JPH0328296A - 冷凍機用潤滑剤 - Google Patents

冷凍機用潤滑剤

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Publication number
JPH0328296A
JPH0328296A JP1138026A JP13802689A JPH0328296A JP H0328296 A JPH0328296 A JP H0328296A JP 1138026 A JP1138026 A JP 1138026A JP 13802689 A JP13802689 A JP 13802689A JP H0328296 A JPH0328296 A JP H0328296A
Authority
JP
Japan
Prior art keywords
lubricant
refrigerator
group
weight
sample
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.)
Granted
Application number
JP1138026A
Other languages
English (en)
Other versions
JP2763589B2 (ja
Inventor
Tamiji Kamakura
民次 鎌倉
Yuji Baba
裕二 馬場
Kimiyoshi Harou
波浪　公義
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=15212317&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=JPH0328296(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Asahi Denka Kogyo KK filed Critical Asahi Denka Kogyo KK
Priority to JP1138026A priority Critical patent/JP2763589B2/ja
Priority to US07/509,632 priority patent/US5032305A/en
Priority to DE69000991T priority patent/DE69000991T3/de
Priority to AT90304583T priority patent/ATE86291T1/de
Priority to EP90304583A priority patent/EP0401969B2/en
Publication of JPH0328296A publication Critical patent/JPH0328296A/ja
Application granted granted Critical
Publication of JP2763589B2 publication Critical patent/JP2763589B2/ja
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
    • C10M105/52—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen containing carbon, hydrogen and halogen only
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    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
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    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
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    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/66—Epoxidised acids or esters
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    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
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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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    • C10M169/04—Mixtures of base-materials and additives
