JP2009235179A - Refrigerating machine oil used for refrigerant - Google Patents
Refrigerating machine oil used for refrigerant Download PDFInfo
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- JP2009235179A JP2009235179A JP2008080885A JP2008080885A JP2009235179A JP 2009235179 A JP2009235179 A JP 2009235179A JP 2008080885 A JP2008080885 A JP 2008080885A JP 2008080885 A JP2008080885 A JP 2008080885A JP 2009235179 A JP2009235179 A JP 2009235179A
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- Prior art keywords
- refrigerant
- refrigerating machine
- oil
- machine oil
- carbon atoms
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- 239000003507 refrigerant Substances 0.000 title claims abstract description 67
- 239000010721 machine oil Substances 0.000 title claims abstract description 32
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 25
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000003921 oil Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 14
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 10
- 239000010726 refrigerant oil Substances 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002826 coolant Substances 0.000 claims description 6
- 239000001282 iso-butane Substances 0.000 claims description 5
- 239000001294 propane Substances 0.000 claims description 5
- 239000002516 radical scavenger Substances 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005069 Extreme pressure additive Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001273 butane Substances 0.000 claims description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 125000005843 halogen group Chemical group 0.000 abstract description 4
- 239000002199 base oil Substances 0.000 description 18
- 235000014113 dietary fatty acids Nutrition 0.000 description 13
- 239000000194 fatty acid Substances 0.000 description 13
- 229930195729 fatty acid Natural products 0.000 description 13
- 150000004665 fatty acids Chemical class 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- -1 polyol esters Chemical class 0.000 description 12
- 238000005057 refrigeration Methods 0.000 description 12
- 239000000654 additive Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000010687 lubricating oil Substances 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 239000002480 mineral oil Substances 0.000 description 8
- 229920005862 polyol Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 7
- 235000010446 mineral oil Nutrition 0.000 description 7
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 4
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- 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
- 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
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 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
- 239000003925 fat Substances 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000005691 triesters Chemical class 0.000 description 2
- INKXYFUMUBZQKV-UHFFFAOYSA-N (2,3,4-triethylphenyl) dihydrogen phosphate Chemical compound CCC1=CC=C(OP(O)(O)=O)C(CC)=C1CC INKXYFUMUBZQKV-UHFFFAOYSA-N 0.000 description 1
- ZVOVXOUDTRRZFF-UHFFFAOYSA-N (2,3,4-tripropylphenyl) dihydrogen phosphate Chemical compound CCCC1=CC=C(OP(O)(O)=O)C(CCC)=C1CCC ZVOVXOUDTRRZFF-UHFFFAOYSA-N 0.000 description 1
- NZADFKWJIQWGNZ-UHFFFAOYSA-N (2-ethylphenyl) diphenyl phosphate Chemical compound CCC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 NZADFKWJIQWGNZ-UHFFFAOYSA-N 0.000 description 1
- ZYURBDFDLBLSAM-UHFFFAOYSA-N (2-phenyl-3,4-dipropylphenyl) dihydrogen phosphate Chemical compound CCCC1=CC=C(OP(O)(O)=O)C(C=2C=CC=CC=2)=C1CCC ZYURBDFDLBLSAM-UHFFFAOYSA-N 0.000 description 1
- XOLRGGJVYFCUFJ-UHFFFAOYSA-N (3,4-diethyl-2-phenylphenyl) dihydrogen phosphate Chemical compound CCC1=CC=C(OP(O)(O)=O)C(C=2C=CC=CC=2)=C1CC XOLRGGJVYFCUFJ-UHFFFAOYSA-N 0.000 description 1
- JCDJGJCAOAFHSD-UHFFFAOYSA-N (4-butylphenyl) diphenyl phosphate Chemical compound C1=CC(CCCC)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 JCDJGJCAOAFHSD-UHFFFAOYSA-N 0.000 description 1
- GBXRUYNQDDTQQS-UHFFFAOYSA-N 1-O-dodecylglycerol Chemical compound CCCCCCCCCCCCOCC(O)CO GBXRUYNQDDTQQS-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-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
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 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
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-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
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- XEWICNQPMLFYFJ-UHFFFAOYSA-N diphenyl (2-propylphenyl) phosphate Chemical compound CCCC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XEWICNQPMLFYFJ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000002994 raw material 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
- 230000000630 rising effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 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 1
Landscapes
- Lubricants (AREA)
Abstract
Description
本発明は、塩素を含有しない水素含有フロン冷媒及び炭化水素冷媒等のオゾン層破壊係数や地球温暖化係数の小さい冷媒を用いる冷媒圧縮式冷凍サイクル装置に好適に用いることができる冷媒用冷凍機油に関する。 TECHNICAL FIELD The present invention relates to a refrigerant refrigerating machine oil that can be suitably used for a refrigerant compression refrigeration cycle apparatus that uses a refrigerant having a small ozone layer depletion coefficient and a global warming coefficient, such as a hydrogen-containing chlorofluorocarbon refrigerant and a hydrocarbon refrigerant. .
