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JP3038062B2 - 冷凍機用潤滑剤 - Google Patents

冷凍機用潤滑剤

Info

Publication number
JP3038062B2
JP3038062B2 JP3266448A JP26644891A JP3038062B2 JP 3038062 B2 JP3038062 B2 JP 3038062B2 JP 3266448 A JP3266448 A JP 3266448A JP 26644891 A JP26644891 A JP 26644891A JP 3038062 B2 JP3038062 B2 JP 3038062B2
Authority
JP
Japan
Prior art keywords
weight
lubricant
parts
present
chlorine
Prior art date
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
JP3266448A
Other languages
English (en)
Other versions
JPH05105896A (ja
Inventor
民次 鎌倉
典義 田中
公義 浪波
幸男 ▲巽▼
直人 並木
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.)
Adeka Corp
Original Assignee
Asahi Denka Kogyo KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asahi Denka Kogyo KK filed Critical Asahi Denka Kogyo KK
Priority to JP3266448A priority Critical patent/JP3038062B2/ja
Priority to AT92309315T priority patent/ATE148738T1/de
Priority to EP92309315A priority patent/EP0537983B1/en
Priority to DE69217322T priority patent/DE69217322T2/de
Publication of JPH05105896A publication Critical patent/JPH05105896A/ja
Priority to US08/512,747 priority patent/US5620950A/en
Application granted granted Critical
Publication of JP3038062B2 publication Critical patent/JP3038062B2/ja
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/108—Phenothiazine
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/32—Wires, ropes or cables lubricants
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    • C—CHEMISTRY; METALLURGY
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Description