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    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/09—Metal enolates, i.e. keto-enol metal complexes
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Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、冷凍機用潤滑剤に関する。詳しくは、冷凍機
内でフロンと相溶性の良いポリオキシアルキレングリコ
ール系の冷凍機用潤滑剤に関する。
〔従来の技術及び発明が解決しようとする課題］フロン
化合物は、化学的安定性、低毒性、不燃性などの面で優
れた物質であり、冷媒、エアゾール、発泡、洗浄などの
分野で広く用いられてきた。しかし、最近では、大気中
に放出されたフロンがＩｆｃＮ圏においてオゾン層を破
壊するとともに、地球の温暖化、いわゆる「温室効果」
の原因となっているとして、特定種類のフロンの生産量
および消費量の削減の動きが強まっている． このため、オゾン層破壊、温室効果の恐れのないフロン
、すなわち分子内に塩素を含まず、比較的分解されやす
いフロンの開発が進んでいる． こうした中で、家庭用冷蔵庫、空調機、業務用小型冷蔵
庫、カーエアコンなどの冷媒として広く用いられてきた
フロン１２　（ジクロロジフルオロメタン）の代替品と
して、フロン１２と物性が類似したフロン１３４ａ　（
１．　１．　１．　２−テトラフルオロエタン）が開発
された． しかしながら、フロン１３４ａは従来冷凍機油として用
いられてきたナフテン系鉱油やアルキルベンゼンとの相
溶性が悪く、蒸発器中での油戻り性の悪化やコンプレッ
サーの焼付け、異常振動などのトラブルを起こすため、
これと相溶性の良い冷凍機油の開発が求められている．
かかるフロン１３４ａを冷媒とした冷凍機油に関しては
、分子量２０００以下の２官能以上のポリオキシアルキ
レングリコールを用いたものがＵＳＰ４７５５３１６に
提案されているが、このものは吸湿しやすく、水分によ
り冷凍機の膨張弁の作動不良や閉塞（水分チッーク）を
起こしたり、フロンの分解を促し、生或したフッ化水素
酸により金属部を腐食させたりする恐れがある．〔課題
を解決するための手段〕 本発明者らは、種々の合戊潤滑油について鋭意検討を行
った結果、ある特定の種類のポリオキシアルキレングリ
コールジアルキルエーテルが、一般のフロン系冷媒だけ
でなく、フロン１３４ａとの相溶性も優れていること、
吸湿性が少ないこと、フロンに対する安定性が優れてい
ることなどを見出し、本発明を完威させた． 即ち、本発明の冷凍機用潤滑剤は、 一般式（１） ＣＩ， （式中ｍは、 ｎは、 ｐは、 ｑは、 ｒは、 ただし、２ １≦ｍ≦８の整数 ｌ≦ｎ≦８の整数 ｌ≦ｐ≦８０の整数 Ｏ≦ｑ≦６０の整数 ０または１ ≦ｍ＋ｎ≦９ ｐ＋ｑ を示す．） で示される化合物を８０重量％以上含有し、かつ４０℃
における動粘度がｆｉｃｓｔ以上、５００　ｃｓｔ以下
であることを特徴とする． 上記一般式（１）において、 ＣＨＩ （ＣＩ！ＣＨＯ）、（ＣＨｚＣＬＯ）、（ＣＨｔＯ）の
各ユニットの配列はブロックでもランダムでも良い．Ｃ
Ｊ！ｓｏ１またはＣ＊Ｈ！ａ＊１で示されるアルキル基
の例としては、メチル基、エチル基、１−プロビル基、
２−プロビル基、１−プチル基、２一プチル基、２−メ
チルーｌ−プロビル基、２一メチル−２−プロビル基、
ｌ−ベンチル基、２−ペンチル基、３−ペンチル基、２
−メチルーｌ−ブチル基、３−メチル−１−ブチル基、
２−メチル−２−ブチル基、ｌ−ヘキシル基、４一メチ
ル−２−ペンチル基、２−エチル−１−ブチル基、ｌ−
ヘプチル基、２−ヘプチル基、３−ヘプチル基、１−オ
クチル基、２−オクチル基、２−エチルヘキシル基など
が挙げられる．このうち、特に好ましいのは、原料の入
手のしやすさから、メチル基、エチル基、１−プロビル
基、１−ブチル基、２−メチル−１−プロビル基、２−
エチルヘキシル基などである．また上記式において、ｍ
＝０またはｎ＝０のものは、吸湿性が高く、冷凍機用潤
滑剤としては不向きである．ｍ＝９以上またはｎ＝９以
上のものは、冷凍機用潤滑剤の実際の使用温度範囲であ
る−５０〜６０℃の間でフロン１３４ａとの分離を起こ
し、種々のトラブルを引き起こし、冷凍機用潤滑剤とし
て好ましくない． また上記式において、 ２≦ｍ＋ｎ≦９ Ｐ＋９ の条件を満足しないものは、冷凍機用潤滑剤の実際の使
用温度範囲である−５０〜６０℃の間でフロン１３４ａ
との分離を起こし、種々のトラブルを引き起こす． かかる本発明のポリオキシアルキレングリコールジアル
キルエーテルは、アルコール類、アルキレンオキサイド
類などを原料とし、通常の付加反応、エーテル化反応な
どを適宜組み合わせて得ることができる。
また、本発明の冷凍機用潤滑剤において、充分な性能を