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（ＣＦＣ）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、最近の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、イソブタン等のなどに転換されてきている。 Conventionally, a refrigerant compression refrigeration cycle apparatus used in a refrigerator, an air conditioner, a refrigerator, or the like has a fluorocarbon having fluorine and chlorine as refrigerants, for example, R-11 (trichloromono) which is chlorofluorocarbon (CFC). Fluoromethane), R-12 (dichlorodifluoromethane), hydrochlorofluorocarbon (HCFC) R-22 (monochlorodifluoromethane) and the like have been used. Its production and use are regulated, and at present, hydrogen-containing chlorofluorocarbon refrigerants that do not contain chlorine, such as difluoromethane (R-32), tetrafluoroethane (R-134 or R-134a), and halogens that have a lower greenhouse effect. Atom-free hydrocarbon refrigerants such as ethane, propane, butane, isobutane, etc. It has been converted to etc..
発明者は、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、作業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。しかしながら、低粘度のポリオールエステルには、酸化安定性及び潤滑性に満足できるものが見当たらない。
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場合、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、本発明の目的は、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. It is effective to use as machine oil. However, when paraffin mineral oil or naphthene mineral oil is used as a base material, 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-described problems, and the object of the present invention is to provide a low-viscosity and safe use with a hydrogen-containing fluorocarbon refrigerant that does not contain chlorine and a hydrocarbon refrigerant that does not contain a halogen atom with a small greenhouse effect. It is providing the refrigerating machine oil for refrigerant | coolants excellent in property 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を主成分とした冷凍機油が、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、良好な潤滑性、省エネルギー性を有しており、安定性も高く、冷媒圧縮式冷凍サイクル装置用潤滑油、すなわち冷媒用冷凍機油として、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 has a refrigeration oil mainly composed of a specific monoester as a base oil in a hydrogen-containing fluorocarbon refrigerant or hydrocarbon refrigerant that does not contain chlorine. It has been found that it has excellent lubricity and energy saving, high stability, and is very excellent as a lubricating oil for refrigerant compression refrigeration cycle equipment, that is, a refrigerating machine oil for refrigerant.
即ち、本発明は、以下のとおりの冷媒用冷凍機油である。
（１） 次の一般式（１）で表されるモノエステルを主成分として含有し、４０℃における動粘度が７ｍｍ２／ｓ未満である冷媒用冷凍機油、
（２） さらに酸捕捉剤を含有する上記（１）に記載の冷媒用冷凍機油。
（３） さらにリンを含む極圧添加剤を含有する上記（１）又は（２）に記載の冷媒用冷凍機油。
（４） さらに２個以上の水酸基を持つ油性剤を含有する上記（１）〜（３）のいずれかに記載の冷媒用冷凍機油。
（５） 引火点が１２０℃以上である上記（１）〜（４）のいずれかに記載の冷媒用冷凍機油。
（６） ４０℃における動粘度が６ｍｍ２／ｓ未満である上記（１）〜（５）のいずれかに記載の冷媒用冷凍機油。
（７） エタン、プロパン、ブタン、イソブタン、又はこれらの混合物である炭化水素冷媒とともに用いる上記（１）〜（６）のいずれかに記載の冷媒用冷凍機油。
That is, the present invention is a refrigerant refrigerating machine oil as follows.
(1) Refrigerating machine oil for refrigerant containing a monoester represented by the following general formula (1) as a main component and having a kinematic viscosity at 40 ° C. of less than 7 mm 2 / s,
(2) The refrigerant refrigerating machine oil according to (1), further including an acid scavenger.
(3) The refrigerating machine oil for refrigerant according to (1) or (2), further including an extreme pressure additive containing phosphorus.
(4) The refrigerating machine oil for refrigerant according to any one of (1) to (3), further including an oily agent having two or more hydroxyl groups.
