JP2004043611A - Lubricating oil for refrigerant compression type refrigerating cycle apparatus and working fluid - Google Patents

Lubricating oil for refrigerant compression type refrigerating cycle apparatus and working fluid Download PDF

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JP2004043611A
JP2004043611A JP2002202016A JP2002202016A JP2004043611A JP 2004043611 A JP2004043611 A JP 2004043611A JP 2002202016 A JP2002202016 A JP 2002202016A JP 2002202016 A JP2002202016 A JP 2002202016A JP 2004043611 A JP2004043611 A JP 2004043611A
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lubricating oil
refrigerant
refrigerant compression
refrigeration cycle
oil
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JP4012441B2 (en
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Takashi Kaimai
開米　貴
Hitoshi Takahashi
高橋　仁
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Eneos Corp
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Japan Energy Corp
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Priority to CNB031475299A priority patent/CN1224686C/en
Priority to KR1020030046747A priority patent/KR100848063B1/en
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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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • 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
    • 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
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Lubricants (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a lubricating oil for a refrigerant compression type refrigerating cycle apparatus, which has proper compatibility with and solubility in a 2-4C hydrocarbon refrigerant having no halogen atom, keeps viscosity not to impair lubricating properties, reduces the amount of the refrigerant filled and has excellent lubricating properties, stability, etc., and a working fluid. <P>SOLUTION: In the lubricating oil for refrigerant compression type refrigerating cycle apparatus with which the 2-4C hydrocarbon refrigerant containing no halogen atom is used, the lubricating oil comprises an ether compound represented by general formula R<SB>1</SB>-A-OR<SB>2</SB>(R<SB>1</SB>and R<SB>2</SB>are each a 1-4C alkyl group; A is a polymerization chain consisting of m oxyethylene groups and n oxypropylene groups; m is an integer of 0-50; n is an integer of 2-50; m/n is ≤1) as a main component and has 10-100 mm<SP>2</SP>/s viscosity at 40°C. The working fluid for the refrigerant compression type refrigerating cycle apparatus comprises the 2-4C hydrocarbon refrigerant containing no halogen atom and the lubricating oil. <P>COPYRIGHT: (C)2004,JPO

