JP7020425B2 - Freezer oil composition and working fluid composition for refrigerators containing it - Google Patents
Freezer oil composition and working fluid composition for refrigerators containing it Download PDFInfo
- Publication number
- JP7020425B2 JP7020425B2 JP2018554996A JP2018554996A JP7020425B2 JP 7020425 B2 JP7020425 B2 JP 7020425B2 JP 2018554996 A JP2018554996 A JP 2018554996A JP 2018554996 A JP2018554996 A JP 2018554996A JP 7020425 B2 JP7020425 B2 JP 7020425B2
- Authority
- JP
- Japan
- Prior art keywords
- ester
- refrigerating machine
- machine oil
- oil composition
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 100
- 239000012530 fluid Substances 0.000 title claims description 15
- 150000002148 esters Chemical class 0.000 claims description 151
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 90
- 239000010721 machine oil Substances 0.000 claims description 79
- 239000000654 additive Substances 0.000 claims description 72
- 125000001931 aliphatic group Chemical group 0.000 claims description 52
- 230000000996 additive effect Effects 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- -1 citric acid triester Chemical class 0.000 claims description 33
- 239000003507 refrigerant Substances 0.000 claims description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- 229930195733 hydrocarbon Natural products 0.000 claims description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 claims description 16
- 150000001735 carboxylic acids Chemical class 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 14
- NMRPBPVERJPACX-UHFFFAOYSA-N octan-3-ol Chemical compound CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 8
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 8
- WQNHWIYLCRZRLR-UHFFFAOYSA-N 2-(3-hydroxy-2,5-dioxooxolan-3-yl)acetic acid Chemical compound OC(=O)CC1(O)CC(=O)OC1=O WQNHWIYLCRZRLR-UHFFFAOYSA-N 0.000 description 7
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 7
- 239000004927 clay Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 6
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 6
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 6
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 6
- NGDNVOAEIVQRFH-UHFFFAOYSA-N 2-nonanol Chemical compound CCCCCCCC(C)O NGDNVOAEIVQRFH-UHFFFAOYSA-N 0.000 description 6
- GYSCXPVAKHVAAY-UHFFFAOYSA-N 3-Nonanol Chemical compound CCCCCCC(O)CC GYSCXPVAKHVAAY-UHFFFAOYSA-N 0.000 description 6
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 6
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 6
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 6
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N hexan-3-ol Chemical compound CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 6
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 6
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 6
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000004378 air conditioning Methods 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 239000001282 iso-butane Substances 0.000 description 4
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000005691 triesters Chemical class 0.000 description 4
- 239000005968 1-Decanol Substances 0.000 description 3
- ACUZDYFTRHEKOS-SNVBAGLBSA-N 2-Decanol Natural products CCCCCCCC[C@@H](C)O ACUZDYFTRHEKOS-SNVBAGLBSA-N 0.000 description 3
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 3
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 3
- QNJAZNNWHWYOEO-UHFFFAOYSA-N 2-ethylheptan-1-ol Chemical compound CCCCCC(CC)CO QNJAZNNWHWYOEO-UHFFFAOYSA-N 0.000 description 3
- UKFQWAVMIMCNEH-UHFFFAOYSA-N 2-ethylpentan-1-ol Chemical compound CCCC(CC)CO UKFQWAVMIMCNEH-UHFFFAOYSA-N 0.000 description 3
- QZESEQBMSFFHRY-UHFFFAOYSA-N 2-methylheptan-1-ol Chemical compound CCCCCC(C)CO QZESEQBMSFFHRY-UHFFFAOYSA-N 0.000 description 3
- LCFKURIJYIJNRU-UHFFFAOYSA-N 2-methylhexan-1-ol Chemical compound CCCCC(C)CO LCFKURIJYIJNRU-UHFFFAOYSA-N 0.000 description 3
- BEGNRPGEHZBNKK-UHFFFAOYSA-N 2-methylnonan-1-ol Chemical compound CCCCCCCC(C)CO BEGNRPGEHZBNKK-UHFFFAOYSA-N 0.000 description 3
- IGVGCQGTEINVOH-UHFFFAOYSA-N 2-methyloctan-1-ol Chemical compound CCCCCCC(C)CO IGVGCQGTEINVOH-UHFFFAOYSA-N 0.000 description 3
- NMRPBPVERJPACX-QMMMGPOBSA-N 3-Octanol Natural products CCCCC[C@@H](O)CC NMRPBPVERJPACX-QMMMGPOBSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- ACUZDYFTRHEKOS-UHFFFAOYSA-N decan-2-ol Chemical compound CCCCCCCCC(C)O ACUZDYFTRHEKOS-UHFFFAOYSA-N 0.000 description 3
- ICEQLCZWZXUUIJ-UHFFFAOYSA-N decan-3-ol Chemical compound CCCCCCCC(O)CC ICEQLCZWZXUUIJ-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 2
- HTRVTKUOKQWGMO-UHFFFAOYSA-N 2-ethyloctan-1-ol Chemical compound CCCCCCC(CC)CO HTRVTKUOKQWGMO-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- WLAMNBDJUVNPJU-BYPYZUCNSA-N 2-Methylbutanoic acid Natural products CC[C@H](C)C(O)=O WLAMNBDJUVNPJU-BYPYZUCNSA-N 0.000 description 1
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 1
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 description 1
- SCRHTSOMOIJEDP-UHFFFAOYSA-N 3-ethylnonan-2-ol Chemical compound CCCCCCC(CC)C(C)O SCRHTSOMOIJEDP-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/34—Esters of monocarboxylic acids
-
- 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
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
-
- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/36—Esters of polycarboxylic acids
-
- 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/76—Esters containing free hydroxy or carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P20/00—Technologies relating to chemical industry
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Description
本発明は、冷凍機油組成物およびこれを含有する冷凍機用作動流体組成物に関する。 The present invention relates to a refrigerating machine oil composition and a working fluid composition for a refrigerating machine containing the same.
従来、ルームエアコン、パッケージエアコンなどの空調機器、家庭用冷凍冷蔵庫、産業用冷凍機、およびハイブリッドカー、電気自動車などのカーエアコン等の冷媒には、塩素を含むクロロフルオロカーボン（ＣＦＣ）冷媒が用いられていた。近年では、オゾン層の破壊などの原因となるこれらＣＦＣ冷媒に代わり、冷媒Ｒ１３４ａ（１，１，１，２－テトラフルオロエタン）、冷媒Ｒ１２５（ペンタフルオロエタン）、冷媒Ｒ４１０Ａ（冷媒Ｒ３２（ジフルオロメタン）および冷媒Ｒ１２５（ペンタフルオロエタン）の混合冷媒）などのハイドロフルオロカーボン（ＨＦＣ）冷媒が使用されている。
しかし、これらのＨＦＣ冷媒は、地球温暖化係数（ＧＷＰ）が１，０００以上と高いことから、いわゆるＦ－ガス規制により使用が制限されつつある。ＨＦＣ冷媒の代替候補としては低ＧＷＰであることが必須であり、その一つとして既に冷蔵庫用として実用化されているイソブタン（冷媒Ｒ６００ａ）のような炭化水素冷媒等が挙げられる。炭化水素冷媒は、ＧＷＰが２０以下と極めて低く、物性値が好適であることから、幅広い利用が検討されている。Conventionally, chlorofluorocarbon (CFC) refrigerants containing chlorine have been used as refrigerants for air conditioners such as room air conditioners and packaged air conditioners, household refrigerators and refrigerators, industrial refrigerators, and car air conditioners such as hybrid cars and electric vehicles. Was there. In recent years, instead of these CFC refrigerants that cause destruction of the ozone layer, refrigerant R134a (1,1,1,2-tetrafluoroethane), refrigerant R125 (pentafluoroethane), and refrigerant R410A (refrigerant R32 (difluoromethane)) ) And a mixed refrigerant of the refrigerant R125 (pentafluoroethane)) and a hydrofluorocarbon (HFC) refrigerant are used.
However, since these HFC refrigerants have a high global warming potential (GWP) of 1,000 or more, their use is being restricted by so-called F-gas regulations. As an alternative candidate for HFC refrigerant, low GWP is indispensable, and one of them is a hydrocarbon refrigerant such as isobutane (refrigerant R600a) which has already been put into practical use for refrigerators. Hydrocarbon refrigerants have an extremely low GWP of 20 or less and have suitable physical property values, and therefore, widespread use is being studied.
一方で、家庭用冷凍冷蔵庫には更なる省エネルギー化が求められ、冷凍機油についても、低粘度化を図った省エネルギータイプの冷凍機油が求められてきている。しかし、冷凍機油の低粘度化に伴い、冷凍圧縮機の圧縮部での潤滑性不足などの問題が懸念されている。炭化水素冷媒共存下では、冷媒の溶解により冷凍機油の粘度が著しく低下することから、従来以上に冷凍機油の潤滑性の向上が求められている。そのため、潤滑性を改善する目的で、これまで種々の添加剤の使用が検討されてきた。例えば特許文献１には、モノエステルと、リン酸エステル等のリンを含む極圧添加剤を含有する炭化水素冷媒用冷凍機油が開示されている。
しかしながら、上記のような添加剤を用いた冷凍機油組成物は、条件によっては潤滑性が十分ではなく、添加剤の添加量を増やす必要がある。ところが、潤滑性向上効果に優れる添加剤には、結晶性が高く、冷凍機油への溶解性が乏しいものがあり、添加量が制限される場合もある。さらに、炭化水素冷媒共存下の条件によっては、加えた添加剤が析出・分離する可能性がある。
以上のことから、添加剤の溶解性が高い冷凍機油組成物の開発が望まれている。On the other hand, further energy saving is required for household refrigerators and freezers, and energy saving type refrigerating machine oil with low viscosity is also required for refrigerating machine oil. However, with the decrease in viscosity of refrigerating machine oil, there are concerns about problems such as insufficient lubricity in the compressed portion of the refrigerating compressor. In the coexistence of a hydrocarbon refrigerant, the viscosity of the refrigerating machine oil is remarkably lowered due to the dissolution of the refrigerant, so that the lubricity of the refrigerating machine oil is required to be improved more than before. Therefore, the use of various additives has been studied so far for the purpose of improving lubricity. For example, Patent Document 1 discloses a refrigerating machine oil for a hydrocarbon refrigerant containing a monoester and an extreme pressure additive containing phosphorus such as a phosphoric acid ester.
