JPH1046169A - Lubricating oil composition for refrigerator - Google Patents

Lubricating oil composition for refrigerator

Info

Publication number
JPH1046169A
JPH1046169A JP8207391A JP20739196A JPH1046169A JP H1046169 A JPH1046169 A JP H1046169A JP 8207391 A JP8207391 A JP 8207391A JP 20739196 A JP20739196 A JP 20739196A JP H1046169 A JPH1046169 A JP H1046169A
Authority
JP
Japan
Prior art keywords
group
carbon atoms
groups
general formula
various
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
JP8207391A
Other languages
Japanese (ja)
Other versions
JP3271905B2 (en
Inventor
Satoshi Nagao
智 永尾
Toyokazu Handa
豊和 半田
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
Original Assignee
Idemitsu Kosan Co Ltd
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Filing date
Publication date
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M171/008—Lubricant compositions compatible with refrigerants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09—Characteristics associated with water
    • C10N2020/097—Refrigerants
    • C10N2020/106—Containing Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a lubricating oil compsn. which has high lubricating and sealing properties in an atmosphere of CO2 as a refrigerant by compounding a refrigerant mainly comprising CO2 with a base oil comprising a polyoxyalkylene glycol or a polyvinyl ether. SOLUTION: This compsn. contains a refrigerant mainly comprising CO2 and a base oil comprising at least either a polyoxyalkylene glycol or a polyvinyl ether and having a kinematic viscosity of 5 cSt or higher at 100 deg.C and is esp. suitable for a compression refrigeration cycle of a compression refrigerator. Esp. remarkable effects are achieved when the compsn. is applied to a compression refrigeration cycle having an oil separator and/or a hot gas line.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は冷凍機用潤滑油組成
物に関し、さらに詳しくは、ＣＯ2 を主成分とする冷媒
を用いた冷凍機用潤滑油組成物に関する。The present invention relates to a lubricating oil composition for a refrigerator, and more particularly, to a lubricating oil composition for a refrigerator using a refrigerant containing CO 2 as a main component.

【０００２】[0002]

【従来の技術】従来、冷凍機、例えば圧縮機，凝縮器，
膨張弁及び蒸発器からなる圧縮式冷凍サイクルには、冷
媒としてジクロロジフルオロメタン（Ｒ−１２）やクロ
ロジフルオロメタン（Ｒ−２２）等のフッ化炭化水素系
のフロン化合物が用いられており、また、それと併用し
て多数の潤滑油が製造され使用されてきた。しかるに、
従来冷媒として使用されてきたこのフロン化合物は、大
気中に放出されたときに、オゾン層を破壊し、環境汚染
問題を惹起する恐れがあると懸念されている。近時、そ
の環境汚染対策の面から、その代替となりうる１，１，
１，２−テトラフルオロエタン（Ｒ−１３４ａ）等のフ
ッ化炭化水素（あるいは塩化フッ化炭化水素）の開発が
進められ、既に、Ｒ−１３４ａをはじめ、環境汚染の恐
れが少なく、上記要求特性を満足しうる各種の所謂代替
フロンが市場に出廻るようになって来ている。しかしな
がら、このようなフッ化炭化水素（あるいは塩化フッ化
炭化水素）においても、地球温暖化能が高いなどの問題
があり、近年このような問題のない自然系冷媒の使用等
が考えられてきた。一方で、炭酸ガスは環境に対して無
害であり、人に対する安全性という観点では優れたもの
であり、更に、経済的な最適水準に近い圧力、従来
の冷媒に比べ、非常に小さい圧力比、通常のオイルと
機械の構造材料に対して優れた適合性、いたる場所で
簡単に入手可能、回収不用，非常に安価である、など
の利点を有しており、従来から冷凍機などの冷媒として
通常使用されてきたものである。しかしながら、このよ
うな炭酸ガスを冷凍機の冷媒として用いた場合、冷凍機
の潤滑油として、従来一般的に使用されている潤滑油で
潤滑すると潤滑性に劣り、耐摩耗性が不充分となり、安
定性に劣る等の結果となる。更に、炭酸ガスを用いた系
では、Ｒ−１３４ａなどを用いた系に比べ吐出圧が高
く、この結果潤滑油の粘度が低下し、系のシール性が悪
化するという問題も生じていた。2. Description of the Related Art Conventionally, refrigerators such as compressors, condensers,
In a compression refrigeration cycle including an expansion valve and an evaporator, a fluorocarbon-based fluorocarbon compound such as dichlorodifluoromethane (R-12) or chlorodifluoromethane (R-22) is used as a refrigerant, and Many lubricating oils have been produced and used in combination therewith. However,
It has been feared that this fluorocarbon compound, which has been conventionally used as a refrigerant, may destroy the ozone layer and cause environmental pollution when released into the atmosphere. Recently, from the viewpoint of environmental pollution countermeasures, 1,1,
The development of fluorohydrocarbons (or chlorofluorohydrocarbons) such as 1,2-tetrafluoroethane (R-134a) has been promoted, and there is already little risk of environmental pollution including R-134a, and the above-mentioned required characteristics A variety of so-called alternative CFCs that can satisfy the requirements have come to market. However, such fluorinated hydrocarbons (or chlorinated fluorinated hydrocarbons) also have problems such as high global warming ability. In recent years, use of natural refrigerants free from such problems has been considered. . On the other hand, carbon dioxide gas is harmless to the environment and is excellent in terms of safety for humans.In addition, the pressure is close to the economically optimal level, the pressure ratio is very small compared to conventional refrigerants, It has the advantages of excellent compatibility with ordinary oil and structural materials of machinery, easy availability everywhere, no need for recovery, and very low cost. It has been commonly used. However, when such a carbon dioxide gas is used as a refrigerant of a refrigerator, lubricating with a lubricating oil generally used conventionally as a lubricating oil for a refrigerator results in poor lubrication and insufficient wear resistance. This results in poor stability and the like. Further, in the system using carbon dioxide gas, the discharge pressure is higher than in the system using R-134a or the like, and as a result, the viscosity of the lubricating oil is reduced, and the sealing performance of the system is deteriorated.

【０００３】[0003]

【発明が解決しようとする課題】本発明は、このような
状況下でなし遂げられたものであり、冷媒としてのＣＯ
2 雰囲気下で、潤滑性能及びシール性が高い冷凍機用潤
滑油組成物を提供することを目的とするものである。SUMMARY OF THE INVENTION The present invention
It was achieved under the circumstances and the CO
TwoUnder lubrication performance, high lubrication performance and sealability
It is intended to provide a lubricating oil composition.

【０００４】[0004]

【課題を解決するための手段】本発明者らは、前記の好
ましい性質を有する冷凍機用潤滑油組成物を開発すべく
鋭意研究を重ねた結果、特定の性状を有する特定の種類
の潤滑油からなる潤滑油組成物の使用によりその目的を
達成しうることを見出した。本発明は、かかる知見に基
づいて完成したものである。すなわち、本発明は、
（Ａ）ＣＯ2 を主成分とする冷媒、及び（Ｂ）ポリオキ
シアルキレングリコール及びポリビニルエーテルから選
ばれる少なくとも一種からなり、１００℃における動粘
度が５ｃＳｔ以上である基油、を含有することを特徴と
する冷凍機用潤滑油組成物を提供するものである。The present inventors have conducted intensive studies to develop a lubricating oil composition for a refrigerator having the above-mentioned preferable properties, and as a result, a specific type of lubricating oil having specific properties has been obtained. It has been found that the object can be achieved by using a lubricating oil composition comprising The present invention has been completed based on such findings. That is, the present invention
(A) a refrigerant mainly composed of CO 2 and (B) a base oil comprising at least one selected from polyoxyalkylene glycols and polyvinyl ethers and having a kinematic viscosity at 100 ° C. of 5 cSt or more. And a lubricating oil composition for a refrigerator.

