JPWO2014112417A1 - 冷凍機油および冷凍機用作動流体組成物 - Google Patents
冷凍機油および冷凍機用作動流体組成物 Download PDFInfo
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- JPWO2014112417A1 JPWO2014112417A1 JP2014557431A JP2014557431A JPWO2014112417A1 JP WO2014112417 A1 JPWO2014112417 A1 JP WO2014112417A1 JP 2014557431 A JP2014557431 A JP 2014557431A JP 2014557431 A JP2014557431 A JP 2014557431A JP WO2014112417 A1 JPWO2014112417 A1 JP WO2014112417A1
- Authority
- JP
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- Prior art keywords
- refrigerating machine
- machine oil
- oil
- refrigerant
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Classifications
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25B1/00—Compression machines, plants or systems with non-reversible cycle
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- C10N2020/106—Containing Carbon dioxide
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/70—Soluble oils
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
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Abstract
Description
[1]基油と、スルフィド化合物と、没食子酸エステルと、を含有し、冷凍機油全量を基準として、前記スルフィド化合物の含有量が0.01〜2.0質量%であり、前記没食子酸エステルの含有量が10〜500質量ppmであり、40℃における動粘度が3〜500mm2/sである冷凍機油。
[2]前記基油が、炭素/酸素モル比が2.5以上5.8以下のエステル及び炭素/酸素モル比が2.5以上5.8以下のエーテルから選ばれる少なくとも1種であり、前記冷凍機油の40℃における動粘度が3〜300mm2/sである、[1]に記載の冷凍機油。
[3]前記基油が、炭素数4以上9以下の脂肪酸と炭素数4以上12以下の多価アルコールとから合成されるポリオールエステル、ポリアルキレングリコール、ポリアルキレングリコールの両末端の水酸基をエーテル化した化合物及びポリビニルエーテルから選ばれる少なくとも1種である、[1]又は[2]に記載の冷凍機油。
[4]冷凍機油全量を基準として正リン酸エステル0.05〜3質量%を更に含有する、[1]〜[3]のいずれか一項に記載の冷凍機油。
[5]前記スルフィド化合物がチオビスフェノール化合物であり、前記没食子酸エステルが炭素数1〜18のアルキル基を有する、[1]〜[4]のいずれか一項に記載の冷凍機油。
[6]冷凍機油全量を基準としてペンタエリスリトールテトラ(2−エチルヘキサノアート)を更に2〜20質量%含有する、[1]〜[5]のいずれか一項に記載の冷凍機油。
[7]地球温暖化係数が700以下である冷媒と、[1]〜[6]のいずれか一項に記載の冷凍機油からなる作動流体組成物。
[8]前記冷媒が、ハイドロフルオロカーボン、ハイドロフルオロオレフィン、二酸化炭素及び炭素数2〜4の炭化水素から選ばれる少なくとも1種を含有する冷媒である、[7]に記載の作動流体組成物。
[9]前記冷媒が、ジフルオロメタン及び2,3,3,3−テトラフルオロプロペンから選ばれる少なくとも1種を含有する冷媒である、[8]に記載の作動流体組成物。
現在は1,1,1,2−テトラフルオロエタン(R134a)が冷蔵庫及びカーエアコン用として、ジフルオロメタン(R32)とペンタフルオロエタン(R125)の質量比1/1の混合冷媒であるR410Aがルームエアコン用として広く使用されている。これらの冷媒用の冷凍機油の基油としては、適度な相互溶解性(相溶性)のあるエステル、ポリエーテル、特にはポリオールエステル、ポリアルキレングリコール、ポリビニルエーテルが適している。
