JP2745585B2 - Composition for compression refrigerator - Google Patents
Composition for compression refrigeratorInfo
- Publication number
- JP2745585B2 JP2745585B2 JP63284011A JP28401188A JP2745585B2 JP 2745585 B2 JP2745585 B2 JP 2745585B2 JP 63284011 A JP63284011 A JP 63284011A JP 28401188 A JP28401188 A JP 28401188A JP 2745585 B2 JP2745585 B2 JP 2745585B2
- Authority
- JP
- Japan
- Prior art keywords
- oil
- composition
- compound
- compressor
- group
- 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
Links
Landscapes
- Lubricants (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は圧縮式冷凍機に用いる圧縮機の摺動部におけ
る摩擦、摩耗及び焼き付き防止等を図る圧縮式冷凍機用
組成物に関するものである。Description: TECHNICAL FIELD The present invention relates to a composition for a compression-type refrigerator for preventing friction, wear, seizure and the like in a sliding portion of a compressor used in the compression-type refrigerator. .
［従来の技術］ 従来、フロン圧縮機用潤滑油としてはナフテン系鉱物
油、パラフィン系鉱物油、アルキルベンゼン系合成油、
ポリ−α−オレフィン系合成油が知られており、圧縮機
摺動部における摩擦、摩耗及び焼き付き防止等を図る目
的より使用されている。[Prior art] Conventionally, naphthenic mineral oil, paraffin mineral oil, alkylbenzene synthetic oil,
Poly-α-olefin-based synthetic oils are known and used for the purpose of preventing friction, wear, seizure and the like in sliding portions of a compressor.
フロン圧縮機用潤滑油として要求される特性として
は、一般の潤滑油と異なり、冷媒としてのフロンとの接
触を伴うため、冷媒に対する安定性が良好であること、
冷媒との溶解性が優れていること、素材として用いられ
るパッキン類等高分子材料を溶解しないこと等が要求さ
れる。The characteristics required as lubricating oil for chlorofluorocarbon compressor, unlike general lubricating oil, because it involves contact with chlorofluorocarbon as a refrigerant, good stability to the refrigerant,
It is required to have excellent solubility in a refrigerant and not to dissolve polymer materials such as packings used as a material.
従来、冷媒として用いられているジクロロジフルオロ
メタン（以下、R12という）に対して、従来使用されて
いるナフテン系鉱物油、パラフィン系鉱物油、アルキル
ベンゼン系合成油、ポリ−α−オレフィン系合成油は前
述の要求条件を満足しているが、完全にハロゲン化され
たフロン類のオゾン層破壊による環境上の問題が指摘さ
れており、R12に代わる新しい冷媒の開発が急務となっ
ている。R12に代わる新規な冷媒として1,1,1,2−テトラ
フルオロエタン（以下R134aという）が有力視されてい
るが、冷媒として使用するに当たっては、潤滑油が必要
不可欠となる。Conventionally, for dichlorodifluoromethane (hereinafter, referred to as R12) used as a refrigerant, conventionally used naphthenic mineral oil, paraffinic mineral oil, alkylbenzene synthetic oil, and poly-α-olefin synthetic oil are used. Despite satisfying the above-mentioned requirements, environmental problems due to the depletion of the ozone layer of completely halogenated chlorofluorocarbons have been pointed out, and there is an urgent need to develop a new refrigerant to replace R12. Although 1,1,1,2-tetrafluoroethane (hereinafter referred to as R134a) is considered to be a promising new refrigerant in place of R12, lubricating oil is indispensable when used as a refrigerant.
［発明が解決しようとする課題］ R134a圧縮機用潤滑油としては、従来知られているナ
フテン系鉱物油、パラフィン系鉱物油、アルキルベンゼ
ン系合成油、ポリ−α−オレフィン系合成油は要求条件
の一つである潤滑油とR134aの溶解性の点において、溶
解性を示さないという欠点を有している。[Problems to be Solved by the Invention] As the lubricating oil for R134a compressor, conventionally known naphthenic mineral oil, paraffinic mineral oil, alkylbenzene synthetic oil and poly-α-olefin synthetic oil are required conditions. In terms of solubility of one of the lubricating oils and R134a, it has a disadvantage of not exhibiting solubility.