Description

【０００１】
【発明の属する技術分野】
本発明は、炭素数２〜４のハロゲン原子を含まない炭化水素、例えばエタン、プロパン、ブタン、イソブタン等の冷媒を用いる冷媒圧縮式冷凍サイクル装置用潤滑油及び作動媒体に関する。
【０００２】
【従来の技術】
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）等のフロン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、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またはＲ−１３４ａ）などの新しい水素含有フロン冷媒に転換されてきている。しかし、これらのＨＦＣは、オゾン層を破壊しないものの温室効果が大きく、近年問題となっている地球温暖化の観点からは必ずしも優れた冷媒ではない。
【０００３】
そこで、ハロゲン原子を含まない炭素数２〜４程度の低級炭化水素やアンモニア、二酸化炭素等がオゾン層を破壊することなく、地球温暖化への影響も前記の塩素系あるいは非塩素系フッ化炭化水素に比べて非常に低いことから、最近、見直されている。すなわち、これらの化合物は冷媒として古くから使用されていたが、上記フロン系冷媒で培われた圧縮機、凝縮器、絞り装置、蒸発器等からなる冷却効率の高い冷凍システムに採用することが検討され、ハロゲン原子を含まない低級炭化水素冷媒用の潤滑剤として、冷媒と相溶性のある、例えばナフテン系又はパラフィン系の鉱物油、アルキルベンゼン油、エーテル油、エステル油、フッ素油が提案されている（特開平１０−１３０６８５号公報）。
【０００４】
しかしながら、ハロゲン原子を含まない炭化水素冷媒は鉱油等の潤滑剤に対する溶解度が大きいため、上記のような潤滑剤を用いると、潤滑剤の粘度が低くなり、潤滑性を確保できなくなるとともに、冷媒の充填量を多くする必要がある。一方、冷媒であるハロゲン原子を含まない炭化水素は可燃性であるため、その充填量はできる限り低くすることが要求されている。
【０００５】
【発明が解決しようとする課題】
本発明は、上記課題を解決したもので、本発明の目的は、ハロゲン原子を含まない炭素数２〜４の炭化水素冷媒に対して適度の相溶性、溶解性を有し、潤滑性を損なわない粘度を保持でき、冷媒の充填量を少なくすることができるとともに、優れた潤滑性や安定性等を有する冷媒圧縮式冷凍サイクル装置用潤滑油及び作動媒体を提供することである。
【０００６】
【課題を解決するための手段】
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、特定のエーテルを主成分とした冷凍機油が、炭化水素冷媒に対し程良い相溶性、溶解性を有するとともに、良好な潤滑性、高い熱・酸化安定性を有しており、ハロゲン原子を含まない炭素数２〜４の炭化水素冷媒とともに用いた場合、冷媒圧縮式冷凍サイクル装置用潤滑油として、非常に優れていることを見出し、本発明に想到した。
【０００７】
すなわち、本発明は、炭素数２〜４のハロゲン原子を含まない炭化水素冷媒を用いる冷媒圧縮式冷凍サイクル装置用潤滑油において、前記潤滑油が下記一般式（１）
Ｒ１−Ａ−ＯＲ２　　　　　（１）
（式中、Ｒ１、Ｒ２は炭素数１〜４のアルキル基、Ａはｍ個のオキシエチレン基とｎ個のオキシプロピレン基からなる重合鎖を示し、ｍは０〜５０の整数、ｎは２〜５０の整数で、ｍ／ｎは１以下である。）で表されるエーテル化合物を主成分とし、４０℃の粘度が１０〜１００ｍｍ２／ｓであるもので、好ましくは前記一般式（１）中のＲ１、Ｒ２がメチル基で、さらには、前記一般式（１）中のオキシエチレン基の個数ｍが０である冷媒圧縮式冷凍サイクル装置用潤滑油、及び炭素数２〜４のハロゲン原子を含まない炭化水素冷媒と前記潤滑油とからなる冷媒圧縮式冷凍サイクル装置用作動媒体で、特に好ましくは、前記炭素数２〜４のハロゲン原子を含まない炭化水素冷媒がプロパン及び／又はイソブタンからなるものである。
【０００８】
【発明の実施の態様】
本発明にいう炭素数２〜４のハロゲン原子を含まない炭化水素冷媒としては、エタン、プロパン、ブタン、イソブタン、及びこれらの２種以上の混合物が用いられるが、特には、プロパン、イソブタン及びこれらの混合物が好適である。
【０００９】
本発明における上記一般式（１）のエーテル化合物は、ポリアルキレングリコールの末端水酸基をアルキル基で置換したものである。このエーテル化合物は、炭化水素冷媒の溶解性が低いものが好ましく、このためには、Ｒ１、Ｒ２の炭素数が１〜４と小さいものがよく、特にはメチル基が好ましい。
【００１０】
また、一般式（１）中のＡの重合鎖は、オキシプロピレン基単独、オキシエチレン基及びオキシプロピレン基の両方を含むもので、オキシエチレン基の個数ｍは、０〜５０の範囲のものであれば支障はないが、潤滑油の吸湿性を小さくするためには、このｍは小さい方がよく、好ましくは５以下、特には０が好ましい。一方、オキシプロピレン基の個数ｎは、２〜５０の範囲のものであれば特に支障なく用いることができる。
【００１１】
上記一般式（１）のエーテル化合物で、重合鎖にオキシエチレン基及びオキシプロピレン基の両方を含むものは、ランダムコポリマーであってもブロックコポリマーであっても良いが、低温特性の点からランダムコポリマーの方が好ましい。
【００１２】
本発明に用いられる潤滑油は、この一般式（１）のエーテル化合物を主成分とするものであり、潤滑油中の少なくとも５０質量％、好ましくは８０質量％以上、特に好ましくは９５質量％以上、当該化合物を含有するようにしたものである。
