JP6791423B1 - 冷凍サイクル装置、冷凍機油および冷媒漏洩防止剤 - Google Patents
冷凍サイクル装置、冷凍機油および冷媒漏洩防止剤 Download PDFInfo
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- JP6791423B1 JP6791423B1 JP2020078080A JP2020078080A JP6791423B1 JP 6791423 B1 JP6791423 B1 JP 6791423B1 JP 2020078080 A JP2020078080 A JP 2020078080A JP 2020078080 A JP2020078080 A JP 2020078080A JP 6791423 B1 JP6791423 B1 JP 6791423B1
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- Prior art keywords
- acid
- refrigerant
- refrigerating machine
- machine oil
- ester
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- 239000003507 refrigerant Substances 0.000 title claims abstract description 214
- 239000010721 machine oil Substances 0.000 title claims abstract description 172
- 239000003112 inhibitor Substances 0.000 title claims description 22
- 239000002245 particle Substances 0.000 claims abstract description 101
- 239000000203 mixture Substances 0.000 claims abstract description 72
- 239000012530 fluid Substances 0.000 claims abstract description 38
- -1 polytetrafluoroethylene Polymers 0.000 claims description 164
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 44
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 44
- 238000005057 refrigeration Methods 0.000 claims description 23
- 229920005989 resin Polymers 0.000 abstract description 95
- 239000011347 resin Substances 0.000 abstract description 95
- 239000003795 chemical substances by application Substances 0.000 abstract description 22
- 238000010586 diagram Methods 0.000 abstract 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 148
- 229930195729 fatty acid Natural products 0.000 description 148
- 239000000194 fatty acid Substances 0.000 description 148
- 150000004665 fatty acids Chemical class 0.000 description 100
- 125000004432 carbon atom Chemical group C* 0.000 description 85
- 239000002253 acid Substances 0.000 description 83
- 150000005846 sugar alcohols Polymers 0.000 description 61
- 150000002148 esters Chemical class 0.000 description 60
- 229910019142 PO4 Inorganic materials 0.000 description 58
- 235000021317 phosphate Nutrition 0.000 description 58
- 239000010452 phosphate Substances 0.000 description 52
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 47
- 150000001875 compounds Chemical class 0.000 description 46