R134aと潤滑油の溶解性が不良であると圧縮機より飛
沫同伴などにより持ち出された潤滑油が凝縮器、蒸発
器、ドライヤ、配管等にて、冷媒と分離することによ
り、粘度が極めて高くなり、圧縮機への油戻りの不良を
生じ、圧縮機内での油量の低下、さらには摺動部におけ
る摩擦、摩耗、圧縮機の巻き付き等の不具合を生じ好ま
しくない。If the solubility of R134a and the lubricating oil is poor, the lubricating oil taken out from the compressor by entrainment will be separated from the refrigerant in the condenser, evaporator, dryer, piping, etc., resulting in extremely high viscosity. This causes unsatisfactory return of oil to the compressor, resulting in a decrease in the amount of oil in the compressor, and further causes problems such as friction and abrasion in the sliding portion and winding of the compressor.
一方、R134aと溶解性を示す潤滑油としては、アルコ
ール性水酸基（OH基）を含有するポリアルキレングリコ
ール油が提案されている（USP 4,755,316等）。しか
し、アルコール性水酸基（OH基）を有する物質は低級脂
肪族ハロゲン化炭化水素と容易に反応し、分解すること
が知られている。一例として、トリクロロフルオロメタ
ンとメタノールの反応を以下に示すが、反応により分解
し、アルデヒドやケトンを生じるといわれている。On the other hand, as a lubricating oil exhibiting solubility with R134a, a polyalkylene glycol oil containing an alcoholic hydroxyl group (OH group) has been proposed (USP 4,755,316 and the like). However, substances having an alcoholic hydroxyl group (OH group) are known to easily react with lower aliphatic halogenated hydrocarbons and decompose. As an example, the reaction between trichlorofluoromethane and methanol is shown below. It is said that the reaction decomposes to produce aldehydes and ketones.
CCl3F＋CH3OH→CHCl2F＋HCHO＋HCl R134aとアルコール性水酸基を有するポリアルキレン
グリコール油の組み合わせにおいても同様の反応が生じ
る。このような分解が生じると、分解の結果生成したハ
ロゲン化水素による機器の腐食、潤滑性能の低下等を生
じ好ましくない。A similar reaction occurs in a combination of CCl 3 F + CH 3 OH → CHCl 2 F + HCHO + HCl R134a and a polyalkylene glycol oil having an alcoholic hydroxyl group. If such decomposition occurs, corrosion of equipment and deterioration of lubricating performance due to hydrogen halide generated as a result of the decomposition are not preferred.
［課題を解決するための手段］ 本発明は前述の問題点を解決すべく、R134a圧縮機用
潤滑油の検討を重ねた結果、本発明者らはアルキレング
リコール油中のアルコール性水酸基（OH基）を下記化合
物（Ｉ）のように改良することが好ましいことを見出
し、本発明を完成するに至った。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present invention has studied the lubricating oil for R134a compressor. As a result, the present inventors have found that alcoholic hydroxyl groups (OH groups) ) Was found to be improved as in the following compound (I), and the present invention was completed.
Ｒ−ＯR1−ＯnR2 ……（Ｉ） ［Ｒは炭化水素基、R1はアルキレン基、R2は含フッ素ア
ルキル基、ｎは上記化合物（Ｉ）の粘度が10〜300cst
（40℃）となる正数］ 即ち、本発明はR134a圧縮機用潤滑油として前記化合
物（Ｉ）を用いることにより圧縮機の摺動部における摩
擦、摩耗及び巻き付き防止等を図ることができる化合物
（Ｉ）及びR134aからなる圧縮式冷凍機用組成物に関す
るものである。 R-OR 1 -O n R 2 ...... (I) [R is a hydrocarbon group, R 1 is an alkylene group, R 2 is a fluorine-containing alkyl group, n is the viscosity of the compound (I) 10~300cst
(40 ° C.) That is, the present invention provides a compound capable of preventing friction, wear, wrapping and the like in a sliding portion of a compressor by using the compound (I) as a lubricating oil for an R134a compressor. The present invention relates to a composition for a compression refrigerator comprising (I) and R134a.
本発明における前記化合物（Ｉ）は、圧縮機の摺動部
における摩擦、摩耗及び焼き付き防止等の機能を充分に
達成するために、その粘度が10〜300cst（40℃）であ
り、化合物（Ｉ）における分子量あるいはｎの値はこの
ような粘度範囲となるような値を選択する。The compound (I) in the present invention has a viscosity of 10 to 300 cst (40 ° C.) in order to sufficiently achieve functions such as friction, wear and seizure in a sliding portion of a compressor. The value of molecular weight or n in ()) is selected so as to fall within such a viscosity range.
