JP5572243B2 - Refrigerator oil, working fluid for refrigerator, and refrigerator - Google Patents
Refrigerator oil, working fluid for refrigerator, and refrigerator Download PDFInfo
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- JP5572243B2 JP5572243B2 JP2013082827A JP2013082827A JP5572243B2 JP 5572243 B2 JP5572243 B2 JP 5572243B2 JP 2013082827 A JP2013082827 A JP 2013082827A JP 2013082827 A JP2013082827 A JP 2013082827A JP 5572243 B2 JP5572243 B2 JP 5572243B2
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- Prior art keywords
- acid
- refrigerant
- refrigerating machine
- refrigerator
- machine oil
- Prior art date
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- 239000012530 fluid Substances 0.000 title claims description 17
- 239000003507 refrigerant Substances 0.000 claims description 48
- 239000010721 machine oil Substances 0.000 claims description 43
- -1 25 to 40% by mass Chemical compound 0.000 claims description 35
- 229920005862 polyol Polymers 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 17
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 16
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 16
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000001282 iso-butane Substances 0.000 claims description 8
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 claims description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002516 radical scavenger Substances 0.000 claims description 6
- 239000001273 butane Substances 0.000 claims description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- 239000004962 Polyamide-imide Substances 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- 229920002312 polyamide-imide Polymers 0.000 claims description 4
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 3
- GORMSINSWZJIKL-UHFFFAOYSA-N [3-(2-ethylhexanoyloxy)-2,2-dimethylpropyl] 2-ethylhexanoate Chemical group CCCCC(CC)C(=O)OCC(C)(C)COC(=O)C(CC)CCCC GORMSINSWZJIKL-UHFFFAOYSA-N 0.000 claims description 3
- 210000003298 dental enamel Anatomy 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 3
- DRRMRHKHTQRWMB-UHFFFAOYSA-N [3-(2-ethylhexanoyloxy)-2,2-bis(2-ethylhexanoyloxymethyl)propyl] 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OCC(COC(=O)C(CC)CCCC)(COC(=O)C(CC)CCCC)COC(=O)C(CC)CCCC DRRMRHKHTQRWMB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 description 20
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- 239000003921 oil Substances 0.000 description 17
- 235000014113 dietary fatty acids Nutrition 0.000 description 16
- 229930195729 fatty acid Natural products 0.000 description 16
- 239000000194 fatty acid Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 13
- 150000004665 fatty acids Chemical class 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005057 refrigeration Methods 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 239000002199 base oil Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229920002545 silicone oil Polymers 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 4
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- RZRNAYUHWVFMIP-HXUWFJFHSA-N glycerol monolinoleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-HXUWFJFHSA-N 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 3
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- NRWMBHYHFFGEEC-KTKRTIGZSA-N (9Z)-1-O-octadec-9-enyl glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCCOCC(O)CO NRWMBHYHFFGEEC-KTKRTIGZSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 2
- NKBWMBRPILTCRD-UHFFFAOYSA-N 2-Methylheptanoic acid Chemical compound CCCCCC(C)C(O)=O NKBWMBRPILTCRD-UHFFFAOYSA-N 0.000 description 2
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- NIJJYAXOARWZEE-UHFFFAOYSA-N Valproic acid Chemical compound CCCC(C(O)=O)CCC NIJJYAXOARWZEE-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000006078 metal deactivator Substances 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- RAZWADXTNBRANC-UHFFFAOYSA-N 1,2-dimethylcyclohexan-1-ol Chemical compound CC1CCCCC1(C)O RAZWADXTNBRANC-UHFFFAOYSA-N 0.000 description 1
- GBXRUYNQDDTQQS-UHFFFAOYSA-N 1-O-dodecylglycerol Chemical compound CCCCCCCCCCCCOCC(O)CO GBXRUYNQDDTQQS-UHFFFAOYSA-N 0.000 description 1
- QWQNFXDYOCUEER-UHFFFAOYSA-N 2,3-ditert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1C(C)(C)C QWQNFXDYOCUEER-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical class OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-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
- LASHFHLFDRTERB-UHFFFAOYSA-N 2-propylpentan-1-ol Chemical compound CCCC(CO)CCC LASHFHLFDRTERB-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- 101001094880 Arabidopsis thaliana Pectinesterase 4 Proteins 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 101710113246 Pectinesterase 3 Proteins 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 229920001887 crystalline plastic Polymers 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000010735 electrical insulating oil Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical group CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000010726 refrigerant oil Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 229960000604 valproic acid Drugs 0.000 description 1
Landscapes
- Lubricants (AREA)
Description
本発明は、省エネルギーに優れた低粘度の冷凍機油およびこれを用いる冷凍機用作動流
体ならびに冷蔵庫に関する。
The present invention relates to a low-viscosity refrigerating machine oil excellent in energy saving, a working fluid for a refrigerating machine using the same, and a refrigerator.
従来、冷凍機、空調機、冷蔵庫等に用いられている冷媒圧縮式冷凍サイクル装置には、
冷媒としてフッ素と塩素を構成元素とするフロン、例えばクロロフルオロカーボン（ＣＦ
Ｃ）であるＲ‐１１（トリクロロモノフルオロメタン）、Ｒ‐１２（ジクロロジフルオロ
メタン）、ハイドロクロロフルオロカーボン（ＨＣＦＣ）であるＲ‐２２（モノクロロジ
フルオロメタン）等が使用されてきたが、オゾン層破壊問題に関連し、国際的にその生産
及び使用が規制され、現在では、塩素を含有しない水素含有フロン冷媒、例えば、ジフル
オロメタン（Ｒ‐３２）、テトラフルオロエタン（Ｒ‐１３４又はＲ‐１３４ａ）や、さ
らに温室効果が小さいハロゲン原子を含まない炭化水素冷媒、例えばエタン、プロパン、
ブタン、イソブタン等に転換されてきている。
Conventionally, the refrigerant compression refrigeration cycle apparatus used in refrigerators, air conditioners, refrigerators, etc.
Fluorocarbons containing fluorine and chlorine as refrigerants, such as chlorofluorocarbon (CF
C) R-11 (trichloromonofluoromethane), R-12 (dichlorodifluoromethane), hydrochlorofluorocarbon (HCFC) R-22 (monochlorodifluoromethane), etc. have been used. In connection with the problem, its production and use are regulated internationally, and hydrogen-containing chlorofluorocarbon refrigerants that do not contain chlorine, such as difluoromethane (R-32), tetrafluoroethane (R-134 or R-134a) And hydrocarbon refrigerants that do not contain halogen atoms and have a smaller greenhouse effect, such as ethane, propane,
It has been converted to butane, isobutane and the like.
