JP4558185B2 - Refrigerator oil composition - Google Patents

Description

［式（１５）中、Ｒ¹⁰〜Ｒ¹³は同一でも異なっていてもよく、それぞれ水素原子、炭素数１〜１０の１価の炭化水素基又は下記一般式（１６）：
【化２】

（式（１６）中、Ｒ¹⁴及びＲ¹⁵は同一でも異なっていてもよく、それぞれ水素原子、炭素数１〜１０の１価の炭化水素基又は炭素数２〜２０のアルコキシアルキル基を表し、Ｒ¹⁶は炭素数２〜５のアルキレン基、アルキル基を置換基として有する総炭素数２〜５の置換アルキレン基又はアルコキシアルキル基を置換基として有する総炭素数４〜１０の置換アルキレン基を表し、ｐは０〜２０の整数を表し、Ｒ¹⁷は炭素数１〜１０の１価の炭化水素基を表す）
で表される基を表し、Ｒ¹⁰〜Ｒ¹³の少なくとも１つが一般式（１６）で表される基である］
で表される構成単位を少なくとも１個有するポリオキシアルキレングリコール誘導体を使用することができる。
【００９７】
上記式（１５）中、Ｒ¹⁰〜Ｒ¹³はそれぞれ水素原子、炭素数１〜１０の１価の炭化水素基又は上記一般式（１６）で表わされる基を表すが、炭素数１〜１０の１価の炭化水素基としては、具体的には、炭素数１〜１０の直鎖状又は分枝状のアルキル基、炭素数２〜１０の直鎖状又は分枝状のアルケニル基、炭素数５〜１０のシクロアルキル基又はアルキルシクロアルキル基、炭素数６〜１０のアリール基又はアルキルアリール基、炭素数７〜１０のアリールアルキル基等があげられる。これらの１価の炭化水素基の中でも、炭素数６以下の１価の炭化水素基、特に炭素数３以下のアルキル基、具体的にはメチル基、エチル基、ｎ−プロピル基、イソプロピル基が好ましい。
【００９８】
また、上記一般式（１６）において、Ｒ¹⁴及びＲ¹⁵はそれぞれ水素原子、炭素数１〜１０の１価の炭化水素基又は炭素数２〜２０のアルコキシアルキル基を表すが、これらの中でも炭素数３以下のアルキル基又は炭素数６以下のアルコキシアルキル基が好ましい。炭素数３以下のアルキル基としては、具体的にはメチル基、エチル基、ｎ−プロピル基、イソプロピル基等が挙げられる。また、炭素数２〜６のアルコキシアルキル基としては、具体的には、メトキシメチル基、エトキシメチル基、ｎ−プロポキシメチル基、イソプロポキシメチル基、ｎ−ブトキシメチル基、イソブトキシメチル基、ｓｅｃ−ブトキシメチル基、ｔｅｒｔ−ブトキシメチル基、ペントキシメチル基（すべての異性体を含む）、メトキシエチル基（すべての異性体を含む）、エトキシエチル基（すべての異性体を含む）、プロポキシエチル基（すべての異性体を含む）、ブトキシエチル基（すべての異性体を含む）、メトキシプロピル基（すべての異性体を含む）、エトキシプロピル基（すべての異性体を含む）、プロポキシプロピル基（すべての異性体を含む）、メトキシブチル基（すべての異性体を含む）、エトキシブチル基（すべての異性体を含む）、メトキシペンチル基（すべての異性体を含む）等が挙げられる。
【００９９】
上記一般式（１２）中、Ｒ¹⁶は炭素数２〜５のアルキレン基、アルキル基を置換基として有する総炭素数２〜５の置換アルキレン基又はアルコキシアルキル基を置換基として有する総炭素数４〜１０の置換アルキレン基、好ましくは炭素数２〜４のアルキレン基及び総炭素数６以下の置換エチレン基を表す。炭素数２〜４のアルキレン基としては、具体的には、エチレン基、プロピレン基、ブチレン基等が挙げられる。また、総炭素数６以下の置換エチレン基としては、具体的には１−（メトキシメチル）エチレン基、２−（メトキシメチル）エチレン基、１−（メトキシエチル）エチレン基、２−（メトキシエチル）エチレン基、１−（エトキシメチル）エチレン基、２−（エトキシメチル）エチレン基、１−メトキシメチル−２−メチルエチレン基、１，１−ビス（メトキシメチル）エチレン基、２，２−ビス（メトキシメチル）エチレン基、１，２−ビス（メトキシメチル）エチレン基、１−メチル−２−メトキシメチルエチレン基、１−メトキシメチル−２−メチルエチレン基、１−エチル−２−メトキシメチルエチレン基、１−メトキシメチル−２−エチルエチレン基、１−メチル−２−エトキシメチルエチレン基、１−エトキシメチル−２−メチルエチレン基、１−メチル−２−メトキシエチルエチレン基、１−メトキシエチル−２−メチルエチレン基等が挙げられる。
【０１００】
上記一般式（１６）中、Ｒ¹⁷は炭素数の１〜１０の１価の炭化水素基を表すが、当該炭化水素基としては、具体的には、炭素数１〜１０の直鎖状又は分枝状のアルキル基、炭素数２〜１０の直鎖状又は分枝状のアルケニル基、炭素数５〜１０のシクロアルキル基又はアルキルシクロアルキル基、炭素数６〜１０のアリール基又はアルキルアリール基、炭素数７〜１０のアリールアルキル基等が挙げられる。これらの中でも、炭素数６以下の１価の炭化水素基が好ましく、特に炭素数３以下のアルキル基、具体的にはメチル基、エチル基、ｎ−プロピル基、イソプロピル基が好ましい。
【０１０１】
上記一般式（１５）中、Ｒ¹⁰〜Ｒ¹³のうち少なくとも１つは上記一般式（１６）で表される基である。特に、Ｒ¹⁰又はＲ¹²はのいずれか一つが上記一般式（１６）で表される基であり、且つＲ¹⁰又はＲ¹²の残りの一つ及びＲ¹¹、Ｒ¹³がそれぞれ水素原子又は炭素数１〜１０の１価の炭化水素基であることが好ましい。
【０１０２】
本発明において好ましく用いられる、上記一般式（１５）で表される構成単位を有するポリオキシアルキレングリコールは、一般式（１５）で表される構成単位のみからなる単独重合体；一般式（１５）で表され且つ構造の異なる２種以上の構成単位からなる共重合体、並びに一般式（１５）で表される構成単位と他の構成単位、例えば下記一般式（１７）：
【化３】

［式（１７）中、Ｒ¹⁸〜Ｒ²¹は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜３のアルキル基を示す］
で表される構成単位からなる共重合体の三種類に大別することができる。上記単独重合体の好適例は、一般式（１５）で表される構成単位Ａを１〜２００個有するとともに、末端基がそれぞれ水酸基、炭素数１〜１０のアシルオキシ基、炭素数１〜１０のアルコキシ基あるいはアリーロキシ基からなるものを挙げることができる。一方、共重合体の好適例は、一般式（１５）で表される二種類の構成単位Ａ、Ｂをそれぞれ１〜２００個有するか、あるいは一般式（１５）で表される構成単位Ａを１〜２００個と一般式（１５）で表される構成単位Ｃを１〜２００個有するとともに、末端基がそれぞれ水酸基、炭素数１〜１０のアシルオキシ基、炭素数１〜１０のアルコキシ基あるいはアリーロキシ基からなるものを挙げることができる。これらの共重合体は、構成単位Ａと構成単位Ｂ(あるいは構成単位Ｃ)との交互共重合、ランダム共重合、ブロック共重合体あるいは構成単位Ａの主鎖に構成単位Ｂがグラフト結合したグラフト共重合体のいずれの重合形式であってもよい。
【０１０３】
また、本発明において用いられるポリビニルエーテルとしては、例えば下記一般式（１８）：
【化４】

［式（１８）中、Ｒ²²〜Ｒ²⁴は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜８の炭化水素基を表し、Ｒ²⁵は炭素数１〜１０の２価の炭化水素基又は炭素数２〜２０の２価のエーテル結合酸素含有炭化水素基を表し、Ｒ²⁶は炭素数１〜２０の炭化水素基を表し、ｑはその平均値が０〜１０の数を表し、Ｒ²²〜Ｒ²⁶は構成単位毎に同一であってもそれぞれ異なっていてもよく、また一般式（１８）で表される構成単位が複数のＲ²⁵Ｏを有するとき、複数のＲ²⁵Ｏは同一でも異なっていてもよい］
で表される構成単位を有するポリビニルエーテル系化合物が挙げられる。
【０１０４】
また、上記一般式（１８）で表される構成単位と、下記一般式（１９）：
【化５】

［式（１９）中、Ｒ²⁷〜Ｒ³⁰は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜２０の炭化水素基を表し、Ｒ²⁷〜Ｒ³⁰は構成単位毎に同一でも異なっていてもよい］
で表される構成単位とを有するブロック共重合体又はランダム共重合体からなるポリビニルエーテル系化合物も使用することができる。
【０１０５】
上記一般式（１８）中のＲ²²〜Ｒ²⁴はそれぞれ水素原子又は炭素数１〜８の炭化水素基（好ましくは１〜４の炭化水素基）を表し、それらは互いに同一でも異なっていてもよい。かかる炭化水素基としては、具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、各種ペンチル基、各種ヘキシル基、各種ヘプチル基、各種オクチル基等のアルキル基；シクロペンチル基、シクロヘキシル基、各種メチルシクロヘキシル基、各種エチルシクロヘキシル基、各種ジメチルシクロヘキシル基などのシクロアルキル基、フェニル基、各種メチルフェニル基、各種エチルフェニル基、各種ジメチルフェニル基等のアリール基；ベンジル基、各種フェニルエチル基、各種メチルベンジル基等のアリールアルキル基、等が挙げられるが、Ｒ²²〜Ｒ²⁴としては素原子が好ましい。
【０１０６】
一方、上記一般式（１８）中のＲ²⁵は、炭素数１〜１０（好ましくは２〜１０）の２価の炭化水素基又は炭素数２〜２０の２価のエーテル結合酸素含有炭化水素基を表す。炭素数１〜１０の２価の炭化水素基としては、具体的には、メチレン基、エチレン基、フェニルエチレン基、１，２−プロピレン基、２−フェニル−１，２−プロピレン基、１，３−プロピレン基、各種ブチレン基、各種ペンチレン基、各種ヘキシレン基、各種ヘプチレン基、各種オクチレン基、各種ノニレン基、各種デシレン基等の２価の脂肪族鎖式炭化水素基；シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、ジメチルシクロヘキサン、プロピルシクロヘキサン等の脂環式炭化水素に２個の結合部位を有する脂環式炭化水素基；各種フェニレン基、各種メチルフェニレン基、各種エチルフェニレン基、各種ジメチルフェニレン基、各種ナフチレン基等の２価の芳香族炭化水素基；トルエン、キシレン、エチルベンゼン等のアルキル芳香族炭化水素のアルキル基部分と芳香族部分にそれぞれ１価の結合部位を有するアルキル芳香族炭化水素基；キシレン、ジエチルベンゼン等のポリアルキル芳香族炭化水素のアルキル基部分に結合部位を有するアルキル芳香族炭化水素基、等が挙げられる。これらの中でも炭素数２〜４の脂肪族鎖式炭化水素基が特に好ましい。
【０１０７】
また、炭素数２〜２０の２価のエーテル結合酸素含有炭化水素基の具体例としては、メトキシメチレン基、メトキシエチレン基、メトキシメチルエチレン基、１，１−ビスメトキシメチルエチレン基、１，２−ビスメトキシメチルエチレン基、エトキシメチルエチレン基、（２−メトキシエトキシ）メチルエチレン基、（１−メチル−２−メトキシ）メチルエチレン基等を好ましく挙げることができる。なお、上記一般式（１８）中のｑはＲ²⁵Ｏの繰り返し数を表し、その平均値が０〜１０、好ましくは０〜５の範囲の数である。同一の構成単位内にＲ²⁵Ｏが複数ある場合には、複数のＲ²⁵Ｏは同一でも異なっていてもよい。
【０１０８】
さらに、上記一般式（１８）におけるＲ²⁶は炭素数１〜２０、好ましくは１〜１０の炭化水素基を表すが、かかる炭化水素基としては、具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、各種ペンチル基、各種ヘキシル基、各種ヘプチル基、各種オクチル基、各種ノニル基、各種デシル基等のアルキル基；シクロペンチル基、シクロヘキシル基、各種メチルシクロヘキシル基、各種エチルシクロヘキシル基、各種プロピルシクロヘキシル基、各種ジメチルシクロヘキシル基等のシクロアルキル基；フェニル基、各種メチルフェニル基、各種エチルフェニル基、各種ジメチルフェニル基、各種プロピルフェニル基、各種トリメチルフェニル基、各種ブチルフェニル基、各種ナフチル基等のアリール基；ベンジル基、各種フェニルエチル基、各種メチルベンジル基、各種フェニルプロピル基、各種フェニルブチル基等のアリールアルキル基、等が挙げられる。なお、Ｒ²²〜Ｒ²⁶は構成単位毎に同一であっても異なっていてもよい。
【０１０９】
本発明にかかるポリビニルエーテルが上記一般式（１８）で表される構成単位のみからなる単独重合体である場合、その炭素／酸素モル比は４．２〜７．０の範囲にあるものが好ましい。当該モル比が４．２未満であると吸湿性が過剰に高くなり、また、７．０を超えると冷媒との相溶性が低下する傾向にある。
【０１１０】
上記一般式（１９）において、Ｒ²⁷〜Ｒ³⁰は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜２０の炭化水素基を表す。ここで、炭素数１〜２０の炭化水素基としては、上記一般式（１８）中のＲ²⁶の説明において例示された炭化水素基が挙げられる。なお、Ｒ²⁷〜Ｒ³⁰は構成単位毎に同一であってもそれぞれ異なっていてもよい。
【０１１１】
本発明にかかるポリビニルエーテルが一般式（１８）で表される構成単位と一般式（１９）で表される構成単位とを有するブロック共重合体又はランダム共重合体である場合、その炭素／酸素モル比は４．２〜７．０の範囲にあることが好ましい。当該モル比が４．２未満であると吸湿性が過剰に高くなり、また、７．０を超えると冷媒との相溶性が低下する傾向にある。
【０１１２】
さらに本発明においては、上記一般式（１８）で表される構成単位のみからなる単独重合体と、上記一般式（１８）で表される構成単位と上記一般式（１９）で表される構成単位とからなるブロック共重合体又はランダム共重合体と、の混合物も使用することができる。これらの単独重合体及び共重合体は、それぞれ対応するビニルエーテル系モノマーの重合、及び対応するオレフィン性二重結合を有する炭化水素モノマーと対応するビニルエーテル系モノマーとの共重合により製造することができる。
【０１１３】
本発明に用いられるポリビニルエーテルとしては、その末端構造のうちの一方が、下記一般式（２０）又は（２１）：
【化６】

