JP2585339B2 - フロン雰囲気用潤滑油組成物 - Google Patents

フロン雰囲気用潤滑油組成物

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Publication number
JP2585339B2
JP2585339B2 JP63017333A JP1733388A JP2585339B2 JP 2585339 B2 JP2585339 B2 JP 2585339B2 JP 63017333 A JP63017333 A JP 63017333A JP 1733388 A JP1733388 A JP 1733388A JP 2585339 B2 JP2585339 B2 JP 2585339B2
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Japan
Prior art keywords
oil
lubricating oil
atmosphere
oil composition
group
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP63017333A
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English (en)
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JPH01193393A (ja
Inventor
啓通 清木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Application filed by Idemitsu Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
Priority to JP63017333A priority Critical patent/JP2585339B2/ja
Priority to KR1019890701780A priority patent/KR950002349B1/ko
Priority to US07/415,236 priority patent/US5084196A/en
Priority to PCT/JP1989/000063 priority patent/WO1989007128A1/ja
Publication of JPH01193393A publication Critical patent/JPH01193393A/ja
Application granted granted Critical
Publication of JP2585339B2 publication Critical patent/JP2585339B2/ja
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明はフロン雰囲気用潤滑油組成物に関し、詳しく
はフロン雰囲気下において安定性にすぐれ、同時に消泡
性にすぐれた潤滑油組成物に関する。
〔従来の技術及び発明が解決しようとする課題〕
一般に、冷凍機油やヒートポンプ油等として用いる潤
滑油には、適性な粘度を有すること,すぐれた低温
特性(低流動点,低フロック点など)を有すること,
冷媒との相溶性が良好であること,冷媒雰囲気下での
高温安定性にすぐれること,すぐれた潤滑性を有する
こと,消泡性にすぐれること等の諸性能が要求されて
いる。
一方、近年に至って、冷凍機やヒートポンプ等は高効
率化,小型軽量化が急速に進行し、またコンプレッサー
がレシプロ方式からロータリー方式に移行し、さらには
インバーターの搭載あるいはヒートポンプによる廃熱回
収のために吐出ガス温度が上昇する傾向にある。そのた
め、冷凍機油等に高温安定性が強く要求されている。
冷凍機やヒートポンプでは、コンプレッサーの起動時
や運転中の負荷変動に伴って、クランク室内の圧力が急
激に降下し、そのため油に溶解している冷媒であるフロ
ンが蒸発して発泡し、様々なトラブルの原因となってい
る。即ち、発泡が激しいときには、泡立ちを起こした油
が、冷媒ガス(フロン)に同伴してコンプレッサーのシ
リンダー内に吸入され、シリンダー内が一時的に多量の
油で充満し、その結果、バルブ機構はリキッドハンマー
現象による大きな衝撃力を受けて破損するおそれがあ
る。一方、このように多量の油が流出するため、コンプ
レッサー内部では油が不足し、金属などの摺動部分の潤
滑に悪影響を与え、焼付き事故を起こす危険がある。
このような事情から、冷凍機やヒートポンプに用いる
潤滑油にすぐれた消泡性を付与することが望まれてい
る。また、例えば、特開昭57−159892号公報には、鉱油
等にジメチルポリシロキサン構造を有するシリコーンオ
イルであって、特定の粘度を持つ消泡剤を添加する技術
