JP2010265428A - Working fluid for car air conditioner - Google Patents
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- JP2010265428A JP2010265428A JP2009120022A JP2009120022A JP2010265428A JP 2010265428 A JP2010265428 A JP 2010265428A JP 2009120022 A JP2009120022 A JP 2009120022A JP 2009120022 A JP2009120022 A JP 2009120022A JP 2010265428 A JP2010265428 A JP 2010265428A
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- working fluid
- car air
- refrigerant
- air conditioner
- tetrafluoropropene
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- 239000012530 fluid Substances 0.000 title claims abstract description 16
- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002199 base oil Substances 0.000 claims abstract description 21
- 239000003507 refrigerant Substances 0.000 claims abstract description 21
- 125000002252 acyl group Chemical group 0.000 claims abstract description 10
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000007348 radical reaction Methods 0.000 claims description 12
- 239000002683 reaction inhibitor Substances 0.000 claims description 12
- 239000002516 radical scavenger Substances 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000010721 machine oil Substances 0.000 claims description 3
- 239000003921 oil Substances 0.000 abstract description 11
- 238000000354 decomposition reaction Methods 0.000 abstract description 9
- 238000001816 cooling Methods 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 24
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 10
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- -1 R-134a Chemical compound 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005057 refrigeration Methods 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000005456 glyceride group Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical compound O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- INEMUVRCEAELBK-UHFFFAOYSA-N 1,1,1,2-tetrafluoropropane Chemical compound CC(F)C(F)(F)F INEMUVRCEAELBK-UHFFFAOYSA-N 0.000 description 1
- CDOOAUSHHFGWSA-UHFFFAOYSA-N 1,3,3,3-tetrafluoropropene Chemical compound FC=CC(F)(F)F CDOOAUSHHFGWSA-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
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000010696 ester oil Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FGIIKMNKAUZBBK-UHFFFAOYSA-N methanediimine;phosphoric acid Chemical compound N=C=N.OP(O)(O)=O FGIIKMNKAUZBBK-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CGPPXVAUDMUIPK-UHFFFAOYSA-N phosphoric acid trihydroxy(sulfanylidene)-lambda5-phosphane Chemical compound OP(O)(O)=O.OP(O)(O)=S CGPPXVAUDMUIPK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000010726 refrigerant oil Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
Description
本発明は、テトラフルオロプロペンを冷媒とするカーエアコン用作動流体に関する。 The present invention relates to a working fluid for a car air conditioner using tetrafluoropropene as a refrigerant.
カーエアコンには冷媒を冷凍機油に溶解させた作動流体が使用されているが、従来から、環境面を配慮してＲ−１３４ａ等のように塩素を含有せず、水素、炭素及びフッ素からなるハイドロフルオロカーボン（ＨＦＣ）冷媒が使用されており、それに伴い、ＨＦＣ冷媒と相溶性があるポリオールエステル油等のエステル系冷凍機油や、ＰＡＧ等のグリコール系冷凍機油が広く用いられている（例えば、特許文献１参照）。 For car air conditioners, a working fluid in which a refrigerant is dissolved in refrigeration oil has been used. Conventionally, considering environmental aspects, it does not contain chlorine like R-134a, etc., and consists of hydrogen, carbon and fluorine. Hydrofluorocarbon (HFC) refrigerants are used, and accordingly, ester-based refrigeration oils such as polyol ester oils compatible with HFC refrigerants and glycol-based refrigeration oils such as PAGs are widely used (for example, patents). Reference 1).