実施例1〜12および比較例1〜10においては、次に示す基油、添加剤を用いて、表1〜3に示す組成を有する冷凍機油を調製した。なお、表1〜3に示した基油及び添加剤の含有割合は、いずれも冷凍機油全量を基準とする含有割合である。
(A−1)ポリオールエステル(POE−1):ペンタエリスリトールと、2−メチルプロパン酸と3,5,5−トリメチルヘキサン酸が質量比で35:65の混合酸とのエステル(動粘度68.1mm2/s@40℃、粘度指数84、流動点−40℃、引火点240℃)
(A−2)ポリオールエステル(POE−2):ペンタエリスリトールと、2−エチルヘキサン酸と3,5,5−トリメチルヘキサン酸が質量比で50:50の混合酸とのエステル(動粘度66.7mm2/s@40℃、粘度指数92、流動点−40℃、引火点248℃)
(A−3)ポリアルキレングリコール(PAG):両末端がメチル基で封鎖されたポリオキシプロピレン(平均分子量1000、動粘度46.0mm2/s@40℃、粘度指数190、流動点−45℃、引火点218℃)
(A−4)ポリビニルエーテル(PVE):エチルビニルエーテルとイソブチルビニルエーテルの共重合体(エチルビニルエーテル:イソブチルビニルエーテルが重量比で7:1)、(平均分子量910、動粘度66.4mm2/s@40℃、粘度指数85、流動点−35℃、引火点210℃)
(A−5)鉱油(MO):パラフィン系精製鉱油(動粘度22.3mm2/s@40℃、粘度指数95、流動点―15℃、引火点200℃)
なお、動粘度及び粘度指数はJIS K2283、流動点はJIS K2269、引火点は JIS K2265に準拠し測定した。
(S−1)ジベンジルスルフィド
(S−2)ジドデシルスルフィド
(S−3)4,4’−チオビス(3−メチル−6−ターシャリーブチルフェノール)
(G−1)没食子酸プロピル(n−プロピルガレート)
(G−2)没食子酸オクチル(n−オクチルガレート)
(P−1)トリクレジルフォスフェート(TCP)
(D−1)ペンタエリスリトールテトラ(2−エチルヘキサノアート)(ペンタエルスリトールと2−エチルヘキサン酸のエステル、酸価0.01mgKOH/g、水酸基価1.2mgKOH/g)
潤滑性試験は、ASTM D3233−73に準拠し、ファレックス(ピン/Vブロック)試験機を用いて、一定荷重での摩耗試験を行った。
ファレクス摩耗試験は、冷媒吹き込み制御雰囲気下(70ml/min)、初期温度50℃、回転数290rpm、荷重50Lbfでならし運転を5分間行い、その後に、同じ回転数で本試験を荷重100Lbfで1時間行い、試験後のピンとVブロックの摩耗量の合計値(mg)を測定した。
なお、吹き込み冷媒としてはR32、HFO−1234yf、R600a(イソブタン)を使用した。
安定性試験は、JIS K2211−09(オートクレーブテスト)に準拠し、含有水分量を100ppmに調整した試料油90gをオートクレーブに秤取し、触媒(鉄、銅、アルミの線、いずれも外径1.6mm×長さ50mm)と各々の冷媒(R32、HFO−1234yf、R600a)10gを封入した後、175℃に加熱し、100時間後の試料油の外観と酸価(JIS C2101)を測定した。
なお、安定性試験前の試料油(新油)の酸価は、すべて0.01mgKOH/gであった。
それに対し、比較例1、2は摩耗量がかなり多く、また、比較例3〜10では、比較例1、2に比べれば摩耗量は低減されるものの、添加剤配合量が実施例より多い場合でも、その耐摩耗の効果は実施例にははるかに及ばないことがわかる。例えば、実施例1、2と比較例3、4を比べると、スルフィド化合物と少量の没食子酸エステルの配合で耐摩耗性が大幅に向上していることがわかる。また、比較例5の没食子酸エステルのみの添加ではそれほどの耐磨耗効果はない。比較例6では耐摩耗性が若干向上しているものの安定性が低下しており、腐食摩耗が加味されている可能性がある。
Claims (9)
- 基油と、スルフィド化合物と、没食子酸エステルと、を含有し、
冷凍機油全量を基準として、前記スルフィド化合物の含有量が0.01〜2.0質量%であり、前記没食子酸エステルの含有量が10〜500質量ppmであり、
40℃における動粘度が3〜500mm2/sである冷凍機油。 - 前記基油が、炭素/酸素モル比が2.5以上5.8以下のエステル及び炭素/酸素モル比が2.5以上5.8以下のエーテルから選ばれる少なくとも1種であり、前記冷凍機油の40℃における動粘度が3〜300mm2/sである、請求項1に記載の冷凍機油。
- 前記基油が、炭素数4以上9以下の脂肪酸と炭素数4以上12以下の多価アルコールとから合成されるポリオールエステル、ポリアルキレングリコール、ポリアルキレングリコールの両末端の水酸基をエーテル化した化合物及びポリビニルエーテルから選ばれる少なくとも1種である、請求項1又は2に記載の冷凍機油。
- 冷凍機油全量を基準として正リン酸エステル0.05〜3質量%を更に含有する、請求項1〜3のいずれか一項に記載の冷凍機油。