【０００５】[0005]

【発明の実施の形態】本発明の冷凍機用潤滑油組成物
は、（Ａ）ＣＯ2 を主成分とする冷媒、及び（Ｂ）ポリ
オキシアルキレングリコール及びポリビニルエーテルか
ら選ばれる少なくとも一種からなり、１００℃における
動粘度が５ｃＳｔ以上である基油、を含有することを特
徴とするものである。本発明において用いられる（Ａ）
成分のＣＯ2 を主成分とする冷媒としては、ＣＯ2 をそ
のまま使用する場合のほか、これを炭化水素，Ｒ−１３
４ａ等のフッ化炭化水素（あるいは塩化フッ化炭化水
素），エーテルなどの冷媒等と混合したものも使用する
ことができる。また、（Ｂ）成分の基油としては、ポリ
オキシアルキレングリコール及びポリビニルエーテルか
ら選ばれる少なくとも一種からなるものが使用される。BEST MODE FOR CARRYING OUT THE INVENTION The lubricating oil composition for a refrigerator according to the present invention comprises (A) a refrigerant mainly composed of CO 2 , and (B) at least one selected from polyoxyalkylene glycol and polyvinyl ether; A base oil having a kinematic viscosity at 100 ° C. of 5 cSt or more. (A) used in the present invention
As the refrigerant mainly containing CO 2 as a component, in addition to the case where CO 2 is used as it is, it is used as a hydrocarbon, R-13.
A mixture of a hydrocarbon such as 4a (or a fluorinated chlorohydrocarbon) and a refrigerant such as ether can also be used. Further, as the base oil of the component (B), one composed of at least one selected from polyoxyalkylene glycol and polyvinyl ether is used.

【０００６】ここで、使用されるポリオキシアルキレン
グリコールとしては、例えば一般式（Ｉ） Ｒ1 −〔（ＯＲ2 ）m −ＯＲ3 〕n ・・・（Ｉ） （式中、Ｒ1 は水素原子，炭素数１〜１０のアルキル
基，炭素数２〜１０のアシル基又は結合部２〜６個を有
する炭素数１〜１０の脂肪族炭化水素基、Ｒ2 は炭素数
２〜４のアルキレン基、Ｒ3 は水素原子，炭素数１〜１
０のアルキル基又は炭素数２〜１０のアシル基、ｎは１
〜６の整数、ｍはｍ×ｎの平均値が６〜８０となる数を
示す。）で表される化合物が挙げられる。上記一般式
（Ｉ）において、Ｒ1 ，Ｒ3 におけるアルキル基は直鎖
状，分岐鎖状，環状のいずれであってもよい。該アルキ
ル基の具体例としては、メチル基，エチル基，ｎ−プロ
ピル基，イソプロピル基，各種ブチル基，各種ペンチル
基，各種ヘキシル基，各種ヘプチル基，各種オクチル
基，各種ノニル基，各種デシル基，シクロペンチル基，
シクロヘキシル基などを挙げることができる。このアル
キル基の炭素数が１０を超えると冷媒との相溶性が低下
し、相分離を生じる場合がある。好ましいアルキル基の
炭素数は１〜６である。The polyoxyalkylene glycol used is, for example, a compound represented by the following general formula (I): R 1 -[(OR 2 ) m -OR 3 ] n (I) wherein R 1 is hydrogen An atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms or an aliphatic hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding portions, and R 2 is an alkylene having 2 to 4 carbon atoms Group, R 3 is a hydrogen atom, having 1 to 1 carbon atoms
0 alkyl group or acyl group having 2 to 10 carbon atoms, n is 1
And m is a number such that the average value of m × n is 6 to 80. )). In the general formula (I), the alkyl group for R 1 and R 3 may be any of linear, branched or cyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups. , Cyclopentyl group,
Examples include a cyclohexyl group. If the carbon number of the alkyl group exceeds 10, the compatibility with the refrigerant is reduced, and phase separation may occur. The preferred alkyl group has 1 to 6 carbon atoms.

【０００７】また、Ｒ1 ，Ｒ3 における該アシル基のア
ルキル基部分は直鎖状，分岐鎖状，環状のいずれであっ
てもよい。該アシル基のアルキル基部分の具体例として
は、上記アルキル基の具体例として挙げた炭素数１〜９
の種々の基を同様に挙げることができる。該アシル基の
炭素数が１０を超えると冷媒との相溶性が低下し、相分
離を生じる場合がある。好ましいアシル基の炭素数は２
〜６である。Ｒ1 及びＲ3 が、いずれもアルキル基又は
アシル基である場合には、Ｒ1 とＲ 3 は同一であっても
よいし、たがいに異なっていてもよい。さらにｎが２以
上の場合は、１分子中の複数のＲ3 は同一であってもよ
いし、異なっていてもよい。Further, R1, RThreeA of the acyl group in
The alkyl group moiety may be linear, branched, or cyclic.
You may. Specific examples of the alkyl group portion of the acyl group
Is a group having 1 to 9 carbon atoms mentioned as a specific example of the alkyl group.
Various groups can be similarly mentioned. The acyl group
If the carbon number exceeds 10, the compatibility with the refrigerant decreases,
Separation may occur. A preferred acyl group has 2 carbon atoms.
~ 6. R1And RThreeIs an alkyl group or
When it is an acyl group, R1And R ThreeAre the same
Good or different. N is 2 or more
In the case above, multiple Rs in one moleculeThreeMay be the same
And may be different.

【０００８】Ｒ1 が結合部位２〜６個を有する炭素数１
〜１０の脂肪族炭化水素基である場合、この脂肪族炭化
水素基は鎖状のものであってもよいし、環状のものであ
ってもよい。結合部位２個を有する脂肪族炭化水素基と
しては、例えばエチレン基，プロピレン基，ブチレン
基，ペンチレン基，ヘキシレン基，ヘプチレン基，オク
チレン基，ノニレン基，デシレン基，シクロペンチレン
基，シクロヘキシレン基などが挙げられる。また、結合
部位３〜６個を有する脂肪族炭化水素基としては、例え
ばトリメチロールプロパン，グリセリン，ペンタエリス
リトール，ソルビトール；１，２，３−トリヒドロキシ
シクロヘキサン；１，３，５−トリヒドロキシシクロヘ
キサンなどの多価アルコールから水酸基を除いた残基を
挙げることができる。この脂肪族炭化水素基の炭素数が
１０を超えると冷媒との相溶性が低下し、相分離が生じ
る場合がある。好ましい炭素数は２〜６である。本発明
においては、上記Ｒ1 及びＲ3 は少なくとも一つがアル
キル基、特に炭素数１〜３のアルキル基であることが好
ましく、とりわけメチル基であることが粘度特性の点か
ら好ましい。更には、上記と同様の理由からＲ1 及びＲ
3 の両方がアルキル基、特にメチル基であることが好ま
しい。R 1 has 1 to 2 carbon atoms having 2 to 6 bonding sites
In the case of an aliphatic hydrocarbon group of 10 to 10, the aliphatic hydrocarbon group may be a chain-like one or a cyclic one. Examples of the aliphatic hydrocarbon group having two bonding sites include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a cyclopentylene group, and a cyclohexylene group. And the like. Examples of the aliphatic hydrocarbon group having 3 to 6 binding sites include trimethylolpropane, glycerin, pentaerythritol, sorbitol; 1,2,3-trihydroxycyclohexane; 1,3,5-trihydroxycyclohexane and the like. And the residue obtained by removing the hydroxyl group from the polyhydric alcohol. If the aliphatic hydrocarbon group has more than 10 carbon atoms, the compatibility with the refrigerant may be reduced, and phase separation may occur. The preferred number of carbon atoms is 2 to 6. In the present invention, at least one of R 1 and R 3 is preferably an alkyl group, particularly an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group from the viewpoint of viscosity characteristics. Further, for the same reason as described above, R 1 and R
It is preferred that both of 3 are alkyl groups, especially methyl groups.