発揮させるためには、上記一般式（１）で示されるポリ
オキシアルキレングリコールジアルキルエーテルを全組
威物中８０重量％以上含有する必要がある。
さらに、本発明の冷凍機用潤滑剤は、４０″Ｃにおける
動粘度が６ｃｓｔ以上、５００　ｃｓｔ以下であること
を要し、４０″Ｃにおける動粘度が６ｃｓｔ未満である
と、充分な潤滑性を出すことが出来ず、また５００　ｃ
ｓｔを越えるものは、コンプレッサーの負荷が増大して
エネルギー的に不利であるばかりでなく、冷凍機の油分
離管内での油戻り性が悪くなる。
本発明の冷凍機用潤滑剤は、上記一般式（１）で示され
るポリオキシアルキレングリコールジアルキルエーテル
からのみで構威されていてもよいが、フロンを冷媒とし
た冷凍機用潤滑剤の添加剤として公知のもの、例えば、
トリクレジルホスフエートなどの燐酸エステル、トリエ
チルホスファイトなどの亜燐酸エステル、エボキシ化大
豆油、ビスフェノールＡジグリシジルエーテルなどのエ
ボキシ化合物、ジブチル錫ラウレートなどの有機錫化合
物、α−ナフチルベンジルアξン、フエノチアジン、Ｂ
ＨＴなとの酸価防止剤を上記範囲内で添加してもよい。
かかる本発明の冷凍機用潤滑剤は、冷凍機用潤滑剤の実
際の使用温度範囲である−５０〜６０゜Ｃの間で、フロ
ン１３４ａと、事実上あらゆる範囲（１：９９〜９９；
１）で完全に溶解しあう。
〔発明の効果〕
本発明の冷凍機用潤滑剤は、冷凍機内でフロンと相溶性
が良く、とりわけフロン１３４ａとの相溶性が良く、広
範な用途での利用が期待される。
〔実施例〕
以下、実施例により、本発明を更に詳細に説明するが、
本発明はこれらの実施例に限定されるものではない。
尚、以下の実施例においては、次に示す試料１〜１７を
用いて相溶性を調べた。
１ ＣＨ３０（ＣＨｔＣＨＯ）７ＣＩｈ 試料２ ＣＨ３ ＣＩ，０（ＣＨ！Ｃ■０）　ｌ　？Ｃ｝＋３試料３ ＣＩＩＳ Ｉ ＣＩｈＯ（ＣＨｔＣＨＯ）＊＊ＣＨｚ ＣＨｓＣｌｈＧＨｚＣ｝ＩｔＯ（ＣＨｚＣＨＯ）ａ（Ｃ
ＨｚＣＨｔＯ）＋ｔｃＨｓＣＨｚＯ　（ＣＨｚＣＨｚＯ
）　ｓ　（ＣｌｂＣＨＯ）　３１１　（ＣＩｈＣＨｔＯ
）　ｓＣＴｏ試料７（ランダム重合物） 試料８（ランダム重合物） ＣＨ３ ＣＨ：＋ＣＨｚＯ　（ＣＩ１２ＣＨＯ）　Ｉｏ　（ＣＩ
ＩｚＣＩ！ｚＯ）　Ｉｏ　（ＣＩｌｚＯ）　ＩＣｌｌ　
ｚｃｔｈ試料９ ＣＨ３ ＣＨ３ＣＨ！ＣＩ！Ｃ｝１２０　（ＣＨｚＣＨＯ）　ｌ
　ｓｃｌｈ試料１０（ランダム重合物） 試料１１（ランダム重合物） ＣＩ， ｌ ＣＬＯ　（ＣＨｚＣＨＯ）　＋　ｑ　（ＣＨｔＣｌｌｚ
Ｏ）　ｔｉｃ貼試料１２（ランダム重合物） ？Ｂ． 」 ＣＨｓＯ（ＣＨ＊ＣＨＯ）ｚ■（ＣＨｚＣＩＩｚＯ）　
６ａｃｌｌｉ試料１３ ＣＨｓ Ｉ ＨＯ（ＣＨｚＣＨＯ）　ｔｌｌ 試料ｌ４ Ｃ１１３ ｌ ＣＨｓＯ（ＣＩＩｚＣＩＩＯ）　Ｊ １ ＩＯ（ＣＨｚＣＨＯ）＋Ｊ １ ＣＨｓＯ（Ｃ４１ｇＣＨＯ）　ｌｔＨ 実施例Ｉ Ｉｆガラス製オートクレープに、■第ｌ表に示す試料１
５重量部、第ｌ表に示すフロン８５重量部、■第１表に
示す試料６０重量部、第ｌ表に示すフロン４０重量部を
仕込み、−５０℃〜６０℃における相溶性を調べた． 結果を第１表に示した。
比較例１ 実施例１■と同様にして第２表に示す試料の相溶性を調
べた。
結果を第２表に示した。
実施例２ １００　ｄビーカーに第３表に示す試料１０ｇを取り、
２０゜Ｃ、湿度６０％の恒温恒湿槽に入れ、２４時間後
の重量変化を調べた。
結果を第３表に示す。
第　　　３　　　表 第 ４ 表 比較例２ 第４表に示す試料を用い、実施例２と同様の方法で吸水
性を調べた。結果を第４表に示す。
第４表から明らかな如く、いずれも、実施例２における
よりも重量の増加が大きく、吸水性が高い． 実施例３ １００　ｄｉ　スｆ　ン１／　ス（ＳＯＳ−３１６　）
製オートクレープに第５表に示す試料（試料Ｎｏ．ｌ．
　　２．　　４）１４重量部、ジプチル錫ラウレート　
（アデカアーガス製マークＢＴ−１１）　０．７重量部
、エボキシ化大豆油（アデカアーガス製アデカサイザー
０−　１３０Ｐ　）０．３重量部、を取り、試験前の冷
凍機用潤滑剤の粘度及び外観を評価した。次いで、これ
にフロン２２を７５重量部加え、さらに、鋼、銅、アル
ξニウムの金属片（５０Ｘ２５Ｘ１．５　ｍｍ）各１枚
を入れ、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２２を
除去し、試験後の冷凍機用潤滑剤の粘度と外観を評価し
た。また、金属片はトルエン及びエタノールで洗浄し、
重量の増減を測定した．本発明の冷凍機用潤滑剤は、い
ずれも粘度変化率がーｌＯ〜−２２％であり、金属への
影響も少なく、フロン共存時における化学的安定性が優
れていることが明らかである。
試験結果は第５表に示す。
比較例３ 実施例３と同様の方法で、第５表に示す各試料（試料Ｎ
α１３〜１７）に対する安定性を調べた。
いずれも実施例３と比較して、粘度変化率が大きく、金
属の影響も大きいことが判明した。
試験結果は第５表に示す。

