JP2009263666A - Refrigerating machine oil composition - Google Patents

Refrigerating machine oil composition Download PDF

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JP2009263666A
JP2009263666A JP2009091523A JP2009091523A JP2009263666A JP 2009263666 A JP2009263666 A JP 2009263666A JP 2009091523 A JP2009091523 A JP 2009091523A JP 2009091523 A JP2009091523 A JP 2009091523A JP 2009263666 A JP2009263666 A JP 2009263666A
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refrigerating machine
oil composition
phosphite
machine oil
composition according
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JP5388662B2 (en
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Masayoshi Muto
正誉 武藤
Shozo Ikejima
昌三 池島
Masafumi Yamashita
雅史 山下
Masayuki Mori
誠之 森
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Iwate University
Denso Corp
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Denso Corp
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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
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/24—Compounds containing phosphorus, arsenic or antimony
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/102—Polyesters
    • C10M2209/1023—Polyesters used as base material
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
    • 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • C10M2209/1045—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only used as base material
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/077—Ionic Liquids
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09—Characteristics associated with water
    • C10N2020/097—Refrigerants
    • C10N2020/106—Containing Carbon dioxide
    • 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
    • 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
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a refrigerating machine oil composition which, in a refrigerating machine using carbon dioxide as a refrigerant, satisfies required performances such as lubricity, compatibility with the refrigerant, stability to heat and hydrolysis, and low hygroscopicity in a balanced manner, by compounding an extreme-pressure agent having a higher wear resistance than a phosphoric ester. <P>SOLUTION: The refrigerating machine oil composition for a refrigerating machine using carbon dioxide as a refrigerant includes at least one phosphorus compound other than phosphoric esters in a base oil comprising a synthetic oil. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本願発明は、冷凍機油組成物に関するものであり、詳しくは合成油からなる基油に、リン系摩耗防止剤を配合した二酸化炭素冷媒用の冷凍機油組成物に関するものである。   The present invention relates to a refrigerating machine oil composition, and more particularly to a refrigerating machine oil composition for carbon dioxide refrigerant in which a phosphorus-based antiwear agent is blended with a base oil made of synthetic oil.

近年、オゾン層破壊問題や地球温暖化問題の観点から、冷媒代替化や冷凍システムの高効率化が検討されている。冷媒代替化においては、ＣＦＣ（クロロフルオロカーボン）やＨＣＦＣ（ハイドロクロロフルオロカーボン）等の塩素含有冷媒からＨＦＣ（ハイドロフルオロカーボン）への切り替えが進められている。また、その一方で、ＨＦＣ冷媒も地球温暖化問題の観点からは規制の対象となり得るため、二酸化炭素やアンモニア、ハイドロカーボン等の自然冷媒の適用が検討されている。   In recent years, from the viewpoint of ozone layer depletion problems and global warming problems, alternative refrigerants and higher efficiency of refrigeration systems have been studied. In refrigerant replacement, switching from chlorine-containing refrigerants such as CFC (chlorofluorocarbon) and HCFC (hydrochlorofluorocarbon) to HFC (hydrofluorocarbon) is being promoted. On the other hand, since HFC refrigerants can also be subject to regulation from the viewpoint of global warming, application of natural refrigerants such as carbon dioxide, ammonia, and hydrocarbons is being studied.

このような冷媒代替化の動きにあわせて、代替冷媒用冷凍機油の開発が進められている。冷凍機油には、潤滑性、冷媒相溶性、熱・加水分解安定性、低吸湿性等多くの性能が要求されるため、冷媒の種類や用途によってこれら要求性能を満たすような化合物が選択される。例えば、ＨＦＣ冷媒１，１，１，２−テトラフルオロエタン（Ｒ１３４ａ）を冷媒として用いた冷凍機においては、ポリオキシアルキレングリコール等を基油として用い（例えば特許文献１参照）、耐焼付き性、耐摩耗性を改善するため、リン酸エステル系極圧剤が配合されている（例えば特許文献２参照）。   In line with such movement of refrigerant substitution, the development of refrigerant refrigerant for alternative refrigerants is underway. Refrigerating machine oils require many performances such as lubricity, refrigerant compatibility, heat / hydrolysis stability, and low hygroscopicity, so compounds that meet these required performances are selected depending on the type and application of the refrigerant. . For example, in a refrigerator using HFC refrigerant 1,1,1,2-tetrafluoroethane (R134a) as a refrigerant, polyoxyalkylene glycol or the like is used as a base oil (see, for example, Patent Document 1), and seizure resistance, In order to improve the wear resistance, a phosphate ester extreme pressure agent is blended (see, for example, Patent Document 2).