However, the refrigerating machine oil composition using the above-mentioned additives does not have sufficient lubricity depending on the conditions, and it is necessary to increase the amount of the additives added. However, some additives having an excellent effect of improving lubricity have high crystallinity and poor solubility in refrigerating machine oil, and the amount of addition may be limited. Further, depending on the conditions in the presence of the hydrocarbon refrigerant, the added additive may precipitate and separate.
From the above, it is desired to develop a refrigerating machine oil composition having high solubility of additives.
本発明はこのような事情に鑑みなされたものであって、その目的は、潤滑性を付与するために添加される添加剤の溶解性に優れる冷凍機油組成物、およびそれを含有する冷凍機用作動流体組成物を提供することにある。 The present invention has been made in view of such circumstances, and an object thereof is a refrigerating machine oil composition having excellent solubility of an additive added to impart lubricity, and a refrigerating machine containing the same. To provide a working fluid composition.
本発明者らは、上記目的を達成するために鋭意検討を行なった結果、クエン酸トリエステルと、炭素数３～１４の脂肪族１価アルコールと炭素数４～１２の脂肪族１価カルボン酸とからなる脂肪族モノエステルとの混合エステルであって、両者を特定の質量比で含有する混合エステルが、冷凍機油として、潤滑性を付与するために添加される添加剤に対し、優れた溶解性を示すことを見出し、本発明を完成するに至った。この知見に基づく本発明は、以下の通りである。 As a result of diligent studies to achieve the above object, the present inventors have made a citric acid triester, an aliphatic monohydric alcohol having 3 to 14 carbon atoms, and an aliphatic monovalent carboxylic acid having 4 to 12 carbon atoms. A mixed ester with an aliphatic monoester consisting of and containing both in a specific mass ratio is excellently dissolved in an additive added to impart lubricity as a refrigerating machine oil. It has been found that it exhibits sexuality, and the present invention has been completed. The present invention based on this finding is as follows.
［１］下記エステル（Ａ）とエステル（Ｂ）との混合エステル、および下記添加剤を含有する冷凍機油組成物であって、エステル（Ａ）とエステル（Ｂ）の含有量比［エステル（Ａ）／エステル（Ｂ）］が質量比にて１／９９～３０／７０であり、下記添加剤を、エステル（Ａ）とエステル（Ｂ）との混合エステル１００質量％に対して、０．０１質量％～１０質量％含有し、エステル（Ａ）とエステル（Ｂ）との混合エステルの４０℃における動粘度が１ｍｍ２／ｓ～２０ｍｍ２／ｓである、冷凍機油組成物。
エステル（Ａ）：クエン酸トリエステル
エステル（Ｂ）：炭素数３～１４の脂肪族１価アルコールと、炭素数４～１２の脂肪族１価カルボン酸とからなる脂肪族モノエステル
添加剤：ヘキサン溶媒中に１質量％の濃度で溶解させたときの曇り点が－２０℃以上である、添加剤
［２］クエン酸トリエステルが、クエン酸と炭素数２～１０の脂肪族１価アルコールとからなるクエン酸トリエステルである、上記［１］記載の冷凍機油組成物。
［３］前記添加剤が、トリフェニルホスフェートおよびグリセリンモノオレエートからなる群より選択される１種以上である、上記[１]又は[２]に記載の冷凍機油組成物。
［４］上記［１］～［３］のいずれか１つに記載の冷凍機油組成物および炭化水素冷媒を含有する、冷凍機用作動流体組成物。[1] A refrigerating machine oil composition containing the following mixed ester of ester (A) and ester (B) and the following additive, wherein the content ratio of ester (A) and ester (B) is [ester (A). ) / Ester (B)] is 1/99 to 30/70 in mass ratio, and the following additives are added to 0.01 with respect to 100% by mass of the mixed ester of the ester (A) and the ester (B). A refrigerating machine oil composition containing 1% by mass to 10% by mass and having a kinematic viscosity of a mixed ester of an ester (A) and an ester (B) at 40 ° C. of 1 mm 2 / s to 20 mm 2 / s.
Ester (A): Citrate Triester Ester (B): An aliphatic monoester consisting of an aliphatic monovalent alcohol having 3 to 14 carbon atoms and an aliphatic monovalent carboxylic acid having 4 to 12 carbon atoms Additive: hexane The cloudiness point when dissolved in a solvent at a concentration of 1% by mass is -20 ° C or higher. Additive [2] Citrate triester contains citric acid and an aliphatic monovalent alcohol having 2 to 10 carbon atoms. The refrigerating machine oil composition according to the above [1], which is a citrate triester comprising the above [1].
[3] The refrigerating machine oil composition according to the above [1] or [2], wherein the additive is at least one selected from the group consisting of triphenylphosphine and glycerin monooleate.
[4] A working fluid composition for a refrigerator containing the refrigerating machine oil composition and the hydrocarbon refrigerant according to any one of the above [1] to [3].
本発明の冷凍機油組成物は、潤滑性を付与するために添加される添加剤の溶解性に優れるため、潤滑性が特に要求される冷凍空調機器や、家庭用冷凍冷蔵庫等のコンプレッサーに好適に用いることができる。また、本発明の冷凍機油組成物は、炭化水素の存在下でも、添加剤の溶解性に優れるため、炭化水素冷媒を含有する冷凍機用作動流体組成物において、好適に用いることができる。 Since the refrigerating machine oil composition of the present invention has excellent solubility of the additive added to impart lubricity, it is suitable for a compressor such as a freezing air-conditioning device or a household refrigerator-freezer where lubricity is particularly required. Can be used. Further, since the refrigerating machine oil composition of the present invention has excellent solubility of additives even in the presence of hydrocarbons, it can be suitably used in working fluid compositions for refrigerating machines containing a hydrocarbon refrigerant.
以下、本発明の冷凍機油組成物および冷凍機用作動流体組成物について説明する。
なお、本明細書において記号「～」を用いて規定された数値範囲は、「～」の両端（上限および下限）の数値を含むものとする。例えば「２～１０」は２以上１０以下を表す。Hereinafter, the refrigerating machine oil composition and the working fluid composition for a refrigerating machine of the present invention will be described.
In addition, the numerical range defined by using the symbol "-" in this specification shall include the numerical values at both ends (upper limit and lower limit) of "-". For example, "2 to 10" represents 2 or more and 10 or less.
［冷凍機油組成物］
本発明の冷凍機油組成物は、（ｉ）エステル（Ａ）とエステル（Ｂ）との混合エステル、および、（ｉｉ）ヘキサン溶媒中に１質量％の濃度で溶解させたときの曇り点が－２０℃以上である添加剤を含有する。
なお、本明細書において、「冷凍機油組成物」とは、一般に、冷凍空調機器におけるコンプレッサーのための潤滑油を意味し、冷凍空調機器としては、例えば、家庭用冷凍冷蔵庫等が挙げられる。[Refrigerator oil composition]
The refrigerating machine oil composition of the present invention has (i) a mixed ester of an ester (A) and an ester (B), and (ii) a clouding point when dissolved in a hexane solvent at a concentration of 1% by mass. Contains additives that are above 20 ° C.
In the present specification, the "refrigerator oil composition" generally means a lubricating oil for a compressor in a refrigerating and air-conditioning device, and examples of the refrigerating and air-conditioning device include a household refrigerator-freezer and the like.
（ｉ）エステル（Ａ）とエステル（Ｂ）との混合エステル
本明細書において、「エステル（Ａ）とエステル（Ｂ）との混合エステル」とは、エステル（Ａ）とエステル（Ｂ）の混合物を意味する。(I) Mixed ester of ester (A) and ester (B) In the present specification, "mixed ester of ester (A) and ester (B)" means a mixture of ester (A) and ester (B). Means.
本発明において用いるエステル（Ａ）は、クエン酸トリエステルである。該クエン酸トリエステルを製造するためのクエン酸としては、工業的に入手可能なクエン酸を使用することができる。また、クエン酸トリエステルの製造には、クエン酸無水物を使用してもよい。 The ester (A) used in the present invention is a citric acid triester. As the citric acid for producing the citric acid triester, industrially available citric acid can be used. Further, citric acid anhydride may be used for the production of citric acid triester.
本発明の目的には、クエン酸トリエステルとしては、クエン酸と脂肪族１価アルコールとからなるクエン酸トリエステルが好ましい。クエン酸とトリエステルを形成する脂肪族１価アルコールとしては、炭素数２～１０の脂肪族１価アルコールが好ましく、より好ましくは炭素数２～９の脂肪族１価アルコールである。
クエン酸とトリエステルを形成する炭素数２～１０の脂肪族１価アルコールは、１種または２種類以上を使用することができる。炭素数２～１０の脂肪族１価アルコールの具体例としては、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、２－メチル－１－プロパノール、２－メチル－２－プロパノール、１－ペンタノール、２－ペンタノール、３－ペンタノール、３－メチル－１－ブタノール、１－ヘキサノール、２－ヘキサノール、３－ヘキサノール、２－メチル－１－ペンタノール、２－エチル－１－ブタノール、１－ヘプタノール、２－ヘプタノール、３－ヘプタノール、２－メチル－１－ヘキサノール、２－エチル－１－ペンタノール、１－オクタノール、２－オクタノール、３－オクタノール、２－メチル－１－ヘプタノール、２－エチル－１－ヘキサノール、１－ノナノール、２－ノナノール、３－ノナノール、２－メチル－１－オクタノール、２－エチル－１－ヘプタノール、１－デカノール、２－デカノール、３－デカノール、２－メチル－１－ノナノール、２－エチル－１－オクタノールなどが挙げられる。For the purposes of the present invention, the citric acid triester is preferably a citric acid triester composed of citric acid and an aliphatic monohydric alcohol. As the aliphatic monohydric alcohol forming a triester with citric acid, an aliphatic monohydric alcohol having 2 to 10 carbon atoms is preferable, and an aliphatic monohydric alcohol having 2 to 9 carbon atoms is more preferable.
