JP4368479B2 - Refrigerator oil composition - Google Patents
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- JP4368479B2 JP4368479B2 JP2000035304A JP2000035304A JP4368479B2 JP 4368479 B2 JP4368479 B2 JP 4368479B2 JP 2000035304 A JP2000035304 A JP 2000035304A JP 2000035304 A JP2000035304 A JP 2000035304A JP 4368479 B2 JP4368479 B2 JP 4368479B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、ＨＦＣ（ハイドロフルオロカーボン）系冷媒に添加される冷凍機油組成物に関する。
【０００２】
【従来の技術】
電気冷蔵庫や空調機等の冷媒として従来広く使用されていたＲ−１２やＲ−２２等のフロン類は、オゾン層破壊等の環境問題から規制対象となっており、今日ではＨＦＣ系冷媒（例えば、ＨＦＣ−１３４ａ、Ｒ−４０７Ｃ、Ｒ４１０Ａ等）への代替化が進んでいる。
【０００３】
一方、電気冷蔵庫や空調機等では、コンプレッサの摺動部分の潤滑のために、通常、潤滑油からなる基油に各種の添加剤を配合してなる冷凍機油組成物を添加した冷媒を使用している。従って、冷凍機油組成物の基油はＨＦＣ系フルオロカーボンと相溶性を有する必要があり、ポリアルキレングリコール（ＰＡＧ）やポリオールエステル（ＰＯＥ）が一般的となっている。例えば、米国特許第４７５５３１６号明細書や特開平２−２７６８８１号公報には１，１，１，２−テトラフルオロエタンとの相溶性に優れたＰＡＧ系冷凍機油組成物が、また米国特許第５０２１１７９号明細書には１，１，１，２−テトラフルオロエタンとの相溶性に優れたＰＥＯ系冷凍機油組成物が記載されている。
【０００４】
【発明が解決しようとする課題】
冷凍機油は通常、冷媒とともに充填された後は無交換で長期にわたり使用される。しかし、上記に挙げた冷凍機油組成物をはじめとして、ＰＯＥやＰＡＧを基油とする冷凍機油組成物では、ＰＯＥやＰＡＧが混入水分や工程剤等の影響を受けやすく、使用期間を経るのに従って加水分解を起こして脂肪酸を生成し、配管等の金属腐食、冷却不良、絶縁抵抗の低下等の種々の問題を引き起こすようになり、経時安定性の点で十分とは言えない。
【０００５】
本発明はこのような状況に鑑みてなされたものであり、基油の分解を抑制して、金属の腐食や冷却不足、絶縁性の低下を招くことが無く、経時安定性に優れたＨＦＣ系冷媒用冷凍機油組成物を提供することを目的とする。
【０００６】
【課題を解決するための手段】
上記の目的を達成するために、本発明は、ＨＦＣ系冷媒に添加される冷凍機油組成物であって、ネオペンチル型アルコールと下記一般式(I)で表される酸残基を有する脂肪酸との脱水反応生成物からなるエステル油を基油とし、前記基油に下記一般式（II)で表される化合物からなる酸性成分反応性添加剤を０．１〜１重量％、下記一般式（III)で表される化合物からなる水・塩酸反応性添加剤を０．１〜１重量％の割合で含有することを特徴とする冷凍機油組成物を提供する。
【０００７】
【化２】
一般式(I)において、Ｒ1、Ｒ2、Ｒ3はそれぞれＣnＨ2n+1（ｎ＝１〜２１）で表される直鎖または分岐のアルキル基もしくは水素原子であり、またＲ1、Ｒ2、Ｒ3は同時に２個以上が水素原子とはならず、かつＲ1、Ｒ2、Ｒ3を合わせたｎの総和は４以上２２以下である。また、一般式（II)において、Ｒ4、Ｒ5はそれぞれ芳香族基もしくはアルキル置換芳香族基であり、同一であっても互いに異なっていてもよい。また、一般式（III)において、Ｒ6は炭素数４〜２０の直鎖または分岐のアルキル基、直鎖または分岐のアシル基、アルキル置換芳香族基である。