【００１３】
また、上記潤滑油は、適正な潤滑性能を有するために潤滑に必要な油膜を保持できる粘度を有することが要求され、冷媒と混合する前の４０℃の粘度が、１０〜１００ｍｍ２／ｓの必要があり、特には、１５〜４６ｍｍ２／ｓのものが好ましい。
【００１４】
さらに、本発明の潤滑油は、安定性の面から酸価が１ｍｇＫＯＨ／ｇ以下、特には０．１ｍｇＫＯＨ／ｇ以下が好ましい。水酸基価は、上記一般式（１）の末端水酸基を完全にアルキル置換することはできないために、水酸基価を下げることはかなり困難であるが、水酸基の残存量が多いと、冷凍機油が低温において白濁し、冷凍サイクルのキャピラリー装置を閉塞させる等、好ましくない現象が起こるため、水酸基価は３０ｍｇＫＯＨ／ｇ以下、１５ｍｇＫＯＨ／ｇ以下とすることが好ましい。
【００１５】
上記一般式（１）で表されるエーテル化合物を主成分とする本発明の潤滑油は、炭化水素冷媒を用いた冷媒圧縮式冷凍サイクル装置用の潤滑油として用いると、低温から高温までの広い領域で、相互に適切な相溶性、溶解性を示してその潤滑性及び熱安定性を大幅に向上させることができる。
【００１６】
なお、本発明に係る潤滑油には、冷媒圧縮式冷凍サイクル装置用の潤滑油としての機能を満足する範囲において、エステル化合物、アルキルベンゼンや鉱油等の潤滑油を適宜混合でき、また従来、冷凍機油等に使用されている酸化防止剤、摩耗防止剤、エポキシ化合物等の添加剤を適宜添加することができる。
【００１７】
本発明の他の一つは、上記炭化水素冷媒と潤滑油とからなる作動媒体であるが、この冷媒と潤滑油との使用比は、冷凍サイクル装置の種類により異なるため一概には言えないが、通常は、質量比で１／１０〜２／１の範囲から適宜選定される。
【００１８】
本発明の潤滑油及び作動媒体は、圧縮機、凝縮器、絞り装置（膨張弁またはキャピラリーチューブ等の冷媒流量制御部）、蒸発器等を有し、これらの間で冷媒を循環させる冷却効率の高い冷媒圧縮式冷凍サイクル装置で、特には、ロータリーコンプレッサ等の高圧コンプレッサを有する冷凍サイクル装置において好適に使用できる。
【００１９】
【実施例】
以下、実施例により本発明を具体的に説明する。
【００２０】
実施例１〜３の供試油
（１）表１に示したエーテル化合物を供試油として用いた
【００２１】
【表１】

Figure 2004043611
【００２２】
（４）比較例１の供試油：パラフィン系鉱油からなる冷凍機油（フレオールＳ１０；ジャパンエナジー製）、４０℃粘度１０ｍｍ２／ｓ
（５）比較例２の供試油：パラフィン系鉱油からなる冷凍機油（フレオールＳ３２；ジャパンエナジー製）、４０℃粘度３２ｍｍ２／ｓ
（６）比較例３の供試油：ナフテン系鉱油からなる冷凍機油（スニソ３ＧＳ；日本サン石油社製）、４０℃粘度３０ｍｍ２／ｓ
（７）比較例４の供試油：ポリオキシプロピレングリコールモノアルキルエーテル（アデカカーポールＭ−３０；旭電化工業社製）、４０℃粘度３３ｍｍ２／ｓ
（８）比較例５の供試油：２−エチルヘキサノールとパルミチン酸のモノエステル（ユニスターＭＢ−８１６；日本油脂社製）、４０℃粘度８ｍｍ２／ｓ
（９）比較例６の供試油：次の２種のカーボネート混合物（酸価０．０１ｍｇＫＯＨ／ｇ）、４０℃粘度８ｍｍ２／ｓ
（ｆ）ジベンジルカーボネート；５０重量部
（ｇ）ベンジル−フェニルエチルカーボネート；５０重量部
【００２３】
溶解性試験
　供試油１５ｇをガラス製耐圧容器に入れ、イソブタン３〜１０ｇ封入し、温度を室温から８０℃の間で数点設定し、イソブタンを溶解した試供油の体積およびその時の圧力から、計算により温度／圧力／溶解度曲線を作成した。その溶解度から代表的な実用条件である６０℃、０．６ＭＰａでの各試供油のイソブタン溶解量（溶解イソブタン／（試供油＋溶解イソブタン）；重量％）を読みとり、この結果を表２に示す。
【００２４】
【表２】
Figure 2004043611
【００２５】
上記供試油について、冷凍機油としての次の各性能を、次に示す条件の下で測定、評価し、その結果を表３に示す。
【００２６】
潤滑性　ＡＳＴＭ　Ｄ−３２３３−７３に準拠し、ファレックス（Ｆａｌｅｘ）焼付荷重をイソブタンの吹き込み制御雰囲気下（７０ｍｌ／ｍｉｎ）で測定した。
【００２７】
熱安定性　ＡＮＳＩ／ＡＳＨＲＡＥ　９７−１９８３に準じ、供試油２０ｇとイソブタン５ｇと触媒（鉄、銅、アルミニウムの各線）をステンレス製ボンベ（１００ｍｌ）に封入し、１７５℃に加熱して１０日間保持した後、供試油の色相（ＡＳＴＭ表示）および酸価を測定した。
【００２８】
吸湿性　１００ｍｌビーカにサンプル油６０ｇを入れ、温度２５℃、湿度７０％の雰囲気にて開放状態で３時間静置後、水分濃度をカールフィッシャー法により測定した。
【００２９】
【表３】
Figure 2004043611
【００３０】
表２および表３から分かるように、本発明に係るエーテル化合物が、比較例１〜３の鉱油系冷凍機油、比較例５のモノエステル、比較例６のカーボネート等と比較すると冷媒の溶解度が適度に低く、冷媒充填量を少なくすることができる。また、比較例４のエーテルは冷媒との溶解性は低いものの、構造内に水酸基を有するため熱安定性が悪く、さらには、吸湿性も高く、冷凍機油として適さないことが分かる。比較例５，６のモノエステル及びカーボネートも本発明のエステルと比較すると冷媒との溶解性だけでなく、潤滑性、熱安定性で劣ることが分かる。
【００３１】
【発明の効果】