しかし、環境保全への要求はより厳しくなってきており、特に欧州では２０１１年以降に生産される自動車のカーエアコンには、新冷媒としてテトラフルオロプロペン（２，３，３，３−テトラフルオロ−１−プロペン；ＨＦＯ−１２３４ｙｆ）を使用することが決定している（２ｎｄ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｗｏｒｋｓｈｏｐ ｏｎ Ｍｏｂｉｌｅ Ａｉｒ Ｃｏｎｄｉｔｉｏｎｉｎｇ ａｎｄ Ａｕｘｉｌｉａｒｙ Ｓｙｓｔｅｍｓ−Ｔｒｏｎｏ，Ｉｔａｌｙ Ｎｏｖ．２９，２００７及びＥｕｒｏｐｅａｎ Ａｕｔｏｍｏｔｉｖｅ Ａ／Ｃ Ｃｏｎｖｅｎｔｉｏｎ， Ｓｅｐ．２２−２３， ２００８）。 However, the demand for environmental protection has become more severe. In particular, in car air conditioners for automobiles produced after 2011, tetrafluoropropene (2,3,3,3-tetrafluoro- 1-propene; HFO-1234yf) has been decided to be used (2nd International Worksshop on Mobile Air Conditioning and Auxiliary Systems-Trono, Italy Novo 29, 2007, Europian 23, Europ. , 2008).
しかし、テトラフルオロプロペンは、従来の冷凍機油に溶解し難く、比較的低温度で二層分離を起こすという問題がある。また、テトラフルオロプロペンは、大気中で分解することにより成層圏への到達を抑えるため、従来のＨＦＣ冷媒に比べて化学的安定性が低くなっている。そのため、分解により発生した重合物による装置配管の閉塞や、分解により発生した酸性化合物による装置の腐食を引き起こす可能性が高く、更には冷凍機油と冷媒劣化物とが反応して冷凍機油の粘度が低下するおそれもある。二層分離により冷却性能が低下して高温になると、このようなテトラフルオロプロペンの分解が顕著になる。 However, tetrafluoropropene is difficult to dissolve in conventional refrigerating machine oil and has a problem of causing two-layer separation at a relatively low temperature. Tetrafluoropropene has a lower chemical stability than conventional HFC refrigerants, because it decomposes in the atmosphere to suppress reaching the stratosphere. For this reason, there is a high possibility that the piping of the equipment will be blocked by the polymer generated by the decomposition, or the equipment will be corroded by the acidic compound generated by the decomposition. There is also a risk of decline. When the cooling performance decreases due to the two-layer separation and the temperature becomes high, such decomposition of tetrafluoropropene becomes remarkable.
そこで本発明は、今後主流となるテトラフルオロプロペンを冷媒とする新たなカーエアコン用作動流体における、テトラフルオロプロペンとの相溶性、テトラフルオロプロペンの分解に係る問題を解消して冷却性能及び安定性を改善することを目的とする。 Therefore, the present invention eliminates problems related to compatibility with tetrafluoropropene and decomposition of tetrafluoropropene in a new automotive air conditioner working fluid that uses tetrafluoropropene as a refrigerant, which will become the mainstream in the future, and provides cooling performance and stability. The purpose is to improve.
上記目的を達成するために本発明は、下記のカーエアコン用作動流体を提供する。
（１）テトラフルオロプロペンを冷媒とし、前記冷媒をポリスチレン換算のGPCによる平均分子量が８００〜１２００で、両末端にアシル基を有するポリプロピレングリコールを基油とする冷凍機油に溶解してなることを特徴とするカーエアコン用作動流体。
（２）フェノール系ラジカル反応抑制剤、分子中にエステル基を持たないエポキシ系酸補足剤及びリン系極圧剤を含有することを特徴とする上記（１）記載のカーエアコン用作動流体。
（３）リン系極圧剤の一部または全部に代えて、グリセリンと、分子中に１または２個の不飽和結合を有する脂肪酸とからなるモノエステルを含有することを特徴とする上記（２）記載のカーエアコン用作動流体。
（４）サイトグラスを備えるカーエアコン用であることを特徴とする上記（１）〜（３）の何れか１項に記載のカーエアコン用作動流体。
In order to achieve the above object, the present invention provides the following working fluid for a car air conditioner.