発明者らは、これらの冷媒に使用する冷媒用冷凍機油としてポリオールなどの多価アル
コールを用いたエステルを基油とする冷媒用冷凍機油を提案してきた（特許文献１）。こ
れにより、作動流体に低級炭化水素冷媒等を用いた場合にオリゴマー（高分子物質）の発
生を防止するという効果を得ることができた。ところが最近は冷凍機、空調機、冷蔵庫等
に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。
特許文献２には、ある種の脂肪酸ポリオールエステルが低粘度で、潤滑性に優れている
ことが開示されているが、脂肪酸ポリオールエステルで粘度を下げるには、脂肪酸の炭素
数が５以下でなければならず、加水分解安定性が著しく低下する。
また、特許文献３には、低粘度で加水分解安定性に優れた冷凍機油として、脂肪族飽和
分岐鎖状カルボン酸モノアルキルエステルの少なくとも１種を含有する冷凍機油が提案さ
れ、またこのエステルと脂肪酸ポリオールエステルとの混合物が開示されている。しかし
ながら、脂肪族飽和分岐鎖状カルボン酸モノアルキルエステルと脂肪酸ポリオールエステ
ルの組み合わせは無数あり、低粘度で、しかも潤滑性に優れ、さらに引火点が高くて安全
性にも優れ、また加水分解安定性を満足できるものを探すことは極めて困難であった。
Patent Document 2 discloses that certain fatty acid polyol esters have low viscosity and excellent lubricity, but in order to reduce the viscosity with fatty acid polyol esters, the number of carbon atoms of the fatty acid must be 5 or less. The hydrolysis stability is significantly reduced.
Patent Document 3 proposes a refrigerating machine oil containing at least one aliphatic saturated branched carboxylic acid monoalkyl ester as a refrigerating machine oil having low viscosity and excellent hydrolysis stability. Mixtures with fatty acid polyol esters are disclosed. However, there are countless combinations of aliphatic saturated branched carboxylic acid monoalkyl esters and fatty acid polyol esters, low viscosity, excellent lubricity, high flash point, excellent safety, and hydrolytic stability. It was extremely difficult to find something that could satisfy the requirements.
上記のように、塩素を含有しない水素含有フロン冷媒や、さらに温室効果が小さいハロ
ゲン原子を含まない炭化水素冷媒を使用する冷凍機において、省エネルギー性を向上させ
るためには粘度の低い潤滑油を冷凍機油として用いることが有効であるが、パラフィン鉱
油あるいはナフテン鉱油を基材とする、いわゆる鉱油系の冷凍機油の場合は、引火点が低
くなり、取り扱いにおいて危険性が高まることが問題である。一方、ポリオールなどの多
価アルコールを用いたエステルを基油とする場合、炭素数の少ない脂肪酸を使用しなけれ
ばならないが、この構造では安定性が著しく低下し、また分解時に発生する脂肪酸による
腐食も懸念される。
本発明は、上記課題を解決するもので、塩素を含有しない水素含有フロン冷媒や、さら
に温室効果が小さいハロゲン原子を含まない炭化水素冷媒とともに使用する、低粘度で、
しかも安全性、安定性に優れた冷媒用冷凍機油を提供することを課題とするものである。
As described above, in refrigerators that use hydrogen-containing chlorofluorocarbon refrigerants that do not contain chlorine and hydrocarbon refrigerants that do not contain halogen atoms that have a small greenhouse effect, a low-viscosity lubricating oil must be refrigerated to improve energy savings. Although it is effective to use as machine oil, in the case of so-called mineral oil-based refrigerating machine oil based on paraffin mineral oil or naphthene mineral oil, there is a problem that the flash point becomes low and the danger increases in handling. On the other hand, when an ester using a polyhydric alcohol such as a polyol is used as a base oil, a fatty acid having a small number of carbon atoms must be used. However, this structure significantly reduces the stability and corrodes the fatty acid generated during decomposition. Is also a concern.
The present invention solves the above-mentioned problems, and is used with a hydrogen-containing chlorofluorocarbon refrigerant that does not contain chlorine, or a hydrocarbon refrigerant that does not contain a halogen atom with a small greenhouse effect, and has a low viscosity,
In addition, it is an object of the present invention to provide a refrigerant refrigerating machine oil that is excellent in safety and stability.
本発明者は、上記目的を達成するために、鋭意研究を進めた結果、基油として特定のモ
ノエステルにポリオールエステルを配合した冷凍機油が、塩素を含有しない水素含有フロ
ン冷媒や炭化水素冷媒において、低粘度で、また良好な潤滑性を有しており、しかも加水
分解安定性が高く、冷媒圧縮式冷凍サイクル装置用潤滑油、すなわち冷凍機油として、非
常に優れていることを見出し、本発明に想到した。
As a result of earnest research to achieve the above object, the inventor of the present invention is a refrigeration oil in which a polyol ester is blended with a specific monoester as a base oil in a hydrogen-containing fluorocarbon refrigerant or hydrocarbon refrigerant that does not contain chlorine. The present invention has been found to be excellent as a lubricating oil for refrigerant compression refrigeration cycle equipment, that is, a refrigerating machine oil, having a low viscosity and good lubricity and high hydrolytic stability. I came up with it.
即ち、本発明は、以下のとおりの冷凍機油および冷凍機用作動流体ならびに冷蔵庫であ
る。
（１）炭素数８の脂肪族モノアルコールと炭素数８の１価脂肪酸とのモノエステルを２５
〜４０質量％と、２‐エチルヘキサン酸および／または３,５,５‐トリメチルヘキサン酸
と炭素数５〜１０のネオペンチルポリオールとのポリオールエステルの少なくとも1種を
６０〜７５質量％含むことからなる冷凍機油。
（２）４０℃における動粘度が４〜７mm2/s、引火点が１３０℃以上、酸価が０.１mgKOH/
g以下、２５℃における体積抵抗率が１０GΩm以上である上記（１）に記載の冷凍機油。
（３）前記モノエステルがｎ‐オクチルアルコールと２‐エチルヘキサン酸のエステルで
ある上記（１）または（２）に記載の冷凍機油。
（４）前記ポリオールエステルが、ネオペンチルグリコール‐ジ‐２エチルヘキサン酸エ
ステルおよび／またはペンタエリスリトール‐テトラ‐２エチルヘキサン酸エステルであ
る上記（１）〜（３）のいずれかに記載の冷凍機油。
That is, this invention is the following refrigerator oil, the working fluid for refrigerators, and a refrigerator.