【０００９】前記一般式（Ｉ）中のＲ2 は炭素数２〜４
のアルキレン基であり、繰り返し単位のオキシアルキレ
ン基としては、オキシエチレン基，オキシプロピレン
基，オキシブチレン基が挙げられる。１分子中のオキシ
アルキレン基は同一であってもよいし、２種以上のオキ
シアルキレン基が含まれていてもよい。とりわけ、オキ
シエチレン基（ＥＯ）とオキシプロピレン基（ＰＯ）を
含む共重合体が好ましく、このような場合、焼付荷重，
粘度特性の点からＥＯ／（ＰＯ＋ＥＯ）の値が0.１〜0.
８の範囲にあることが好ましく、また、吸湿性の点から
はＥＯ／（ＰＯ＋ＥＯ）の値が0.３〜0.６の範囲にある
ことが好ましい。In the general formula (I), R 2 has 2 to 4 carbon atoms.
And the oxyalkylene group of the repeating unit includes an oxyethylene group, an oxypropylene group, and an oxybutylene group. The oxyalkylene groups in one molecule may be the same, or may contain two or more oxyalkylene groups. Particularly, a copolymer containing an oxyethylene group (EO) and an oxypropylene group (PO) is preferable. In such a case, a seizure load,
From the viewpoint of viscosity characteristics, the value of EO / (PO + EO) is 0.1 to 0.1.
8, and from the viewpoint of hygroscopicity, the value of EO / (PO + EO) is preferably in the range of 0.3 to 0.6.

【００１０】前記一般式（Ｉ）中のｎは１〜６の整数
で、Ｒ1 の結合部位の数に応じて定められる。例えばＲ
1 がアルキル基やアシル基の場合、ｎは１であり、Ｒ1
が結合部位２，３，４，５及び６個を有する脂肪族炭化
水素基である場合、ｎはそれぞれ２，３，４，５及び６
となる。また、ｍはｍ×ｎの平均値が６〜８０となる数
であり、ｍ×ｎの平均値が前記範囲を逸脱すると本発明
の目的は十分に達せられない。前記一般式（Ｉ）で表さ
れるポリアルキレングリコールは、末端に水酸基を有す
るポリアルキレングリコールを包含するものであり、該
水酸基の含有量が全末端基に対して、５０モル％以下に
なるような割合であれば、含有していても好適に使用す
ることができる。この水酸基の含有量が５０モル％を超
えると吸湿性が増大し、粘度指数が低下するので好まし
くない。このようなポリアルキレングリコールとして
は、一般式In the general formula (I), n is an integer of 1 to 6, and is determined according to the number of R 1 binding sites. For example, R
When 1 is an alkyl group or an acyl group, n is 1 and R 1
Is an aliphatic hydrocarbon group having 2, 3, 4, 5 and 6 bonding sites, n is 2, 3, 4, 5 and 6 respectively
Becomes Further, m is a number such that the average value of m × n is 6 to 80. If the average value of m × n is out of the above range, the object of the present invention cannot be sufficiently achieved. The polyalkylene glycol represented by the general formula (I) includes a polyalkylene glycol having a hydroxyl group at a terminal, and the content of the hydroxyl group is 50 mol% or less based on all terminal groups. If it is contained in a suitable ratio, it can be suitably used even if it is contained. If the content of the hydroxyl group exceeds 50 mol%, the hygroscopicity increases and the viscosity index decreases, which is not preferable. As such a polyalkylene glycol, a general formula

【００１１】[0011]

【化１】 Embedded image

【００１２】（式中、ｘは６〜８０の数を示す。）で表
されるポリオキシプロピレングリコールジメチルエーテ
ル、一般式Wherein x is a number from 6 to 80, a polyoxypropylene glycol dimethyl ether represented by the general formula:

【００１３】[0013]

【化２】 Embedded image

【００１４】（式中、ａ及びｂは、それぞれ１以上で、
かつそれらの合計が６〜８０となる数を示す。）で表さ
れるポリオキシエチレンポリオキシプロピレングリコー
ルジメチルエーテルが経済性及び効果の点で好適であ
り、また一般式(Where a and b are each 1 or more,
In addition, the numbers indicate a total of 6 to 80. The polyoxyethylene polyoxypropylene glycol dimethyl ether represented by the general formula (1) is preferred in terms of economy and effect, and

【００１５】[0015]

【化３】 Embedded image

【００１６】（式中、ｘは６〜８０の数を示す。）で表
されるポリオキシプロピレングリコールモノブチルエー
テル、さらにはポリオキシプロピレングリコールジアセ
テートなどが、経済性等の点で好適である。なお、上記
一般式（Ｉ）で表されるポリアルキレングリコールにつ
いては、特開平２−３０５８９３号公報に詳細に記載さ
れたものをいずれも使用することができる。本発明にお
いては、上記ポリオキシアルキレングリコールとして、
一般式（II）(Where x represents a number of 6 to 80), polyoxypropylene glycol monobutyl ether, and polyoxypropylene glycol diacetate are preferred from the viewpoint of economy and the like. As the polyalkylene glycol represented by the general formula (I), any of those described in detail in JP-A-2-305893 can be used. In the present invention, as the polyoxyalkylene glycol,
General formula (II)

【００１７】[0017]

【化４】 〔Ｒ4 〜Ｒ7 はそれぞれ水素，炭素数１〜１０の一価の
炭化水素基または一般式（III)Embedded image [R 4 to R 7 are each hydrogen, a monovalent hydrocarbon group having 1 to 10 carbon atoms or a general formula (III)

【００１８】[0018]

【化５】 Embedded image

【００１９】（Ｒ8 及びＲ9 はそれぞれ水素，炭素数１
〜１０の一価炭化水素基又は炭素数２〜２０のアルコキ
シアルキル基を示し、Ｒ10は炭素数２〜５のアルキレン
基，アルキル基を置換基として有する総炭素数２〜５の
置換アルキレン基又はアルコキシアルキル基を置換基と
して有する総炭素数４〜１０の置換アルキレン基を示
し、ｎは０〜２０の整数、Ｒ11は炭素数１〜１０の一価
炭化水素を示す。)で表される基であり、Ｒ4 〜Ｒ7 の
少なくとも１つが一般式(III) で表される基である〕で
表される構成単位を少なくとも１個有するポリオキシア
ルキレングリコール誘導体を使用することができる。こ
こで、式中Ｒ4 〜Ｒ7 はそれぞれ水素，炭素数１〜１０
の一価の炭化水素基または上記一般式（III)で表わされ
るものであるが、炭素数１〜１０の一価炭化水素基とし
ては、炭素数６以下の一価の炭化水素基を好ましく使用
でき、特に炭素数３以下のアルキル基が最適である。(R 8 and R 9 each represent hydrogen, carbon number 1
A monovalent hydrocarbon group of 10 to 10 or an alkoxyalkyl group of 2 to 20 carbon atoms, wherein R 10 is an alkylene group of 2 to 5 carbon atoms, or a substituted alkylene group of 2 to 5 carbon atoms having an alkyl group as a substituent Or a substituted alkylene group having a total of 4 to 10 carbon atoms having an alkoxyalkyl group as a substituent, n is an integer of 0 to 20, and R 11 is a monovalent hydrocarbon of 1 to 10 carbon atoms. ) Wherein at least one of R 4 to R 7 is a group represented by the general formula (III)]. be able to. Here, in the formula, R 4 to R 7 are each hydrogen and have 1 to 10 carbon atoms.
A monovalent hydrocarbon group or a group represented by the above general formula (III). As the monovalent hydrocarbon group having 1 to 10 carbon atoms, a monovalent hydrocarbon group having 6 or less carbon atoms is preferably used. Most preferably, an alkyl group having 3 or less carbon atoms is optimal.