(5) The refrigerant | coolant refrigeration oil in any one of said (1)-(4) whose flash point is 120 degreeC or more.
(6) The refrigerant | coolant refrigeration oil in any one of said (1)-(5) whose kinematic viscosity in 40 degreeC is less than 6 mm < 2 > / s.
(7) The refrigerant oil for refrigerant according to any one of the above (1) to (6), which is used together with a hydrocarbon refrigerant which is ethane, propane, butane, isobutane, or a mixture thereof.
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、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 a medium compression refrigeration cycle. Can be used.
本発明を詳細に説明する。
本発明は、次の一般式（１）で表されるモノエステルを主成分として含有し、４０℃における動粘度が７ｍｍ２／ｓ未満である冷媒用冷凍機油である。
本発明の冷媒用冷凍機油は、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、本発明の冷媒用冷凍機油は、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や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（Ｒ１７０）、プロパン（Ｒ２９０）、ブタン（Ｒ６００）、イソブタン（Ｒ６００ａ）等の冷媒に使用する冷凍機として好適に用いることができる。
The present invention will be described in detail.
The present invention is a refrigerant refrigerating machine oil containing a monoester represented by the following general formula (1) as a main component and having a kinematic viscosity at 40 ° C. of less than 7 mm 2 / s.
The refrigerant oil for refrigerant of the present invention can be suitably used with a refrigerant that does not contain chlorine, and further with a refrigerant that does not contain halogen. That is, the refrigerating machine oil for refrigerant of the present invention does not contain chlorine and has a small ozone layer destruction coefficient, such as a hydrogen-containing fluorocarbon refrigerant such as difluoromethane (R-32), tetrafluoroethane (R-134 or R-134a), Especially, it is used for hydrocarbon refrigerants that do not contain halogen and have a low ozone depletion coefficient and global warming coefficient, such as ethane (R170), propane (R290), butane (R600), isobutane (R600a), etc. It can be suitably used as a refrigerator.
本発明において、冷媒用冷凍機油の主成分として用いられるモノエステルは一般式（１）で表される。
また、Ｒ１及びＲ２の炭素数の合計は１３〜１７であり、炭素数の合計が１３未満では、粘度が低下しすぎて潤滑性が不足し、さらに引火点も低下して取り扱い上の危険性が増すなどの問題が生ずることから好ましくない。また、炭素数の合計が１７を超えると、粘度が高くなり、圧縮機における省エネルギー効果に乏しくなるという問題が生じる。さらに、Ｒ１の炭素数が５未満の場合、加水分解したときに炭素数が小さくなればなるほど酸強度の強い１価脂肪酸（カルボン酸）生成し、周囲の設備材料を腐食する等の危害を与えるので好ましくない。 In addition, the total number of carbon atoms of R 1 and R 2 is 13 to 17, and if the total number of carbon atoms is less than 13, the viscosity is too low and the lubricity is insufficient, and the flash point is also reduced, and handling is difficult. This is not preferable because problems such as increased danger occur. On the other hand, when the total number of carbon atoms exceeds 17, there is a problem that the viscosity increases and the energy saving effect in the compressor becomes poor. Furthermore, when the carbon number of R 1 is less than 5, the smaller the carbon number when hydrolyzed, the more monovalent fatty acid (carboxylic acid) with stronger acid strength is produced, and the hazards such as corrosion of surrounding equipment materials are caused. Since it gives, it is not preferable.
本発明で用いるこのようなモノエステルは、一般式（１）の化学式から分かるように炭素数６〜１０の一価脂肪酸（カルボン酸）と、炭素数８〜１０の一価アルコールをエステル化して合成することができる。本発明においてモノエステルの製造方法を限定するものではなく、一価脂肪酸に相当する化合物として、一価脂肪酸の塩化物やカルボン酸無水物などを用いて合成してもよく、さらにモノエステルのアルコイシル基やアシル基を他のアルコイシル基やアシル基と交換するエステル交換反応を利用して合成することができる。 Such a monoester used in the present invention is obtained by esterifying a monovalent fatty acid (carboxylic acid) having 6 to 10 carbon atoms and a monohydric alcohol having 8 to 10 carbon atoms, as can be seen from the chemical formula of the general formula (1). Can be synthesized. In the present invention, the production method of the monoester is not limited, and the compound corresponding to the monovalent fatty acid may be synthesized using a monovalent fatty acid chloride, carboxylic acid anhydride, or the like. It can be synthesized using an ester exchange reaction in which a group or an acyl group is exchanged with another alkoysyl group or an acyl group.
