JP6195429B2 - 冷凍機用作動流体組成物及び冷凍機油 - Google Patents
冷凍機用作動流体組成物及び冷凍機油 Download PDFInfo
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Description
本発明の第1実施形態に係る冷凍機油は、鉱油及び合成油から選ばれる少なくとも1種の潤滑油基油と、炭素数3〜5のアルキル基を1つ有するモノ(アルキルフェニル)ジフェニルフォスフェート及び炭素数3〜5のアルキル基を2つ有するジ(アルキルフェニル)フェニルフォスフェートから選ばれる少なくとも1種のリン化合物と、を含有し、該リン化合物の含有量が冷凍機油全量を基準として0.01〜5質量%のものである。かかる冷凍機油は、炭素数2〜4の炭化水素冷媒と共に用いられる。
[式中、R1,R2およびR3は同一でも異なっていてもよく、それぞれ水素原子または炭素数1〜8の炭化水素基を示し、R4は炭素数1〜10の二価の炭化水素基または炭素数2〜20の二価のエーテル結合酸素含有炭化水素基を示し、R5は炭素数1〜20の炭化水素基を示し、mは前記ポリビニルエーテルについてのmの平均値が0〜10となるような数を示し、R1〜R5は構造単位毎に同一であっても異なっていてもよく、一の構造単位においてmが2以上である場合には、複数のR4Oは同一でも異なっていてもよい。]
(R6−Ph)n−P(=O)−(Ph)3−n (2)
[式中、R6は炭素数3〜5のアルキル基を示し、Phはフェニル基を示し、nは1又は2の整数を示す。]
本発明の第2実施形態に係る冷凍機用作動流体組成物は、鉱油及び合成油から選ばれる少なくとも1種の潤滑油基油並びに炭素数3〜5のアルキル基を1つ有するモノ(アルキルフェニル)ジフェニルフォスフェート及び炭素数3〜5のアルキル基を2つ有するジ(アルキルフェニル)フェニルフォスフェートから選ばれる少なくとも1種のリン化合物を含有し、該リン化合物の含有量が冷凍機油全量を基準として0.01〜5質量%である冷凍機油と、炭素数2〜4の炭化水素冷媒と、を含有する。なお、本実施形態に係る冷凍機用作動流体組成物に含まれる冷凍機油は上記の第1実施形態に係る冷凍機油と同様であるため、ここでは重複する説明を省略する。
実施例1〜8及び比較例1〜6においては、それぞれ以下に示す潤滑油基油及び添加剤を用いて、表1〜4に示す組成を有する冷凍機油を調製した。
(A)潤滑油基油
A1:ペンタエリスリトールと、2−エチルヘキサン酸及び3,5,5−トリメチルヘキサン酸の混合酸(質量比1:1)とのエステル(40℃における動粘度68.0mm2/s、粘度指数90、流動点−40℃、引火点260℃)
A2:ジオクチルセバケート(40℃における動粘度11.6mm2/s、粘度指数150、流動点−50℃、引火点220℃)
A3:両末端がメチル基でエーテル封鎖されたポリオキシプロピレン(平均分子量1000、40℃における動粘度46.0mm2/s、粘度指数190、流動点−45℃、引火点218℃)
A4:パラフィン系精製鉱油、(40℃における動粘度22.0mm2/s、粘度指数95、流動点−15℃、引火点210℃)
A5:直鎖型アルキルベンゼン、(40℃における動粘度8.1mm2/s、粘度指数45、流動点−50℃、引火点154℃)
(B)一般式(2)で示されるリン化合物
B1:モノ(n−ブチルフェニル)ジフェニルフォスフェート
B2:ジ(イソプロピルフェニル)フェニルフォスフェート
B3:モノ(tert.−ブチルフェニル)ジフェニルフォスフェート/ジ(tert.−ブチルフェニル)フェニルフォスフェート=65/35(質量比)の混合物
(C)その他の添加剤
C1:油性剤:グリセロールモノオレエート(GMO)
C2:耐摩耗剤;トリフェニルフォスフェート(TPP)
C3:耐摩耗剤:トリクレジルフォスフェート(TCP)