特開平８−３１１４７２号公報JP-A-8-311472 特開２００２−９７４８６号公報JP 2002-97486 A

しかしながら、前記したＲ１３４ａを冷媒として用いた冷凍機に比べ二酸化炭素を冷媒として用いた冷凍機では、同じリン酸エステル系極圧剤を配合した冷凍機油を用いた場合、しゅう動部では極圧剤の反応量が少なく、耐摩耗性が劣るという問題がある。したがって二酸化炭素を冷媒として用いた冷凍機では、リン酸エステルよりも耐摩耗性の高い極圧剤を配合し、潤滑性、冷媒相溶性、熱・加水分解安定性、低吸湿性等の要求性能をバランスよく満たす冷凍機油の開発が望まれていた。   However, in the refrigerator using carbon dioxide as the refrigerant, compared to the refrigerator using R134a as the refrigerant, when the refrigerator oil containing the same phosphate ester extreme pressure agent is used, the extreme pressure agent is used in the sliding portion. There is a problem that the reaction amount is small and the wear resistance is poor. Therefore, refrigerators using carbon dioxide as a refrigerant are blended with an extreme pressure agent that has higher wear resistance than phosphate esters, and the required performance such as lubricity, refrigerant compatibility, heat / hydrolysis stability, and low hygroscopicity. The development of refrigerating machine oil that satisfies the above requirements has been desired.

即ち、本願発明の目的は、二酸化炭素を冷媒として用いた冷凍機において、リン酸エステルよりも耐摩耗性の高い極圧剤を配合し、潤滑性、冷媒相溶性、熱・加水分解安定性、低吸湿性等の要求性能をバランスよく満たす冷凍機油を提供することにある。   That is, the object of the present invention is to combine an extreme pressure agent having higher wear resistance than phosphate ester in a refrigerator using carbon dioxide as a refrigerant, lubricity, refrigerant compatibility, thermal / hydrolysis stability, The object is to provide a refrigerating machine oil that satisfies the required performance such as low hygroscopicity in a well-balanced manner.

そこで発明者らは、上記の課題に対し、ポリオキシアルキレングリコール、ポリオールエステル等からなる基油に、リン酸エステル系極圧剤よりも反応性の高い亜リン酸エステル系極圧剤、又はリンを含むイオン性液体を配合することによって上記目的が達成されることを見出した。   Therefore, the inventors addressed the above-mentioned problems by adding a phosphite ester extreme pressure agent or a phosphorous ester ester extreme pressure agent, which is more reactive than a phosphate ester extreme pressure agent, to a base oil composed of polyoxyalkylene glycol, polyol ester or the like. It has been found that the above object can be achieved by blending an ionic liquid containing

本願の請求項１に記載の発明（以下「本実施形態」ともいう）は、冷媒として二酸化炭素を用いる冷凍機用の冷凍機油組成物であって、合成油からなる基油に、リン酸エステルを除く少なくとも１種のリン化合物を含有することを特徴とする冷凍機油組成物を提供するものである。   The invention according to claim 1 of the present application (hereinafter also referred to as “this embodiment”) is a refrigerating machine oil composition for a refrigerating machine using carbon dioxide as a refrigerant, and a phosphate ester is added to a base oil made of synthetic oil. A refrigerating machine oil composition characterized by containing at least one phosphorus compound excluding the above.

かかる本実施形態の冷凍機油組成物は、リン酸エステルよりも耐摩耗性の高い極圧剤が配合されたことによって、冷媒として二酸化炭素を用いる冷凍機用の冷凍機油として、潤滑性、冷媒相溶性、熱・加水分解安定性、低吸湿性等の要求性能をバランスよく満たすものである。   Such a refrigerating machine oil composition of the present embodiment is blended with an extreme pressure agent having higher wear resistance than a phosphate ester, so that the refrigerating machine oil for a refrigerating machine using carbon dioxide as a refrigerant has a lubricating property and a refrigerant phase. It satisfies the required performance such as solubility, heat / hydrolysis stability and low hygroscopicity in a well-balanced manner.