本発明の冷凍機油は、炭化水素冷媒に対し程良い相溶性、溶解性を有するとともに、低い吸湿性、良好な潤滑性、高い熱酸化安定性を有しているため、冷凍機油として総合性能に優れているという格別の効果を有する。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a lubricating oil and a working medium for a refrigerant compression refrigeration cycle device using a hydrocarbon having no halogen atom having 2 to 4 carbon atoms, such as ethane, propane, butane, and isobutane.
[0002]
[Prior art]
Conventionally, a refrigerant compression refrigeration cycle device used in refrigerators, air conditioners, refrigerators, and the like includes a fluorocarbon containing fluorine and chlorine as constituent elements, for example, R-11 (trichloromonocarbon) which is chlorofluorocarbon (CFC). Although fluorocarbons such as fluoromethane), R-12 (dichlorodifluoromethane), and hydrochlorofluorocarbon (HCFC) R-22 (monochlorodifluoromethane) have been used, in connection with the recent problem of ozone depletion, international Its production and use have been regulated, and it has now been converted to chlorine-free, new hydrogen-containing Freon refrigerants such as difluoromethane (R-32), tetrafluoroethane (R-134 or R-134a). Is coming. However, these HFCs do not destroy the ozone layer but have a large greenhouse effect, and are not necessarily excellent refrigerants from the viewpoint of global warming, which has recently become a problem.
[0003]
Therefore, the lower hydrocarbons containing no halogen atoms and having about 2 to 4 carbon atoms, such as ammonia and carbon dioxide, do not destroy the ozone layer and have an effect on global warming. It is recently reviewed because it is much lower than hydrogen. In other words, these compounds have been used as refrigerants for a long time, but their use in high-refrigeration refrigeration systems consisting of compressors, condensers, throttle devices, evaporators, etc. cultivated with the above-mentioned CFC-based refrigerants is being considered. As a lubricant for a lower hydrocarbon refrigerant containing no halogen atom, for example, a naphthenic or paraffinic mineral oil, an alkylbenzene oil, an ether oil, an ester oil, and a fluorine oil that are compatible with the refrigerant have been proposed. (Japanese Patent Application Laid-Open No. 10-130686).
[0004]
However, a hydrocarbon refrigerant containing no halogen atom has a high solubility in a lubricant such as mineral oil, and therefore, when the above-described lubricant is used, the viscosity of the lubricant becomes low, and the lubricating property cannot be secured. It is necessary to increase the filling amount. On the other hand, since hydrocarbons containing no halogen atoms, which are refrigerants, are flammable, it is required that the filling amount be as low as possible.