【００２０】また一般式（III)において、Ｒ8 およびＲ
9 はそれぞれ水素，炭素数１〜１０の一価の炭化水素基
または炭素数２〜２０のアルコキシアルキル基を示す
が、これらの中で炭素数３以下のアルキル基または炭素
数６以下のアルコキシアルキル基が好ましい。Ｒ10は炭
素数２〜５のアルキレン基，アルキル基を置換基として
有する総炭素数２〜５の置換アルキレン基又はアルコキ
シアルキル基を置換基として有する総炭素数４〜１０の
置換アルキレン基を示すが、好ましくは炭素数６以下の
エチレン基及び置換エチレン基である。Ｒ11は炭素数１
〜１０の一価炭化水素基を示すが、これらの中で炭素数
６以下の炭化水素基が好ましく、炭素数３以下の炭化水
素基が特に好ましい。なお、前述の一般式(II)における
Ｒ4 〜Ｒ7 のうち少なくとも１つは、一般式(III) で表
される基である。特に、Ｒ4 ，Ｒ6 のいずれか一つが一
般式(III) の基であって、Ｒ4 ，Ｒ6 の残りの一つ及び
Ｒ5,Ｒ7 がそれぞれ水素または炭素数１〜１０の一価炭
化水素基であるのが好ましい。In the general formula (III), R 8 and R
Reference numeral 9 represents hydrogen, a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, and among these, an alkyl group having 3 or less carbon atoms or an alkoxyalkyl having 6 or less carbon atoms. Groups are preferred. R 10 represents an alkylene group having 2 to 5 carbon atoms, a substituted alkylene group having 2 to 5 carbon atoms having an alkyl group as a substituent or a substituted alkylene group having 4 to 10 carbon atoms having an alkoxyalkyl group as a substituent. Is preferably an ethylene group having 6 or less carbon atoms and a substituted ethylene group. R 11 has 1 carbon atom
And a monovalent hydrocarbon group of 10 to 10, of which a hydrocarbon group having 6 or less carbon atoms is preferable, and a hydrocarbon group having 3 or less carbon atoms is particularly preferable. In addition, at least one of R 4 to R 7 in the general formula (II) is a group represented by the general formula (III). In particular, one of R 4 and R 6 is a group represented by the general formula (III), and the other one of R 4 and R 6 and R 5 and R 7 are each hydrogen or a group having 1 to 10 carbon atoms. It is preferably a valent hydrocarbon group.

【００２１】上記ポリオキシアルキレングリコール誘導
体は、前記一般式(II)で表される構成単位を少なくとも
１つ含有するものであるが、より詳しくはこの一般式
（II)の構成単位からなる単独重合体，一般式(II)に含
まれる２つ以上の異なる構成単位からなる共重合体，及
び一般式(II)の構成単位と他の構成単位、例えば一般式
(IV)The above polyoxyalkylene glycol derivative contains at least one structural unit represented by the general formula (II). More specifically, the polyoxyalkylene glycol derivative has a single polymer consisting of the structural unit represented by the general formula (II). A copolymer comprising two or more different structural units contained in the general formula (II), and a structural unit of the general formula (II) and another structural unit, for example, a general formula
(IV)

【００２２】[0022]

【化６】 Embedded image

【００２３】〔Ｒ12〜Ｒ15はそれぞれ水素又は炭素数１
〜３のアルキル基を示す。〕で表される構成単位からな
る共重合体の三種類に大別することができる。上記単独
重合体の好適例は、一般式(II)で表される構成単位Ａを
１〜２００個有するとともに、末端基がそれぞれ水酸
基，炭素数１〜１０のアシルオキシ基，炭素数１〜１０
のアルコキシ基あるいはアリーロキシ基からなるものを
あげることができる。一方、共重合体の好適例は、一般
式(II)で表される二種類の構成単位Ａ，Ｂをそれぞれ１
〜２００個有するか、あるいは一般式(II)で表される構
成単位Ａを１〜２００個と一般式(III) で表される構成
単位Ｃを１〜２００個有するとともに、末端基がそれぞ
れ水酸基，炭素数１〜１０のアシルオキシ基，炭素数１
〜１０のアルコキシ基あるいはアリーロキシ基からなる
ものをあげることができる。これらの共重合体は、構成
単位Ａと構成単位Ｂ(あるいは構成単位Ｃ)との交互共重
合，ランダム共重合，ブロック共重合体あるいは構成単
位Ａの主鎖に構成単位Ｂがグラフト結合したグラフト共
重合体など様々なものがある。（Ｂ）成分である基油と
して用いられるポリビニルエーテルとしては、例えば一
般式（Ｖ）[R 12 to R 15 are each hydrogen or carbon 1
And represents an alkyl group of 1 to 3. And the copolymers comprising the structural units represented by the following general formulas: A preferred example of the homopolymer has 1 to 200 structural units A represented by the general formula (II), and has a hydroxyl group, an acyloxy group having 1 to 10 carbon atoms, and an end group having 1 to 10 carbon atoms, respectively.
And those comprising an alkoxy group or an aryloxy group. On the other hand, preferred examples of the copolymer include two types of structural units A and B represented by the general formula (II) each having 1
Or 200 to 200 or 1 to 200 structural units A represented by the general formula (II) and 1 to 200 structural units C represented by the general formula (III), and each of the terminal groups has a hydroxyl group. , An acyloxy group having 1 to 10 carbon atoms, 1 carbon atom
And 10 to 10 alkoxy groups or aryloxy groups. These copolymers are obtained by alternating copolymerization of a structural unit A and a structural unit B (or a structural unit C), random copolymerization, a block copolymer or a graft in which the structural unit B is graft-bonded to the main chain of the structural unit A. There are various things such as copolymers. As the polyvinyl ether used as the base oil as the component (B), for example, the general formula (V)

【００２４】[0024]

【化７】 Embedded image

【００２５】（式中、Ｒ16，Ｒ17及びＲ18はそれぞれ水
素原子又は炭素数１〜８の炭化水素基を示し、それらは
たがいに同一でも異なっていてもよく、Ｒ19は炭素数１
〜１０の二価の炭化水素基又は炭素数２〜２０の二価の
エーテル結合酸素含有炭化水素基、Ｒ20は炭素数１〜２
０の炭化水素基、ｋはその平均値が０〜１０の数を示
し、Ｒ16〜Ｒ20は構成単位毎に同一であってもそれぞれ
異なっていてもよく、またＲ19Ｏが複数ある場合には、
複数のＲ19Ｏは同一でも異なっていてもよい。）で表さ
れる構成単位を有するポリビニルエーテル系化合物が挙
げられる。また、上記一般式（Ｖ）で表される構成単位
と、一般式（VI)(Wherein, R 16 , R 17 and R 18 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R 19 has 1 carbon atom.
A divalent hydrocarbon group having 10 to 10 carbon atoms or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, and R 20 has 1 to 2 carbon atoms.
0 represents a hydrocarbon group, k represents a number having an average value of 0 to 10, R 16 to R 20 may be the same or different for each structural unit, and when there are a plurality of R 19 Os In
A plurality of R 19 Os may be the same or different. A) a polyvinyl ether-based compound having a structural unit represented by the formula: Further, the structural unit represented by the general formula (V) and the general formula (VI)

【００２６】[0026]

【化８】 Embedded image

【００２７】（式中、Ｒ21〜Ｒ24は、それぞれ水素原子
又は炭素数１〜２０の炭化水素基を示し、それらはたが
いに同一でも異なっていてもよく、またＲ21〜Ｒ24は構
成単位毎に同一であってもそれぞれ異なっていてもよ
い。）で表される構成単位とを有するブロック又はラン
ダム共重合体からなるポリビニルエーテル系化合物も使
用することができる。上記一般式（Ｖ）におけるＲ16，
Ｒ17及びＲ18はそれぞれ水素原子又は炭素数１〜８、好
ましくは１〜４の炭化水素基を示し、それらはたがいに
同一でも異なっていてもよい。ここで炭化水素基とは、
具体的にはメチル基，エチル基，ｎ−プロピル基，イソ
プロピル基，ｎ−ブチル基，イソブチル基，ｓｅｃ−ブ
チル基，ｔｅｒｔ−ブチル基，各種ペンチル基，各種ヘ
キシル基，各種ヘプチル基，各種オクチル基のアルキル
基、シクロペンチル基，シクロヘキシル基，各種メチル
シクロヘキシル基，各種エチルシクロヘキシル基，各種
ジメチルシクロヘキシル基などのシクロアルキル基、フ
ェニル基，各種メチルフェニル基，各種エチルフェニル
基，各種ジメチルフェニル基のアリール基、ベンジル
基，各種フェニルエチル基，各種メチルベンジル基のア
リールアルキル基を示す。なお、これらのＲ 16，Ｒ17，
Ｒ18としては、特に水素原子が好ましい。Where Rtwenty one~ Rtwenty fourIs a hydrogen atom
Or a hydrocarbon group having 1 to 20 carbon atoms,
May be the same or different.twenty one~ Rtwenty fourHa
It may be the same or different for each unit
No. Or a block having a structural unit represented by)
Polyvinyl ether compounds consisting of dam copolymers are also used.
Can be used. R in the above general formula (V)16,
R17And R18Each represents a hydrogen atom or a carbon number of 1 to 8,
Preferably they represent 1 to 4 hydrocarbon groups, each of which
They may be the same or different. Here, the hydrocarbon group is
Specifically, methyl, ethyl, n-propyl, iso-
Propyl group, n-butyl group, isobutyl group, sec-butyl
Tyl group, tert-butyl group, various pentyl groups, various
Alkyl of xyl group, various heptyl groups, various octyl groups
Group, cyclopentyl group, cyclohexyl group, various methyl
Cyclohexyl group, various ethylcyclohexyl groups, various
Cycloalkyl groups such as dimethylcyclohexyl,
Phenyl group, various methylphenyl groups, various ethylphenyl
Groups, aryl groups of various dimethylphenyl groups, benzyl
Groups, various phenylethyl groups, various methylbenzyl groups
Represents a reel alkyl group. Note that these R 16, R17,
R18Is particularly preferably a hydrogen atom.