【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明は冷凍機用潤滑剤に関し、
詳しくはフロン１３４ａ（１，１，１，２−テトラフル
オロエタン）等のような塩素を含まないフロン系冷媒を
使用した冷凍機用の潤滑剤に関する。
【０００２】
【従来の技術】従来から冷凍機には、化学的に安定でか
つ毒性の低い優れた冷媒としてフロン系冷媒が使用され
てきた。しかしながら、このフロン系冷媒のうちクロロ
フルオロカーボン、例えばフロン１２（ジクロロジフル
オロメタン）は、成層圏に存在するオゾン層の破壊や地
球温暖化の原因になるとして、２０００年全廃が先のモ
ントリオール議定書において決定している。
【０００３】こうした中で、フロン１２の代替としてフ
ロン１３４ａ等に代表される、分子中に塩素を含まない
フロン系冷媒が開発された。
【０００４】しかしながら、これらフロン１３４ａ等の
分子中に塩素を含まないフロン系冷媒はフロン１２に比
べて極性が高く、今までに冷凍機用潤滑剤として用いら
れてきたナフテン鉱油やアルキルベンゼン等との相溶性
が悪く、これを改善するため米国特許第４，７５５，３
１６号明細書、特開平３−２８２９６号公報等に使用さ
れるポリアルキレングリコール系冷凍機用潤滑剤や、特
開平２−２６８０６８号公報、特開平３−８８８９２号
公報、特開平３−１２８９９１号公報、特開平３−１２
８９９２号公報等に示されるエステル系冷凍機用潤滑剤
が提案されている。
【０００５】一方、冷凍機のコンプレッサー内には微量
の水分及び酸素が存在しており、上記ポリアルキレング
リコール系冷凍機油を潤滑油として使用した場合、酸化
劣化して酸価上昇する傾向があり、また、エステル系冷
凍機油を潤滑油として使用すると加水分解して遊離酸を
生成するため、実用性に乏しかった。
【０００６】これらを改善するために、特願平２−７３
６４９号、特願平２−１６４４３１号にフロン１３４ａ
等と相溶性の良いクリシジルエーテル型のエポキシ化合
物の安定剤としての使用が提案されている。
【０００７】
【発明が解決しようとする課題】しかしながら、特願平
２−７３６４９号、特願平２−１６４４３１号に提案さ
れているフロン１３４ａ等と相溶性のよいグリシジルエ
ーテル型のエポキシ化合物は、製品中に塩素が必ず残存
しており環境上好ましくないうえに、遊離酸等との反応
が遅いため生成した遊離酸による腐食の抑制が不十分で
ある等の欠点があった。
【０００８】従って、本発明の目的は、速やかに遊離酸
と反応し、かつフロン１３４ａ等の塩素を含まないフロ
ン系冷媒と相溶性のよい安定剤を含有する冷凍機用潤滑
剤を提供することにある。
【０００９】
【課題を解決するための手段】本発明者らは、塩素を含
まないフロン系冷媒を使用する冷凍機用の潤滑剤につい
て鋭意研究した結果、本発明に到達した。即ち、本発明
は合成油１００重量部に対して、分子中に次式
【化２】 （式中、Ｒ1及びＲ2は水素またはメチル基であり、同一
であっても異なっていてもよい）で示される官能基を１
個含有し、且つ残基の炭素数が２〜６である脂環式エポ
キシ化合物を０．０５〜１５重量部配合したことを特徴
とする、分子中に塩素を含まないフロン系冷媒を使用す
る冷凍機用潤滑剤に係わる。
【００１０】
【発明の実施の形態】上記式（１）で示される官能基を
１個含有する化合物として好ましいものは、例えば式
（１）で示される官能基の残基として、炭素原子数が２
〜６のアルキル基、アルケニル基、アリル基、アリール
基等の炭化水素基または炭素原子数が２〜６のエポキシ
基、ヒドロキシル基、エステル基、エーテル基等の含酸
素基等を含有する脂環式エポキシ化合物を挙げることが
でき、具体的には、下記の表３に示されるものである。
【００１１】
【表３】
【００１２】上記表１中、Ｒは炭素原子数１〜６の直鎖
または分岐のアルキル基またはアルケニル基であるが、
上記式（１）で示される官能基の残基の炭素原子数の合
計は２〜６である。
【００１３】本発明に用いられる脂環式エポキシ化合物
としてフロン１３４ａ等との相溶性の点で特に好ましい
のは、上記式（１）で示される官能基の残基の炭素数が
２〜６の場合であり、これらのうちでも更に遊離酸との
反応性の点から最も好ましいものは下記の表４に示され
るものである。
【００１４】
【表４】
【００１５】本発明に使用する上記脂環式エポキシ化合
物の添加量は合成系冷凍機基油１００重量部に対して
０．０５〜１５重量部の範囲であればよく、好ましくは
０．５〜１０重量部、更に好ましくは０．５〜５重量部
である。
【００１６】上記量未満の添加量では充分な効果が得ら
れず、上記量を超えても添加効果はさほど向上せず、逆
にポリメリゼイションを起こしスラッジの原因となる。
【００１７】更に、本発明に使用される合成油としては
フロン１３４ａ等の分子内に塩素を含有しないフロン系
冷媒と相溶性のよいものであれば特に限定されないが、
好ましくはフロン１３４ａ等の分子内に塩素を含有しな
いフロン系冷媒と−３０℃〜５０℃の範囲で事実上相溶
し、かつ１００℃における動粘度が２〜５０ｃＳｔであ
ればよく、例えばポリオキシアルキレングリコール及び
その変性物、ネオペンチルポリオールエステル、二塩基
酸エステル、ポリエステル、フッ素化油等が適用でき、
これらのうち１種または１種以上の混合物として使用す
ることができる。
【００１８】これらの合成油を具体的に説明すると、ポ
リオキシアルキレングリコールとしては、ポリオキシプ
ロピレングリコール、ポリオキシエチレングリコール、
ポリオキシエチレンポリオキシプロピレングリコール等
が挙げられ、これらは好ましくは分子量２００〜３００
０がよい。また、ポリオキシエチレンポリオキシプロピ
レングリコール中のオキシエチレン基とオキシプロピレ
ン基はランダム状でもブロック状でもよい。
【００１９】ポリオキシアルキレングリコールの変性物
としてはポリオキシアルキレングリコールモノアルキル
エーテル、ポリオキシアルキレングリコールジアルキル