［式（２０）中、Ｒ³¹〜Ｒ³³は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜８の炭化水素基を表し、Ｒ³⁴は炭素数１〜１０の２価の炭化水素基又は炭素数２〜２０の２価のエーテル結合酸素含有炭化水素基を表し、Ｒ³⁵は炭素数１〜２０の炭化水素基を表し、ｒはその平均値が０〜１０の数を表し、上記一般式（２０）で表される末端構造が複数のＲ³⁴Ｏを有するとき、複数のＲ³⁴Ｏはそれぞれ同一でも異なっていてもよい］
【０１１４】
【化７】

［式（２１）中、Ｒ³⁶〜Ｒ³⁹は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜２０の炭化水素基を表す］
で表されるものであり、且つ他方が下記一般式（２２）又は（２３）：
【化８】

［式（２２）中、Ｒ⁴⁰〜Ｒ⁴²は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜８の炭化水素基を表し、Ｒ⁴³は炭素数１〜１０の２価の炭化水素基又は炭素数２〜２０の２価のエーテル結合酸素含有炭化水素基を表し、Ｒ⁴⁴は炭素数１〜２０の炭化水素基を表し、ｓはその平均値が０〜１０の数を表し、上記一般式（２２）で表される末端構造が複数のＲ⁴³Ｏを有するとき、複数のＲ⁴³Ｏはそれぞれ同一でも異なっていてもよい］
【０１１５】
【化９】

［式（２３）中、Ｒ⁴⁵〜Ｒ⁴⁸は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜２０の炭化水素基を表す］
で表される構造を有するもの；及び
その末端の一方が、上記一般式（２０）又は（２１）で表され、且つ他方が下記一般式（２４）：
【化１０】

［式（２４）中、Ｒ⁴⁹〜Ｒ⁵¹は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜８の炭化水素基を表す］
で表される構造を有するものが好ましい。このようなポリビニルエーテルの中でも、次に挙げるものが特に好適である。
（１）末端の一方が一般式（２０）又は（２１）で表され、他方が一般式（２２）又は（２３）で表される構造を有しており、一般式（１８）におけるＲ²²〜Ｒ²⁴がいずれも水素原子であり、ｑが０〜４の数であり、Ｒ²⁵が炭素数２〜４の２価の炭化水素基であり、且つＲ²⁶が炭素数１〜２０の炭化水素基であるもの；
（２）一般式（１８）で表される構成単位のみを有するものであって、その末端の一方が一般式（２０）で表され、他方が一般式（２１）で表される構造を有しており、一般式（１８）におけるＲ²²〜Ｒ²⁴がいずれも水素原子であり、ｑが０〜４の数であり、Ｒ²⁵が炭素数２〜４の２価の炭化水素基であり、且つＲ²⁶が炭素数１〜２０の炭化水素基であるもの；
（３）末端の一方が一般式（２０）又は（２１）で表され、他方が一般式（２２）で表される構造を有しており、一般式（１８）におけるＲ²²〜Ｒ²⁴がいずれも水素原子であり、ｑが０〜４の数であり、Ｒ²⁵が炭素数２〜４の２価の炭化水素基であり、且つＲ²⁶が炭素数１〜２０の炭化水素基であるもの；
（４）一般式（１８）で表される構成単位のみを有するものであって、その末端の一方が一般式（２０）で表され、他方が一般式（２３）で表される構造を有しており、一般式（１８）におけるＲ²²〜Ｒ²⁴がいずれも水素原子であり、ｑが０〜４の数であり、Ｒ²⁵が炭素数２〜４の２価の炭化水素基であり、且つＲ²⁶が炭素数１〜２０の炭化水素基であるもの。
【０１１６】
また、本発明においては、上記一般式（１８）で表される構成単位を有し、その末端の一方が一般式（２０）で表され、かつ他方が下記一般式（２５）：
【化１１】

［式（２５）中、Ｒ⁵²〜Ｒ⁵⁴は同一でも異なっていてもよく、それぞれ水素原子又は炭素数１〜８の炭化水素基を表し、Ｒ⁵⁵及びＲ⁵⁷は同一でも異なっていてもよく、それぞれ炭素数２〜１０の２価の炭化水素基を表し、Ｒ⁵⁶及びＲ⁵⁸は同一でも異なっていてもよく、それぞれ炭素数１〜１０の炭化水素基を表し、ｔ及びｕは同一でも異なっていてもよく、それぞれその平均値が０〜１０の数を表し、上記一般式（２５）で表される末端構造が複数のＲ⁵⁵Ｏ又はＲ⁵⁷Ｏを有するとき、複数のＲ⁵⁵Ｏ又はＲ⁵⁷Ｏは同一であっても異なっていてもよい］
で表される構造を有するポリビニルエーテル系化合物も使用することができる。
【０１１７】
さらに、本発明においては、下記一般式（２６）又は（２７）：
【化１２】

［式（２６）中、Ｒ⁵⁹は炭素数１〜８の炭化水素基を示す］
【０１１８】
【化１３】

［式（２７）中、Ｒ⁶⁰は炭素数１〜８の炭化水素基を示す］
で表される構成単位からなり、かつ重量平均分子量が３００〜５,０００であって、末端の一方が下記一般式（２８）又は（２９）：
【化１４】

［式（２８）中、Ｒ⁶¹は炭素数１〜３のアルキル基を表し、Ｒ⁶²は炭素数１〜８の炭化水素基を示す］
【０１１９】
【化１５】

［式（２９）中、Ｒ⁶³は炭素数１〜８の炭化水素基を示す］
で表される構造を有するアルキルビニルエーテルの単独重合物又は共重合物からなるポリビニルエーテル系化合物も使用することができる。
【０１２０】
本発明においては、上記した鉱油及び合成油からなる群より選ばれる１種のみを単独で用いてもよく、２種以上を組み合わせて用いてもよいが、上記の鉱油及び合成油の中でも、ＨＦＣ系冷媒を使用する場合、カーエアコン等の開放型圧縮機用としてポリオキシアルキレングリコール、エステル、ポリビニルエーテル、冷蔵庫や空調機器等の密閉型圧縮機用としてアルキルベンゼン、エステル、ポリビニルエーテルが好ましく用いられる。
【０１２１】
本発明の冷凍機油の耐摩耗性、耐荷重性をさらに改良するために、リン酸エステル、酸性リン酸エステル、酸性リン酸エステルのアミン塩、塩素化リン酸エステル、亜リン酸エステル及びフォスフォロチオネートからなる群より選ばれる少なくとも１種のリン化合物を配合することが好ましい。これらのリン化合物は、リン酸、亜リン酸又はチオリン酸とアルカノール、ポリエーテル型アルコールとのエステルあるいはその誘導体である。
【０１２２】
かかるリン化合物のうち、リン酸エステルとしては、トリブチルホスフェート、トリペンチルホスフェート、トリヘキシルホスフェート、トリヘプチルホスフェート、トリオクチルホスフェート、トリノニルホスフェート、トリデシルホスフェート、トリウンデシルホスフェート、トリドデシルホスフェート、トリトリデシルホスフェート、トリテトラデシルホスフェート、トリペンタデシルホスフェート、トリヘキサデシルホスフェート、トリヘプタデシルホスフェート、トリオクタデシルホスフェート、トリオレイルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート等；
酸性リン酸エステルとしては、モノブチルアシッドホスフェート、モノペンチルアシッドホスフェート、モノヘキシルアシッドホスフェート、モノヘプチルアシッドホスフェート、モノオクチルアシッドホスフェート、モノノニルアシッドホスフェート、モノデシルアシッドホスフェート、モノウンデシルアシッドホスフェート、モノドデシルアシッドホスフェート、モノトリデシルアシッドホスフェート、モノテトラデシルアシッドホスフェート、モノペンタデシルアシッドホスフェート、モノヘキサデシルアシッドホスフェート、モノヘプタデシルアシッドホスフェート、モノオクタデシルアシッドホスフェート、モノオレイルアシッドホスフェート、ジブチルアシッドホスフェート、ジペンチルアシッドホスフェート、ジヘキシルアシッドホスフェート、ジヘプチルアシッドホスフェート、ジオクチルアシッドホスフェート、ジノニルアシッドホスフェート、ジデシルアシッドホスフェート、ジウンデシルアシッドホスフェート、ジドデシルアシッドホスフェート、ジトリデシルアシッドホスフェート、ジテトラデシルアシッドホスフェート、ジペンタデシルアシッドホスフェート、ジヘキサデシルアシッドホスフェート、ジヘプタデシルアシッドホスフェート、ジオクタデシルアシッドホスフェート、ジオレイルアシッドホスフェート等；
酸性リン酸エステルのアミン塩としては、前記酸性リン酸エステルのメチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ペンチルアミン、ヘキシルアミン、ヘプチルアミン、オクチルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミン、ジペンチルアミン、ジヘキシルアミン、ジヘプチルアミン、ジオクチルアミン、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミン、トリペンチルアミン、トリヘキシルアミン、トリヘプチルアミン、トリオクチルアミン等のアミンとの塩等；
塩素化リン酸エステルとしては、トリス・ジクロロプロピルホスフェート、トリス・クロロエチルホスフェート、トリス・クロロフェニルホスフェート、ポリオキシアルキレン・ビス［ジ（クロロアルキル）］ホスフェート等；
亜リン酸エステルとしては、ジブチルホスファイト、ジペンチルホスファイト、ジヘ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、ジフェニルホスファイト、ジクレジルホスファイト、トリブチルホスファイト、トリペンチルホスファイト、トリヘキシルホスファイト、トリヘプチルホスファイト、トリオクチルホスファイト、トリノニルホスファイト、トリデシルホスファイト、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、トリオレイルホスファイト、トリフェニルホスファイト、トリクレジルホスファイト等；
フォスフォロチオネートとしては、トリブチルフォスフォロチオネート、トリペンチルフォスフォロチオネート、トリヘキシルフォスフォロチオネート、トリヘプチルフォスフォロチオネート、トリオクチルフォスフォロチオネート、トリノニルフォスフォロチオネート、トリデシルフォスフォロチオネート、トリウンデシルフォスフォロチオネート、トリドデシルフォスフォロチオネート、トリトリデシルフォスフォロチオネート、トリテトラデシルフォスフォロチオネート、トリペンタデシルフォスフォロチオネート、トリヘキサデシルフォスフォロチオネート、トリヘプタデシルフォスフォロチオネート、トリオクタデシルフォスフォロチオネート、トリオレイルフォスフォロチオネート、トリフェニルフォスフォロチオネート、トリクレジルフォスフォロチオネート、トリキシレニルフォスフォロチオネート、クレジルジフェニルフォスフォロチオネート、キシレニルジフェニルフォスフォロチオネート、トリス（ｎ−プロピルフェニル）フォスフォロチオネート、トリス（イソプロピルフェニル）フォスフォロチオネート、トリス（ｎ−ブチルフェニル）フォスフォロチオネート、トリス（イソブチルフェニル）フォスフォロチオネート、トリス（ｓ−ブチルフェニル）フォスフォロチオネート、トリス（ｔ−ブチルフェニル）フォスフォロチオネート等、が挙げられる。また、これらの混合物も使用できる。
【０１２３】
これらのリン化合物を本発明の冷凍機油組成物に配合する場合、その配合量は特に制限されないが、通常、冷凍機油組成物全量基準（基油と全配合添加剤の合計量基準）でその含有量が０．０１〜５．０質量％、より好ましくは０．０２〜３．０質量％となるような量のリン化合物を配合することが望ましい。
【０１２４】
また、本発明の冷凍機油において、その熱・加水分解安定性をさらに改良するために、
（１）フェニルグリシジルエーテル型エポキシ化合物
（２）アルキルグリシジルエーテル型エポキシ化合物
（３）グリシジルエステル型エポキシ化合物
（４）アリルオキシラン化合物
（５）アルキルオキシラン化合物
（６）脂環式エポキシ化合物
（７）エポキシ化脂肪酸モノエステル
（８）エポキシ化植物油
からなる群より選ばれる少なくとも１種のエポキシ化合物を配合することが好ましい。
【０１２５】
（１）フェニルグリシジルエーテル型エポキシ化合物としては、具体的には、フェニルグリシジルエーテル又はアルキルフェニルグリシジルエーテルが例示できる。ここでいうアルキルフェニルグリシジルエーテルとは、炭素数１〜１３のアルキル基を１〜３個有するものが挙げられ、中でも炭素数４〜１０のアルキル基を１個有するもの、例えばｎ−ブチルフェニルグリシジルエーテル、ｉ−ブチルフェニルグリシジルエーテル、ｓｅｃ−ブチルフェニルグリシジルエーテル、ｔｅｒｔ−ブチルフェニルグリシジルエーテル、ペンチルフェニルグリシジルエーテル、ヘキシルフェニルグリシジルエーテル、ヘプチルフェニルグリシジルエーテル、オクチルフェニルグリシジルエーテル、ノニルフェニルグリシジルエーテル、デシルフェニルグリシジルエーテル等が好ましいものとして例示できる。
【０１２６】
（２）アルキルグリシジルエーテル型エポキシ化合物としては、具体的には、デシルグリシジルエーテル、ウンデシルグリシジルエーテル、ドデシルグリシジルエーテル、トリデシルグリシジルエーテル、テトラデシ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、ネオペンチルグリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、ソルビトールポリグリシジルエーテル、ポリアルキレングリコールモノグリシジルエーテル、ポリアルキレングリコールジグリシジルエーテル等が例示できる。
【０１２７】
（３）グリシジルエステル型エポキシ化合物としては、具体的には下記一般式（３０）：
【化１６】

（上記式（３０）中、Ｒは炭素数１〜１８の炭化水素基を表す）
で表される化合物が挙げられる。
【０１２８】
上記式（３０）中、Ｒは炭素数１〜１８の炭化水素基を表すが、このような炭化水素基としては、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数５〜７のシクロアルキル基、炭素数６〜１８のアルキルシクロアルキル基、炭素数６〜１０のアリール基、炭素数７〜１８のアルキルアリール基、炭素数７〜１８のアリールアルキル基等が挙げられる。この中でも、炭素数５〜１５のアルキル基、炭素数２〜１５のアルケニル基、フェニル基及び炭素数１〜４のアルキル基を有するアルキルフェニル基が好ましい。
【０１２９】
グリシジルエステル型エポキシ化合物の中でも、好ましいものとしては、具体的には例えば、グリシジル−２，２−ジメチルオクタノエート、グリシジルベンゾエート、グリシジル−ｔｅｒｔ−ブチルベンゾエート、グリシジルアクリレート、グリシジルメタクリレート等が例示できる。
【０１３０】
（４）アリルオキシラン化合物としては、具体的には、１，２−エポキシスチレン、アルキル−１，２−エポキシスチレン等が例示できる。
【０１３１】
（５）アルキルオキシラン化合物としては、具体的には、１，２−エポキシブタン、１，２−エポキシペンタン、１，２−エポキシヘキサン、１，２−エポキシヘプタン、１，２−エポキシオクタン、１，２−エポキシノナン、１，２−エポキシデカン、１，２−エポキシウンデカン、１，２−エポキシドデカン、１，２−エポキシトリデカン、１，２−エポキシテトラデカン、１，２−エポキシペンタデカン、１，２−エポキシヘキサデカン、１，２−エポキシヘプタデカン、１，１，２−エポキシオクタデカン、２−エポキシノナデカン、１，２−エポキシイコサン等が例示できる。
【０１３２】
（６）脂環式エポキシ化合物としては、下記一般式（３１）：
【化１７】

