ−ヘプタノール、１−メチルへプタノール、２−メチルへプタノール、ｎ−オクタノール、２−エチルヘキサノール、ｎ−ノナノール、イソノナノール、イソデカノールなどを例示することができる。 As the alcohol, a linear or branched alkyl alcohol having 6 to 10 carbon atoms can be used. Examples include n-hexanol, isohexanol, 2-methylhexanol, n-heptanol, 1-methylheptanol, 2-methylheptanol, n-octanol, 2-ethylhexanol, n-nonanol, isononanol, isodecanol and the like. be able to.
上記アルコールを単独で用いれば、Ｒ１およびＲ２が同一のアルキル基を導入でき、異なるアルコールの混合物を用いると、Ｒ１とＲ２が異なるアルキル基を導入できる。本製造方法においては触媒を用いることができる。触媒としては、硫酸、燐酸、メタンスルホン酸、トリフルオロメタンスルホン酸、ベンゼンスルホン酸、トルエンスルホン酸等の酸が例示できパラトルエンスルホン酸が好ましい。本製造方法は無溶媒で実施されるが、トルエン、キシレン等の溶媒を用いることも可能である。 If the alcohol is used alone, R 1 and R 2 can introduce the same alkyl group, and if a mixture of different alcohols is used, an alkyl group having different R 1 and R 2 can be introduced. In this production method, a catalyst can be used. Examples of the catalyst include acids such as sulfuric acid, phosphoric acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid, and paratoluenesulfonic acid is preferable. Although this production method is carried out without a solvent, it is also possible to use a solvent such as toluene or xylene.
反応は通常１００〜１４０℃の範囲で、通常１０〜２００時間行うのが好ましい。反応後、触媒を中和し、低沸点物を留去して式（１）と(２)の混合物を得ることができる。得られた混合物にオクタノール等のアルコールを式(２)の化合物に対し過剰等量加え、触媒を添加して加熱し、式（２）の化合物をエステル交換ならびに脱水縮合することにより、式（１）で表される化合物と式(２)のｎ＝１の化合物等が得られる。これから式（１）の化合物以外の低沸物を留去することにより、式（１）の化合物が得られる。
式（１）の化合物のみを得る場合、通常の反応後、触媒を中和せず低沸点物を留去し、これに式(２)の化合物に対し過剰等量のアルコールを加え加熱し、式（１）以外の低沸物を留去すれば良い。
The reaction is usually preferably performed in the range of 100 to 140 ° C. and usually for 10 to 200 hours. After the reaction, the catalyst is neutralized, and the low-boiling substances are distilled off to obtain a mixture of the formulas (1) and (2). An excess amount of alcohol such as octanol is added to the resulting mixture with respect to the compound of the formula (2), a catalyst is added and heated, and the compound of the formula (2) is transesterified and subjected to dehydration condensation. ) And the compound of n = 1 in the formula (2) are obtained. From this, the compound of formula (1) is obtained by distilling off the low-boiling substances other than the compound of formula (1).
When only the compound of the formula (1) is obtained, after the usual reaction, the low boiling point product is distilled off without neutralizing the catalyst, and an excess equivalent amount of alcohol is added to the compound of the formula (2) and heated. What is necessary is just to distill low-boiling substances other than Formula (1).
以下に、本発明の製造方法についてより詳しく説明する。
式（３）のラクトン化合物と先に例示したアルコールに触媒を加え、通常１００〜１４０℃、好ましくは１１５〜１３５℃で約１０〜２００時間、好ましくは５０〜１７０時間の共沸脱水で水を分離する。引続いて減圧濃縮により未反応原料を回収し、冷却後、アルカリを添加し触媒を中和し、続いて炭酸で過剰のアルカリを中和した後、析出した結晶を濾別して濾過物を得る。
この濾過物を濃縮後、蒸留塔を用いて分留し、更に精留し、場合により得られた留分を活性炭と活性白土で吸着精製し高純度の式(１)の化合物及び式(２)の化合物の混合物を得る。
Below, the manufacturing method of this invention is demonstrated in detail.
A catalyst is added to the lactone compound of the formula (3) and the alcohol exemplified above, and water is added by azeotropic dehydration usually at 100 to 140 ° C., preferably 115 to 135 ° C. for about 10 to 200 hours, preferably 50 to 170 hours. To separate. Subsequently, the unreacted raw material is recovered by concentration under reduced pressure. After cooling, the alkali is added to neutralize the catalyst, and then the excess alkali is neutralized with carbonic acid. Then, the precipitated crystals are separated by filtration to obtain a filtrate.
The filtrate is concentrated, fractionated using a distillation column, further rectified, and the fraction obtained in some cases is adsorbed and purified with activated carbon and activated clay to obtain a highly pure compound of formula (1) and formula (2 ) To obtain a mixture of compounds.
この混合物にアルコールと触媒を加え、通常１００〜１４０℃、好ましくは１１５〜１３５℃で約２〜１５０時間、好ましくは１０〜１００時間加熱する。冷却後、アルカリを添加して触媒を中和し、続いて炭酸で過剰のアルカリを中和した後、析出した結晶を濾別して濾過物を得る。
この濾過物を濃縮後、蒸留塔を用いて分留し、更に精留し、場合により得られた留分を活性炭と活性白土で吸着精製し高純度の式(１)の化合物を得る。
ラクトン化合物がγ−ブチロラクトン、アルコールが２−エチルへキサノールの場合の反応スキームを以下に示す。
Alcohol and a catalyst are added to this mixture, and it is normally heated at 100-140 degreeC, Preferably it is 115-135 degreeC for about 2-150 hours, Preferably it is 10-100 hours. After cooling, the alkali is added to neutralize the catalyst, and then the excess alkali is neutralized with carbonic acid. Then, the precipitated crystals are separated by filtration to obtain a filtrate.