- 239000003921 oil Substances 0.000 description 46
- 235000019198 oils Nutrition 0.000 description 46
- 229920005862 polyol Polymers 0.000 description 36
- 239000000843 powder Substances 0.000 description 34
- 150000002430 hydrocarbons Chemical class 0.000 description 31
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- 229920001289 polyvinyl ether Polymers 0.000 description 29
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 28
- 125000000217 alkyl group Chemical group 0.000 description 28
- 238000009826 distribution Methods 0.000 description 28
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 24
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 21
- 229940117969 neopentyl glycol Drugs 0.000 description 21
- 239000004593 Epoxy Substances 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 19
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- 150000003077 polyols Chemical class 0.000 description 16
- 239000011148 porous material Substances 0.000 description 16
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 16
- 239000010696 ester oil Substances 0.000 description 15
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 14
- 230000002378 acidificating effect Effects 0.000 description 14
- 229930195733 hydrocarbon Natural products 0.000 description 14
- 239000004215 Carbon black (E152) Substances 0.000 description 13
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 13
- 239000000654 additive Substances 0.000 description 13
- 150000001412 amines Chemical class 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- OVBFMEVBMNZIBR-UHFFFAOYSA-N 2-methylvaleric acid Chemical compound CCCC(C)C(O)=O OVBFMEVBMNZIBR-UHFFFAOYSA-N 0.000 description 12
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 10
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 10
- 150000001298 alcohols Chemical class 0.000 description 10
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 10
- FGKJLKRYENPLQH-UHFFFAOYSA-N isocaproic acid Chemical compound CC(C)CCC(O)=O FGKJLKRYENPLQH-UHFFFAOYSA-N 0.000 description 10
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000000700 radioactive tracer Substances 0.000 description 10
- NZQMQVJXSRMTCJ-UHFFFAOYSA-N 3-Methyl-hexanoic acid Chemical compound CCCC(C)CC(O)=O NZQMQVJXSRMTCJ-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000002199 base oil Substances 0.000 description 9