で表される化合物のように、エポキシ基を構成する炭素原子が直接脂環式環を構成している化合物が挙げられる。
【０１３３】
脂環式エポキシ化合物としては、具体的には、１，２−エポキシシクロヘキサン、１，２−エポキシシクロペンタン、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート、ビス（３，４−エポキシシクロヘキシルメチル）アジペート、エキソ−２，３−エポキシノルボルナン、ビス（３，４−エポキシ−６−メチルシクロヘキシルメチル）アジペート、２−（７−オキサビシクロ［４．１．０］ヘプト−３−イル）−スピロ（１，３−ジオキサン−５，３’−［７］オキサビシクロ［４．１．０］ヘプタン、４−（１’−メチルエポキシエチル）−１，２−エポキシ−２−メチルシクロヘキサン、４−エポキシエチル−１，２−エポキシシクロヘキサン等が例示できる。
【０１３４】
（７）エポキシ化脂肪酸モノエステルとしては、具体的には、エポキシ化された炭素数１２〜２０の脂肪酸と炭素数１〜８のアルコール又はフェノール、アルキルフェノールとのエステル等が例示できる。特にエポキシステアリン酸のブチル、ヘキシル、ベンジル、シクロヘキシル、メトキシエチル、オクチル、フェニル及びブチルフェニルエステルが好ましく用いられる。
【０１３５】
（８）エポキシ化植物油としては、具体的には、大豆油、アマニ油、綿実油等の植物油のエポキシ化合物等が例示できる。
【０１３６】
これらのエポキシ化合物の中でも、より熱・加水分解安定性を向上させることができることから、フェニルグリシジルエーテル型エポキシ化合物、グリシジルエステル型エポキシ化合物、脂環式エポキシ化合物、エポキシ化脂肪酸モノエステルが好ましく、グリシジルエステル型エポキシ化合物、脂環式エポキシ化合物がより好ましい。
【０１３７】
これらのエポキシ化合物を本発明の冷凍機油組成物に配合する場合、その配合量は特に制限されないが、通常、冷凍機油組成物全量基準（基油と全配合添加剤の合計量基準）でその含有量が０．１〜５．０質量％、より好ましくは０．２〜２．０質量％となるような量のエポキシ化合物を配合することが望ましい。
【０１３８】
また、上記リン化合物及びエポキシ化合物を２種以上併用してもよいことは勿論である。
【０１３９】
さらに本発明における冷凍機油組成物に対して、その性能をさらに高めるため、必要に応じて従来より公知の冷凍機油添加剤、例えばジ−ｔｅｒｔ−ブチル−ｐ−クレゾール、ビスフェノールＡ等のフェノール系の酸化防止剤、フェニル−α−ナフチルアミン、Ｎ，Ｎ−ジ（２−ナフチル）−ｐ−フェニレンジアミン等のアミン系の酸化防止剤、ジチオリン酸亜鉛等の摩耗防止剤、塩素化パラフィン、硫黄化合物等の極圧剤、脂肪酸等の油性剤、シリコーン系等の消泡剤、ベンゾトリアゾール等の金属不活性化剤、粘度指数向上剤、流動点降下剤、清浄分散剤等の添加剤を単独で、又は数種類組み合わせて配合することも可能である。これらの添加剤の合計配合量は特に制限されないが、冷凍機油組成物全量基準（基油と全配合添加剤の合計量基準）で好ましくは１０質量％以下、より好ましくは５質量％以下である。
【０１４０】
本発明の冷凍機油組成物の体積抵抗率は特に限定されないが、１．０×１０⁹Ω・ｃｍ以上であることが好ましい。特に、密閉型冷凍機に用いる場合には高い電気絶縁性が必要となる傾向にある。なお、ここでいう体積抵抗率とは、ＪＩＳＣ ２１０１「電気絶縁油試験方法」に準拠して測定した２５℃での値［Ω・ｃｍ］を意味する。
【０１４１】
さらに、本発明の冷凍機油組成物の水分含有量は特に限定されないが、冷凍機油組成物全量基準で好ましくは２００ｐｐｍ以下、より好ましくは１００ｐｐｍ以下、最も好ましくは５０ｐｐｍ以下とすることができる。特に密閉型の冷凍機用に用いる場合には、油の熱・加水分解安定性や電気絶縁性への影響の観点から、水分含有量が少ないことが求められる。
【０１４２】
さらにまた、本発明の冷凍機油組成物の全酸価は特に限定されないが、冷凍機又は配管に用いられている金属への腐食を防止するため、好ましくは０．１ｍｇＫＯＨ／ｇ以下、より好ましくは０．０５ｍｇＫＯＨ／ｇ以下とすることができる。なお、ここでいう全酸価とは、ＪＩＳ Ｋ ２５０１「石油製品及び潤滑油−中和価試験方法」に準拠して測定した値［ｍｇＫＯＨ／ｇ］を意味する。
【０１４３】
さらにまた、本発明の冷凍機油組成物の灰分は特に限定されないが、本発明の冷凍機油組成物の熱・加水分解安定性を高めスラッジ等の発生を抑制するため、好ましくは１００ｐｐｍ以下、より好ましくは５０ｐｐｍ以下とすることができる。なお、本発明において、灰分とは、ＪＩＳ Ｋ ２２７２「原油及び石油製品の灰分並びに硫酸灰分試験方法」に準拠して測定した値［ｐｐｍ］を意味する。
【０１４４】
本発明の冷凍機油組成物を用いる冷凍機に用いられる冷媒は、ＨＦＣ冷媒、パーフルオロエーテル類等の含フッ素エーテル系冷媒、ジメチルエーテル等の非フッ素含有エーテル系冷媒及び二酸化炭素やアンモニア，炭化水素等の自然系冷媒であるが、これらは各々単独で用いてもよいし、２種以上の混合物として用いてもよい。
【０１４５】
ＨＦＣ冷媒としては、炭素数１〜３、好ましくは１〜２のハイドロフルオロカーボンが挙げられる。具体的には例えば、ジフルオロメタン（ＨＦＣ−３２）、トリフルオロメタン（ＨＦＣ−２３）、ペンタフルオロエタン（ＨＦＣ−１２５）、１，１，２，２−テトラフルオロエタン（ＨＦＣ−１３４）、１，１，１，２−テトラフルオロエタン（ＨＦＣ−１３４ａ）、１，１，１−トリフルオロエタン（ＨＦＣ−１４３ａ）、１，１−ジフルオロエタン（ＨＦＣ−１５２ａ）等のＨＦＣ、又はこれらの２種以上の混合物等が挙げられる。これらの冷媒は用途や要求性能に応じて適宜選択されるが、例えばＨＦＣ−３２単独；ＨＦＣ−２３単独；ＨＦＣ−１３４ａ単独；ＨＦＣ−１２５単独；ＨＦＣ−１３４ａ／ＨＦＣ−３２＝６０〜８０質量％／４０〜２０質量％の混合物；ＨＦＣ−３２／ＨＦＣ−１２５＝４０〜７０質量％／６０〜３０質量％の混合物；ＨＦＣ−１２５／ＨＦＣ−１４３ａ＝４０〜６０質量％／６０〜４０質量％の混合物；ＨＦＣ−１３４ａ／ＨＦＣ−３２／ＨＦＣ−１２５＝６０質量％／３０質量％／１０質量％の混合物；ＨＦＣ−１３４ａ／ＨＦＣ−３２／ＨＦＣ−１２５＝４０〜７０質量％／１５〜３５質量％／５〜４０質量％の混合物；ＨＦＣ−１２５／ＨＦＣ−１３４ａ／ＨＦＣ−１４３ａ＝３５〜５５質量％／１〜１５質量％／４０〜６０質量％の混合物等が好ましい例として挙げられる。さらに具体的には、ＨＦＣ−１３４ａ／ＨＦＣ−３２＝７０／３０質量％の混合物；ＨＦＣ−３２／ＨＦＣ−１２５＝６０／４０質量％の混合物；ＨＦＣ−３２／ＨＦＣ−１２５＝５０／５０質量％の混合物（Ｒ４１０Ａ）；ＨＦＣ−３２／ＨＦＣ−１２５＝４５／５５質量％の混合物（Ｒ４１０Ｂ）；ＨＦＣ−１２５／ＨＦＣ−１４３ａ＝５０／５０質量％の混合物（Ｒ５０７Ｃ）；ＨＦＣ−３２／ＨＦＣ−１２５／ＨＦＣ−１３４ａ＝３０／１０／６０質量％の混合物；ＨＦＣ−３２／ＨＦＣ−１２５／ＨＦＣ−１３４ａ＝２３／２５／５２質量％の混合物（Ｒ４０７Ｃ）；ＨＦＣ−３２／ＨＦＣ−１２５／ＨＦＣ−１３４ａ＝２５／１５／６０質量％の混合物（Ｒ４０７Ｅ）；ＨＦＣ−１２５／ＨＦＣ−１３４ａ／ＨＦＣ−１４３ａ＝４４／４／５２質量％の混合物（Ｒ４０４Ａ）等が挙げられる
また、自然系冷媒としては二酸化炭素やアンモニア、炭化水素等が挙げられる。ここで、炭化水素冷媒としては、２５℃、１気圧で気体のものが好ましく用いられる。具体的には炭素数１〜５、好ましくは１〜４のアルカン、シクロアルカン、アルケン又はこれらの混合物である。具体的には例えば、メタン、エチレン、エタン、プロピレン、プロパン、シクロプロパン、ブタン、イソブタン、シクロブタン、メチルシクロプロパン又はこれらの２種以上の混合物等があげられる。これらの中でも、プロパン、ブタン、イソブタン又はこれらの混合物が好ましい。
【０１４６】
本発明の冷凍機油組成物は、通常、冷凍機中においては上述したような冷媒と混合された冷凍機用流体組成物の形で存在している。この流体組成物における冷凍機油と冷媒との配合割合は特に制限されないが、冷媒１００重量部に対して冷凍機油が好ましくは１〜５００重量部、より好ましくは２〜４００重量部である。
【０１４７】
本発明の冷凍機油組成物は、潤滑性、冷媒相溶性、低温流動性、安定性などの要求性能全てをバランスよく十分に満足させるものであり、往復動式あるいは回転式の開放型や半密閉型又は密閉型圧縮機を有する冷凍機器あるいはヒートポンプなどに好適に使用することができる。特に、アルミニウム系部材を用いた冷凍機器に用いた場合には、アルミニウム系部材の摩耗防止性と熱・化学的安定性との双方を高水準で両立することが可能となる。かかる冷凍機器として、より具体的には、自動車用エアコン、除湿器、冷蔵庫、冷凍冷蔵倉庫、自動販売機、ショーケース、化学プラントなどの冷却装置、住宅用エアコン、給湯用ヒートポンプ等が挙げられる。
【０１４８】
【実施例】
以下、実施例及び比較例に基づいて本発明をさらに具体的に説明するが、本発明は以下の実施例に何ら限定されるものではない。
【０１４９】
実施例１〜１２、比較例１〜８
実施例１〜１２及び比較例１〜８においては、それぞれ以下に示す基油及び添加剤を用いて試料油を調製した。各試料油における基油の種類、サルコシン誘導体の種類及び含有量、酸捕捉剤の含有量、リン化合物の含有量、並びに得られた試料油の全酸価を表１に示す。
【０１５０】
（基油）
基油１：ポリプロピレングリコールモノメチルエーテル（数平均分子量：１０００、１００℃における動粘度：１０ｍｍ²／ｓ）
基油２：ビニルエチルエーテルとビニルイソブチルエーテルとのランダム共重合体（ビニルエチルエーテルとビニルイソブチルエーテルとのモル比：７／１、数平均分子量：９００、１００℃における動粘度：８ｍｍ²／ｓ）。
【０１５１】
（添加剤）
サルコシン誘導体１：Ｎ−オレオイルサルコシンメチルエステル
サルコシン誘導体２：Ｎ−オレオイルサルコシンカリウム塩
サルコシン誘導体３：Ｎ−オレオイルサルコシングリセリンモノエステル
サルコシン誘導体４：Ｎ−オレオイルサルコシン
エポキシ化合物：フェニルグリシジルエーテル
リン化合物：トリクレジルホスフェート。
【０１５２】
次に、実施例１〜１２及び比較例１〜８の試料油を用いて以下に示す試験を行った。
【０１５３】
（冷媒雰囲気下での熱・化学的安定性試験）
オートクレーブ中に試料油７０ｇ、冷媒（ＨＦＣ−１３４ａ）３０ｇ及び触媒（１．６ｍｍφ×５０ｍｍの鉄線、銅線、アルミニウム線各３本）を封入して、１７５℃で２週間保持した。その後、試料油から冷媒を除去し、試料油の全酸価を測定した。また、エポキシ化合物を含有する実施例４〜１２及び比較例３、４、７、８の試料油についてはエポキシ化合物の残存率を測定した。得られた結果を表１に示す。
【０１５４】
（潤滑性試験）
ＡＳＴＭ Ｄ２６７０に準拠して、ＦＡＬＥＸ摩耗試験機を用いて、試料油温度８０℃、荷重１５０ｌｂの条件下、冷媒（ＨＦＣ−１３４ａ）を試料油に吹き込みながら１時間の摩耗試験を行った。本試験においては、試験片として、アルミニウム製ピン（Ａ３９０）と鋼製ブロック（ＡＩＳＩ １１３７）とを用い、試験後のピンとブロックとの合計の摩耗量を測定した。得られた結果を表１に示す。
【０１５５】
【表１】