【００２８】一方、一般式（Ｖ）中のＲ19は、炭素数１
〜１０、好ましくは２〜１０の二価の炭化水素基又は炭
素数２〜２０の二価のエーテル結合酸素含有炭化水素基
を示すが、ここで炭素数１〜１０の二価の炭化水素基と
は、具体的にはメチレン基；エチレン基；フェニルエチ
レン基；１，２−プロピレン基；２−フェニル−１，２
−プロピレン基；１，３−プロピレン基；各種ブチレン
基；各種ペンチレン基；各種ヘキシレン基；各種ヘプチ
レン基；各種オクチレン基；各種ノニレン基；各種デシ
レン基の二価の脂肪族基、シクロヘキサン；メチルシク
ロヘキサン；エチルシクロヘキサン；ジメチルシクロヘ
キサン；プロピルシクロヘキサンなどの脂環式炭化水素
に２個の結合部位を有する脂環式基、各種フェニレン
基；各種メチルフェニレン基；各種エチルフェニレン
基；各種ジメチルフェニレン基；各種ナフチレン基など
の二価の芳香族炭化水素基、トルエン；キシレン；エチ
ルベンゼンなどのアルキル芳香族炭化水素のアルキル基
部分と芳香族部分にそれぞれ一価の結合部位を有するア
ルキル芳香族基、キシレン；ジエチルベンゼンなどのポ
リアルキル芳香族炭化水素のアルキル基部分に結合部位
を有するアルキル芳香族基などがある。これらの中で炭
素数２から４の脂肪族基が特に好ましい。On the other hand, R 19 in the general formula (V) has 1 carbon atom.
A divalent hydrocarbon group having 10 to 10, preferably 2 to 10 or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, wherein a divalent hydrocarbon group having 1 to 10 carbon atoms Specifically, methylene group; ethylene group; phenylethylene group; 1,2-propylene group; 2-phenyl-1,2
-Propylene group; 1,3-propylene group; various butylene groups; various pentylene groups; various hexylene groups; various heptylene groups; various octylene groups; various nonylene groups; divalent aliphatic groups of various decylene groups; cyclohexane; methylcyclohexane Alicyclic groups having two binding sites to an alicyclic hydrocarbon such as ethylcyclohexane; dimethylcyclohexane; propylcyclohexane; various phenylene groups; various methylphenylene groups; various ethylphenylene groups; various dimethylphenylene groups; various naphthylene Aromatic hydrocarbon group such as a group, toluene; xylene; an alkyl aromatic group having a monovalent bonding site in each of an alkyl group portion and an aromatic portion of an alkyl aromatic hydrocarbon such as ethylbenzene, xylene; diethylbenzene, etc. Polyalkyl aromatic carbonization It is an alkyl aromatic group having a bonding site in the alkyl group moiety of the unit. Of these, aliphatic groups having 2 to 4 carbon atoms are particularly preferred.

【００２９】また、炭素数２〜２０の二価のエーテル結
合酸素含有炭化水素基の具体例としては、メトキシメチ
レン基；メトキシエチレン基；メトキシメチルエチレン
基；１，１−ビスメトキシメチルエチレン基；１，２−
ビスメトキシメチルエチレン基；エトキシメチルエチレ
ン基；（２−メトキシエトキシ）メチルエチレン基；
（１−メチル−２−メトキシ）メチルエチレン基などを
好ましく挙げることができる。なお、一般式（Ｖ）にお
けるｋはＲ19Ｏの繰り返し数を示し、その平均値が０〜
１０、好ましくは０〜５の範囲の数である。Ｒ19Ｏが複
数ある場合には、複数のＲ19Ｏは同一でも異なっていて
もよい。Specific examples of the divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms include a methoxymethylene group; a methoxyethylene group; a methoxymethylethylene group; a 1,1-bismethoxymethylethylene group; 1,2-
Bismethoxymethylethylene group; ethoxymethylethylene group; (2-methoxyethoxy) methylethylene group;
A (1-methyl-2-methoxy) methylethylene group can be preferably exemplified. Here, k in the general formula (V) indicates the number of repetitions of R 19 O, and the average value thereof is 0 to
It is a number in the range of 10, preferably 0-5. When the R 19 O is plural, plural R 19 O may be the same or different.

【００３０】さらに、一般式（Ｖ）におけるＲ20は炭素
数１〜２０、好ましくは１〜１０の炭化水素基を示す
が、この炭化水素基とは、具体的にはメチル基，エチル
基，ｎ−プロピル基，イソプロピル基，ｎ−ブチル基，
イソブチル基，ｓｅｃ−ブチル基，ｔｅｒｔ−ブチル
基，各種ペンチル基，各種ヘキシル基，各種ヘプチル
基，各種オクチル基，各種ノニル基，各種デシル基のア
ルキル基、シクロペンチル基，シクロヘキシル基，各種
メチルシクロヘキシル基，各種エチルシクロヘキシル
基，各種プロピルシクロヘキシル基，各種ジメチルシク
ロヘキシル基などのシクロアルキル基、フェニル基，各
種メチルフェニル基，各種エチルフェニル基，各種ジメ
チルフェニル基，各種プロピルフェニル基，各種トリメ
チルフェニル基，各種ブチルフェニル基，各種ナフチル
基などのアリール基、ベンジル基，各種フェニルエチル
基，各種メチルベンジル基，各種フェニルプロピル基，
各種フェニルブチル基のアリールアルキル基などを示
す。なお、該Ｒ16〜Ｒ20は構成単位毎に同一であっても
異なっていてもよい。Further, R 20 in the general formula (V) represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group,
Isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl alkyl groups, cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups , Various ethylcyclohexyl groups, various propylcyclohexyl groups, various cycloalkyl groups such as dimethylcyclohexyl groups, phenyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various Aryl groups such as butylphenyl group and various naphthyl groups, benzyl group, various phenylethyl groups, various methylbenzyl groups, various phenylpropyl groups,
And the arylalkyl groups of various phenylbutyl groups. Note that R 16 to R 20 may be the same or different for each structural unit.

【００３１】上記一般式（Ｖ）で表されるポリビニルエ
ーテル系化合物（１）は、その炭素／酸素モル比が4.２
〜7.０の範囲にあるものが好ましい。このモル比が4.２
未満では、吸湿性が高く、また7.０を超えると、冷媒と
の相溶性が低下する場合がある。上記一般式（VI) にお
いて、Ｒ21〜Ｒ24は、それぞれ水素原子又は炭素数１〜
２０の炭化水素基を示し、それらはたがいに同一でも異
なっていてもよい。ここで、炭素数１〜２０の炭化水素
基としては、上記一般式（Ｖ）におけるＲ20の説明にお
いて例示したものと同じものを挙げることができる。な
お、Ｒ21〜Ｒ24は構成単位毎に同一であってもそれぞれ
異なっていてもよい。The polyvinyl ether compound (1) represented by the general formula (V) has a carbon / oxygen molar ratio of 4.2.
Those in the range of ~ 7.0 are preferred. This molar ratio is 4.2
If it is less than 7, the hygroscopicity is high, and if it exceeds 7.0, the compatibility with the refrigerant may decrease. In the general formula (VI), R 21 to R 24 each represent a hydrogen atom or a carbon atom
Shows 20 hydrocarbon groups, which may be the same or different. Examples of the hydrocarbon group having 1 to 20 carbon atoms may include the same as those exemplified in the description of R 20 in formula (V). R 21 to R 24 may be the same or different for each structural unit.