As the aliphatic monohydric alcohol having 2 to 10 carbon atoms forming a triester with citric acid, one kind or two or more kinds can be used. Specific examples of aliphatic monohydric alcohols having 2 to 10 carbon atoms include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol. , 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 2-ethyl-1 -Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-methyl-1-hexanol, 2-ethyl-1-pentanol, 1-octanol, 2-octanol, 3-octanol, 2-methyl-1- Heptanol, 2-ethyl-1-hexanol, 1-nonanol, 2-nonanol, 3-nonanol, 2-methyl-1-octanol, 2-ethyl-1-heptanol, 1-decanol, 2-decanol, 3-decanol, Examples thereof include 2-methyl-1-nonanol and 2-ethyl-1-octanol.
クエン酸とトリエステルを形成する炭素数２～１０の脂肪族１価アルコールとしては、炭素数２～５の脂肪族１価アルコール（成分（ａ１））と、炭素数６～１０の脂肪族１価アルコール（成分（ａ２））とを併用することが好ましい。これら成分（ａ１）および成分（ａ２）としては、それぞれ、１種類を使用してもよく、また２種類以上を使用してもよい。 The aliphatic monohydric alcohol having 2 to 10 carbon atoms forming a triester with citric acid includes an aliphatic monohydric alcohol having 2 to 5 carbon atoms (component (a1)) and an aliphatic 1 alcohol having 6 to 10 carbon atoms. It is preferable to use it in combination with a valent alcohol (component (a2)). As the component (a1) and the component (a2), one type may be used, or two or more types may be used.
成分（ａ１）としては、例えば、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、２－メチル－１－プロパノール、２－メチル－２－プロパノール、１－ペンタノール、２－ペンタノール、３－ペンタノール、３－メチル－１－ブタノールなどが挙げられる。
成分（ａ１）としては、炭素数２～５の直鎖状の飽和脂肪族１価アルコールが好ましい。
なお、１－ブタノールを使用すると、低温安定性に優れるクエン酸トリエステルを得ることができるので、成分（ａ１）としては、１－ブタノールを含む態様が特に好ましい。Examples of the component (a1) include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol and 2-. Examples thereof include pentanol, 3-pentanol and 3-methyl-1-butanol.
As the component (a1), a linear saturated aliphatic monohydric alcohol having 2 to 5 carbon atoms is preferable.
When 1-butanol is used, a citric acid triester having excellent low temperature stability can be obtained. Therefore, as the component (a1), an embodiment containing 1-butanol is particularly preferable.
成分（ａ２）としては、例えば、１－ヘキサノール、２－ヘキサノール、３－ヘキサノール、２－メチル－１－ペンタノール、２－エチル－１－ブタノール、１－ヘプタノール、２－ヘプタノール、３－ヘプタノール、２－メチル－１－ヘキサノール、２－エチル－１－ペンタノール、１－オクタノール、２－オクタノール、３－オクタノール、２－メチル－１－ヘプタノール、２－エチル－１－ヘキサノール、１－ノナノール、２－ノナノール、３－ノナノール、２－メチル－１－オクタノール、２－エチル－１－ヘプタノール、１－デカノール、２－デカノール、３－デカノール、２－メチル－１－ノナノール、２－エチル－１－オクタノールなどが挙げられる。
クエン酸トリエステル中のアルコールに由来するアルキル基が分岐鎖状である場合、クエン酸トリエステルの低温安定性が優れる傾向が見られるので、成分（ａ２）としては、炭素数６～１０の分岐鎖飽和脂肪族１価アルコールが好ましく、炭素数７～９の分岐鎖飽和脂肪族１価アルコールがより好ましい。
なお、脂肪族１価アルコールとして、２－エチル－１－ヘキサノールを使用することによって、低温安定性に優れるクエン酸トリエステルを得ることができるので、成分（ａ２）としては、２－エチル－１－ヘキサノールを含む態様が特に好ましい。Examples of the component (a2) include 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, and the like. 2-Methyl-1-hexanol, 2-ethyl-1-pentanol, 1-octanol, 2-octanol, 3-octanol, 2-methyl-1-heptanol, 2-ethyl-1-hexanol, 1-nonanol, 2 -Nonanol, 3-nonanol, 2-methyl-1-octanol, 2-ethyl-1-heptanol, 1-decanol, 2-decanol, 3-decanol, 2-methyl-1-nonanol, 2-ethyl-1-octanol And so on.
When the alkyl group derived from the alcohol in the citrate triester is in the form of a branched chain, the low temperature stability of the citrate triester tends to be excellent. Therefore, the component (a2) is branched with 6 to 10 carbon atoms. A chain saturated aliphatic monohydric alcohol is preferable, and a branched chain saturated aliphatic monohydric alcohol having 7 to 9 carbon atoms is more preferable.
By using 2-ethyl-1-hexanol as the aliphatic monohydric alcohol, a citric acid triester having excellent low temperature stability can be obtained. Therefore, as the component (a2), 2-ethyl-1 is used. -Ethylhexanol-containing embodiments are particularly preferred.
クエン酸トリエステルを構成する成分（ａ１）と成分（ａ２）のモル比［（成分（ａ１）／成分（ａ２）］は、２０／８０～９５／５であることが好ましく、６０／４０～９５／５であることがより好ましい。成分（ａ１）と成分（ａ２）のモル比を前記範囲に調整することによって、析出した添加剤を再溶解させる性能（添加剤再溶解性）に優れるクエン酸トリエステルを得ることができる。
添加剤再溶解性の観点からは、成分（ａ１）と成分（ａ２）のモル比［成分（ａ１）／成分（ａ２）］は、さらに好ましくは６５／３５～９０／１０であり、さらにより好ましくは６５／３５～８５／１５である。The molar ratio [(component (a1) / component (a2)] of the component (a1) and the component (a2) constituting the citric acid triester is preferably 20/80 to 95/5, and is preferably 60/40 to. It is more preferably 95/5. By adjusting the molar ratio of the component (a1) and the component (a2) to the above range, citric acid having excellent performance (additive resolubility) to redissolve the precipitated additive is excellent. An acid triester can be obtained.
From the viewpoint of additive resolubility, the molar ratio of the component (a1) to the component (a2) [component (a1) / component (a2)] is more preferably 65/35 to 90/10, and even more. It is preferably 65/35 to 85/15.
クエン酸トリエステルを構成する上記成分（ａ１）と成分（ａ２）のモル比［（成分（ａ１）／成分（ａ２）］を調整する方法は特に限定されない。例えば、クエン酸またはクエン酸無水物と、成分（ａ１）および成分（ａ２）の混合物とを反応させてもよいし、クエン酸またはクエン酸無水物と、成分（ａ１）および成分（ａ２）のそれぞれとを反応させた生成物を混合してもよい。 The method for adjusting the molar ratio [(component (a1) / component (a2)]] of the above component (a1) and the component (a2) constituting the citric acid triester is not particularly limited. For example, citric acid or citric acid anhydride. And a mixture of the component (a1) and the component (a2) may be reacted, or a product obtained by reacting citric acid or citric acid anhydride with each of the component (a1) and the component (a2). It may be mixed.
クエン酸トリエステルを構成する成分（ａ１）と成分（ａ２）のモル比［（成分（ａ１）／成分（ａ２）］は、ガスクロマトグラフィーによって分析することができる。例えば、クエン酸トリエステル（０．１ｇ）を、質量比が８０／２０であるトルエン／メタノールの混合溶媒（５ｇ）で希釈し、次いで２８質量％ナトリウムメトキシドメタノール溶液（和光純薬工業株式会社製）（０．３ｇ）を加え、常温にて３０分静置することにより、クエン酸トリエステルを加メタノール分解する。得られた前記エステル分解物溶液をガスクロマトグラフィーで分析し、得られた成分（ａ１）および成分（ａ２）のピーク面積比から、クエン酸トリエステルを構成する成分（ａ１）と成分（ａ２）のモル比［成分（ａ１）／成分（ａ２）］を算出することができる。なお、各アルコールをそれぞれ単独でガスクロマトグラフィーにより分析することで、クエン酸トリエステルを構成するアルコールの種類を同定することができる。 The molar ratio [(component (a1) / component (a2)] of the component (a1) and the component (a2) constituting the citric acid triester can be analyzed by gas chromatography, for example, the citric acid triester (). 0.1 g) is diluted with a mixed solvent (5 g) of toluene / methanol having a mass ratio of 80/20, and then a 28 mass% sodium methoxydomine methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) (0.3 g). The citric acid triester is decomposed with methanol by allowing it to stand at room temperature for 30 minutes. The obtained ester decomposition product solution is analyzed by gas chromatography, and the obtained component (a1) and the component (a1) are analyzed. From the peak area ratio of a2), the molar ratio [component (a1) / component (a2)] of the component (a1) and the component (a2) constituting the citric acid triester can be calculated. The types of alcohols constituting the citric acid triester can be identified by analyzing each of them independently by gas chromatography.
クエン酸トリエステルは、例えば、クエン酸またはクエン酸無水物および脂肪族１価アルコールを反応器に仕込み、常圧での窒素雰囲気下または減圧下にて、例えば１５０℃～２５０℃で、反応水を留去しつつエステル化反応を行なうことによって、製造することができる。得られるクエン酸トリエステルの酸価は、好ましくは１０ｍｇＫＯＨ／ｇ以下であり、より好ましくは５ｍｇＫＯＨ／ｇ以下であり、さらに好ましくは２ｍｇＫＯＨ／ｇ以下である。前記エステル化反応は無触媒で行なってもよく、ブレンステッド酸触媒やルイス酸触媒を使用して行ってもよい。
なお、上記エステルの「酸価」は、例えば、日本工業規格（ＪＩＳ） Ｃ２１０１：１９９９に準拠して測定される。The citric acid triester is prepared by charging, for example, citric acid or citric acid anhydride and an aliphatic monohydric alcohol into a reactor, and reacting water under a nitrogen atmosphere at normal pressure or under reduced pressure, for example, at 150 ° C to 250 ° C. It can be produced by carrying out an esterification reaction while distilling off. The acid value of the obtained citric acid triester is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, and further preferably 2 mgKOH / g or less. The esterification reaction may be carried out without a catalyst, or may be carried out using a Bronsted acid catalyst or a Lewis acid catalyst.
The "acid value" of the ester is measured, for example, in accordance with Japanese Industrial Standards (JIS) C2101: 1999.