(1) Tetrafluoropropene is used as a refrigerant, and the refrigerant is dissolved in a refrigerating machine oil having an average molecular weight of 800 to 1200 based on polystyrene-equivalent GPC and having a polypropylene glycol having an acyl group at both ends as a base oil. Working fluid for car air conditioner.
(2) The working fluid for a car air conditioner according to (1) above, comprising a phenolic radical reaction inhibitor, an epoxy acid scavenger having no ester group in the molecule, and a phosphorus extreme pressure agent.
(3) The above-mentioned (2), which contains a monoester composed of glycerin and a fatty acid having 1 or 2 unsaturated bonds in the molecule instead of part or all of the phosphorus-based extreme pressure agent ) Working fluid for car air conditioners.
(4) The working fluid for a car air conditioner according to any one of the above (1) to (3), which is for a car air conditioner including a sight glass.
本発明において冷凍機油の基油に用いる、特定の分子量で、かつ両末端にアシル基を有するプロピレングリコールは、流動性及びテトラフルオロプロペンとの相溶性に優れるため、今後主流となるテトラフルオロプロペンを冷媒とするカーエアコンの運転を長期にわたり安定に維持できる。 In the present invention, propylene glycol having a specific molecular weight and an acyl group at both ends used for the base oil of refrigerator oil is excellent in fluidity and compatibility with tetrafluoropropene. The operation of the car air conditioner as a refrigerant can be stably maintained over a long period of time.
以下、本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明のカーエアコン用作動流体では、冷媒としてテトラフルオロプロペンを使用する。テトラフルオロプロペンには異性体が存在し、２，３，３，３−テトラフルオロ−１−プロペン及び１，３，３，３−テトラフルオロ−１−プロペンがあり、本発明では両方が対象となる。 In the working fluid for a car air conditioner of the present invention, tetrafluoropropene is used as a refrigerant. There are isomers in tetrafluoropropene, including 2,3,3,3-tetrafluoro-1-propene and 1,3,3,3-tetrafluoro-1-propene. Become.
冷凍機油の基油には、上記のテトラフルオロプロペンとの相溶性を高めるために、両末端にアシル基を有するプロピレングリコール（以下「両末端アシル基変性プロピレングリコール」）を用いる。この両末端アシル基変性プロピレングリコールにより、二層分離温度が高まり、通常の使用温度で冷媒／冷凍機油混合液が均一に溶解して白濁しないため、カーエアコンの冷媒充填量を確認するサイトグラスで適正な充填量判断が可能となる。アシル基以外の官能基で変性しても、テトラフルオロプロペンとの相溶性が低く、二層分離温度も低くなる。 In order to improve the compatibility with the above tetrafluoropropene, propylene glycol having an acyl group at both ends (hereinafter referred to as “both end acyl group-modified propylene glycol”) is used for the base oil of the refrigerator oil. This two-terminal acyl group-modified propylene glycol increases the two-layer separation temperature, and the refrigerant / refrigerant oil mixture is uniformly dissolved at normal operating temperatures and does not become cloudy. Appropriate filling amount can be determined. Even if it is modified with a functional group other than an acyl group, the compatibility with tetrafluoropropene is low and the two-layer separation temperature is also low.
また、基油として実用上必要な粘性は、１００℃での動粘度で９ｍｍ２／ｓ以上とされており、このような粘性を満足するために両末端アシル基変性プロピレングリコールの分子量をポリスチレン換算のGPC測定で８００〜１２００、好ましくは９５０〜１１００とする。 In addition, the viscosity necessary for practical use as a base oil is 9 mm 2 / s or more in terms of kinematic viscosity at 100 ° C. In order to satisfy such viscosity, the molecular weight of both end acyl group-modified propylene glycol is converted to polystyrene. The GPC measurement is 800 to 1200, preferably 950 to 1100.