【００３２】該一般式（Ｖ）で表される構成単位と一般
式（VI) で表される構成単位とを有するブロック又はラ
ンダム共重合体からなるポリビニルエーテル系化合物
（２）は、その炭素／酸素モル比が4.２〜7.０の範囲に
あるものが好ましく用いられる。このモル比が4.２未満
では、吸湿性が高く、7.０を超えると、冷媒との相溶性
が低下する場合がある。さらに本発明においては、上記
ポリビニルエーテル系化合物（１）と上記ポリビニルエ
ーテル系化合物（２）との混合物も使用することができ
る。本発明に用いられるポリビニルエーテル系化合物
（１）及び（２）は、それぞれ対応するビニルエーテル
系モノマーの重合、及び対応するオレフィン性二重結合
を有する炭化水素モノマーと対応するビニルエーテル系
モノマーとの共重合により製造することができる。本発
明に用いられるポリビニルエーテル系化合物としては、
次の末端構造を有するもの、すなわちその一つの末端
が、一般式(VII) 又は（VIII)The polyvinyl ether compound (2) comprising a block or random copolymer having the structural unit represented by the general formula (V) and the structural unit represented by the general formula (VI) has a carbon / carbon Those having an oxygen molar ratio in the range of 4.2 to 7.0 are preferably used. If the molar ratio is less than 4.2, the hygroscopicity is high, and if it exceeds 7.0, the compatibility with the refrigerant may be reduced. Furthermore, in the present invention, a mixture of the polyvinyl ether compound (1) and the polyvinyl ether compound (2) can also be used. The polyvinyl ether compounds (1) and (2) used in the present invention are obtained by polymerizing the corresponding vinyl ether monomers and copolymerizing the corresponding hydrocarbon monomers having an olefinic double bond with the corresponding vinyl ether monomers. Can be manufactured. As the polyvinyl ether compound used in the present invention,
Those having the following terminal structure, that is, one terminal of which has the general formula (VII) or (VIII)

【００３３】[0033]

【化９】 Embedded image

【００３４】（式中、Ｒ25，Ｒ26及びＲ27は、それぞれ
水素原子又は炭素数１〜８の炭化水素基を示し、Ｒ25，
Ｒ26及びＲ27はたがいに同一でも異なっていてもよく、
Ｒ30，Ｒ31，Ｒ32及びＲ33は、それぞれ水素原子又は炭
素数１〜２０の炭化水素基を示し、Ｒ30，Ｒ31，Ｒ32及
びＲ33はたがいに同一でも異なっていてもよい。Ｒ28は
炭素数１〜１０の二価の炭化水素基又は炭素数２〜２０
の二価のエーテル結合酸素含有炭化水素基、Ｒ29は炭素
数１〜２０の炭化水素基、ｐはその平均値が０〜１０の
数を示し、Ｒ28Ｏが複数ある場合には、複数のＲ28Ｏは
同一でも異なっていてもよい。）で表され、かつ残りの
末端が一般式（IX）又は（Ｘ)[0034] (wherein, R 25, R 26 and R 27 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R 25,
R 26 and R 27 may be the same or different,
R 30 , R 31 , R 32 and R 33 each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 30 , R 31 , R 32 and R 33 may be the same or different. . R 28 is a divalent hydrocarbon group having 1 to 10 carbon atoms or 2 to 20 carbon atoms.
Wherein R 29 is a hydrocarbon group having 1 to 20 carbon atoms, p is a number having an average value of 0 to 10, and when there are a plurality of R 28 O, of R 28 O may be the same or different. ) And the remaining terminal is represented by the general formula (IX) or (X)

【００３５】[0035]

【化１０】 Embedded image

【００３６】（式中、Ｒ34，Ｒ35及びＲ36は、それぞれ
水素原子又は炭素数１〜８の炭化水素基を示し、Ｒ34，
Ｒ35及びＲ36はたがいに同一でも異なっていてもよく、
Ｒ39，Ｒ40，Ｒ41及びＲ42は、それぞれ水素原子又は炭
素数１〜２０の炭化水素基を示し、Ｒ39，Ｒ40，Ｒ41及
びＲ42はたがいに同一でも異なっていてもよい。Ｒ37は
炭素数１〜１０の二価の炭化水素基又は炭素数２〜２０
の二価のエーテル結合酸素含有炭化水素基、Ｒ38は炭素
数１〜２０の炭化水素基、ｑはその平均値が０〜１０の
数を示し、Ｒ37Ｏが複数ある場合には、複数のＲ37Ｏは
同一でも異なっていてもよい。）で表される構造を有す
るもの、及びその一つの末端が、上記一般式（VII)又は
（VIII) で表され、かつ残りの末端が一般式（XI)[0036] (wherein, R 34, R 35 and R 36 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R 34,
R 35 and R 36 may be the same or different,
R 39 , R 40 , R 41 and R 42 each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 39 , R 40 , R 41 and R 42 may be the same or different. . R 37 is a divalent hydrocarbon group having 1 to 10 carbon atoms or 2 to 20 carbon atoms;
R 38 is a hydrocarbon group having 1 to 20 carbon atoms, q is a number having an average value of 0 to 10, and when there are a plurality of R 37 O, R 37 O may be the same or different. ) And one end thereof is represented by the above general formula (VII) or (VIII), and the other end is represented by the general formula (XI)

【００３７】[0037]

【化１１】 Embedded image

【００３８】（式中、Ｒ43，Ｒ44及びＲ45は、それぞれ
水素原子又は炭素数１〜８の炭化水素基を示し、それら
はたがいに同一でも異なっていてもよい。）で表される
構造を有するものが好ましい。このようなポリビニルエ
ーテル系化合物の中で、特に次に挙げるものが本発明に
おいては好適である。 （１）その一つの末端が一般式（VII)又は（VIII) で表
され、かつ残りの末端が一般式（IX）又は（Ｘ) で表さ
れる構造を有し、一般式（Ｖ）におけるＲ16，Ｒ 17及び
Ｒ18が共に水素原子、ｋが０〜４の数、Ｒ19が炭素数２
〜４の二価の炭化水素基及びＲ20が炭素数１〜２０の炭
化水素基であるもの。 （２）一般式（Ｖ）で表される構成単位のみを有するも
のであって、その一つの末端が一般式(VII) で表され、
かつ残りの末端が一般式（IX）で表される構造を有し、
一般式（Ｖ）におけるＲ16，Ｒ17及びＲ18が共に水素原
子、ｋが０〜４の数、Ｒ19が炭素数２〜４の二価の炭化
水素基及びＲ20が炭素数１〜２０の炭化水素基であるも
の。(Wherein R43, R44And R45Respectively
A hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms,
They may be the same or different. )
Those having a structure are preferred. Such polyvinyl alcohol
Among the compounds based on ether, the following compounds are particularly preferred in the present invention.
In this case, it is preferable. (1) One terminal is represented by the general formula (VII) or (VIII).
And the remaining terminal is represented by the general formula (IX) or (X).
Having a structure represented by the general formula (V)16, R 17as well as
R18Are both hydrogen atoms, k is a number from 0 to 4, R19Has 2 carbon atoms
To 4 divalent hydrocarbon groups and R20Is charcoal having 1 to 20 carbon atoms
What is a hydride group. (2) having only the structural unit represented by the general formula (V)
Wherein one end is represented by the general formula (VII),
And the remaining terminal has a structure represented by the general formula (IX),
R in the general formula (V)16, R17And R18Are both hydrogen sources
Child, k is a number from 0 to 4, R19Is a divalent carbon having 2 to 4 carbon atoms
Hydrogen group and R20Is a hydrocarbon group having 1 to 20 carbon atoms
of.