【０００９】
【発明の実施の形態】
以下、本発明に関して詳細に説明する。
本発明の冷凍機油組成物において、基油は、ネオペンチル型アルコールと、下記一般式(I)で表される酸残基を有する脂肪酸とを脱水反応させて得られるエステル油である。
【００１０】
【化３】
尚、一般式(I)において、Ｒ1、Ｒ2、Ｒ3はそれぞれＣnＨ2n+1（ｎ＝１〜２１）で表される直鎖または分岐のアルキル基もしくは水素原子であり、またＲ1、Ｒ2、Ｒ3は同時に２個以上が水素原子とはならず、かつＲ1、Ｒ2、Ｒ3を合わせた炭素数（ｎ）の総和は４以上２２以下である。
【００１２】
この一般式(I)で表される酸残基を有する脂肪酸は、オレフィンと、一酸化炭素と、フッ化水素とを反応させることにより容易に得られる。この反応に際してオレフィンの大部分は、当初の炭素数よりも少ない炭素数の種々のフラグメントに分解し、それらフラグメントが一般式(I)のＲ1、Ｒ2及びＲ3として結合する。従って、一般式(I)で表される酸残基を有する脂肪酸は、種々の炭素数からなるアルキル基または水素原子がＲ1、Ｒ2及びＲ3としてランダムに結合した脂肪酸の混合物となる。尚、オレフィンとしては、Ｒ1、Ｒ2及びＲ3の炭素数の総数が２２を超えないように、余り炭素数の多いものを使用することは好ましくなく、例えばブチレン、ペンテン、ヘキセン、オクテン等を好ましく使用することができる。また、これらのオレフィンは、必要に応じて、炭素数の異なるものを混合して用いることもできる。
【００１３】
一方、ネオペンチル型アルコールとしては、ネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトールまたはジペンタエリスリトールが好ましく、これらを単独で、もしくは複数種を組み合わせて使用することができる。
【００１４】
上記ネオペンチル型アルコールと、一般式(I)で表される酸残基を有する脂肪酸とを脱水反応させて得られるエステル油は、酸残基側のＣ＝Ｏ結合の隣のα炭素が２級もしくは３級構造のα−ブランチ構造を有し、他方アルコール残基側のＯ−Ｃ結合を形成するβ炭素も分岐構造を有する。これにより、加水分解反応に係わるエステル結合部分が両分岐構造により遮蔽されるため、エステル油自体が加水分解反応を起こし難い分子構造を有するようになる。従って、一般式(I)で表される酸残基において、Ｒ1、Ｒ2、Ｒ3が上記した定義を満足しない場合には、このような遮蔽効果が得られない。また、この遮蔽効果は、一般式(I)で表される酸残基において、３級の分岐構造である場合に最も高くなる。
【００１５】
上記エステル油からなる基油には、下記一般式（II)で表される化合物からなる有機脂肪酸成分反応性添加剤及び下記一般式（III)で表される化合物からなる水・塩酸反応性添加剤が添加される。
【００１６】
【化４】
尚、一般式（II)において、Ｒ4、Ｒ5はそれぞれ芳香族基もしくはアルキル置換芳香族基であり、また同一であっても互いに異なっていてもよい。この一般式（II)で表される有機脂肪酸成分反応性添加剤としては、例えば４，４−ジメチルジフェニルカルボジイミド、２，６，２，６−テトラメチルジフェニルカルボジイミド、３．５．３．５−テトラメチルジフェニルカルボジイミド、４，４−ジイソプロピルジフェニルカルボジイミド、２，６，２，６−テトライソプロピルジフェニルカルボジイミド、３．５．３．５−テトライソプロピルジフェニルカルボジイミド、４，４−ジターシャルブチルジフェニルカルボジイミド、２，６，２，６−テトラターシャルブチルジフェニルカルボジイミド、３，５，３，５−テトラターシャルブチルジフェニルカルボジイミド、ジフェニルカルボジイミド等を挙げることができる。
