JP2837861B2 - Tetrafluoroethane refrigerator composition - Google Patents
Tetrafluoroethane refrigerator compositionInfo
- Publication number
- JP2837861B2 JP2837861B2 JP1001344A JP134489A JP2837861B2 JP 2837861 B2 JP2837861 B2 JP 2837861B2 JP 1001344 A JP1001344 A JP 1001344A JP 134489 A JP134489 A JP 134489A JP 2837861 B2 JP2837861 B2 JP 2837861B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- tetrafluoroethane
- oil
- refrigerator
- general formula
- 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 - Lifetime
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、テトラフルオロエタン系冷凍機用組成物に
関するものである。Description: TECHNICAL FIELD The present invention relates to a composition for a tetrafluoroethane-based refrigerator.
［従来の技術］ 冷蔵庫やカーエアコンなどの冷凍サイクルにおいて、
Ｒ−12（ジクロロジフルオロメタン）が良好な冷媒とし
て使用されている。しかしＲ−12は成層圏のオゾン層を
破壊し、生体系に悪影響を与える可能性があり、代替物
質の検討がなされている。Ｒ−12の代替物質としては、
Ｒ−134aが最も有力と考えられているが、Ｒ−12用の一
般的な冷凍機油であるナフテン系鉱油、パラフィン系鉱
油はＲ−134aと相溶しない。したがって、Ｒ−134a用の
冷凍機油として、ナフテン系鉱油、パラフィン系鉱油は
使用することができない。Ｒ−134aと比較的よく相溶す
る物質として、表１のような構造のポリエーテル油が知
られている。[Prior art] In refrigeration cycles such as refrigerators and car air conditioners,
R-12 (dichlorodifluoromethane) has been used as a good refrigerant. However, R-12 has the potential to destroy the stratospheric ozone layer and adversely affect biological systems, and alternative materials are being investigated. As a substitute for R-12,
Although R-134a is considered to be the most influential, naphthenic mineral oil and paraffinic mineral oil, which are common refrigeration oils for R-12, are not compatible with R-134a. Therefore, naphthenic mineral oil and paraffinic mineral oil cannot be used as the refrigerating machine oil for R-134a. As a substance relatively compatible with R-134a, a polyether oil having a structure as shown in Table 1 is known.
（ア）については、例えばDu pontのReserch Disclos
ure（17483 Oct.1978）に記載されている。（イ）につ
いては、例えばU.S.Pat.4,755,316号に記載されてい
る。For (a), for example, Du Pont's Research Disclos
ure (17483 Oct. 1978). (A) is described, for example, in US Pat. No. 4,755,316.
［発明が解決しようとする課題］ しかし表１のようなポリエーテルは、吸湿性が高く、
水分を吸収しやすいという欠点があった。水分が上昇す
ると、絶縁抵抗の低下、金属に対する腐食性の増大とい
った悪影響をもたらす。[Problems to be Solved by the Invention] However, the polyethers shown in Table 1 have high hygroscopicity,
There was a drawback that water was easily absorbed. An increase in moisture has adverse effects such as a decrease in insulation resistance and an increase in corrosiveness to metals.
［課題を解決するための手段］ 本発明者らは、前述の問題を解決するにあたり、鋭意
努力した結果、ポリエーテル油の吸湿性が高いのは末端
ヒドロキシル基に原因があると推定した。そこで、末端
ヒドロキシル基の数が１〜３の範囲のポリエーテルを用
い、各末端ヒドロキシル基の全てまたは一部を、アルキ
ル化した化合物を用いて、Ｒ−134a用冷凍機油としての
評価を実施した。その結果、吸湿性の向上だけでなく、
粘度指数についても向上していることを見出し、本発明
を完成した。 [Means for Solving the Problems] The present inventors have made intensive efforts to solve the above-mentioned problems, and as a result, have presumed that polyether oil has high hygroscopicity due to terminal hydroxyl groups. Therefore, using a polyether in which the number of terminal hydroxyl groups is in the range of 1 to 3, all or part of each terminal hydroxyl group was used as an alkylated compound, and evaluation was performed as a refrigerator oil for R-134a. . As a result, not only is the moisture absorption improved,
The present inventors have found that the viscosity index has also been improved, and have completed the present invention.