[0005]
[Problems to be solved by the invention]
The present invention has solved the above-mentioned problems, and an object of the present invention is to have appropriate compatibility and solubility in a hydrocarbon refrigerant having 2 to 4 carbon atoms that does not contain a halogen atom, which impairs lubricity. An object of the present invention is to provide a lubricating oil and a working medium for a refrigerant compression refrigeration cycle device, which can maintain a low viscosity, can reduce the amount of refrigerant to be charged, and have excellent lubricity and stability.
[0006]
[Means for Solving the Problems]
The present inventor has conducted intensive studies to achieve the above object, and as a result, a refrigerating machine oil containing a specific ether as a main component has moderate compatibility and solubility in hydrocarbon refrigerants. It has lubricating properties, high thermal and oxidative stability, and is extremely excellent as a lubricating oil for refrigerant compression refrigeration cycle devices when used with a hydrocarbon refrigerant having 2 to 4 carbon atoms that does not contain halogen atoms. The present inventors have found that the present invention has been made.
[0007]
That is, the present invention provides a lubricating oil for a refrigerant compression refrigeration cycle device using a hydrocarbon refrigerant containing no halogen atom having 2 to 4 carbon atoms, wherein the lubricating oil has the following general formula (1)
R 1 -A-OR 2 (1)
(Wherein, R 1 and R 2 represent an alkyl group having 1 to 4 carbon atoms, A represents a polymer chain composed of m oxyethylene groups and n oxypropylene groups, m is an integer of 0 to 50, n Is an integer of 2 to 50, and m / n is 1 or less.) And has a viscosity at 40 ° C. of 10 to 100 mm 2 / s, preferably the general formula R 1 and R 2 in (1) are methyl groups, and further, a lubricating oil for a refrigerant compression refrigeration cycle device in which the number m of oxyethylene groups in the general formula (1) is 0, and a carbon number of 2 A working medium for a refrigerant compression refrigeration cycle device comprising a hydrocarbon refrigerant containing no halogen atoms of 4 to 4 and the lubricating oil, particularly preferably the hydrocarbon refrigerant containing no halogen atoms having 2 to 4 carbon atoms is propane. And / or isobutane.
[0008]
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Ethane, propane, butane, isobutane, and a mixture of two or more thereof are used as the hydrocarbon refrigerant containing no halogen atom having 2 to 4 carbon atoms according to the present invention, and in particular, propane, isobutane and these Are preferred.
[0009]
The ether compound of the general formula (1) in the present invention is obtained by substituting the terminal hydroxyl group of the polyalkylene glycol with an alkyl group. The ether compound preferably has low solubility in a hydrocarbon refrigerant. For this purpose, R 1 and R 2 preferably have a small carbon number of 1 to 4 and particularly preferably a methyl group.
[0010]
In addition, the polymer chain of A in the general formula (1) includes an oxypropylene group alone, both an oxyethylene group and an oxypropylene group, and the number m of the oxyethylene groups is in a range of 0 to 50. There is no problem if it is present, but in order to reduce the hygroscopicity of the lubricating oil, it is better that m is small, preferably 5 or less, particularly preferably 0. On the other hand, if the number n of the oxypropylene groups is in the range of 2 to 50, it can be used without any particular problem.
[0011]
The ether compound of the above general formula (1) containing both an oxyethylene group and an oxypropylene group in the polymer chain may be a random copolymer or a block copolymer. Is preferred.
[0012]
The lubricating oil used in the present invention contains the ether compound of the general formula (1) as a main component, and is at least 50% by mass, preferably 80% by mass or more, particularly preferably 95% by mass or more in the lubricating oil. , Containing the compound.
[0013]
Further, the lubricating oil is required to have a viscosity capable of maintaining an oil film required for lubrication in order to have proper lubricating performance, and the viscosity at 40 ° C. before mixing with the refrigerant is 10 to 100 mm 2 / s. It is necessary, and especially, the one of 15 to 46 mm 2 / s is preferable.
[0014]
Further, the lubricating oil of the present invention has an acid value of preferably 1 mgKOH / g or less, particularly preferably 0.1 mgKOH / g or less from the viewpoint of stability. As for the hydroxyl value, it is very difficult to lower the hydroxyl value because the terminal hydroxyl group of the above general formula (1) cannot be completely alkyl-substituted. Undesirable phenomena occur, such as cloudiness and blockage of the capillary device of the refrigeration cycle. Therefore, the hydroxyl value is preferably 30 mgKOH / g or less and 15 mgKOH / g or less.