本発明の冷凍機油組成物の評価に使用した密閉ＨＦＲＲ（高速往復動）摩耗試験装置を模式的に示す説明図である。It is explanatory drawing which shows typically the sealed HFRR (high-speed reciprocating motion) abrasion test apparatus used for evaluation of the refrigerator oil composition of this invention.

本実施形態における冷凍機油組成物の好ましい一つの態様として、そのリン化合物が、無機リン酸の金属塩、無機リン酸のアミン塩、亜リン酸エステル、有機亜リン酸の金属塩、有機亜リン酸のアミン塩、及びリンを含むイオン性液体から成る群から選択される少なくとも一種であることを特徴とする、冷凍機油組成物が挙げられる。尚、これらのリン化合物は、２種以上が混合されて用いられても良いが、通常単独で用いるのが好ましい。   As one preferable aspect of the refrigerating machine oil composition according to the present embodiment, the phosphorus compound is a metal salt of inorganic phosphoric acid, an amine salt of inorganic phosphoric acid, a phosphite, a metal salt of organic phosphorous acid, or organic phosphorous. A refrigerating machine oil composition characterized by being at least one selected from the group consisting of an amine salt of an acid and an ionic liquid containing phosphorus. In addition, although these phosphorus compounds may be used in mixture of 2 or more types, it is usually preferable to use them alone.

また、本実施形態における冷凍機油組成物の好ましいもう一つの態様として、そのリン化合物が亜リン酸エステル類から成る群から選択される少なくとも一種である、冷凍機油組成物が挙げられる。尚、その亜リン酸エステルは、２種以上が混合されて用いられても良いが、通常単独で用いるのが好ましい。   Moreover, another preferable aspect of the refrigerating machine oil composition in the present embodiment is a refrigerating machine oil composition in which the phosphorus compound is at least one selected from the group consisting of phosphites. The phosphite ester may be used as a mixture of two or more kinds, but it is usually preferable to use it alone.

また、本実施形態における冷凍機油組成物の好ましいもう一つの態様として、その亜リン酸エステル類が、トリフェニルホスファイト、トリオクチルホスファイト、ジブチルホスファイト、トリエチルホスファイト、トリブチルホスファイト、トリデシルホスファイト、トリラウリルホスファイト、ジフェニルホスファイト及びジラウリルホスファイトから成る群から選択される少なくとも一種である、冷凍機油組成物が挙げられる。   Further, as another preferred aspect of the refrigerating machine oil composition in the present embodiment, the phosphites are triphenyl phosphite, trioctyl phosphite, dibutyl phosphite, triethyl phosphite, tributyl phosphite, tridecyl. A refrigerating machine oil composition that is at least one selected from the group consisting of phosphite, trilauryl phosphite, diphenyl phosphite and dilauryl phosphite can be mentioned.

また、本実施形態における冷凍機油組成物の更に好ましいもう一つの態様として、その亜リン酸エステル類が、トリフェニルホスファイト、トリオクチルホスファイト及びジブチルホスファイトから成る群から選択される少なくとも一種である、冷凍機油組成物が挙げられる。尚、これらの態様における亜リン酸エステル類は、２種以上が混合されて用いられても良いが、通常単独で用いるのが好ましい。   Further, as another preferred aspect of the refrigerator oil composition in the present embodiment, the phosphite is at least one selected from the group consisting of triphenyl phosphite, trioctyl phosphite and dibutyl phosphite. A refrigerating machine oil composition is mentioned. In addition, although the phosphite ester in these aspects may be used in mixture of 2 or more types, it is usually preferable to use it alone.

さらに、本実施形態における冷凍機油組成物の好ましいもう一つの態様として、そのリン化合物がリンを含むイオン性液体である、冷凍機油組成物が挙げられる。かかるリンを含むイオン性液体類としては、トリｎ-ブチルメチルホスフォニウムジメチルホスフェート、リン酸‐１‐ブチル‐３‐メチルイミダゾリウム、デカン酸トリヘキシル（テトラデシル）ホスフォニウム等が挙げられる。   Furthermore, another preferable aspect of the refrigerating machine oil composition in the present embodiment is a refrigerating machine oil composition in which the phosphorus compound is an ionic liquid containing phosphorus. Examples of ionic liquids containing phosphorus include tri-n-butylmethylphosphonium dimethyl phosphate, phosphate-1-butyl-3-methylimidazolium phosphate, trihexyl (tetradecyl) phosphonium decanoate, and the like.