本発明において、一般式（１）のモノエステルの合成に好適に用いることができる一価脂肪酸としては、へキサン酸、ヘプタン酸、オクタン酸、２−エチルヘキサン酸、ノナン酸、３，５，５−トリメチルヘキサン酸、デカン酸が挙げられ、これらの中でも炭素数８のオクタン酸又は２−エチルヘキサン酸が特に好ましい。 In the present invention, monovalent fatty acids that can be suitably used for the synthesis of the monoester of the general formula (1) include hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, 3, 5, Examples thereof include 5-trimethylhexanoic acid and decanoic acid. Among these, octanoic acid having 8 carbon atoms or 2-ethylhexanoic acid is particularly preferable.
本発明において、一般式（１）のモノエステルの合成に好適に用いることができる一価アルコールとしてはオクタノール、２−エチルヘキサノール、デカノールが挙げられ、これらの中でも炭素数８のオクタノール又は２−エチルヘキサノールが好適である。
なお、直鎖の一価脂肪酸と一価アルコールから得られたエステルは、粘度指数が高く耐摩耗性に優れる。また、分岐の、特にはカルボキシル基を有する炭素原子が２個のアルキル基を有する分岐の一価脂肪酸や水酸基を有する炭素原子が２個のアルキル基を有する分岐の一価アルコールから得られたエステルは、粘度が低く、特に耐加水分解安定性に優れる。したがって、一価脂肪酸と一価アルコールは少なくともいずれか一方が前記のような２個のアルキル基を有するものであることが好ましい。
In the present invention, examples of the monohydric alcohol that can be suitably used for the synthesis of the monoester of the general formula (1) include octanol, 2-ethylhexanol, and decanol, and among these, octanol having 8 carbon atoms or 2-ethyl. Hexanol is preferred.
An ester obtained from a linear monohydric fatty acid and a monohydric alcohol has a high viscosity index and excellent wear resistance. Also, esters obtained from branched monovalent fatty acids having branched, especially branched carbon atoms having two alkyl groups, and branched monohydric alcohols having two alkyl groups having carbon atoms having hydroxyl groups. Has a low viscosity and is particularly excellent in hydrolysis resistance. Therefore, it is preferable that at least one of the monohydric fatty acid and the monohydric alcohol has two alkyl groups as described above.
本発明で用いるモノエステルは、冷媒用冷凍機油の主成分を構成するので、冷媒用冷凍機油と同様に、４０℃における動粘度は７ｍｍ２／ｓ未満であることが好ましい。より好ましくは６ｍｍ２／ｓ未満であり、さらに好ましくは２〜５ｍｍ２／ｓである。７ｍｍ２／ｓを超える場合には省エネルギー効果が得られなくなる。動粘度と引火点は必ずしも比例するものではないが、通常動粘度が低いと引火点の低くなる。冷凍機油は密閉系で使われることが多く、引火点が問題になることは少ないが、冷凍機に充填される以前での取扱における安全性を確保する上で、引火点は１２０℃以上とすることが好ましい。より好ましくは１３０℃以上であり、特に好ましくは１４０℃以上である。 Since the monoester used in the present invention constitutes the main component of the refrigerant oil for refrigerant, the kinematic viscosity at 40 ° C. is preferably less than 7 mm 2 / s, similarly to the refrigerant oil for refrigerant. More preferably, it is less than 6 mm < 2 > / s, More preferably, it is 2-5 mm < 2 > / s. When it exceeds 7 mm 2 / s, the energy saving effect cannot be obtained. The kinematic viscosity and the flash point are not necessarily proportional to each other, but usually the flash point is lowered when the kinematic viscosity is low. Refrigerator oil is often used in a closed system, and the flash point is rarely a problem, but the flash point should be 120 ° C or higher in order to ensure safety in handling before filling the refrigerator. It is preferable. More preferably, it is 130 degreeC or more, Most preferably, it is 140 degreeC or more.