【００１８】
また、一般式（III)において、Ｒ6は炭素数４〜２０の直鎖または分岐のアルキル基、直鎖または分岐のアシル基、アルキル置換芳香族基である。この一般式（III)で表される水・塩酸反応性添加剤としては、例えばｎ−ブチルグリシジルエーテル、イソブチルグリシジルエーテル、ｎ−ヘキシルグリシジルエーテル、２−メチルペンチルグリシジルエーテル、ｎ−オクチルグリシジルエーテル、２−エチルヘキシルグリシジルエーテル、２−メチルオクチルグリシジルエーテル、ｎ−ウンデカングリシジルエーテル、ネオオクタン酸グリシジルエステル、ネオデカン酸グリシジルエステル、フェニルグリシジルエーテル、４−ｓｅｃ−ブチルフェニルグリシジルエーテル等を挙げることができる。
【００１９】
上記の酸性成分反応性添加剤は、各種の酸性成分との反応性に富んだ添加剤であり、加水分解により生成した脂肪酸を消失させる。一方、上記の水・塩酸反応性添加剤は水との反応性が高く、混入水分を捕捉する。従って、酸性成分反応性添加剤と水・塩酸反応性添加剤とを含有させることにより、両者の相乗作用により、基油の加水分解反応がより一層抑制される。
【００２０】
上記の酸性成分反応性添加剤は、冷凍機油組成物中に０．１〜１重量％、また水・塩酸反応性添加剤は０．１〜１重量％の割合で添加されることが好ましい。両添加剤とも、含有量が前記の量未満では基油の加水分解反応の進行を抑制する効果が不十分となり、一方１重量％を超える場合には増分に見合う効果が得られず不経済であるばかりでなく、配管の目詰まりを起こす等冷媒の循環に悪影響を及ぼすようになる。
【００２１】
尚、本発明の冷凍機油組成物には本発明の効果を損なわない範囲で従来公知の添加剤、例えば摩耗防止材、極圧剤、酸化防止剤、消泡剤等を添加してもよい。
【００２２】
また、上記したように酸性成分反応性添加剤及び水・塩酸反応性添加剤は、両者の相乗効果により基油の加水分解反応の進行をより効果的に抑制するため、両者の含有量は略同量であることが特に好ましい。酸性成分反応性添加剤の含有量と水・塩酸反応性添加剤の含有量との差が大きくなるほど、両者のバランスが崩れて加水分解反応の抑制効果が十分に発揮されなくなる。
【００２３】
本発明の冷凍機油組成物は、それぞれ上記に挙げたアルコールと一般式(I)で表される酸残基を有する脂肪酸とを、常法に従って脱水反応させてエステル油を作製しておき、このエステル油に酸性成分反応性添加剤と水・塩酸反応性添加剤とを所定量添加して得られる。従って、特別な装置や複雑な工程、過酷な製造条件等を要することなく、冷凍機油組成物が得られる。
【００２４】
【実施例】
以下に実施例を挙げて更に本発明を明確にするが、本発明はこれにより何ら制限されるものではない。
【００２５】
（基油の調製）
表１に示すように、オレフィンとしてヘキセン（Ｃ６）及びオクテン（Ｃ８）を用い、一酸化炭素及びフッ化水素と反応させて脂肪酸を作製した。得られた脂肪酸は何れも、一般式(I)におけるＲ1、Ｒ2、Ｒ3が総炭素数４〜２２の範囲で分岐した脂肪酸残基を有する種々の脂肪酸の混合物であった。次いで、この脂肪酸混合物とＮＰＧ、ＴＭＰ又はＰＥとを脱水反応させて基油Ａ、基油Ｂ及び基油Ｃを調製した。
【００２６】
また、比較のために、表２に示すように、アルコール及び脂肪酸の種類を変えて脱水反応させて基油Ｄ及び基油Ｅを調製した。更に、ＰＡＧを基油Ｆとし、鉱物油を基油Ｇとして用いた。
【００２７】