さらに、本実施形態における冷凍機油組成物の好ましいもう一つの態様として、そのリンを含むイオン性液体がトリｎ-ブチルメチルホスフォニウムジメチルホスフェートである、冷凍機油組成物が挙げられる。   Furthermore, another preferable aspect of the refrigerating machine oil composition in the present embodiment is a refrigerating machine oil composition in which the ionic liquid containing phosphorus is tri-n-butylmethylphosphonium dimethyl phosphate.

さらに、本実施形態における冷凍機油組成物の好ましいもう一つの態様として、そのリン化合物の配合量が０．１〜３重量％である、冷凍機油組成物が挙げられる。さらに好ましいリン化合物の配合量は０．３〜３重量％である。尚、かかるリン化合物の配合量とは、冷凍機油組成物全体に対するリン化合物の重量％を意味する。   Furthermore, another preferable aspect of the refrigerating machine oil composition in the present embodiment is a refrigerating machine oil composition having a phosphorus compound content of 0.1 to 3% by weight. A more preferable amount of the phosphorus compound is 0.3 to 3% by weight. In addition, the compounding quantity of this phosphorus compound means weight% of the phosphorus compound with respect to the whole refrigerating machine oil composition.

さらに、本実施形態における冷凍機油組成物の好ましいもう一つの態様として、その合成油が、ポリオキシアルキレングリコール類及びポリオールエステル類から選ばれる少なくとも一種である、冷凍機油組成物が挙げられる。尚、これらの合成油は、２種以上が混合されて用いられても良いが、通常単独で用いるのが好ましい。   Furthermore, another preferable aspect of the refrigerating machine oil composition in the present embodiment is a refrigerating machine oil composition in which the synthetic oil is at least one selected from polyoxyalkylene glycols and polyol esters. These synthetic oils may be used as a mixture of two or more kinds, but are usually preferably used alone.

ポリオキシアルキレングリコール類の例としては、下記一般式（１）で表される構造を有するものが挙げられる。
Ｒ1−Ｏ−（ＡＯ）m−Ｒ２ ・・・・・・・・・・・・・・・・・・・・・・・（１）
ここで、Ｒ１及びＲ２はそれぞれ独立に、水素原子又は炭素数１〜８の炭化水素基を示し、これらのうち特にＲ１及びＲ２がともにメチル基である場合が好ましい。Ｒ１及びＲ２は互いに同一でもよいし、異なっていてもよい。次に、Ａは炭素数２〜８のアルキレン基を示し、特に、炭素数３のアルキレン基が好ましい。また、ｍは１以上の整数を示し、ｍが２以上の場合は複数のＡは同一でも異なってもよい。 Examples of polyoxyalkylene glycols include those having a structure represented by the following general formula (1).
R 1 —O— (AO) m —R 2 (1)
Here, R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and it is particularly preferable that R 1 and R 2 are both methyl groups. R 1 and R 2 may be the same as or different from each other. Next, A represents an alkylene group having 2 to 8 carbon atoms, and an alkylene group having 3 carbon atoms is particularly preferable. M represents an integer of 1 or more, and when m is 2 or more, a plurality of A may be the same or different.

ポリオールエステル類としては、ジオールあるいは水酸基を３〜２０個有するポリオールと、炭素数６〜２０の脂肪酸とのエステルが好ましく用いられる。ここで、ジオールとして具体的には、エチレングリコール、ネオペンチルグリコール、１，３−プロパンジオール、プロピレングリコール、１，４−ブタンジオール等があげられ、ポリオールとしては具体的には、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、ペンタエリスリトール、ジペンタエリスリトール等があげられる。脂肪酸として具体的には、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、オレイン酸、イソペンタン酸、２−メチルヘキサン酸、２−エチルペンタン酸、２−エチルへキサン酸および３，５，５−トリメチルへキサン酸等があげられる。   As the polyol ester, an ester of a diol or a polyol having 3 to 20 hydroxyl groups and a fatty acid having 6 to 20 carbon atoms is preferably used. Here, specific examples of the diol include ethylene glycol, neopentyl glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, and the polyol specifically includes trimethylolethane, Examples include trimethylolpropane, trimethylolbutane, pentaerythritol, dipentaerythritol and the like. Specific examples of fatty acids include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid and 3,5 , 5-trimethylhexanoic acid and the like.