- 前記スルフィド化合物がチオビスフェノール化合物であり、前記没食子酸エステルが炭素数1〜18のアルキル基を有する、請求項1〜4のいずれか一項に記載の冷凍機油。
- 冷凍機油全量を基準としてペンタエリスリトールテトラ(2−エチルヘキサノアート)2〜20質量%を更に含有する、請求項1〜5のいずれか一項に記載の冷凍機油。
- 地球温暖化係数が700以下である冷媒と、請求項1〜6のいずれか一項に記載の冷凍機油からなる冷凍機用作動流体組成物。
- 前記冷媒が、ハイドロフルオロカーボン、ハイドロフルオロオレフィン、二酸化炭素及び炭素数2〜4の炭化水素から選ばれる少なくとも1種を含有する冷媒である、請求項7に記載の冷凍機用作動流体組成物。
- 前記冷媒が、ジフルオロメタン及び2,3,3,3−テトラフルオロプロペンから選ばれる少なくとも1種を含有する冷媒である、請求項7又は8に記載の冷凍機用作動流体組成物。
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WO2014132676A1 (ja) * | 2013-02-26 | 2014-09-04 | Jx日鉱日石エネルギー株式会社 | 冷凍機油及び冷凍機用作動流体組成物 |
JP6586722B2 (ja) * | 2014-08-29 | 2019-10-09 | 出光興産株式会社 | 冷凍機油、冷凍機油組成物、及び冷凍機 |
KR102605776B1 (ko) * | 2014-10-09 | 2023-11-30 | 에네오스 가부시키가이샤 | 냉동기유 및 냉동기용 작동 유체 조성물 |
WO2016158615A1 (ja) * | 2015-03-30 | 2016-10-06 | 出光興産株式会社 | 冷凍機潤滑油及び冷凍機用混合組成物 |
GB201521507D0 (en) * | 2015-12-07 | 2016-01-20 | Mexichem Fluor Sa De Cv | Composition |
WO2019108720A1 (en) * | 2017-11-30 | 2019-06-06 | The Lubrizol Corporation | Aromatic ester lubricant for use with low global warming potential refrigerants |
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FR3077822B1 (fr) | 2018-02-15 | 2020-07-24 | Arkema France | Compositions de transfert de chaleur en remplacement du r-134a |
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WO2023073826A1 (ja) * | 2021-10-27 | 2023-05-04 | 友光商事株式会社 | 冷媒圧縮式冷凍サイクル装置用作動媒体および該作動媒体を用いた冷凍サイクル装置 |
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JP2011117003A (ja) * | 2011-03-17 | 2011-06-16 | Jx Nippon Oil & Energy Corp | 冷凍機油組成物 |
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TWI599652B (zh) | 2017-09-21 |
WO2014112417A1 (ja) | 2014-07-24 |
KR20150084011A (ko) | 2015-07-21 |
EP2947136B1 (en) | 2020-11-04 |
KR20170010084A (ko) | 2017-01-25 |
US9365760B2 (en) | 2016-06-14 |
BR112015016722A2 (pt) | 2017-07-11 |
EP2947136A1 (en) | 2015-11-25 |
KR101987631B1 (ko) | 2019-06-12 |
CN104919029A (zh) | 2015-09-16 |
TW201430121A (zh) | 2014-08-01 |
US20150307762A1 (en) | 2015-10-29 |
SG11201503792VA (en) | 2015-08-28 |
EP2947136A4 (en) | 2016-02-24 |
JP6063486B2 (ja) | 2017-01-18 |
CN104919029B (zh) | 2018-04-06 |
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