(1) 25 monoesters of an aliphatic monoalcohol having 8 carbon atoms and a monovalent fatty acid having 8 carbon atoms
From 40 to 75% by mass and from 60 to 75% by mass of polyol ester of 2-ethylhexanoic acid and / or 3,5,5-trimethylhexanoic acid and neopentyl polyol having 5 to 10 carbon atoms Refrigerating machine oil that becomes.
(2) Kinematic viscosity at 40 ° C. is 4 to 7 mm 2 / s, flash point is 130 ° C. or more, and acid value is 0.1 mgKOH /
The refrigerating machine oil according to the above (1), wherein the volume resistivity at 25 ° C. is 10 GΩm or more.
(3) The refrigerating machine oil according to (1) or (2), wherein the monoester is an ester of n-octyl alcohol and 2-ethylhexanoic acid.
(4) The refrigerating machine oil according to any one of (1) to (3), wherein the polyol ester is neopentylglycol-di-2-ethylhexanoate and / or pentaerythritol-tetra-2-ethylhexanoate. .
（５）エポキシ環を有する化合物またはカルボジイミド化合物からなる酸捕捉剤を０.０
１〜１質量％添加した上記（１）〜（４）のいずれかに記載の冷凍機油。
（６）ベンゾトリアゾールの構造を有する金属不活性化剤を１〜１００質量ppm添加した
上記（１）〜（５）のいずれかに記載の冷凍機油。
（７）分子内に２個以上の水酸基を有する油性剤を０.０１〜１質量％添加した上記（１
）〜（６）のいずれかに記載の冷凍機油。
（８）シリコーン油、末端をポリアルキレングリコール又はエステルで変性したシリコー
ン油、またはフッ素化シリコーン油から選ばれる消泡剤の少なくとも１種を１〜１００質
量ppm添加した上記（１）〜（７）のいずれかに記載の冷凍機油。
(5) An acid scavenger comprising a compound having an epoxy ring or a carbodiimide compound is adjusted to 0.0.
The refrigerating machine oil according to any one of (1) to (4), wherein 1 to 1% by mass is added.
(6) The refrigerating machine oil according to any one of (1) to (5), wherein 1 to 100 mass ppm of a metal deactivator having a benzotriazole structure is added.
(7) The above (1) in which 0.01 to 1% by mass of an oily agent having two or more hydroxyl groups in the molecule is added.
) Refrigerating machine oil according to any one of (6).
(8) The above (1) to (7), wherein 1 to 100 mass ppm of at least one antifoaming agent selected from silicone oil, silicone oil modified with polyalkylene glycol or ester, or fluorinated silicone oil is added. Refrigerating machine oil according to any one of the above.
（９）上記（１）〜（８）のいずれかに記載の冷凍機油とエタン、プロパン、ブタン、ま
たはイソブタンから選ばれた少なくとも１種の炭化水素冷媒とを含有する冷凍機用作動流
体。
(9) A working fluid for a refrigerating machine comprising the refrigerating machine oil according to any one of the above (1) to (8) and at least one hydrocarbon refrigerant selected from ethane, propane, butane, or isobutane.
（１０）上記（９）に記載の冷凍機用作動流体と、この流体を圧縮する密閉形圧縮機と、
冷媒を凝縮させる凝縮器と、冷媒を膨張させる膨張機構と、冷媒を蒸発させる蒸発器から
なり、前記密閉形圧縮機は回転子と固定子を有するモータを備えており、前記モータには
ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリアミドイミドコートポ
リエステル、ポリフェニレンサルファイド及びポリエーテルエーテルケトンのいずれか１
種の絶縁フィルムを備え、前記固定子にはガラス転移温度１２０℃以上のエナメル材で被
覆した巻き線を備えた冷蔵庫。
（１１）前記密閉形圧縮機が往復動式である上記（１０）に記載の冷蔵庫。
(10) The working fluid for a refrigerator according to (9) above, a hermetic compressor that compresses the fluid,
The hermetic compressor includes a motor having a rotor and a stator, and the motor includes polyethylene terephthalate. The condenser includes a condenser that condenses the refrigerant, an expansion mechanism that expands the refrigerant, and an evaporator that evaporates the refrigerant. , Any one of polybutylene terephthalate, polyamideimide-coated polyester, polyphenylene sulfide, and polyetheretherketone
A refrigerator comprising a seed insulating film, wherein the stator includes a winding covered with an enamel material having a glass transition temperature of 120 ° C. or higher.
(11) The refrigerator according to (10), wherein the hermetic compressor is a reciprocating type.
本発明の冷凍機油は、低粘度で省エネルギーに優れ、しかも潤滑性に優れており、さ
らに引火点が高くて安全性にも優れ、また加水分解安定性や酸化安定性等を満足できると
いう効果を奏する。また、かかる冷凍機油を用いる本発明の冷凍機用作動流体は、冷凍シ
ステムの各機器や部品を損傷することなく、当該冷凍システムを長期間にわたって、安定
的に運転できるという効果を奏する。さらに、この冷凍機油を用いる冷凍庫にあっては、
省エネルギーで、長期間、安定して稼働することができるという効果を奏する。
The refrigerating machine oil of the present invention has an effect of low viscosity, excellent energy saving, excellent lubricity, high flash point, excellent safety, and satisfactory hydrolytic stability and oxidation stability. Play. Moreover, the working fluid for refrigerators of the present invention using such refrigerator oil has an effect that the refrigeration system can be stably operated over a long period of time without damaging each device and part of the refrigeration system. Furthermore, in a freezer using this refrigerating machine oil,
It has the effect of being able to operate stably for a long time with energy saving.
本発明では、炭素数８の脂肪族モノアルコールと炭素数８の１価脂肪酸とのモノエステ
ルを用いる。アルコールおよび酸の炭素数が８であることにより、低粘度を達成でき、ま
た引火点を高くでき、加水分解安定性が優れている。
In the present invention, a monoester of an aliphatic monoalcohol having 8 carbon atoms and a monovalent fatty acid having 8 carbon atoms is used. When the alcohol and acid have 8 carbon atoms, low viscosity can be achieved, the flash point can be increased, and hydrolysis stability is excellent.