さらに、本実施形態における冷凍機油組成物の好ましいもう一つの態様として、その基油の１００℃における動粘度が２〜５０ｍｍ２／ｓである、冷凍機油組成物が挙げられる。 Furthermore, another preferable aspect of the refrigerating machine oil composition in the present embodiment includes a refrigerating machine oil composition in which the kinematic viscosity of the base oil at 100 ° C. is 2 to 50 mm 2 / s.

本発明の実施態様として、以下に示すものが挙げられる。   Examples of the present invention include the following.

即ち、本発明の冷凍機油組成物の基油としての合成油としては、上記のポリオキシアルキレングリコール類及びポリオールエステル類の他に、アルキルベンゼン、アルキルナフタレン、ポリ−α−オレフィン、ポリビニルエーテル、ポリビニルエーテル−ポリアルキレングリコール共重合体、ポリカーボネート等が挙げられる。   That is, as the synthetic oil as the base oil of the refrigerating machine oil composition of the present invention, in addition to the above polyoxyalkylene glycols and polyol esters, alkylbenzene, alkylnaphthalene, poly-α-olefin, polyvinyl ether, polyvinyl ether -A polyalkylene glycol copolymer, a polycarbonate, etc. are mentioned.

また、本発明のリン化合物である亜リン酸エステル類としては、上記のものの他に、例えばトリクレジルホスファイト、トリ（ノニルフェニル）ホスファイト、トリ（２−エチルヘキシル）ホスファイト、トリイソオクチルホスファイト、ジフェニルイソデシルホスファイト、トリステアリルホスファイト、トリオレイルホスファイト、ジペンチルホスファイト、ジへキシルホスファイト、ジヘプチルホスファイト、ジオクチルホスファイト、ジノニルホスファイト、ジデシルホスファイト、ジウンデシルホスファイト、ジドデシルホスファイト、ジオレイルホスファイト、ジクレジルホスファイト、トリペンチルホスファイト、トリヘキシルホスファイト、トリへプチルホスファイト、トリノニルホスファイト、トリウンデシルホスファイト、トリドデシルホスファイト等を挙げることができる。   The phosphites that are the phosphorus compounds of the present invention include, for example, tricresyl phosphite, tri (nonylphenyl) phosphite, tri (2-ethylhexyl) phosphite, triisooctyl other than those described above. Phosphite, diphenylisodecyl phosphite, tristearyl phosphite, trioleyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite, diundecyl Phosphite, didodecyl phosphite, dioleyl phosphite, dicresyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trinonyl phosphite, triundecyl phosphite , Mention may be made of the bird-dodecyl phosphite.

以下に本願発明についての実施例を挙げて更に具体的に本願発明を説明するが、それらの実施例によって本願発明が何ら限定されるものではない。
実施例１〜３４
冷凍機油組成物の評価は、以下の方法により行った。 Examples of the present invention will be described below more specifically with reference to examples of the present invention. However, the present invention is not limited to these examples.
Examples 1-34
Evaluation of the refrigerating machine oil composition was performed by the following method.