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 9
- 239000011810 insulating material Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 150000008301 phosphite esters Chemical class 0.000 description 9
- 235000007586 terpenes Nutrition 0.000 description 9
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 8
- YSEQNZOXHCKLOG-UHFFFAOYSA-N 2-methyl-octanoic acid Chemical compound CCCCCCC(C)C(O)=O YSEQNZOXHCKLOG-UHFFFAOYSA-N 0.000 description 8
- CVKMFSAVYPAZTQ-UHFFFAOYSA-N 2-methylhexanoic acid Chemical compound CCCCC(C)C(O)=O CVKMFSAVYPAZTQ-UHFFFAOYSA-N 0.000 description 8
- ATUUSOSLBXVJKL-UHFFFAOYSA-N 3-ethylpentanoic acid Chemical compound CCC(CC)CC(O)=O ATUUSOSLBXVJKL-UHFFFAOYSA-N 0.000 description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 125000002252 acyl group Chemical group 0.000 description 8
- 125000002947 alkylene group Chemical group 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000470 constituent Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- SZSSMFVYZRQGIM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-propylpropane-1,3-diol Chemical compound CCCC(CO)(CO)CO SZSSMFVYZRQGIM-UHFFFAOYSA-N 0.000 description 7
- WLAMNBDJUVNPJU-BYPYZUCNSA-N 2-Methylbutanoic acid Natural products CC[C@H](C)C(O)=O WLAMNBDJUVNPJU-BYPYZUCNSA-N 0.000 description 7
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 7
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 description 7
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 7
- DIVCBWJKVSFZKJ-UHFFFAOYSA-N 4-methyl-hexanoic acid Chemical compound CCC(C)CCC(O)=O DIVCBWJKVSFZKJ-UHFFFAOYSA-N 0.000 description 7
- MHPUGCYGQWGLJL-UHFFFAOYSA-N 5-methyl-hexanoic acid Chemical compound CC(C)CCCC(O)=O MHPUGCYGQWGLJL-UHFFFAOYSA-N 0.000 description 7
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 7
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- NIJJYAXOARWZEE-UHFFFAOYSA-N Valproic acid Chemical compound CCCC(C(O)=O)CCC NIJJYAXOARWZEE-UHFFFAOYSA-N 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
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- 239000007850 fluorescent dye Substances 0.000 description 7