【０１５６】
表１に示した結果から明らかなように、本発明の冷凍機油組成物である実施例１〜１２の試料油においては、熱・化学的安定性試験での全酸価の増加が十分に抑制されていた。また、エポキシ化合物を含有する実施例４〜１２の試料油においては、熱・化学的安定性試験後の酸捕捉剤の残存率が十分に高い値を示した。
さらに、これらの試料油においては、潤滑性試験でのピンとブロックとの摩耗が十分に抑制されていた。これらの結果は、本発明の冷凍機油組成物によって、基油や酸捕捉剤等の劣化を生じることなく、アルミニウム系部材の摩耗を十分に抑制することが可能となることを示唆するものである。
【０１５７】
【発明の効果】
以上説明した通り、本発明の冷凍機油組成物は十分に高い潤滑性と十分に高い熱・化学安定性とを有するものである。したがって、本発明の冷凍機油組成物をアルミニウム系部材を備える冷凍機器に用いた場合に、基油や酸捕捉剤等の劣化を生じることなくアルミニウム系部材の摩耗を十分に抑制することが可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a refrigerator oil composition.
[0002]
[Prior art]
In recent years, due to the ozone depletion problem, CFC (chlorofluorocarbon) and HCFC (hydrochlorofluorocarbon), which have been used as refrigerants in conventional refrigeration equipment, are subject to regulation, and HFC (hydrofluorocarbon) as an alternative refrigerant instead. in use. Furthermore, HFC refrigerants also have problems such as high global warming ability, and the use of natural refrigerants as alternative refrigerants to replace these fluorocarbon refrigerants has been studied.
[0003]
The above-mentioned alternative refrigerant has a lower extreme pressure effect as compared with chlorine-containing refrigerants such as CFC and HCFC, and may be used under high-pressure conditions. Therefore, the refrigerating machine oil used with such an alternative refrigerant is required to have a higher level of performance than that used with a chlorine-containing refrigerant. In particular, in recent years, aluminum-based members have been widely used as materials for refrigeration equipment, and with refrigeration oils blended with conventional anti-wear agents, the refrigeration equipment using aluminum-based members always achieves sufficient wear resistance. I can't.
[0004]
Therefore, methods for improving the wear resistance of aluminum-based members have been studied, and various refrigeration oils have been proposed. For example, JP 2000-282076 A discloses a refrigerating machine oil composition in which organic acids such as N-oleoyl sarcosine are blended.
[0005]
[Problems to be solved by the invention]
However, even in the refrigerating machine oil composition disclosed in the above Japanese Patent Laid-Open No. 2000-282076, the organic acids contained in the refrigerating machine oil composition are subject to oxidative degradation of base oil and other additives and corrosion of metal materials. Therefore, it has not been sufficient to achieve both high wear resistance and thermal / chemical stability of the aluminum-based member at a sufficiently high level. In particular, when an acid scavenger is added to refrigeration oil in order to capture various degraded acids generated in the refrigerant circulation system with the use of refrigeration equipment, the organic acids and the acid scavenger react with each other. As a result, the thermal and chemical stability of the refrigerating machine oil is significantly impaired.
[0006]
The present invention has been made in view of the above-described problems of the prior art, and has a sufficiently high lubricity and a sufficiently high thermal / chemical stability, and is used in a refrigeration apparatus including an aluminum-based member. An object of the present invention is to provide a refrigerating machine oil composition that can sufficiently suppress wear of an aluminum-based member without causing deterioration of a base oil, an acid scavenger and the like.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have used a refrigerating machine oil composition containing a mineral oil and / or synthetic oil as a base oil and a compound having a specific structure. It has been found that wear of the aluminum-based member is sufficiently suppressed and sufficiently high thermal and chemical stability is achieved, and the present invention has been completed.
[0008]
That is, the refrigerating machine oil composition of the present invention uses mineral oil and / or synthetic oil as a base oil and has the following general formulas (1) to (3):
R¹-CO-NR²-(CH₂)_l-COOX (1)
[In formula (1), R¹Represents an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms;²Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 1 to 30 carbon atoms, and l represents an integer of 1 to 4].
[R^Three-CO-NR^Four-(CH₂)_m-COO]_{m '}Y (2)
[In formula (2), R^ThreeRepresents an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms;^FourRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y represents an alkali metal atom or an alkaline earth metal atom, m represents an integer of 1 to 4, and m 'represents an integer of 1 or 2.]
[R^Five-CO-NR⁶-(CH₂)_n-COO]_{n '}-Z- (OH)_{n "}  (3)
[In formula (3), R^FiveRepresents an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms;⁶Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z represents a residue obtained by removing a hydroxyl group from a dihydric or higher polyhydric alcohol, n represents an integer of 1 to 4, and n ′ represents 1 or more. Represents an integer, n ″ represents an integer of 0 or more, and n ′ + n ″ represents the valence of the group represented by Z]
Is contained in an amount of 0.001 to 5 mass% based on the total amount of the composition.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described in detail.
[0010]
The refrigerating machine oil composition of the present invention is based on mineral oil and / or synthetic oil and has the following general formulas (1) to (3):
R¹-CO-NR²-(CH₂)_l-COOX (1)
[In formula (1), R¹Represents an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms;²Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 1 to 30 carbon atoms, and l represents an integer of 1 to 4].
[R^Three-CO-NR^Four-(CH₂)_m-COO]_{m '}Y (2)
[In formula (2), R^ThreeRepresents an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms;^FourRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y represents an alkali metal atom or an alkaline earth metal atom, m represents an integer of 1 to 4, and m 'represents an integer of 1 or 2.]
[R^Five-CO-NR⁶-(CH₂)_n-COO]_{n '}-Z- (OH)_{n "}  (3)
[In formula (3), R^FiveRepresents an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms;⁶Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z represents a residue obtained by removing a hydroxyl group from a dihydric or higher polyhydric alcohol, n represents an integer of 1 to 4, and n ′ represents 1 or more. Represents an integer, n ″ represents an integer of 0 or more, and n ′ + n ″ represents the valence of the group represented by Z]
Is contained in an amount of 0.001 to 5 mass% based on the total amount of the composition.
[0011]
In the general formulas (1) to (3), R¹, R^ThreeAnd R^FiveEach represents an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms. From the viewpoint of lubricity, the alkyl group or alkenyl group having 6 or more carbon atoms is required. Moreover, it is necessary that it is a C30 or less alkyl group or alkenyl group from points, such as refrigerant | coolant solubility. The refrigerant solubility referred to here is a property in which components (compounds represented by the above general formulas (1) to (3)) contained in the refrigeration oil do not precipitate when the refrigerant and the refrigeration oil are mixed. Say.
[0012]
Specific examples of such alkyl and alkenyl groups include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl Group, octadecyl group, nonadecyl group, icosyl group, etc. (these alkyl groups may be linear or branched); hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group , Alkenyl groups such as tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group (these alkenyl groups may be linear or branched, and the position of the double bond Is optional).
[0013]
Among the above alkyl groups and alkenyl groups, an alkyl group or alkenyl group having 7 or more carbon atoms (more preferably 8 or more carbon atoms) is preferable from the viewpoint of lubricity and the like, and 24 or less carbon atoms from the viewpoint of refrigerant solubility. An alkyl group or an alkenyl group (more preferably having 20 or less carbon atoms) is preferred.
[0014]
In the general formulas (1) to (3), R², R^FourAnd R⁶Are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. R², R^FourAnd R⁶Is an alkyl group, it is necessary that it is an alkyl group having 4 or less carbon atoms from the viewpoint of refrigerant solubility, etc., preferably 3 or less carbon atoms, more preferably 2 or less carbon atoms. . As such an alkyl group, specifically, the above R¹, R^ThreeAnd R^FiveAmong the alkyl groups exemplified in the above description, those having a carbon number satisfying the above-described conditions can be mentioned.
[0015]
In general formulas (1) to (3), l, m, and n each represent an integer of 1 to 4. From the viewpoint of refrigerant solubility and the like, each of l, m, and n needs to be an integer of 4 or less, preferably 3 or less, and more preferably 2 or less.
[0016]
In general formula (1), X represents a C1-C30 alkyl group or a C1-C30 alkenyl group. The number of carbon atoms of the alkyl group and alkenyl group represented by X is required to be 30 or less from the viewpoint of refrigerant meltability, etc., preferably 20 or less, and more preferably 10 or less.
[0017]
Specific examples of such an alkyl group or alkenyl group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. (These alkyl groups may be linear or branched); alkenyl groups such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl (these alkenyl groups) May be linear or branched, and the position of the double bond is arbitrary). Moreover, it is preferable that it is an alkyl group from points, such as being excellent in thermal stability.
[0018]
In the general formula (2), Y represents an alkali metal atom or an alkaline earth metal atom. Specific examples of the alkali metal atom and alkaline earth metal atom include sodium, potassium, magnesium, calcium and the like. Among these, alkali metals are preferable from the viewpoint of improving lubricity.
[0019]
In general formula (2), m ′ represents an integer of 1 or 2, m ′ is 1 when Y is an alkali metal, and m ′ is 2 when Y is an alkaline earth metal. .
[0020]
In the general formula (3), Z represents a residue excluding a hydroxyl group of a dihydric or higher polyhydric alcohol. Specific examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-octanediol, 2 such as 1,8-octanediol, isoprene glycol, 3-methyl-1,5-pentanediol, sorbite, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, dimer diol, etc. Hydric alcohol; glycerin, 2- (hydroxymethyl) -1,3-propanediol, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol 2-methyl-2,3,4-butanetri 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4 -Trihydric alcohols such as dimethyl-2,3,4-pentanetriol, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, trimethylolpropane; pentaerythritol, erythritol, 1, 2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin, sorbitan Tetrahydric alcohols such as adonitol, arabitol, xylitol, triglycerin, etc .; dipentaerythritol, sol Examples include hexavalent alcohols such as tall, mannitol, iditol, inositol, dulcitol, talose, and allose; octavalent alcohols such as sucrose; polyglycerin or dehydration condensates thereof; and the group represented by Z And a residue obtained by removing a hydroxyl group from the polyhydric alcohol.
[0021]
In the general formula (3), n ′ is an integer of 1 or more, n ″ is an integer of 0 or more, and n ′ + n ″ is the valence of Z (the number of hydroxyl groups of a polyhydric alcohol having 2 or more valences). It is. That is, the group represented by Z is such that all the hydroxyl groups of the polyhydric alcohol are R^Five-CO-NR⁶-(CH₂)_nIt may be substituted with a group represented by —COO—, or may be substituted with only a part of the hydroxyl group.
[0022]
In the present invention, one of the compounds represented by the general formulas (1) to (3) may be used alone, or two or more may be used in combination. Among the compounds represented by (1) to (3), it is preferable to contain at least one compound of the compounds represented by the general formula (1) or (2).
[0023]
The content of the compound represented by the general formulas (1) to (3) in the refrigerating machine oil composition of the present invention needs to be 5% by mass or less, preferably 2% by mass based on the total amount of the composition. Hereinafter, it is more preferably 1% by mass or less. Even if the content of the compounds represented by the above general formulas (1) to (3) exceeds 5% by mass, no further improvement in lubricity corresponding to the content is observed, and the refrigerant solubility is poor. It will be enough.
[0024]
The content of the compounds represented by the general formulas (1) to (3) needs to be 0.001% by mass or more based on the total amount of the composition, preferably 0.003% by mass or more, More preferably, it is 0.005 mass% or more. When the content of the compounds represented by the general formulas (1) to (3) is less than 0.001% by mass, the lubricity becomes insufficient.
[0025]
In the present invention, the compounds represented by the general formulas (1) to (3) are blended in a base oil composed of mineral oil and / or synthetic oil described later.
[0026]
Here, as the mineral oil, for example, with respect to the lubricating oil fraction obtained by atmospheric distillation and vacuum distillation of paraffin-based crude oil, intermediate-based crude oil or naphthenic-based crude oil, solvent removal, solvent extraction, Examples include paraffinic mineral oils or naphthenic mineral oils obtained by applying a suitable combination of one or two or more purification means of hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment. .
[0027]
Among these mineral oils, it is preferable to use highly refined mineral oil (hereinafter referred to as “highly refined mineral oil”) from the viewpoint of superior thermal stability. Specific examples of highly refined mineral oils include distillate oil obtained by atmospheric distillation of paraffinic crude oil, intermediate crude oil or naphthenic crude oil, or by distilling residual oil of atmospheric distillation under reduced pressure according to a conventional method. Refined oil obtained by refining; deep dewaxed oil obtained by further deep dewaxing after refining; hydrotreated oil obtained by hydrotreating, and the like.
[0028]
The purification method in the purification step is not particularly limited, and a conventionally known method can be used. For example, (a) hydrogenation treatment, (b) dewaxing treatment (solvent dewaxing or hydrogenation) Dewaxing), (c) Solvent extraction treatment, (d) Alkali washing or sulfuric acid washing treatment, (e) Clay clay treatment alone or in combination of two or more in an appropriate order Is mentioned. It is also effective to repeat any one of the processes (a) to (e) in a plurality of stages.
More specifically, (i) a method of hydrotreating the distillate, or a method of performing an alkali washing or sulfuric acid washing treatment after the hydrogenation treatment; (ii) dehydrating the distillate oil after the hydrogenation treatment. A method of wax treatment; (iii) a method of subjecting the distillate to solvent extraction and then hydrotreating; (iv) subjecting the distillate to a two-stage or three-stage hydrotreatment, or subsequent alkali washing or sulfuric acid (V) A method of dewaxing again to obtain a deep dewaxed oil after the above-described treatments (i) to (iv).
[0029]
Among highly refined mineral oils obtained by the above refining method, naphthenic mineral oils and mineral oils obtained by deep dewaxing are preferred from the viewpoints of low temperature fluidity and no wax precipitation at low temperatures. This deep dewaxing process is usually performed by a solvent dewaxing process under severe conditions, a catalytic dewaxing process using a zeolite catalyst, or the like.
[0030]
Further, the non-aromatic unsaturation (unsaturation) of such highly refined mineral oil is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.1% by mass. % Or less. When the non-aromatic unsaturated content exceeds 10% by mass, sludge is likely to be generated, and as a result, the expansion mechanism such as a capillary constituting the refrigerant circulation system tends to be blocked.
[0031]
On the other hand, synthetic oils used in the present invention include hydrocarbon oils such as olefin polymers, naphthalene compounds, alkylbenzenes; esters, polyoxyalkylene glycols, polyvinyl ethers, ketones, polyphenyl ethers, silicones, polysiloxanes, perfluoros. Examples thereof include oxygen-containing synthetic oils such as ether.
[0032]
Examples of the olefin polymer according to the present invention include those obtained by polymerizing olefins having 2 to 12 carbon atoms and those obtained by hydrogenating a compound obtained by the polymerization, such as polybutene, polyisobutene, and carbon number 5 ˜12 α-olefin oligomers (polyα olefins), ethylene-propylene copolymers, and hydrogenated products thereof are preferably used.
[0033]
The production method of the olefin polymer is not particularly limited, and can be produced by various known methods. For example, poly α-olefin is produced by using α-olefin produced from ethylene as a raw material and treating it with a known polymerization method such as Ziegler catalyst method, radical polymerization method, aluminum chloride method, boron fluoride method and the like. .
[0034]
The naphthalene compound according to the present invention is not particularly limited as long as it has a naphthalene skeleton, but it has 1 to 4 alkyl groups having 1 to 10 carbon atoms and is alkylated from the viewpoint of excellent compatibility with the refrigerant. Those having 1 to 10 carbon atoms in total are preferred, those having 1 to 3 alkyl groups having 1 to 8 carbon atoms, and those having 3 to 8 carbon atoms in total are more preferred.
[0035]
Specific examples of the alkyl group having 1 to 10 carbon atoms that the naphthalene compound has include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a linear or branched butyl group, a linear or branched group. A branched pentyl group, a linear or branched hexyl group, a linear or branched heptyl group, a linear or branched octyl group, a linear or branched nonyl group, Examples thereof include a linear or branched decyl group.
[0036]
In addition, when using a naphthalene compound, the compound of a single structure may be used independently, and 2 or more types of the compounds from which a structure differs may be used in combination.
[0037]
Moreover, the manufacturing method in particular of the said naphthalene compound is not restrict | limited, It can manufacture with a various well-known method. Examples of this include, for example, hydrocarbon halides having 1 to 10 carbon atoms, olefins having 2 to 10 carbon atoms, or styrenes having 8 to 10 carbon atoms, sulfuric acid, phosphoric acid, silicotungstic acid, hydrofluoric acid, etc. And a method of adding to naphthalene in the presence of an acid catalyst such as Friedel-Crafts catalyst which is a solid acidic substance such as mineral acid, acidic clay and activated clay, or a metal halide such as aluminum chloride and zinc chloride.
[0038]
Although it does not specifically limit as alkylbenzene concerning this invention, From the point which is excellent in compatibility with a refrigerant | coolant, it has 1-4 C1-C40 alkyl groups, and the total carbon number of an alkyl group is 1-40. Some are preferable, and those having 1 to 4 alkyl groups having 1 to 30 carbon atoms and having 3 to 30 carbon atoms in total are more preferable.
[0039]
Specific examples of the alkyl group having 1 to 40 carbon atoms that the alkylbenzene has include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a linear or branched butyl group, a linear or branched group. Pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, straight Linear or branched decyl group, linear or branched undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched Tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched heptadecyl group, linear or branched octadecyl group, linear -Like or branched nonadecyl group, linear or branched icosyl group, linear or branched Straight chain or branched docosyl group, linear or branched tricosyl group, linear or branched tetracosyl group, linear or branched pentacosyl group, straight chain Linear or branched hexacosyl group, linear or branched heptacosyl group, linear or branched octacosyl group, linear or branched nonacosyl group, linear or branched Triacontyl group, linear or branched hentriacontyl group, linear or branched dotriacontyl group, linear or branched tritriacontyl group, linear or branched tetra Triacontyl group, linear or branched pentatriacontyl group, linear or branched hexatriacontyl group, linear or branched heptatriacontyl group, linear Or branched octatriacontyl group, linear or branched Nona triacontyl group, such as straight or branched tetracontyl group (including all isomers).
[0040]
The alkyl group may be linear or branched, but linear alkylbenzene is preferred from the viewpoint of compatibility with the organic material used in the refrigerant circulation system. On the other hand, branched alkyl groups are preferable from the viewpoint of refrigerant compatibility, thermal stability, lubricity, etc., and branched alkyls derived from oligomers of olefins such as propylene, butene and isobutylene are particularly preferable from the viewpoint of availability. Groups are more preferred.
[0041]
In addition, when using alkylbenzene, the compound of a single structure may be used independently, and 2 or more types of the compounds from which a structure differs may be used in combination.
[0042]
Although the manufacturing method of the said alkylbenzene is arbitrary and is not limited at all, For example, it can manufacture by the synthesis method shown below.
[0043]
Specific examples of the aromatic compound used as a raw material include benzene, toluene, xylene, ethylbenzene, methylethylbenzene, diethylbenzene, and mixtures thereof. Further, as the alkylating agent, a linear or branched olefin having 6 to 40 carbon atoms obtained by polymerization of lower monoolefin (preferably propylene) such as ethylene, propylene, butene, isobutylene; wax, heavy oil, C6-C40 linear or branched olefins obtained by pyrolysis of petroleum fractions, polyethylene, polypropylene, etc .; n-paraffins are separated from petroleum fractions such as kerosene, light oil, etc. It is possible to use a linear olefin having 9 to 40 carbon atoms, a mixture of these, and the like obtained by converting into a carbon atom.
[0044]
In addition, when the aromatic compound and the alkylating agent are reacted, Friedel-Crafts type catalysts such as aluminum chloride and zinc chloride, sulfuric acid, phosphoric acid, silicotungstic acid, hydrofluoric acid, activated clay, etc. Conventionally known alkylation catalysts such as acidic catalysts can be used.
[0045]
Examples of the ester according to the present invention include aromatic esters, dibasic acid esters, polyol esters, complex esters, carbonate esters, and mixtures thereof.
[0046]
As such aromatic ester, 1 to 6 valent, preferably 1 to 4 valent, more preferably 1 to 3 valent aromatic carboxylic acid, and C 1 to 18, preferably 1 to 12 aliphatic alcohol. Examples include esters. Specific examples of the monovalent to hexavalent aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and mixtures thereof. Further, the aliphatic alcohol having 1 to 18 carbon atoms may be linear or branched, and specifically, methanol, ethanol, linear or branched propanol, Linear or branched butanol, linear or branched pentanol, linear or branched hexanol, linear or branched heptanol, linear or branched octanol , Linear or branched nonanol, linear or branched decanol, linear or branched undecanol, linear or branched dodecanol, linear or branched tridecanol Linear or branched tetradecanol, linear or branched pentadecanol, linear or branched hexadecanol, linear or branched heptadecanol, straight Chain or branched octadecanol and these Mixtures thereof, and the like.