すなわち、本発明は下記一般式 X1−ＯR1Ｏ1R2 〔式中、R1はアルキレン基、R2はアルキル基、X1はアル
キル基又はモノヒドロキシ化合物の水酸基を除いた残
基、１は上記化合物の動粘度が10〜300cst（40℃）とな
る正数である。〕から選ばれるポリエーテルの少なくと
も１種及びテトラフルオロエタンからなるテトラフルオ
ロエタン系冷凍機用組成物に関するものである。That is, the present invention provides the following general formula X 1 -OR 1 O 1 R 2 wherein R 1 is an alkylene group, R 2 is an alkyl group, X 1 is an alkyl group or a residue of the monohydroxy compound excluding a hydroxyl group, 1 is a positive number such that the kinematic viscosity of the compound becomes 10 to 300 cst (40 ° C.). And a tetrafluoroethane refrigerator composition comprising at least one polyether selected from the group consisting of:
また、本発明は上記ポリエーテルからなるテトラフル
オロエタン系冷凍機用冷凍機油に関するものである。The present invention also relates to a refrigerating machine oil for a tetrafluoroethane-based refrigerating machine comprising the above polyether.
一般式におけるX1としては、アルキル基又はモノヒド
ロキシ化合物の水酸基を除いた残基である。モノヒドロ
キシ化合物の水酸基を除いた残基としては、メチル基、
エチル基、プロピル基、ブチル基、２−エチルヘキシル
基、ノニル基等のアルキル基やフェニル基等のアリール
基が好ましい。X 1 in the general formula is an alkyl group or a residue obtained by removing a hydroxyl group of a monohydroxy compound. Residues other than the hydroxyl group of the monohydroxy compound include a methyl group,
Preferred are an alkyl group such as an ethyl group, a propyl group, a butyl group, a 2-ethylhexyl group and a nonyl group, and an aryl group such as a phenyl group.
一般式におけるR1としては、エチレン基、プロピレン
基、ブチレン基、テトラメチレン基等のアルキレン基で
あり、これらの単独あるいはこれらがランダム又はブロ
ック状に併存していてもよく、併存する場合はプロピレ
ン基を主成分とすることが好ましい。R 1 in the general formula is an alkylene group such as an ethylene group, a propylene group, a butylene group, and a tetramethylene group, and these may be used alone or in combination in a random or block form. It is preferred that the base is a main component.
一般式におけるR2はアルキル基である。アルキル基と
してはメチル基、エチル基、プロピル基、ブチル基、２
−エチルヘキシル基等を挙げることができる。R 2 in the general formula is an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group,
-Ethylhexyl group and the like.
前記一般式で表わされる化合物としては、冷凍機油と
して圧縮機等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、その動粘度とし
て10〜300cst（40℃）、好ましくは15〜200cst（40℃）
となるようなものが望ましく、一般式における分子量あ
るいはｌの値はこのような粘度範囲となるような値を選
択することが好ましい。ｌの値はおよそ３〜60、好まし
くは６〜30であり、同一でも異なっていてもよい。As the compound represented by the general formula, as a refrigerating machine oil, in order to sufficiently achieve functions such as friction, abrasion and anti-seizure in sliding parts of a compressor or the like, its kinematic viscosity is 10 to 300 cst (40 ° C.), Preferably 15 to 200 cst (40 ° C)
It is desirable that the molecular weight or the value of l in the general formula be selected so as to fall within such a viscosity range. The value of l is approximately 3 to 60, preferably 6 to 30, and may be the same or different.
前記一般式で表わされる化合物とR134aの重量比は1/9
9〜99/1、好ましくは5/95〜60/40である。R134aには、
1,1,2,2−テトラフルオロエタン（R134）が少量含まれ
ていてもよい。一般式の化合物は単独で、又はこれらの
混合物として使用することができる。The weight ratio of the compound represented by the general formula to R134a is 1/9.
It is 9-99 / 1, preferably 5 / 95-60 / 40. R134a has
A small amount of 1,1,2,2-tetrafluoroethane (R134) may be contained. The compounds of the general formula can be used alone or as a mixture thereof.
本発明の組成物及び冷凍機油は、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 composition and the refrigerating machine oil of the present invention are particularly effective in the case of application of a refrigeration cycle for low-temperature to high-temperature refrigeration, refrigeration and air conditioning, but also for various other heat recovery technologies such as a Rankine cycle. Can be used.