The filtrate is concentrated, fractionated using a distillation column, and further rectified, and the fraction obtained in some cases is adsorbed and purified with activated carbon and activated clay to obtain a highly pure compound of formula (1).
A reaction scheme when the lactone compound is γ-butyrolactone and the alcohol is 2-ethylhexanol is shown below.
上記化２で、式（１）と式（２）を含む混合物が得られる。さらに、化３で、該混合物にプロトン酸触媒と過剰等量の２−エチルヘキサノールを添加して加熱し、式（２）の化合物をエステル交換ならびに脱水縮合することにより、式（１）で表される化合物と式(２)のｎ＝１の化合物およびγ−ブチロラクトンが生成する。これから式（１）以外の低沸物を留去することにより、式（１）の化合物を得ることができる。 By the said Chemical formula 2, the mixture containing Formula (1) and Formula (2) is obtained. Further, in Chemical Formula 3, the mixture is heated by adding a protonic acid catalyst and an excess amount of 2-ethylhexanol to the mixture, and the compound of formula (2) is transesterified and subjected to dehydration condensation. And n = 1 of the formula (2) and γ-butyrolactone are produced. From this, the compound of formula (1) can be obtained by distilling off low-boiling substances other than formula (1).
式（２）の化合物において、ｎは１以上の整数を表わし、好ましくは１〜５、更に好ましくは２〜３の整数を表わす。式(２)の化合物の分子量はｎの値により一義的に定まり、そのｎは１Ｈ−ＮＭＲの４.１ｐｐｍと２.４ｐｐｍのピーク積分値の比に１を加えて得ることができる。好ましい分子量は２７２〜８７０、更に好ましくは３５８〜６４０である。
式（１）の化合物と式（２）の化合物は構成元素組成および分子量ならびに官能基組成と個数も同じの構造異性体である。然るに、沸点や親和性ならびに粘性等の物理的性質も酷似しており、蒸留法や吸着法で２つの物質を分離する事は非常に困難である。この為、両化合物の混合による諸特性の差は小さく、前記エステル交換を生じるような条件下で使用される場合を除き、その混合割合は任意の比率で用いる事ができる。
逆に前記エステル交換を生じるような条件下で使用される場合は式（２）の化合物の割合が少ないほど良く、式（１）の化合物単独使用が好ましい。
In the compound of the formula (2), n represents an integer of 1 or more, preferably 1 to 5, more preferably an integer of 2 to 3. The molecular weight of the compound of formula (2) is uniquely determined by the value of n, which can be obtained by adding 1 to the ratio of the peak integral values of 4.1 ppm and 2.4 ppm of 1 H-NMR. The preferred molecular weight is 272 to 870, more preferably 358 to 640.
The compound of the formula (1) and the compound of the formula (2) are structural isomers having the same constituent element composition and molecular weight and functional group composition and number. However, physical properties such as boiling point, affinity and viscosity are very similar, and it is very difficult to separate two substances by distillation or adsorption. For this reason, the difference of the various characteristics by mixing of both compounds is small, and the mixing ratio can be used at any ratio except when used under conditions that cause the transesterification.
Conversely, when used under conditions that cause transesterification, the smaller the proportion of the compound of formula (2), the better, and the use of the compound of formula (1) alone is preferred.
本発明の化合物および組成物は、各種潤滑油、たとえば軸受油、流体軸受油、含油軸受油、含油プラスチックス油、ギヤ油、エンジン油、自動変速機油、その他の機械油、作動油などの基油として用いることができるだけでなく、グリースの基油としても用いることができる。また、他の合成基油に添加または併用することも可能であり、潤滑油設計の幅を広げる化合物としても好適である。その他、潤滑油用途だけでなく、例えば可塑剤、冷凍機油などに利用できる。 The compounds and compositions of the present invention are based on various lubricating oils such as bearing oils, fluid bearing oils, oil-impregnated bearing oils, oil-impregnated plastics oils, gear oils, engine oils, automatic transmission oils, other machine oils and hydraulic oils. Not only can it be used as an oil, it can also be used as a base oil for grease. It can also be added to or used in combination with other synthetic base oils, and is also suitable as a compound that broadens the range of lubricant design. Besides, it can be used not only for lubricating oil but also for plasticizer, refrigerating machine oil, and the like.
式（１）及び／又は式（２）で示される化合物は、潤滑流体全量基準で５０重量％以上含有されることが好ましく、８０重量％以上含有されることがより好ましく、９５重量％以上含有されることが最も好ましい。上限は１００重量％以下、好ましくは９９.９重量％以下である。 The compound represented by the formula (1) and / or the formula (2) is preferably contained in an amount of 50% by weight or more based on the total amount of the lubricating fluid, more preferably 80% by weight or more, and 95% by weight or more. Most preferably. The upper limit is 100% by weight or less, preferably 99.9% by weight or less.