本発明で用いるモノエステルは、エステル化で原料として用いた脂肪酸、アルコールやそれらの誘導体などが残存していないことが好ましい。モノエステルの酸価としては、０．１ｍｇＫＯＨ／ｇ以下が好ましく、０．０５ｍｇＫＯＨ／ｇ以下がより好ましく、０．０３ｍｇＫＯＨ／ｇ以下が特に好ましい。また、水酸基価としては、１０ｍｇＫＯＨ／ｇ以下が好ましく、５．０ｍｇＫＯＨ／ｇ以下がより好ましく、３．０ｍｇＫＯＨ／ｇ以下が特に好ましい。 The monoester used in the present invention preferably has no fatty acid, alcohol or derivative thereof used as a raw material in esterification. The acid value of the monoester is preferably 0.1 mgKOH / g or less, more preferably 0.05 mgKOH / g or less, and particularly preferably 0.03 mgKOH / g or less. Moreover, as a hydroxyl value, 10 mgKOH / g or less is preferable, 5.0 mgKOH / g or less is more preferable, 3.0 mgKOH / g or less is especially preferable.
モノエステルは、それ単独で、あるいはその他の潤滑油基材とともに各種の添加剤と混合して冷媒用冷凍機油を調製することができる。その他の潤滑油基材としては、鉱油系の潤滑油基材、合成油系の潤滑油基材、及びそれらの混合物を用いることができる。鉱油系の潤滑油基材としては、ナフテン系又はパラフィン系の鉱物油、合成油系の潤滑油基材としては、アルキルベンゼン、ポリアルファオレフィン、ポリオールエステル、ジエステル、ポリエーテルなどが挙げられる。これらの混合用基材は、混合したときの４０℃における動粘度が高くなりすぎないように、４０℃における動粘度が１０ｍｍ２／ｓ未満であることが好ましい。より好ましくは８ｍｍ２／ｓ未満である。
これらの潤滑油基材の中で、ポリオールエステル、ジエステル、ポリエーテルなどはモノエステルと組み合わせて特に好ましく使用することができる。これらは分子内に酸素原子を持つ化合物であり、同様に分子内に酸素原子を持つモノエステルと混合したときに親和性が高いので、好ましい。
The monoester can be used alone or mixed with various additives together with other lubricating oil bases to prepare refrigerant refrigerant oil. As other lubricant base materials, mineral oil base lubricant bases, synthetic oil base lubricant base materials, and mixtures thereof can be used. Examples of the mineral oil base material include naphthenic or paraffinic mineral oils, and examples of the synthetic oil base materials include alkylbenzene, polyalphaolefin, polyol ester, diester, and polyether. These mixing base materials preferably have a kinematic viscosity at 40 ° C. of less than 10 mm 2 / s so that the kinematic viscosity at 40 ° C. when mixed is not too high. More preferably, it is less than 8 mm 2 / s.
Among these lubricating oil base materials, polyol esters, diesters, polyethers, and the like can be particularly preferably used in combination with monoesters. These are compounds having an oxygen atom in the molecule, and are also preferable because they have high affinity when mixed with a monoester having an oxygen atom in the molecule.
その他の潤滑油基材の物性としては、できるだけモノエステルと同等程度の物性を有することが好ましい。すなわち、４０℃における動粘度は７ｍｍ２／ｓ未満であることが好ましく、より好ましくは６ｍｍ２／ｓ未満であり、さらに好ましくは２〜５ｍｍ２／ｓである。引火点は１２０℃以上が好ましい。より好ましくは１３０℃以上であり、特に好ましくは１４０℃以上である。その他の潤滑油基材の酸価としては、０．１ｍｇＫＯＨ／ｇ以下が好ましく、０．０５ｍｇＫＯＨ／ｇ以下がより好ましく、０．０３ｍｇＫＯＨ／ｇ以下が特に好ましい。 As other physical properties of the lubricating oil base material, it is preferable to have physical properties as high as possible as the monoester. That is, the kinematic viscosity at 40 ° C. is preferably less than 7 mm 2 / s, more preferably less than 6 mm 2 / s, and even more preferably 2 to 5 mm 2 / s. The flash point is preferably 120 ° C. or higher. More preferably, it is 130 degreeC or more, Most preferably, it is 140 degreeC or more. The acid value of the other lubricating oil base is preferably 0.1 mgKOH / g or less, more preferably 0.05 mgKOH / g or less, and particularly preferably 0.03 mgKOH / g or less.