本発明の組成物及び冷凍機油は、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、トリフェノキシ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、本発明の一般式で表わされる化合
物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パーフルオロポ
リエーテル油、含フッ素シリコーン油あるいは本発明の
ポリエーテル油以外のポリエーテル油等と混合使用する
ことが可能である。The composition and the refrigerating machine oil of the present invention have excellent heat stability and do not require a stabilizer under normal use conditions, but when heat stability needs to be improved due to severe use conditions, A small amount of a phosphite compound such as dimethyl phosphite, diisopropyl phosphite or diphenyl phosphite, a phosphine sulfide compound such as triphenoxy phosphine sulfide or trimethyl phosphine sulfide, or a stabilizer such as glycidyl ether may be added. Further, the compound represented by the general formula of the present invention and conventionally used naphthenic mineral oil, paraffinic mineral oil, alkylbenzene synthetic oil, poly-α-olefin synthetic oil, perfluoropoly which is a fluorine-based lubricating oil It is possible to use a mixture with ether oil, fluorine-containing silicone oil or polyether oil other than the polyether oil of the present invention.
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
本発明の組成物や冷凍機油にされに添加しても良い。Also, various additives such as a phenolic or amine-based antioxidant, a sulfur or phosphorus-based extreme pressure additive, a silicone-based antifoaming agent, or a metal deactivator such as benzotriazole may be added to the composition of the present invention. It may be added to the refrigerating machine oil.
［作用］ 本発明において、末端のヒドロキシル基をアルキアル
化することにより、親水性が低下し、吸湿性が低下する
ものと考えられる。また、末端ヒドロキシル基をアルキ
ル化することにより、分子間の水素結合等による相互作
用が減少し、粘度指数が向上するものと考えられる。[Action] In the present invention, it is considered that by alkylating a terminal hydroxyl group, hydrophilicity is reduced and hygroscopicity is reduced. In addition, it is considered that by alkylating the terminal hydroxyl group, the interaction due to hydrogen bonding between molecules is reduced and the viscosity index is improved.
［実施例］ 実施例１〜３、比較例１〜６ 実施例１〜３及び比較例１〜６に用いた油の構造、吸
湿性、粘度指数、Ｒ−134aとの相溶性、40℃における動
粘度の結果を表２に示す。[Examples] Examples 1 to 3 and Comparative Examples 1 to 6 The structures, hygroscopicity, viscosity index, compatibility with R-134a of the oil used in Examples 1 to 3 and Comparative Examples 1 to 6, at 40 ° C Table 2 shows the results of the kinematic viscosity.
粘度指数 潤滑油の粘度の温度依存性を表わす値であり、値が大
きい程、粘度の温度による変化が少ないため、潤滑性能
に優れたものとなる。 Viscosity index This is a value indicating the temperature dependence of the viscosity of a lubricating oil. The larger the value, the smaller the change in viscosity with temperature, and the better the lubricating performance.
Ｒ−134aとの相溶性 油とＲ−134aを重量比15:85で混合、密閉する。温度
を25℃に保ち、状態を観察した。Compatibility with R-134a The oil and R-134a are mixed at a weight ratio of 15:85 and sealed. The temperature was maintained at 25 ° C., and the condition was observed.
［発明の効果］ 本発明の組成物及び冷凍機油は、吸湿性が低いため、
水分の混入が低下し、絶縁抵抗の低下を防止できるとと
もに、水分による銅、パイプ等の金属腐食の進行を防止
することができる。更に粘度指数が高いために、広い温
度範囲で、圧縮機等の摺動部における摩擦、摩耗及び焼
き付き防止等の潤滑機能を充分に発揮することができ
る。[Effects of the Invention] Since the composition and the refrigerating machine oil of the present invention have low hygroscopicity,
It is possible to prevent water from being mixed and prevent insulation resistance from lowering, and to prevent the progress of metal corrosion of copper, pipes and the like due to water. Further, since the viscosity index is high, a lubricating function such as prevention of friction, wear and seizure in a sliding portion of a compressor or the like can be sufficiently exhibited in a wide temperature range.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ｃ１０Ｎ 20:02 30:00 40:30 (56)参考文献 特開 平２−305893（ＪＰ，Ａ) 特開 平２−102296（ＪＰ，Ａ) 特開 平１−259094（ＪＰ，Ａ) 特開 平１−198694（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C10M 111/04,105/52,105/18,107/34 C10N 40:30──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification symbol FI // C10N 20:02 30:00 40:30 (56) References JP-A-2-305893 (JP, A) JP-A-2 -102296 (JP, A) JP-A-1-259909 (JP, A) JP-A-1-198694 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C10M 111 / 04,105 / 52,105 / 18,107 / 34 C10N 40:30
Claims (2)
キル基又はモノヒドロキシ化合物の水酸基を除いた残
基、１は上記化合物の動粘度が10〜300cst（40℃）とな
る正数である。〕から選ばれるポリエーテルの少なくと
も１種及びテトラフルオロエタンからなるテトラフルオ
ロエタン系冷凍機用組成物 （但し、上記ポリエーテルのうち、一般式において、
平均分子量が700以下のもの、又は、R1がエチレン基
とプロピレン基の両者を示し、かつX1とR2のいずれか一
方がメチル基、他方がメチル基またはブチル基であるも
のを除く。）。A compound represented by the following general formula: X 1 -OR 1 O 1 R 2 wherein R 1 is an alkylene group, R 2 is an alkyl group, X 1 is an alkyl group or a residue of a monohydroxy compound excluding a hydroxyl group, 1 is a positive number such that the kinematic viscosity of the compound becomes 10 to 300 cst (40 ° C.). And a tetrafluoroethane-based refrigerator composition comprising at least one polyether selected from the group consisting of tetrafluoroethane (provided that, among the above polyethers,
Excluding those having an average molecular weight of 700 or less, or those in which R 1 represents both an ethylene group and a propylene group, and one of X 1 and R 2 is a methyl group and the other is a methyl group or a butyl group. ).