炭素数８の脂肪族モノアルコールとしては、ｎ‐オクチルアルコール、イソオクチルア
ルコール、２‐エチルヘキサノール、１‐メチルヘプタノール、２‐メチルヘプタノール
、２‐プロピルペンタノール、ジメチルシクロヘキサノール等を例示できる。このうちで
も、入手が容易なｎ‐オクチルアルコールを用いることが好ましい。
Examples of the aliphatic monoalcohol having 8 carbon atoms include n-octyl alcohol, isooctyl alcohol, 2-ethylhexanol, 1-methylheptanol, 2-methylheptanol, 2-propylpentanol, and dimethylcyclohexanol. . Among these, it is preferable to use n-octyl alcohol which is easily available.
炭素数８の１価脂肪酸としては、ｎ‐オクタン酸、イソオクタン酸、２‐エチルヘキサ
ン酸、１‐メチルヘプタン酸、２‐メチルヘプタン酸、２‐プロピルペンタン酸、ジメチ
ルシクロヘキサン酸等を例示できる。入手が容易な２‐エチルヘキサン酸を用いることが
好ましい。
Examples of the monovalent fatty acid having 8 carbon atoms include n-octanoic acid, isooctanoic acid, 2-ethylhexanoic acid, 1-methylheptanoic acid, 2-methylheptanoic acid, 2-propylpentanoic acid and dimethylcyclohexane acid. It is preferable to use 2-ethylhexanoic acid which is easily available.
また、本発明では、２‐エチルヘキサン酸および／または３,５,５‐トリメチルヘキサ
ン酸と炭素数５〜１０のネオペンチルポリオールとのポリオールエステルを用いる。上記
モノエステルの所定量にこのポリオールエステルを所定量配合することにより、所望の動
粘度に合わせることができ、また加水分解安定性を高めることができる。
In the present invention, a polyol ester of 2-ethylhexanoic acid and / or 3,5,5-trimethylhexanoic acid and neopentyl polyol having 5 to 10 carbon atoms is used. By blending a predetermined amount of this polyol ester with a predetermined amount of the monoester, it is possible to match the desired kinematic viscosity and to improve the hydrolysis stability.
ネオペンチルポリオールとは、ネオペンタンの構造をもつ２価以上のアルコールで、本
発明では、炭素数５〜１０のものを用いる。炭素数１０を超えるものは、動粘度の調整が
難しくなり、また冷媒との相溶性が悪化する。このネオペンチルポリオールとしては、ネ
オペンチルグリコール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリ
スリトールを用いることができるが、特には、ネオペンチルグリコールおよびペンタエリ
スリトールを用いることが好ましい。
Neopentyl polyol is a divalent or higher valent alcohol having a neopentane structure, and in the present invention, one having 5 to 10 carbon atoms is used. Those having more than 10 carbon atoms are difficult to adjust the kinematic viscosity, and the compatibility with the refrigerant deteriorates. As this neopentyl polyol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol can be used, and in particular, neopentyl glycol and pentaerythritol are preferably used.
本発明に用いるエステルは、上記特定のアルコールまたはポリオールと特定の脂肪酸
との脱水反応によるエステル化反応、あるいは脂肪酸の誘導体である酸無水物、酸クロラ
イド等を経由しての一般的なエステル化反応や各誘導体のエステル交換反応によって得る
ことができる。
The ester used in the present invention is an esterification reaction by dehydration reaction between the specific alcohol or polyol and a specific fatty acid, or a general esterification reaction via an acid anhydride or acid chloride which is a derivative of a fatty acid. Or by transesterification of each derivative.
なお、本発明の冷凍機油は、モノエステルとポリオールエステルとを含むものであるが
、この調製に当たっては、まず、上記手段により、モノエステルとポリオールエステルと
を別々に合成した後に、両者を所定比率で混合してもよく、先に、モノアルコール、１価
脂肪酸、２‐エチルヘキサン酸および／または３,５,５‐トリメチルヘキサン酸、および
ネオペンチルポリオール、あるいはこれらの誘導体を、必要量、混合して上記手段により
合成してもよい。なお、この場合、ポリオールエステルは１種類であっても、２種類以上
が混合しているようにしてもよい。
The refrigerating machine oil of the present invention contains a monoester and a polyol ester. In this preparation, the monoester and the polyol ester are first synthesized separately by the above means, and then mixed in a predetermined ratio. First, monoalcohol, monohydric fatty acid, 2-ethylhexanoic acid and / or 3,5,5-trimethylhexanoic acid, and neopentyl polyol, or a derivative thereof may be mixed in the required amount. You may synthesize | combine by the said means. In this case, the polyol ester may be one type or two or more types may be mixed.
上記方法で得られるエステルは、未反応で残存する酸およびアルコールを特に制限する
ものではないが、カルボキシル基はできるだけ残存しないことが好ましい。カルボキシル
基の残存量が多いと、冷凍機内部に使用されている金属との反応により金属石けんなどを
生成し、沈殿するなどの好ましくない現象も起こるため、本発明の冷凍機油の酸価は０.
１mgKOH/g以下のものが好ましい。この酸価は、ＪＩＳ Ｋ２５０１「石油製品及び潤滑
油―中和価試験方法、指示薬滴定法」に規定する方法によるものである。
The ester obtained by the above method does not particularly limit the unreacted remaining acid and alcohol, but it is preferable that the carboxyl group does not remain as much as possible. If the residual amount of carboxyl groups is large, an undesirable phenomenon such as generation and precipitation of metal soap due to reaction with the metal used in the refrigerator occurs, so that the acid value of the refrigerator oil of the present invention is 0. .
1 mgKOH / g or less is preferable. This acid value is based on the method prescribed in JIS K2501 “Petroleum products and lubricants—neutralization number test method, indicator titration method”.
本発明の冷凍機油は、上記モノエステルを２５〜４０質量％とポリオールエステルを６
０〜７５質量％を含有させたものである。この配合比率にすることにより、低粘度、すな
わち、ＶＧ５グレードの粘度の冷凍機油とすることができ、また、潤滑性に優れ、引火点
および体積抵抗率が高くて安全性、さらに加水分解安定性、相溶性に優れたものとするこ
とができる。
The refrigerating machine oil of the present invention comprises 25 to 40% by mass of the above monoester and 6 of the polyol ester.
0 to 75% by mass is contained. By using this blending ratio, a refrigerating machine oil having a low viscosity, that is, a VG5 grade viscosity can be obtained, and it has excellent lubricity, high flash point and volume resistivity, safety, and hydrolytic stability. , Excellent compatibility can be obtained.