本発明の潤滑流体には、式（１）及び／又は式（２）で示される化合物に加えて、鉱油、オレフィン重合体、アルキルベンゼン等の炭化水素系油や、ポリグリコール、ポリビニルエーテル、ケトン、ポリフェニルエーテル、シリコーン、ポリシロキサン、パーフルオロエーテル、式（１）または式（２）で示される化合物以外のエステルやエーテル等の酸素含有合成油を用いてもよい。 In addition to the compounds represented by formula (1) and / or formula (2), the lubricating fluid of the present invention includes mineral oil, olefin polymer, hydrocarbon oil such as alkylbenzene, polyglycol, polyvinyl ether, ketone, Oxygen-containing synthetic oils such as esters and ethers other than the compounds represented by polyphenyl ether, silicone, polysiloxane, perfluoroether, formula (1) or formula (2) may be used.
本発明の潤滑流体には、基油としての式（１）及び／又は式（２）で示される化合物に加えて、実用性能を向上させるために、各種の添加剤を配合することができる。このような添加剤として、フェノール系酸化防止剤、アミン系酸化防止剤、硫黄系酸化防止剤、リン系酸化防止剤、耐加水分解性向上剤としてエポキシ化合物、また金属不活性化剤としてベンゾトリアゾール誘導体等の添加剤から１種又は２種以上をそれぞれ０.０１〜５重量%配合することも効果的である。 In addition to the compound represented by Formula (1) and / or Formula (2) as the base oil, various additives can be blended in the lubricating fluid of the present invention in order to improve practical performance. Such additives include phenolic antioxidants, amine antioxidants, sulfur antioxidants, phosphorus antioxidants, epoxy compounds as hydrolysis resistance improvers, and benzotriazoles as metal deactivators. It is also effective to add 0.01 to 5% by weight of one or more of additives such as derivatives.
本発明の流体軸受は、この流体軸受用潤滑流体を用いることを特徴とする。本発明の流体軸受は、ボールベアリング等の機構を有さず、スリーブと軸とからなり、それらの間に収容された潤滑流体によって互いに直接接触することがないように間隔が保持される流体軸受であれば、機械的に特に限定されるものではない。本発明の流体軸受は、回転軸及びスリーブの何れかに又はそれらの両方に動圧発生溝が設けられ、回転軸が動圧によって支持される流体軸受、また回転軸に垂直方向に動圧を生じるようにスラストプレートが設けられている流体軸受等も含む。 The fluid dynamic bearing according to the present invention is characterized by using the lubricating fluid for the fluid dynamic bearing. The hydrodynamic bearing of the present invention does not have a mechanism such as a ball bearing, and includes a sleeve and a shaft, and the hydrodynamic bearing is maintained at a distance so as not to be in direct contact with each other by a lubricating fluid accommodated between them. If it is, it will not be specifically limited mechanically. The hydrodynamic bearing of the present invention is provided with a dynamic pressure generating groove in either or both of the rotating shaft and the sleeve, and the rotating shaft is supported by the dynamic pressure, and the dynamic pressure is applied in a direction perpendicular to the rotating shaft. It also includes a fluid bearing or the like provided with a thrust plate so as to occur.
流体軸受は、非回転時には動圧が生じないためにスリーブと回転軸あるいはスリーブとスラストプレートが部分的あるいは全面接触しており、回転により動圧が生じて非接触状態となる。こうしたことから接触、非接触を繰り返し、スリーブと回転軸あるいはスリーブとスラストプレートの金属摩耗が起こったり、回転中の一時的な接触により焼き付きを起こすことがある。しかしながら、優れた省エネルギー性、耐熱性及び低温特性を有する本発明の流体軸受用動圧軸受装置を用いることによって、長期に亘り高速回転安定性及び耐久性が保持され、特に高速において優れた省エネルギー性を示す。 Since the hydrodynamic bearing does not generate dynamic pressure when not rotating, the sleeve and the rotary shaft or the sleeve and the thrust plate are in partial or full contact with each other, and dynamic pressure is generated by the rotation, resulting in a non-contact state. For this reason, contact and non-contact may be repeated, and metal wear may occur between the sleeve and the rotating shaft or the sleeve and the thrust plate, or seizure may occur due to temporary contact during rotation. However, by using the hydrodynamic bearing device for hydrodynamic bearings of the present invention having excellent energy saving properties, heat resistance and low temperature characteristics, high-speed rotational stability and durability are maintained over a long period of time, and particularly excellent energy saving properties at high speeds. Indicates.
以下実施例で本発明をさらに詳しく説明するが、本発明の範囲は以下の実施例に限定して解釈されるべきではない。 The present invention will be described in more detail with reference to the following examples. However, the scope of the present invention should not be construed as being limited to the following examples.