クエン酸トリエステルを製造するためのエステル化反応は、クエン酸またはクエン酸無水物に対して過剰量の脂肪族１価アルコールを用いて行うことが好ましい。この場合、エステル化反応後、過剰なアルコールを減圧下で留去する。得られたクエン酸トリエステルは、例えば吸着剤（酸性白土、活性白土、シリカ－アルミナ系吸着剤等）を用いて精製処理することが好ましい。 The esterification reaction for producing a citric acid triester is preferably carried out using an excess amount of an aliphatic monohydric alcohol with respect to citric acid or citric acid anhydride. In this case, after the esterification reaction, excess alcohol is distilled off under reduced pressure. The obtained citric acid triester is preferably purified using, for example, an adsorbent (acidic clay, activated clay, silica-alumina-based adsorbent, etc.).
本発明において、上記したエステル（Ａ）（クエン酸トリエステル）は、１種または２種以上を使用することができる。 In the present invention, one kind or two or more kinds of the above-mentioned ester (A) (citric acid triester) can be used.
本発明において用いるエステル（Ｂ）は、脂肪族モノエステルである。該脂肪族モノエステルとしては、下記の成分（ｂ１）と成分（ｂ２）からなる脂肪族モノエステル（すなわち、下記の成分（ｂ１）と成分（ｂ２）から形成される脂肪族モノエステル）であることが好ましい。
（ｂ１）炭素数３～１４の脂肪族１価アルコール
（ｂ２）炭素数４～１２の脂肪族１価カルボン酸The ester (B) used in the present invention is an aliphatic monoester. The aliphatic monoester is an aliphatic monoester composed of the following components (b1) and component (b2) (that is, an aliphatic monoester formed from the following components (b1) and component (b2)). Is preferable.
(B1) Aliphatic monohydric alcohol having 3 to 14 carbon atoms (b2) Aliphatic monovalent carboxylic acid having 4 to 12 carbon atoms
成分（ｂ１）の炭素数３～１４の脂肪族１価アルコールとしては、炭素数３～１４の直鎖又は分岐鎖の飽和脂肪族１価アルコールが好ましい。具体的には、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、２－メチル－１－プロパノール、２－メチル－２－プロパノール、１－ペンタノール、２－ペンタノール、３－ペンタノール、３－メチル－１－ブタノール、１－ヘキサノール、２－ヘキサノール、３－ヘキサノール、２－メチル－１－ペンタノール、２－エチル－１－ブタノール、１－ヘプタノール、２－ヘプタノール、３－ヘプタノール、２－メチル－１－ヘキサノール、２－エチル－１－ペンタノール、１－オクタノール、２－オクタノール、３－オクタノール、２－メチル－１－ヘプタノール、２－エチル－１－ヘキサノール、１－ノナノール、２－ノナノール、３－ノナノール、２－メチル－１－オクタノール、２－エチル－１－ヘプタノール、１－デカノール、２－デカノール、３－デカノール、２－メチル－１－ノナノール、２－エチル－１－オクタノール、８－メチル－１－ノナノール、１－ウンデカノール、３－エチル－２－ノナノール、１－ドデカノール、１－トリデカノール、１１－メチル－１－ドデカノール、１－テトラデカノールなどが挙げられる。
成分（ｂ１）の炭素数３～１４の直鎖又は分岐鎖の飽和脂肪族１価アルコールとしては、炭素数３～１４の分岐鎖の飽和脂肪族１価アルコールがより好ましく、炭素数が４～９の分岐鎖の飽和脂肪族１価アルコールがさらに好ましく、２-メチル－１－プロパノールおよび２－エチル－１－ヘキサノールが特に好ましい。As the aliphatic monohydric alcohol having 3 to 14 carbon atoms of the component (b1), a linear or branched saturated aliphatic monohydric alcohol having 3 to 14 carbon atoms is preferable. Specifically, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pen Tanol, 3-methyl-1-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol , 2-Methyl-1-hexanol, 2-ethyl-1-pentanol, 1-octanol, 2-octanol, 3-octanol, 2-methyl-1-heptanol, 2-ethyl-1-hexanol, 1-nonanol, 2-Nonanol, 3-Nonanol, 2-Methyl-1-octanol, 2-ethyl-1-Heptanol, 1-decanol, 2-decanol, 3-decanol, 2-methyl-1-nonanol, 2-ethyl-1- Examples thereof include octanol, 8-methyl-1-nonanol, 1-undecanol, 3-ethyl-2-nonanol, 1-dodecanol, 1-tridecanol, 11-methyl-1-dodecanol, 1-tetradecanol and the like.
As the linear or branched saturated aliphatic monohydric alcohol having 3 to 14 carbon atoms of the component (b1), the saturated aliphatic monohydric alcohol having a branched chain having 3 to 14 carbon atoms is more preferable, and the saturated aliphatic monohydric alcohol has 4 to 14 carbon atoms. Saturated aliphatic monohydric alcohols having a branched chain of 9 are more preferable, and 2-methyl-1-propanol and 2-ethyl-1-hexanol are particularly preferable.
成分（ｂ２）の炭素数４～１２の脂肪族１価カルボン酸としては、炭素数４～１２の直鎖又は分岐鎖の飽和脂肪族１価カルボン酸が好ましく、特に低温安定性に優れるエステルが得られる点から、炭素数が４～１０の分岐鎖の飽和脂肪族１価カルボン酸がより好ましい。かかる脂肪族１価カルボン酸の具体例としては、例えば、２－メチルプロパン酸、２－メチルブタン酸、２－エチルヘキサン酸、３，５，５－トリメチルヘキサン酸、ネオデカン酸などが挙げられる。特に好ましくは、２－エチルヘキサン酸である。 As the aliphatic monovalent carboxylic acid having 4 to 12 carbon atoms of the component (b2), a linear or branched saturated aliphatic monovalent carboxylic acid having 4 to 12 carbon atoms is preferable, and an ester having particularly excellent low temperature stability is used. From the viewpoint obtained, a saturated aliphatic monovalent carboxylic acid having a branched chain having 4 to 10 carbon atoms is more preferable. Specific examples of such an aliphatic monovalent carboxylic acid include 2-methylpropanoic acid, 2-methylbutanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylcaproic acid, neodecanoic acid and the like. Particularly preferred is 2-ethylhexanoic acid.
エステル（Ｂ）は、例えば、成分（ｂ１）の炭素数３～１４の脂肪族１価アルコールと、成分（ｂ２）の炭素数４～１２の脂肪族１価カルボン酸とを反応器に仕込み、常圧での窒素雰囲気下または減圧下にて、例えば１５０℃～２５０℃で、反応水を留去しつつエステル化を行うことによって、製造することができる。エステル化反応は無触媒で行ってもよく、ブレンステッド酸触媒やルイス酸触媒を使用して行ってもよい。また、上記エステル化反応を行う際、カルボキシ基またはヒドロキシ基の過剰率を適宜調整することができる。エステル化反応後、過剰の脂肪族１価カルボン酸または脂肪族１価アルコールを減圧下で留去することにより得られた粗エステルを、例えば吸着剤（酸性白土、活性白土、シリカ－アルミナ系吸着剤等）を用いて精製処理することが好ましい。 For the ester (B), for example, an aliphatic monohydric alcohol having 3 to 14 carbon atoms of the component (b1) and an aliphatic monovalent carboxylic acid having 4 to 12 carbon atoms of the component (b2) are charged into a reactor. It can be produced by performing esterification under a nitrogen atmosphere at normal pressure or under reduced pressure, for example, at 150 ° C. to 250 ° C. while distilling off the reaction water. The esterification reaction may be carried out without a catalyst, or may be carried out using a Bronsted acid catalyst or a Lewis acid catalyst. Further, when the esterification reaction is carried out, the excess ratio of the carboxy group or the hydroxy group can be appropriately adjusted. After the esterification reaction, the crude ester obtained by distilling off excess aliphatic monovalent carboxylic acid or aliphatic monohydric alcohol under reduced pressure can be used as, for example, an adsorbent (acidic clay, activated clay, silica-alumina-based adsorption). It is preferable to carry out purification treatment using an agent or the like).
本発明において、エステル（Ｂ）は、低粘度であるという観点から、４０℃における動粘度が１ｍｍ２／ｓ～１０．０ｍｍ２／ｓであることが好ましく、１ｍｍ２／ｓ～８ｍｍ２／ｓであることがより好ましく、１ｍｍ２／ｓ～５ｍｍ２／ｓであることがさらに好ましい。なお、ここでいう「動粘度」は、例えば、ＪＩＳ Ｋ２２８３：２０００に記載の方法により測定される。In the present invention, the ester (B) preferably has a kinematic viscosity of 1 mm 2 / s to 10.0 mm 2 / s at 40 ° C. from the viewpoint of low viscosity, 1 mm 2 / s to 8 mm 2 / s. It is more preferably 1 mm 2 / s to 5 mm 2 / s. The "kinematic viscosity" referred to here is measured by, for example, the method described in JIS K2283: 2000.
本発明において、エステル（Ｂ）は、冷凍機油としての熱安定性の観点から、酸価が１０ｍｇＫＯＨ／ｇ以下であることが好ましく、５ｍｇＫＯＨ／ｇ以下であることがより好ましく、２ｍｇＫＯＨ／ｇ以下であることがさらに好ましい。なお、ここでいう酸価は、例えば、ＪＩＳ Ｃ２１０１：１９９９に記載の方法により測定される。 In the present invention, the ester (B) preferably has an acid value of 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, and 2 mgKOH / g or less, from the viewpoint of thermal stability as a refrigerating machine oil. It is more preferable to have. The acid value referred to here is measured by, for example, the method described in JIS C2101: 1999.