[0015]
When the lubricating oil of the present invention containing the ether compound represented by the general formula (1) as a main component is used as a lubricating oil for a refrigerant compression refrigeration cycle device using a hydrocarbon refrigerant, it has a wide range from low to high temperatures. In the region, it is possible to significantly improve the lubricating and thermal stability by exhibiting mutually appropriate compatibility and solubility.
[0016]
Note that the lubricating oil according to the present invention may be appropriately mixed with a lubricating oil such as an ester compound, an alkylbenzene or a mineral oil within a range satisfying the function as a lubricating oil for a refrigerant compression refrigeration cycle device. Additives such as an antioxidant, an antiwear agent, an epoxy compound and the like used in the above can be appropriately added.
[0017]
Another one of the present invention is a working medium composed of the hydrocarbon refrigerant and the lubricating oil. However, since the usage ratio between the refrigerant and the lubricating oil differs depending on the type of the refrigeration cycle device, it cannot be unconditionally described. Usually, the weight ratio is appropriately selected from the range of 1/10 to 2/1.
[0018]
The lubricating oil and the working medium according to the present invention include a compressor, a condenser, a throttle device (a refrigerant flow control unit such as an expansion valve or a capillary tube), an evaporator, and the like. It can be suitably used in a high refrigerant compression refrigeration cycle device, particularly in a refrigeration cycle device having a high-pressure compressor such as a rotary compressor.
[0019]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples.
[0020]
Test oils of Examples 1 to 3 (1) The ether compounds shown in Table 1 were used as test oils.
[Table 1]
Figure 2004043611
[0022]
(4) Test oil of Comparative Example 1: Refrigeration oil composed of paraffinic mineral oil (Freol S10; manufactured by Japan Energy), viscosity at 40 ° C. 10 mm 2 / s
(5) Test oil of Comparative Example 2: Refrigeration oil composed of paraffinic mineral oil (Freol S32; manufactured by Japan Energy), viscosity at 40 ° C. 32 mm 2 / s
(6) Test oil of Comparative Example 3: Refrigeration oil composed of naphthenic mineral oil (Suniso 3GS; manufactured by Nippon Sun Oil Co., Ltd.), viscosity at 40 ° C. 30 mm 2 / s
(7) Test oil of Comparative Example 4: polyoxypropylene glycol monoalkyl ether (ADEKA CARPOL M-30; manufactured by Asahi Denka Kogyo KK), viscosity at 40 ° C. 33 mm 2 / s
(8) Test oil of Comparative Example 5: Monoester of 2-ethylhexanol and palmitic acid (Unistar MB-816; manufactured by NOF CORPORATION), viscosity at 40 ° C. 8 mm 2 / s
(9) Test oil of Comparative Example 6: a mixture of the following two carbonates (acid value 0.01 mg KOH / g), viscosity at 40 ° C. 8 mm 2 / s
(F) dibenzyl carbonate; 50 parts by weight (g) benzyl-phenylethyl carbonate; 50 parts by weight
15 g of test oil for solubility test was placed in a glass pressure vessel, 3 to 10 g of isobutane was sealed, and the temperature was set at several points between room temperature and 80 ° C. From the volume of the test oil in which isobutane was dissolved and the pressure at that time, A temperature / pressure / solubility curve was created by calculation. The isobutane dissolution amount (dissolved isobutane / (sample oil + dissolved isobutane); wt%) of each test oil at 60 ° C. and 0.6 MPa, which are typical practical conditions, was read from the solubility, and the results are shown in Table 2. .
[0024]
[Table 2]
Figure 2004043611
[0025]
The following properties of the test oil as a refrigerating machine oil were measured and evaluated under the following conditions, and the results are shown in Table 3.
[0026]
Lubricity According to ASTM D-3233-73, the Falex baking load was measured under a controlled atmosphere of isobutane blowing (70 ml / min).
[0027]
Heat stability According to ANSI / ASHRAE 97-1983, 20 g of test oil, 5 g of isobutane and a catalyst (each wire of iron, copper and aluminum) are sealed in a stainless steel cylinder (100 ml), heated to 175 ° C. and maintained for 10 days. After that, the hue (ASTM display) and the acid value of the test oil were measured.