モノエステルをその他の潤滑油基材とともに用いる場合、モノエステルとその他の潤滑油基材との配合割合（質量比）は３０／７０以上、さらには４０／６０以上とすることが好ましい。より好ましくは６０／４０以上であり、特に好ましくは８０／２０以上である。なお、その他の潤滑油基材を全く使用せずに、モノエステル１００％であってよいことは断るまでもない。 When the monoester is used together with another lubricating oil base material, the blending ratio (mass ratio) of the monoester and the other lubricating oil base material is preferably 30/70 or more, more preferably 40/60 or more. More preferably, it is 60/40 or more, and particularly preferably 80/20 or more. It goes without saying that the monoester may be 100% without using any other lubricant base material.
本発明の冷媒用冷凍機油は、冷凍機油としての性能をさらに高めるために、冷凍機油に用いられている各種の添加剤を配合することができる。例えば、酸捕捉剤を添加することにより、さらに安定性を高めることが可能である。また、本発明の冷媒用冷凍機油は、適当な潤滑性が得られるように主成分を構成する潤滑油基油の構造を特定しているが、粘度が非常に低いために使用条件によっては摺動部で金属接触が生じる可能性がある。これに対処するにはリンを含む極圧添加剤及び／又は２個以上の水酸基を持つ油性剤を添加することが効果的である。 The refrigerant refrigerating machine oil of the present invention can be blended with various additives used in refrigerating machine oil in order to further enhance the performance as a refrigerating machine oil. For example, the stability can be further increased by adding an acid scavenger. In addition, the refrigerant refrigerating machine oil of the present invention specifies the structure of the lubricating base oil that constitutes the main component so that appropriate lubricity can be obtained. However, since the viscosity is very low, it depends on the usage conditions. Metal contact may occur at moving parts. In order to cope with this, it is effective to add an extreme pressure additive containing phosphorus and / or an oily agent having two or more hydroxyl groups.
酸捕捉剤としては、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。配合量は０．１〜１．０質量％が好ましく、０．２〜０．７質量％がさらに好ましい。 Examples of the acid scavenger include glycidyl ether group-containing compounds, glycidyl ester group-containing compounds, epoxidized fatty acid monoesters, epoxidized fats and oils, 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 blending amount is preferably 0.1 to 1.0% by mass, and more preferably 0.2 to 0.7% by mass.
リンを含む極圧添加剤としては、リン酸の水酸基の一つ以上がエステル化されたリン酸エステルが挙げられる。リン酸エステルは、トリエステルであっても、ジエステルであっても、モノエステルであってもよいが、トリエステルが最も好ましい。具体的には、トリフェニルホスフェート、トリクレジルホスフェート、トリエチルフェニルホスフェート、トリプロピルフェニルホスフェート、トリブチルフェニルホスフェート、クレジルジフェニルホスフェート、エチルフェニルジフェニルホスフェート、プロピルフェニルジフェニルホスフェート、ブチルフェニルジフェニルホスフェート、ジクレジルフェニルホスフェート、ジエチルフェニルフェニルホスフェート、ジプロピルフェニルフェニルホスフェート、ジブチルフェニルフェニルホスフェート等のトリアリールホスフェートが挙げられる。この中でもトリクレジルホスフェート（ＴＣＰ）が特に好ましい。配合量は０．１〜２．０質量％が好ましく、０．２〜１．５質量％がさらに好ましい。 Examples of extreme pressure additives containing phosphorus include phosphate esters in which one or more hydroxyl groups of phosphoric acid are esterified. The phosphate ester may be a triester, a diester, or a monoester, but the triester is most preferred. Specifically, triphenyl phosphate, tricresyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, tributylphenyl phosphate, cresyl diphenyl phosphate, ethylphenyl diphenyl phosphate, propylphenyl diphenyl phosphate, butylphenyl diphenyl phosphate, dicresyl phenyl Triaryl phosphates such as phosphate, diethylphenylphenyl phosphate, dipropylphenylphenyl phosphate, dibutylphenylphenyl phosphate and the like can be mentioned. Of these, tricresyl phosphate (TCP) is particularly preferable. The blending amount is preferably 0.1 to 2.0% by mass, and more preferably 0.2 to 1.5% by mass.
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。配合量は０．１〜１．０質量％が好ましく、０．２〜０．５質量％がさらに好ましい。 Examples of the oily agent having two or more hydroxyl groups include glycerin monooleate, glycerin monooleyl ether, and glycerin monolauryl ether, and glycerin monooleate or glycerin monooleyl ether is particularly preferable. The blending amount is preferably 0.1 to 1.0% by mass, and more preferably 0.2 to 0.5% by mass.