上記基油には、種々の添加剤を添加することができるが、テトラフルオロプロペンの分解を抑制するためにフェノール系ラジカル反応抑制剤を添加することが好ましい。フェノール系ラジカル反応抑制剤は、テトラフルオロプロペンの不飽和結合に起因する分解・劣化を効果的に抑制することができる。ラジカル反応抑制剤として、フェノール系以外にもチオリン酸系のものも広く使用されているが、硫黄化合物が析出して好ましくない。フェノール系ラジカル反応抑制剤としては、公知のもので構わないが、２，６‐ジターシャリーブチル‐４‐メチルフェノール、４，４’−ビス（２，６‐ジターシャリーブチルフェノールなどが好適である。 Although various additives can be added to the base oil, it is preferable to add a phenol-based radical reaction inhibitor in order to suppress the decomposition of tetrafluoropropene. The phenol-based radical reaction inhibitor can effectively suppress decomposition / deterioration due to the unsaturated bond of tetrafluoropropene. As a radical reaction inhibitor, thiophosphoric acid-based inhibitors are widely used in addition to phenol-based compounds, but sulfur compounds are not preferable. As the phenol radical reaction inhibitor, known ones may be used, but 2,6-ditertiarybutyl-4-methylphenol, 4,4'-bis (2,6-ditertiarybutylphenol) and the like are suitable.
また、エポキシ系酸捕捉剤を添加することにより、テトラフルオロプロペンが分解した場合、発生した酸成分を捕捉して冷凍システム内の腐食等を抑えることができる。酸捕捉効果が高いことから、グリリジルエーテルのような分子中にエステル基を持たないエポキシ系酸捕捉剤が好ましく、特にテトラフルオロプロパン及び基油との親和性からポリプロピレングリコールの両末端をグリシジル化したエポキシ系酸捕捉剤を用いることが好ましい。また、炭素数１０以下のアルコールをグリシジル化したエポキシ系酸捕捉剤は、テトラフルオロプロペン中での分散性が高いことから酸捕捉能力が向上して好ましい。 Moreover, by adding an epoxy-based acid scavenger, when tetrafluoropropene is decomposed, the generated acid component can be captured and corrosion in the refrigeration system can be suppressed. Epoxy acid scavengers that do not have an ester group in the molecule, such as glycidyl ether, are preferred because of their high acid scavenging effect. Especially, both ends of polypropylene glycol are glycidylated due to their affinity with tetrafluoropropane and base oil. It is preferable to use an epoxy acid scavenger prepared. An epoxy acid scavenger obtained by glycidylation of an alcohol having 10 or less carbon atoms is preferable because of its high dispersibility in tetrafluoropropene and thus improved acid scavenging ability.
また、リン酸系極圧剤を添加することにより、摺動部分の金属面に極圧剤が作用して摩耗や焼付きを防止することができ、更には潤滑性が高まり摩擦熱が少なくなることからテトラフルオロプロペンの分解を抑えることもできる。また、リン酸系極圧剤は金属の腐食を起こし難いことから、冷凍システム内の腐食等を抑制する効果もある。極圧剤として、リン酸系以外にもチオリン酸系のものが広く使用されているが、硫黄化合物が析出して好ましくない。リン酸系極圧剤としては、公知のもので構わないが、トリクレジルホスフェート、トリオクチルホスフェートなどが好適である。 In addition, by adding a phosphoric acid extreme pressure agent, the extreme pressure agent acts on the metal surface of the sliding portion to prevent wear and seizure, and further, lubricity increases and frictional heat decreases. Therefore, decomposition of tetrafluoropropene can also be suppressed. In addition, since the phosphoric acid extreme pressure agent hardly causes metal corrosion, it has an effect of suppressing corrosion in the refrigeration system. As extreme pressure agents, those other than phosphoric acid are widely used. However, sulfur compounds are not preferable because they are precipitated. The phosphoric acid extreme pressure agent may be a known one, but tricresyl phosphate, trioctyl phosphate, and the like are suitable.