また、本発明の冷凍機油は、ＶＧ５グレードの粘度の冷凍機油とするためには、４０
℃における動粘度が４〜７mm2/sであることが好ましく、また、取扱い上の安全性を確保
するために、引火点が１３０℃以上、感電防止などの安全上の観点から２５℃の体積抵抗
率が１０GΩm以上とすることが好ましい。
４０℃における動粘度は、ＪＩＳ Ｋ２２８３「原油及び石油製品―動粘度試験方法及
び粘度指数算出方法」に規定する方法で測定、引火点はＪＩＳ Ｋ２２６５−４「引火点
の求め方―第４部：クリーブランド開放法」に規定する方法で測定、２５℃の体積抵抗率
はＪＩＳ Ｃ ２１０１「電気絶縁油試験方法、２４．体積抵抗率試験」に規定する方法に
準じて、試料温度２５℃で測定するものである。
In order to make the refrigeration oil of the present invention into a VG5 grade viscosity refrigerating machine oil,
The kinematic viscosity at 4 ° C. is preferably 4 to 7 mm 2 / s, and in order to ensure safety in handling, the flash point is 130 ° C. or higher, and the volume is 25 ° C. from the viewpoint of safety such as prevention of electric shock. It is preferable that the resistivity be 10 GΩm or more.
The kinematic viscosity at 40 ° C. is measured by the method specified in JIS K2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”. The flash point is JIS K2265-4 “How to determine the flash point—Part 4: Measured by the method prescribed in “Cleveland Opening Method”, volume resistivity at 25 ° C. is measured at a sample temperature of 25 ° C. in accordance with the method prescribed in JIS C 2101 “Electrical insulating oil test method, 24. Volume resistivity test”. Is.
上記モノエステルは、ｎ‐オクチルアルコールと２‐エチルヘキサン酸のエステル、す
なわち、２‐エチルヘキサン酸‐ｎ‐オクチルを用いると、ＶＧ５グレードの粘度調整が
容易となるため好ましい。
また同様に、ポリオールエステルとして、２‐エチルヘキサン酸とネオペンチルグリコ
ールのエステルであるネオペンチルグリコール‐ジ‐２‐エチルヘキサン酸エステルまた
は２‐エチルヘキサン酸とペンタエリスリトールとのエステルであるペンタエリスリトー
ル‐テトラ‐２‐エチルヘキサン酸エステルを用いることが好ましい。
As the monoester, it is preferable to use an ester of n-octyl alcohol and 2-ethylhexanoic acid, that is, 2-ethylhexanoic acid-n-octyl, because the viscosity of VG5 grade can be easily adjusted.
Similarly, as the polyol ester, neopentyl glycol-di-2-ethylhexanoate which is an ester of 2-ethylhexanoic acid and neopentyl glycol or pentaerythritol which is an ester of 2-ethylhexanoic acid and pentaerythritol- It is preferable to use tetra-2-ethylhexanoic acid ester.
本発明の冷凍機油においては、加水分解安定性を向上させるために、上記エステルか
らなるものに、さらにエポキシ環を有する化合物やカルボジイミド化合物などの酸捕捉剤
を添加することが好ましい。エポキシ環を有する化合物とは、グリシジルエーテル基含有
化合物、グリシジルエステル基含有化合物、エポキシ化脂肪酸モノエステル類、エポキシ
化油脂、エポキシシクロアルキル基含有化合物などが挙げられる。この中で特にはグリシ
ジルエーテル基含有化合物、グリシジルエステル基含有化合物、エポキシ化脂肪酸モノエ
ステル類、エポキシ化油脂、エポキシシクロアルキル基含有化合物がより好ましい。
この酸捕捉剤の添加量は冷凍機油全体を基準として、０.０１〜１質量％が好ましく、
０.２〜０.７質量％がさらに好ましい。
In the refrigerating machine oil of the present invention, in order to improve hydrolysis stability, it is preferable to add an acid scavenger such as a compound having an epoxy ring or a carbodiimide compound to the above-mentioned ester. Examples of the compound having an epoxy ring include glycidyl ether group-containing compounds, glycidyl ester group-containing compounds, epoxidized fatty acid monoesters, epoxidized oils and fats, and epoxycycloalkyl group-containing compounds. Of these, glycidyl ether group-containing compounds, glycidyl ester group-containing compounds, epoxidized fatty acid monoesters, epoxidized fats and oils, and epoxycycloalkyl group-containing compounds are particularly preferred.
The addition amount of the acid scavenger is preferably 0.01 to 1% by mass based on the whole refrigerating machine oil,
0.2-0.7 mass% is further more preferable.
また、同様に、加水分解安定性を向上させるために、金属不活性化剤であるベンゾトリ
アゾール構造を有する化合物を添加することが好ましい。ベンゾトリアゾール構造を有す
る化合物とは、次の一般式化１で示される化合物で、
又は酸素原子を含有する炭素数０〜２０の基を示す）、
冷凍機油全体を基準として１〜１００質量ppm、さらには１０〜８０質量ppm程度含有され
るよう添加することが好ましい。
Similarly, in order to improve hydrolysis stability, it is preferable to add a compound having a benzotriazole structure as a metal deactivator. The compound having a benzotriazole structure is a compound represented by the following general formula 1,
Or a group having 0 to 20 carbon atoms containing an oxygen atom),
It is preferable to add so that it may contain about 1-100 mass ppm with reference to the whole refrigerating machine oil, Furthermore, about 10-80 mass ppm.
さらに、潤滑性を向上させるために、分子内に２個以上の水酸基を持つ油性剤を添加
することが好ましい。この分子内に２個以上の水酸基を持つ油性剤としては、グリセリン
モノオレート、グリセリンモノオレイルエーテル、グリセリンモノラウリルエーテル等が
挙げられ、特にはグリセリンモノオレート又はグリセリンモノオレイルエーテルが好まし
い。添加量は、冷凍機油全体を基準として０.０１〜１質量％が好ましく、０.１〜０.５
質量％がさらに好ましい。
Furthermore, in order to improve lubricity, it is preferable to add an oily agent having two or more hydroxyl groups in the molecule. Examples of the oily agent having two or more hydroxyl groups in the molecule include glycerol monooleate, glycerol monooleyl ether, glycerol monolauryl ether and the like, and glycerol monooleate or glycerol monooleyl ether is particularly preferable. The addition amount is preferably 0.01 to 1% by mass based on the whole refrigerating machine oil, and is preferably 0.1 to 0.5.
More preferred is mass%.