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、腐食性化合物を捕捉して冷凍機内の材料の劣化、冷媒や潤滑油の劣化を防ぐカルボジイミド化合物などの安定剤、ベンゾトリアゾールなどの金属不活性化剤、ポリジメチルシロキサンやポリメタクリアクリレートなどの消泡剤又は制泡剤などが挙げられる。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配合される。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-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 4,4-methylene-bis- (2,6-di-tertiary). Butyl-p-cresol), p, p'-di-octyl-di-phenylamine, and other phenolic or amine-based antioxidants, corrosive compounds are captured, deterioration of the material in the refrigerator, refrigerant and lubricating oil Stabilizers such as carbodiimide compounds that prevent deterioration of the resin, metal deactivators such as benzotriazole, and antifoaming agents or antifoaming agents such as polydimethylsiloxane and polymethacrylate. In addition, additives such as known detergent dispersants, viscosity index improvers, rust inhibitors, corrosion inhibitors, pour point depressants, and the like can be appropriately blended as necessary. These additives are usually blended so that the refrigerating machine oil of the present invention contains about 1 mass ppm to 2 mass%. In particular, by adding about 0.01 to 0.5% by mass of a phenol-based or amine-based antioxidant, the stability and durability of the lubricant can be greatly improved.
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。 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.
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
モノエステル１〜８：表１に示すモノエステル
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 monoesters 1-8: monoesters shown in Table 1
ポリオールエステル２（ＰＥ−２）：ＮＰＧのヘキサン酸エステル
ポリオールエステル３（ＰＥ−３）：ＮＰＧの２−エチルヘキサン酸エステル
鉱油１（ＭＯ−１）：パラフィン系潤滑油基油（４０℃動粘度：７．８mm2/s）
鉱油２（ＭＯ−２）：パラフィン系潤滑油基油（４０℃動粘度：５．２mm2/s）
鉱油３（ＭＯ−３）：ナフテン系潤滑油基油（４０℃動粘度：５．０mm2/s）
Mineral oil 2 (MO-2): Paraffin-based lubricating base oil (kinematic viscosity at 40 ° C .: 5.2 mm 2 / s)
Mineral oil 3 (MO-3): naphthenic lubricant base oil (kinematic viscosity at 40 ° C .: 5.0 mm 2 / s)
添加剤：
酸捕捉剤：２−エチルヘキシルグリシジルエーテル
極圧剤：トリクレジルホスフェート
油性剤：グリセリンモノオレート
Additive:
Acid scavenger: 2-ethylhexyl glycidyl ether extreme pressure agent: tricresyl phosphate oil agent: glycerin monooleate
上記の基油及び添加剤を用い、表２、表３及び表４の上部に示す割合（質量％）で調合して、実施例及び比較例の冷凍機油を得た。表２は実施例１〜８の冷凍機油を示し、表３は実施例９〜１３の冷凍機油を示し、表４は比較例１〜９の冷凍機油を示す。 Refrigerating machine oils of Examples and Comparative Examples were obtained using the above base oils and additives and blended at the ratio (mass%) shown in the upper part of Tables 2, 3 and 4. Table 2 shows the refrigeration oils of Examples 1 to 8, Table 3 shows the refrigeration oils of Examples 9 to 13, and Table 4 shows the refrigeration oils of Comparative Examples 1 to 9.
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及び表３の下部に示す。
なお、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。
動粘度（４０℃）：
ＪＩＳ Ｋ ２２８３に準拠し、アトランティック粘度計の改良型を用いて測定した。
引火点：
ＪＩＳ Ｋ ２２６５に準拠し、クリーブランド開放式（ＣＯＣ）の試験方法で測定した。
酸価：
ＪＩＳ Ｋ ２５０１に準拠し、指示薬滴定法にて全酸価を測定した。
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 at the bottom of Tables 2 and 3.
The physical property measurement and performance evaluation tests were performed as follows.
Kinematic viscosity (40 ° C) :
Based on JIS K 2283, it measured using the improved type of an atlantic viscometer.
Flash point:
Based on JIS K 2265, it was measured by the Cleveland open type (COC) test method.
Acid value:
Based on JIS K 2501, the total acid value was measured by the indicator titration method.
相溶性：
ＪＩＳ Ｋ ２２１１の附属書３に準拠し、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）、プロパン（Ｒ２９０）及び１，１，１，２−テトラフルオロエタン（Ｒ−１３４ａ）を用い、また、供試油／冷媒比（重量）は２／８の条件で測定した。
Compatibility:
In accordance with Annex 3 of JIS K 2211, the two-layer separation temperature was measured. As the refrigerant, isobutane (R600a), propane (R290) and 1,1,1,2-tetrafluoroethane (R-134a) are used, and the sample oil / refrigerant ratio (weight) is 2/8. It measured on condition of this.