[0047]
Specific examples of the aromatic ester obtained by using the aromatic compound and the aliphatic alcohol include dibutyl phthalate, di (2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, and didodecyl phthalate. , Ditridecyl phthalate, tributyl trimellitic acid, tri (2-ethylhexyl) trimellitic acid, trinonyl trimellitic acid, tridecyl trimellitic acid, tridodecyl trimellitic acid, and tritridecyl trimellitic acid. Of course, when a divalent or higher valent aromatic carboxylic acid is used, it may be a simple ester composed of one kind of aliphatic alcohol, or a complex ester composed of two or more kinds of aliphatic alcohol. May be.
[0048]
Examples of the dibasic acid ester according to the present invention include carbon such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, and 4-cyclohexene-1,2-dicarboxylic acid. A chain or cyclic aliphatic dibasic acid of 5 to 10 and methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecane Ester with linear or branched monohydric alcohol having 1 to 15 carbon atoms, such as diol, and a mixture thereof are preferably used. More specifically, ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, Ditridecylua Pete, di2-ethylhexyl sebacate, diester of 1,2-cyclohexanedicarboxylic acid and monohydric alcohol having 4 to 9 carbon atoms, 4-cyclohexene-1,2-dicarboxylic acid and monohydric alcohol having 4 to 9 carbon atoms And diesters thereof and mixtures thereof.
[0049]
Moreover, as a polyol ester concerning this invention, the ester of the polyol which has 3-20 diol or a hydroxyl group, and a C6-C20 fatty acid is used preferably. Specific examples of the diol include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, , 5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3 -Propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecane Diol etc. are mentioned. Specific examples of the polyol include trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol), tri- ( Pentaerythritol), glycerin, polyglycerin (2-20 mer of glycerin), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, polyvalent alcohols such as adonitol, arabitol, xylitol, mannitol, xylose Arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gel Chianosu, sugars and their partial etherification such as melezitose, and methyl glucoside (glycosides) and the like. Among these, as the polyol, neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, di- (pentaerythritol), tri Hindered alcohols such as-(pentaerythritol) are preferred.
[0050]
In the fatty acid used in the polyol ester according to the present invention, the carbon number thereof is not particularly limited, but those having 1 to 24 carbon atoms are usually used. Among the fatty acids having 1 to 24 carbon atoms, those having 3 or more carbon atoms are preferable from the viewpoint of lubricity, those having 4 or more carbon atoms are more preferable, those having 5 or more carbon atoms are further preferable, and those having 10 or more carbon atoms. Is particularly preferred. Moreover, from a compatibility point with a refrigerant | coolant, a C18 or less thing is preferable, a C12 or less thing is more preferable, and a C9 or less thing is further more preferable.
[0051]
The fatty acid may be either a linear fatty acid or a branched fatty acid, but a linear fatty acid is preferable from the viewpoint of lubricity, and a branched fatty acid is preferable from the viewpoint of hydrolysis stability. . Furthermore, the fatty acid may be either a saturated fatty acid or an unsaturated fatty acid.
[0052]
As the fatty acid used in the present invention, specifically, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, Examples include heptadecanoic acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, oleic acid, etc. These fatty acids may be either linear fatty acids or branched fatty acids, and the α carbon atom is a quaternary carbon atom. It may be a fatty acid (neo acid). Among these, valeric acid (n-pentanoic acid), caproic acid (n-hexanoic acid), enanthic acid (n-heptanoic acid), caprylic acid (n-octanoic acid), pelargonic acid (n-nonanoic acid), caprin Acid (n-decanoic acid), oleic acid (cis-9-octadecenoic acid), isopentanoic acid (3-methylbutanoic acid), 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid and 3,5,5 5-Trimethylhexanoic acid is preferably used.
[0053]
In addition, as long as it has two or more ester groups, the polyol ester according to the present invention may be a partial ester in which some of the hydroxyl groups of the polyol remain without being esterified. May be an esterified complete ester, or a mixture of a partial ester and a complete ester, but is preferably a complete ester.
[0054]
The complex ester according to the present invention is an ester of a fatty acid and a dibasic acid, a monohydric alcohol and a polyol, and the fatty acid, dibasic acid, monohydric alcohol and polyol include the dibasic acid ester and polyol. The fatty acids, dibasic acids, monohydric alcohols and polyols exemplified in the ester description can be used.
[0055]
Further, the carbonate ester according to the present invention has the following formula (4):
-O-CO-O- (4)
It is a compound which has the carbonate ester bond represented by these. In addition, the number of carbonate ester bonds represented by the above formula (4) may be one per molecule or two or more.
[0056]
As alcohol which comprises carbonate ester, the monohydric alcohol illustrated by the description of the said dibasic acid ester and polyol ester, a polyol, etc., and what added polyglycol to polyglycol and a polyol can be used. Moreover, you may use the compound obtained from a carbonic acid and a fatty acid and / or a dibasic acid.
[0057]
As a matter of course, when an ester is used, a compound having a single structure may be used alone, or two or more compounds having different structures may be used in combination.
[0058]
Among the above esters, dibasic acid ester, polyol ester, and carbonate ester are preferable because of excellent compatibility with the refrigerant.
[0059]
Furthermore, among dibasic acid esters, alicyclic dicarboxylic acid esters such as 1,2-cyclohexanedicarboxylic acid and 4-cyclohexene-1,2-dicarboxylic acid are compatible with refrigerants, and are stable in heat and hydrolysis. From the point of view, it is more preferable.
[0060]
Specific examples of the dibasic acid ester preferably used in the present invention include at least one monohydric alcohol selected from the group consisting of butanol, pentanol, hexanol, heptanol, octanol and nonanol, and 1,2-cyclohexanedicarboxylic acid. , Dibasic acid esters obtained from at least one dibasic acid selected from the group consisting of 4-cyclohexene-1,2-dicarboxylic acid, and mixtures thereof.
[0061]
In the dibasic acid ester according to the present invention, the low-temperature characteristics of the refrigerating machine oil composition and the compatibility with the refrigerant tend to be improved, so that there are two or more monohydric alcohols constituting the dibasic acid ester. It is preferable. The dibasic acid ester composed of two or more monohydric alcohols is a mixture of two or more esters of a dibasic acid and one alcohol, and a dibasic acid and two or more mixed alcohols. These esters are included.
[0062]
Among polyol esters, since they are more excellent in hydrolytic stability, neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), penta More preferred are esters of hindered alcohols such as erythritol, di- (pentaerythritol), tri- (pentaerythritol), more preferred are esters of neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane and pentaerythritol, The ester of pentaerythritol is most preferred because it is particularly excellent in compatibility with the refrigerant and hydrolytic stability.
[0063]
Specific examples of the polyol ester preferably used in the present invention include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, From the group consisting of at least one fatty acid selected from the group consisting of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid, and neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane and pentaerythritol. Examples include diesters, triesters, tetraesters and mixtures thereof obtained from at least one selected alcohol.
[0064]
In the polyol ester concerning this invention, since the low temperature characteristic of a refrigerating machine oil composition and the compatibility with a refrigerant | coolant tend to improve, it is preferable that the fatty acid which comprises a polyol ester is 2 or more types. The polyol ester composed of two or more fatty acids includes a mixture of two or more esters of polyol and one fatty acid, and an ester of a polyol and two or more mixed fatty acids. .
[0065]
Among the carbonic acid esters, the following general formula (5):
(X¹O)_b-B- [O- (A¹O)_c-CO-O- (A²O)_d-Y¹]_a  (5)
[In Formula (5), X¹Is a hydrogen atom, an alkyl group, a cycloalkyl group or the following general formula (6):
Y²-(OA^Three)_e-(6)
(In formula (6), Y²Represents a hydrogen atom, an alkyl group or a cycloalkyl group, and A^ThreeRepresents an alkylene group having 2 to 4 carbon atoms, and e represents an integer of 1 to 50)
Represents a group represented by¹And A²May be the same or different and each represents an alkylene group having 2 to 4 carbon atoms;¹Represents a hydrogen atom, an alkyl group or a cycloalkyl group, B represents a residue of a compound having 3 to 20 hydroxyl groups, a is an integer of 1 to 20, b is 0 to 19 and a + b is 3 to 20 C represents an integer of 0 to 50, and d represents an integer of 1 to 50]
What has the structure represented by these is preferable.
[0066]
In the above formula (5), X¹Represents a hydrogen atom, an alkyl group, a cycloalkyl group or a group represented by the above formula (6). Although carbon number of an alkyl group here is not restrict | limited in particular, Usually, 1-24, Preferably it is 1-18, More preferably, it is 1-12. The alkyl group may be linear or branched.
[0067]
Specific examples of the alkyl group having 1 to 24 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, linear chain Or a branched pentyl group, a linear or branched hexyl group, a linear or branched heptyl group, a linear or branched octyl group, a linear or branched nonyl group, a linear or branched decyl group, a linear or branched Branched undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched heptadecyl Group, linear or branched octadecyl group, linear or branched nonadecyl group, linear or branched icosyl group, linear or branched heicosyl group, linear or branched docosyl group, linear or branched tricosyl group, Linear or branched tet Cosyl group, and the like.
[0068]
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
[0069]
In the above formula (5), A^ThreeSpecific examples of the alkylene group having 2 to 4 carbon atoms represented by: ethylene group, propylene group, trimethylene group, butylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, Examples include 1,1-dimethylethylene group and 1,2-dimethylethylene group.
[0070]
Y in the above formula (2)²Represents a hydrogen atom, an alkyl group or a cycloalkylalkyl group. Although carbon number of an alkyl group here is not restrict | limited in particular, Usually, 1-24, Preferably it is 1-18, More preferably, it is 1-12. The alkyl group may be linear or branched. Examples of the alkyl group having 1 to 24 carbon atoms include the above X¹Examples thereof include the alkyl groups exemplified in the description.
[0071]
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
[0072]
Y above²Among these groups, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferable, and a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, or an iso-butyl group. , Sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, n-hexyl group, iso-hexyl group, n-heptyl group, iso-heptyl group, n-octyl group , Iso-octyl group, n-nonyl group, iso-nonyl group, n-decyl group, iso-decyl group, n-undecyl group, iso-undecyl group, n-dodecyl group or iso-dodecyl group It is more preferable that E represents an integer of 1 to 50.
[0073]
X¹Is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group represented by the above general formula (6), a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group. , Iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, n-hexyl group, iso-hexyl group N-heptyl group, iso-heptyl group, n-octyl group, iso-octyl group, n-nonyl group, iso-nonyl group, n-decyl group, iso-decyl group, n-undecyl group, iso-undecyl group , N-dodecyl group, iso-dodecyl group or a group represented by formula (6) is more preferable.
[0074]
Specific examples of the compound having 3 to 20 hydroxyl groups with B as a residue include the aforementioned polyols.
[0075]
A¹And A²May be the same or different and each represents an alkylene group having 2 to 4 carbon atoms. Specific examples of the alkylene group include ethylene, propylene, trimethylene, butylene, tetramethylene, 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1 , 2-dimethylethylene group and the like.
[0076]
Y¹Represents a hydrogen atom, an alkyl group or a cycloalkyl group. Although carbon number of an alkyl group here is not restrict | limited in particular, Usually, 1-24, Preferably it is 1-18, More preferably, it is 1-12. The alkyl group may be linear or branched. Specific examples of the alkyl group having 1 to 24 carbon atoms include X¹Examples thereof include the alkyl groups exemplified in the description.
[0077]
Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and the like.
[0078]
Among these, Y¹Is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso group. -Butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, n-hexyl group, iso-hexyl group, n-heptyl group, iso-heptyl group, n -Of the octyl group, iso-octyl group, n-nonyl group, iso-nonyl group, n-decyl group, iso-decyl group, n-undecyl group, iso-undecyl group, n-dodecyl group or iso-dodecyl group It is more preferable that it is either.
[0079]
In the above formulas (5) and (6), c, d and e represent the degree of polymerization of the polyoxyalkylene chain, but the polyoxyalkylene chains in the molecule may be the same or different. In addition, when the carbonic acid ester represented by the above formula (5) has a plurality of different polyoxyalkylene chains, there is no particular limitation on the polymerization mode of the oxyalkylene group, and block copolymerization is performed even if random copolymerization is performed. Also good.
[0080]
The method for producing the carbonate ester used in the present invention is arbitrary. For example, a polyalkylene glycol polyol ether is produced by adding an alkylene oxide to a polyol compound, and this and chloroformate are mixed with sodium hydroxide, hydroxide. It can be obtained by reacting at 0 to 30 ° C. in the presence of an alkali metal hydroxide such as potassium, an alkali metal alkoxide such as sodium methoxide or sodium ethoxide, or an alkali such as metal sodium. Or polyalkylene glycol polyol ether, carbonic acid diester, carbon dioxide such as phosgene, alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, alkali metal alkoxide such as sodium methoxide and sodium ethoxide or metal sodium It can be obtained by reacting at 80 to 150 ° C. in the presence of an alkali such as. Thereafter, the free hydroxyl group is etherified as necessary.
[0081]
By-products and unreacted materials may be removed by purifying the product obtained from the above raw materials, but a small amount of by-products and unreacted materials impairs the excellent performance of the lubricating oil of the present invention. Unless it exists, there is no problem even if it exists.
[0082]
In the present invention, when a carbonate ester is used, a compound having a single structure may be used alone, or two or more compounds having different structures may be used in combination. The molecular weight of the carbonate ester according to the present invention is not particularly limited, but the number average molecular weight is preferably 200 to 4000, more preferably 300 to 3000, from the viewpoint of further improving the hermeticity of the compressor. More preferred. Furthermore, the kinematic viscosity of the carbonate according to the present invention is preferably 2 to 150 mm at 100 ° C.²/ S, more preferably 4 to 100 mm²/ S.
[0083]
Examples of the polyoxyalkylene glycol used in the lubricating oil of the present invention include the following general formula (7):
R⁷-[(OR⁸)_f-OR⁹]_g   (7)
[In formula (7), R⁷Represents a residue of a compound having 2 to 8 hydrogen atoms, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a hydroxyl group, and R⁸Represents an alkylene group having 2 to 4 carbon atoms, and R⁹Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms, f represents an integer of 1 to 80, and g represents an integer of 1 to 8]
The compound represented by these is mentioned.
[0084]
In the general formula (7), R⁷, R⁹The alkyl group represented by may be linear, branched or cyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a linear or branched butyl group, a linear or branched pentyl group, a linear or branched group. Hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, cyclopentyl Group, cyclohexyl group and the like. If the alkyl group has more than 10 carbon atoms, the compatibility with the refrigerant is lowered, and phase separation tends to occur. The carbon number of a preferable alkyl group is 1-6.
[0085]
R⁷, R⁹The alkyl group part of the acyl group represented by may be linear, branched or cyclic. Specific examples of the alkyl group portion of the acyl group include those having 1 to 9 carbon atoms among the alkyl groups exemplified as the specific examples of the alkyl group. When the number of carbon atoms in the acyl group exceeds 10, compatibility with the refrigerant may be reduced, and phase separation may occur. A preferable acyl group has 2 to 6 carbon atoms.
[0086]
R⁷, R⁹When both of the groups represented by the above are alkyl groups, or both are acyl groups, R⁷, R⁹The groups represented by may be the same or different. Furthermore, when g is 2 or more, a plurality of R in the same molecule⁷, R⁹The groups represented by may be the same or different.
[0087]
R⁷Is a residue of a compound having 2 to 8 hydroxyl groups, the compound may be a chain or a cyclic one. Specific examples of the compound having two hydroxyl groups include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, and 2-methyl-1,3-propanediol. 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1 , 3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12 -Dodecanediol etc. are mentioned.
[0088]
Specific examples of the compound having 3 to 8 hydroxyl groups include trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, -(Pentaerythritol), tri- (pentaerythritol), glycerol, polyglycerol (glycerin 2-6 mer), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerol condensate, adonitol, arabitol, xylitol , Polyhydric alcohols such as mannitol, xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, skull Scan, raffinose, gentianose, saccharides such as rhamnose, and their partially etherified products, and include methyl glucoside (glycoside) and the like.
[0089]
Among the polyoxyalkylene glycols represented by the general formula (7), R⁷, R⁹At least one of them is preferably an alkyl group (more preferably an alkyl group having 1 to 4 carbon atoms), and particularly preferably a methyl group from the viewpoint of refrigerant compatibility. Furthermore, from the viewpoint of thermal and chemical stability, R⁷And R⁹Are preferably alkyl groups (more preferably alkyl groups having 1 to 4 carbon atoms), and it is particularly preferable that both are methyl groups. Also, from the viewpoint of manufacturing ease and cost, R⁷Or R⁹Is preferably an alkyl group (more preferably an alkyl group having 1 to 4 carbon atoms), and the other is preferably a hydrogen atom, more preferably one is a methyl group and the other is a hydrogen atom. .
[0090]
R in the general formula (7)⁸Represents an alkylene group having 2 to 4 carbon atoms, and specific examples of such an alkylene group include an ethylene group, a propylene group, and a butylene group. OR⁸Examples of the oxyalkylene group of the repeating unit represented by the formula include an oxyethylene group, an oxypropylene group, and an oxybutylene group. The oxyalkylene groups in the same molecule may be the same, or two or more oxyalkylene groups may be included.
[0091]
Among the polyoxyalkylene glycols represented by the general formula (7), from the viewpoint of refrigerant compatibility and viscosity-temperature characteristics, a copolymer containing an oxyethylene group (EO) and an oxypropylene group (PO) is used. Preferably, in such a case, the ratio of the oxyethylene group to the total of the oxyethylene group and the oxypropylene group (EO / (PO + EO)) is 0.1 to 0.8 from the standpoint of baking load and viscosity-temperature characteristics. It is preferable that it exists in the range, and it is more preferable that it exists in the range of 0.3-0.6.
[0092]
In terms of hygroscopicity and thermal oxidation stability, the value of EO / (PO + EO) is preferably in the range of 0 to 0.5, more preferably in the range of 0 to 0.2, and 0 (that is, Most preferred is a propylene oxide homopolymer).
[0093]
F in the said General formula (7) is an integer of 1-80, g is an integer of 1-8. For example R⁷When is an alkyl group or an acyl group, g is 1. R⁷Is the residue of a compound having 2 to 8 hydroxyl groups, g is the number of hydroxyl groups of the compound.
[0094]
In addition, the product of f and g (f × g) is not particularly limited, but in order to satisfy the required performance as the above-described lubricating oil for a refrigerator in a balanced manner, the average value of f × g is 6 to 80. It is preferable to do so.
[0095]
Among the polyoxyalkylene glycols having the above structure, the following general formula (8):
CH_ThreeO- (C_ThreeH₆O)_h-CH_Three  (8)
(In the formula, h represents a number of 6 to 80)
And polyoxypropylene glycol dimethyl ether represented by the following general formula (9):
CH_ThreeO- (C₂H_FourO)_i-(C_ThreeH₆O)_j-CH_Three  (9)
(In the formula, i and j are each 1 or more, and i and j represent a number of 6 to 80)
The polyoxyethylene polyoxypropylene glycol dimethyl ether represented by the formula is suitable from the viewpoint of economy and the above-mentioned effects, and the following general formula (10):
C_FourH₉O- (C_ThreeH₆O)_k-H (10)
(In the formula, k represents a number of 6 to 80)
In addition, polyoxypropylene glycol monobutyl ether represented by the following general formula (11):
CH_ThreeO- (C_ThreeH₆O)_{h '}-H (11)
(Wherein h 'represents a number of 6 to 80)
Polyoxypropylene glycol monomethyl ether represented by the following general formula (12):
CH_ThreeO- (C₂H_FourO)_{i '}-(C_ThreeH₆O)_{j '}-H (12)
(In the formula, i 'and j' are each 1 or more, and the sum of i and j is 6 to 80)
Polyoxyethylene polyoxypropylene glycol monomethyl ether represented by the following general formula (13):
C_FourH₉O- (C₂H_FourO)_{i "}-(C_ThreeH₆O)_{j "}-H (13)
(In the formula, i ″ and j ″ are each 1 or more, and the sum of i and j is 6 to 80)
Polyoxyethylene polyoxypropylene glycol monobutyl ether, the following general formula (14):
CH_ThreeCOO- (C_ThreeH₆O)_{k '}-COCH_Three  (14)
(Wherein k 'represents a number of 6 to 80)
Is preferable in terms of economy and the like.
[0096]
In the present invention, the polyoxyalkylene glycol is represented by the general formula (15):
[Chemical 1]