エステル（Ｂ）を構成する成分（ｂ１）および成分（ｂ２）のそれぞれの組成は、ガスクロマトグラフィーによって分析することができる。例えば、エステル（Ｂ）（０．１ｇ）を、質量比が８０／２０であるトルエン／メタノールの混合溶媒（５ｇ）で希釈し、次いで２８質量％ナトリウムメトキシドメタノール溶液（和光純薬工業株式会社製）（０．３ｇ）を加え、常温にて３０分静置することにより、エステル（Ｂ）を加メタノール分解する。得られた前記エステル分解物溶液をガスクロマトグラフィーで分析し、得られた成分（ｂ１）および成分（ｂ２）のピーク面積比から、エステル（Ｂ）を構成する成分（ｂ１）と成分（ｂ２）のモル比を算出することができる。なお、各成分を単独でガスクロマトグラフィーにより分析することで、エステル（Ｂ）を構成する成分（ｂ１）と成分（ｂ２）の種類を同定することができる。 The composition of each of the components (b1) and the component (b2) constituting the ester (B) can be analyzed by gas chromatography. For example, ester (B) (0.1 g) is diluted with a mixed solvent (5 g) of toluene / methanol having a mass ratio of 80/20, and then a 28 mass% sodium methoxide methanol solution (Wako Pure Chemical Industries, Ltd.). (M.) (0.3 g) is added and allowed to stand at room temperature for 30 minutes to decompose the ester (B) into methanol. The obtained ester decomposition product solution is analyzed by gas chromatography, and the peak area ratios of the obtained component (b1) and component (b2) are used to determine the component (b1) and the component (b2) constituting the ester (B). The molar ratio of can be calculated. By analyzing each component independently by gas chromatography, the types of the component (b1) and the component (b2) constituting the ester (B) can be identified.
本発明の冷凍機油組成物は、上述のエステル（Ａ）とエステル（Ｂ）の混合エステルを含有する。混合エステルにおけるエステル（Ａ）とエステル（Ｂ）の含有量比［エステル（Ａ）／エステル（Ｂ）］は質量比にて１／９９～３０／７０であり、該含有量比がこの範囲内にあれば、後述する添加剤に対し、優れた溶解性を得ることができる。
エステル（Ａ）とエステル（Ｂ）の含有量比［エステル（Ａ）／エステル（Ｂ）］が１／９９より小さい場合、添加剤溶解性が低下する傾向があり、エステル（Ａ）とエステル（Ｂ）の含有量比［エステル（Ａ）／エステル（Ｂ）］が３０／７０より大きくなると、添加剤溶解性の向上効果が頭打ちとなり、エステル（Ａ）の含有量に見合った添加剤溶解性が得られ難くなる場合がある。
エステル（Ａ）とエステル（Ｂ）を混合する方法は、特に限定されないが、例えば、エステル（Ａ）とエステル（Ｂ）の任意の量をビーカー等の容器に測り採り、撹拌羽を用いて撹拌混合する方法が挙げられる。
本発明の目的には、エステル（Ａ）とエステル（Ｂ）の含有量比［エステル（Ａ）／エステル（Ｂ）］は、質量比にて１／９９～２５／７５であることが好ましく、３／９７～２０／８０であることがより好ましい。The refrigerating machine oil composition of the present invention contains the above-mentioned mixed ester of ester (A) and ester (B). The content ratio of the ester (A) to the ester (B) in the mixed ester [ester (A) / ester (B)] is 1/99 to 30/70 in terms of mass ratio, and the content ratio is within this range. If it is, excellent solubility can be obtained for the additives described later.
When the content ratio [ester (A) / ester (B)] of the ester (A) to the ester (B) is smaller than 1/99, the solubility of the additive tends to decrease, and the ester (A) and the ester (ester (A)) When the content ratio [ester (A) / ester (B)] of B) is larger than 30/70, the effect of improving the solubility of the additive reaches a plateau, and the solubility of the additive is commensurate with the content of the ester (A). May be difficult to obtain.
The method for mixing the ester (A) and the ester (B) is not particularly limited, but for example, an arbitrary amount of the ester (A) and the ester (B) is measured in a container such as a beaker and stirred using a stirring blade. The method of mixing is mentioned.
For the purpose of the present invention, the content ratio of the ester (A) to the ester (B) [ester (A) / ester (B)] is preferably 1/99 to 25/75 in terms of mass ratio. It is more preferably 3/97 to 20/80.
本発明の冷凍機油組成物に含有されるエステル（Ａ）とエステル（Ｂ）との混合エステルの４０℃における動粘度は、好ましくは１ｍｍ２／ｓ～２０ｍｍ２／ｓであり、より好ましくは１ｍｍ２／ｓ～１７ｍｍ２／ｓであり、さらに好ましくは１ｍｍ２／ｓ～１５ｍｍ２／ｓである。また、その酸価は、好ましくは１０ｍｇＫＯＨ／ｇ以下であり、より好ましくは５ｍｇＫＯＨ／ｇ以下であり、さらに好ましくは２ｍｇＫＯＨ／ｇ以下であり、特に好ましくは１ｍｇＫＯＨ／ｇ以下である。
なお、ここでいう「動粘度」は、ＪＩＳ Ｋ２２８３：２０００に準拠して測定することができる。また、「酸価」は、ＪＩＳ Ｃ２１０１：１９９９に準拠して測定することができる。The kinematic viscosity of the mixed ester of the ester (A) and the ester (B) contained in the refrigerating machine oil composition of the present invention at 40 ° C. is preferably 1 mm 2 / s to 20 mm 2 / s, more preferably 1 mm. It is 2 / s to 17 mm 2 / s, more preferably 1 mm 2 / s to 15 mm 2 / s. The acid value thereof is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, still more preferably 2 mgKOH / g or less, and particularly preferably 1 mgKOH / g or less.
The "kinematic viscosity" referred to here can be measured in accordance with JIS K2283: 2000. Further, the "acid value" can be measured according to JIS C2101: 1999.
（ｉｉ）ヘキサン溶媒中に１質量％の濃度で溶解させたときの曇り点が－２０℃以上である添加剤
本発明の冷凍機油組成物は、上述の混合エステルに加えて、ヘキサン溶媒中に１質量％の濃度で溶解させたときの曇り点が－２０℃以上である添加剤を含有する。(Ii) Additive having a clouding point of −20 ° C. or higher when dissolved in a hexane solvent at a concentration of 1% by mass The refrigerating machine oil composition of the present invention is added to the above-mentioned mixed ester in a hexane solvent. It contains an additive having a clouding point of −20 ° C. or higher when dissolved at a concentration of 1% by mass.
ここで、添加剤の上記「曇り点」とは、１質量％の添加剤のヘキサン溶液を冷却していったとき、添加剤が析出または分離して溶液が曇り始めたときの温度をいい、ＪＩＳ Ｋ２２６９：１９８７に従い、測定することができる。 Here, the above-mentioned "cloud point" of the additive means the temperature at which the additive precipitates or separates and the solution begins to become cloudy when the hexane solution of the additive is cooled by 1% by mass. It can be measured according to JIS K2269: 1987.
本発明において、上記添加剤としては、冷凍機油組成物に潤滑性を付与するために添加される添加剤であって、上述の条件で測定した曇り点が－２０℃以上であるものであれば、任意のものを使用することができる。本発明において、冷凍機油として含有される上記混合エステルは、上記添加剤の溶解性に優れており、本発明の冷凍機油組成物では、曇り点が高く、通常の冷凍機油には溶解し難い添加剤を用いることができる。上記条件で測定される上記添加剤の曇り点は、好ましくは－１５℃以上である。 In the present invention, the additive is an additive added to impart lubricity to the refrigerating machine oil composition, as long as the cloud point measured under the above conditions is −20 ° C. or higher. , Anything can be used. In the present invention, the mixed ester contained as the refrigerating machine oil has excellent solubility of the additive, and the refrigerating machine oil composition of the present invention has a high cloud point and is difficult to dissolve in ordinary refrigerating machine oil. Agents can be used. The cloud point of the additive measured under the above conditions is preferably −15 ° C. or higher.
また、上記添加剤としては、本発明の効果がより顕著に得られる点で、融点が０℃以上であるものが好ましい。
添加剤の融点は、示差走査熱量分析計により測定される。示差走査熱量分析計としては、たとえば、セイコーインスツル株式会社製の「ＤＳＣ－６２００」等を使用することができる。測定は、たとえば、約１０ｍｇの添加剤を試料ホルダーに入れ、リファレンス材料としてアルミナ１０ｍｇを用い、－２０℃から１５０℃まで、昇温速度を毎分１０℃として行なう。そして、前記測定の結果、得られた吸熱ピークのピークトップの温度を融点とする。Further, as the additive, those having a melting point of 0 ° C. or higher are preferable in that the effect of the present invention can be obtained more remarkably.
The melting point of the additive is measured by a differential scanning calorimeter. As the differential scanning calorimeter, for example, "DSC-6200" manufactured by Seiko Instruments Inc. can be used. The measurement is carried out, for example, by placing about 10 mg of an additive in a sample holder, using 10 mg of alumina as a reference material, and increasing the temperature from −20 ° C. to 150 ° C. at a heating rate of 10 ° C. per minute. Then, the temperature of the peak top of the endothermic peak obtained as a result of the measurement is defined as the melting point.
上記添加剤としては、例えば耐荷重添加剤、酸化防止剤、金属不活性化剤、酸捕捉剤等が挙げられる。冷凍機油の低粘度化に伴い、潤滑条件が厳しくなることから、上記添加剤としては、耐荷重添加剤が好ましい。ここで「耐荷重添加剤」とは、金属摩擦面を油膜で隔てることができずに、金属摩擦面が互いに接触する際に機能する添加剤を意味し、例えば、油性向上剤、摩耗防止剤、極圧剤等が挙げられる。 Examples of the additive include a load-bearing additive, an antioxidant, a metal deactivating agent, an acid scavenger, and the like. As the viscosity of the refrigerating machine oil decreases, the lubrication conditions become stricter. Therefore, the load-bearing additive is preferable as the additive. Here, the "load-bearing additive" means an additive that functions when the metal friction surfaces come into contact with each other without being able to separate the metal friction surfaces with an oil film, and for example, an oiliness improver and an anti-wear agent. , Extreme pressure agent and the like.
耐荷重添加剤としては、例えば、脂肪酸エステル系添加剤、エーテル系添加剤、リン酸エステル系添加剤、およびチオリン酸エステル系添加剤等が挙げられる。これらの中で、脂肪酸エステル系添加剤、リン酸エステル系添加剤、およびチオリン酸エステル系添加剤が、潤滑性向上効果の面で好ましく、脂肪酸エステル系添加剤、およびリン酸エステル系添加剤がより好ましい。リン酸エステル系添加剤としては、例えばトリフェニルホスフェートが挙げられる。脂肪酸エステル系添加剤としては、グリセリンモノオレエートが挙げられる。上記添加剤としては、トリフェニルホスフェートおよびグリセリンモノオレエートが特に好ましい。
上記した添加剤は、１種のみを単独で使用してもよく、２種以上を併用してもよい。本発明の目的には、ヘキサン溶媒中に１質量％の濃度で溶解させたときの曇り点が－２０℃以上である添加剤として、トリフェニルホスフェートおよびグリセリンモノオレエートからなる群より選択される１種以上を用いることが特に好ましい。Examples of the load-bearing additive include fatty acid ester-based additives, ether-based additives, phosphate ester-based additives, and thiophosphate-based additives. Among these, fatty acid ester-based additives, phosphoric acid ester-based additives, and thiophosphate-based additives are preferable in terms of the effect of improving lubricity, and fatty acid ester-based additives and phosphoric acid ester-based additives are preferable. More preferred. Examples of the phosphoric acid ester-based additive include triphenyl phosphate. Examples of the fatty acid ester-based additive include glycerin monooleate. As the above additives, triphenylphosphate and glycerin monooleate are particularly preferable.