安定性：
いわゆるオートクレーブテストを実施して劣化後の冷凍機油の色相、酸価をテストした。すなわち、内容量１００ｍｌのステンレス鋼製耐圧容器（オートクレーブ）に供試油３０ｇと冷媒１０ｇ、及び触媒としてＦｅ、Ｃｕ、Ａｌの針金を入れ、密封し、１７５℃の恒温槽に１４日間放置した。劣化後のサンプルを取り出しで色、酸価を確認した。冷媒に関してはＲ６００ａとＲ−１３４ａを用い、それぞれについて評価した。なお、酸価は上記と同じ方法で測定した。
潤滑性：
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。
Stability:
A so-called autoclave test was performed to test the hue and acid value of the refrigeration oil after deterioration. That is, 30 g of test oil, 10 g of refrigerant, and a wire of Fe, Cu, and Al as a catalyst were placed in a stainless steel pressure vessel (autoclave) having an internal volume of 100 ml, sealed, and left in a constant temperature bath at 175 ° C. for 14 days. The sample after deterioration was taken out and the color and acid value were confirmed. Regarding the refrigerant, R600a and R-134a were used and evaluated for each. The acid value was measured by the same method as described above.
Lubricity:
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.
モノエステルのＲ１とＲ２の合計が１３から１７であるＭＥ−２〜６を基油として用いた実施例１〜８およびＭＥ−４を基油の一つとし、ＰＥ−３をもう一つの基油とした実施例９〜１３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、安定性にも優れている。潤滑性も良好である。
ＭＥ−１を基油として比較例１は、Ｒ１とＲ２の合計が１１と少ないため、粘度と引火点が下がりすぎ、実用とすることは困難である。冷媒との安定性にもおとり、試験後の酸価が上昇している。
ＭＥ−７とＭＥ−８を基油として比較例２及び３は、冷媒との適合性、特に相溶性に劣るため、実用的に用いることは困難である。
ＰＥ−１およびＰＥ−２を基油とした比較例４、５は安定性に劣っている。また、ＰＥ−３を基油とした比較例６では動粘度が目的の範囲内とすることが困難である。
ＭＯ−１を基油とした比較例７も比較例６と同様、動粘度が目的の範囲内にならない。ＭＯ−２および３を基油とした比較例８、９では引火点が低く、安全性に劣っている。
Examples 1 to 8 and ME-4 using ME-2 to 6 as the base oil in which the total of R 1 and R 2 of the monoester is 13 to 17 are used as the base oil, and PE-3 is the other. Examples 9 to 13, which are two base oils, are low viscosity oils, have high flash points, and are excellent in compatibility and stability with refrigerants. Good lubricity.
In Comparative Example 1 using ME-1 as the base oil, since the total of R 1 and R 2 is as small as 11, the viscosity and flash point are too low, and it is difficult to put it into practical use. The acid value after the test is rising due to the stability with the refrigerant.
Since Comparative Examples 2 and 3 using ME-7 and ME-8 as base oils are inferior in compatibility with the refrigerant, particularly in compatibility, it is difficult to use them practically.
Comparative Examples 4 and 5 using PE-1 and PE-2 as base oils are inferior in stability. In Comparative Example 6 using PE-3 as the base oil, it is difficult to make the kinematic viscosity within the target range.
Similarly to Comparative Example 6, Comparative Example 7 using MO-1 as a base oil does not have a kinematic viscosity within the target range. In Comparative Examples 8 and 9 using MO-2 and 3 as base oils, the flash point is low and the safety is poor.
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| CN201410045869.8A CN103789070B (en) | 2008-03-26 | 2009-03-25 | refrigerating machine oil for refrigerant |
| CN200910132449.2A CN101544925B (en) | 2008-03-26 | 2009-03-25 | Refrigerator oil for refrigerant |
| KR1020090025441A KR101580319B1 (en) | 2008-03-26 | 2009-03-25 | Refrigerating Machine Oil For Refrigerant |
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| CN101544925B (en) | 2014-08-13 |
| CN101544925A (en) | 2009-09-30 |
| JP5231060B2 (en) | 2013-07-10 |
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