上記のフェノール系ラジカル反応抑制剤、エポキシ系酸捕捉剤及びリン酸系極圧剤は、３者を併用することにより、それぞれ単独で使用する場合に比べて効果が高まる。また、それぞれの添加量は、効果が現れる限り制限はないが、基油に対してフェノール系ラジカル反応抑制剤は０．５〜２質量％、エポキシ系酸捕捉剤は０．５〜４質量％、リン酸系極圧剤は０．５〜２質量％とすることが好ましい。添加量がこれより少ないと、それぞれの効果が十分に発現できず、これより多くても効果が飽和するだけでなく、相対的に基油量が減って潤滑性が劣るようになる。 The above-mentioned phenol-based radical reaction inhibitor, epoxy-based acid scavenger and phosphoric acid-based extreme pressure agent are more effective when used in combination with the three than when used alone. The amount of each additive is not limited as long as the effect appears, but the phenol-based radical reaction inhibitor is 0.5 to 2% by mass and the epoxy acid scavenger is 0.5 to 4% by mass with respect to the base oil. The phosphoric acid extreme pressure agent is preferably 0.5 to 2% by mass. If the addition amount is less than this, the respective effects cannot be sufficiently exhibited, and if the addition amount is more than this, not only the effect is saturated, but also the base oil amount is relatively reduced and the lubricity becomes inferior.
尚、リン酸系極圧剤は、分解した場合に酸を発生することから、その一部もしくは全部を、グリセリンと、分子中に１または２個の不飽和結合を有する脂肪酸とからなるモノエステルで代替してリン酸系極圧剤の含有量を０．５質量％以下にすることが好ましい。このモノエステルは油性向上剤として機能し、摩擦熱の発生を抑えてテトラフルオロプロペンの熱分解を抑える。また、酸を発生し難いため、酸によるテトラフルオロプロペンの分解も抑えることができる。 In addition, since a phosphoric acid extreme pressure agent generates an acid when it is decomposed, a part or all of it is a monoester composed of glycerin and a fatty acid having one or two unsaturated bonds in the molecule. It is preferable that the content of the phosphoric acid extreme pressure agent be 0.5% by mass or less. This monoester functions as an oiliness improver and suppresses the generation of frictional heat and suppresses thermal decomposition of tetrafluoropropene. Moreover, since it is hard to generate | occur | produce an acid, decomposition | disassembly of the tetrafluoro propene by an acid can also be suppressed.
その他にも、上記以外の性能を向上させる目的で通常用いられる添加剤を添加してもよい。 In addition, additives that are usually used for the purpose of improving the performance other than the above may be added.
以下に試験例を挙げて本発明を更に説明するが、本発明はこれにより何ら制限されるものではない。尚、試験例３、４は添加剤の効果を確認するものであり、何れも実施例である。 Hereinafter, the present invention will be further described with reference to test examples, but the present invention is not limited thereto. In addition, Test Examples 3 and 4 confirm the effect of the additive, and all are examples.
（試験例１：高温冷媒溶解性）
冷媒として２，３，３，３−テトラフルオロ−１−プロペンを用い、表１に示す基油とともに規定のガラス管に封入し、湯浴によりゆっくり加熱した。そして、均一な層から油層と冷媒層とに分かれる温度を測定した。尚、基油量は５質量％または１５質量％とした。結果を表１に併記する。
(Test Example 1: High-temperature refrigerant solubility)
2,3,3,3-tetrafluoro-1-propene was used as a refrigerant, sealed in a specified glass tube together with the base oil shown in Table 1, and slowly heated in a hot water bath. And the temperature which separates into an oil layer and a refrigerant | coolant layer from a uniform layer was measured. The base oil amount was 5% by mass or 15% by mass. The results are also shown in Table 1.