実施例１
発明品１及び発明品２の製造
発明品１：式（１ａ）の化合物（２−エチルへキシルオキシカルボニルプロピルエーテル）
発明品２：式（１ａ）の化合物及び式（２ａ）の化合物［４−（２−エチルへキシルオキシ）ブタン酸−３−（２−エチルへキシルオキシカルボニル）プロピルエステル］の混合物
１０リットルのガラス製反応器にガンマーブチロラクトン４６７０ｇ、２−エチルへキサノール４５３０ｇ、パラトルエンスルホン酸１水和物４０ｇを仕込み、減圧調整をしつつ１２５〜１３５℃で約５０時間の共沸脱水で約７５０ｇの水を分離した。引続いてダイヤフラムポンプを用いた減圧濃縮により未反応原料５８７０ｇを回収した。３０℃以下に冷却後、２５％ＫＯＨ水溶液５６ｇを添加し１時間の攪拌でパラトルエンスルホン酸を中和し、続いて炭酸ガスで過剰のＫＯＨを中和した後、析出した結晶を濾過助剤を用いて濾別して濾過物２７００ｇを得た。
この濾過物を０.１〜０.３ｔｏｒｒで蒸留塔を用いて分留し、目的物５８５ｇを得た。この物を精留して１８０〜１９０℃／約０.１ｔｏｒｒの留分４８０ｇを得た。更にこの留分を活性炭と活性白土で吸着精製し、ガスクロマトグラフィーによる純度９９.６％の発明品２を４５５ｇ得た（収率１３.７％）。図−１にそのガスクロマトグラフィーチャートを示す。
ガスクロマトグラフィーでは図１の如く単一ピークであるが、プロトンＮＭＲでは図２の如く式（１）の化合物と式（２）の化合物に由来するスペクトルが観られ、両者の混合物である事が判る。このスペクトルのピーク積分値より算出した式（１）と式（２）の化合物の存在比は凡そ３：２であった。
この混合物（発明品２）のキャノンフェンスケ粘度計による測定値は、４０℃動粘度が９.７８６ｍｍ２／ｓｅｃで、１００℃動粘度は２.７５５ｍｍ２／ｓｅｃであり、粘度指数は１３２であった。
更に、この発明品２を用いて以下の処理を行い、発明品１を得た。
５００ｍｌのガラス製四つ口フラスコに本発明品２を３１５ｇ秤取し、これに２−エチルへキサノール８０ｇとパラトルエンスルホン酸１水和物１.１５ｇを添加して、１２８〜１３４℃で９１時間加熱した。３０℃以下に冷却後、２０％ＫＯＨ水溶液２.０ｇを添加し１時間攪拌してパラトルエンスルホン酸を中和し、続いて炭酸ガスで過剰のＫＯＨを中和した後、析出結晶を濾別して濾過物３９３ｇを得た。この物を蒸留塔を用いて分留し、１６１〜１８９℃／約０.１ｔｏｒｒの目的留分１７７ｇを得た。
これを精留して１６８〜１９０℃／約０.１ｔｏｒｒの留分１６５ｇを得、この留分を活性炭と活性白土で吸着精製し、ガスクロマトグラフィーによる純度９９.２％の発明品１を１５８ｇ得た（回収率８５.５％）。図３にそのガスクロマトグラフィーチャートを示す。
この物のプロトンＮＭＲは図４の如く、式（２）の化合物に由来する３.３ｐｐｍ及び４.１ｐｐｍのスペクトルが微小となっており、このスペクトルの３.２から４.５ｐｐｍのピーク積分比より、式（２）の化合物の残存率は１％未満と算定した。
Example 1
Production of
Invention 2: Mixture of compound of formula (1a) and compound of formula (2a) [4- (2-ethylhexyloxy) butanoic acid-3- (2-ethylhexyloxycarbonyl) propyl ester] 10 liters of glass A reactor made of 4670 g of gamma-butyrolactone, 4530 g of 2-ethylhexanol and 40 g of paratoluenesulfonic acid monohydrate was charged, and about 750 g of water was obtained by azeotropic dehydration at 125 to 135 ° C. for about 50 hours while adjusting the vacuum. separated. Subsequently, 5870 g of unreacted raw material was recovered by vacuum concentration using a diaphragm pump. After cooling to 30 ° C. or lower, 56 g of 25% KOH aqueous solution was added, and paratoluenesulfonic acid was neutralized by stirring for 1 hour, followed by neutralizing excess KOH with carbon dioxide gas, and then the precipitated crystals were filtered out. And 2700 g of a filtrate was obtained.
This filtrate was fractionally distilled at 0.1 to 0.3 torr using a distillation tower to obtain 585 g of the desired product. This product was rectified to obtain 480 g of a fraction at 180 to 190 ° C./about 0.1 torr. Further, this fraction was purified by adsorption with activated carbon and activated clay to obtain 455 g of Inventive Product 2 having a purity of 99.6% by gas chromatography (yield 13.7%). Fig. 1 shows the gas chromatography chart.
In gas chromatography, it has a single peak as shown in FIG. 1, but in proton NMR, a spectrum derived from the compound of formula (1) and the compound of formula (2) is seen as shown in FIG. 2, and it is a mixture of both. I understand. The abundance ratio of the compounds of formula (1) and formula (2) calculated from the peak integration value of this spectrum was about 3: 2.
The measured value of this mixture (Invention 2) with a Canon Fenceke viscometer is as follows: 40 ° C. kinematic viscosity is 9.786 mm 2 / sec, 100 ° C. kinematic viscosity is 2.755 mm 2 / sec, and the viscosity index is 132. there were.
Further, the invention 2 was subjected to the following treatment to obtain the
315 g of the product 2 of the present invention was weighed into a 500 ml glass four-necked flask, and 80 g of 2-ethylhexanol and 1.15 g of paratoluenesulfonic acid monohydrate were added thereto. Heated for hours. After cooling to 30 ° C. or less, 2.0 g of 20% KOH aqueous solution was added and stirred for 1 hour to neutralize paratoluenesulfonic acid, then neutralize excess KOH with carbon dioxide gas, and then precipitate crystals were filtered off. 393 g of a filtrate was obtained. This product was fractionally distilled using a distillation column to obtain 177 g of a target fraction of 161 to 189 ° C./about 0.1 torr.
This was rectified to obtain 165 g of a fraction of 168 to 190 ° C./about 0.1 torr. This fraction was adsorbed and purified with activated carbon and activated clay, and 158 g of
As shown in FIG. 4, the proton NMR of this product has a minute spectrum of 3.3 ppm and 4.1 ppm derived from the compound of formula (2), and the peak integration ratio of 3.2 to 4.5 ppm of this spectrum. Accordingly, the residual ratio of the compound of the formula (2) was calculated to be less than 1%.