また、冷凍機油が冷凍システム内で泡立つのを抑えるために、シリコーン油、末端をポ
リアルキレングリコール又はエステルで変性したシリコーン油、またはフッ素化シリコー
ン油から選ばれる消泡剤の少なくとも１種を添加することが好ましい。添加量としては、
冷凍機油全体を基準として、１〜１００ppmが好ましく、特には１０〜８０ppmが好ましい
。
Further, in order to prevent the refrigerating machine oil from foaming in the refrigeration system, at least one antifoaming agent selected from silicone oil, silicone oil modified with polyalkylene glycol or ester at the end, or fluorinated silicone oil is added. It is preferable. As addition amount,
1-100 ppm is preferable on the basis of the whole refrigerating machine oil, and 10-80 ppm is particularly preferable.
本発明の冷凍機油には、必要に応じて上記以外の添加剤をさらに適宜配合してもよい。
このような添加剤として、例えば、２,６‐ジ‐ターシャリーブチルフェノール、２,６‐
ジ‐ターシャリーブチル‐ｐ‐クレゾール、４,４‐メチレン‐ビス‐（２,６‐ジ‐ター
シャリーブチル‐ｐ‐クレゾール）、ｐ,ｐ'‐ジ‐オクチル‐ジ‐フェニルアミンなどの
フェノール系又はアミン系の酸化防止剤、その他、周知の清浄分散剤、粘度指数向上剤、
防錆剤、腐食防止剤、流動点降下剤などの添加剤も必要に応じて適宜配合することができ
る。これらの添加剤は、通常本発明の冷凍機油に１質量ppm〜２質量％程度含有されるよ
うに添加される。特に、フェノール系又はアミン系の酸化防止剤は、０.０１〜０.５質量
％程度添加することにより、潤滑剤の安定性、耐久性を大幅に改善することができる。
In the refrigerating machine oil of the present invention, additives other than those described above may be further appropriately blended as necessary.
Examples of such additives include 2,6-ditertiary butylphenol and 2,6-
Phenols such as di-tertiarybutyl-p-cresol, 4,4-methylene-bis- (2,6-di-tertiarybutyl-p-cresol), p, p'-di-octyl-di-phenylamine -Based or amine-based antioxidants, other well-known detergent dispersants, viscosity index improvers,
Additives such as a rust inhibitor, a corrosion inhibitor, and a pour point depressant can be appropriately blended as necessary. These additives are usually added so that the refrigerating machine oil of the present invention contains about 1 mass ppm to 2 mass%. In particular, the stability and durability of the lubricant can be greatly improved by adding about 0.01 to 0.5% by mass of a phenol-based or amine-based antioxidant.
本発明の冷凍機油は、塩素を含有しない冷媒とともに、さらにはハロゲンを含有しない
冷媒とともに好適に用いることができる。すなわち、本発明の冷凍機油は、塩素を含有せ
ずオゾン層破壊係数の小さい水素含有フロン冷媒、例えば、ジフルオロメタン（Ｒ−３２
）、テトラフルオロエタン（Ｒ‐１３４又はＲ‐１３４ａ）や、特にハロゲンを含有せず
オゾン層破壊係数、地球温暖化係数がともに小さい炭化水素冷媒、例えば、エタン（Ｒ１
７０）、プロパン（Ｒ２９０）、ブタン（Ｒ６００）、イソブタン（Ｒ６００ａ）、ある
いはこれらの２種以上の混合冷媒等を使用する冷凍機に好適に用いられる。
The refrigerating machine oil of the present invention can be suitably used together with a refrigerant that does not contain chlorine and also a refrigerant that does not contain halogen. That is, the refrigerating machine oil of the present invention does not contain chlorine and contains a hydrogen-containing chlorofluorocarbon refrigerant having a low ozone depletion coefficient, such as difluoromethane (R-32).
), Tetrafluoroethane (R-134 or R-134a), and especially hydrocarbon refrigerants that do not contain halogen and have low ozone depletion potential and low global warming potential, such as ethane (R1)
70), propane (R290), butane (R600), isobutane (R600a), or a refrigerator using a mixed refrigerant of two or more thereof.
本発明の冷凍機油は、これらの冷媒と混合されることにより作動流体 となり、冷凍装
置の潤滑をつかさどる。本発明の冷凍機油と冷媒とを５：９５〜８０：２０の割合で混合
することにより作動流体として使用することが可能である。この範囲を外れ、油が少ない
場合には、潤滑不良になる危険性があり、油が多すぎる場合には、効率が低下するため好
ましくない。
The refrigerating machine oil of the present invention becomes a working fluid when mixed with these refrigerants, and controls lubrication of the refrigerating apparatus. It can be used as a working fluid by mixing the refrigerating machine oil of the present invention and the refrigerant in a ratio of 5:95 to 80:20. If this range is exceeded and the amount of oil is small, there is a risk of poor lubrication. If the amount of oil is too large, the efficiency decreases, which is not preferable.
そして、本発明の冷凍機用作動流体は、少なくとも圧縮機、凝縮器、膨張機構及び蒸発
器を有する冷媒圧縮式冷凍装置、例えば、冷凍機、空調機、冷蔵庫等の作動流体として用
いられるが、特には、主に炭化水素冷媒が使用される冷蔵庫に用いることが好ましい。
The working fluid for a refrigerator of the present invention is used as a working fluid for a refrigerant compression refrigeration apparatus having at least a compressor, a condenser, an expansion mechanism, and an evaporator, for example, a refrigerator, an air conditioner, a refrigerator, In particular, it is preferably used for a refrigerator in which mainly hydrocarbon refrigerant is used.
本発明の作動流体が用いられる冷蔵庫においては、一般には密閉形のロータリー式ある
いは往復動式の圧縮機が用いられるが、これらの冷媒圧縮機のモータ部の電気絶縁システ
ム材料である絶縁フィルムとしては、ガラス転移温度５０℃以上の結晶性プラスチックフ
ィルム、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリアミ
ドイミドコートポリエステル、ポリフェニレンサルファイド、ポリエーテルエーテルケト
ン、あるいは、ガラス転移温度の低いフィルム上にガラス転移温度の高い樹脂層を被覆す
る複合フィルムなどが使用されている。
In a refrigerator in which the working fluid of the present invention is used, a sealed rotary type or reciprocating type compressor is generally used. As an insulating film which is an electrical insulation system material of a motor part of these refrigerant compressors, , A crystalline plastic film having a glass transition temperature of 50 ° C. or higher, such as polyethylene terephthalate, polybutylene terephthalate, polyamideimide-coated polyester, polyphenylene sulfide, polyetheretherketone, or a film having a low glass transition temperature. A composite film that covers the resin layer is used.