【００３９】（３）その一つの末端が一般式（VII)又は
（VIII）で表され、かつ残りの末端が一般式(XI)で表さ
れる構造を有し、一般式（Ｖ）におけるＲ16，Ｒ17及び
Ｒ18が共に水素原子、ｋが０〜４の数、Ｒ19が炭素数２
〜４の二価の炭化水素基及びＲ 20が炭素数１〜２０の炭
化水素基であるもの。 （４）一般式（Ｖ）で表される構成単位のみを有するも
のであって、その一つの末端が一般式（VII)で表され、
かつ残りの末端が一般式（Ｘ）で表される構造を有し、
一般式（Ｖ）におけるＲ16，Ｒ17及びＲ18が共に水素原
子、ｋが０〜４の数、Ｒ19が炭素数２〜４の二価の炭化
水素基及びＲ20が炭素数１〜２０の二価の炭化水素基及
びＲ20が炭素数１〜２０の炭化水素基であるもの。また
本発明においては、前記一般式（Ｖ）で表される構成単
位を有し、その一つの末端が一般式（VII)で表され、か
つ残りの末端が一般式（XII)(3) The one terminal is represented by the general formula (VII) or
(VIII), and the remaining terminal is represented by the general formula (XI).
Having a structure represented by the general formula (V)16, R17as well as
R18Are both hydrogen atoms, k is a number from 0 to 4, R19Has 2 carbon atoms
To 4 divalent hydrocarbon groups and R 20Is charcoal having 1 to 20 carbon atoms
What is a hydride group. (4) having only the structural unit represented by the general formula (V)
Wherein one terminal is represented by the general formula (VII),
And the remaining terminal has a structure represented by the general formula (X),
R in the general formula (V)16, R17And R18Are both hydrogen sources
Child, k is a number from 0 to 4, R19Is a divalent carbon having 2 to 4 carbon atoms
Hydrogen group and R20Is a divalent hydrocarbon group having 1 to 20 carbon atoms and
And R20Is a hydrocarbon group having 1 to 20 carbon atoms. Also
In the present invention, the structural unit represented by the general formula (V)
One end of which is represented by the general formula (VII),
The remaining terminal is the general formula (XII)

【００４０】[0040]

【化１２】 Embedded image

【００４１】（式中、Ｒ46，Ｒ47及びＲ48は、それぞれ
水素原子又は炭素数１〜８の炭化水素基を示し、それら
はたがいに同一であっても異なっていてもよく、Ｒ49及
びＲ51はそれぞれ炭素数２〜１０の二価の炭化水素基を
示し、それらは互いに同一であっても異なっていてもよ
く、Ｒ50及びＲ52はそれぞれ炭素数１〜１０の炭化水素
基を示し、それらは互いに同一であっても異なっていて
もよく、ｃ及びｄはそれぞれその平均値が０〜１０の数
を示し、それらは互いに同一であっても異なっていても
よく、また複数のＲ49Ｏがある場合には複数のＲ49Ｏは
同一であっても異なっていてもよいし、複数のＲ51Ｏが
ある場合には複数のＲ51Ｏは同一であっても異なってい
てもよい。）で表される構造を有するポリビニルエーテ
ル系化合物も使用することができる。さらに、本発明に
おいては、一般式（XIII) 又は（XIV)[0041] (wherein, R 46, R 47 and R 48 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, they may be different even identical to each other, R 49 And R 51 each represent a divalent hydrocarbon group having 2 to 10 carbon atoms, which may be the same or different, and R 50 and R 52 each represent a hydrocarbon group having 1 to 10 carbon atoms. And they may be the same or different from each other, c and d each represent a number having an average value of 0 to 10, they may be the same or different from each other, and it is more R 49 O if there are R 49 O may be the same or different and when there are a plurality of R 51 O is a plurality of R 51 O are independently identical or different And a polyvinyl ether compound having a structure represented by the following formula: It is possible to use. Further, in the present invention, the compound represented by the general formula (XIII) or (XIV)

【００４２】[0042]

【化１３】 Embedded image

【００４３】（式中、Ｒ53は炭素数１〜８の炭化水素基
を示す。）で表される構成単位からなり、かつ重量平均
分子量が３００〜5,０００であって、片末端が一般式
（XV) 又は（XVI)(Wherein, R 53 represents a hydrocarbon group having 1 to 8 carbon atoms), the weight average molecular weight is 300 to 5,000, and one terminal is generally Formula (XV) or (XVI)

【００４４】[0044]

【化１４】 Embedded image

【００４５】（式中、Ｒ54は炭素数１〜３のアルキル
基、Ｒ55は炭素数1 〜8 の炭化水素基を示す。）で表さ
れる構造を有するアルキルビニルエーテルの単独重合物
又は共重合物からなるポリビニルエーテル系化合物も使
用することができる。なお、上記のポリビニルエーテル
については、特開平６−１２８５７８号公報又は特願平
５−１２５６４９号，特願平５−１２５６５０号，特願
平５−３０３７３６号各明細書のそれぞれに詳細に記載
されているものをいずれも使用することができる。(Wherein, R 54 represents an alkyl group having 1 to 3 carbon atoms, and R 55 represents a hydrocarbon group having 1 to 8 carbon atoms). A polyvinyl ether compound composed of a polymer can also be used. The above-mentioned polyvinyl ether is described in detail in JP-A-6-128578 or Japanese Patent Application Nos. 5-125649, 5-125650 and 5-303736. Any of these can be used.

【００４６】上記（Ｂ）成分の基油は、１００℃におけ
るその動粘度が５ｃＳｔ以上である。この粘度が５ｃＳ
ｔより小さい場合はシール性が悪く、かつ潤滑性能が低
下し好ましくない。このような観点から、この粘度範囲
は１０ｃＳｔ以上、特に１０〜５００ｃＳｔであること
が更に好ましい。本発明においては、上記（Ａ）成分の
ＣＯ2 冷媒と（Ｂ）成分の基油の使用量については、
（Ａ）成分／（Ｂ）成分の重量比で９９／１〜１０／９
０の範囲にあることが好ましい。（Ａ）成分の量が上記
範囲より少ない場合は冷凍能力が低下し、また上記範囲
より多い場合はシール性が悪くかつ潤滑性能が低下す
る。このような観点から、上記（Ａ）成分／（Ｂ）成分
の重量比は、９５／５〜３０／７０の範囲にあることが
更に好ましい。The kinematic viscosity at 100 ° C. of the base oil (B) is 5 cSt or more. This viscosity is 5 cS
If it is smaller than t, the sealing performance is poor and the lubricating performance is undesirably reduced. From such a viewpoint, the viscosity range is more preferably 10 cSt or more, particularly preferably 10 to 500 cSt. In the present invention, the amounts of the CO 2 refrigerant (A) and the base oil (B) are as follows.
99/1 to 10/9 by weight ratio of component (A) / component (B)
It is preferably in the range of 0. When the amount of the component (A) is less than the above range, the refrigerating capacity is reduced. From such a viewpoint, the weight ratio of the component (A) / the component (B) is more preferably in the range of 95/5 to 30/70.

【００４７】本発明の冷凍機油組成物には、必要に応じ
公知の各種添加剤、例えばトリクレジルホスフェート
（ＴＣＰ）などのリン酸エステルやトリスノニルフェニ
ルホスファイトなどの亜リン酸エステルなどの極圧剤；
フェノール系酸化防止剤、アミン系酸化防止剤、さらに
はフェニルグリシジルエーテル，シクロヘキセンオキシ
ド，エポキシ化大豆油などのエポキシ化合物などの安定
剤；ベンゾトリアゾール，ベンゾトリアゾール誘導体な
どの銅不活性化剤；シリコーン油やフッ化シリコーン油
などの消泡剤などを適宜配合することができる。更に、
耐荷重添加剤，塩素補足剤，清浄分散剤，粘度指数向上
剤，油性剤，防錆剤，腐食防止剤，流動点降下剤等を所
望に応じて添加することができる。これらの添加剤は通
常、本発明の組成物中に0.０１〜１０重量％含有され
る。本発明の潤滑油組成物は、種々の冷凍機に使用可能
であるが、特に、圧縮型冷凍機の圧縮式冷凍サイクルに
好ましく適用できる。とりわけ、本発明の潤滑油組成物
は、例えば添付図１〜３の各々で示されるような油分離
器及び／又はホットガスラインを有する圧縮式冷凍サイ
クルに適用する場合にその効果を有効に奏するものであ
る。The refrigerator oil composition of the present invention may contain, if necessary, various known additives such as phosphates such as tricresyl phosphate (TCP) and phosphites such as trisnonylphenyl phosphite. Pressure agent;
Stabilizers such as phenolic antioxidants, amine antioxidants, and epoxy compounds such as phenylglycidyl ether, cyclohexene oxide, and epoxidized soybean oil; copper deactivators such as benzotriazole and benzotriazole derivatives; silicone oil And a defoaming agent such as fluorinated silicone oil. Furthermore,
Load-bearing additives, chlorine scavengers, detergents / dispersants, viscosity index improvers, oil agents, rust inhibitors, corrosion inhibitors, pour point depressants and the like can be added as desired. These additives are usually contained in the composition of the present invention in an amount of 0.01 to 10% by weight. Although the lubricating oil composition of the present invention can be used for various refrigerators, it can be particularly preferably applied to a compression refrigeration cycle of a compression refrigerator. In particular, the lubricating oil composition of the present invention exerts its effects effectively when applied to, for example, a compression refrigeration cycle having an oil separator and / or a hot gas line as shown in each of FIGS. Things.