実施例２
発明品１の製造
実施例１と同様に、ガンマーブチロラクトン４２７５ｇ、２−エチルへキサノール４２２６ｇ、パラトルエンスルホン酸１水和物４０ｇを用いて、１２５〜１３５℃で約９０時間の共沸脱水を行った。引続いてダイヤフラムポンプを用いた減圧濃縮で未反応原料３６８５ｇを回収し、濃縮物４３００ｇを得た。
この濃縮物のプロトンＮＭＲ積分値から求めた式（２）の化合物の含有量が２.３モルであったことから、３倍当量の２−エチルへキサノール９００ｇを添加して１２０〜１３０℃？で約６５時間の式（２）の化合物の除去反応を行った。引続いてダイヤフラムポンプを用いた減圧濃縮により残存原料１３３０ｇを回収した。３０℃以下に冷却後、１５％ＫＯＨ水溶液９５ｇを添加し１時間の攪拌でパラトルエンスルホン酸を中和し、続いて炭酸ガスで過剰のＫＯＨを中和した後、水層を分液除去し、水洗・芒硝脱水・濾過の後、濾過物２９３０ｇを得た。この濾過物を０.１〜０.３ｔｏｒｒで蒸留塔を用いて分留し、目的物６６２ｇを得た。この物を精留して１８３〜１９２℃／約０.１ｔｏｒｒの留分５１１ｇを得た。更にこの留分を活性炭と活性白土で吸着精製し、ガスクロマトグラフィーによる純度９９.５％の発明品１を４６４ｇ得た。（収率１０.５％）
この物は図５の１Ｈ−ＮＭＲスペクトルの３.２から４.５ｐｐｍのピーク積分比より、式（２）の化合物の残存率は約３％と算定した。
Example 2
Production of
Since the content of the compound of the formula (2) obtained from the proton NMR integrated value of this concentrate was 2.3 mol, 900 g of 3-fold equivalent of 2-ethylhexanol was added to 120 to 130 ° C.? The removal reaction of the compound of formula (2) was carried out for about 65 hours. Subsequently, 1330 g of the remaining raw material was recovered by vacuum concentration using a diaphragm pump. After cooling to 30 ° C or lower, 95 g of a 15% KOH aqueous solution was added, and paratoluenesulfonic acid was neutralized by stirring for 1 hour, followed by neutralizing excess KOH with carbon dioxide, and then separating and removing the aqueous layer. After washing with water, sodium sulfate dehydration, and filtration, 2930 g of a filtrate was obtained. This filtrate was fractionated at 0.1 to 0.3 torr using a distillation column to obtain 662 g of the desired product. This product was rectified to obtain 511 g of a fraction of 183 to 192 ° C./about 0.1 torr. Further, this fraction was adsorbed and purified with activated carbon and activated clay to obtain 464 g of
From this peak integration ratio of 3.2 to 4.5 ppm in the 1 H-NMR spectrum of FIG. 5, the residual ratio of the compound of formula (2) was calculated to be about 3%.
実施例３
発明品３（２エチルへキシル＋ｎオクチル）の製造
２リットルのガラス製反応器に、ガンマーブチロラクトン６６０ｇ、２−エチルへキサノール２５０ｇ、ｎ−オクタノール２５０ｇ、パラトルエンスルホン酸１水和物２.８ｇを用い、下記フローの如く１２５〜１３２℃で約１００時間の共沸脱水反応を行った。
Example 3
Production of Invention 3 (2-ethylhexyl + n-octyl) In a 2-liter glass reactor, 660 g of gamma-butyrolactone, 250 g of 2-ethylhexanol, 250 g of n-octanol and 2.8 g of paratoluenesulfonic acid monohydrate were added. The azeotropic dehydration reaction was carried out at 125 to 132 ° C. for about 100 hours as shown in the flow below.
３０℃以下に冷却後、２５％ＫＯＨ水溶液４.５ｇを添加し１時間の攪拌でパラトルエンスルホン酸を中和し、続いて炭酸ガスで過剰のＫＯＨを中和した。引続いてダイヤフラムポンプを用いた減圧濃縮で未反応原料６６０ｇを回収し、析出した結晶を濾過助剤を用いて濾別して濾過物３５５ｇを得た。
この濾過物を蒸留塔を用いて分留し、収率約１９％で１６７〜１７４℃／０.０５ｔｏｒｒの目的留分６６ｇを得た。図６の如く、この物のガスクロマトグラフィーによる純度は約９４％で、低沸点物０.９％と高沸点物４.５％を含んでいた。又、この主成分はｎが２の下記６成分の混合物と考えられるが、前記の発明品２の場合と同様に、１と６、２と５、３と４が夫々重なって３本のピークと成っているものと思われる。
この物は、図７の１Ｈ−ＮＭＲスペクトルの３.２から４.２ｐｐｍのピーク積分比より、式（１）と式（２）の化合物の比率が４８：５２の混合物と算定した。
この物の４０℃動粘度は１０.３０ｍｍ２／ｓｅｃであった。
After cooling to 30 ° C. or less, 4.5 g of 25% KOH aqueous solution was added, and paratoluenesulfonic acid was neutralized by stirring for 1 hour, and then excess KOH was neutralized with carbon dioxide gas. Subsequently, 660 g of unreacted raw material was recovered by vacuum concentration using a diaphragm pump, and the precipitated crystals were filtered using a filter aid to obtain 355 g of a filtrate.