（１）密閉ＨＦＲＲ摩耗試験
ＨＦＲＲ（高速往復動）摩擦試験機（PCS Instruments社製）を用い、図１に示すように、密閉容器１内に試験機２を設置した。荷重：２Ｎ、周波数：２０Ｈｚ、ストローク：１ｍｍ、時間：６０分、試験油３：２ｃｍ３、試験油温度：６０℃、試験雰囲気：二酸化炭素（二酸化炭素源４から供給されて、ロータリーポンプ５により排出される）、雰囲気圧：０．１ＭＰａ、ボール６：ＳＵＪ２（Φ６ｍｍ）、プレート７：ＳＵＪ２等の条件で、摩擦試験を行った。表１に示されるリン化合物を、表１に示される各々の配合量で基油であるポリプロピレングリコールモノメチルエーテルに添加して混合した試験油３を用いて、各々の摩擦試験を行って、得られたボール６の表面に生じたボール摩耗痕の大きさ（相当直径）（μｍ）を評価した。尚、その相当直径とは、ボール摩耗痕の全面積と同等の面積を有する円の直径を言う。 (1) Sealed HFRR Wear Test Using a HFRR (high speed reciprocating) friction tester (manufactured by PCS Instruments), a tester 2 was installed in the sealed container 1 as shown in FIG. Load: 2N, frequency: 20 Hz, stroke: 1 mm, time: 60 minutes, test oil 3: 2 cm 3 , test oil temperature: 60 ° C., test atmosphere: carbon dioxide (supplied from carbon dioxide source 4, by rotary pump 5 Friction test was performed under the conditions of atmospheric pressure: 0.1 MPa, ball 6: SUJ2 (Φ6 mm), plate 7: SUJ2, and the like. Each of the phosphorus compounds shown in Table 1 was obtained by performing each friction test using test oil 3 in which the compounding amounts shown in Table 1 were added to and mixed with polypropylene glycol monomethyl ether as a base oil. The size (equivalent diameter) (μm) of the ball wear scar generated on the surface of the ball 6 was evaluated. The equivalent diameter means the diameter of a circle having an area equivalent to the total area of the ball wear scar.

（２）化学安定性試験
含有水分量を２０００ｐｐｍに調整した、基油であるポリプロピレングリコールモノメチルエーテル、２，６‐ジ‐tert‐ブチル‐４‐メチルフェノール０．５％及びフェニルグリシジルエーテル１％と、表１に示される各々の配合量のリン化合物から成る、各々の試験油４０ｇをガラス瓶に秤量し、触媒Ｆｅ／Ｃｕ／ＡｌとともにＳＵＳ製耐圧容器（容量２００ｃｃ）に入れ、二酸化炭素８ｇを充填し密閉した。１７５℃で９０時間保持したのち、不溶解物の析出の有無を評価した。 (2) Chemical stability test Polypropylene glycol monomethyl ether, 0.56% 2,6-di-tert-butyl-4-methylphenol and 1% phenylglycidyl ether, which are base oils, with water content adjusted to 2000 ppm , Each test oil 40g consisting of phosphorus compound of each compounding amount shown in Table 1 is weighed into a glass bottle, put into a SUS pressure vessel (capacity 200cc) together with catalyst Fe / Cu / Al, and filled with 8g of carbon dioxide. And sealed. After maintaining at 175 ° C. for 90 hours, the presence or absence of precipitation of insoluble matter was evaluated.

表１に示す各々のリン化合物を、表１に示す量で基油であるポリプロピレングリコールモノメチルエーテルと配合して調製した試験油（冷凍機油組成物）について、上記方法に従って評価した結果を、ボール摩耗痕の相当直径及び化学安定性で表1に示す。   For the test oil (refrigeration machine oil composition) prepared by blending each phosphorus compound shown in Table 1 with polypropylene glycol monomethyl ether, which is the base oil, in the amount shown in Table 1, the results of evaluation according to the above method were evaluated as ball wear. The equivalent diameter and chemical stability of the marks are shown in Table 1.

比較例１
リン化合物を含有しないであるポリプロピレングリコールモノメチルエーテルのみから成る試験油を用いて、上記方法に従って評価した結果を表１に示す。 Comparative Example 1
Table 1 shows the results of evaluation according to the above method using a test oil composed only of polypropylene glycol monomethyl ether which does not contain a phosphorus compound.

Figure 2009263666
Figure 2009263666

表１に示される結果より、冷凍機油組成物中のリン酸エステルを除くリン化合物の配合量が０．１〜３重量％の範囲にある冷凍機油組成物の場合には、化学安定性試験で不溶解物が析出することも無く、ＨＦＲＲ摩耗試験においても相当直径が１００μｍよりも小さなボール摩耗痕しかボール６の表面に付かず、非常に安定していることが分かった。   From the results shown in Table 1, in the case of a refrigerating machine oil composition in which the blending amount of the phosphorus compound excluding the phosphate ester in the refrigerating machine oil composition is in the range of 0.1 to 3% by weight, the chemical stability test Insoluble matter did not precipitate, and in the HFRR wear test, it was found that only a ball wear trace having an equivalent diameter smaller than 100 μm was attached to the surface of the ball 6 and was very stable.