[0028]
60 g of the sample oil was placed in a 100 ml hygroscopic beaker, allowed to stand in an open state in an atmosphere of a temperature of 25 ° C. and a humidity of 70% for 3 hours, and then the water concentration was measured by the Karl Fischer method.
[0029]
[Table 3]
Figure 2004043611
[0030]
As can be seen from Tables 2 and 3, when the ether compound according to the present invention is compared with the mineral oil-based refrigerating machine oils of Comparative Examples 1 to 3, the monoester of Comparative Example 5, and the carbonate of Comparative Example 6, the solubility of the refrigerant is moderate. And the refrigerant charging amount can be reduced. In addition, although the ether of Comparative Example 4 has low solubility in the refrigerant, it has poor thermal stability due to having a hydroxyl group in the structure, and further has high hygroscopicity, which is not suitable as a refrigerating machine oil. It can be seen that the monoesters and carbonates of Comparative Examples 5 and 6 are inferior not only in solubility with the refrigerant but also in lubricity and thermal stability as compared with the esters of the present invention.
[0031]
【The invention's effect】
The refrigerating machine oil of the present invention has moderate compatibility and solubility with hydrocarbon refrigerants, and also has low hygroscopicity, good lubricity, and high thermal oxidation stability. It has a special effect of being excellent.

Claims (5)

炭素数２〜４のハロゲン原子を含まない炭化水素冷媒を用いる冷媒圧縮式冷凍サイクル装置用潤滑油において、前記潤滑油が下記一般式（１）
Ｒ１−Ａ−ＯＲ２　　　　　（１）
（式中、Ｒ１、Ｒ２は炭素数１〜４のアルキル基、Ａはｍ個のオキシエチレン基とｎ個のオキシプロピレン基からなる重合鎖を示し、ｍは０〜５０の整数、ｎは２〜５０の整数で、ｍ／ｎは１以下である。）で表されるエーテル化合物を主成分とし、４０℃の粘度が１０〜１００ｍｍ２／ｓであることを特徴とする冷媒圧縮式冷凍サイクル装置用潤滑油。In a lubricating oil for a refrigerant compression refrigeration cycle device using a hydrocarbon refrigerant containing no halogen atom having 2 to 4 carbon atoms, the lubricating oil is represented by the following general formula (1):
R 1 -A-OR 2 (1)
(Wherein, R 1 and R 2 represent an alkyl group having 1 to 4 carbon atoms, A represents a polymer chain composed of m oxyethylene groups and n oxypropylene groups, m is an integer of 0 to 50, n Is an integer of 2 to 50, and m / n is 1 or less.) The refrigerant compression type is characterized by having an ether compound represented by the following formula as a main component, and having a viscosity at 40 ° C. of 10 to 100 mm 2 / s. Lubricating oil for refrigeration cycle equipment. 前記一般式（１）中のＲ１、Ｒ２がメチル基であることを特徴とする請求項１に記載の冷媒圧縮式冷凍サイクル装置用潤滑油。The lubricating oil for a refrigerant compression refrigeration cycle device according to claim 1 , wherein R 1 and R 2 in the general formula (1) are methyl groups. 前記一般式（１）中のオキシエチレン基の個数ｍが０であることを特徴とする請求項１〜２に記載の冷媒圧縮式冷凍サイクル装置用潤滑油。3. The lubricating oil for a refrigerant compression refrigeration cycle device according to claim 1, wherein the number m of oxyethylene groups in the general formula (1) is 0. 4. 炭素数２〜４のハロゲン原子を含まない炭化水素冷媒と請求項１〜３に記載の潤滑油とからなる冷媒圧縮式冷凍サイクル装置用作動媒体。A working medium for a refrigerant compression refrigeration cycle device, comprising a hydrocarbon refrigerant containing no halogen atom having 2 to 4 carbon atoms and the lubricating oil according to claim 1. 請求項１〜４において、炭素数２〜４のハロゲン原子を含まない炭化水素冷媒がプロパン及び／又はイソブタンであることを特徴とする冷媒圧縮式冷凍サイクル装置用潤滑油及び作動媒体。5. The lubricating oil and working medium for a refrigerant compression refrigeration cycle device according to claim 1, wherein the hydrocarbon refrigerant containing no halogen atoms having 2 to 4 carbon atoms is propane and / or isobutane.
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