が開示されているが、本発明者がフロン雰囲気下での高
温安定性について調べた結果、このようなシリコーンオ
イルは高温安定性を低下させ、フロン雰囲気用消泡剤と
しては必ずしも好適なものではないことがわかった。従
ってフロン雰囲気下においてすぐれた消泡性と高温安定
性を持つ潤滑油の出現が望まれてきた。
そこで本発明者は、上記従来の冷凍機油等の課題を解
決し、フロン雰囲気下において安定性にすぐれるととも
に消泡性の向上した潤滑油を開発すべく鋭意研究を重ね
た。
〔課題を解決するための手段〕
その結果、潤滑油基油にエポキシ構造を有する高粘度
のポリシロキサンを一定範囲で配合することによって、
上記課題を解決できることを見出した。本発明はかかる
知見に基いて完成したものである。
すなわち本発明は、40℃における動粘度が5〜500cSt
の基油100重量部に、25℃における動粘度が1000cSt以上
のエポキシ構造を有するポリシロキサンを0.0001〜1重
量部の割合で配合したことを特徴とするフロン雰囲気用
潤滑油組成物を提供するものである。
本発明の潤滑油組成物において、基油(潤滑油基油)
としては、鉱油,合成油を単独であるいは両者を混合し
たもの用いればよい。また、この基油の性状について
は、通常は40℃における動粘度が5〜500cSt、好ましく
は10〜300cStであればよく、他の性状については特に制
限はない。ここで動粘度が5cSt未満のものでは、蒸発に
よる油消費量が多く、また油潤滑量が多くなり、さらに
シール性が悪いという問題がある。この基油として用い
る鉱油の例としては、パラフィン基系原油,中間基系原
油あるいはナフテン基系原油を常圧蒸留するかあるいは
常圧蒸留の残渣油を減圧蒸留して得られる留出油、また
はこれを常法にしたがって精製することによって得られ
る精製油、例えば溶剤精製油,水添精製油,脱ロウ処理
油,白土処理油等をあげることができる。なお、この脱
ロウ処理油としては、ゼオライト触媒を用いた水添脱ロ
ウ処理などにより高度に脱ロウ処理を行った深脱ロウ処
理油が特に好ましい。
また、合成油としては特に制限はなく、各種のものが
使用できるが、例えばアルキルベンゼン(直鎖アルキル
ベンゼン,分岐アルキルベンゼン),アルキルジフェニ
ル,ポリα−オレフィン,ポリブテン,エステル(ヒン
ダードエステル,二塩基酸エステル,コンプレックスエ
ステル,リン酸エステル),ポリエーテル(ポリフェニ
ルエーテル,ポリグリコールエーテル),シリコーンオ
イルなどがある。
次に、本発明の潤滑油組成物では、上記基油にエポキ
シ構造を有するポリシロキサンを配合することが必要で
ある。このエポキシ構造を有するポリシロキサンは、25
℃における動粘度が1000cSt以上のものであればよく、
各種のものがあるが、通常は 下記一般式 〔式中、R1〜R6はそれぞれ炭素数1〜20のアルキル基,
炭素数6〜30のシクロアルキル基,炭素数6〜30のアル
キルアリール基あるいは炭素数1〜20のアルコキシ基を
示し、R7,R8はそれぞれ炭素数1〜20のアルキル基,炭
素数6〜30のアルキルアリール基あるいは炭素数6〜30
のシクロアルキル基を示し、R9は炭素数1〜20のアルキ
ル基,炭素数6〜30のアルキルアリール基,炭素数6〜
30のシクロアルキル基あるいはエポキシ構造を有する基
を示す。また、Epはエポキシ構造を有する基を示し、x,
yはx≧0,y>0,x+y=50〜2000を満たす整数であ
る。〕 で表わされる化合物をあげることができる。なお、上記
一般式(I)では便宜上ブロック共重合の形状のものを
示したが、ランダム共重合,グラフト共重合,交互共重
合など様々な形態を取り得る。またここで、Epはエポキ
シ構造を有する基を示すものであるが、具体的にはグリ
シドキシメチル基,β−グリシドキシエチル基,γ−グ
リシドキシプロピル基,δ−グリシドキシブチル基,グ
リシドキシオクチル基,β−(3,4−エポキシシクロヘ
キシル)エチル基,β−(3,4−エポキシフェニル)エ
チル基などがある。さらに、R1〜R6はそれぞれ前記の如
き置換基を示すが、特にR1,R2についてはメチル基が好
ましく、またR3〜R6についてはメチル基あるいはメトキ
シ基が好ましい。R7〜R9に関してもそれぞれ前記の如き
置換基を示すが、いずれもメチル基が好ましく、またx,
yに関しては前記式を満足する整数であればよいが、更
にx+y=100〜1000であることが好ましく、その上y/
(x+y)=0.01〜0.60、とりわけy/(x+y)=0.02
〜0.50であることが好ましい。
本発明の潤滑油組成物において用いるエポキシ構造を
有するポリシロキサンは、上述した一般式で表わされる
ものが使用できるが、さらにその25℃における動粘度が
1000cSt以上、特に2500以上のものであり、しかもエポ
キシ価が0.01〜0.5グラム当量/100g、とりわけ0.02〜0.
4グラム当量/100gのものが好適である。動粘度が小さす