表１に示すように、実施例１、２の基油は、分子量が８００〜１２００の範囲の両末端アシル基変性プロピレングリコールであるが、２，３，３，３−テトラフルオロ−１−プロペンとの相溶性が高く、二層分離温度も高くなっている。これに対し、アシル基以外で変性したプロピレングリコールでは、２，３，３，３−テトラフルオロ−１−プロペンとの相溶性が低く、二層分離温度も低くなっている。また、比較例１１の基油は、両末端アシル基変性プロピレングリコールであるが、分子量が１２００を超えており、二層分離温度が低くカーエアコン用としては実用的ではない。 As shown in Table 1, the base oils of Examples 1 and 2 are both terminal acyl group-modified propylene glycol having a molecular weight in the range of 800 to 1200, but 2,3,3,3-tetrafluoro-1-propene. And the two-layer separation temperature is also high. On the other hand, propylene glycol modified with other than acyl groups has low compatibility with 2,3,3,3-tetrafluoro-1-propene, and the two-layer separation temperature is also low. Moreover, although the base oil of the comparative example 11 is a both-ends acyl group modification | denaturation propylene glycol, molecular weight exceeds 1200, two-layer separation temperature is low, and it is not practical as an object for car air conditioners.
（試験例２：動粘度）
試験例１で用いた実施例１、２、比較例１、３、９、１１、１２の各基油の動粘度及び粘度指数を測定した。結果を表２に示すが、実施例１、２の基油は動粘度及び粘度指数ともに実用的である。これに対し、比較例１２の基油は、両末端アシル基変性プロピレングリコールであるが、分子量が８００未満であり、流動性に劣り実用的ではない。
(Test Example 2: Kinematic viscosity)
The kinematic viscosity and viscosity index of each base oil of Examples 1 and 2 and Comparative Examples 1, 3, 9, 11, and 12 used in Test Example 1 were measured. The results are shown in Table 2, and the base oils of Examples 1 and 2 are practical in both kinematic viscosity and viscosity index. On the other hand, the base oil of Comparative Example 12 is a propylene glycol modified with acyl groups at both ends, but has a molecular weight of less than 800 and is not practical because of poor fluidity.
（試験例３：化学安定性）
実施例１の基油に表３に示す如く添加剤を添加し、２，３，３，３−テトラフルオロ−１−プロペンと混合して試料を調製した。尚、添加量は基油に対する割合である。そして、シールドチューブ試験（ＪＩＳ Ｋ２２１１準拠）により試料の変色、全酸価及び析出物の有無を評価した。試験条件は下記の通りであり、結果を表３に併記する。
・油／冷媒 ： ２ｍL／２ｍL
・試験温度 ： １７５℃
・試験期間 ： １４日間
・油中水分量： ２０００ｐｐｍ
・管内空気量： 分圧０．１ｍｍＨｇ以下
・触媒 ： 鉄線、銅線、アルミ線を各３ｃｍ
(Test Example 3: Chemical stability)
An additive was added to the base oil of Example 1 as shown in Table 3 and mixed with 2,3,3,3-tetrafluoro-1-propene to prepare a sample. In addition, the addition amount is a ratio with respect to the base oil. And the discoloration of a sample, the total acid value, and the presence or absence of the deposit were evaluated by the shield tube test (JISK2211 conformity). The test conditions are as follows, and the results are shown in Table 3.