The above-mentioned additives may be used alone or in combination of two or more. An object of the present invention is selected from the group consisting of triphenyl phosphate and glycerin monooleate as additives having a clouding point of −20 ° C. or higher when dissolved in a hexane solvent at a concentration of 1% by mass. It is particularly preferable to use one or more.
本発明の冷凍機油組成物において、上記添加剤の含有量は、エステル（Ａ）とエステル（Ｂ）の混合エステル１００質量％に対して、０．０１質量％～１０質量％であり、好ましくは０．１質量％～７質量％である。上記添加剤の含有量が前記範囲内である場合、本発明の冷凍機油組成物において添加剤の析出が抑制され、添加量に見合った各種添加剤の効果を得ることができる。 In the refrigerating machine oil composition of the present invention, the content of the additive is 0.01% by mass to 10% by mass, preferably 0.01% by mass, based on 100% by mass of the mixed ester of the ester (A) and the ester (B). It is 0.1% by mass to 7% by mass. When the content of the additive is within the above range, the precipitation of the additive is suppressed in the refrigerating machine oil composition of the present invention, and the effects of various additives commensurate with the amount of the additive can be obtained.
[冷凍機用作動流体組成物]
本発明はまた、冷凍機用作動流体組成物を提供することができる。
ここで、「冷凍機用作動流体組成物」とは、冷凍機油組成物と冷媒を混合したものをいう。
本発明の冷凍機用作動流体組成物は、上記冷凍機油組成物と、炭化水素冷媒とを含有する。冷凍機油組成物と炭化水素冷媒との含有量比（冷凍機油組成物：炭化水素冷媒）に特に制限はないが、好ましくは、質量比にて１０：９０～９０：１０である。炭化水素冷媒の含有率が前記範囲より高いと、得られる冷凍機用作動流体組成物の粘度が低下し、潤滑不良を起こすおそれがある。炭化水素冷媒の含有率が前記範囲より低い場合には、得られる冷凍機用作動流体組成物を冷凍機器に用いた場合に、冷凍効率が低下するおそれがある。[Working fluid composition for refrigerators]
The present invention can also provide a working fluid composition for a refrigerator.
Here, the "working fluid composition for a refrigerator" refers to a mixture of a refrigerating machine oil composition and a refrigerant.
The working fluid composition for a refrigerator of the present invention contains the above-mentioned refrigerating machine oil composition and a hydrocarbon refrigerant. The content ratio of the refrigerating machine oil composition to the hydrocarbon refrigerant (refrigerating machine oil composition: hydrocarbon refrigerant) is not particularly limited, but is preferably 10:90 to 90:10 in terms of mass ratio. If the content of the hydrocarbon refrigerant is higher than the above range, the viscosity of the obtained working fluid composition for a refrigerator may decrease, resulting in poor lubrication. When the content of the hydrocarbon refrigerant is lower than the above range, the refrigerating efficiency may decrease when the obtained working fluid composition for a refrigerator is used in a refrigerating machine.
上記炭化水素冷媒としては、例えば、エタン、プロパン、プロピレン、ノルマルブタン、イソブタンなどが挙げられる。これらは、単独で用いてもよいし、２種以上の混合冷媒として用いてもよい。なかでもイソブタン（冷媒Ｒ６００ａ）は冷蔵庫用の炭化水素冷媒として使用されており、本発明の冷凍機油組成物は、特にイソブタン冷媒用として好適に用いることができる。 Examples of the hydrocarbon refrigerant include ethane, propane, propylene, normal butane, isobutane and the like. These may be used alone or as a mixed refrigerant of two or more kinds. Among them, isobutane (refrigerant R600a) is used as a hydrocarbon refrigerant for a refrigerator, and the refrigerating machine oil composition of the present invention can be particularly preferably used for an isobutane refrigerant.
以下、実施例により、本発明を更に詳細に説明するが、本発明は、下記実施例に制限されるものではない。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.
[エステル（Ａ）の合成]
製造例１
クエン酸無水物（２８２ｇ、１．４７ｍｏｌ）、１－ブタノール（２９４ｇ、３．９７ｍｏｌ）、および２－エチル－１－ヘキサノール（１１４ｇ、０．８７ｍｏｌ）を四つ口フラスコに仕込み、窒素雰囲気下、２００℃で反応水を留去しつつ常圧で５時間反応を行なった。その後、２００℃で酸価が２ｍｇＫＯＨ／ｇ以下となるまで反応を継続した。次いで、１ｋＰａ～５ｋＰａの減圧下にて２００℃で過剰なアルコールを留去し、粗エステルを得た。粗エステルを冷却し、これに酸性白土およびシリカ－アルミナ系の吸着剤を、それぞれ理論上得られるエステル量の１．０質量％となるように添加して、吸着処理した（吸着処理温度：１００℃、圧力：１ｋＰａ～５ｋＰａ、吸着処理時間：２時間）。最後に孔径１μｍのフィルターを用いて濾過を行い、目的のクエン酸トリエステル（酸価＝０．１ｍｇＫＯＨ／ｇ以下）（以下「エステルＡ１」と記載する。）を得た。[Synthesis of ester (A)]
Production Example 1
Citric acid anhydride (282 g, 1.47 mol), 1-butanol (294 g, 3.97 mol), and 2-ethyl-1-hexanol (114 g, 0.87 mol) were placed in a four-necked flask and placed in a nitrogen atmosphere. The reaction was carried out at normal pressure for 5 hours while distilling off the reaction water at 200 ° C. Then, the reaction was continued at 200 ° C. until the acid value became 2 mgKOH / g or less. Then, the excess alcohol was distilled off at 200 ° C. under a reduced pressure of 1 kPa to 5 kPa to obtain a crude ester. The crude ester was cooled, and acidic clay and silica-alumina-based adsorbents were added thereto so as to be 1.0% by mass of the amount of the ester theoretically obtained, respectively, and adsorbed (adsorption treatment temperature: 100). ° C., pressure: 1 kPa to 5 kPa, adsorption processing time: 2 hours). Finally, filtration was performed using a filter having a pore size of 1 μm to obtain a desired citric acid triester (acid value = 0.1 mgKOH / g or less) (hereinafter referred to as “ester A1”).
製造例２
クエン酸無水物（２８２ｇ、１．４７ｍｏｌ）、エタノール（４０ｇ、０．８７ｍｏｌ）、および１－ヘキサノール（４０６ｇ、３．９７ｍｏｌ）を四つ口フラスコに仕込み、窒素雰囲気下、２００℃で反応水を留去しつつ常圧で５時間反応を行なった。以降の工程は製造例１と同様にして行い、目的のクエン酸トリエステル（酸価＝０．１ｍｇＫＯＨ／ｇ以下）（以下「エステルＡ２」と記載する。）を得た。 Manufacturing example 2
Citric acid anhydride (282 g, 1.47 mol), ethanol (40 g, 0.87 mol), and 1-hexanol (406 g, 3.97 mol) were placed in a four-necked flask, and the reaction water was added to the reaction water at 200 ° C. under a nitrogen atmosphere. The reaction was carried out at normal pressure for 5 hours while distilling off. The subsequent steps were carried out in the same manner as in Production Example 1 to obtain the desired citric acid triester (acid value = 0.1 mgKOH / g or less) (hereinafter referred to as “ester A2”).
[エステル（Ｂ）の合成]
製造例３
２－メチル－１－プロパノール（４９０ｇ、６．６０ｍｏｌ）、２－エチルヘキサン酸（１０００ｇ、６．９３ｍｏｌ）を四つ口フラスコに仕込み、窒素雰囲気下、１５０℃で反応水を留去しつつ常圧で水酸基価が５．０ｍｇＫＯＨ／ｇ以下になるまで反応を行った。ついで、２００℃、１ｋＰａ～５ｋＰａの減圧下にて過剰な２－エチルヘキサン酸を留去し、粗エステルを得た。粗エステルを冷却し、これに酸性白土およびシリカ－アルミナ系の吸着剤を、それぞれ理論上得られるエステル量の１．０質量％となるように添加して吸着処理した。吸着処理温度、圧力、および吸着処理時間は、それぞれ１００℃、１ｋＰａ～５ｋＰａおよび２時間とした。最後に孔径１μｍのフィルターを用いて濾過を行い、目的のモノエステル（以下「エステルＢ１」と記載する。）を得た。[Synthesis of ester (B)]
Production example 3
2-Methyl-1-propanol (490 g, 6.60 mol) and 2-ethylhexanoic acid (1000 g, 6.93 mol) were placed in a four-necked flask, and the reaction water was distilled off at 150 ° C. under a nitrogen atmosphere. The reaction was carried out until the hydroxyl value became 5.0 mgKOH / g or less under pressure. Then, excess 2-ethylhexanoic acid was distilled off under a reduced pressure of 200 ° C. and 1 kPa to 5 kPa to obtain a crude ester. The crude ester was cooled, and an acidic white clay and a silica-alumina-based adsorbent were added to the crude ester so as to be 1.0% by mass of the theoretically obtained ester amount, respectively, for adsorption treatment. The adsorption treatment temperature, pressure, and adsorption treatment time were set to 100 ° C., 1 kPa to 5 kPa, and 2 hours, respectively. Finally, filtration was performed using a filter having a pore size of 1 μm to obtain a desired monoester (hereinafter referred to as “ester B1”).