同様にモータ部に使われるマグネットワイヤも、ガラス転移温度１２０℃以上のエナメ
ル被覆、例えば、ポリエステルイミド、ポリアミド、ポリアミドイミド等の単一層、ある
いはガラス転移温度の低いものを下層に、ガラス転移温度の高いものを上層に複合したエ
ナメル被膜などが使用されている。
Similarly, the magnet wire used in the motor part is also enameled with a glass transition temperature of 120 ° C. or higher, for example, a single layer of polyester imide, polyamide, polyamide imide or the like, or a lower layer of glass transition temperature. Enamel films, etc., in which a high layer is combined with the upper layer, are used.
なお、本発明の冷凍機用作動流体は、低粘度であるため、シール性の高い往復動式の密
閉形圧縮機に好適に用いられる。
In addition, since the working fluid for refrigerators of this invention is low-viscosity, it is used suitably for a reciprocating hermetic type compressor with high sealing performance.
以下、本発明を実施例及び比較例に基づいてより詳しく説明するが、本発明は実施例に
限定されるものではない。
本発明を評価するために、実施例及び比較例の冷媒用冷凍機油（供試油）を用意した。
供試油に使用した基油、添加剤は下記の通りである。
（基油）
ＭＥ‐１：ｎ‐ヘキサン酸‐ｎ‐ヘキシル
ＭＥ‐２：２‐エチルヘキサン酸‐ｎ‐オクチル
ＭＥ‐３：ｎ‐デカン酸‐ｎ‐デシル
ＰＥ‐１：ネオペンチルグリコール‐ジ‐ｎ‐ヘキサン酸エステル
ＰＥ‐２：ネオペンチルグリコール‐ジ‐２‐エチルヘキサン酸エステル
ＰＥ‐３：ペンタエリスリトール‐テトラ‐２‐エチルヘキサン酸エステル
ＰＥ‐４：２‐エチルヘキサン酸（５０質量％）と３,５,５‐トリメチルヘキサン酸（
５０質量％）の混合酸とペンタエリスリトールとのエステル
EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to an Example.
In order to evaluate the present invention, refrigerant refrigerant oils (sample oils) for Examples and Comparative Examples were prepared.
The base oils and additives used in the test oil are as follows.
(Base oil)
ME-1: n-hexanoic acid-n-hexyl ME-2: 2-ethylhexanoic acid-n-octyl ME-3: n-decanoic acid-n-decyl PE-1: neopentylglycol-di-n-hexane Acid ester PE-2: Neopentyl glycol-di-2-ethylhexanoic acid ester PE-3: Pentaerythritol-tetra-2-ethylhexanoic acid ester PE-4: 2-ethylhexanoic acid (50% by mass) and 3, 5,5-trimethylhexanoic acid (
50% by mass) ester of mixed acid and pentaerythritol
（添加剤）
酸捕捉剤：２−エチルヘキシルグリシジルエーテル〔ＥＰＯ〕
ジアルキルフェニルカルボジイミド〔ＣＤＩ〕
油性剤：グリセリンモノオレート〔ＧＭＯ〕
金属捕捉剤：ベンゾトリアゾール〔ＢＴＡ〕
消泡剤：ジメチルシロキサン（１０００mPa.s@25℃）〔シリコーン油〕
(Additive)
Acid scavenger: 2-ethylhexyl glycidyl ether [EPO]
Dialkylphenylcarbodiimide [CDI]
Oiliness agent: Glycerol monooleate [GMO]
Metal scavenger: Benzotriazole [BTA]
Antifoaming agent: Dimethylsiloxane (1000mPa.s@25°C) [Silicone oil]
上記の基油及び添加剤を用い、表１の上部に示す割合（質量％）で調合して、実施例及
び比較例の供試油（冷凍機油）を得た。
Using the above base oil and additives, blending was performed at the ratio (mass%) shown in the upper part of Table 1 to obtain sample oils (refrigeration machine oils) of Examples and Comparative Examples.
これらの実施例及び比較例の冷凍機油について、その物性及び相溶性や安定性などの性
能を測定し、評価した。その結果を表２に示す。
なお、前述した測定法以外の物性測定及び性能評価の試験は以下のようにして行った。
The refrigeration oils of these examples and comparative examples were measured and evaluated for properties such as physical properties, compatibility and stability. The results are shown in Table 2.
The physical property measurement and performance evaluation tests other than the measurement methods described above were performed as follows.
泡立ち：
ＪＩＳ Ｋ２５１８「石油製品−潤滑油泡立ち試験法」に規定の方法により、２４℃で
の泡立ち度、および泡安定度を測定した。
二層分離温度：
ＪＩＳ Ｋ ２２１１の附属書３「冷媒との相溶性試験方法」に規定の方法により、二
層分離温度を測定した。なお、冷媒としては、イソブタン（Ｒ６００ａ）を用い、また、
供試油／冷媒比（重量）は２／８の条件で測定した。
Foaming:
The degree of foaming at 24 ° C. and the degree of foam stability were measured by the methods specified in JIS K2518 “Petroleum product-lubricating oil foaming test method”.
Two-layer separation temperature:
The two-layer separation temperature was measured by the method specified in Appendix 3 “Testing method for compatibility with refrigerant” of JIS K 2211. As a refrigerant, isobutane (R600a) is used, and
The sample oil / refrigerant ratio (weight) was measured under the condition of 2/8.
加水分解安定性：
ＪＩＳ Ｋ２２１１の付属書２「冷媒との化学的安定性試験方法（シールドチューブテ
スト）に規定の方法により、供試油７ｍｌとイソブタン冷媒（Ｒ６００ａ）３ｍｌとの混
合物を油中水分量５００ppm、温度１７５℃の環境下に１４日間おき、全酸価を測定した
。
潤滑性（FALEX焼付）：
ＡＳＴＭ Ｄ３２３３に準拠するファレックス（Ｆａｌｅｘ）試験（２９０rpm、室温
）を行い、試験片が焼付きを生じた時の荷重を測定した。
潤滑性（SRV摩耗痕）：
ボール（ＳＵＪ‐２製）／ディスク（ＳＵＪ‐２製）のＳＲＶ摩擦試験機を用い、荷重
１００Ｎ、振幅数５０Hz、振幅１mm、温度６０℃の条件で、試験時間２５分経過後の摩耗
痕を測定した。
Hydrolytic stability:
A mixture of 7 ml of the test oil and 3 ml of isobutane refrigerant (R600a) was added to an oil content of 500 ppm at a temperature of 175 according to the method specified in Annex 2 “Test method for chemical stability with refrigerant (shield tube test)” of JIS K2211. The total acid value was measured every 14 days in an environment of ° C.