Claims (10)

冷媒として二酸化炭素を用いる冷凍機用の冷凍機油組成物であって、合成油からなる基油に、リン酸エステルを除く少なくとも１種のリン化合物を含有することを特徴とする、冷凍機油組成物。   A refrigerating machine oil composition for a refrigerating machine using carbon dioxide as a refrigerant, wherein the base oil comprising a synthetic oil contains at least one phosphorus compound excluding a phosphate ester. . 前記リン化合物が、無機リン酸の金属塩、無機リン酸のアミン塩、亜リン酸エステル、有機亜リン酸の金属塩、有機亜リン酸のアミン塩、及びリンを含むイオン性液体から成る群から選択される少なくとも一種であることを特徴とする、請求項１に記載の冷凍機油組成物。   The phosphorous compound is composed of a metal salt of inorganic phosphoric acid, an amine salt of inorganic phosphoric acid, a phosphorous ester, a metal salt of organic phosphorous acid, an amine salt of organic phosphorous acid, and an ionic liquid containing phosphorus. The refrigerating machine oil composition according to claim 1, wherein the oil composition is at least one selected from the group consisting of: 前記リン化合物が、亜リン酸エステル類から成る群から選択される少なくとも一種であることを特徴とする、請求項２に記載の冷凍機油組成物。   The refrigerating machine oil composition according to claim 2, wherein the phosphorus compound is at least one selected from the group consisting of phosphites. 前記亜リン酸エステル類が、トリフェニルホスファイト、トリオクチルホスファイト、ジブチルホスファイト、トリエチルホスファイト、トリブチルホスファイト、トリデシルホスファイト、トリラウリルホスファイト、ジフェニルホスファイト及びジラウリルホスファイトから成る群から選択される少なくとも一種であることを特徴とする、請求項３に記載の冷凍機油組成物。   The phosphites comprise triphenyl phosphite, trioctyl phosphite, dibutyl phosphite, triethyl phosphite, tributyl phosphite, tridecyl phosphite, trilauryl phosphite, diphenyl phosphite and dilauryl phosphite. The refrigerating machine oil composition according to claim 3, wherein the refrigerating machine oil composition is at least one selected from the group. 前記亜リン酸エステル類が、トリフェニルホスファイト、トリオクチルホスファイト及びジブチルホスファイトから成る群から選択される少なくとも一種であることを特徴とする、請求項３に記載の冷凍機油組成物。   The refrigerating machine oil composition according to claim 3, wherein the phosphites are at least one selected from the group consisting of triphenyl phosphite, trioctyl phosphite and dibutyl phosphite. 前記リン化合物がリンを含むイオン性液体類から成る群から選択される少なくとも一種であることを特徴とする、請求項１に記載の冷凍機油組成物。   The refrigerating machine oil composition according to claim 1, wherein the phosphorus compound is at least one selected from the group consisting of ionic liquids containing phosphorus. 前記リンを含むイオン性液体がトリｎ-ブチルメチルホスフォニウムジメチルホスフェートであることを特徴とする、請求項６に記載の冷凍機油組成物。   The refrigerating machine oil composition according to claim 6, wherein the ionic liquid containing phosphorus is tri-n-butylmethylphosphonium dimethyl phosphate. 前記リン化合物の配合量が０．１〜３重量％であることを特徴とする、請求項１〜７のいずれか一項に記載の冷凍機油組成物。   The refrigerating machine oil composition according to any one of claims 1 to 7, wherein a blending amount of the phosphorus compound is 0.1 to 3% by weight. 前記合成油が、ポリオキシアルキレングリコール類及びポリオールエステル類から選ばれる少なくとも一種であることを特徴とする、請求項１〜８のいずれか一項に記載の冷凍機油組成物。   The refrigerating machine oil composition according to any one of claims 1 to 8, wherein the synthetic oil is at least one selected from polyoxyalkylene glycols and polyol esters. 前記基油の１００℃における動粘度が２〜５０ｍｍ２／ｓであることを特徴とする、請求項１〜９のいずれか一項に記載の冷凍機油組成物。 The refrigerating machine oil composition according to any one of claims 1 to 9, wherein the base oil has a kinematic viscosity at 100 ° C of 2 to 50 mm 2 / s.
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