- YUCFVHQCAFKDQG-UHFFFAOYSA-N fluoromethane Chemical compound F[CH] YUCFVHQCAFKDQG-UHFFFAOYSA-N 0.000 description 7
- 230000006870 function Effects 0.000 description 7
- 235000011187 glycerol Nutrition 0.000 description 7
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- 238000002156 mixing Methods 0.000 description 7
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/06—Particles of special shape or size
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B41/00—Fluid-circulation arrangements
- F25B41/40—Fluid line arrangements
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
- C10M107/38—Lubricating compositions characterised by the base-material being a macromolecular compound containing halogen
-
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Abstract
Description
[1] 2.0μm〜10.0μmのD50および4.0〜14.0のD90/D10を有する樹脂粒子を含む冷凍機油と、
冷媒を含む冷媒組成物と、
を含む冷凍機用作動流体を含む、冷凍サイクル装置。
[2] 樹脂粒子は3.0μm〜8.0μmの標準偏差を有する、上記[1]に記載の冷凍サイクル装置。
[3] 樹脂粒子は含フッ素樹脂粒子である、上記[1]または[2]に記載の冷凍サイクル装置。
[4] 含フッ素樹脂粒子はポリテトラフルオロエチレン粒子である、上記[3]に記載の冷凍サイクル装置。
[5] 2.0μm〜10.0μmのD50および4.0〜14.0のD90/D10を有する樹脂粒子を含む冷凍機油。
[6] 樹脂粒子は3.0μm〜8.0μmの標準偏差を有する、上記[5]に記載の冷凍機油。
[7] 樹脂粒子は含フッ素樹脂粒子である、上記[5]または[6]に記載の冷凍機油。
[8] 含フッ素樹脂粒子はポリテトラフルオロエチレン粒子である、上記[7]に記載の冷凍機油。
[9] 上記[5]〜[8]のいずれかに記載の冷凍機油を含む冷媒漏洩防止剤。
本開示の冷凍サイクル装置は、後述の(4)の欄に記載の冷媒組成物と、冷凍機油とを含む。
冷凍機油は、冷媒組成物と共存させて冷凍サイクル等の冷凍サイクルを行わせることで、冷凍サイクル装置内の潤滑性を高めることが可能であり、効率的なサイクル性能を発揮させることも可能となる。
含酸素系合成油であるエステル系冷凍機油やエーテル系冷凍機油は、主として、炭素原子と酸素原子を有して構成されている。エステル系冷凍機油やエーテル系冷凍機油においては、この炭素原子と酸素原子の比率(炭素/酸素モル比)が小さすぎると吸湿性が高くなり、当該比率が大きすぎると冷媒との相溶性が低下してしまうことから、当該比率はモル比で2以上7.5以下であることが好ましい。
エステル系冷凍機油としては、化学的安定性の観点から、二塩基酸と1価アルコールとの二塩基酸エステル油、ポリオールと脂肪酸とのポリオールエステル油、またはポリオールと多価塩基酸と1価アルコール(又は脂肪酸)とのコンプレックスエステル油、ポリオール炭酸エステル油等が基油成分として挙げられる。
二塩基酸エステル油としては、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、フタル酸、イソフタル酸、テレフタル酸等の二塩基酸、特に、炭素数5〜10の二塩基酸(グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等)と、直鎖または分枝アルキル基を有する炭素数1〜15の一価アルコール(メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、ノナノール、デカノール、ウンデカノール、ドデカノール、トリデカノール、テトラデカノール、ペンタデカノール等)とのエステルが好ましい。この二塩基酸エステル油としては、具体的には、グルタル酸ジトリデシル、アジピン酸ジ(2−エチルヘキシル)、アジピン酸ジイソデシル、アジピン酸ジトリデシル、セバシン酸ジ(3−エチルヘキシル)等が挙げられる。
ポリオールエステル油とは、多価アルコールと脂肪酸(カルボン酸)とから合成されるエステルであり、炭素/酸素モル比が2以上7.5以下、好ましくは3.2以上5.8以下のものである。