・ Oil / refrigerant: 2mL / 2mL
Test temperature: 175 ° C
・ Test period: 14 days ・ Water content in oil: 2000 ppm
・ Pipe air volume: Partial pressure 0.1mmHg or less ・ Catalyst: Iron wire, copper wire, aluminum wire 3cm each
フェノール系ラジカル反応抑制剤：ジアルキルメチルフェノール
チオリン酸系ラジカル反応抑制剤：ジアルキルジチオリン酸亜鉛
グリシジルエーテル系酸捕捉剤：アルキルグリシジルエーテル
イミド系酸捕捉剤：ビス（ジアルキルフェニル）カルボジイミド
リン酸系極圧剤：トリアリールホスフェート
チオリン酸系極圧剤：トリアルキルフェニルチオホスフェート
グリセリド系油性向上剤：グリセリンモノエステル
硫化油脂：硫化なたね油
Phenolic radical reaction inhibitor: Dialkylmethylphenol thiophosphate radical reaction inhibitor: Dialkyldithiophosphate zinc glycidyl ether acid scavenger: Alkyl glycidyl ether imide acid scavenger: Bis (dialkylphenyl) carbodiimide phosphate extreme pressure agent : Triaryl phosphate thiophosphate extreme pressure agent: Trialkylphenyl thiophosphate glyceride oil improver: Glycerin monoester sulfurized oil: Sulfur rapeseed oil
表３の試行例１〜１０に示すように、フェノール系ラジカル反応抑制剤、グリシジルエーテル系酸捕捉剤、リン酸系極圧剤、あるいはリン酸系極圧剤の一部もしくは全部に代えてグリセリド系油性向上剤を添加することにより、両末端アシル基変性ポリプロピレングリコールの安定性を大きく向上させることができる。また、試行例１１〜２０に示すように、これら何れかの添加剤を含まないと、安定性の向上効果は少なくなる。 As shown in Trial Examples 1 to 10 in Table 3, instead of a phenol radical reaction inhibitor, a glycidyl ether acid scavenger, a phosphoric acid extreme pressure agent, or a part or all of a phosphoric acid extreme pressure agent, glycerides By adding a system oiliness improver, the stability of both terminal acyl group-modified polypropylene glycols can be greatly improved. Moreover, as shown in Trial Examples 11 to 20, if any of these additives is not included, the stability improvement effect is reduced.
（試験例４：潤滑性）
実施例１の基油に、試験例３で用いたフェノール系ラジカル反応抑制剤を１質量％、グリシジルエーテル系酸捕捉剤を１質量％添加し、更に表４に示す如く試験例３で用いたリン酸系極圧及びグリセリド系油性向上剤を添加し、２，３，３，３−テトラフルオロ−１−プロペンと混合して試料を調製した。尚、添加量は基油に対する割合である。そして、ＦＡＬＥＸ試験（Ｐｉｎ−Ｖｅｅ Ｂｌｏｃｋ）により耐焼付性及び耐摩耗性を評価した。試験条件は下記の通りであり、結果を表４に併記する。
・耐焼付性：５０℃、慣らし２５０ｌｂｓ×５分、回転数２９０ｒｐｍ
・耐摩耗性：５０℃、３００ｌｂｓ×２時間、回転数２９０ｒｐｍ
(Test Example 4: Lubricity)
1% by mass of the phenol-based radical reaction inhibitor used in Test Example 3 and 1% by mass of the glycidyl ether-based acid scavenger were added to the base oil of Example 1, and further used in Test Example 3 as shown in Table 4. A phosphoric acid extreme pressure and a glyceride oiliness improver were added and mixed with 2,3,3,3-tetrafluoro-1-propene to prepare a sample. In addition, the addition amount is a ratio with respect to the base oil. Then, seizure resistance and wear resistance were evaluated by a FALEX test (Pin-Vee Block). The test conditions are as follows, and the results are shown in Table 4.
Seizure resistance: 50 ° C., break-in 250 lbs × 5 minutes, rotation speed 290 rpm
Abrasion resistance: 50 ° C., 300 lbs × 2 hours, rotation speed 290 rpm
表４の試行例２１〜２４に示すように、リン酸系極圧剤及びグリセリド系油性向上剤の少なくとも一方を適量添加することにより、全く添加しない試行例２５や、過剰に添加した試行例２６、２７に比べて化学安定性や冷媒溶解性を良好にしたまま耐焼付性や耐摩耗性をより向上させることができる。 As shown in Trial Examples 21 to 24 in Table 4, by adding an appropriate amount of at least one of a phosphoric acid extreme pressure agent and a glyceride oiliness improver, Trial Example 25 not added at all or Trial Example 26 added excessively. , 27, the seizure resistance and the wear resistance can be further improved while the chemical stability and the refrigerant solubility are improved.
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