ASTM D−2714−88のファレックス ブロック・オン・リング摩擦摩耗試験機を用い、テストピースは ブロック:合金工具鋼SKS3(JIS G4404)、リング:ニッケルクロムモリブデン鋼SNCM220(JIS G4103) で、試験条件を 荷重:300N 周速:0.1m/s 温度:50℃ 試験時間:30分 とし、摩擦摩耗試験を行った。なお、試料油量は100mlであるが、炭化水素冷媒で希釈されることを模擬し、ガス化しない炭化水素であるノルマルデカンを20ml加えて希釈し、トータルのサンプル量を120mlとした。
試験結果として、摩擦係数は試験後半(おおよそ25分)で安定した時の値を、摩耗については試験終了後のブロック上の摩耗痕径(mm)を目盛り付き顕微鏡で計測し、示した。得られた結果を表1〜4に示す。
含有水分量を100ppm以下に調整した試料油90gをオートクレーブに秤取し、触媒(鉄、銅、アルミの線、いずれも外径1.6mm×50mm)とイソブタン冷媒10gを封入した後、175℃に加熱し、100時間後の試料油の外観と酸価(JIS C2101)を測定した。得られた結果を表1〜4に示す。なお、熱安定性試験前の試料油(新油)の酸価はすべて0.01mgKOH/gであった。
次に、実施例1〜8と比較例2、4とを比較すると、摩耗の指標である摩耗痕径は比較例2、4の場合にはるかに大きい値を示した。この結果は、吸着タイプである油性剤は摩擦係数を一定レベルにはするが、耐摩耗性は劣ることを支持するものである。
また、実施例1〜8と比較例3、5、6とを比較すると、比較例3、5、6の摩擦係数は実施例1〜8より約20%高い値を示した。これは、冷凍機コンプレッサの省電力の観点からは大きな差であるといえる。
これらの結果から、実施例1〜8の冷凍機油は、安定性が良好で、潤滑性については炭化水素で希釈された場合でも耐摩耗が高く、摩擦係数を低く維持できる冷凍機油であることが分かる。
Claims (6)
- 鉱油及び合成油から選ばれる少なくとも1種の潤滑油基油並びに炭素数3〜5のアルキル基を1つ有するモノ(アルキルフェニル)ジフェニルフォスフェート及び炭素数3〜5のアルキル基を2つ有するジ(アルキルフェニル)フェニルフォスフェートから選ばれる少なくとも1種からなるリン化合物を含有し、該リン化合物の含有量が冷凍機油全量を基準として0.01〜5質量%である冷凍機油と、
炭素数2〜4の炭化水素冷媒と、
を含有する冷凍機用作動流体組成物。 - 前記リン化合物が、炭素数4のアルキル基を1つ有するモノ(ブチルフェニル)ジフェニルフォスフェート及び炭素数4のアルキル基を2つ有するジ(ブチルフェニル)フェニルフォスフェートから選ばれる少なくとも1種である、請求項1に記載の冷凍機用作動流体組成物。
- 前記潤滑油基油が、鉱油、アルキルベンゼン、ポリ−α−オレフィン、エステル及びエーテルから選ばれる少なくとも1種であり、該潤滑油基油の40℃における動粘度が3〜500mm2/sである、請求項1又は2に記載の冷凍機用作動流体組成物。
- 前記潤滑油基油が、鉱油、アルキルベンゼン、ポリ−α−オレフィン、ジエステル、ポリオールエステル、コンプレックスエステル、ポリアルキレングリコール、ポリアルキレングリコール化合物及びポリビニルエーテルから選ばれる少なくとも1種以上であり、該潤滑油基油の40℃における動粘度が3〜300mm2/sである、請求項1〜3のいずれか一項に記載の冷凍機用作動流体組成物。
- 前記炭化水素冷媒が、プロパン、プロピレン、ノルマルブタン及びイソブタンから選ばれる少なくとも1種である、請求項1〜4のいずれか一項に記載の冷凍機用作動流体組成物。
- 鉱油及び合成油から選ばれる少なくとも1種の潤滑油基油と、
炭素数3〜5のアルキル基を1つ有するモノ(アルキルフェニル)ジフェニルフォスフェート及び炭素数3〜5のアルキル基を2つ有するジ(アルキルフェニル)フェニルフォスフェートから選ばれる少なくとも1種からなるリン化合物と、
を含有し、
該リン化合物の含有量が冷凍機油全量を基準として0.01〜5質量%であり、
炭素数2〜4の炭化水素冷媒と共に用いられる、冷凍機油。
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