Lubricity (FALEX seizure):
A Falex test (290 rpm, room temperature) in accordance with ASTM D3233 was performed, and the load when the test piece was seized was measured.
Lubricity (SRV wear marks):
Using a ball (SUJ-2) / disk (SUJ-2) SRV friction tester, wear marks after a test time of 25 minutes under the conditions of load 100N, amplitude 50Hz, amplitude 1mm, temperature 60 ° C It was measured.
コンプレッサーテスト：
冷蔵庫用コンブレッサーに供試油を２２０ml入れ、冷媒としてイソブタンを３０ｇ使用
し、次の条件で耐久テストを行った。
＜条件＞ 吐出圧力：１０kg/cm2Ｇ、吸入圧力：０kg/cm2Ｇ、コンプレッサー表面温度（
頂上）：１００℃、運転時間：１０００時間
耐久テスト後にコンプレッサーを分解し、吐出弁の汚れ及び摺動部の摩耗評価を行った
。
Compressor test:
An endurance test was conducted under the following conditions using 220 ml of test oil in a refrigerator compressor and 30 g of isobutane as a refrigerant.
<Conditions> Discharge pressure: 10 kg / cm 2 G, suction pressure: 0 kg / cm 2 G, compressor surface temperature (
Top): 100 ° C., operation time: 1000 hours After the endurance test, the compressor was disassembled, and the discharge valve dirt and sliding part wear were evaluated.
炭素数８の脂肪族モノアルコールであるｎ-オクタノールと炭素数８の1価脂肪酸である
２-エチルヘキサン酸とのエステルであるＭＥ‐２：２‐エチルヘキサン酸（ｎ‐オクチ
ル）と、２-エチルヘキサン酸または３,５,５-トリメチルヘキサン酸と炭素数５〜１０の
ネオペンチルアルコールであるネオペンチルグリコールまたはペンタエリスリトールのエ
ステルであるＰＥ-１〜ＰＥ-４の混合物を基油として用いた実施例１〜７は、低粘度油で
ありながら、引火点が高く、また冷媒との相溶性、加水分解安定性、体積抵抗率にも優れ
、しかも潤滑性も良好である。
ME-2: 2-ethylhexanoic acid (n-octyl) which is an ester of n-octanol which is an aliphatic monoalcohol having 8 carbon atoms and 2-ethylhexanoic acid which is a monovalent fatty acid having 8 carbon atoms; -A mixture of ethylhexanoic acid or 3,5,5-trimethylhexanoic acid and neopentyl glycol or pentaerythritol, which is a neopentyl alcohol having 5 to 10 carbon atoms, is used as a base oil. Examples 1 to 7, which are low-viscosity oils, have a high flash point, excellent compatibility with refrigerants, hydrolysis stability, volume resistivity, and good lubricity.
一方、モノエステルＭＥ-１〜ＭＥ-３およびネオペンチルポリオールのエステルＰＥ-
１を単独で基油として用いた比較例１〜４は、加水分解安定性が悪く、また、比較例１〜
４では、潤滑性のＳＲＶ摩耗痕も悪い。特に比較例1は、引火点、体積抵抗率、潤滑性の
ＦＡＬＥＸ焼付も悪い。なお、ＰＥ-２を単独で用いた比較例５は、粘度が高く、省エネ
ルギーを十分に達成できない。また、炭素数６や炭素数１０のアルコールや酸のエステル
を用いたものは、ネオペンチルポリオールのエステルと混合しても（比較例６〜８）、加
水分解安定性が悪く、また、比較例６〜７は体積抵抗率も低い。これらの基油を用いたも
のは、添加剤を添加しても（比較例９〜１１）、改善できなかった。
On the other hand, monoesters ME-1 to ME-3 and neopentyl polyol ester PE-
Comparative Examples 1 to 4 using 1 as the base oil alone have poor hydrolysis stability, and Comparative Examples 1 to 1
No. 4, the lubricating SRV wear scar is also bad. In particular, Comparative Example 1 has poor flash point, volume resistivity, and lubricating FALEX seizure. In addition, the comparative example 5 which used PE-2 independently has a high viscosity, and cannot fully achieve energy saving. Moreover, what used the ester of C6 or C10 alcohol and acid, even if it mixes with the ester of neopentyl polyol (Comparative Examples 6-8), hydrolysis stability is bad, and a comparative example 6-7 have a low volume resistivity. Those using these base oils could not be improved even when additives were added (Comparative Examples 9 to 11).
本発明により、塩素を含有しない水素含有フロン冷媒や、さらに温室効果が小さいハロ
ゲン原子を含まない炭化水素冷媒に使用する、低粘度でしかも安定性に優れた冷媒用冷凍
機油を提供することを可能とした。したがって、地球の温暖化等の環境に与える影響が小
さく、しかも、低粘度で省エネルギーにも期待されることから、冷媒圧縮式冷凍サイクル
を利用する冷凍機、空調機、冷蔵庫等に有効に好適に用いることができる。
According to the present invention, it is possible to provide a refrigerant refrigerating machine oil having a low viscosity and excellent stability, which is used for a hydrogen-containing fluorocarbon refrigerant not containing chlorine or a hydrocarbon refrigerant not containing a halogen atom having a small greenhouse effect. It was. Therefore, since it has a small impact on the environment such as global warming and is expected to save energy with low viscosity, it is effectively suitable for refrigerators, air conditioners, refrigerators, etc. that use refrigerant compression refrigeration cycles. Can be used.
Claims (5)
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| JPS494107B1 (en) * | 1970-07-08 | 1974-01-30 | ||
| ID30548A (en) * | 1999-05-10 | 2001-12-20 | New Japan Chem Co Ltd | LUBRICATING OIL FOR COOLING MACHINERY, COMPOSITION OF WORKING FLUID FOR COOLING MACHINERY, AND METHOD OF LUBRICATION MACHINE REFRIGERATION |
| JP3909744B2 (en) * | 2001-07-31 | 2007-04-25 | 株式会社ジャパンエナジー | Refrigerating machine oil for hydrocarbon refrigerant |
| JP4493373B2 (en) * | 2004-03-04 | 2010-06-30 | 新日本石油株式会社 | Refrigerator oil composition |
| JP4855175B2 (en) * | 2006-08-04 | 2012-01-18 | Ｊｘ日鉱日石エネルギー株式会社 | Lubricating oil composition for refrigerator |
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