ラフルオロエタン系冷凍機用冷凍機油。2. A refrigerator oil for a tetrafluoroethane refrigerator comprising the polyether according to claim 1.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1001344A JP2837861B2 (en) | 1989-01-10 | 1989-01-10 | Tetrafluoroethane refrigerator composition |
| DE68927858T DE68927858T3 (en) | 1988-11-11 | 1989-11-09 | TETRAFLUORETHANGEMISCH FOR A REFRIGERATOR |
| AU45087/89A AU616073B2 (en) | 1988-11-11 | 1989-11-09 | Tetrafluoroethane composition for a refrigerator |
| EP89912503A EP0406433B9 (en) | 1988-11-11 | 1989-11-09 | Tetrafluoroethane composition for a regrigerator |
| PCT/JP1989/001150 WO1990005172A1 (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 |
|---|---|---|---|
| JP1001344A JP2837861B2 (en) | 1989-01-10 | 1989-01-10 | Tetrafluoroethane refrigerator composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7342129A Division JP2781766B2 (en) | 1995-12-28 | 1995-12-28 | Tetrafluoroethane refrigerator composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02182780A JPH02182780A (en) | 1990-07-17 |
| JP2837861B2 true JP2837861B2 (en) | 1998-12-16 |
Family
ID=11498879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1001344A Expired - Lifetime JP2837861B2 (en) | 1988-11-11 | 1989-01-10 | Tetrafluoroethane refrigerator composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2837861B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2773266B2 (en) * | 1989-07-19 | 1998-07-09 | 旭硝子株式会社 | Tetrafluoroethane refrigerator composition |
| JPH0768534B2 (en) * | 1988-12-06 | 1995-07-26 | 出光興産株式会社 | Lubricating oil for compression type refrigerator |
| JP2507160B2 (en) * | 1990-09-14 | 1996-06-12 | 株式会社日立製作所 | Refrigeration equipment |
| EP0521650B1 (en) * | 1991-07-01 | 1997-08-13 | Kao Corporation | Working fluid composition for use in refrigeration system |
| JP3200127B2 (en) | 1991-12-18 | 2001-08-20 | 旭電化工業株式会社 | Lubricants for refrigerators |
| WO2007105718A1 (en) * | 2006-03-13 | 2007-09-20 | Asahi Glass Company, Limited | Composition for refrigerating machine |
| JP2012513527A (en) * | 2008-12-23 | 2012-06-14 | シュリーブ ケミカル プロダクツ インコーポレーテッド | Refrigerant lubricant composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06102792B2 (en) * | 1987-10-30 | 1994-12-14 | 出光興産株式会社 | Lubricating oil for fluorine-containing alkane refrigerant |
| JP2556548B2 (en) * | 1988-04-08 | 1996-11-20 | 株式会社ジャパンエナジー | Lubricating oil used for CFC compressors |
| JP2700155B2 (en) * | 1988-10-07 | 1998-01-19 | 東燃株式会社 | 1.1.1.2 Lubricating oil for refrigerators using tetrafluoroethane refrigerant |
| JPH0768534B2 (en) * | 1988-12-06 | 1995-07-26 | 出光興産株式会社 | Lubricating oil for compression type refrigerator |
-
1989
- 1989-01-10 JP JP1001344A patent/JP2837861B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02182780A (en) | 1990-07-17 |
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