This filtrate was fractionated using a distillation column to obtain 66 g of a target fraction of 167 to 174 ° C./0.05 torr in a yield of about 19%. As shown in FIG. 6, the purity of this product by gas chromatography was about 94%, which contained 0.9% of low-boiling substances and 4.5% of high-boiling substances. This main component is considered to be a mixture of the following 6 components with n = 2, but as in the case of the invention 2 described above, 1 and 6, 2 and 5, 3 and 4 overlap each other and there are 3 peaks. It seems that it is made up of.
This product was calculated as a mixture of 48:52 ratio of the compounds of formula (1) and formula (2) from the peak integration ratio of 3.2 to 4.2 ppm of 1 H-NMR spectrum of FIG.
The kinematic viscosity at 40 ° C. of this product was 10.30 mm 2 / sec.
実施例４
発明品４：式（１ｂ）の化合物及び式（２ｂ）の化合物の混合物の製造
式（１ｂ）の化合物：２−エチルへキシルオキシカルボニルペンチルエーテル
式（２ｂ）の化合物：６−（２−エチルへキシルオキシ）ヘキサン酸−５−（２−エチルへキシルオキシカルボニル）ペンチルエステル
１リットルのガラス製反応器で、ε−カプロラクトン２７０ｇと２−エチルへキサノール３３０ｇ及びパラトルエンスルホン酸１水和物０.９ｇを用い、１２５〜１３２℃で約３.５時間の下記フローの第一工程の反応を行った後、２００℃で１５時間の第二工程の反応を行った。
その後、実施例３と同様に処理と濃縮ならびに蒸留を行い、２００〜２１０℃／１２０〜１３５Ｐａの目的留分７５ｇを得た。図８の如く、この物のＧＣ純度は約９０％ｗで、低沸物と高沸物をそれぞれ約３％ずつ含んでいた。
この物は、図９のプロトンＮＭＲスペクトルの３.２から４.２ｐｐｍのピーク積分比より、式（１）と式（２）の化合物の比率が凡そ４：１の混合物であった。
この混合物の４０℃動粘度は１３.０３ｍｍ２／ｓｅｃであった。
Example 4
Invention 4: Preparation of mixture of compound of formula (1b) and compound of formula (2b) Compound of formula (1b): 2-ethylhexyloxycarbonylpentyl ether Compound of formula (2b): 6- (2-ethyl Hexyloxy) hexanoic acid-5- (2-ethylhexyloxycarbonyl) pentyl ester In a 1 liter glass reactor, 270 g of ε-caprolactone, 330 g of 2-ethylhexanol and paratoluenesulfonic acid monohydrate 9 g was used, and the reaction in the first step of the following flow at 125 to 132 ° C. for about 3.5 hours was performed, followed by the reaction in the second step at 200 ° C. for 15 hours.
Thereafter, treatment, concentration and distillation were performed in the same manner as in Example 3 to obtain 75 g of a target fraction of 200 to 210 ° C./120 to 135 Pa. As shown in FIG. 8, the GC purity of this product was about 90% w, and each contained about 3% of low and high boiling substances.
This product was a mixture in which the ratio of the compounds of formula (1) and formula (2) was about 4: 1 from the peak integration ratio of 3.2 to 4.2 ppm in the proton NMR spectrum of FIG.
The 40 ° C. kinematic viscosity of this mixture was 13.03 mm 2 / sec.
実施例５
発明品５：式（２ｃ）の化合物の製造
式（２ｃ）の化合物：４−（２−エチルへキシルオキシ）ブタン酸−５−（２−エチルへキシルオキシカルボニル）ペンチルエステル
１リットルのガラス製反応器を用い、ε−カプロラクトン２３３ｇと実施例１及び２で副生する４−（２−エチルへキシルオキシ）ブタン酸２−エチルへキシルエステル６２７ｇ及びパラトルエンスルホン酸１水和物１.９ｇを用い、１９０〜２１０℃で２４時間の上記フローの反応を行った。続いて重曹水洗浄と脱水の後、減圧蒸留により１８５〜２０５℃／７０〜８０Ｐａの主留分１６０ｇ（収率１８.７％）と２０６〜２２０℃／９０〜１００Ｐａの後留分１０６ｇ（収率１２.３％）を得た。
主留分は図１０、図１１のプロトンＮＭＲとＧＣ分析から、上記フローの目的物（ｎ＝１）を主成分（含有率７５％）とする物であり、その４０℃動粘度は１３.７７ｍｍ２／ｓｅｃであった。
後留分は図１２、図１３のプロトンＮＭＲとＧＣ分析から、上記フローのｎ＝２を主成分としｎ＝３を約１５％含む物である事が判った。また、この物の４０℃動粘度は２３.５１ｍｍ２／ｓｅｃであった。
Example 5
Invention product 5: Preparation of compound of formula (2c) Compound of formula (2c): 4- (2-ethylhexyloxy) butanoic acid-5- (2-ethylhexyloxycarbonyl)
The main fraction is based on the proton NMR and GC analysis of FIGS. 10 and 11 and has the target product (n = 1) as the main component (content 75%), and its 40 ° C. kinematic viscosity is 13. It was 77 mm 2 / sec.
From the proton NMR and GC analysis of FIGS. 12 and 13, it was found that the after-fraction had a main component of n = 2 in the above flow and about 15% of n = 3. Moreover, the 40 degreeC kinematic viscosity of this thing was 23.51 mm < 2 > / sec.