[In formula (15), R^Ten~ R¹³May be the same or different and each is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or the following general formula (16):
[Chemical 2]

(In formula (16), R¹⁴And R¹⁵May be the same or different and each represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, R¹⁶Represents an alkylene group having 2 to 5 carbon atoms, a substituted alkylene group having 2 to 5 carbon atoms having an alkyl group as a substituent, or a substituted alkylene group having 4 to 10 carbon atoms having an alkoxyalkyl group as a substituent, p Represents an integer of 0 to 20, R¹⁷Represents a monovalent hydrocarbon group having 1 to 10 carbon atoms)
R represents a group represented by^Ten~ R¹³Is at least one group represented by the general formula (16)]
A polyoxyalkylene glycol derivative having at least one structural unit represented by can be used.
[0097]
In the above formula (15), R^Ten~ R¹³Each represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms or a group represented by the general formula (16). Specific examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms include Is a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an alkylcycloalkyl group. , An aryl group having 6 to 10 carbon atoms or an alkylaryl group, an arylalkyl group having 7 to 10 carbon atoms, and the like. Among these monovalent hydrocarbon groups, a monovalent hydrocarbon group having 6 or less carbon atoms, particularly an alkyl group having 3 or less carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. preferable.
[0098]
In the general formula (16), R¹⁴And R¹⁵Each represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, among which an alkyl group having 3 or less carbon atoms or an alkoxyalkyl group having 6 or less carbon atoms Is preferred. Specific examples of the alkyl group having 3 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Specific examples of the alkoxyalkyl group having 2 to 6 carbon atoms include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, sec -Butoxymethyl group, tert-butoxymethyl group, pentoxymethyl group (including all isomers), methoxyethyl group (including all isomers), ethoxyethyl group (including all isomers), propoxyethyl Groups (including all isomers), butoxyethyl groups (including all isomers), methoxypropyl groups (including all isomers), ethoxypropyl groups (including all isomers), propoxypropyl groups ( All isomers included), methoxybutyl group (including all isomers), ethoxybutyl group (all isomers) Including), etc. methoxybutyl group (including all isomers).
[0099]
In the general formula (12), R¹⁶Is an alkylene group having 2 to 5 carbon atoms, a substituted alkylene group having 2 to 5 carbon atoms having an alkyl group as a substituent, or a substituted alkylene group having 4 to 10 carbon atoms having an alkoxyalkyl group as a substituent, preferably carbon An alkylene group having 2 to 4 carbon atoms and a substituted ethylene group having 6 or less total carbon atoms are represented. Specific examples of the alkylene group having 2 to 4 carbon atoms include an ethylene group, a propylene group, and a butylene group. Specific examples of the substituted ethylene group having 6 or less total carbon atoms include 1- (methoxymethyl) ethylene group, 2- (methoxymethyl) ethylene group, 1- (methoxyethyl) ethylene group, and 2- (methoxyethyl). ) Ethylene group, 1- (ethoxymethyl) ethylene group, 2- (ethoxymethyl) ethylene group, 1-methoxymethyl-2-methylethylene group, 1,1-bis (methoxymethyl) ethylene group, 2,2-bis (Methoxymethyl) ethylene group, 1,2-bis (methoxymethyl) ethylene group, 1-methyl-2-methoxymethylethylene group, 1-methoxymethyl-2-methylethylene group, 1-ethyl-2-methoxymethylethylene Group, 1-methoxymethyl-2-ethylethylene group, 1-methyl-2-ethoxymethylethylene group, 1-ethoxymethyl-2-methyl Ethylene, 1-methyl-2-methoxyethyl ethylene group, 1-methoxyethyl-2-methylethylene group, and the like.
[0100]
In the general formula (16), R¹⁷Represents a monovalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples of the hydrocarbon group include straight-chain or branched alkyl groups having 1 to 10 carbon atoms and 2 carbon atoms. -10 linear or branched alkenyl group, C5-C10 cycloalkyl group or alkylcycloalkyl group, C6-C10 aryl group or alkylaryl group, C7-C10 arylalkyl Groups and the like. Among these, a monovalent hydrocarbon group having 6 or less carbon atoms is preferable, and an alkyl group having 3 or less carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is preferable.
[0101]
In the general formula (15), R^Ten~ R¹³At least one of them is a group represented by the general formula (16). In particular, R^TenOr R¹²Is one of the groups represented by the general formula (16), and R^TenOr R¹²The remaining one and R¹¹, R¹³Are preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
[0102]
The polyoxyalkylene glycol having a structural unit represented by the general formula (15), preferably used in the present invention, is a homopolymer consisting only of the structural unit represented by the general formula (15); And a copolymer composed of two or more structural units having different structures, and a structural unit represented by the general formula (15) and other structural units, for example, the following general formula (17):
[Chemical Formula 3]