ぎる場合あるいはエポキシ価が大きすぎる場合には消泡
性が低下し、またエポキシ価が小さすぎると安定性が低
下することとなる。
本発明の潤滑油組成物においては、上記エポキシ構造
を有するポリシロキサンを、前記基油100重量部に対し
て0.0001〜1重量部、好ましくは0.001〜0.1重量部の割
合で配合する。ここでエポキシ構造を有するポリシロキ
サンの配合割合が少なすぎると目的とする消泡効果が充
分に発現せず、また多すぎると溶解性が低下して様々な
不都合を生ずる。
本発明の潤滑油組成物は、以上の如き基油及びエポキ
シ構造を有するポリシロキサンを主成分とするものであ
るが、さらに必要に応じて各種添加剤、例えば酸化防止
剤,極圧剤,油性剤,銅不活性化剤,等を適宜配合する
こともできる。
ここで、酸化防止剤としては2,6−ジ−t−ブチル−
p−クレゾール;2,6−ジ−t−ブチル−p−エチルフェ
ノール;4,4′−メチレンビス(2,6−ジ−t−ブチルフ
ェノール)などのフェノール系酸化防止剤やフェニル−
α−ナフチルアミン;オクチル化−フェニル−α−ナフ
チルアミン;モノ−オクチル化ジフェニルアミン;ジ−
オクチル化ジフェニルアミンなどのアミン系酸化防止剤
がある。
また、極圧剤としてはリン系極圧剤やイオウ系極圧剤
があげられるが、このうちリン系極圧剤は、ホスフェー
ト系(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(イソプロピルフェニル)ホスフェート,
トリブチルホスフェート,トリオクチルホスフェート,
トリフェニルチオホスフェート,トリクレジルチオホス
フェートなど)及びホスファイト系(トリフェニルホス
ファイト,トリクレジルホスファイト,トリ(ノニルフ
ェニル)ホスファイト,トリラウリルホスファイト,ト
リステアリルホスファイト,トリラウリルチオホスファ
イトなど)に分類することができる。またイオウ系極圧
剤の具体例としては、ジ−ラウリルチオジプロピオネー
ト,ジトリデシルチオジプロピオネート,ジステアリル
チオジプロピオネート,チオフェン,ベンゾチオフェ
ン,ドデシルサルファイド,ステアリルメルカプタンな
どが挙げられる。
さらに、油性剤としてはジ(2−エチルヘキシル)セ
バケート,ジ(2−エチルヘキシル)アゼレートなどが
あり、銅不活性化剤としてはベンゾトリアゾール,メチ
ルベンゾトリアゾール,ジメチルベンゾトリアゾール,
メルカプトベンゾチアゾールなどがあげられる。
〔実施例〕
次に、本発明を実施例および比較例に基いて更に詳し
く説明する。
実施例1〜5および比較的1〜6 第1表に示す基油に、第2表に示すエポキシ構造を有
するポリシロキサン等を所定割合で配合して潤滑油組成
物を調製し、得られた潤滑油組成物についてシールドチ
ューブ試験および泡立ち性試験を行った。その結果を第
3表に示す。
なお、シールドチューブ試験は次の如く行った。即
ち、鋼,銅およびアルミニウム線を入れた内容量10mlの
ガラス製耐圧アンプルに試料油4mlを注射器で入れ、脱
気処理した。液体窒素で冷却しながら冷媒ジクロロジフ
ルオロメタンを2g入れた後、バーナーでシールした。こ
のシールしたアンプルを175℃の油浴に480時間放置し
た。試験終了後、アンプルを液体窒素で冷却して開封
し、この開封端を約100mlの蒸留水に吸収させ、しかる
後に0.1規定の水酸化カリウム溶液で滴定して塩酸発生
量を算出するとともに、油の外観度化を観察した。
また、泡立ち性試験はJIS K−2518に準拠して行っ
た。
上記第3表から次の(1)〜(5)のことがわかる。
(1) 比較例1及び6では、基油単独の評価を行って
いるが、シールドチューブ試験特性は悪く、また泡立ち
も多い。
(2) 比較例2及び3は、低粘度(25℃の動粘度が10
00cSt未満)のエポキシ構造を有するポリシロキサンを
配合した組成物であり、新油及び劣化油とも泡立ちが多
い。
(3) 比較例4は、従来から汎用されている消泡剤で
あるジメチルシリコーンを用いた例であるが、シールド
チューブ試験特性が悪い。
(4) 比較例5は、従来から汎用されている塩酸捕捉
剤であるフェニルグリシジルエーテルを用いた例である
が、泡立ちが多い。
(5) 実施例1〜5は、鉱油あるいは合成油からなる
基油に、高粘度(25℃の動粘度が1000cSt以上)のエポ
キシ構造を有するポリシロキサンを配合した組成物であ
り、シールドチューブ試験特性が良好であるとともに、
新油及び劣化油とも泡立ちが少ない。
〔発明の効果〕
以上説明した如く、本発明の潤滑油組成物は、フロン
等の各種冷媒の存在下において、高温安定性ならびに消
泡性にすぐれたものである。
したがって、本発明の潤滑油組成物は、冷凍機油,ヒ
ートポンプ油等として有効に利用される。
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 C10N 20:02 30:18 40:30