Claims (1)

  1. 【特許請求の範囲】 一般式（１） ▲数式、化学式、表等があります▼ （式中ｍは、１≦ｍ≦８の整数 ｎは、１≦ｎ≦８の整数 ｐは、１≦ｐ≦８０の整数 ｑは、０≦ｑ≦６０の整数 ｒは、０または１ ただし、２≦ｍ＋ｎ≦９ −８＜ｍ＋ｎ−（２０×ｑ）／（ｐ＋ｑ）＜４を示す。 ） で示される化合物を８０重量％以上含有し、かつ４０℃
    における動粘度が６ｃｓｔ以上、５００ｃｓｔ以下であ
    ることを特徴とする冷凍機用潤滑剤。
JP1138026A 1989-05-31 1989-05-31 冷凍機用潤滑剤 Expired - Fee Related JP2763589B2 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP1138026A JP2763589B2 (ja) 1989-05-31 1989-05-31 冷凍機用潤滑剤
US07/509,632 US5032305A (en) 1989-05-31 1990-04-13 Lubricant for refrigerant
DE69000991T DE69000991T3 (de) 1989-05-31 1990-04-26 Schmiermittel für Kühlapparate.
AT90304583T ATE86291T1 (de) 1989-05-31 1990-04-26 Schmiermittel fuer kuehlapparate.
EP90304583A EP0401969B2 (en) 1989-05-31 1990-04-26 Lubricant for refrigerant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1138026A JP2763589B2 (ja) 1989-05-31 1989-05-31 冷凍機用潤滑剤

Publications (2)

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JPH0328296A true JPH0328296A (ja) 1991-02-06
JP2763589B2 JP2763589B2 (ja) 1998-06-11

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US (1) US5032305A (ja)
EP (1) EP0401969B2 (ja)
JP (1) JP2763589B2 (ja)
AT (1) ATE86291T1 (ja)
DE (1) DE69000991T3 (ja)

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US5620950A (en) * 1991-10-15 1997-04-15 Asahi Denka Kogyo K.K. Lubricated refrigerant composition containing alicyclic epoxy compounds
US6217791B1 (en) 1991-12-18 2001-04-17 Asahi Denka Kogyo K.K. Refrigerant incorporating a polyoxyalkylene glycol monomethylether
US6379581B1 (en) 1991-08-05 2002-04-30 Asahi Denka Kogyo, K.K. Lubricated refrigerant composition containing fluorocarbon-type refrigerant, synthetic oil and molybdenumoxysulfide derivatives
WO2007026647A1 (ja) * 2005-08-31 2007-03-08 Idemitsu Kosan Co., Ltd. 冷凍機油組成物

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EP0449406B1 (en) * 1990-01-31 1997-04-09 Tonen Corporation Esters as lubricants for a haloalkane refrigerant
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ATE184310T1 (de) * 1992-06-03 1999-09-15 Henkel Corp Polyol/ester-gemisch als schmiermittel für wärmeträgerflüssigkeiten in kälteanlagen
JP3521216B2 (ja) * 1992-06-03 2004-04-19 コグニス コーポレーション 高温で運転する冷凍コンプレッサー用ポリオールエステル潤滑剤
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US6379581B1 (en) 1991-08-05 2002-04-30 Asahi Denka Kogyo, K.K. Lubricated refrigerant composition containing fluorocarbon-type refrigerant, synthetic oil and molybdenumoxysulfide derivatives
US5620950A (en) * 1991-10-15 1997-04-15 Asahi Denka Kogyo K.K. Lubricated refrigerant composition containing alicyclic epoxy compounds
US6217791B1 (en) 1991-12-18 2001-04-17 Asahi Denka Kogyo K.K. Refrigerant incorporating a polyoxyalkylene glycol monomethylether
WO2007026647A1 (ja) * 2005-08-31 2007-03-08 Idemitsu Kosan Co., Ltd. 冷凍機油組成物
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Also Published As

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ATE86291T1 (de) 1993-03-15
EP0401969B1 (en) 1993-03-03
US5032305A (en) 1991-07-16
EP0401969A1 (en) 1990-12-12
DE69000991D1 (de) 1993-04-08
DE69000991T2 (de) 1993-07-22
JP2763589B2 (ja) 1998-06-11
DE69000991T3 (de) 1997-04-10
EP0401969B2 (en) 1996-09-11

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