製造例４
２－エチル－１－ヘキサノール（３２８ｇ、２．５２ｍｏｌ）、２－エチルヘキサン酸（３６９ｇ、２．５６ｍｏｌ）を四つ口フラスコに仕込み、窒素雰囲気下、２００℃で反応水を留去しつつ常圧で水酸基価が５．０ｍｇＫＯＨ／ｇ以下になるまで反応を行った。ついで、２００℃、１ｋＰａ～５ｋＰａの減圧下にて過剰な２－エチルヘキサン酸を留去し、粗エステルを得た。粗エステルを冷却し、これに酸性白土およびシリカ－アルミナ系の吸着剤を、それぞれ理論上得られるエステル量の１．０質量％となるように添加して吸着処理した。吸着処理温度、圧力、および吸着処理時間は、それぞれ１００℃、１ｋＰａ～５ｋＰａおよび２時間とした。最後に孔径１μｍのフィルターを用いて濾過を行い、目的のモノエステル（以下「エステルＢ２」と記載する。）を得た。 Production example 4
2-Ethyl-1-hexanol (328 g, 2.52 mol) and 2-ethylhexanoic acid (369 g, 2.56 mol) were placed in a four-necked flask, and the reaction water was always distilled off at 200 ° C. under a nitrogen atmosphere. The reaction was carried out until the hydroxyl value became 5.0 mgKOH / g or less under pressure. Then, excess 2-ethylhexanoic acid was distilled off under a reduced pressure of 200 ° C. and 1 kPa to 5 kPa to obtain a crude ester. The crude ester was cooled, and an acidic white clay and a silica-alumina-based adsorbent were added to the crude ester so as to be 1.0% by mass of the theoretically obtained ester amount, respectively, for adsorption treatment. The adsorption treatment temperature, pressure, and adsorption treatment time were set to 100 ° C., 1 kPa to 5 kPa, and 2 hours, respectively. Finally, filtration was performed using a filter having a pore size of 1 μm to obtain a desired monoester (hereinafter referred to as “ester B2”).
上述の製造例１、２のエステルＡ１、Ａ２の製造に使用したクエン酸および脂肪族１価アルコール（成分（ａ１）および成分（ａ２））を下記表１に示す。また、上述の製造例３、４のエステルＢ１、Ｂ２の製造に使用した脂肪族１価カルボン酸（成分（ｂ２））および脂肪族１価アルコール（成分（ｂ１））を下記表２に示す。 The citric acid and aliphatic monohydric alcohols (components (a1) and (a2)) used in the production of the esters A1 and A2 of Production Examples 1 and 2 described above are shown in Table 1 below. In addition, the aliphatic monovalent carboxylic acid (component (b2)) and the aliphatic monohydric alcohol (component (b1)) used in the production of the esters B1 and B2 of Production Examples 3 and 4 described above are shown in Table 2 below.
エステルＡ１、Ａ２およびエステルＢ１、Ｂ２の酸価および流動点を、下記の通り測定した。その結果を表１、２に併せて示した。 The acid value and pour point of esters A1 and A2 and esters B1 and B2 were measured as follows. The results are also shown in Tables 1 and 2.
[エステルＡ１、Ａ２を構成する脂肪族１価アルコール成分のモル比［成分（ａ１）／成分（ａ２）］]
エステルＡ１、Ａ２について、各エステル（０．１ｇ）を、質量比が８０／２０であるトルエン／メタノールの混合溶媒（５ｇ）で希釈し、次いで２８質量％ナトリウムメトキシドメタノール溶液（和光純薬工業株式会社製）（０．３ｇ）を加え、常温にて３０分静置することにより、エステルを加メタノール分解した。得られたエステル分解物溶液をガスクロマトグラフィーで分析し、得られた脂肪族１価アルコールのピーク面積比から、エステルＡ１、Ａ２を構成する脂肪族１価アルコール成分のモル比［成分（ａ１）／成分（ａ２）］を算出し、表１に併せて示した。
なお、実施したガスクロマトグラフィーの分析条件は、次の通りである。
測定機器：ガスクロマトグラフ「ＧＣ－２０１４」（株式会社島津製作所製）
カラム ：ジーエルサイエンス株式会社製「ＯＶ－１」を充填した長さ１．１ｍ、内径３．２ｍｍのパックドカラム
測定温度：導入口温度３２０℃、検出器温度３３０℃の条件において、測定開始からカラム温度を１００℃から３２０℃まで１０℃／分の速度で昇温し、３２０℃で２０分保持した。
検出器 ：水素イオン化検出器（ＦＩＤ）[Mole ratio of aliphatic monohydric alcohol components constituting esters A1 and A2 [component (a1) / component (a2)]]
For esters A1 and A2, each ester (0.1 g) is diluted with a mixed solvent (5 g) of toluene / methanol having a mass ratio of 80/20, and then a 28 mass% sodium methoxide methanol solution (Wako Pure Chemical Industries, Ltd.). (Manufactured by Co., Ltd.) (0.3 g) was added, and the mixture was allowed to stand at room temperature for 30 minutes to decompose the ester with methanol. The obtained ester decomposition product solution was analyzed by gas chromatography, and from the peak area ratio of the obtained aliphatic monohydric alcohol, the molar ratio of the aliphatic monohydric alcohol components constituting the esters A1 and A2 [component (a1). / Component (a2)] was calculated and shown in Table 1.
The analysis conditions of the gas chromatography performed are as follows.
Measuring equipment: Gas chromatograph "GC-2014" (manufactured by Shimadzu Corporation)
Column: Packed column with a length of 1.1 m and an inner diameter of 3.2 mm filled with "OV-1" manufactured by GL Sciences Co., Ltd. Measurement temperature: Column from the start of measurement under the conditions of inlet temperature 320 ° C and detector temperature 330 ° C. The temperature was raised from 100 ° C. to 320 ° C. at a rate of 10 ° C./min and maintained at 320 ° C. for 20 minutes.
Detector: Hydrogen ionization detector (FID)
[酸価]
ＪＩＳ Ｃ２１０１：１９９９に準拠して、エステルＡ１、Ａ２およびエステルＢ１、Ｂ２の酸価を測定した。[Acid value]
The acid values of esters A1 and A2 and esters B1 and B2 were measured according to JIS C2101: 1999.
[流動点]
ＪＩＳ Ｋ２２６９－１９８７に準拠して、エステルＡ１、Ａ２およびエステルＢ１、Ｂ２の流動点を測定した。
ここで、エステルの「流動点」は、エステルの低温流動性を示す数値であり、エステルが流動する最低温度となる。[Pour point]
The pour points of esters A1 and A2 and esters B1 and B2 were measured according to JIS K2269-1987.
Here, the "pour point" of the ester is a numerical value indicating the low temperature fluidity of the ester, and is the lowest temperature at which the ester flows.
[実施例１～１０]
上述のエステルＡ１、Ａ２とエステルＢ１、Ｂ２、および添加剤を下記表３、４に示す組成比で混合し、実施例１～１０の冷凍機油組成物を調製した。
実施例１～１０の各冷凍機油組成物において用いた各冷凍機油（すなわちエステルＡ１またはエステルＡ２とエステルＢ１またはエステルＢ２との混合エステル）について、ＪＩＳ Ｋ２２８３：２０００に準拠して４０℃における動粘度を測定した。測定結果は、表３、４中に示した。[Examples 1 to 10]
The above-mentioned esters A1 and A2, esters B1 and B2, and additives were mixed at the composition ratios shown in Tables 3 and 4 below to prepare the refrigerating machine oil compositions of Examples 1 to 10.
For each refrigerating machine oil used in each refrigerating machine oil composition of Examples 1 to 10 (that is, a mixed ester of ester A1 or ester A2 and ester B1 or ester B2), kinematic viscosity at 40 ° C. according to JIS K2283: 2000. Was measured. The measurement results are shown in Tables 3 and 4.
本発明の実施例１～１０の各冷凍機油組成物について、下記の通り溶解性試験を実施した。 Solubility tests were carried out for each of the refrigerating machine oil compositions of Examples 1 to 10 of the present invention as follows.
［溶解性試験1］
ＪＩＳ Ｋ２２６９：１９８７に準拠して、実施例１～５の各冷凍機油組成物について、曇り点を測定した。その際、エステルＢ１（１００質量％）に対し、グリセリンモノオレエートを７質量％添加した冷凍機油組成物（「エステルＢ１・グリセリンモノオレエート混合冷凍機油組成物」という）、およびエステルＢ２（１００質量％）に対し、グリセリンモノオレエートを７質量％添加した冷凍機油組成物（「エステルＢ２・グリセリンモノオレエート混合冷凍機油組成物」という）を調製し、それぞれについて、同様に曇り点を測定した。
実施例１、４の冷凍機油組成物については、エステルＢ１・グリセリンモノオレエート混合冷凍機油組成物の曇り点からの下がり幅の絶対値を記録した。また、実施例２、３、５の各冷凍機油組成物については、エステルＢ２・グリセリンモノオレエート混合冷凍機油組成物の曇り点からの下がり幅の絶対値を記録した。
結果は、表３に併せて示した。[Solubility test 1]
The cloud point was measured for each refrigerating machine oil composition of Examples 1 to 5 according to JIS K2269: 1987. At that time, a refrigerating machine oil composition (referred to as "ester B1 and glycerin monooleate mixed refrigerating machine oil composition") in which 7% by mass of glycerin monooleate was added to ester B1 (100% by mass), and ester B2 (100). A refrigerating machine oil composition (referred to as "ester B2 / glycerin monooleate mixed refrigerating machine oil composition") containing 7% by mass of glycerin monooleate was prepared with respect to (% by mass), and the cloudiness point was measured in the same manner for each. did.
For the refrigerating machine oil compositions of Examples 1 and 4, the absolute value of the amount of decrease from the cloud point of the ester B1 / glycerin monooleate mixed refrigerating machine oil composition was recorded. Further, for each of the refrigerating machine oil compositions of Examples 2, 3 and 5, the absolute value of the amount of decrease from the cloud point of the ester B2 / glycerin monooleate mixed refrigerating machine oil composition was recorded.
The results are also shown in Table 3.