[In formula (17), R¹⁸~ R^{twenty one}May be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms]
Can be roughly divided into three types of copolymers consisting of structural units represented by: The preferred examples of the homopolymer have 1 to 200 structural units A represented by the general formula (15), and the terminal groups are each a hydroxyl group, an acyloxy group having 1 to 10 carbon atoms, and a carbon atom having 1 to 10 carbon atoms. The thing which consists of an alkoxy group or an aryloxy group can be mentioned. On the other hand, suitable examples of the copolymer have 1 to 200 of the two types of structural units A and B represented by the general formula (15), respectively, or the structural unit A represented by the general formula (15). 1 to 200 and 1 to 200 structural units C represented by the general formula (15), and each terminal group is a hydroxyl group, an acyloxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or aryloxy The thing which consists of groups can be mentioned. These copolymers include alternating copolymerization of the structural unit A and the structural unit B (or the structural unit C), a random copolymer, a block copolymer, or a graft in which the structural unit B is graft-bonded to the main chain of the structural unit A. Any polymerization form of the copolymer may be used.
[0103]
Examples of the polyvinyl ether used in the present invention include the following general formula (18):
[Formula 4]

[In formula (18), R^{twenty two}~ R^{twenty four}May be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms;^{twenty five}Represents a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, and R²⁶Represents a hydrocarbon group having 1 to 20 carbon atoms, q represents a number having an average value of 0 to 10, R^{twenty two}~ R²⁶May be the same or different for each structural unit, and the structural unit represented by the general formula (18) is a plurality of R^{twenty five}When having O, multiple R^{twenty five}O may be the same or different.
The polyvinyl ether type compound which has a structural unit represented by these is mentioned.
[0104]
Moreover, the structural unit represented by the general formula (18) and the following general formula (19):
[Chemical formula 5]

[In formula (19), R²⁷~ R³⁰May be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms;²⁷~ R³⁰May be the same or different for each structural unit]
A polyvinyl ether compound comprising a block copolymer or a random copolymer having a structural unit represented by
[0105]
R in the general formula (18)^{twenty two}~ R^{twenty four}Each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms (preferably a hydrocarbon group having 1 to 4 carbon atoms), which may be the same as or different from each other. Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, and various hexyl groups. Group, various heptyl groups, various octyl groups and other alkyl groups; cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, various dimethylcyclohexyl groups and other cycloalkyl groups, phenyl groups, various methylphenyl groups, various ethyl groups Aryl groups such as phenyl group and various dimethylphenyl groups; arylalkyl groups such as benzyl group, various phenylethyl groups and various methylbenzyl groups, etc.^{twenty two}~ R^{twenty four}Is preferably an elementary atom.
[0106]
On the other hand, R in the general formula (18)^{twenty five}Represents a divalent hydrocarbon group having 1 to 10 carbon atoms (preferably 2 to 10 carbon atoms) or a divalent ether bond oxygen-containing hydrocarbon group having 2 to 20 carbon atoms. Specific examples of the divalent hydrocarbon group having 1 to 10 carbon atoms include methylene group, ethylene group, phenylethylene group, 1,2-propylene group, 2-phenyl-1,2-propylene group, 1, Divalent aliphatic chain hydrocarbon groups such as 3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, and various decylene groups; cyclohexane, methylcyclohexane, Cycloaliphatic hydrocarbon groups having two bonding sites on cycloaliphatic hydrocarbons such as ethylcyclohexane, dimethylcyclohexane, propylcyclohexane; various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, various Divalent aromatic hydrocarbon groups such as naphthylene groups; toluene, xylene, ethylbenzene, etc. An alkyl aromatic hydrocarbon group having a monovalent bonding site on each of the alkyl group part and the aromatic part of the alkyl aromatic hydrocarbon; an alkyl having a binding site on the alkyl group part of a polyalkyl aromatic hydrocarbon such as xylene or diethylbenzene An aromatic hydrocarbon group, and the like. Among these, an aliphatic chain hydrocarbon group having 2 to 4 carbon atoms is particularly preferable.
[0107]
Specific examples of the divalent ether bond oxygen-containing hydrocarbon group having 2 to 20 carbon atoms include methoxymethylene group, methoxyethylene group, methoxymethylethylene group, 1,1-bismethoxymethylethylene group, 1,2 Preferred examples include -bismethoxymethylethylene group, ethoxymethylethylene group, (2-methoxyethoxy) methylethylene group, (1-methyl-2-methoxy) methylethylene group, and the like. In the general formula (18), q is R^{twenty five}Represents the number of repetitions of O, and the average value is a number in the range of 0 to 10, preferably 0 to 5. R in the same structural unit^{twenty five}When there are a plurality of O, a plurality of R^{twenty five}O may be the same or different.
[0108]
Further, R in the general formula (18)²⁶Represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, etc. alkyl groups; cyclopentyl group, cyclohexyl groups, various methyls Cyclohexyl group, various ethylcyclohexyl groups, various propylcyclohexyl groups, various cycloalkyl groups such as dimethylcyclohexyl groups; phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups , Various butylphenyl groups, various naphthyl groups, etc. Le group; a benzyl group, various phenylethyl groups, various methylbenzyl groups, various phenylpropyl groups, arylalkyl groups such as various phenylbutyl groups, and the like. R^{twenty two}~ R²⁶May be the same or different for each structural unit.
[0109]
When the polyvinyl ether according to the present invention is a homopolymer consisting only of the structural unit represented by the general formula (18), the carbon / oxygen molar ratio is preferably in the range of 4.2 to 7.0. . If the molar ratio is less than 4.2, the hygroscopicity becomes excessively high, and if it exceeds 7.0, the compatibility with the refrigerant tends to be reduced.
[0110]
In the general formula (19), R²⁷~ R³⁰May be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Here, as a C1-C20 hydrocarbon group, R in the said General formula (18)²⁶The hydrocarbon group illustrated in the description of (1) is mentioned. R²⁷~ R³⁰May be the same or different for each structural unit.
[0111]
When the polyvinyl ether according to the present invention is a block copolymer or a random copolymer having a structural unit represented by the general formula (18) and a structural unit represented by the general formula (19), the carbon / oxygen thereof The molar ratio is preferably in the range of 4.2 to 7.0. If the molar ratio is less than 4.2, the hygroscopicity becomes excessively high, and if it exceeds 7.0, the compatibility with the refrigerant tends to be reduced.
[0112]
Furthermore, in this invention, the homopolymer which consists only of the structural unit represented by the said General formula (18), the structural unit represented by the said General formula (18), and the structure represented by the said General formula (19) Mixtures of block copolymers or random copolymers composed of units can also be used. These homopolymers and copolymers can be produced by polymerization of corresponding vinyl ether monomers and copolymerization of corresponding hydrocarbon monomers having olefinic double bonds and corresponding vinyl ether monomers.
[0113]
As the polyvinyl ether used in the present invention, one of the terminal structures has the following general formula (20) or (21):
[Chemical 6]

[In formula (20), R³¹~ R³³May be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms;³⁴Represents a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, and R³⁵Represents a hydrocarbon group having 1 to 20 carbon atoms, r represents an average number of 0 to 10, and the terminal structure represented by the general formula (20) has a plurality of Rs.³⁴When having O, multiple R³⁴O may be the same or different.
[0114]
[Chemical 7]

[In formula (21), R³⁶~ R³⁹May be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms]
And the other is represented by the following general formula (22) or (23):
[Chemical 8]

[In formula (22), R⁴⁰~ R⁴²May be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms;⁴³Represents a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, and R⁴⁴Represents a hydrocarbon group having 1 to 20 carbon atoms, s represents an average number of 0 to 10, and the terminal structure represented by the general formula (22) has a plurality of Rs.⁴³When having O, multiple R⁴³O may be the same or different.
[0115]
[Chemical 9]

[In formula (23), R⁴⁵~ R⁴⁸May be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms]
Having a structure represented by: and
One of the terminals is represented by the general formula (20) or (21), and the other is represented by the following general formula (24):
Embedded image

[In formula (24), R⁴⁹~ R⁵¹May be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms]
What has the structure represented by these is preferable. Among such polyvinyl ethers, the following are particularly suitable.
(1) One of the terminals has a structure represented by the general formula (20) or (21) and the other has the structure represented by the general formula (22) or (23), and R in the general formula (18)^{twenty two}~ R^{twenty four}Are hydrogen atoms, q is a number from 0 to 4, and R^{twenty five}Is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R²⁶Is a hydrocarbon group having 1 to 20 carbon atoms;
(2) It has only the structural unit represented by the general formula (18), and one end thereof is represented by the general formula (20) and the other has a structure represented by the general formula (21). R in the general formula (18)^{twenty two}~ R^{twenty four}Are hydrogen atoms, q is a number from 0 to 4, and R^{twenty five}Is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R²⁶Is a hydrocarbon group having 1 to 20 carbon atoms;
(3) One of the terminals has a structure represented by the general formula (20) or (21) and the other is represented by the general formula (22), and R in the general formula (18)^{twenty two}~ R^{twenty four}Are hydrogen atoms, q is a number from 0 to 4, and R^{twenty five}Is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R²⁶Is a hydrocarbon group having 1 to 20 carbon atoms;
(4) It has only the structural unit represented by the general formula (18), and one end of the structural unit is represented by the general formula (20) and the other has the structure represented by the general formula (23). R in the general formula (18)^{twenty two}~ R^{twenty four}Are hydrogen atoms, q is a number from 0 to 4, and R^{twenty five}Is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R²⁶Is a hydrocarbon group having 1 to 20 carbon atoms.
[0116]
Moreover, in this invention, it has a structural unit represented by the said General formula (18), One of the terminal is represented by General formula (20), and the other is following General formula (25):
Embedded image

[In formula (25), R⁵²~ R⁵⁴May be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms;⁵⁵And R⁵⁷May be the same or different and each represents a divalent hydrocarbon group having 2 to 10 carbon atoms;⁵⁶And R⁵⁸May be the same or different, each represents a hydrocarbon group having 1 to 10 carbon atoms, t and u may be the same or different, and each of the average values represents a number of 0 to 10; The terminal structure represented by (25) has a plurality of R⁵⁵O or R⁵⁷When having O, multiple R⁵⁵O or R⁵⁷O may be the same or different.
A polyvinyl ether compound having a structure represented by the formula can also be used.
[0117]
Furthermore, in the present invention, the following general formula (26) or (27):
Embedded image

[In formula (26), R⁵⁹Represents a hydrocarbon group having 1 to 8 carbon atoms]
[0118]
Embedded image