(i)ブタン酸、2−メチルプロパン酸、ペンタン酸、2−メチルブタン酸、3−メチルブタン酸、2,2−ジメチルプロパン酸、2−メチルペンタン酸、3−メチルペンタン酸、4−メチルペンタン酸、2,2−ジメチルブタン酸、2,3−ジメチルブタン酸、3,3−ジメチルブタン酸およびヘキサン酸から選ばれる1〜13種と、2−メチルヘキサン酸、3−メチルヘキサン酸、4−メチルヘキサン酸、5−メチルヘキサン酸、2,2−ジメチルペンタン酸、2,3−ジメチルペンタン酸、2,4−ジメチルペンタン酸、3,3−ジメチルペンタン酸、3,4−ジメチルペンタン酸、4,4−ジメチルペンタン酸、2−エチルペンタン酸、3−エチルペンタン酸および2−エチル−3−メチルブタン酸から選ばれる1〜13種との組合せ;
(ii)ブタン酸、2−メチルプロパン酸、ペンタン酸、2−メチルブタン酸、3−メチルブタン酸、2,2−ジメチルプロパン酸、2−メチルペンタン酸、3−メチルペンタン酸、4−メチルペンタン酸、2,2−ジメチルブタン酸、2,3−ジメチルブタン酸、3,3−ジメチルブタン酸およびヘキサン酸から選ばれる1〜13種と、2−メチルヘプタン酸、3−メチルヘプタン酸、4−メチルヘプタン酸、5−メチルヘプタン酸、6−メチルヘプタン酸、2,2−ジメチルヘキサン酸、3,3−ジメチルヘキサン酸、4,4−ジメチルヘキサン酸、5,5−ジメチルヘキサン酸、2,3−ジメチルヘキサン酸、2,4−ジメチルヘキサン酸、2,5−ジメチルヘキサン酸、3,4−ジメチルヘキサン酸、3,5−ジメチルヘキサン酸、4,5−ジメチルヘキサン酸、2,2,3−トリメチルペンタン酸、2,3,3−トリメチルペンタン酸、2,4,4−トリメチルペンタン酸、3,4,4−トリメチルペンタン酸、2−エチルヘキサン酸、3−エチルヘキサン酸、2−プロピルペンタン酸、2−メチル−2−エチルペンタン酸、2−メチル−3−エチルペンタン酸および3−メチル−3−エチルペンタン酸から選ばれる1〜25種との組合せ;
(iii)ブタン酸、2−メチルプロパン酸、ペンタン酸、2−メチルブタン酸、3−メチルブタン酸、2,2−ジメチルプロパン酸、2−メチルペンタン酸、3−メチルペンタン酸、4−メチルペンタン酸、2,2−ジメチルブタン酸、2,3−ジメチルブタン酸、3,3−ジメチルブタン酸およびヘキサン酸から選ばれる1〜13種と、2−メチルオクタン酸、3−メチルオクタン酸、4−メチルオクタン酸、5−メチルオクタン酸、6−メチルオクタン酸、7−メチルオクタン酸、8−メチルオクタン酸、2,2−ジメチルヘプタン酸、3,3−ジメチルヘプタン酸、4,4−ジメチルヘプタン酸、5,5−ジメチルヘプタン酸、6,6−ジメチルヘプタン酸、2,3−ジメチルヘプタン酸、2,4−ジメチルヘプタン酸、2,5−ジメチルヘプタン酸、2,6−ジメチルヘプタン酸、3,4−ジメチルヘプタン酸、3,5−ジメチルヘプタン酸、3,6−ジメチルヘプタン酸、4,5−ジメチルヘプタン酸、4,6−ジメチルヘプタン酸、2−エチルヘプタン酸、3−エチルヘプタン酸、4−エチルヘプタン酸、5−エチルヘプタン酸、2−プロピルヘキサン酸、3−プロピルヘキサン酸、2−ブチルペンタン酸、2,2,3−トリメチルヘキサン酸、2,2,3−トリメチルヘキサン酸、2,2,4−トリメチルヘキサン酸、2,2,5−トリメチルヘキサン酸、2,3,4−トリメチルヘキサン酸、2,3,5−トリメチルヘキサン酸、3,3,4−トリメチルヘキサン酸、3,3,5−トリメチルヘキサン酸、3,5,5−トリメチルヘキサン酸、4,4,5−トリメチルヘキサン酸、4,5,5−トリメチルヘキサン酸、2,2,3,3−テトラメチルペンタン酸、2,2,3,4−テトラメチルペンタン酸、2,2,4,4−テトラメチルペンタン酸、2,3,4,4−テトラメチルペンタン酸、3,3,4,4−テトラメチルペンタン酸、2,2−ジエチルペンタン酸、2,3−ジエチルペンタン酸、3,3−ジエチルペンタン酸、2−エチル−2,3,3−トリメチル酪酸、3−エチル−2,2,3−トリメチル酪酸および2,2−ジイソプロピルプロピオン酸から選ばれる1〜50種との組合せ。
(i)2−メチルプロパン酸と、2−メチルヘキサン酸、3−メチルヘキサン酸、4−メチルヘキサン酸、5−メチルヘキサン酸、2,2−ジメチルペンタン酸、2,3−ジメチルペンタン酸、2,4−ジメチルペンタン酸、3,3−ジメチルペンタン酸、3,4−ジメチルペンタン酸、4,4−ジメチルペンタン酸、2−エチルペンタン酸、3−エチルペンタン酸および2−エチル−3−メチルブタン酸から選ばれる1〜13種との組合せ;
(ii)2−メチルプロパン酸と、2−メチルヘプタン酸、3−メチルヘプタン酸、4−メチルヘプタン酸、5−メチルヘプタン酸、6−メチルヘプタン酸、2,2−ジメチルヘキサン酸、3,3−ジメチルヘキサン酸、4,4−ジメチルヘキサン酸、5,5−ジメチルヘキサン酸、2,3−ジメチルヘキサン酸、2,4−ジメチルヘキサン酸、2,5−ジメチルヘキサン酸、3,4−ジメチルヘキサン酸、3,5−ジメチルヘキサン酸、4,5−ジメチルヘキサン酸、2,2,3−トリメチルペンタン酸、2,3,3−トリメチルペンタン酸、2,4,4−トリメチルペンタン酸、3,4,4−トリメチルペンタン酸、2−エチルヘキサン酸、3−エチルヘキサン酸、2−プロピルペンタン酸、2−メチル−2−エチルペンタン酸、2−メチル−3−エチルペンタン酸および3−メチル−3−エチルペンタン酸から選ばれる1〜25種との組合せ;