［溶解性試験２］
実施例１～５の各冷凍機油組成物とヘキサンを質量比にて２：５の割合で混合し、ＪＩＳ Ｋ２２６９：１９８７に準拠して、各混合物の曇り点を測定した。上記溶解性試験１の場合と同様に、実施例１、４の冷凍機油組成物とヘキサンとの混合物については、エステルＢ１・グリセリンモノオレエート混合冷凍機油組成物とヘキサンとの混合物の曇り点からの下がり幅の絶対値を記録した。また、実施例２、３、５の各冷凍機油組成物とヘキサンとの混合物については、エステルＢ２・グリセリンモノオレエート混合冷凍機油組成物とヘキサンとの混合物の曇り点からの下がり幅の絶対値を記録した。
結果は、表３に併せて示した。[Solubility test 2]
The refrigerating machine oil compositions of Examples 1 to 5 and hexane were mixed at a mass ratio of 2: 5, and the cloudiness point of each mixture was measured according to JIS K2269: 1987. As in the case of the above solubility test 1, the mixture of the refrigerating machine oil composition of Examples 1 and 4 and hexane was prepared from the cloudiness point of the mixture of the ester B1 / glycerin monooleate mixed refrigerating machine oil composition and hexane. The absolute value of the fall width of was recorded. For the mixture of each of the refrigerating machine oil compositions of Examples 2, 3 and 5 and hexane, the absolute value of the amount of decrease from the cloud point of the mixture of the ester B2 / glycerin monooleate mixed refrigerating machine oil composition and hexane. Was recorded.
The results are also shown in Table 3.
［溶解性試験３］
ＪＩＳ Ｋ２２６９：１９８７に準拠して、実施例６～１０の各冷凍機油組成物の曇り点を測定した。その際、エステルＢ１（１００質量％）に対し、トリフェニルホスフェートを７質量％添加した冷凍機油組成物（「エステルＢ１・トリフェニルホスフェート混合冷凍機油組成物」という）、およびエステルＢ２（１００質量％）に対し、トリフェニルホスフェートを７質量％添加した冷凍機油組成物（「エステルＢ２・トリフェニルホスフェート混合冷凍機油組成物」という）を調製し、それぞれについて、同様に曇り点を測定した。実施例６、９の冷凍機油組成物については、エステルＢ１・トリフェニルホスフェート混合冷凍機油組成物の曇り点からの下がり幅の絶対値を記録した。また、実施例７、８、１０の各冷凍機油組成物については、エステルＢ２・トリフェニルホスフェート混合冷凍機油組成物の曇り点からの下がり幅の絶対値を記録した。
結果は、表４に併せて示した。[Solubility test 3]
The cloud point of each refrigerating machine oil composition of Examples 6 to 10 was measured according to JIS K2269: 1987. At that time, a refrigerating machine oil composition (referred to as "ester B1 and triphenyl phosphate mixed refrigerating machine oil composition") in which 7% by mass of triphenyl phosphate was added to ester B1 (100% by mass), and ester B2 (100% by mass). ), A refrigerating machine oil composition (referred to as "ester B2 / triphenyl phosphate mixed refrigerating machine oil composition") to which 7% by mass of triphenyl phosphate was added was prepared, and the cloudiness point was measured in the same manner for each. For the refrigerating machine oil compositions of Examples 6 and 9, the absolute value of the amount of decrease from the cloud point of the ester B1 / triphenylphosphine mixed refrigerating machine oil composition was recorded. Further, for each of the refrigerating machine oil compositions of Examples 7, 8 and 10, the absolute value of the amount of decrease from the cloud point of the ester B2 / triphenylphosphine mixed refrigerating machine oil composition was recorded.
The results are also shown in Table 4.
［溶解性試験４］
実施例６～１０の各冷凍機油組成物とヘキサンを質量比にて２：５の割合で混合し、ＪＩＳ Ｋ２２６９：１９８７に準拠して、各混合物の曇り点を測定した。上記溶解性試験３の場合と同様に、実施例６、９の冷凍機油組成物とヘキサンとの混合物については、エステルＢ１・トリフェニルホスフェート混合冷凍機油組成物とヘキサンとの混合物の曇り点からの下がり幅の絶対値を記録した。また、実施例７、８、１０の各冷凍機油組成物とヘキサンとの混合物については、エステルＢ２・トリフェニルホスフェート混合冷凍機油組成物とヘキサンとの混合物の曇り点からの下がり幅の絶対値を記録した。
結果は、表４に併せて示した。[Solubility test 4]
The refrigerating machine oil compositions of Examples 6 to 10 and hexane were mixed at a mass ratio of 2: 5, and the cloudiness point of each mixture was measured according to JIS K2269: 1987. As in the case of the solubility test 3, the mixture of the refrigerating machine oil composition of Examples 6 and 9 and hexane was taken from the cloud point of the mixture of the ester B1 / triphenyl phosphate mixed refrigerating machine oil composition and hexane. The absolute value of the fall width was recorded. For the mixture of each of the refrigerating machine oil compositions of Examples 7, 8 and 10 and hexane, the absolute value of the amount of decrease from the cloud point of the mixture of the ester B2 / triphenylphosphine mixed refrigerating machine oil composition and hexane is used. Recorded.
The results are also shown in Table 4.
上記実施例１～１０の冷凍機油組成物に含有される添加剤（グリセリンモノオレエートおよびトリフェニルホスフェート）について、ヘキサン溶媒中に１質量％の濃度で溶解させたときの曇り点を、ＪＩＳ ２２６９：１９８７に従って測定した。この条件で測定したグリセリンモノオレエートの曇り点は－５℃であり、トリフェニルホスフェートの曇り点は－１０℃であった。 The cloudiness point when the additives (glycerin monooleate and triphenyl phosphate) contained in the refrigerating machine oil compositions of Examples 1 to 10 were dissolved in a hexane solvent at a concentration of 1% by mass was determined by JIS 2269. : Measured according to 1987. The cloud point of glycerin monooleate measured under these conditions was −5 ° C., and the cloud point of triphenylphosphine was −10 ° C.
上記表３、４から明らかなように、エステル（Ａ）およびエステル（Ｂ）の混合エステルと添加剤を含有する本発明の冷凍機油組成物では、エステル（Ｂ）と添加剤を含有する冷凍機油組成物に比べて曇り点の低下が認められ、添加剤の溶解性が優れていることが示された。
また、炭化水素であるヘキサンと混合した場合においても、本発明の冷凍機油組成物は優れた添加剤溶解性を示すことが認められた。As is clear from Tables 3 and 4 above, in the refrigerating machine oil composition of the present invention containing the mixed ester of the ester (A) and the ester (B) and the additive, the refrigerating machine oil containing the ester (B) and the additive. A lower cloud point was observed as compared with the composition, indicating that the solubility of the additive was excellent.
It was also found that the refrigerating machine oil composition of the present invention exhibited excellent additive solubility even when mixed with hexane, which is a hydrocarbon.
本発明の冷凍機油組成物は、潤滑性を付与するために添加される添加剤に対し優れた溶解性を示し、炭化水素冷媒を含有する冷凍機用作動流体組成物に好適に用いることができる。
本発明の冷凍機油組成物および冷凍機用作動流体組成物は、潤滑性が特に要求される冷凍空調機器や家庭用冷凍冷蔵庫におけるコンプレッサー等に好適に使用することができる。The refrigerating machine oil composition of the present invention exhibits excellent solubility in additives added to impart lubricity, and can be suitably used for working fluid compositions for refrigerating machines containing a hydrocarbon refrigerant. ..
The refrigerating machine oil composition and the working fluid composition for a refrigerating machine of the present invention can be suitably used for a refrigerating and air-conditioning device in which lubricity is particularly required, a compressor in a household refrigerating and refrigerator, and the like.
本願は、日本国で出願された特願２０１６－２３６１８５を基礎としており、それらの内容は本明細書にすべて包含されるものである。 The present application is based on Japanese Patent Application No. 2016-236185 filed in Japan, the contents of which are all incorporated herein by reference.
Claims (3)
エステル（Ａ）：クエン酸トリエステル
エステル（Ｂ）：炭素数３～１４の脂肪族１価アルコールと、炭素数４～１２の脂肪族１価カルボン酸とからなる脂肪族モノエステル
添加剤：トリフェニルホスフェートおよびグリセリンモノオレエートからなる群より選択される１種以上である、添加剤 A refrigerating machine oil composition containing the following ester (A) and ester (B) mixed ester and the following additives, wherein the content ratio of ester (A) to ester (B) is [ester (A) / ester. (B)] is 1/99 to 30/70 in mass ratio, and the following additives are added in an amount of 0.01% by mass to 100% by mass of the mixed ester of the ester (A) and the ester (B). A refrigerating machine oil composition containing 10% by mass and having a kinematic viscosity of a mixed ester of an ester (A) and an ester (B) at 40 ° C. of 1 mm 2 / s to 20 mm 2 / s.
Ester (A): Citrate Triester Ester (B): An aliphatic monoester consisting of an aliphatic monohydric alcohol having 3 to 14 carbon atoms and an aliphatic monovalent carboxylic acid having 4 to 12 carbon atoms Additive: Tri . An additive that is one or more selected from the group consisting of phenyl phosphate and glycerin monooleate .
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| PCT/JP2017/043550 WO2018105575A1 (en) | 2016-12-05 | 2017-12-05 | Refrigerating machine oil composition, and working fluid composition for refrigerating machines containing same |
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| DE4209502A1 (en) * | 1992-03-24 | 1993-09-30 | Hoechst Ag | Use of esters of citric acid as a lubricant for refrigerant compressors |
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| CA2487587C (en) * | 2003-11-21 | 2012-04-24 | Nof Corporation | A polyol ester for use within a refrigeration lubricant composition compatible with chlorine-free hydrofluorocarbon refrigerants |
| US7696136B2 (en) * | 2004-03-11 | 2010-04-13 | Crompton Corporation | Lubricant compositions containing hydroxy carboxylic acid and hydroxy polycarboxylic acid esters |
| JP4961666B2 (en) * | 2004-12-02 | 2012-06-27 | 日油株式会社 | Lubricating oil composition for refrigerator |
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| AU2008343198B2 (en) * | 2007-12-21 | 2013-07-04 | Chevron U.S.A. Inc. | Refrigeration oil from gas-to-liquid derived and bio-derived triesters |
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| JP5681659B2 (en) * | 2012-03-02 | 2015-03-11 | Ｊｘ日鉱日石エネルギー株式会社 | Working fluid composition for refrigerator, refrigerator oil and method for producing the same |
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| CN104830455A (en) * | 2015-04-19 | 2015-08-12 | 青岛启源振东电气有限公司 | Mechanical refrigeration lubricating oil |
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