上記の各基油について、粘度グレード、密度、色、粘度（４０℃、１００℃）、引火点、流動点、全酸化、含有水分、破壊電圧、体積抵抗率、Ｐ−１３４ａ臨界溶解温度、銅板腐食、ＦＡＬＥＸ焼付荷重及び耐湿性について測定した。測定結果を表１及び表２に示すが、本発明に従う基油Ａ、基油Ｂ及び基油Ｃは何れも他の基油と比較して、Ｒ−１３４ａとの相溶性も良好で、また体積抵抗率が高く、吸湿性も低くなっていることが分かる。
【００２８】
【表１】
【表２】
また、基油Ａ〜基油Ｅについて、シールドチューブ法に従い加水分解性試験を行った。即ち、基油１０ｇに対して２ｇのＨＦＣ−１３４ａを混合した混合油と、触媒としての鉄、銅及びアルミニウムと、１０００ｐｐｍの水とを封入したチューブを、１７５℃の恒温槽に２０日間または４０日間入れた後、チューブを開封して混合油及び触媒を取り出し、混合油の色及び全酸価、触媒の状態、沈殿物の有無を測定または観察した。結果を表３に示す。
【００３１】
【表３】
表３から、本発明に従う基油Ａ、基油Ｂ及び基油Ｃは、何れも全酸価が調製時の値と変わらず、基油の加水分解に起因する脂肪酸の発生が抑えられていることが分かる。これに対して基油Ｄ及び基油Ｅは、全酸価が高く、しかも保持期間が長い程その値が大きくなっており、基油の加水分解が起こっている。また、４０日程度の保持期間では、全ての基油において触媒の状態に変化は見られず、沈殿物も生成していないが、基油Ｄ及び基油Ｅは全酸価の増加度合から見て、４０日以降の比較的早い時期に触媒の変化や沈殿物の生成が起こることが予測される。
【００３３】
（実施例１〜４、比較例１〜３）
有機脂肪酸成分反応性添加剤として４．４−ジメチルジフェニルカルボンジイミドを、水・塩酸反応性添加剤として２−エチルヘキシルグリシジルエーテルを用い、上記の基油Ａにそれぞれ配合量を変えて添加して冷凍機油組成物を調製した。そして、各冷凍機油組成物について、シールドチューブ法に従い加水分解性試験を行った。即ち、冷凍機油組成物５ｇに対して１ｇのＲ−４１０Ａを混合した混合油と、触媒としての鉄、銅及びアルミニウムと、１０００ｐｐｍの水とを封入したチューブを、２００℃の恒温槽に２８日間入れた後、チューブを開封して混合油及び触媒を取り出し、混合油の色及び全酸価、触媒の状態、沈殿物の有無を測定または観察した。結果を表４に示す。
【００３４】
【表４】
表４から、本発明に従い、有機脂肪酸成分反応性添加剤を０．１〜１重量％、水・塩酸反応性添加剤油を０．１〜１重量％含有する冷凍機油組成物は、何れも全酸価が調製時の値と変わらず（実施例２〜４）、もしくは増加しても０．０３〔ｍｇＫＯＨ／ｇ〕と低く、加水分解に起因する脂肪酸の発生が抑えられていることが分かる。これに対して有機脂肪酸成分反応性添加剤と水・塩酸反応性添加剤の何れか一方しか含有しない冷凍機油組成物（比較例１、比較例２）、並びに有機脂肪酸成分反応性添加剤及び水・塩酸反応性添加剤油の含有量が本発明の範囲外である冷凍機油組成物（比較例３）では、全酸価が高く、加水分解が起こっている。また、実施例及び比較例ともに、触媒の状態に変化は見られず、沈殿物も生成していないが、比較例の冷凍機油組成物では全酸価から見て、２８日以降の比較的早い時期に触媒の変化や沈殿物の生成が起こることが予測される。
【００３６】
【発明の効果】
以上説明してきたように、本発明によれば、特定のエステル油を基油とし、これに有機脂肪酸成分反応性添加剤と水・塩酸反応性添加剤とを両方、特定量配合させることにより、基油の加水分解反応に対する耐性がより高められ、金属の腐食や冷却不足、絶縁抵抗の低下を招くことが無く、経時安定性に優れたＨＦＣ系冷媒用冷凍機油組成物が提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a refrigerating machine oil composition added to an HFC (hydrofluorocarbon) refrigerant.