試験例１
発明品１、発明品２、発明品３ およびセバシン酸ジ２−エチルヘキシル（以下ＤＯＳと略す）を比較例１として用い、以下の試験項目を測定して物性と潤滑油としての特性を評価した。物性測定及び性能評価試験は、次の方法で行った。
１） ４０℃動粘度：ＪＩＳ Ｋ ２２８３に準じ、キャノン−フェンスケ粘度計を用いて動粘度を測定した。
２） １００℃動粘度：ＪＩＳ Ｋ ２２８３に準じ、キャノン−フェンスケ粘度計を用いて動粘度を測定した。
３） −４０℃絶対粘度：ＡＳＴＭ Ｄ ５１３３に準じ、回転式粘度計を用い絶対粘度を測定した。
４） 蒸発性試験：９ｍｌガラス瓶に、試料２ｇを量りとり、１２０℃、Ａｉｒ雰囲気下で７２時間後及び２６０時間後の蒸発量（％）を観察した。
５） 酸化防止剤としてジオクチルジフェニルアミンを使用した。
物性測定、熱安定性の評価結果を表１、表２に示す。
Test example 1
1) Kinematic viscosity at 40 ° C .: Kinematic viscosity was measured using a Canon-Fenske viscometer according to JIS K 2283.
2) 100 degreeC kinematic viscosity: According to JISK2283, kinematic viscosity was measured using the Canon-Fenske viscometer.
3) −40 ° C. absolute viscosity: The absolute viscosity was measured using a rotary viscometer according to ASTM D 5133.
4) Evaporation test: A 2 g sample was weighed into a 9 ml glass bottle, and the evaporation amount (%) after 72 hours and 260 hours was observed at 120 ° C. in an Air atmosphere.
5) Dioctyl diphenylamine was used as an antioxidant.
Tables 1 and 2 show the results of physical property measurement and thermal stability evaluation.
試験例２
次に、本発明の潤滑油組成物を用いる一実施形態である動圧流体軸受について説明する。図１４は本発明に関わる動圧流体軸受が記録ディスク駆動用のスピンドルモーターと一体化された一例の概略断面図である。
動圧流体軸受は静止体のスリーブと回転体のシャフトに一体化されたスラスト軸受の上下でしっかりと支える構造となっている。動圧流体軸受は回転体と静止体のとの隙間に充填された本発明の潤滑流体が回転体と共に回転方向に流れると、隙間に設けられた溝が動圧上昇部分を作り、回転体が浮上する。溝はシャフトとスラスト軸受上下に設けられており、Ｖ字形で、それぞれ回転方向に対して等間隔に並んでいる。
当該動圧流体軸受は軸を浮上させて軸方向を支えるスラスト軸受と、軸の振れを抑えて径方向を支えるジャーナル軸受で構成されている。
本構造のスピンドルモーターは、効果的なメカニカルシールの作用で２万ｒｐｍ超の高速回転に対しても潤滑流体の飛散が無く、安定した回転を実現する事ができる。
軸受性能の指標となるＮＲＲＯ（Ｎｏｎ−ｒｅｐｅａｔａｂｌｅ Ｒｕｎｏｕｔ：繰り返し位置決め精度）試験には分解能１ｎｍの静電容量型非接触変位計を用い、２.５インチハードディスク周辺部の変位測定を行った結果、軸方向の変位は１００ｎｍ未満の良好なものであった。
Test example 2
Next, a hydrodynamic bearing which is an embodiment using the lubricating oil composition of the present invention will be described. FIG. 14 is a schematic sectional view of an example in which a hydrodynamic bearing according to the present invention is integrated with a spindle motor for driving a recording disk.
The hydrodynamic bearing is structured to be firmly supported above and below a thrust bearing integrated with a stationary sleeve and a rotating shaft. In the hydrodynamic bearing, when the lubricating fluid of the present invention filled in the gap between the rotating body and the stationary body flows in the rotation direction together with the rotating body, the groove provided in the gap creates a dynamic pressure increasing portion, Surface. The grooves are provided above and below the shaft and the thrust bearing, are V-shaped, and are arranged at equal intervals in the rotational direction.
The hydrodynamic bearing is composed of a thrust bearing that floats the shaft and supports the axial direction, and a journal bearing that supports the radial direction while suppressing shaft deflection.
The spindle motor of this structure can realize a stable rotation without scattering of the lubricating fluid even at a high speed rotation exceeding 20,000 rpm by an effective mechanical seal.
For the NRRO (Non-repeatable Runout) test, which is an index of bearing performance, a displacement non-contact displacement meter with a resolution of 1 nm was used to measure the displacement around the 2.5 inch hard disk. The directional displacement was good with less than 100 nm.
本発明の実施例の潤滑油剤は常温領域で低粘度かつ−４０℃において良好な流動性を有し、また顕著な添加剤効果を有しており、潤滑剤として有効に使用できるものであり、動圧流体軸受用潤滑流体としても有効な物であることが分かる。
更に、体積抵抗率がＤＯＳの１／１０００の１０９オーダーである事から、油剤自身で帯電防止能を有しており、静電気問題に敏感なハードディスクドライブ等の精密電気・電子機器用の潤滑剤として有用なものである。
The lubricating oil of the example of the present invention has a low viscosity in the normal temperature region and good fluidity at -40 ° C, and has a remarkable additive effect, and can be used effectively as a lubricant. It can be seen that this is also effective as a lubricating fluid for a hydrodynamic bearing.
Further, the volume resistivity is 10 9 order of 1/1000 of DOS, have antistatic performance in oil itself, lubricants for precision electric and electronic equipment such as a sensitive hard disk drive static problems As useful as.