[In formula (27), R⁶⁰Represents a hydrocarbon group having 1 to 8 carbon atoms]
And has a weight average molecular weight of 300 to 5,000, and one of the terminals is represented by the following general formula (28) or (29):
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[In formula (28), R⁶¹Represents an alkyl group having 1 to 3 carbon atoms, and R⁶²Represents a hydrocarbon group having 1 to 8 carbon atoms]
[0119]
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[In formula (29), R⁶³Represents a hydrocarbon group having 1 to 8 carbon atoms]
A polyvinyl ether compound comprising a homopolymer or copolymer of an alkyl vinyl ether having a structure represented by
[0120]
In the present invention, only one kind selected from the group consisting of the above-described mineral oil and synthetic oil may be used alone, or two or more kinds may be used in combination. When the system refrigerant is used, polyoxyalkylene glycol, ester, polyvinyl ether is preferably used for an open type compressor such as a car air conditioner, and alkylbenzene, ester, polyvinyl ether is preferably used for a closed type compressor such as a refrigerator or an air conditioner.
[0121]
In order to further improve the wear resistance and load resistance of the refrigerating machine oil of the present invention, phosphoric acid ester, acidic phosphoric acid ester, amine salt of acidic phosphoric acid ester, chlorinated phosphoric acid ester, phosphorous acid ester and phosphor It is preferable to blend at least one phosphorus compound selected from the group consisting of thionates. These phosphorus compounds are esters of phosphoric acid, phosphorous acid or thiophosphoric acid with alkanols and polyether-type alcohols or derivatives thereof.
[0122]
Among such phosphorus compounds, phosphate esters include tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate, tritridecyl Phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xyl Renyl diphenyl phosphate and the like;
Examples of acidic phosphate esters include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, monododecyl Acid phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl acid phosphate, dibutyl acid phosphate, dipentyl acid , Dihexyl reed Dophosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid phosphate, diundecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate, dipentadecyl acid, dipentadecyl acid Hexadecyl acid phosphate, diheptadecyl acid phosphate, dioctadecyl acid phosphate, dioleyl acid phosphate, etc .;
Examples of the amine salt of acidic phosphate ester include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, Salts with amines such as dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, etc .;
Examples of the chlorinated phosphate ester include tris-dichloropropyl phosphate, tris-chloroethyl phosphate, tris-chlorophenyl phosphate, polyoxyalkylene bis [di (chloroalkyl)] phosphate, and the like;
As phosphites, dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite, diundecyl phosphite, didodecyl phosphite, dioleyl Phosphite, diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl phosphite Phyto, tridodecyl phosphite, trioleyl phosphite, triphenyl phosphite, tricresyl phosphite etc .;
The phosphorothioates include tributyl phosphorothioate, tripentyl phosphorothioate, trihexyl phosphorothioate, triheptyl phosphorothioate, trioctyl phosphorothionate, trinonyl phosphorothionate, tridecyl Phosphorothioate, triundecyl phosphorothionate, tridodecyl phosphorothioate, tritridecyl phosphorothioate, tritetradecyl phosphorothionate, tripentadecyl phosphorothionate, trihexadecyl phosphorothionate , Triheptadecyl phosphorothioate, trioctadecyl phosphorothioate, trioleyl phosphorothioate, triphenyl phosphorothioate, tri Resyl phosphorothioate, trixylenyl phosphorothioate, cresyl diphenyl phosphorothioate, xylenyl diphenyl phosphorothioate, tris (n-propylphenyl) phosphorothionate, tris (isopropylphenyl) phosphor Phosphorothionate, tris (n-butylphenyl) phosphothionate, tris (isobutylphenyl) phosphothionate, tris (s-butylphenyl) phosphothionate, tris (t-butylphenyl) phosphothionate, etc. . Mixtures of these can also be used.
[0123]
When these phosphorus compounds are blended in the refrigerating machine oil composition of the present invention, the blending amount is not particularly limited, but the content is usually based on the total amount of the refrigerating machine oil composition (based on the total amount of base oil and all blended additives). It is desirable to mix the phosphorus compound in such an amount that the amount is 0.01 to 5.0% by mass, more preferably 0.02 to 3.0% by mass.
[0124]
Further, in the refrigerating machine oil of the present invention, in order to further improve the heat and hydrolysis stability,
(1) Phenyl glycidyl ether type epoxy compound
(2) Alkyl glycidyl ether type epoxy compound
(3) Glycidyl ester type epoxy compound
(4) Allyloxirane compounds
(5) Alkyloxirane compounds
(6) Alicyclic epoxy compound
(7) Epoxidized fatty acid monoester
(8) Epoxidized vegetable oil
It is preferable to blend at least one epoxy compound selected from the group consisting of:
[0125]
(1) Specific examples of the phenyl glycidyl ether type epoxy compound include phenyl glycidyl ether and alkylphenyl glycidyl ether. Examples of the alkylphenyl glycidyl ether herein include those having 1 to 3 alkyl groups having 1 to 13 carbon atoms, and those having one alkyl group having 4 to 10 carbon atoms, such as n-butylphenyl glycidyl. Ether, i-butylphenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, pentylphenyl glycidyl ether, hexylphenyl glycidyl ether, heptylphenyl glycidyl ether, octylphenyl glycidyl ether, nonylphenyl glycidyl ether, decylphenyl A glycidyl ether etc. can be illustrated as a preferable thing.
[0126]
(2) As the alkyl glycidyl ether type epoxy compound, specifically, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl glycol di Examples thereof include glycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol monoglycidyl ether, polyalkylene glycol diglycidyl ether and the like.
[0127]
(3) As a glycidyl ester type epoxy compound, specifically, the following general formula (30):
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(In the above formula (30), R represents a hydrocarbon group having 1 to 18 carbon atoms)
The compound represented by these is mentioned.
[0128]
In said formula (30), R represents a C1-C18 hydrocarbon group, As such a hydrocarbon group, a C1-C18 alkyl group, a C2-C18 alkenyl group, carbon A cycloalkyl group having 5 to 7 carbon atoms, an alkylcycloalkyl group having 6 to 18 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, an arylalkyl group having 7 to 18 carbon atoms, and the like. Can be mentioned. Among these, an alkylphenyl group having an alkyl group having 5 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, a phenyl group, and an alkyl group having 1 to 4 carbon atoms is preferable.
[0129]
Among the glycidyl ester type epoxy compounds, preferred examples include glycidyl-2,2-dimethyloctanoate, glycidyl benzoate, glycidyl-tert-butyl benzoate, glycidyl acrylate, glycidyl methacrylate, and the like.
[0130]
(4) Specific examples of the allyloxirane compound include 1,2-epoxystyrene, alkyl-1,2-epoxystyrene, and the like.
[0131]
(5) Specific examples of the alkyloxirane compound include 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1 , 2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1, 2,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,1,2-epoxyoctadecane, 2-epoxynonadecane, 1,2-epoxyicosane and the like.
[0132]
(6) As an alicyclic epoxy compound, the following general formula (31):
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And a compound in which the carbon atom constituting the epoxy group directly constitutes an alicyclic ring.
[0133]
Specific examples of the alicyclic epoxy compound include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and bis (3,4 -Epoxycyclohexylmethyl) adipate, exo-2,3-epoxynorbornane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (7-oxabicyclo [4.1.0] hept-3- Yl) -spiro (1,3-dioxane-5,3 ′-[7] oxabicyclo [4.1.0] heptane, 4- (1′-methylepoxyethyl) -1,2-epoxy-2-methyl Examples include cyclohexane and 4-epoxyethyl-1,2-epoxycyclohexane.
[0134]
(7) Specific examples of the epoxidized fatty acid monoester include esters of an epoxidized fatty acid having 12 to 20 carbon atoms with an alcohol or phenol having 1 to 8 carbon atoms or an alkylphenol. In particular, butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl and butylphenyl esters of epoxy stearate are preferably used.
[0135]
(8) Specific examples of epoxidized vegetable oils include epoxy compounds of vegetable oils such as soybean oil, linseed oil, and cottonseed oil.
[0136]
Among these epoxy compounds, phenyl glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, alicyclic epoxy compounds, and epoxidized fatty acid monoesters are preferable because glycidyl ether can be further improved in heat and hydrolysis stability. An ester type epoxy compound and an alicyclic epoxy compound are more preferable.
[0137]
When these epoxy compounds are blended in the refrigerating machine oil composition of the present invention, the blending amount is not particularly limited, but the content is usually based on the total amount of the refrigerating machine oil composition (based on the total amount of base oil and all blended additives). It is desirable to mix the epoxy compound in such an amount that the amount is 0.1 to 5.0% by mass, more preferably 0.2 to 2.0% by mass.
[0138]
Of course, two or more of the above phosphorus compounds and epoxy compounds may be used in combination.
[0139]
Furthermore, in order to further enhance the performance of the refrigerating machine oil composition according to the present invention, conventionally known refrigerating machine oil additives such as di-tert-butyl-p-cresol, bisphenol A and other phenol-based ones are used. Antioxidants, amine-based antioxidants such as phenyl-α-naphthylamine, N, N-di (2-naphthyl) -p-phenylenediamine, antiwear agents such as zinc dithiophosphate, chlorinated paraffin, sulfur compounds, etc. Alone, additives such as oil-based agents such as fatty acids, antifoaming agents such as silicones, metal deactivators such as benzotriazole, viscosity index improvers, pour point depressants, detergent dispersants, etc. Or it is also possible to mix | blend and combine several types. The total blending amount of these additives is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less on the basis of the total amount of the refrigerating machine oil composition (based on the total amount of the base oil and all the blending additives). .
[0140]
The volume resistivity of the refrigerating machine oil composition of the present invention is not particularly limited, but 1.0 × 10⁹It is preferable that it is Ω · cm or more. In particular, high electrical insulation tends to be required when used in a closed refrigerator. Here, the volume resistivity means a value [Ω · cm] at 25 ° C. measured in accordance with JISC 2101 “Electrical Insulating Oil Test Method”.
[0141]
Furthermore, although the water content of the refrigerating machine oil composition of the present invention is not particularly limited, it is preferably 200 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less, based on the total amount of the refrigerating machine oil composition. In particular, when used for a closed type refrigerator, the water content is required to be low from the viewpoint of the influence on the heat and hydrolysis stability of oil and electrical insulation.
[0142]
Furthermore, the total acid value of the refrigerating machine oil composition of the present invention is not particularly limited, but is preferably 0.1 mgKOH / g or less, more preferably, in order to prevent corrosion of the metal used in the refrigerating machine or piping. It can be 0.05 mgKOH / g or less. The total acid value referred to here means a value [mg KOH / g] measured in accordance with JIS K 2501 “Petroleum products and lubricating oils—neutralization number test method”.
[0143]
Furthermore, the ash content of the refrigerating machine oil composition of the present invention is not particularly limited, but is preferably 100 ppm or less, more preferably, in order to increase the heat / hydrolysis stability of the refrigerating machine oil composition of the present invention and suppress the generation of sludge and the like. Can be 50 ppm or less. In the present invention, ash means a value [ppm] measured in accordance with JIS K 2272 “Testing method for ash and sulfated ash of crude oil and petroleum products”.
[0144]
Refrigerants used in the refrigerator using the refrigerator oil composition of the present invention include HFC refrigerants, fluorine-containing ether refrigerants such as perfluoroethers, non-fluorine-containing ether refrigerants such as dimethyl ether, carbon dioxide, ammonia, hydrocarbons, etc. These natural refrigerants may be used alone or as a mixture of two or more.
[0145]
Examples of the HFC refrigerant include hydrofluorocarbons having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms. Specifically, for example, difluoromethane (HFC-32), trifluoromethane (HFC-23), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1, HFC such as 1,1,2-tetrafluoroethane (HFC-134a), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), or two or more of these And the like. These refrigerants are appropriately selected depending on the application and required performance. For example, HFC-32 alone; HFC-23 alone; HFC-134a alone; HFC-125 alone; HFC-134a / HFC-32 = 60 to 80 mass % / 40-20 mass% mixture; HFC-32 / HFC-125 = 40-70 mass% / 60-30 mass% mixture; HFC-125 / HFC-143a = 40-60 mass% / 60-40 mass % Mixture; HFC-134a / HFC-32 / HFC-125 = 60 wt% / 30 wt% / 10 wt% mixture; HFC-134a / HFC-32 / HFC-125 = 40-70 wt% / 15- 35 mass% / 5 to 40 mass% mixture; HFC-125 / HFC-134a / HFC-143a = 35-55 mass% / 1-15 mass% / 40-60 mass Mixtures of preferred examples include. More specifically, a mixture of HFC-134a / HFC-32 = 70/30 mass%; a mixture of HFC-32 / HFC-125 = 60/40 mass%; HFC-32 / HFC-125 = 50/50 mass % Mixture (R410A); HFC-32 / HFC-125 = 45/55 wt% mixture (R410B); HFC-125 / HFC-143a = 50/50 wt% mixture (R507C); HFC-32 / HFC -125 / HFC-134a = 30/10/60 wt% mixture; HFC-32 / HFC-125 / HFC-134a = 23/25/52 wt% mixture (R407C); HFC-32 / HFC-125 / HFC-134a = 25/15/60 mass% mixture (R407E); HFC-125 / HFC-134a / HFC-143a = Include mixtures of 4/4/52 wt% (R404A) etc.
Examples of natural refrigerants include carbon dioxide, ammonia, and hydrocarbons. Here, as the hydrocarbon refrigerant, a gas refrigerant at 25 ° C. and 1 atm is preferably used. Specifically, it is an alkane, cycloalkane, alkene or a mixture thereof having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include methane, ethylene, ethane, propylene, propane, cyclopropane, butane, isobutane, cyclobutane, methylcyclopropane, or a mixture of two or more thereof. Among these, propane, butane, isobutane or a mixture thereof is preferable.
[0146]
The refrigerating machine oil composition of the present invention is usually present in the form of a refrigerating machine fluid composition mixed with the refrigerant as described above in the refrigerating machine. The blending ratio of the refrigerating machine oil and the refrigerant in this fluid composition is not particularly limited, but the refrigerating machine oil is preferably 1 to 500 parts by weight, more preferably 2 to 400 parts by weight with respect to 100 parts by weight of the refrigerant.
[0147]
The refrigerating machine oil composition of the present invention sufficiently satisfies all the required performance such as lubricity, refrigerant compatibility, low temperature fluidity, stability, etc., and is a reciprocating or rotating open type or semi-sealed type. It can be suitably used for refrigeration equipment or heat pumps having a mold or hermetic compressor. In particular, when it is used in a refrigeration apparatus using an aluminum-based member, it is possible to achieve both high wear resistance and thermal / chemical stability of the aluminum-based member at a high level. More specifically, examples of such refrigeration equipment include automobile air conditioners, dehumidifiers, refrigerators, refrigerator / freezer warehouses, vending machines, showcases, cooling equipment for chemical plants, residential air conditioners, hot water supply heat pumps, and the like.
[0148]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.
[0149]
Examples 1-12, Comparative Examples 1-8
In Examples 1 to 12 and Comparative Examples 1 to 8, sample oils were prepared using the base oils and additives shown below. Table 1 shows the type of base oil, the type and content of sarcosine derivatives, the content of acid scavengers, the content of phosphorus compounds, and the total acid value of the obtained sample oil in each sample oil.
[0150]
(Base oil)
Base oil 1: Polypropylene glycol monomethyl ether (number average molecular weight: 1000, kinematic viscosity at 100 ° C .: 10 mm²/ S)
Base oil 2: Random copolymer of vinyl ethyl ether and vinyl isobutyl ether (molar ratio of vinyl ethyl ether to vinyl isobutyl ether: 7/1, number average molecular weight: 900, kinematic viscosity at 100 ° C .: 8 mm²/ S).
[0151]
(Additive)
Sarcosine derivative 1: N-oleoyl sarcosine methyl ester
Sarcosine derivative 2: N-oleoyl sarcosine potassium salt
Sarcosine derivative 3: N-oleoyl sarcosine glycerin monoester
Sarcosine derivative 4: N-oleoyl sarcosine
Epoxy compound: Phenyl glycidyl ether
Phosphorus compound: tricresyl phosphate.
[0152]
Next, the following tests were performed using the sample oils of Examples 1 to 12 and Comparative Examples 1 to 8.
[0153]
(Thermal and chemical stability tests under refrigerant atmosphere)
70 g of sample oil, 30 g of refrigerant (HFC-134a), and catalyst (1.6 mmφ × 50 mm iron wire, copper wire, and aluminum wire each) were sealed in an autoclave and held at 175 ° C. for 2 weeks. Thereafter, the refrigerant was removed from the sample oil, and the total acid value of the sample oil was measured. Moreover, the residual rate of the epoxy compound was measured about the sample oils of Examples 4 to 12 and Comparative Examples 3, 4, 7, and 8 containing the epoxy compound. The obtained results are shown in Table 1.
[0154]
(Lubricity test)
In accordance with ASTM D2670, a 1 hour wear test was conducted using a FALEX wear tester under conditions of a sample oil temperature of 80 ° C. and a load of 150 lb while blowing refrigerant (HFC-134a) into the sample oil. In this test, an aluminum pin (A390) and a steel block (AISI 1137) were used as test pieces, and the total wear amount of the pin and block after the test was measured. The obtained results are shown in Table 1.
[0155]
[Table 1]

[0156]
As is clear from the results shown in Table 1, in the sample oils of Examples 1 to 12, which are the refrigerating machine oil compositions of the present invention, the increase in the total acid value in the thermal and chemical stability test is sufficiently suppressed. It had been. In addition, in the sample oils of Examples 4 to 12 containing the epoxy compound, the residual ratio of the acid scavenger after the thermal / chemical stability test showed a sufficiently high value.
Further, in these sample oils, wear of the pins and blocks in the lubricity test was sufficiently suppressed. These results suggest that the refrigerating machine oil composition of the present invention can sufficiently suppress the wear of the aluminum-based member without causing deterioration of the base oil, the acid scavenger and the like. .
[0157]
【The invention's effect】
As described above, the refrigerating machine oil composition of the present invention has sufficiently high lubricity and sufficiently high thermal / chemical stability. Therefore, when the refrigerating machine oil composition of the present invention is used in a refrigeration apparatus including an aluminum-based member, it is possible to sufficiently suppress wear of the aluminum-based member without causing deterioration of the base oil, the acid scavenger, etc. Become.

Claims (1)

Mineral oil and / or synthetic oil is used as a base oil, and the following general formulas (1) to (3):
R ¹ —CO—NR ² — (CH ₂ ) ₁ —COOX (1)
[In Formula (1), R ¹ represents an alkyl or alkenyl group having 6 to 30 carbon atoms having from 6 to 30 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is carbon Represents an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 1 to 30 carbon atoms, and l represents an integer of 1 to 4]
^{[R 3 -CO-NR 4 -} (CH 2) m -COO] m 'Y (2)
[In the formula (2), R ³ represents an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Y represents an alkali. A metal atom or an alkaline earth metal atom, m represents an integer of 1 to 4, and m ′ represents an integer of 1 or 2]
^{[R 5 -CO-NR 6 -} (CH 2) n -COO] n '-Z- (OH) n "(3)
[In the formula (3), R ⁵ represents an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z represents 2 Represents a residue obtained by removing a hydroxyl group from a polyhydric alcohol having a valence of at least, n represents an integer of 1 to 4, n ′ represents an integer of 1 or more, n ″ represents an integer of 0 or more, and n ′ + n ″ Is the valence of the group represented by Z]
A refrigerating machine oil composition comprising 0.001 to 5% by mass of at least one of the compounds represented by formula (1) based on the total amount of the composition.