エーテル、ポリオキシアルキレングリコールモノエステ
ル、ポリオキシアルキレングリコールジエステルアルキ
レンジアミンのアルキレンオキサイド付加物等が使用で
き、具体的には上記ポリオキシアルキレングリコールと
炭素原子数１〜１８の直鎖または分岐のアルキル基との
エーテル、炭素原子数２〜１８の脂肪族カルボン酸との
エステルやエチレンジアミン、ジエチレントリアミン、
トリエチレンテチラアミンのプロピレンオキサイド付加
物、エチレンオキサイド付加物、エチレンオキサイドプ
ロピレンオキサイドランダム付加物、エチレンオキサイ
ドプロピレンオキサイドブロック付加物等が挙げられ、
更にポリオキシアルキレングリコールグリセロールトリ
エーテル、ポリオキシアルキレングリコールハロゲン化
物（特に塩素化物がよい）も上記ポリオキシアルキレン
グリコールの変性物として挙げることができる。
【００２０】ネオペンチルポリオールエステルとして
は、炭素原子数２〜１８、好ましくは２〜９の脂肪族カ
ルボン酸とネオペンチルポリオールとのエステルが好ま
しく、特にトリメチロールプロパン、ペンタエリスリト
ール、ジペンタエリスリトール、トリペンタエリスリト
ールとのエステルが好ましい。
【００２１】二塩基酸エステルとして好ましいのは、炭
素原子数４〜１２の二価カルボン酸と炭素原子数４〜１
８の１級または２級アルコールとのエステルであり、具
体的にはブチルフタレート、ジヘキシルフタレート等を
挙げることができる。
【００２２】ポリエステルとしては、特開平３−１２８
９９１号公報、特開平３−１２８９９２号公報等に記載
された化合物、例えば炭素原子数５〜１２の２価アルコ
ール及び／または炭素原子数１５以下の３価以上の多価
アルコール等の多価アルコールと、炭素原子数２〜１８
の１価脂肪酸及び／または炭素原子数４〜１４の多塩基
酸からなるポリエステルを挙げることができる。
【００２３】フッ素化油としては特開平３−７７９８号
公報に記載のパーフルオロエーテル等を挙げることがで
きる。
【００２４】本発明の冷凍機用潤滑剤は他のエポキシ化
合物との併用を妨げるものではない。
【００２５】また、本発明の冷凍機用潤滑剤は、本発明
の目的の範囲内で所望により極圧剤例えばトリクレジル
ホスフェートあるいはα−ナフチルベンジルアミン、フ
ェノチアジン、ＢＨＴなどの酸化防止剤を通常の添加量
の範囲内で使用することもできる。
【００２６】
【実施例】以下、実施例により本発明を詳細に説明する
が、本発明はこれらの実施例に限定されるものではな
い。なお、実施例には以下に示す試料１〜６の添加剤及
び試料７〜８の基油を用いた。
【００２７】試料１ 次の式で示されるエポキシ化合物。
【化３】
【００２８】試料２ 次の式で示されるエポキシ化合物。
【化４】
【００２９】試料３ 次の式で示されるエポキシ化合物。
【化５】
【００３０】試料４ 次の式で示されるエポキシ化合物。
【化６】
【００３１】試料５ フェニルグリシジルエーテル。 試料６ エポシキ化大豆油。
【００３２】試料７ 次の式で示されるポリプロピレングリコールジアセテー
ト。
【化７】 （１００℃における動粘度は９．８ｃＳｔ）
【００３３】試料８ ２−メチルブタン酸及びヘキサン酸（モル比＝１：１）
の混合物とペンタエリスリトールのフルエステル。（１
００℃における動粘度は４．２ｃＳｔ）
【００３４】実施例１及び比較例１ 表５に示す各種冷凍機油組成物１５重量部及びフロン１
３４ａを８５重量部仕込み、−５０〜６０℃における相
溶性を調べた。結果は表５に示す通り、本発明品はフロ
ン１３４ａとの相溶性に優れていた。
【００３５】
【表５】
【００３６】実施例２及び比較例２ 試料７、８を表６に示す有機酸で表６に示す酸価に調整
した後、２００ｇずつ３００ｍｌのガラス製ビーカーに
取り、添加剤を２ｇずつ添加してそれぞれ６０℃で加熱
撹拌し、経時的に採取し酸価を測定した。結果を表６に
示す。表６から明らかなように本発明品は素早く酸価を
低減した。試料７、８の初期酸価はそれぞれ０．０１、
０．０２であった。
【００３７】
【表６】
【００３８】実施例３及び比較例３ 表７に示す各種冷凍機油組成物に水１０００ｐｐｍを加
えた後、その各混合物２０重量部及びフロン１３４ａ８
０重量部を１００ｍｌステンレス（ＳＵＳ−３１６）製
オートクレーブに入れ、更に鋼、銅、アルミニウムの金
属片（５０×２５×１．５ｍｍ）を各１枚加え密封した
後、１５０℃で１４日間（３３６時間）加熱した。加熱
試験終了後、真空脱気してフロン１３４ａ及び水分を除
去し、試験後の冷凍機油組成物の動粘度、外観、酸価を
評価した。また、金属片はトルエン及びメタノールで洗
浄し、重量の増減を測定した。結果をまとめて表８に示
す。
【００３９】
【表７】
【００４０】
【表８】
【００４１】
【発明の効果】本発明の効果は、速やかに遊離酸と反応
し、かつフロン１３４ａ等の塩素を含まないフロン系冷
媒と相溶性のよい安定剤を含有する冷凍機用潤滑剤を提
供したことにある。即ち、本発明の冷凍機用潤滑剤は、 冷凍機内でフロン１３４ａ等との相溶性に優れている
ため、蒸発器中でのトラブルがない； 冷凍機内で発生した遊離酸、酸化物及びその他の活性
基と速やかに反応し、腐食を防止する、 等の利点を有するものである。
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ１０Ｎ 30:00 40:30 (72)発明者 ▲巽▼ 幸男 東京都荒川区東尾久７丁目２番35号 旭 電化工業株式会社内 (72)発明者 並木 直人 東京都荒川区東尾久７丁目２番35号 旭 電化工業株式会社内 (56)参考文献 特開 平５−209171（ＪＰ，Ａ) 特開 平５−17792（ＪＰ，Ａ) 特開 平５−5098（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C10M 105/38 C10M 129/18 C10M 129/52 C10N 40:30