(iii)2−メチルプロパン酸と、2−メチルオクタン酸、3−メチルオクタン酸、4−メチルオクタン酸、5−メチルオクタン酸、6−メチルオクタン酸、7−メチルオクタン酸、8−メチルオクタン酸、2,2−ジメチルヘプタン酸、3,3−ジメチルヘプタン酸、4,4−ジメチルヘプタン酸、5,5−ジメチルヘプタン酸、6,6−ジメチルヘプタン酸、2,3−ジメチルヘプタン酸、2,4−ジメチルヘプタン酸、2,5−ジメチルヘプタン酸、2,6−ジメチルヘプタン酸、3,4−ジメチルヘプタン酸、3,5−ジメチルヘプタン酸、3,6−ジメチルヘプタン酸、4,5−ジメチルヘプタン酸、4,6−ジメチルヘプタン酸、2−エチルヘプタン酸、3−エチルヘプタン酸、4−エチルヘプタン酸、5−エチルヘプタン酸、2−プロピルヘキサン酸、3−プロピルヘキサン酸、2−ブチルペンタン酸、2,2,3−トリメチルヘキサン酸、2,2,3−トリメチルヘキサン酸、2,2,4−トリメチルヘキサン酸、2,2,5−トリメチルヘキサン酸、2,3,4−トリメチルヘキサン酸、2,3,5−トリメチルヘキサン酸、3,3,4−トリメチルヘキサン酸、3,3,5−トリメチルヘキサン酸、3,5,5−トリメチルヘキサン酸、4,4,5−トリメチルヘキサン酸、4,5,5−トリメチルヘキサン酸、2,2,3,3−テトラメチルペンタン酸、2,2,3,4−テトラメチルペンタン酸、2,2,4,4−テトラメチルペンタン酸、2,3,4,4−テトラメチルペンタン酸、3,3,4,4−テトラメチルペンタン酸、2,2−ジエチルペンタン酸、2,3−ジエチルペンタン酸、3,3−ジエチルペンタン酸、2−エチル−2,3,3−トリメチル酪酸、3−エチル−2,2,3−トリメチル酪酸および2,2−ジイソプロピルプロピオン酸から選ばれる1〜50種との組合せ。
コンプレックスエステル油とは、脂肪酸および二塩基酸と、一価アルコールおよびポリオールとのエステルである。脂肪酸、二塩基酸、一価アルコール、ポリオールとしては、上述と同様のものを用いることができる。
ポリオール炭酸エステル油とは、炭酸とポリオールとのエステルである。
エーテル系冷凍機油としては、ポリビニルエーテル油、ポリオキシアルキレン油等が挙げられる。
ポリビニルエーテル油としては、ビニルエーテルモノマーの重合体、ビニルエーテルモノマーとオレフィン性二重結合を有する炭化水素モノマーとの共重合体、オレフィン性二重結合とポリオキシアルキレン鎖を有するモノマーとビニルエーテルモノマーとの共重合体等が挙げられる。
ビニルエーテル系モノマーとしては、下記一般式(3)の化合物が挙げられる。
ポリオキシアルキレン油としては、炭素数2〜4のアルキレンオキシド(エチレンオキシド、プロピレンオキシド等)を、水や水酸基含有化合物を開始剤として重合させる方法等により得られたポリオキシアルキレン化合物が挙げられる。また、ポリオキシアルキレン化合物の水酸基をエーテル化またはエステル化したものであってもよい。ポリオキシアルキレン油中のオキシアルキレン単位は、1分子中において同一であってもよく、2種以上のオキシアルキレン単位が含まれていてもよい。1分子中に少なくともオキシプロピレン単位が含まれることが好ましい。
(式中、hは6〜80の数を表す。)
(式中、iおよびjはそれぞれ1以上であり且つiとjとの合計が6〜80となる数を表す。)
(式中、hは6〜80の数を示す。)
(式中、hは6〜80の数を表す。)
(式中、iおよびjはそれぞれ1以上であり且つiとjとの合計が6〜80となる数を表す。)
(式中、iおよびjはそれぞれ1以上であり且つiとjとの合計が6〜80となる数を表す。)
(式中、hは6〜80の数を表す。)
炭化水素系冷凍機油としては、例えば、アルキルベンゼンを用いることができる。
本開示において、冷凍機油は、特定の粒度分布を有する樹脂粒子を含む。樹脂粒子とは、樹脂で形成された粒状物の集合体である。尚、便宜上、本開示では、「樹脂粒子」は、冷凍機油中に分散している状態にあることを意味し、また、後述の「樹脂粉末」は、樹脂で形成された粒状物の集合体であるが、乾燥した状態にあることを意味する。「特定の粒度分布」を有するとは、樹脂粒子の粒子径が比較的ブロードで幅が広い粒度分布を有することを意味する。
冷凍機油には、1種または2種以上の添加剤が含まれていてもよい。
リン酸エステル類としては、リン酸エステル、亜リン酸エステル、酸性リン酸エステル、及び酸性亜リン酸エステル等を用いることができ、リン酸エステル、亜リン酸エステル、酸性リン酸エステル、及び酸性亜リン酸エステルのアミン塩を含むものを用いることもできる。
図1に、冷凍サイクル装置である空気調和装置1が有する冷媒回路10の一例を示す。
室内ユニット3は、室内の天井面や壁面に設置されており、液側冷媒連絡配管9およびガス側冷媒連絡配管8を介して室外ユニット2に接続されており、冷媒回路10の一部を構成している。なお、室内ユニット3は、冷媒回路10において互いに並列に複数接続されていてもよい。
室外ユニット2は、室外に設置されており、液側冷媒連絡配管9およびガス側冷媒連絡配管8を介して室内ユニット3に接続されている。
空気調和装置1では、冷房運転時には、四路切換弁10が冷房運転接続状態となっており、圧縮機4から吐出された高温高圧冷媒は、冷媒の凝縮器として機能する室外熱交換器5において凝縮し、膨張弁6を通過する際に減圧され、液側冷媒連絡配管9を介して室内ユニット3のガス側に供給される。室内ユニット3に供給された冷媒は、冷媒の蒸発器として機能する室内熱交換器7において蒸発し、ガス側冷媒連絡配管8を介して、室外ユニット2のアキュームレータ11を介して圧縮機4に吸入される。