前記化合物（Ｉ）におけるＲは飽和又は不飽和の直鎖
又は分岐の炭化水素基であり、好ましくは炭素数１〜10
のアルキル基である。R1Oとしてはエチレンオキサイ
ド、プロピレンオキサイド、ブチレンオキサイド等が好
ましく、特にプロピレンオキサイドが好ましい。又、こ
れらのアルキレンオキサイドを２種以上組み合わせたブ
ロック又はランダム結合でもよく、この場合プロピレン
オキサイドを主体とすることが好ましい。R2としては炭
素数１〜20の直鎖又は分岐状含フッ素アルキル基であ
り、アルキル基の水素原子がすべてフッ素原子で置換さ
れたパーフルオロアルキル基や水素原子の一部又は全部
がフッ素原子さらには塩素原子等のハロゲン原子で置換
されたポリフルオロアルキル基である。R in the compound (I) is a saturated or unsaturated linear or branched hydrocarbon group, and preferably has 1 to 10 carbon atoms.
Is an alkyl group. As R 1 O, ethylene oxide, propylene oxide, butylene oxide and the like are preferable, and propylene oxide is particularly preferable. Further, a block or a random bond in which two or more of these alkylene oxides are combined may be used, and in this case, it is preferable to mainly use propylene oxide. R 2 is a linear or branched fluorine-containing alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms, or a part or all of the hydrogen atoms is a fluorine atom Further, it is a polyfluoroalkyl group substituted with a halogen atom such as a chlorine atom.
前記化合物（Ｉ）とR134aの重量比は1/99〜99/1、好
ましくは5/95〜60/40である。本発明の組成物は、低温
〜高温分野の冷凍、冷蔵及び空調を目的とした冷凍サイ
クルの応用の場合に特に有効であるが、ランキンサイク
ル等のその他各種の熱回収技術用としても使用可能であ
る。The weight ratio of the compound (I) to R134a is 1/99 to 99/1, preferably 5/95 to 60/40. The composition of the present invention is particularly effective in the application of a refrigeration cycle for low-temperature to high-temperature refrigeration, refrigeration and air conditioning, but can also be used for various other heat recovery technologies such as a Rankine cycle. is there.
本発明の組成物は、熱安定性が優れており、通常の使
用条件においては安定剤を必要としないが、過酷な使用
条件のため熱安定性の向上が必要な場合には、ジメチル
ホスファイト、ジイソプロピルホスファイト、ジフェニ
ルホスファイト等のホスファイト系化合物、トリフェニ
ルホスフィンサルファイド、トリメチルホスフィンサル
ファイド等のホスフィンサルファイド系化合物その他グ
リシジルエーテル類等の安定剤を少量添加すれば良い。
又、本発明の化合物（Ｉ）と従来使用されているナフテ
ン系鉱物油、パラフィン系鉱物油、アルキルベンゼン系
合成油、ポリ−α−オレフィン系合成油、フッ素系潤滑
油である含フッ素ポリエーテル油、含フッ素シリコーン
油等、又水酸基を有するポリアルキレングリコール油等
と混合使用することが可能である。The composition of the present invention is excellent in thermal stability and does not require a stabilizer under normal use conditions, but when the heat stability needs to be improved due to severe use conditions, dimethyl phosphite is used. A small amount of a phosphite compound such as diisopropyl phosphite or diphenyl phosphite, a phosphine sulfide compound such as triphenyl phosphine sulfide or trimethyl phosphine sulfide or a stabilizer such as glycidyl ether may be added.
The compound (I) of the present invention and conventionally used naphthenic mineral oils, paraffinic mineral oils, alkylbenzene synthetic oils, poly-α-olefin synthetic oils, and fluorinated polyether oils which are fluorine lubricating oils And a fluorine-containing silicone oil or the like, or a polyalkylene glycol oil having a hydroxyl group.
又、フェノール系やアミン系の酸化防止剤、イオウや
リン系の極圧添加剤、シリコーン系の消泡剤、あるいは
ベンゾトリアゾール等の金属不活性剤等の各種添加剤を
本発明の組成物にさらに添加しても良い。Also, various additives such as phenolic or amine-based antioxidants, sulfur or phosphorus-based extreme pressure additives, silicone-based antifoaming agents, or metal deactivators such as benzotriazole are added to the composition of the present invention. It may be further added.