[0002]
[Prior art]
Fluorocarbons such as R-12 and R-22, which have been widely used as refrigerants for electric refrigerators, air conditioners and the like, are subject to regulation due to environmental problems such as ozone layer destruction. Today, HFC refrigerants (for example, HFC-134a, R-407C, R410A, etc.).
[0003]
On the other hand, electric refrigerators, air conditioners, etc., usually use a refrigerant in which a refrigerating machine oil composition comprising various additives and a base oil made of lubricating oil is added to lubricate sliding parts of a compressor. ing. Therefore, the base oil of the refrigerating machine oil composition needs to be compatible with the HFC fluorocarbon, and polyalkylene glycol (PAG) and polyol ester (POE) are generally used. For example, in US Pat. No. 4,755,316 and JP-A-2-276881, a PAG refrigerator oil composition having excellent compatibility with 1,1,1,2-tetrafluoroethane is disclosed in US Pat. No. 5,021,179. The specification describes a PEO refrigerating machine oil composition excellent in compatibility with 1,1,1,2-tetrafluoroethane.
[0004]
[Problems to be solved by the invention]
The refrigerating machine oil is normally used for a long time without replacement after being filled with the refrigerant. However, in the refrigerating machine oil composition based on POE and PAG, including the refrigerating machine oil compositions listed above, POE and PAG are easily affected by mixed water and process agents, etc. Hydrolysis causes fatty acids to cause various problems such as corrosion of pipes and the like, poor cooling, and a decrease in insulation resistance, which is not sufficient in terms of stability over time.
[0005]
The present invention has been made in view of such a situation, and suppresses decomposition of the base oil, and does not cause metal corrosion, lack of cooling, or deterioration of insulation, and is an HFC system having excellent temporal stability. It aims at providing the refrigerating machine oil composition for refrigerant | coolants.
[0006]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides a refrigerating machine oil composition added to an HFC refrigerant, comprising a neopentyl alcohol and a fatty acid having an acid residue represented by the following general formula (I): An ester oil composed of a dehydration reaction product is used as a base oil, and 0.1 to 1 wt% of an acidic component reactive additive composed of a compound represented by the following general formula (II) is added to the base oil. A refrigerating machine oil composition comprising 0.1 to 1% by weight of a water / hydrochloric acid reactive additive comprising a compound represented by formula (1) is provided.
[0007]
[Chemical formula 2]
In the general formula (I), R 1 , R 2 and R 3 are each a linear or branched alkyl group represented by C n H 2n + 1 (n = 1 to 21) or a hydrogen atom, and R 1 , R 2 , R 3 are not two or more hydrogen atoms at the same time, and the total sum of n including R 1 , R 2 , R 3 is 4 or more and 22 or less. In the general formula (II), R 4 and R 5 are each an aromatic group or an alkyl-substituted aromatic group, and may be the same or different from each other. In the general formula (III), R 6 is a linear or branched alkyl group having 4 to 20 carbon atoms, a linear or branched acyl group, or an alkyl-substituted aromatic group.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
In the refrigerator oil composition of the present invention, the base oil is an ester oil obtained by dehydrating a neopentyl alcohol and a fatty acid having an acid residue represented by the following general formula (I).
[0010]
[Chemical 3]
In the general formula (I), R 1 , R 2 and R 3 are each a linear or branched alkyl group represented by C n H 2n + 1 (n = 1 to 21) or a hydrogen atom, Two or more of R 1 , R 2 , and R 3 are not hydrogen atoms at the same time, and the total number of carbon atoms (n) including R 1 , R 2 , and R 3 is 4 or more and 22 or less.
[0012]
The fatty acid having an acid residue represented by the general formula (I) can be easily obtained by reacting an olefin, carbon monoxide, and hydrogen fluoride. In this reaction, most of the olefin is decomposed into various fragments having a carbon number smaller than the original carbon number, and these fragments are bonded as R 1 , R 2 and R 3 in the general formula (I). Therefore, the fatty acid having an acid residue represented by the general formula (I) is a mixture of fatty acids in which alkyl groups having various carbon numbers or hydrogen atoms are randomly bonded as R 1 , R 2 and R 3 . In addition, it is not preferable to use an olefin having an excessively large number of carbon atoms so that the total number of carbon atoms of R 1 , R 2 and R 3 does not exceed 22, for example, butylene, pentene, hexene, octene, etc. Can be preferably used. Moreover, these olefins can also be used by mixing those having different carbon numbers as required.
[0013]
On the other hand, neopentyl glycol is preferably neopentyl glycol, trimethylolpropane, pentaerythritol or dipentaerythritol, and these can be used alone or in combination.
[0014]
The ester oil obtained by dehydrating the neopentyl alcohol and the fatty acid having an acid residue represented by the general formula (I) has a secondary α carbon adjacent to the C = O bond on the acid residue side. Alternatively, it has a tertiary α-branch structure, and the β carbon that forms an O—C bond on the alcohol residue side also has a branched structure. As a result, the ester bond portion involved in the hydrolysis reaction is shielded by both branched structures, so that the ester oil itself has a molecular structure that hardly causes the hydrolysis reaction. Therefore, when R 1 , R 2 , R 3 do not satisfy the above definition in the acid residue represented by the general formula (I), such a shielding effect cannot be obtained. Further, this shielding effect is highest when the acid residue represented by the general formula (I) has a tertiary branched structure.
[0015]
To the base oil composed of the above ester oil, an organic fatty acid component reactive additive composed of a compound represented by the following general formula (II) and a water / hydrochloric acid reactive additive composed of a compound represented by the following general formula (III) Agent is added.
[0016]
[Formula 4]
In the general formula (II), R 4 and R 5 are each an aromatic group or an alkyl-substituted aromatic group, and may be the same or different from each other. Examples of the organic fatty acid component reactive additive represented by the general formula (II) include 4,4-dimethyldiphenylcarbodiimide, 2,6,2,6-tetramethyldiphenylcarbodiimide, 3.5.3.5- Tetramethyldiphenylcarbodiimide, 4,4-diisopropyldiphenylcarbodiimide, 2,6,2,6-tetraisopropyldiphenylcarbodiimide, 3.5.3.5-tetraisopropyldiphenylcarbodiimide, 4,4-ditertiarybutyldiphenylcarbodiimide, 2 , 6,2,6-tetratertiarybutyldiphenylcarbodiimide, 3,5,3,5-tetratertiarybutyldiphenylcarbodiimide, diphenylcarbodiimide and the like.
[0018]
In the general formula (III), R 6 is a linear or branched alkyl group having 4 to 20 carbon atoms, a linear or branched acyl group, or an alkyl-substituted aromatic group. Examples of the water / hydrochloric acid reactive additive represented by the general formula (III) include n-butyl glycidyl ether, isobutyl glycidyl ether, n-hexyl glycidyl ether, 2-methylpentyl glycidyl ether, n-octyl glycidyl ether, Examples include 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, n-undecane glycidyl ether, neooctanoic acid glycidyl ester, neodecanoic acid glycidyl ester, phenyl glycidyl ether, and 4-sec-butylphenyl glycidyl ether.
[0019]
The above acidic component reactive additive is an additive rich in reactivity with various acidic components and eliminates fatty acids generated by hydrolysis. On the other hand, the above-mentioned water / hydrochloric acid reactive additive is highly reactive with water and traps mixed water. Therefore, by including the acidic component reactive additive and the water / hydrochloric acid reactive additive, the hydrolysis reaction of the base oil is further suppressed by the synergistic action of both.
[0020]
The acidic component reactive additive is preferably added to the refrigerating machine oil composition in an amount of 0.1 to 1% by weight, and the water / hydrochloric acid reactive additive is preferably added in an amount of 0.1 to 1% by weight. In both additives, if the content is less than the above-mentioned amount, the effect of suppressing the progress of the hydrolysis reaction of the base oil becomes insufficient. On the other hand, if it exceeds 1% by weight, an effect commensurate with the increment cannot be obtained and it is uneconomical. Not only does this affect the circulation of the refrigerant, it also causes clogging of the piping.
[0021]
In the refrigerating machine oil composition of the present invention, conventionally known additives such as antiwear agents, extreme pressure agents, antioxidants, antifoaming agents and the like may be added to the extent that the effects of the present invention are not impaired.
[0022]
In addition, as described above, the acidic component reactive additive and the water / hydrochloric acid reactive additive more effectively suppress the progress of the hydrolysis reaction of the base oil due to the synergistic effect of both, so the content of both is approximately The same amount is particularly preferred. As the difference between the content of the acidic component reactive additive and the content of the water / hydrochloric acid reactive additive increases, the balance between the two is lost and the effect of suppressing the hydrolysis reaction is not sufficiently exhibited.
[0023]
The refrigerating machine oil composition of the present invention is an ester oil prepared by dehydrating each of the alcohols listed above and a fatty acid having an acid residue represented by the general formula (I) according to a conventional method. It is obtained by adding a predetermined amount of an acidic component reactive additive and water / hydrochloric acid reactive additive to ester oil. Therefore, a refrigerating machine oil composition can be obtained without requiring special equipment, complicated processes, harsh production conditions, and the like.
[0024]
【Example】
EXAMPLES The present invention will be further clarified by examples below, but the present invention is not limited thereby.
[0025]
(Preparation of base oil)
As shown in Table 1, hexene (C6) and octene (C8) were used as olefins and reacted with carbon monoxide and hydrogen fluoride to produce fatty acids. All the fatty acids obtained were a mixture of various fatty acids having fatty acid residues in which R 1 , R 2 and R 3 in the general formula (I) were branched in the range of 4 to 22 carbon atoms. Subsequently, base oil A, base oil B, and base oil C were prepared by dehydrating this fatty acid mixture with NPG, TMP, or PE.
[0026]
For comparison, as shown in Table 2, base oil D and base oil E were prepared by dehydration reaction by changing the types of alcohol and fatty acid. Further, PAG was used as base oil F, and mineral oil was used as base oil G.
[0027]
For each of the above base oils, viscosity grade, density, color, viscosity (40 ° C., 100 ° C.), flash point, pour point, total oxidation, moisture content, breakdown voltage, volume resistivity, P-134a critical melting temperature, copper plate Corrosion, FALEB seizure load and moisture resistance were measured. The measurement results are shown in Tables 1 and 2, and the base oil A, base oil B, and base oil C according to the present invention are all more compatible with R-134a than other base oils. It can be seen that the volume resistivity is high and the hygroscopicity is also low.
[0028]
[Table 1]
[Table 2]
Moreover, about the base oil A-base oil E, the hydrolyzability test was done according to the shield tube method. That is, a tube in which 2 g of HFC-134a is mixed with 10 g of base oil, iron, copper, and aluminum as catalysts and 1000 ppm of water is sealed in a thermostatic bath at 175 ° C. for 20 days or 40 After putting in for a day, the tube was opened, the mixed oil and the catalyst were taken out, and the color and total acid value of the mixed oil, the state of the catalyst, and the presence or absence of precipitates were measured or observed. The results are shown in Table 3.
[0031]
[Table 3]
From Table 3, base oil A, base oil B, and base oil C according to the present invention all have the same total acid value as the value at the time of preparation, and the generation of fatty acids due to hydrolysis of the base oil is suppressed. I understand that. On the other hand, the base oil D and the base oil E have a high total acid value, and the longer the retention period, the larger the value, and hydrolysis of the base oil occurs. Further, in the retention period of about 40 days, no change was observed in the state of the catalyst in all base oils, and no precipitate was formed, but the base oil D and the base oil E were seen from the degree of increase in the total acid value. Thus, it is predicted that catalyst changes and precipitate formation will occur relatively early after the 40th day.