Claims (1)

    (57)【特許請求の範囲】
  1. 【請求項1】40℃における動粘度が5〜500cStの基油10
    0重量部に、25℃における動粘度が1000cSt以上のエポキ
    シ構造を有するポリシロキサンを0.0001〜1重量部の割
    合で配合したことを特徴とするフロン雰囲気用潤滑油組
    成物。
JP63017333A 1988-01-29 1988-01-29 フロン雰囲気用潤滑油組成物 Expired - Fee Related JP2585339B2 (ja)

Priority Applications (4)

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JP63017333A JP2585339B2 (ja) 1988-01-29 1988-01-29 フロン雰囲気用潤滑油組成物
KR1019890701780A KR950002349B1 (ko) 1988-01-29 1989-01-25 프론 분위기용 윤활유 조성물
US07/415,236 US5084196A (en) 1988-01-29 1989-01-25 Lubricating oil composition for flon atmosphere comprising a polysiloxane having epoxy structure
PCT/JP1989/000063 WO1989007128A1 (en) 1988-01-29 1989-01-25 Lubricating oil composition for use in flon atmosphere

Applications Claiming Priority (1)

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US5185089A (en) * 1990-05-10 1993-02-09 Allied-Signal Inc. Lubricants useful with 1,1-dichloro-2,2,2-trifluoroethane
WO1992017559A1 (en) * 1991-04-05 1992-10-15 Allied-Signal Inc. Stabilized dichlorotrifluoroethane refrigeration compositions
US5431835A (en) * 1992-02-18 1995-07-11 Idemitsu Kosan Co., Ltd. Lubricant refrigerant comprising composition containing fluorohydrocarbon
US5976399A (en) 1992-06-03 1999-11-02 Henkel Corporation Blended polyol ester lubricants for refrigerant heat transfer fluids
WO1993024585A1 (en) 1992-06-03 1993-12-09 Henkel Corporation Polyol ester lubricants for refrigerant heat transfer fluids
US6183662B1 (en) 1992-06-03 2001-02-06 Henkel Corporation Polyol ester lubricants, especially those compatible with mineral oils, for refrigerating compressors operating at high temperatures
RU2161642C2 (ru) * 1995-07-10 2001-01-10 Идемицу Козан Ко., Лтд. Холодильное масло и способ смазывания системы охлаждения
KR100199281B1 (ko) * 1996-08-17 1999-06-15 김광호 냉동압축기의 소음을 감쇄시킬 수 있는 압축기 윤활제 조성물
CN1304540C (zh) * 2003-05-28 2007-03-14 中国科学院上海有机化学研究所 一种氟硅润滑油和合成方法
US7399734B2 (en) * 2003-07-22 2008-07-15 Crompton Corporation Polysiloxane additives for lubricants and fuels
CN113563949B (zh) * 2021-06-25 2022-05-17 中铁第五勘察设计院集团有限公司 一种阻燃性手涂型盾尾密封油脂及其制备方法

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US3219624A (en) * 1960-04-25 1965-11-23 Gen Electric Epoxy organopolysiloxanes
BE794875A (fr) * 1972-02-02 1973-08-01 Rhone Poulenc Sa Procede de desaeration de composes liquides
US4185140A (en) * 1974-07-24 1980-01-22 Xerox Corporation Polymeric release agents for electroscopic thermoplastic toners
JPS57159892A (en) * 1981-03-27 1982-10-02 Matsushita Refrig Co Lubricant oil for freezer
JPS57177097A (en) * 1981-04-23 1982-10-30 Nippon Oil Co Ltd Oil composition for refrigerator
JPS5869298A (ja) * 1981-10-20 1983-04-25 Matsushita Refrig Co 冷凍機用潤滑油
JPS61266494A (ja) * 1985-05-20 1986-11-26 Nippon Mining Co Ltd フロン雰囲気下で用いる潤滑油
JPS6291560A (ja) * 1985-10-18 1987-04-27 Asahi Glass Co Ltd 潤滑性樹脂組成物

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US5084196A (en) 1992-01-28
KR950002349B1 (ko) 1995-03-16
WO1989007128A1 (en) 1989-08-10
JPH01193393A (ja) 1989-08-03
KR900700582A (ko) 1990-08-16

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