【００４８】[0048]

【実施例】次に、本発明を実施例によりさらに具体的に
説明するが、本発明はこれらの例によってなんら限定さ
れるものではない。なお、潤滑油組成物の性状及び性能
は、次の方法に従って求めた。 （１）溶解性 油１００ｇに５０ｋｇ／ｃｍ2 の加圧条件下で炭酸ガス
を吹き込み、油中における炭酸ガスの溶解量（重量％）
を測定した。 （２）シールドチューブ試験 ガラス管に触媒Ｆｅ／Ｃｕ／Ａｌを入れ、炭酸ガス／油
／水＝0.５ｇ／４ｇ／0.０２ｇの割合で試料を充填し封
管した。１７５℃で１０日間保持した後、油外観，触媒
外観，全酸価及びスラッジ有無を評価した。 （３）吸湿性試験 油１０ｇを湿度８５％Ｒ．Ｈ．（３０℃）にて１２０時
間放置した後の吸湿量（重量％）を求めた。 （４）ファレックス焼付試験 ファレックス試験機を用い、ピン／ブロック材料をＡＩ
ＳＩＣ１１３７／ＳＡＥ３１３５とした。ピン／ブロッ
クをセットし、試験容器内に試料の油２００ｇを入れ炭
酸ガスを５リットル／ｈで吹き込んだ後、回転数２９０
ｒｐｍ、油温５０℃で焼付荷重を測定した。EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The properties and performance of the lubricating oil composition were determined according to the following methods. (1) Solubility Carbon dioxide gas is blown into 100 g of oil under a pressurized condition of 50 kg / cm 2 , and the dissolved amount of carbon dioxide gas in the oil (% by weight)
Was measured. (2) Shield tube test The catalyst Fe / Cu / Al was put in a glass tube, and a sample was filled at a ratio of carbon dioxide / oil / water = 0.5 g / 4 g / 0.02 g and sealed. After maintaining at 175 ° C. for 10 days, oil appearance, catalyst appearance, total acid value, and presence or absence of sludge were evaluated. (3) Hygroscopicity test 10 g of oil at 85% RH. H. The amount of moisture absorption (% by weight) after standing at (30 ° C.) for 120 hours was determined. (4) Falex baking test Using a Falex testing machine, the pin / block material was AI
SIC1137 / SAE3135. The pin / block was set, 200 g of the sample oil was put into the test container, and carbon dioxide gas was blown at 5 liter / h.
The seizure load was measured at 50 rpm at an oil temperature of 50 rpm.

【００４９】実施例１〜１１及び比較例１〜４ 第１表に示す性状の基油を用いて、その各々について上
記の方法で各試験を行い評価を行った。結果を第２表に
示す。Examples 1 to 11 and Comparative Examples 1 to 4 Each of the base oils having the properties shown in Table 1 was subjected to each of the tests described above and evaluated. The results are shown in Table 2.

【００５０】[0050]

【表１】 [Table 1]

【００５１】[0051]

【表２】 [Table 2]

【００５２】[0052]

【発明の効果】本発明によれば、冷媒としてのＣＯ2 雰
囲気下で潤滑性能に優れ、シール性の高い冷凍機用潤滑
油組成物を提供することができる。According to the present invention, it is possible to provide a lubricating oil composition for a refrigerator having excellent lubricating performance and high sealability in a CO 2 atmosphere as a refrigerant.

【図面の簡単な説明】[Brief description of the drawings]

【図１】油分離機及びホットガスラインを有する圧縮式
冷凍サイクルの一例を示す流れ図である。FIG. 1 is a flowchart showing an example of a compression refrigeration cycle having an oil separator and a hot gas line.

【図２】油分離機を有する圧縮式冷凍サイクルの一例を
示す流れ図である。FIG. 2 is a flowchart showing an example of a compression refrigeration cycle having an oil separator.

【図３】ホットガスラインを有する圧縮式冷凍サイクル
の一例を示す流れ図である。FIG. 3 is a flowchart showing an example of a compression refrigeration cycle having a hot gas line.

【図４】圧縮式冷凍サイクルの流れ図である。FIG. 4 is a flowchart of a compression refrigeration cycle.

【符号の説明】[Explanation of symbols]

１：圧縮機 ２：凝縮器 ３：膨張弁 ４：蒸発器 ５：油分離器 ６：ホットガスライン ７：ホットガスライン用弁 1: Compressor 2: Condenser 3: Expansion valve 4: Evaporator 5: Oil separator 6: Hot gas line 7: Valve for hot gas line

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 30:06 40:30 Continued on the front page (51) Int.Cl. 6 Identification number Agency reference number FI Technical display location C10N 30:06 40:30

Claims (5)

【特許請求の範囲】[Claims] 【請求項１】 （Ａ）ＣＯ2 を主成分とする冷媒、及び
（Ｂ）ポリオキシアルキレングリコール及びポリビニル
エーテルから選ばれる少なくとも一種からなり、１００
℃における動粘度が５ｃＳｔ以上である基油、を含有す
ることを特徴とする冷凍機用潤滑油組成物。1. A refrigerant comprising (A) a refrigerant mainly composed of CO 2 and (B) at least one selected from polyoxyalkylene glycols and polyvinyl ethers.
A lubricating oil composition for refrigerators, comprising: a base oil having a kinematic viscosity at 5 ° C. of 5 cSt or more. 【請求項２】 （Ｂ）成分の基油がポリオキシアルキレ
ングリコールである請求項１記載の冷凍機用潤滑油組成
物。2. The lubricating oil composition for a refrigerator according to claim 1, wherein the base oil as the component (B) is a polyoxyalkylene glycol. 【請求項３】 ポリオキシアルキレングリコールの少な
くとも一つの末端基がアルキル基である請求項２記載の
冷凍機用潤滑油組成物。3. The lubricating oil composition for a refrigerator according to claim 2, wherein at least one terminal group of the polyoxyalkylene glycol is an alkyl group. 【請求項４】 ポリオキシアルキレングリコールの両末
端基がアルキル基である請求項３記載の冷凍機用潤滑油
組成物。4. The lubricating oil composition for a refrigerator according to claim 3, wherein both terminal groups of the polyoxyalkylene glycol are alkyl groups. 【請求項５】 （Ｂ）成分の基油の１００℃における動
粘度が１０ｃＳｔ以上である請求項１記載の冷凍機用潤
滑油組成物。5. The lubricating oil composition for a refrigerator according to claim 1, wherein the kinematic viscosity at 100 ° C. of the base oil (B) is 10 cSt or more.
JP20739196A 1996-08-06 1996-08-06 Lubricating oil composition for refrigerator Expired - Lifetime JP3271905B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP20739196A JP3271905B2 (en) 1996-08-06 1996-08-06 Lubricating oil composition for refrigerator

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP20739196A JP3271905B2 (en) 1996-08-06 1996-08-06 Lubricating oil composition for refrigerator

Publications (2)

Publication Number Publication Date
JPH1046169A true JPH1046169A (en) 1998-02-17
JP3271905B2 JP3271905B2 (en) 2002-04-08

Family

ID=16538971

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Link
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