(4−1)用語の定義
本明細書において用語「冷媒」には、ISO817(国際標準化機構)で定められた、冷媒の種類を表すRで始まる冷媒番号(ASHRAE番号)が付された化合物が少なくとも含まれ、さらに冷媒番号が未だ付されていないとしても、それらと同等の冷媒としての特性を有するものが含まれる。冷媒は、化合物の構造の面で、「フルオロカーボン系化合物」と「非フルオロカーボン系化合物」とに大別される。「フルオロカーボン系化合物」には、クロロフルオロカーボン(CFC)、ハイドロクロロフルオロカーボン(HCFC)及びハイドロフルオロカーボン(HFC)が含まれる。「非フルオロカーボン系化合物」としては、プロパン(R290)、プロピレン(R1270)、ブタン(R600)、イソブタン(R600a)、二酸化炭素(R744)及びアンモニア(R717)等が挙げられる。なお、「冷媒」には、複数種類の冷媒が混合された混合物も含まれる。
本開示の冷媒は、冷凍機における作動流体として好ましく使用することができる。
本開示の冷媒組成物は、本開示の冷媒を少なくとも含み、本開示の冷媒と同じ用途のために使用することができる。また、本開示の冷媒組成物は、さらに少なくとも冷凍機油と混合することにより冷凍機用作動流体を得るために用いることができる。
本開示の冷媒組成物は微量の水を含んでもよい。冷媒組成物における含水割合は、冷媒全体に対して、0.1質量%以下とすることが好ましい。
トレーサーは、本開示の冷媒組成物が希釈、汚染、その他何らかの変更があった場合、その変更を追跡できるように検出可能な濃度で本開示の冷媒組成物に添加される。
HCC-40(クロロメタン、CH3Cl)
HFC-23(トリフルオロメタン、CHF3)
HFC-41(フルオロメタン、CH3Cl)
HFC-125(ペンタフルオロエタン、CF3CHF2)
HFC-134a(1,1,1,2−テトラフルオロエタン、CF3CH2F)
HFC-134(1,1,2,2−テトラフルオロエタン、CHF2CHF2)
HFC-143a(1,1,1−トリフルオロエタン、CF3CH3)
HFC-143(1,1,2−トリフルオロエタン、CHF2CH2F)
HFC-152a(1,1−ジフルオロエタン、CHF2CH3)
HFC-152(1,2−ジフルオロエタン、CH2FCH2F)
HFC-161(フルオロエタン、CH3CH2F)
HFC-245fa(1,1,1,3,3−ペンタフルオロプロパン、CF3CH2CHF2)
HFC-236fa(1,1,1,3,3,3−ヘキサフルオロプロパン、CF3CH2CF3)
HFC-236ea(1,1,1,2,3,3−ヘキサフルオロプロパン、CF3CHFCHF2)
HFC-227ea(1,1,1,2,3,3,3−ヘプタフルオロプロパン、CF3CHFCF3)
HCFC-22(クロロジフルオロメタン、CHClF2)
HCFC-31(クロロフルオロメタン、CH2ClF)
CFC-1113(クロロトリフルオロエチレン、CF2=CClF)
HFE-125(トリフルオロメチル−ジフルオロメチルエーテル、CF3OCHF2)
HFE-134a(トリフルオロメチル−フルオロメチルエーテル、CF3OCH2F)
HFE-143a(トリフルオロメチル−メチルエーテル、CF3OCH3)
HFE-227ea(トリフルオロメチル−テトラフルオロエチルエーテル、CF3OCHFCF3)
HFE-236fa(トリフルオロメチル−トリフルオロエチルエーテル、CF3OCH2CF3)
本開示の冷媒組成物は、紫外線蛍光染料として、一種を単独で含有してもよいし、二種以上を含有してもよい。
本開示の冷媒組成物は、安定剤として、一種を単独で含有してもよいし、二種以上を含有してもよい。
本開示の冷媒組成物は、重合禁止剤として、一種を単独で含有してもよいし、二種以上を含有してもよい。
本開示の冷凍機油含有作動流体は、本開示の冷媒又は冷媒組成物と、冷凍機油とを少なくとも含み、冷凍機における作動流体として用いられる。具体的には、本開示の冷凍機油含有作動流体は、冷凍機の圧縮機において使用される冷凍機油と、冷媒又は冷媒組成物とが互いに混じり合うことにより得られる。冷凍機油含有作動流体には冷凍機油は一般に10〜50質量%含まれる。
国際公開第2009/020187号に開示の実施例7に記載の方法により低分子量PTFEの水性分散液を得た。得られた低分子量PTFE水性分散液3000gに硝酸20gを加え、激しい攪拌を与えることで凝析させ、その後、中和するため、24質量%の水酸化ナトリウム水溶液20gを加え、湿潤状態のPTFE樹脂の粉末を得た。
国際公開第2018/026012号に開示の実施例2に記載の方法により低分子量PTFE樹脂粉末を得た。
日本電子株式会社製レーザー回折式粒度分布測定装置(HELOS&RODOS)を用いて、カスケードは使用せず、分散圧力3.0barで測定を行い、得た樹脂粉末の粒度分布(D10、D50およびD90)を測定した。D50を平均粒子径とした。