Claims (3)

    (57)【特許請求の範囲】
  1. 【請求項１】 合成油１００重量部に対して、分子中に
    次式 【化１】 （式中、Ｒ1及びＲ2は水素またはメチル基であり、同一
    であっても異なっていてもよい） で示される官能基を１個含有し、且つ残基の炭素数が２
    〜６である脂環式エポキシ化合物を０．０５〜１５重量
    部配合したことを特徴とする、分子中に塩素を含まない
    フロン系冷媒を使用する冷凍機用潤滑剤。
  2. 【請求項２】 残基が、以下の何れかの基である、請求
    項１記載の冷凍機用潤滑剤： 【表１】
  3. 【請求項３】 脂環式エポキシ化合物が、以下の何れか
    の化合物である、請 求項１記載の冷凍機用潤滑剤： 【表２】
JP3266448A 1991-10-15 1991-10-15 冷凍機用潤滑剤 Expired - Fee Related JP3038062B2 (ja)

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JP3266448A JP3038062B2 (ja) 1991-10-15 1991-10-15 冷凍機用潤滑剤
AT92309315T ATE148738T1 (de) 1991-10-15 1992-10-13 Schmiermittel für kältemaschinen
EP92309315A EP0537983B1 (en) 1991-10-15 1992-10-13 Lubricant for refrigerators
DE69217322T DE69217322T2 (de) 1991-10-15 1992-10-13 Schmiermittel für Kältemaschinen
US08/512,747 US5620950A (en) 1991-10-15 1995-08-08 Lubricated refrigerant composition containing alicyclic epoxy compounds

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JP3266448A JP3038062B2 (ja) 1991-10-15 1991-10-15 冷凍機用潤滑剤

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JPH05105896A JPH05105896A (ja) 1993-04-27
JP3038062B2 true JP3038062B2 (ja) 2000-05-08

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EP (1) EP0537983B1 (ja)
JP (1) JP3038062B2 (ja)
AT (1) ATE148738T1 (ja)
DE (1) DE69217322T2 (ja)

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DE69217322D1 (de) 1997-03-20
US5620950A (en) 1997-04-15
JPH05105896A (ja) 1993-04-27
EP0537983A1 (en) 1993-04-21
ATE148738T1 (de) 1997-02-15
EP0537983B1 (en) 1997-02-05
DE69217322T2 (de) 1997-09-11

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