[0033]
(Examples 1-4, Comparative Examples 1-3)
Freeze by adding 4.4-dimethyldiphenylcarbondiimide as an organic fatty acid component reactive additive and 2-ethylhexyl glycidyl ether as a water / hydrochloric acid reactive additive and changing the blending amount to the above base oil A. A machine oil composition was prepared. And about each refrigerator oil composition, the hydrolyzability test was done according to the shield tube method. That is, a mixed oil in which 1 g of R-410A is mixed with 5 g of a refrigerating machine oil composition, a tube containing iron, copper and aluminum as a catalyst, and 1000 ppm of water, is placed in a constant temperature bath at 200 ° C. for 28 days. After the addition, the tube was opened to remove the mixed oil and the catalyst, and the color and total acid value of the mixed oil, the state of the catalyst, and the presence or absence of precipitates were measured or observed. The results are shown in Table 4.
[0034]
[Table 4]
From Table 4, in accordance with the present invention, any refrigerating machine oil composition containing 0.1 to 1% by weight of organic fatty acid component reactive additive and 0.1 to 1% by weight of water / hydrochloric acid reactive additive oil The total acid value is not different from the value at the time of preparation (Examples 2 to 4), or even if it is increased, it is as low as 0.03 [mg KOH / g], and the generation of fatty acids due to hydrolysis is suppressed. I understand. In contrast, a refrigerating machine oil composition (Comparative Example 1, Comparative Example 2) containing only one of an organic fatty acid component reactive additive and a water / hydrochloric acid reactive additive, and an organic fatty acid component reactive additive and water In the refrigerator oil composition (Comparative Example 3) in which the content of the hydrochloric acid reactive additive oil is outside the range of the present invention, the total acid value is high and hydrolysis occurs. Further, in both the examples and the comparative examples, no change was observed in the state of the catalyst and no precipitate was formed, but the comparative refrigeration oil composition was relatively early after 28 days in terms of the total acid value. It is anticipated that catalyst changes and precipitate formation will occur over time.
[0036]
【The invention's effect】
As described above, according to the present invention, a specific ester oil is used as a base oil, and by adding a specific amount of both an organic fatty acid component reactive additive and a water / hydrochloric acid reactive additive, Provided is a refrigerating machine oil composition for HFC-based refrigerants that is more resistant to hydrolysis of base oil, does not cause metal corrosion, lack of cooling, and lower insulation resistance, and has excellent temporal stability.
Claims (2)
ネオペンチル型アルコールと下記一般式(I)で表される酸残基を有する脂肪酸との脱水反応生成物からなるエステル油を基油とし、前記基油に下記一般式（II)で表される化合物からなる酸性成分反応性添加剤を０．１〜１重量％、下記一般式（III)で表される化合物からなる水・塩酸反応性添加剤を０．１〜１重量％の割合で含有することを特徴とする冷凍機油組成物。
また、一般式（II)において、Ｒ4、Ｒ5はそれぞれ芳香族基もしくはアルキル置換芳香族基であり、同一であっても互いに異なっていてもよい。
また、一般式（III)において、Ｒ6は炭素数４〜２０の直鎖または分岐のアルキル基、直鎖または分岐のアシル基、アルキル置換芳香族基である。A refrigerating machine oil composition added to an HFC refrigerant,
A compound represented by the following general formula (II) based on an ester oil comprising a dehydration reaction product of a neopentyl alcohol and a fatty acid having an acid residue represented by the following general formula (I): 0.1 to 1% by weight of an acidic component reactive additive comprising: 0.1 to 1% by weight of a water / hydrochloric acid reactive additive comprising a compound represented by the following general formula (III) A refrigerating machine oil composition characterized by the above.
In the general formula (II), R 4 and R 5 are each an aromatic group or an alkyl-substituted aromatic group, and may be the same or different from each other.
In the general formula (III), R 6 is a linear or branched alkyl group having 4 to 20 carbon atoms, a linear or branched acyl group, or an alkyl-substituted aromatic group.
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