液体クロマトグラフ質量分析計(Waters, LC−MS ACQUITY UPLC/TQD)を用い、パーフルオロオクタン酸及びその塩の含有量の測定を行った。測定粉末1gにアセトニトリル5mlを加え、60分間の超音波処理を行い、パーフルオロオクタン酸を抽出した。得られた液相について、MRM(Multiple Reaction Monitoring)法を用いて測定した。移動相としてアセトニトリル(A)と酢酸アンモニウム水溶液(20mmol/L)(B)を、濃度勾配(A/B=40/60−2min−80/20−1min)で送液した。分離カラム(ACQUITY UPLC BEH C18 1.7μm)を使用し、カラム温度は40℃、注入量は5μLとした。イオン化法はESI(Electrospray ionization)Negativeを使用し、コーン電圧は25Vに設定し、プリカーサーイオン分子量/プロダクトイオン分子量は413/369を測定した。パーフルオロオクタン酸及びその塩の含有量は外部標準法を用い、算出した。この測定における検出限界は5ppbである。
樹脂粒子を含む冷凍機油(市販の冷凍機油(エーテル系冷凍機油)100質量部に対して樹脂粒子0.5質量部を含む)を超音波振動機にて30分間処理して均一な分散液を得、遠心沈降式粒度分布測体装置(CAPA-700、Horiba)にて粒度分布(D10、D50およびD90ならびに標準偏差)を測定した。
冷凍サイクル装置として空調装置(冷媒R−410A:充填量0.75kg、市販の冷凍機油(エーテル系冷凍機油)充填量0.3L)を冷房運転した。外気温および室内温度は共に40℃であり、冷媒圧力は3.2MPa以上となるようにした。運転時間は150時間とした。
(冷媒漏洩率)=[(運転後漏洩速度)/(運転前漏洩速度)]×100(%)
市販の冷凍機油(エーテル系冷凍機油)100質量部に下記表3に示す実施例1のPTFE樹脂粉末(平均粒子径4.2μm)を1.0質量部加え、ホモジナイザーを用いて混合して本開示の冷凍機油を得た。得られた冷凍機油50mlを特開2013−139934号に準拠して、室外ユニットの圧縮機に吸入させて本開示の冷凍サイクル装置とした。この冷凍サイクル装置は、本開示の冷凍機油と冷媒組成物とを含む。その後、空調装置を運転した。
実施例1のPTFE樹脂粉末の代わりに、下記表3に示す実施例2のPTFE樹脂粉末(平均粒子径5.8μm)を用いたこと以外は実施例1と同様に吸入させて空調装置を運転した。
実施例1のPTFE樹脂粉末の代わりに、下記表3に示す実施例3のPTFE樹脂粉末(平均粒子径5.8μm)を用いたこと以外は実施例1と同様に吸入させて空調装置を運転した。
実施例1のPTFE樹脂粉末の代わりに、下記表3に示す実施例4のPTFE樹脂粉末(平均粒子径8.6μm)を用いたこと以外は実施例1と同様に吸入させて空調装置を運転した。
実施例1のPTFE樹脂粉末の代わりに、下記表3に示す実施例5のPTFE樹脂粉末(平均粒子径6.2μm)を用いたこと以外は実施例1と同様に吸入させて空調装置を運転した。
実施例1のPTFE樹脂粉末の代わりに、下記表3に示す実施例6のPTFE樹脂粉末(平均粒子径7.1μm)を用いたこと以外は実施例1と同様に吸入させて空調装置を運転した。
実施例1のPTFE樹脂粉末の代わりに、下記表3に示す実施例7のPTFE樹脂粉末(平均粒子径4.3μm)を用いたこと以外は実施例1と同様に吸入させて空調装置を運転した。
実施例1のPTFE樹脂粉末の代わりに、下記表3に示す比較例1のPTFE樹脂粉末(ダイキン工業製L−2、平均粒子径1.3μm)を用いたこと以外は実施例1と同様に吸入させて空調装置を運転した。
実施例1のPTFE樹脂粉末の代わりに、下記表3に示す比較例2のPTFE樹脂粉末(喜多村製 8N、平均粒子径4.3μm)を用いたこと以外は実施例1と同様に吸入させて空調装置を運転した。
実施例1のPTFE樹脂粉末の代わりに、下記表3に示す比較例3のPTFE樹脂粉末(ヘロフロン製 5GR、平均粒子径6.0μm)を用いたこと以外は実施例1と同様に吸入させて空調装置を運転した。
2 室外ユニット
3 室内ユニット
4 圧縮機
5 室外熱交換器
6 膨張弁
7 室外熱交換器
8 ガス側冷媒連絡配管
9 液側冷媒連絡配管
10 冷媒回路または四路切換弁
11 アキュームレータ
12 室外ファン
13 室内ファン
14 液側閉鎖弁
15 ガス側閉鎖弁
Claims (6)
- 2.0μm〜10.0μmのD50および4.0〜14.0のD90/D10を有する含フッ素樹脂粒子を含む冷凍機油と、
冷媒を含む冷媒組成物と、
を含む冷凍機用作動流体を含む、冷凍サイクル装置。 - 含フッ素樹脂粒子は3.0μm〜8.0μmの標準偏差を有する請求項1に記載の冷凍サイクル装置。
- 含フッ素樹脂粒子はポリテトラフルオロエチレン粒子である請求項1または2に記載の冷凍サイクル装置。
- 2.0μm〜10.0μmのD 50 および4.0〜14.0のD 90 /D 10 を有する含フッ素樹脂粒子を含む冷凍機油を含む冷媒漏洩防止剤。
- 含フッ素樹脂粒子は3.0μm〜8.0μmの標準偏差を有する請求項4に記載の冷媒漏洩防止剤。
- 含フッ素樹脂粒子はポリテトラフルオロエチレン粒子である請求項4または5に記載の冷媒漏洩防止剤。
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