本発明の化合物および組成物は、各種潤滑油、たとえば軸受油、流体軸受油、含油軸受油、含油プラスチックス油、ギヤ油、エンジン油、自動変速機油、その他の機械油、作動油などの基油として用いることができるだけでなく、グリースの基油としても用いることができる。また、他の合成基油に添加または併用することも可能であり、潤滑油設計の幅を広げる化合物としても好適である。その他、潤滑油用途だけでなく、例えば可塑剤、冷凍機油などに利用できる。 The compounds and compositions of the present invention are based on various lubricating oils such as bearing oils, fluid bearing oils, oil-impregnated bearing oils, oil-impregnated plastics oils, gear oils, engine oils, automatic transmission oils, other machine oils and hydraulic oils. Not only can it be used as an oil, it can also be used as a base oil for grease. It can also be added to or used in combination with other synthetic base oils, and is also suitable as a compound that broadens the range of lubricant design. Besides, it can be used not only for lubricating oil but also for plasticizer, refrigerating machine oil, and the like.
Claims (7)
Ｒ１−Ｏ−（Ａ−ＣＯＯ−）ｎ−Ｒ２ （２）
ここで、ｎは、２〜５の整数をあらわし、Ｒ１およびＲ２は、同一又は異なって炭素数６〜１０の直鎖または分岐のアルキル基であり、Ａは同一又は異なって、炭素数３〜５の直鎖または分岐のアルキレン基である。 Lubricating base oil composition containing a mixture of compounds represented by formula (2) R 1 —O— (A—COO—) n—R 2 (2)
Here, n represents an integer of 2 to 5, R 1 and R 2 are the same or different and are linear or branched alkyl groups having 6 to 10 carbon atoms, and A is the same or different and has a carbon number 3 to 5 linear or branched alkylene groups.
Ｒ１−Ｏ−（Ａ−ＣＯＯ−）ｎ−Ｒ２ （２）
ここで、ｎは、２〜３の整数をあらわし、Ｒ１およびＲ２は、同一又は異なって炭素数６〜１０の直鎖または分岐のアルキル基であり、Ａは同一又は異なって、炭素数３〜５の直鎖または分岐のアルキレン基である。 Lubricating base oil composition containing a mixture of compounds represented by formula (2) R 1 —O— (A—COO—) n—R 2 (2)
Here, n represents an integer of 2 to 3, R 1 and R 2 are the same or different and are linear or branched alkyl groups having 6 to 10 carbon atoms, and A is the same or different and has a carbon number 3 to 5 linear or branched alkylene groups.
Ｒ１−Ｏ−（Ａ−ＣＯＯ−）ｎ−Ｒ２ （２）
ここで、ｎは、２の整数をあらわし、Ｒ１およびＲ２は、同一又は異なって炭素数６〜１０の直鎖または分岐のアルキル基であり、Ａは同一又は異なって、炭素数３〜５の直鎖または分岐のアルキレン基である。 Lubricating base oil composition containing a mixture of compounds represented by formula (2) R 1 —O— (A—COO—) n—R 2 (2)
Here, n represents an integer of 2, R 1 and R 2 are the same or different and are linear or branched alkyl groups having 6 to 10 carbon atoms, and A is the same or different and has 3 to 3 carbon atoms. 5 linear or branched alkylene groups.
Ｒ１−Ｏ−（Ａ−ＣＯＯ−）ｎ−Ｒ２ （２）
ここで、ｎは、２〜５の整数をあらわし、Ｒ１およびＲ２は、同一又は異なって炭素数６〜１０の直鎖または分岐のアルキル基であり、Ａは同一又は異なって、炭素数３〜５の直鎖または分岐のアルキレン基である。 Lubricating fluid for bearings containing a mixture of compounds represented by formula (2) R 1 —O— (A—COO—) n—R 2 (2)
Here, n represents an integer of 2 to 5, R 1 and R 2 are the same or different and are linear or branched alkyl groups having 6 to 10 carbon atoms, and A is the same or different and has a carbon number 3 to 5 linear or branched alkylene groups.
Ｒ１−Ｏ−（Ａ−ＣＯＯ−）ｎ−Ｒ２ （２）
ここで、ｎは、２〜３の整数をあらわし、Ｒ１およびＲ２は、同一又は異なって炭素数６〜１０の直鎖または分岐のアルキル基であり、Ａは同一又は異なって、炭素数３〜５の直鎖または分岐のアルキレン基である。 Lubricating fluid for bearings containing a mixture of compounds represented by formula (2) R 1 —O— (A—COO—) n—R 2 (2)
Here, n represents an integer of 2 to 3, R 1 and R 2 are the same or different and are linear or branched alkyl groups having 6 to 10 carbon atoms, and A is the same or different and has a carbon number 3 to 5 linear or branched alkylene groups.
Ｒ１−Ｏ−（Ａ−ＣＯＯ−）ｎ−Ｒ２ （２）
ここで、ｎは、２の整数をあらわし、Ｒ１およびＲ２は、同一又は異なって炭素数６〜１０の直鎖または分岐のアルキル基であり、Ａは同一又は異なって、炭素数３〜５の直鎖または分岐のアルキレン基である。 Lubricating fluid for bearings containing a mixture of compounds represented by formula (2) R 1 —O— (A—COO—) n—R 2 (2)
Here, n represents an integer of 2, R 1 and R 2 are the same or different and are linear or branched alkyl groups having 6 to 10 carbon atoms, and A is the same or different and has 3 to 3 carbon atoms. 5 linear or branched alkylene groups.
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