［実施例］ 下記第１表及び第２表に示す化合物（Ｉ）を用い、R1
34aとの溶解性及び安定性の試験を実施した。化合物
（Ｉ）とR134aの混合物（実施例）及びスニソ4GSとR134
aの混合物（比較例）をいずれも重量比30/70にてガラス
アンプル中に封止し、［化合物（Ｉ）とR134a］及び
［スニソ4GSとR134a］それぞれの溶解の有無を二液界面
の有無により肉眼観察により求めた。その結果を比較例
とともに第１表に示す。[Examples] Compounds (I) shown in Tables 1 and 2 below were used to prepare R1
A solubility and stability test with 34a was performed. Mixture of Compound (I) and R134a (Example) and Suniso 4GS and R134
A mixture (Comparative Example) was sealed in a glass ampoule at a weight ratio of 30/70, and the presence or absence of dissolution of each of [Compound (I) and R134a] and [Suniso 4GS and R134a] was determined at the two-liquid interface. The presence or absence was determined by visual observation. The results are shown in Table 1 together with Comparative Examples.
化合物（Ｉ）とR134aを重量比50/50にてSUS 316製耐
圧容器へ代表的金属であるSS41とCuと共に封止し、恒温
槽にて175℃の恒温下で14日間放置し、試験後の化合物
（Ｉ）、R134a、金属の劣化の状況を従来使用されてい
るR12とスニソ4GSの組み合わせ（参考例）での劣化度合
いの相対比較にて確認した。その結果を第２表に示す ［発明の効果］ 本発明の圧縮式冷凍機用組成物は実施例から明らかな
ように、溶解性、安定性が良好であり、圧縮機の摺動部
における摩擦、摩耗及び焼き付け防止を図ることができ
る優れたものである。 Compound (I) and R134a were sealed in a SUS 316 pressure vessel together with typical metals SS41 and Cu at a weight ratio of 50/50, left in a thermostat at a constant temperature of 175 ° C for 14 days, and tested. Of the compound (I), R134a, and the metal were confirmed by a relative comparison of the degree of deterioration of a conventionally used combination of R12 and Suniso 4GS (Reference Example). The results are shown in Table 2. [Effects of the Invention] As is clear from the examples, the composition for a compression refrigerator of the present invention has good solubility and stability, and aims to prevent friction, abrasion and seizure in sliding parts of the compressor. It is an excellent thing.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ１０Ｎ 40:30 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C10N 40:30
Claims (1)
ルキル基、ｎは上記化合物（Ｉ）の粘度が10〜300cst
（40℃）となる正数］ で表わされる化合物及び1,1,1,2−テトラフルオロエタ
ンからなる圧縮式冷凍機用組成物。1. A general formula R-OR 1 -O n R 2 ...... (I) [R hydrocarbon group, R 1 is an alkylene group, R 2 is a fluorine-containing alkyl group, n the compounds of (I) Viscosity is 10 ~ 300cst
(Positive number which becomes 40 ° C.)] and a composition for a compression refrigerator comprising 1,1, 1, 2-tetrafluoroethane.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63284011A JP2745585B2 (en) | 1988-11-11 | 1988-11-11 | Composition for compression refrigerator |
| PCT/JP1989/001150 WO1990005172A1 (en) | 1988-11-11 | 1989-11-09 | Tetrafluoroethane composition for a regrigerator |
| AU45087/89A AU616073B2 (en) | 1988-11-11 | 1989-11-09 | Tetrafluoroethane composition for a refrigerator |
| DE68927858T DE68927858T3 (en) | 1988-11-11 | 1989-11-09 | TETRAFLUORETHANGEMISCH FOR A REFRIGERATOR |
| EP89912503A EP0406433B9 (en) | 1988-11-11 | 1989-11-09 | Tetrafluoroethane composition for a regrigerator |
| CA002002693A CA2002693C (en) | 1988-11-11 | 1989-11-10 | Tetrafluoroethane composition for a refrigerator |
| KR1019900701488A KR960007698B1 (en) | 1988-11-11 | 1990-07-11 | Tetrafluoroethane composition for a refrigerator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63284011A JP2745585B2 (en) | 1988-11-11 | 1988-11-11 | Composition for compression refrigerator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02132179A JPH02132179A (en) | 1990-05-21 |
| JP2745585B2 true JP2745585B2 (en) | 1998-04-28 |
Family
ID=17673141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63284011A Expired - Fee Related JP2745585B2 (en) | 1988-11-11 | 1988-11-11 | Composition for compression refrigerator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2745585B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69221553T2 (en) * | 1991-07-01 | 1997-12-11 | Kao Corp | Working fluid composition for use in refrigeration systems |
-
1988
- 1988-11-11 JP JP63284011A patent/JP2745585B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02132179A (en) | 1990-05-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |