JP4067551B2 - Fluorine-containing aromatic compound - Google Patents

Description

Currently, CFC-12 is mainly used as a refrigerant for refrigerators for car air conditioners and refrigerators, and HCFC-22 is used as a refrigerant for refrigerators for room air conditioners. From the standpoint of ozone layer protection, CFC- Development of refrigerants that can replace chlorine-containing refrigerants such as No. 12 and HCFC-22 is desired.
As an alternative refrigerant, the above-described lower hydrofluorocarbon having 1 to 5 carbon atoms is promising, and among them, a hydrofluorocarbon having 1 to 2 carbon atoms such as HFC-134a is particularly preferable.

In a refrigeration system using CFC-12 or HCFC-22, mineral oil or alkylbenzene is used as a lubricating oil for a compressor. Since CFC-12 and HCFC-22 contain chlorine atoms, they are highly lipophilic and compatible with mineral oil and alkylbenzene over a wide temperature range, so that refrigerant and lubricating oil are separated even in refrigeration systems where the refrigerant repeatedly evaporates and condenses. Never do.
However, since various hydrofluorocarbon refrigerants and hydrogen-containing fluorine-containing ether refrigerants do not contain chlorine atoms, they do not have sufficient compatibility with mineral oils and hydrocarbon compounds such as alkylbenzenes, and hydrocarbons such as mineral oils and alkylbenzenes are used as lubricating oils. When using a series compound, for example, the lubricating oil is replaced by refrigerant in the compressor, resulting in insufficient lubrication, and the lubricating oil adheres to the inner wall of the heat exchanger, resulting in a poor heat exchange rate. A serious problem occurs.

As a lubricating oil for a refrigerator using a hydrofluorocarbon such as HFC-134a or a fluorine-containing ether compound containing a hydrogen atom as a refrigerant, it is at least in the range of 0 ° C to 50 ° C, preferably in the range of -20 ° C to 70 ° C, particularly preferably. Must be compatible with hydrofluorocarbons such as HFC-134a and fluorine-containing ether compounds containing hydrogen atoms in a temperature range of −40 ° C. to 90 ° C., and further in a wider temperature range.
Various types of polyalkylene glycol compounds, polyol ester compounds, and polycarbonate compounds have been proposed as lubricating oils that have been used with hydrofluorocarbons such as HFC-134a so far and have good compatibility with hydrofluorocarbons such as HFC-134a. Yes. For example, polyalkylene glycol (particularly polyoxypropylene glycol) having two or more hydroxyl groups disclosed in Patent Document 1 is said to have a wide temperature range showing compatibility. However, the temperature range showing the compatibility is not yet sufficient as a lubricating oil, and it is particularly necessary to improve the compatibility in a high temperature region.

In addition, polyoxyalkylene glycol has insufficient lubricity under the conditions of use of lubricating oil, and also has high hygroscopicity, so that metal corrosion and volume resistivity decrease (sealed refrigeration such as refrigerators). It is not a practically excellent refrigeration system lubricating oil.
In addition, the polyol ester compounds disclosed in Patent Document 2, Patent Document 3 and the like, and the polycarbonate compounds disclosed in Patent Document 4 and Patent Document 5 are also considered to have excellent compatibility with HFC-134a. However, since it contains a polar group, it has high hygroscopicity, and there is a problem in durability such as hydrolysis resistance.
Fluorine atom-containing oils are considered as oils that are expected to have an affinity with hydrofluorocarbons such as HFC-134a other than polyalkylene glycols, polyester compounds, and polycarbonate compounds. The following patents have been filed as publicly known documents relating to fluorine atom-containing oils.

  In Patent Document 6, when a fluorocarbon lubricating oil such as fluorinated silicone or perfluoropolyether is used in a fluorocarbon working medium used for a heat pump or the like, the heat resistance of the fluorocarbon working medium is improved. It is disclosed. This patent makes no mention of the compatibility between the lubricating oil and the hydrofluorocarbon used as the working medium. Further, Patent Document 7 discloses the use of fluorine compounds such as perfluoropolyether and fluorinated silicone as lubrication for fluorocarbon refrigerants. However, these fluorine compounds and hydrofluorocarbons have a low temperature around room temperature or lower. There is no discussion about compatibility in the region.

Further, there is no description about the compatibility of hydrofluorcarbons with fluorine compounds other than perfluoropolyether or fluorinated silicone.
Therefore, the present inventor includes the following perfluoropolyethers (Fomlin Y-06, Y-25, Y-45 manufactured by Japan Montedison Co., Ltd.) listed in Examples of Patent Document 6 and Patent Document 7. When the compatibility of perfluoropolyethers with various structures as described above and fluorinated alkanes such as HFC-134a, HFC-134, and HFC-152a was examined, there may be cases where they are compatible near room temperature or higher. It was found that the compatibility in the low temperature region was insufficient, and it was not suitable as a lubricating oil for refrigerators using fluorinated alkanes such as HFC-134a, HFC-134, and HFC-152a as refrigerants. Furthermore, since the perfluoropolyether is not compatible with various hydrocarbon oils such as alkylbenzene and mineral oil, it can be mixed with hydrocarbon oil and used as a lubricating oil for refrigerators that use hydrofluorocarbon refrigerant. I can't.

On the other hand, Patent Document 8 discloses that a fluorine-containing aromatic compound having a structure represented by the general formula (1) exhibits good compatibility with a hydrofluorocarbon refrigerant in a wide temperature range from a low temperature region to a high temperature region, and is heat resistant. It has excellent physical properties such as lubricity, lubrication properties, and durability, and is a single or perfluoropolyether oil, perfluoropolyether oil with polar substituent, chlorofluorocarbon oil, polyalkylene glycol oil, ester A method of mixing with other oils such as oil and fluorinated silicone oil and using it as lubricating oil for refrigerators has been disclosed, but further low temperature fluidity, low moisture absorption, electrical insulation, lubricity, etc. Improvement of physical properties and cost reduction are desired.
The present inventors have studied to further improve the characteristics of the lubricating oil having the structure described in Patent Document 8.

US Pat. No. 4,755,316 Japanese Patent Laid-Open No. 3-128991 JP-A-3-17991 JP-A-5-32688 JP-A-5-86391 JP 60-96684 A JP-A-1-118598 JP-A-5-86382

  The problem of the present invention is that it exhibits good compatibility with hydrofluorocarbon refrigerants such as HFC-134a or a hydrogen atom-containing fluorine-containing ether refrigerant in a wide temperature range from a low temperature region to a high temperature region, and low temperature fluidity, low Providing a practical lubricating oil composition that satisfies all performance requirements for high-performance lubricating oil for refrigerators, such as hygroscopicity, electrical insulation, durability, lubrication characteristics, bioconcentration safety, low cost, etc. There is to do.

In view of the above points, the present inventors have intensively studied to develop a lubricating oil composition for a refrigerator that satisfies all the performances.
That is, the main invention of the present invention is a fluorine-containing aromatic compound (A) represented by the general formula (1), a structure in which an alkyl group is bonded to an aromatic nucleus selected from a benzene ring and a naphthalene ring, or a derivative thereof. And an aromatic compound (B) having a kinematic viscosity at 40 ° C. in the range of 0.1 to 500 centistokes, and containing 0.1 to 99.9% by weight of the component (A). And a kinematic viscosity at 40 ° C. in the range of 2 to 500 centistokes.
R (XRf) n (1)

[However, X is an oxygen atom or a sulfur atom. n represents an integer of 1 to 4.
R is an aromatic nucleus selected from a benzene ring and a naphthalene ring, a binuclear structure in which the aromatic nuclei are linked, or a substituted product thereof. The number of carbon atoms in R is in the range of 6 to 60, and the number of bonding sites between R and XRf is n. The aromatic nucleus content in R is in the range of 0.10 to 1.0 as a ratio of (number of carbon atoms forming aromatic nucleus) / (number of carbon atoms in R as a whole).
Rf represents a fluorinated hydrocarbon group selected from a fluoroalkyl group, a fluoroalkylaryl group, a fluoroalkenyl group, a fluoroaryl group, and a fluoroaraalkyl group, or 1 to 7 between carbon-carbon single bonds in the fluorinated hydrocarbon group. Represents those containing one ether bond and their substitutes. The number of carbon atoms in Rf is in the range of 1-25, and the ratio of (number of fluorine atoms) / (number of carbon atoms) in Rf is in the range of 0.6-3.
When n is 2 or more, the compound represented by the general formula (1) may be composed of a plurality of types of -XRf groups. ]

However, the present inventors have conducted detailed studies on the compatibility of various oils with the compound of the general formula (1), and among the various oils, in particular, the aromatic oil (B) having at least one aromatic nucleus is the general formula. It has been found that the compound (1) exhibits a particularly excellent compatibility with a wide range of compositions.
Aromatic oil (B) is inexpensive and excellent in low-temperature fluidity, low hygroscopicity, and electrical insulation, but exhibits some solubility in hydrofluorocarbon, but for refrigerators using hydrofluorocarbon as a refrigerant. As a lubricating oil, the solubility of hydrofluorocarbon is insufficient, and the aromatic oil (B) has a problem that its own lubricity is insufficient.

  However, since the present inventors show that the fluorine-containing aromatic compound (A) represented by the general formula (1) has particularly good compatibility with the aromatic oil (B) as described above, Even if a large amount of the aromatic oil (B) is mixed with the aromatic compound (A), the lubricating oil composition can be obtained by using a hydrofluorocarbon refrigerant (HFC) such as HFC-134a or HFC-32 or a fluorine atom-containing fluorine-containing ether system. It was found that the refrigerant (HFE) is sufficiently compatible as a lubricating oil for refrigerators. It was also found that the lubricating oil composition significantly improved the lubricity of the aromatic oil (B). Furthermore, surprisingly, the lubricating oil composition may exhibit lubricity superior to both the fluorine-containing aromatic compound (A) and the aromatic oil (B) represented by the general formula (1). Things were confirmed.

  As described above, according to the present invention, by mixing a fluorinated aromatic compound and an aromatic oil, a hydrofluoroalkane-based refrigerant and a fluorinated ether-based refrigerant can be used in a wide temperature range from a low temperature region to a high temperature region. Good compatibility. In addition, the fluorine-containing aromatic compound alone has been desired to further improve the low-temperature fluidity, low moisture absorption, and electrical insulation, but by mixing with aromatic oil, the characteristics are improved, low-temperature fluidity, lubrication characteristics, An oil composition having good properties such as low hygroscopicity and electrical insulation durability can be obtained. Further, the oil composition of the fluorinated aromatic compound and the aromatic oil according to the present invention can adjust the amount of the hydrofluorocarbon-based refrigerant dissolved in the refrigerating machine oil composition. As a result, the viscosity and lubrication of the refrigerant composition can be adjusted. Therefore, there is an advantage that a lubricating oil composition for a refrigerator suitable for various refrigerant systems can be provided.

Further, among the fluorine-containing aromatic compounds represented by the general formula (1), the compounds represented by the general formula (2) and the compounds represented by the general formula (3) are practically used as described below. It was also found that it has excellent important characteristics.
1) Since the so-called “bioconcentration”, which is a measure of the ease of concentration in a living body, is low, it can be used safely.
2) Low hygroscopicity and good electrical insulation.
3) Since the compatibility with hydrocarbon oils such as alkylbenzene and mineral oil is particularly excellent,
Can be used by mixing with a large amount of hydrocarbon oil. In addition, the mixed oil has greatly improved characteristics such as low-temperature fluidity, low moisture absorption, and electrical insulation as compared with the oil of the general formula (1), and can provide a low-cost lubricating oil.

4) Excellent stability such as heat resistance and oxidation resistance.
5) As an effective additive to improve oil return in a refrigeration system that combines hydrocarbon lubricants such as alkylbenzenes and mineral oils that have insufficient compatibility with hydrofluorocarbons and hydrofluorocarbon refrigerants. It is also possible to use it.
6) It may be used not only as a lubricating oil for refrigerators that use hydrofluorocarbon refrigerants, but also as a general purpose lubricating oil, or as a modifier for various oily substances and polymer materials. it can.

The present invention is described in further detail below.
In the general formula (1), R is an aromatic nucleus composed of a benzene ring and a naphthalene ring, a binuclear structure in which the aromatic nucleus is linked, or a substituted product thereof. The number of carbon atoms in the entire R is 6 to
60, preferably 6 to 40, particularly preferably 6 to 30. R may contain a substituent or linking group having 50 or less carbon atoms, preferably 20 or less, and more preferably 15 or less.

As the types of aromatic nuclei in R, various aromatic groups can be used, and they may contain heteroatoms such as nitrogen atoms, oxygen atoms and sulfur atoms. However, it is usually selected from aromatic hydrocarbon groups having 6 to 14 carbon atoms because of stability and availability of raw materials. Among them, as the aromatic nucleus contained in R, an aromatic nucleus selected from a benzene ring and a naphthalene ring is used, and a benzene nucleus is particularly preferably used.
When R in the general formula (1) is an aromatic ring-containing group, the compound of the general formula (1) has a high affinity with any of the HFC-based refrigerant, HFE-based refrigerant, and aromatic oil (B). is important. Therefore, the structure of R is not particularly limited as long as it contains an aromatic ring at a certain ratio, and various substituents may be bonded to the aromatic ring. A structure in which comrades are linked by various linking groups may be used.

The substituent or linking group may be various hydrocarbon groups, or may be various polar groups that are stable under the conditions of use of the refrigerator or a structure containing polar groups.
Even when R contains various structural groups, the compound of the general formula (1) exhibits good compatibility with HFC-based and HFE-based refrigerants. This is because HFC-based and HFE-based refrigerants have C—H bonds polarized by the electron withdrawing properties of fluorine atoms, and the polarized C—H bonds exhibit strong interactions with various polar groups. Even when R contains a polar group, the compatibility between the compound of the general formula (1) and the HFC or HFE refrigerant is not disturbed.

That is, it is sufficient that R contains a certain amount or more of aromatic nuclei, and the ratio of [number of carbon atoms forming aromatic nuclei in R] / [number of carbon atoms in R as a whole] is usually 0. 1 or more, preferably 0.2 or more, particularly preferably 0.5 or more.
Among R in the general formula (1), the compound of the general formula (1) having particularly excellent stability is particularly preferable in the case of R having a structure in which an aromatic nucleus is directly linked to -XRf.
A typical example of the structure of R described above is, for example, general formula (1a).

b ₁ ): a monovalent hydrocarbon group selected from an alkyl group having 1 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, and a cycloalkenyl group.
b ₂ ): a monovalent substituent selected from a hydroxyl group, a thiol group, a nitrile group, a nitro group, a fluorine atom, and a chlorine atom.
b ₃ ): a monovalent substituent of b ₂ ) and a monovalent hydrocarbon group of b ₁ ) containing at least one divalent group a ₂ ) used for the linking groups Y and Y ′ Derivative.
The total number of monovalent substituents b ₂ ) and divalent groups a ₂ ) in b _{3 is} in the range of 1 to 3. In addition, the upper limit of the number of carbon atoms in the hydrocarbon group derivative of b ₃ ) is 50.

b ₄ ) b ₁ ) and b ₃ ) Monovalent substituents in which part or all of the hydrogen atoms of the carbon-hydrogen bond are substituted with fluorine atoms.
The total number of substituents bonded to the aromatic nuclei of Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ and the number of linking groups Y and Y ′ is in the range of zero to 4 for each aromatic nuclei. In general formula (1a), the position bonded to —XRf may be any carbon atom in general formula (1a). ]

In the general formula (1a), P represents an integer of 0 to 2, and P ′ represents an integer of 0 to 4. L and L ′ are zero or 1, m represents an integer of 0 to 2, and m ′ represents an integer of 0 to 5.
Ar ₁ , Ar ₂ , Ar ₃ , and Ar ₄ are an aromatic nucleus (preferably a benzene ring) selected from a benzene ring and a naphthalene ring, or a substituent in which a monovalent substituent is bonded to the aromatic nucleus. The substituent in the substituent will be described later.
Y and Y ′ are polyvalent groups selected from the following a ₁ ) to a ₃ ), and Y is 2 to 4 valent, preferably 2 to 3 valent, and particularly preferably 2 valent. Y ′ is 2 to 6 valent, preferably 2 to 3 valent, particularly preferably 2 valent.

a ₁ ): a divalent to hexavalent saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms or a fluorine atom substituted product thereof. The number of carbon atoms contained in the polyvalent group is in the range of 1 to 20 valences, preferably 1 to 15 and particularly preferably 1 to 10. When the polyvalent group is a fluorine atom-substituted product, the ratio of [number of fluorine atoms] / [number of carbon atoms] in the polyvalent group is 0.2 to 2, preferably 0.5 to 2 range. Examples of the polyvalent group are shown below.

Examples of other structures include

がある。 As an example of Y ′ in the case of (1a) where l = 0, l ′ = 1, m = 5, and p ′ = 1,

There is.

a ₂ ): a divalent or trivalent polyvalent group selected from the following (1) to (4). The number of carbon atoms in the polyvalent group is in the range of 0 to 20, preferably in the range of 0 to 12, particularly preferably in the range of 0 to 8.
(1) Oxygen atom (-O-)
(2) A carbonyl-containing polyvalent group selected from a carbonyl group, an ester bond, an amide bond, and a carbonate bond.
(3) A sulfur atom-containing polyvalent group selected from a sulfur atom (—S—), a sulfonyl group, and a sulfinyl group.
(4) A nitrogen atom, phosphorus atom, or silicon atom-containing polyvalent group selected from the following groups.

（Ａは単結合、水素原子、または炭素数１〜６のアルキル基のいずれかである。Ｂは単結合または酸素原子（−Ｏ−）を表す。Ｄは単結合、酸素原子（−Ｏ−、−Ｒ，−ＯＲのいずれかである。Ｒは炭素数１〜２０個のアルキル基である。）

(A is a single bond, a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms. B represents a single bond or an oxygen atom (—O—). D represents a single bond, an oxygen atom (—O—). , -R, -OR, where R is an alkyl group having 1 to 20 carbon atoms.)

  In addition, as the linking groups Y and Y ′ of the aromatic nucleus, a structure in which two or three of the above polyvalent groups are further combined may be formed. It may combine to form a heteroatom-containing ring. An example is shown below.

のように両方の構造を意味するものとする。以下にａ₂ ）の多価基の具体例を示す。 Further, in the above polyvalent group, a group having an asymmetric structure such as an ester bond, that is, the following structure:

Both structures are meant as follows. Specific examples of the polyvalent group a ₂ ) are shown below.

a ₃ ): a divalent to hexavalent polyvalent group having a structure in which the polyvalent group of a ₂ ) is bonded or inserted into the terminal or inside of the carbon skeleton group shown in a ₁ ). That carbon carbon backbone group, at least one is shown either, or / and a ₁₎ binding of the polyvalent groups shown in a ₂₎ to the carbon skeleton group depicted in a ₁₎ - between carbon bond ₂ to 6 having a structure in which at least one of the polyvalent groups shown in a ₂ ) is inserted
Valent polyvalent group. The number of carbon atoms contained in the group is in the range of 1-50.
The number of a ₂ ) polyvalent groups contained in the group is usually in the range of 1 to 6, preferably 1 to 4, particularly preferably 1 to 3. However, when the group includes a polyalkylene oxide structure or a polydimethylsiloxane structure, the upper limit of the number of polyvalent groups is 20. The number of carbon atoms contained in the group is usually in the range of 1 to 20, preferably 1 to 12, particularly preferably 2 to 8. However, when the group contains a polyalkylene oxide structure or a polydimethylsiloxane structure, the upper limit of the carbon number is 50.

Specific examples of the polyvalent group of a ₃ ) are shown below.

The monovalent substituent bonded to the aromatic nucleus in Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ is at least one selected from the following b ₁ ) to b ₄ ).
b ₁ ): a monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, particularly preferably 1 to 15 carbon atoms, and selected from an alkyl group, an alkenyl group, a cycloalkyl group, and a cyclokelenyl group.
b ₂ ): a monovalent substituent selected from a hydroxyl group, a thiol group, a nitrile group, a nitro group, and a fluorine atom chlorine atom.

b _3-1): derivatives of hydrocarbon groups of b ₁₎ is a structure substituted with a substituent of a portion of the hydrogen atoms of the hydrocarbon group b ₂₎ of b _1).
b _3-2 ): the carbon-carbon bond of the hydrocarbon group of b ₁ ) or the derivative of the hydrocarbon group of b _3-1 ) _{2 of} a ₂ ) exemplified as the aforementioned linking groups Y and Y ′ It is a structure in which at least one kind of valent group is inserted. b ₁ ) Derivatives of hydrocarbon groups.
The number of substituents and / or divalent groups a ₂ ) in b _3-1 ) and b _3-2 ) is usually 1 to 3, preferably 1 to 2, particularly preferably 1. However, each of the polyalkylene glycol structure and the polydimethylsiloxane structure is counted as a monovalent divalent group. When these long-chain divalent groups are contained, the upper limit of the number of carbon atoms in the substituents of Ar _{1 to} Ar ₄ is 50, preferably 40.

b ₄ ): a monovalent substituent in which part or all of the hydrogen atoms of the carbon-hydrogen bond in b ₁ ), b _3-1 ) and b _3-2 ) are substituted with fluorine atoms. In the case of a fluorine atom-containing substituent, the ratio of [number of fluorine atoms] / [number of carbon atoms] in the substituent is 0.05 to 3, preferably 0.2 to 2, and particularly preferably 0.8. It is the range of 5-2.
However, the fluorine atom-containing substituents excluding those corresponding to -XRf in the general formula (1a) are excluded. The total number of substituents bonded to each aromatic nucleus of Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ and the number of linking groups Y and Y ′ is usually from 0 to 4 per aromatic nucleus, preferably Is 1 to 2, particularly preferably 1.
In general formula (1a), the position bonded to —XRf may be any carbon atom in general formula (1a), but preferably bonded to the carbon atom in the aromatic nucleus in Ar ₁ , Ar ₂ , Ar ₃ , Ar ₄ . desirable. Specific examples of the substituent bonded to the Ar _{1 to} Ar ₄ aromatic nucleus are shown below.

In addition, the following are mentioned as a specific example of R containing the following substituents and a coupling group.

In addition, the following are mentioned as a specific example of R containing the following substituents and a coupling group.

X in the general formula (1) is an O or S atom. When X is O, (1) a fluorine-containing aromatic compound can be synthesized economically with a high yield using an inexpensive synthetic raw material. (2) The fluorine-containing aromatic ether compound is particularly preferable because it has extremely high stability.
In the general formula (1), Rf represents a monovalent fluorinated hydrocarbon group or a derivative thereof. The fluorinated hydrocarbon group means a structure in which part or all of various monovalent hydrocarbon group hydrogen atoms are substituted with fluorine atoms. Examples thereof include, for example, a fluoroalkyl group having a saturated structure, a fluoroalkenyl group having an unsaturated structure, a fluoroaryl group having an aromatic nucleus or a fluoroaraalkyl group. Particularly, a fluoroalkyl group and a fluoroalkenyl group are Easy to synthesize and useful. Rf may contain an ether bond in the main chain of the fluorinated hydrocarbon group. When Rf contains an ether bond, the number of ether bonds is preferably in the range of 1 to 7, particularly preferably in the range of 1 to 3. Furthermore, as Rf, the fluorinated hydrocarbon group or an ether derivative thereof may be further substituted with another substituent. When Rf contains a substituent other than a fluorine atom and an ether bond, the number of the substituent is usually in the range of 1 to 4, preferably 1 to 2, particularly preferably 1.

The substituent for Rf is not particularly limited as long as it is stable under the conditions of use of the refrigerator, and examples thereof include the following.
(1) Halogen atoms other than fluorine atoms. That is, a chlorine atom, a bromine atom, and an iodine atom, but a chlorine atom is particularly preferable.
(2) An active hydrogen group selected from a hydroxyl group, an amino group, and a thiol group. (However, a structure in which an active hydrogen group is bonded to a carbon atom bonded to a halogen atom is not taken.)
(3) a thioalkoxy group, an alkyl-substituted amino group, and an organic acid derivative such as an anyl group, aniloxy group, carboalkoxy group, nitrile group, amide group, imide group or the like, preferably within 10 carbon atoms, preferably within 6 carbon atoms, Particularly preferably, no more than 3 substituents. The substituent may contain a fluorine atom.

The ratio of [number of substituents of (1) to (3) above in Rf] / [total number of fluorine atoms and hydrogen atoms in Rf] is 1.5 or less, preferably 1.0 or less. Among the above-mentioned substituted fluorinated hydrocarbon groups, ether bond-containing fluorinated hydrocarbon groups and chlorine atom-containing fluorinated hydrocarbon groups are particularly preferred because they are easy to synthesize and exhibit good stability.
The ratio of the number of fluorine atoms / the number of carbon atoms in Rf is not particularly critical and a wide ratio can be used, but it is usually 0.6 or more and 3 or less, preferably 1 or more and 3 or less, Particularly preferably, 1.5 or more and 3 or less are used. When the ratio of the number of fluorine atoms / number of carbon atoms in Rf is too low, the compatibility with hydrofluorocarbon refrigerants and hydrogen-containing fluorine-containing ether refrigerants tends to be low, and the stability tends to decrease. This is not preferable. The number of carbon atoms in Rf is usually in the range of 1 to 25, preferably in the range of 1 to 10, particularly preferably in the range of 1 to 3. When the number of carbon atoms in Rf is more than 25, it is not preferable because it is difficult to obtain or synthesize the raw materials, and the synthesis purification becomes complicated and the viscosity becomes too high.

The structure of Rf is not particularly limited as long as the above requirements are satisfied. General formula (1b) is a typical example of the structure, but is not limited to this structure.

_{However, A 1, A 2, A} 3 1-6 fluorine atoms or carbon atoms, preferably 1 to 3 fluorinated alkyl group, particularly preferably a fluorine atom or -CF _3.
B ₁ , B ₂ and B ₃ are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably a hydrogen atom or —CH ₃ .
Z is a hydrogen atom or a fluorine atom.
n ₁ is zero to 25, preferably an integer of 1 to 20, n ₂ is an integer of zero to 10, n ₃ is an integer of zero to 10, n ₄ is an integer of zero to 7. However, (n ₁ + n ₃ ) is never zero.
In (1b), when n ₁ , n ₂ , and n ₃ are integers of 2 or more, each may have the same or different structure. In (1b), each unit of (CA ₁ A ₂ ), (CB ₁ B ₂ ), (CA ₃ B ₃ ) may have a plurality of structures, may be arranged at random, Each may be linked to form a double bond, or an alicyclic or aromatic cyclic structure may be formed.

The following units will not be linked. The following units are not located at the end of (1b) or next to Z.

In addition, as Rf, one part of the fluorine atom or hydrogen atom having the structure of (1b) is preferably in the range of 1 to 4 and a halogen atom other than the aforementioned fluorine atom, an active hydrogen machine, and a carbon number. A structure substituted with at least one substituent selected from 10 or less substituents may be used.
Examples of Rf- in the substance represented by the general formula (1) used in the present invention are illustrated below. Examples of Rf shown here are substances of the general formula (1) synthesized by various methods. A part of the example of Rf in the inside is illustrated and not limited thereto.

〔Ｚ⁷ ＝Ｆ，Ｃｌ，Ｉ，Ｈ；L ₁ ＝１〜１８の整数; L ₂ ＝０，１，２〕

[Z ⁷ = F, Cl, I, H; L ₁ = 1 to 18; L ₂ = 0, 1, 2]

Specific examples of the compound of formula (4) include the following.

Specific examples of the group of the general formula include the following.

Further, the following groups can be used.

Among the fluorine-containing aromatic compounds represented by the general formula (1), those that exhibit good compatibility with the aromatic oil (B) are usually the number of fluorine atoms / (the number of fluorine atoms + The ratio of the number of hydrogen atoms) is from 0.03 to 0.85, preferably from 0.05 to 0.6, particularly preferably from 0.1 to 0.5. Moreover, as a fluorine-containing aromatic compound (A) of General formula (1), several types can also be mixed and used.
The value of n in the general formula (1) depends on the valence of R, and is usually selected from 1, 2, 3, 4 for reasons such as ease of synthesis and taking an appropriate viscosity range. , Preferably an integer selected from 2, 3, 4 and particularly preferably an integer selected from 2. Moreover, when n is 2 or more in General formula (1), the substance of General formula (1) may be comprised by several Rf.

Specific examples of the fluorine-containing aromatic compound (A) of the general formula (1) used in the present invention include fluorine-containing aromatic compounds of the general formula (1) disclosed in JP-A-5-86382. used.
The substance represented by the general formula (1) used in the present invention can be synthesized by various methods.

In the following, in the general formula (1), a synthesis example in the case of n = 1 is illustrated, but the synthesis is also performed in the same manner in the case of n = 2, 3, and 4.
1) Reaction of phenols or thiophenols with fluorine-containing olefins.
Numerous reaction examples are known for the synthesis of fluorine-containing aromatic compounds by reaction of phenols or thiophenols with fluorine-containing olefins.
A typical example of the reaction is shown below by taking the case of perfluoroolefin as an example.

The reaction examples of phenols and fluorine-containing olefins are shown below.
For example, Advance in Fluorine Chemistry, 4, 50 (1965) includes (1 ′), (2 ′) by ionic reaction between various fluorine-containing olefins and phenols, or alcohols or thiophenols as described below. A reaction example similar to the formula is shown.

CF ₂ = CF ₂ , CF ₂ = CFCl, CF ₂ = CFBr, CF ₂ = CFH, CF ₂ = CHCl, CF ₂ = CCl ₂ , CHF = CCl ₂ , CF ₃ CF = CF ₂ , CClF ₂ CF = CF ₂ CF ₃ CCl = CF ₂ , CF ₃ CF = CCl ₂ , CF ₃ CCl = CClF, CF ₃ CH═CH ₂ , CF ₃ CH═CHCl, CF ₃ CCl = CHCl, CF ₃ CCl = CCl ₂ , CF ₃ CF _{2 CCF = CF 2, CF 3} CF = CFCF 3, (CF 3) 2 C = CF 2, CF 2 = CFCF = CF 2,

CF ₃ CCl = CClCF ₃ , CCl ₂ FCClFCF = CClF,
CF _3- (CF ₂ ) ₄ -CF = CF ₂

Reaction formula of formula (3 ′);

Furthermore, an oligomer of hexafluoropropene (HFP) represented by the general formula (10 ′), an oligomer of tetrafluoroethylene (TFE) represented by the general formula (11 ′), an oligomer of chlorotrifluoroethylene, etc. An oligomer containing an unsaturated bond derived from various fluorine-containing olefins represented by the formula (1) can also be used as a raw material for the synthesis reaction represented by the formulas (1 ′) and (2 ′).
C _3m F _6m (10 ')
[M: an integer of 2 or more, preferably an integer of 2 to 6]
C _{2m '} F _4m' (11 ')
[M ′: an integer of 2 or more, preferably an integer of 2 to 10]
Examples of such oligomer reaction include the following examples.

Journal of the Chemical Society of Japan, 1978, 253
Reaction formula of formula (14 ′):

Many reactions of TFE pentamers (C10F20) and HFP trimers (C9 F18) with phenols as represented by the following reactions are shown.
Reaction formulas of formulas (15 ′), (16 ′), (17 ′);

Reaction formulas of the formulas (18 ′) and (19 ′);

In addition, Journal of Chemistry 54, 162 (1991) reports the addition reaction of phenols and perfluorovinyl ether as represented by the formulas (20 ′) and (21 ′).
Reaction formulas of the formulas (20 ′) and (21 ′);

Also, Izbest. Akad. Nauk S.M. S. S. R. , Otdel, Khim, Nauk, 1952, 261-7 report the addition reaction of thiophenol with chlorotrifluoroethylene or tetrafluoroethylene as shown in the reaction formula (22 ′).
Reaction formula of formula (22 ′);

Bull, Soc. Chim. Fr. , 1972, (8), 3202-5 include (2
The addition reaction of thiophenol and chlorotrifluoroethylene as in the formula 3 ′) has been reported.

〔ここで、ＸはＯ又はＳ原子を表す。またＸ⁵、Ｘ⁶はハロゲン原子、−ＯＳＯ₂Ｍｅ、−ＯＣＯＣＦ₃、−ＯＳＯ₂ＣＦ₃、−ＯＳＯ₂ＣＣｌ₃、−ＯＳＯ₂Ｃｌ (2) Reaction of phenols or thiophenols with saturated fluorocarbons There are many possible methods for the reaction of fluorine-containing aromatic compounds by reaction of phenols or thiophenols with saturated fluorocarbons. Examples of typical reaction methods include the following reactions.

[Wherein X represents an O or S atom. X ⁵ and X ⁶ are a halogen atom, —OSO ₂ Me, —OCOCF ₃ , —OSO ₂ CF ₃ , —OSO ₂ CCl ₃ , —OSO ₂ Cl

等のアニオンとして脱離しやすい置換基を表す。
Ａｒ’は一価の芳香族基を表す。Ｒｆ’は一般式（１）中のＲｆと同じもので、Ｒｆ’Ｘ- のアニオン構造を取り得るものを表す。〕

It represents a substituent that is easily eliminated as an anion such as.
Ar ′ represents a monovalent aromatic group. Rf ′ is the same as Rf in the general formula (1) and represents an anion structure of Rf′X−. ]

Actual, Chem. , 1987, 151
Reaction formulas of the formulas (26 ′) and (27 ′);

  “Chemistry of Organic Fluorine Compounds” Halted Press, 2nd Edition, P279 includes fluorine-containing ethers and fluorine-containing compounds by alkylation at the oxygen or sulfur atom part of alcohols, phenols and thiols (Alkylation at Oxygen or Sulfur). A number of methods for synthesizing thioether compounds have been shown.

Journal of Organic Chemistry, 50, 4047 (1985)
Reaction formula of formula (28 ′);

Industrial and Engineering Chemistry, 39, 412 (1947)
Reaction formulas of formulas (29 ′) and (30 ′);

Pure and Applied Chemistry, 59, 1015 (1987)
Many reactions of various fluorine-containing halides represented by the general formula (32 ′) with phenoxide are shown.
CZ ₂ Z ₃ Z ₄ CFZ ₃ Z ₄ (32 ')
[Where Z ₂ = Cl, Br, I and Z ₃ = Z ₄ = F, Cl, Br, CF ₃ , H]

Journal of Organic Chemistry, 25, 2009 (1960)
Reaction formula of formula (35 ′);

In addition, the fluorine-containing aromatic compound of the general formula (1) can be synthesized by using various ether bonds or thioether bonds.
As an example, for example, the following ether formation reaction by reaction of a hydroxyl group and an epoxy group can be mentioned.

〔ここで、Ａｒ’は一価の芳香族基を表し、Ｒｆ”は炭素数１〜１６のフルオロカーボン基を表す。〕 Reaction formulas of the formulas (36 ′) and (37 ′);

[Wherein Ar ′ represents a monovalent aromatic group, and Rf ″ represents a fluorocarbon group having 1 to 16 carbon atoms.]

Furthermore, a method of introducing a fluorine atom into the precursor material of the material represented by the general formula (1) by various methods can be used, or various reaction products synthesized by the various methods shown so far can be used. It may be converted into a desired substance represented by the general formula (1) by conversion.
Examples thereof include the following method.

〔ここで、Ｒ3 は（２６’）、（２７’）式のＲ3 と同じ〕 Actual. Chem. , 1987, 151
Reaction formula of formula (38 ′);

[Where R3 is the same as R3 in formulas (26 ') and (27'))

In addition, fluorine-containing compounds such as fluorine-containing olefins and saturated fluorocarbons used in the above reaction can be synthesized by various known methods.
Examples thereof include, for example, “Advanceds in Fluorine Chemistry”, Butterworth, vol. 3, Synthesis method by halogen exchange shown in P181, “Chemistry of Organic Fluorine C”
a method described in “ounds” Halted Press, or a method for synthesizing oligomers of fluoroolefins described in JP-A-50-117705, JP-B 43-11185, JP-B 47-22563, etc. However, the present invention is not limited to this.
The fluorine-containing aromatic compound represented by the general formula [I] can be synthesized by various methods, and the reactions shown so far are examples of specific examples. Therefore, the synthesis method of the substance of the general formula (1) is not limited to these methods.
Moreover, the refrigerating machine oil used for this invention should just have the structure represented by General formula (1), and is not limited at all by the manufacturing method.

As described above, the fluorine-containing aromatic compound of the general formula (1) used in the present application is produced by various methods, and can be further purified by a treatment such as distillation, extraction, adsorption and the like.
There are various compounds as the aromatic oil (B) used in the present invention, and if it is an oily substance containing an aromatic nucleus selected from at least one benzene ring and naphthalene ring, the further restrictions are particularly great. However, from the viewpoint of easy handling, those having a kinematic viscosity at 40 ° C. of 0.1 to 500 cst are preferred, those having 1 to 300 cst are more preferred, and those having 3 to 100 cst are particularly preferred.

Examples of the aromatic nucleus in the aromatic oil (B) include a benzene ring and a naphthalene ring. The number of aromatic nuclei in the aromatic oil (B) is usually in the range of 1 to 4, preferably in the range of 1 to 2, and particularly preferably 1. If the number of aromatic nuclei is 5 or more, the viscosity becomes too high.
In addition, as a constituent ratio of the aromatic nucleus in the aromatic oil (B), a ratio of [number of carbon atoms forming the aromatic nucleus] / [number of carbon atoms in the whole molecule of the aromatic oil (B)] is usually used. Is in the range of 0.10 to 1.0, preferably in the range of 0.15 to 0.9, particularly preferably in the range of 0.20 to 0.8. If the composition ratio of the aromatic nucleus in the aromatic oil (B) is too low, the compatibility between the aromatic oil (B) and the fluorine-containing aromatic compound (A), or the aromatic oil (B) and the fluorine-containing aromatic Since the compatibility with the hydrofluorocarbon refrigerant | coolant and fluorine-containing ether type refrigerant | coolant of the mixed oil composition which consists of a compound (A) becomes low, it is unpreferable.

  Representative examples of the aromatic oil (B) used in the present application include alkylbenzene, alkylnaphthalene, and derivatives thereof in which an alkyl group is bonded to an aromatic nucleus. The number of carbon atoms in the substituent selected from the alkyl group bonded to the aromatic nucleus or a derivative thereof is usually in the range of 1 to 30, and preferably in the range of 4 to 25. As the derivatives of alkylbenzene used in the present application, those having a multinuclear structure in which a plurality of alkylbenzenes are linked by a divalent group such as an alkylene group, an ether group, an ester group, a carbonate group, a carbonyl group, a sulfonyl group or a single bond are also possible. Or they may be substituted.

Therefore, a representative example of the aromatic oil (B) used in the present application includes, for example, an aromatic compound having a structure represented by the general formula (B-1).

However, Ara and Arb are a benzene ring or a naphthalene ring.
n ₁ is zero to 4, preferably an integer of 1 to 3, n ₂ is zero or 1 to 3, preferably 1 or 2, n ₃ is 1 to 3, preferably 1 or 2, particularly preferably 1. An integer, n ₄ is 0, 1, 2 (n ₁ ≠ 0 when n ₄ = 0, and (n ₁ + n ₂ ) ≠ 0 when n ₄ ≠ 0.
K is a linking group selected from the following 1) to 3).
1) Single bond 2) Oxygen atom

，スルホニル基およびカルボニル基より選ばれる２価基。好ましくは酸素原子である。
３） 炭素数１〜１２（好ましくは１〜４、特に好ましくは１）の２価〜４価（好ましくは２価）の飽和炭化水素基またはその置換体。
Ｒ₁ ，Ｒ₂ は炭素数１〜３０（好ましくは４〜２５）のアルキル基またはその置換体であり、エーテル結合を含んでも良い。Ｒ₁ ，Ｒ₂ ，Ｋ，Ａｒｂは各々複数の構造をとりうる。

, A divalent group selected from a sulfonyl group and a carbonyl group. Preferably it is an oxygen atom.
3) A divalent to tetravalent (preferably divalent) saturated hydrocarbon group having 1 to 12 carbon atoms (preferably 1 to 4, particularly preferably 1) or a substituted product thereof.
R ₁ and R ₂ are each an alkyl group having 1 to 30 carbon atoms (preferably 4 to 25) or a substituted product thereof, and may include an ether bond. R ₁ , R ₂ , K, and Arb can each have a plurality of structures.

In addition, the aromatic oil (B) represented by the structure of the general formula (B-1) contains an ether bond at a ratio within 1/3, preferably within 1/5 of the total number of carbon atoms. Also good. That is, within the oxygen atom content range, R ₁ and R ₂ may be an alkyl group, a structure containing an oxygen atom at the terminal or inside of the alkyl group, or a substituted product thereof.
The aromatic oil (B) represented by (B-1) has a hydrogen atom within 1/3, preferably within 1/5 of the total number of hydrogen atoms, a chlorine atom, an amino group, (-NRR ') It may be substituted with a polar group such as an anyl group, an acyloxy group, a carboalkoxyl group or a nitrile group. In addition, the above-mentioned various aromatic oils (B) may be those in which a part of the total number of hydrogen atoms, preferably a hydrogen atom within one-half, is substituted with a fluorine atom. Examples include 2,2,2-trifluoroethyl substituted aromatic compounds, 3,3,3-trifluoropropyl substituted aromatic compounds, and various fluorine-substituted alkylbenzenes such as CF ₃ CHFCF ₂ substituted alkylbenzenes. In the case where the aromatic oil (B) contains an alkoxy group substituted with a fluorine atom, the ratio of [number of fluorine atoms] / [number of carbon atoms] in the fluorinated alkoxy group is less than 0.6. It is.

Further, in the oil (B) represented by the general formula (B-1), carbon atoms that do not form an aromatic ring may be further bonded to form a double bond or a cyclic structure. Also, two or more kinds of aromatic oils (B) can be mixed and used, and a part of the aromatic oil (B), preferably within 2/3, particularly preferably within 1/2. It can also be used as a mixed oil replaced with an aromatic hydrocarbon compound. The aromatic oil (B) used in the present invention will be specifically described below. Representative examples of the aromatic oil (B) used in the present invention include alkylbenzene, alkylnaphthalene, and aromatic compounds such as alkylated biphenyls, polyphenyl-substituted hydrocarbons, and styrene oligomers that can be considered as derivatives of alkylbenzenes. I can do it. Preferably, it is a lubricating oil composition with alkylbenzene that can be obtained at low cost. As the alkylbenzene, monoalkylbenzene, dialkylbenzene, polyalkylbenzene having 3 or more substitutions, and the like can be used, but mono and dialkylbenzene are easy to use industrially because they are easily available. As the alkyl benzene, both branched alkyl benzene and straight chain alkyl benzene can be used. Particularly preferred are branched alkyl benzenes having particularly good compatibility with yes-fluorocarbon refrigerants. Furthermore, various derivatives of the above alkylbenzene and alkylnaphthalene can also be used in the present invention. Examples of specific structure of the aromatic oil (B) used in the present invention are shown below.

Examples of branched alkylbenzenes include, for example:

Examples of linear alkylbenzenes include, for example:

[R: H or an alkyl group having 1 to 30 (preferably 4 to 25) carbon atoms R ': H, an alkyl group having 1 to 10 (preferably 1 to 5) carbon atoms, 7 to 20 carbon atoms (preferably 7 To 10) an aralkyl group, an aryl group having 6 to 20 carbon atoms (preferably 6 to 14 carbon atoms), or a substituted product thereof. n = zero or an integer of 1-10, preferably an integer of 1-6, particularly preferably an integer of 1-3]

Examples of the structure of the formula (18) include the following.
In the lubricating oil composition comprising the fluorine-containing aromatic compound (A) represented by the general formula (1) and the aromatic oil (B) of the present invention, the mixing ratio of the component (A) is 0.1 to 99.99. It is 9% by weight, preferably 1 to 99% by weight, particularly preferably 5 to 95% by weight, and further preferably 10 to 90% by weight. When the mixing ratio of the component (A) is smaller than the above lower limit, the improvement effect on the compatibility and lubrication characteristics with respect to the hydrofluorocarbon refrigerant and the hydrogen atom-containing fluorine-containing ether refrigerant is not sufficiently exhibited. When the proportion of the component A) is larger than the above upper limit, improvement effects such as low-temperature fluidity, low hygroscopicity, and electrical insulation are not sufficient.
In the lubricating oil composition comprising the fluorine-containing aromatic compound (A) and the aromatic oil (B), a composition having a high ratio of (A), for example, (A) is 40% by weight to 99.9% by weight, preferably In the case where (A) is a composition of 60 wt% to 99.9 wt%, a refrigerant composition combined with a hydrofluorocarbon refrigerant or a hydrogen atom-containing fluorine-containing ether refrigerant has a uniform composition over a wide temperature range. Can be formed.

  On the other hand, in the case of a composition having a high ratio of (B), a lubricating oil composition comprising a fluorine-containing aromatic compound (A) and an aromatic oil (B), a hydrofluorocarbon refrigerant, a hydrogen atom-containing fluorine-containing ether refrigerant, In the combined refrigerant composition, a case where a part of the component (B) as a main component is phase-separated may occur depending on conditions. However, since the component (A) shows good affinity with the component (B), the hydrofluorocarbon refrigerant, and the hydrogen atom-containing fluorine-containing ether refrigerant, even in the composition causing such phase separation, the component (A) A component acts as an effective oil return agent, and the composition with such a high ratio of (B) component can also be used. The proportion of the component (A) in the lubricating oil composition comprising the fluorinated aromatic compound (A) and the aromatic oil (B) for effectively promoting oil return is usually 5% by weight or more, preferably 10 % By weight, more preferably 40% by weight or more. The higher the proportion of the component (A) in the lubricating oil composition, the more the oil return property tends to be improved. Therefore, there is no particular upper limit on the proportion of the component (A), and it can usually be used up to 99.9% by weight. In order to improve the lubrication characteristics, the proportion of the component (A) is 0.1 wt% to 99.9 wt%, preferably 1 wt% to 99 wt%, particularly preferably 10 wt% to It may be 90% by weight.

As the fluorine-containing aromatic compound (A) and aromatic oil (B) represented by the general formula (1) used in the present invention, there are no particular restrictions on the respective viscosities. As the viscosity, a kinematic viscosity at 40 ° C. is preferably in the range of 2 to 500 cSt, more preferably in the range of 3 to 300 cSt, particularly preferably in the range of 5 to 150 cSt. If the viscosity is too low, it is not preferable because sufficient lubricity in the compressor portion cannot be obtained, and if the viscosity is too high, the rotational torque of the compressor portion becomes too high.

The reason why the compound (A) of the general formula (1) exhibits excellent compatibility with various HFC-based and HFE-based refrigerants typified by HFC-134a (CF ₃ CH ₂ F) has not been clarified. The following reasons are possible.
Since both the HFC refrigerant and the HFE refrigerant contain a C—F bond and a C—H bond, each refrigerant is regarded as a hybrid structure composed of a fluorocarbon residue and a hydrocarbon residue.

For conventional perfluorinated oils such as perfluoropolyether, it is thought that the fluorinated carbon residue in the refrigerant shows affinity, but the hydrocarbon residue shows no affinity at all. It is not considered. Although HFC refrigerants such as HFC-134a show some compatibility with perfluoropolyether oil, it has been confirmed that the compatibility in the low temperature range is insufficient. This is probably because it contains a hydrocarbon residue having a low affinity with perfluoropolyether. On the other hand, the compound represented by the general formula (1) used in the present invention has a structure in which an aromatic ring-containing group R and a fluorine atom-containing group Rf are linked by X (oxygen atom or sulfur atom).
R (XRf) n (1)
The R part of the compound of the general formula (1) has affinity with hydrocarbon residues of HFC and HFE refrigerants, and the Rf part has affinity with fluorocarbon residues of HFC refrigerants and HFE refrigerants. It is thought to show.

As described above, the compound of the general formula (1) shows affinity for both the fluorinated carbon residue and the hydrocarbon residue of the HFC or HFE refrigerant, and as a result, the HFC or HFE refrigerant has a wide temperature range. It is estimated that good compatibility is expressed over a range.
It is also suggested from the following fact that the fluorine-containing group represented by Rf in the compound of the general formula (1) plays an extremely important role in the compatibility with HFC and HFE refrigerants.
That is, in the general formula (1), the compounds of the following (1-1) and (1-2) in which the Rf part is —CF ₂ CF ₂ H or —CF ₂ H are HFC-134a and −78 ° C. to In the case of the structure (1-0) in which the Rf part is —CH ₂ CH ₃ containing no fluorine atom while being compatible in all measurement temperature ranges at 90 ° C., room temperature to 90 ° C. Any of these temperatures is incompatible with HFC-134a.

  The fact that the oil having a hybrid structure composed of Rf and R as described above exhibits good compatibility with a refrigerant having a hybrid structure composed of a fluorocarbon residue and a hydrocarbon residue (that is, an HFC-based refrigerant and an HFE-based refrigerant). This is a new concept discovered for the first time by the present inventors. In addition, as a structure of R part of General formula (1), the direction of the thing containing an aromatic ring generally shows high stability compared with the case of a saturated hydrocarbon group. The reason for this is not clear, but it is probably because the stability of the R—X—Rf bond is better when R contains an aromatic ring than when R is a saturated hydrocarbon group. Therefore, R and Rf in the general formula (1) are not further limited as long as the requirements defined in the general formula (1) are satisfied, and a wide structure can be adopted.

Further, the reason why the lubricating oil composition composed of the compound (A) of the general formula (1) and the aromatic oil (B) and the HFC-based refrigerant and the HFE-based refrigerant exhibit good compatibility is unknown. The following reasons are presumed. As described above, the compound (A) represented by the general formula (1) exhibits good compatibility with HFC and HFE refrigerants. On the other hand, it has been confirmed that the compound (A) represented by the general formula (1) exhibits good compatibility with various aromatic oils (B) used in the present application. As described above, the compound (A) represented by the general formula (1) used in the present application exhibits an amphiphilic property that exhibits good affinity with any of the HFC or HFE refrigerant and the aromatic oil (B). It has properties. Therefore,
(1) Compound (A) represented by general formula (1)
(2) Aromatic oil (B) and
(3) In a three-component refrigerant composition comprising an HFC or HFE refrigerant, the compound (A) represented by the general formula (1) is a compatibilization of the aromatic oil (B) with the HFC or HFE refrigerant. It may be functioning as an agent.

According to another aspect of the present invention, there is provided a refrigerant composition comprising the lubricating oil composition according to claim 1 and a hydrofluorocarbon refrigerant.
In the present invention, the refrigerant that can be used together with the lubricating oil for refrigerators is a lower hydrofluorocarbon that can be used as a refrigerant (for example, a hydrofluorocarbon having about 1 to 5 carbon atoms), preferably a hydrofluorocarbon having 1 to 4 carbon atoms. Is mentioned. Typical examples thereof include HFC-134a (CF ₃ CH ₂ F), HFC-134 (CHF ₂ CHF ₂ ), HFC-143a (CF ₃ CH ₃ ), HFC-152a (CH ₃ CHF ₂ ), and HFC-32. (CH ₂ F ₂ ), HFC-125 (CF ₃ CHF ₂ ), CF ₃ CH ₂ CHF ₂ , CF ₃ CHFCF ₃ , CHF ₂ CF ₂ CHF ₂ , CF ₃ CF ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CH ₃ , CF ₃ CHFCHFCF ₃ , CF ₃ CF ₂ CH ₃ , CHF ₂ CF ₂ CH ₂ F, CF ₃ CHFCHFCF ₂ CF _{3 and} other hydrofluores such as fluorinated methane, fluorinated ethane, fluorinated propane and fluorinated butane Fluorocarbon is mentioned.

These hydrofluorocarbons can also be used as a mixture. For example, HFC-32 / 125, HFC-32 / 134a, HFC-32 / 125 / 134a, which are promising for HCFC-22 substitution, HFC-32 / 125/290 / 134a, HFC-125 / 134a, HFC-125 / 143a, HFC-125 / 143a / 134a, HFC-32 / 125 / 143a, etc. can be mentioned.
Furthermore, mixed refrigerants of chlorine-containing fluorocarbons and hydrofluorocarbons such as HCFC-22 (CHClF ₂ ) and CFC-12 (CCl ₂ F ₂ ) can also be used. When using a mixed refrigerant of a chlorine-containing fluorocarbon and a hydrofluorocarbon, the chlorine-containing fluorocarbon is preferably contained in an amount of 0.01 to 80% by weight, more preferably 0.01 to 60% by weight, particularly preferably 0.01 to 40% by weight. And use it.

  Further, from the fluorine-containing aromatic compound represented by the general formulas (1), (2), (3), and (3a) in the present invention, and the fluorine-containing aromatic compound and aromatic oil or a partially substituted product thereof. It was confirmed that the lubricating oil composition exhibited good compatibility with a hydrogen atom-containing fluorine-containing ether refrigerant that has attracted attention as a global warming potential lower than that of the hydrofluorocarbon refrigerant. Therefore, (1) the fluorine-containing aromatic compound represented by the general formula (1), (2), (3), (3a) in the present invention, or (2) the fluorine-containing aromatic compound and the aromatic carbonization A lubricating oil composition comprising a hydrogen compound or a partially substituted product thereof can be combined with a hydrogen atom-containing fluorine-containing ether refrigerant to provide a novel refrigerant composition.

As the hydrogen atom-containing fluorine-containing ether refrigerant, various compounds can be used, but various compounds in which the sum of the number of carbon atoms and the number of oxygen atoms in the molecule is 3 to 6, and the hydrogen atoms in the molecule are One or more compounds are particularly preferred because of their low global warming potential.
For example, the following hydrogen atom-containing fluorine-containing ether-based refrigerants are exemplified, but not limited thereto.

In the present invention, the weight ratio of the total amount of refrigerant / the total amount of lubricating oil in the refrigeration system is usually in the range of 99/1 to 1/99, preferably in the range of 95/5 to 5/95, particularly preferably 90/10 to 10. The range is / 90.
Furthermore, according to the other one aspect | mode of this invention, the lubricating oil composition by which a fluorine-containing aromatic compound (A) is represented by General formula (2), and a refrigerant | coolant composition are provided.

R ¹ and R ² in the general formula (2) represent an alkyl group having 1 to 19 carbon atoms or a hydrogen atom, and the total number of carbon atoms of R ¹ and R ² is 4 or more and 19 or less, preferably 5 The range is 16 or less, particularly preferably 5 to 12. When the total number of carbon atoms of R ¹ and R ² is 3 or less, high bioconcentration is exhibited. On the other hand, when the total number of carbon atoms of R ¹ and R ² is 20 or more, compatibility with hydrofluorocarbon refrigerants such as HFC-134a and fluorine-containing ether refrigerants is reduced, and raw materials are very difficult to obtain. It becomes difficult. Further, from the viewpoint of stability, it is preferable that either R ¹ or R ² is an alkyl group rather than a hydrogen atom. Rf represents a fluorocarbon group or a partially substituted product thereof as in the general formula (1), and the definition thereof is also the same.
According to another aspect of the present invention, there are provided a lubricating oil composition and a refrigerant composition in which the fluorine-containing aromatic compound (A) is represented by the general formula (3).

[However, R < ³ >, R < ⁴ >, R < ⁵ > is a C1-C20 alkyl group. n represents an integer of 1 to 3. When n is 2 or 3, the compound represented by the general formula (3) may be composed of a plurality of types of R ³ R ⁴ R ⁵ C— groups. In the general formula (3), the total number of carbon atoms of all R ³ R ⁴ R ⁵ C— groups bonded to the aromatic nucleus is in the range of 4 to 25.
On the other ^{hand, R 3, R 4, R} 5 in the general formula (3) used in the present invention are 1-20 alkyl group carbon atoms. n represents an integer of 1 to 3. When n is 2 or 3, the compound represented by the general formula (3) may be composed of a plurality of types of R ³ R ⁴ R ⁵ C— groups. In the general formula (3), the total number of carbon atoms of all R ³ R ⁴ R ⁵ C— groups bonded to the aromatic nucleus is in the range of 4 to 25.
When the total number of carbon atoms of all R ³ R ⁴ R ⁵ C-groups is 26 or more, the compatibility with hydrofluorocarbon refrigerants such as HFC-134a or various hydrogen atom-containing fluorine-containing ether refrigerants decreases. Moreover, it becomes very difficult to obtain raw materials. Rf represents a fluorocarbon group or a partially substituted product thereof as in the general formula (1), and the definition thereof is also the same.

The alkyl groups R ¹ , R ² , R ³ , R ⁴ , and R ⁵ may contain a substituent and a linking group. Examples thereof include unsaturated hydrocarbon residues, chlorine and fluorine. Such as halogen atom, hydroxyl group, thiol group, alkoxy group, nitrile group, nitro group, ether group, thioether group, ester group, carbonyl group, sulfonyl group, sulfinyl group, carboxyl group, carboxylate group, amino group, thiocarbamate group Various oxygenates such as amide group, imide group, pyridine group, pyrimidine group, piperidine group, triazine group, phosphine group, benzimidazole group, phosphite group, triazole group, tetrazole group, thiazole group, thiadiazole group, Examples include nitrogen-containing, phosphorus-containing atoms, and sulfur-containing polar groups. Among these, a fluorine atom and an ether group are particularly preferable because of high stability. The number of the above substituents and linking groups is usually 5 or less, preferably 3 or less, particularly preferably 1 or less.

Specific examples of R ¹ , R ² , R ³ , R ⁴ and R ⁵ are shown below using the general formula (2) or (3).

In General Formula (2) or (3), Rf represents the same fluorocarbon group as Rf in General Formula (1) or a partially substituted product thereof, and the definition thereof is also the same. The Rf, fluoroalkyl group is in the range of 1 to 25 carbon atoms, may be a fluoroalkenyl group, the following specific examples, for example _{-C 6 F 11, -C 6 F} 12 H, -C 9 F _17, include -C ₉ F ₁₈ H, and the like. Rf has preferably 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms. Rf may be a fluoroalkyl group having 2 to 25 carbon atoms and containing 1 to 7 ether bonds in the main chain. Furthermore, Rf may be a structure of the general formula (1b) substituted with 1 to 4 chlorine atoms.

が使用できる。
なお、炭素数１〜３個のフルオロアルキル基の具体例としては、例えば、−ＣＦ₂ Ｈ、−ＣＦ₃ 、−ＣＦ₂ ＣＦ₂ Ｈ、−ＣＦ₂ −ＣＦ₃ 、−ＣＨ₂ −ＣＦ₃ 、−ＣＦ₂ ＣＨＦＣＦ₃ 、−ＣＦ₂ ＣＦ₂ ＣＦ₃ 等が挙げられる。 More preferably, a fluoroalkyl group having 1 to 3 carbon atoms, —CF═CFCF ₃ , —CF ₂ CFClH, —CF═CFCl, and

Can be used.
As specific examples of the fluoroalkyl group having 1 to 3 carbon atoms, for example, —CF ₂ H, —CF ₃ , —CF ₂ CF ₂ H, —CF ₂ —CF ₃ , —CH ₂ —CF ₃ , -CF ₂ CHFCF _3, etc. -CF ₂ CF ₂ CF ₃ and the like.

Among the fluorine-containing aromatic compounds represented by the general formula (2) or (3), those exhibiting good compatibility with the aromatic hydrocarbon compound (B) include the number of fluorine atoms / (fluorine The ratio of (number of atoms + number of hydrogen atoms) is 0.03 or more and 0.85 or less, preferably 0.05 or more and 0.6 or less, and particularly preferably 0.1 or more and 0.5 or less. In addition, as the fluorine-containing aromatic compound (A) of the general (2) and / or (3), a plurality of types can be mixed and used.
The fluorine-containing aromatic compound (A) represented by the general formula (2) or / and (3) is a hydrofluorocarbon refrigerant or a hydrogen atom-containing fluorine-containing ether refrigerant, either alone or in combination of a plurality of types. Can be advantageously used as a lubricating oil for a refrigeration system. For example, the fluorine-containing aromatic compounds represented by the general formulas (2) and (3) can be mixed and used.

Furthermore, the fluorine-containing aromatic compound (A) of the general formula (2) or / and (3) can obtain the following effects, for example, in addition to the effect of improving the compatibility.
(1) The fluorine-containing aromatic compound (A) represented by the general formula (2) or / and (3) has a hybrid structure composed of a fluorocarbon residue and a hydrocarbon residue, and is an ester oil, In order to show good compatibility with various oils such as polyalkylene glycol oils, mineral oils, and hydrocarbon oils represented by alkylbenzene, they can be used by mixing with other oils.

  Other oils that can be used by mixing with the fluorine-containing aromatic compound (A) represented by the general formula (2) or / and (3) include, for example, naphthenic mineral oil, paraffinic mineral oil, alkylbenzene, alkylnaphthalene, poly Hydrocarbon compounds typified by α-olefins, ether compounds such as polyalkylene glycols and polyphenyl ethers, perfluoropolyethers, carboxyl groups, carboxylate groups, amide groups, carbonyl groups such as ketone groups and ester groups Perfluoropolyethers containing polar substituents such as groups, hydroxyl groups, amino groups, imide groups, ether groups, benzimidazole groups, phosphite groups, phosphine groups, nitrile groups, phosphotorazine groups or triazine groups, Polychlorotrifluoroethylene, chlorofluoro Fluorine compounds such as carbon, ester compounds such as polyol esters and mixed esters, carbonate compounds such as polycarbonate, silicon compounds such as silicate esters, silicones, and fluorinated silicones, aryl phosphates, alkylaryl phosphates And phosphorus-based oils such as alkyl phosphates. Usually, among these, an appropriate type of lubricant is considered in consideration of the viscosity or lubricating properties of the lubricating composition obtained by mixing with the fluorine-containing aromatic compound (A) of the general formula (2) or / and (3). The one is selected.

(2) By mixing the fluorine-containing aromatic compound (A) of the general formula (2) and / or (3) with a polar oil typified by an ester, polyalkylene glycol, carbonate or the like, It is possible to improve characteristics such as hygroscopicity, stability and lubrication characteristics which are problems.
(3) The fluorine-containing aromatic compound (A) of the general formula (2) or / and (3) is: 1) mineral oil such as paraffinic mineral oil, naphthenic mineral oil, 2) olefin (co) polymer, and 3 ) In order to show particularly good compatibility with hydrocarbon compounds such as aromatic hydrocarbon compounds such as alkylbenzene, alkylnaphthalene, alkylated biphenyl, polyphenyl substituted hydrocarbon, styrene oligomer, etc. It can be used by mixing.

(4) Since the compound (A) represented by the general formula (2) and / or (3) is very well compatible with the aromatic oil (B) such as alkylbenzene, a large amount of the aromatic oil (B) Can be mixed and used. In addition, the mixed oil composition does not impair good compatibility with the hydrofluorocarbon-based refrigerant possessed by the compound represented by the general formula (2) or / and (3). Physical properties such as electrical insulation are effectively improved.
(5) Since the fluorine-containing aromatic compound (A) of the general formula (2) and / or (3) exhibits good compatibility with both hydrocarbon compounds and hydrofluorocarbon refrigerants, it is soluble in hydrofluorocarbons. It can also be used as an effective additive to improve the oil return in the refrigeration system of aromatic hydrocarbon compounds such as alkylbenzenes or partially substituted products thereof, and mineral oils, etc. Is possible.

(6) Among the fluorine-containing aromatic compounds represented by the general formula (1), the specific fluorine-containing aromatic compound (A) represented by the general formula (2) or / and (3) is particularly high. It is characterized by showing stability. For example, nonylphenol type and dodecylphenol type oils represented by general formulas (17) and (18) described in JP-A-5-86382 are oxidized or thermally decomposed when heated in air, The fluorine-containing aromatic compound (A) represented by the general formula (2) or / and (3) does not decompose even when heated in air at 175 ° C. for a long time.

  Further, the fluorine-containing aromatic compound (A) of the general formula (2) or / and (3) is coexisted with a metal such as copper or brass, aluminum and carbon steel and a hydrofluorocarbon such as HFC-134a. When subjected to a heating stability evaluation test (so-called shield tube test), the fluorinated aromatic compound (A) and the hydrofluorocarbon of the general formula (2) or / and (3) are stable even at 175 ° C. It shows a good result that the metal surface hardly changes.

(7) Chemical substances released into the environment are more likely to come into contact with living organisms as the substance is more stable in the environment. It may be taken up and concentrated to become an environmental pollutant.
The present inventors examined the relationship between the structure of various lubricating oils represented by the general formula (1) and bioconcentration from the standpoint of environmental toxicology. As a result, it was confirmed that the fluorine-containing aromatic compound (A) represented by the general formula (2) or / and (3) showed low bioconcentration in a bioconcentration test.

  (8) The lubricating properties of the fluorinated aromatic compound (A) represented by the general formula (2) and / or (3) were evaluated in the presence and absence of hydrofluorocarbon. It was confirmed that the baking load), the abrasion resistance, and the friction coefficient showed extremely good performance. For example, most of the compound (A) of the general formula (2) or / and (3) is a refrigerating machine oil for conventional refrigerants such as mineral oil or alkylbenzene, or a refrigerating oil for HFC-134a such as polyalkylene glycol or polyester oil. It shows much better lubricating properties than the candidate oil.

Furthermore, the mixed oil of the fluorine-containing aromatic compound (A) of the above general formula (2) and / or (3) and the aromatic oil (B) is compatible with the hydrofluorocarbon refrigerant, low temperature fluidity, low It is a practically excellent oil that satisfies all the characteristics required for refrigerating machine oil such as hygroscopicity, electrical insulation, and lubrication characteristics. In this case, in the lubricating oil composition for a refrigerator comprising the fluorine-containing aromatic compound (A) represented by the general formula (2) and / or (3) and the aromatic oil (B), the component (A) The mixing ratio is 0.1 to 99.9% by weight, preferably 1 to 99% by weight, particularly preferably 5 to 95% by weight, and further preferably 10 to 90% by weight. When the mixing ratio of the component (A) is smaller than the above lower limit, the lubricity and the compatibility with the hydrofluorocarbon refrigerant are not sufficient. On the other hand, when the ratio of the component (A) is larger than the above upper limit, Improvement effects such as property, low hygroscopicity, and electrical insulation are not sufficient.

  As the fluorine-containing aromatic compound (A) and aromatic oil (B) represented by the general formula (2) or / and (3) used in the present invention, there are no particular restrictions on the respective viscosities. As the viscosity of the mixed oil composition, usually, the kinematic viscosity at 40 ° C. is preferably in the range of 2 to 500 cSt, more preferably in the range of 3 to 300 cSt, and particularly preferably in the range of 5 to 150 cSt. Is used. If the viscosity is too low, it is not preferable because sufficient lubricity in the compressor portion cannot be obtained, and if the viscosity is too high, the rotational torque of the compressor portion becomes too high.

In addition, when the fluorine-containing aromatic compound (A) represented by the general formula (2) or / and (3) is used as a single product or a mixture of a plurality of types, or mixed with other oils The viscosity is the same as the viscosity range of the mixed oil composition comprising the fluorinated aromatic compound (A) and the aromatic oil (B) represented by the general formula (2) or / and (3). Just enter the range.
Furthermore, even when the fluorine-containing aromatic compound (A) represented by the general formula (2) or / and (3) is a solid, the viscosity of the HFC refrigerant and the refrigerant composition comprising the substance is A refrigerant composition comprising a mixed oil composition comprising (3) a fluorine-containing aromatic compound (A) and an aromatic oil (B) represented by the general formula (2) or / and (3) of various kinematic viscosities; If it is about the same, it can be used.

In the present invention, the weight ratio of the total amount of refrigerant / the total amount of lubricating oil in the refrigeration system is usually in the range of 99/1 to 1/99, preferably in the range of 95/5 to 5/95, particularly preferably 90/10 to 10. The range is / 90.
Specific effects of the lubricating oil composition comprising the fluorine-containing aromatic compound (A) and the aromatic oil (B) represented by the general formula (2) or / and (3) are as follows, for example: There is.

(1) When subjected to the stability evaluation test described above, the fluorine-containing aromatic compound (A), the aromatic oil (B) and the hydrofluorocarbon of the general formula (2) or / and (3) are stable, Good results are obtained that the metal surface does not change at all.
(2) Although the fluorine-containing aromatic compound (A) represented by the general formula (2) or / and (3) exhibits low hygroscopicity, it is represented by the general formula (2) or / and (3). Hygroscopicity is further improved by mixing the aromatic oil (B) with the fluorine-containing aromatic compound, freezing of moisture in the refrigerator system, metal corrosion due to water, and decomposition of hydrofluorocarbons such as HFC-134a. There is no problem such as promotion.

(3) By mixing the aromatic oil (B) with the fluorine-containing aromatic compound (A) represented by the general formula (2) or / and (3), the deterioration of electrical characteristics due to moisture absorption is greatly improved. .
(4) When the aromatic oil (B) is mixed with the fluorine-containing aromatic compound (A) represented by the general formula (2) or / and (3), as shown in Example 66 described later, (A), (B) An unexpected effect that the lubrication characteristics were further improved compared to any of the results was confirmed. Although the above-mentioned lubrication characteristics can be measured by various testing machines, for example, extreme pressure properties and abrasion resistance are measured by a Falex testing machine.

In order to further improve the wear resistance and extreme pressure property of the lubricating oil composition comprising the fluorine-containing aromatic compound (A) represented by the general formula (1) and the aromatic oil (B) of the present invention, Agents (oil-based agents, antiwear agents, extreme pressure agents) can be added. In particular, since the fluorine-containing aromatic compound (A) represented by the general formula (2) or / and (3) is better dissolved with the existing additives, various additives can be used.
"Petroleum product additive", Koshobo (1979) states that oily agents reduce the coefficient of friction by adsorbing to the metal surface, and antiwear agents are the effect of preventing wear at relatively low loads. The extreme pressure agent and the extreme pressure agent are described as reacting with the metal surface to prevent seizure and wear under high temperature and high pressure. However, it is described that one additive often plays a role of not only an oily agent but also two or three as an antiwear agent or extreme pressure agent.

  Examples of oil-based agents include higher fatty acids, hydroxy aryl fatty acids, carboxylic acid-containing polyhydric alcohol esters, aromatic carboxylic acids and the like in carboxylic acids, higher alcohols in alcohols, Residual alcohol polyhydric alcohol esters, phenolic groups include alkylphenols, polyhydric phenols, etc., ester type higher fatty acid esters such as methyl laurate and methyl oleate, polyhydric alcohol esters , Acrylate esters, higher fatty acid amides such as lauric acid amide and oleic acid amide, etc., and metal salts of carboxylic acids such as alkali metal salts such as sodium and potassium, magnesium and calcium, etc. Examples of the alkaline earth metal salt include carboxylic acid salts with aluminum and the like. Specific examples of the carboxylic acid series include linear saturation such as caproic acid, caprylic acid, capric acid, undecyl acid, lauric acid, myristic acid, palmitic acid, pelargonic acid, stearic acid, arachidic acid, serotic acid, and lactenoic acid. Fatty acids include branched saturated fatty acids such as isotridecanoic acid, isomyristic acid, isostearic acid and isoarachidic acid, unsaturated fatty acids such as oleic acid and linoleic acid, and alcohol-based specific examples include lauryl. Alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, glycerol monooleate, glycerol monostearate, glycerol dilaurate, etc., as phenols, 3-pentadecylphenol , 4-heptylphenol, octylphenol, noni Phenol, dodecyl phenol or alkyl catechols.

Other load-bearing additives include sulfur-based thiophenes such as thiophene and benzothiophene, monosulfides such as di-n-dodecyl sulfide and dibenzyl sulfide, disulfides such as diphenyl disulfide, polysulfides, and sulfones thiosulfine. -Thioacetic acids, sulfurized fats and oils, thiocarbonates, thiazoles, methanesulfonic acid esters, thioacetic acids such as n-dodecylthioacetic acid, alkyl mercaptans such as n-octadecyl mercaptan, etc. Benzotriazole derivatives such as alkyl-substituted benzotriazoles, chlorinated hydrocarbons such as chlorofluorocarbons such as chlorinated paraffin and trifluoroethylene chloride (CTFE) oligomers in the halogen series, chlorinated carboxylic acids Chlorinated additives such as derivatives, fluorination Aliphatic alcohols, fluorinated aliphatic carboxylic acids, fluorinated aliphatic carboxylic acid esters, perfluoropolyether carboxylic acids, perfluoropolyether carboxylic acid esters, perfluoroalkyl triazines and Polar group-containing fluorine compounds such as fluoropolyethertriazine, fluorine-based additives such as fluorinated graphite and fluorinated ethylene oligomers, bromine-based additives such as alkane bromide, alkene bromide and alkyne bromide, iodine And iodine-based additives such as fluorinated hydrocarbons. Phosphoric acid monoesters, phosphoric acid diesters, phosphoric acid triesters, halogenated phosphoric acid esters, etc., phosphoric acid esters, phosphorous acid monoesters, phosphorous acid diesters, phosphorous acid triesters Phosphites such as esters and halogenated phosphites, tertiary phosphines, tertiary phosphine oxides, tertiary phosphine sulfides, phosphonates, phosphonites, phosphines Thiophosphates such as acid esters, phosphinites, and thiophosphate triesters, thiophosphites, thiophosphonates, thiophosphinates, phosphoramidates, acidic phosphates And amine salts of phosphazene and the like. Silicone-based organic silicon compounds such as fluorinated silicone and carboxyl group-containing silicone, metal-based compounds such as zinc naphthenate and lead naphthenate, naphthenates such as fatty acid lead, fatty acid salts such as fatty acid lead, zinc-dithiophosphate Thiophosphates such as antimony, antimony-dithiophosphates, zinc-dithiocarbamates, antimony-dithiocarbamates, thiocarbamates such as lead-dithiocarbamates, molybdenium oxysulfide dithiocarbamates Organic molybdenum compounds such as oxymolybdenium phosphorodithioate, organotin compounds, organogermanium compounds, organotitanium compounds, borate esters, diethylsilicate, and other organosilicates, iron sulfide, iron chloride Such as metal sulfide, metal chloride, or before It can be mentioned of the complex type.

  Specific examples of the fluorine-based load-bearing additive include polar group-containing fluorine compounds such as 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoroocta 1H, 1H, 7H-dodecafluoro-1-heptanol, 1H, 1H, 11H-eicosafluoro-1-undecanol, 2,2,3,3,4,4-hexafluoro-1 , Fluorinated aliphatic alcohols such as 5-pentanediol, fluorinated aliphatic carboxylic acid esters such as methyl perfluorooctanoate and methyl perfluorononanoate, hexafluoropropene oxide oligomer dicarboxylic acid Perfluoropolyether carboxylic acid esters such as esters, methyl perfluoro-2,5-dimethyl-3,6-dioxanonanilate, and fluorinated fats such as perfluorononanoic acid Group carboxylic acids, Pa - fluoro-2,5-dimethyl-3,6 Jiokisanonaniru acids such Pas - Furuoroporie - Terukarubon acids and the like.

Specific examples of phosphorus additives include orthophosphoric acid esters such as tricresyl phosphate, triphenyl phosphate, triisopropylphenyl phosphate, tris (2-ethylhexyl) phosphate, di-acid. (2-ethylhexyl) tridecyl phosphate, di (2-ethylhexyl) allyl phosphate, trioctyl phosphate, trilauryl phosphate, tristearyl phosphate, trioleyl phosphate, tris [poly ( Oxyethylene) tridecyl] phosphate, tris [polyoxyethylene) -2-ethylhexyl] phosphate, tris [poly (oxyethylene) isooctyl] phosphate, tris [poly (oxyethylene)-(poly (oxypropylene) -n-octyl] Phosphate, Tris [Poly (O Ciethylene) carbonyl-1-ethylpentyl] phosphate, tris [poly (oxyethylene) poly (oxypropylene) carbonyl-1-ethylpentyl] phosphate, tris [poly (oxyethylene) propyleneoxycarbonyl-1-methylvinyl] phosphate, Tris [3-poly (oxyethylene) -methyl-2-methylpropionate] phosphate, tris [poly (oxyethylene) -2-hydroxyoctyl] phosphate, tris (p-octylphenoxyethylene) phosphate, tris [poly ( Oxyethylene) -poly (oxypropylene) -p-methylphenoxy] phosphate, tris [4-poly (oxyethylene) ethylphenylacetate] phosphate, tris [poly (oxyethylene) poly (oxy) Propylene) -p-butoxyphenyl] phosphate, 2-ethylhexyl [poly (oxyethylene) -2-ethylhexyl] phosphate, polyoxyalkylene bis (diallyl) phosphate and the like are diacid diesters. Tetradecyl acid phosphate, dipentadecyl acid phosphate, dihexadecyl acid phosphate, diheptadecyl acid phosphate, dioctadecyl acid phosphate, di (polyoxyethylene nonylphenyl) Ether) phosphate, etc., as the amine salt of acidic phosphate ester, methyl phosphate, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethyl Amine, dipropylamine, dibutylamine, dipentylamine, dihexylamine,
Examples thereof include salts with amines such as diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine and the like. Examples of chlorinated phosphate esters include tris (dichloropropyl) phosphate, tris (chloroethyl) phosphate, polyoxyalkylene bis [di (chloroalkyl)] phosphate, and tris (chlorophenyl) phosphate. Can be mentioned.

  Examples of the brominated phosphate ester include tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (2,4-di-tert-butylphenyl) phosphate, and the like. Examples of the fluorinated phosphate ester include tris (polyfluoroalkyl) phosphate and tris (polyfluorophenyl) phosphate. Phosphites include dibutyl phosphite, tributyl phosphite, dipentyl phosphite, tripentyl phosphite, dihexyl phosphite, trihexyl phosphite, diheptyl phosphite, triheptyl phosphite, dioctyl phosphite, trioctyl phosphite. Phyto, dinonyl phosphite, didecyl phosphite, diundecyl phosphite, triundecyl phosphite, didodecyl phosphite, tridodecyl phosphite, diphenyl phosphite, triphenyl phosphite, dicresyl phosphite, tricresyl Phosphite, triisodecyl phosphite, diphenyloctyl phosphite, diphenyl decyl phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen Phosphite, tris (2,4-di-tert-butylphenyl) phosphite, trinonylphenyl phosphite, polyoxyalkylene bis (diaryl) phosphite, 1,1,3-tris (2-methyl- 4-ditridecyl phosphite-5-tert-butylphenyl) butane, tetraphenyl dipropylene glycol diphosphite, tetradecyl diethylene glycol diphosphite and the like. Examples of phosphonic acid esters include O, O-dimethyldodecylphosphonate, O, O-diethyldodecylphosphonate, O, O-di-n-butyldecylphosphonate, O, O-di-2-ethylhexyldecylphosphonate, O, O- Di-2-ethylhexyl-2-ethylhexylphosphonate, O, O-di-2-ethylhexylisooctylphosphonate, O, O-di-2-ethylhexylphenylphosphonate, O, O-dimethylphosphonomethylene (dimethyl) succinate, O , O-di-2-ethylhexyl-3-phosphonomethylpropionate, O, O-di-2-ethylhexyltris (ethylene glycol) methylenephosphonate, O, O-di (decylpolyoxyethylene) (decylpolyoxy) Ethylene) phosphonate, O, O-di- - ethylhexyl hydroxy methylene phosphonate, O, O- di-2-ethylhexyl phosphono methylene polyethylene glycol. Examples of the phosphinic acid ester, O- alkyl dialkyl phosphinate Ne - DOO and the like.

  The above load-bearing additives may be used alone or in admixture of several kinds. When these load-bearing additives are blended, 1) the fluorine-containing aromatic compound (A) represented by the general formula (1) of the present invention and the aromatic hydrocarbon compound (B) or a partially substituted product thereof. Lubricating oil composition 2) Lubricating oil composition comprising the fluorine-containing aromatic compound (A) represented by the general formula (2) or / and (3) of the present invention and the aromatic oil (B) or a partially substituted product thereof 3) The load-bearing additive is usually 0.01 to 25% by weight with respect to the fluorine-containing aromatic compound (A) represented by the general formula (2) or / and (3) of the present invention, preferably Is preferably 0.05 to 5.0% by weight, more preferably 0.1 to 2.0% by weight. When the ratio of the load-bearing additive is less than 0.01% by weight, the effect on wear resistance and extreme pressure property is not sufficient. On the other hand, if it exceeds 25% by weight, the properties of the refrigerating machine oil such as electrical insulation may be adversely affected and may not be used. However, this does not apply to additives with good electrical insulation and stability.

1) Lubricating oil composition comprising a fluorine-containing aromatic compound (A) represented by the general formula (1) of the present invention and an aromatic oil (B), 2) General formula (2) of the present invention and / or ( 3) Lubricating oil composition comprising a fluorine-containing aromatic compound (A) and an aromatic oil (B) represented by 3), or 3) represented by the general formula (2) or / and (3) of the present invention In order to further improve the corrosion resistance of the metal surface when the fluorine-containing aromatic compound (A) is used as a refrigerating machine oil, a corrosion inhibitor can be blended.

  Corrosion inhibitors include oleic acid and stearic acid for carboxylic acids, Mg, Ca and Ba salts of fatty acids and lanolin fatty acids for carboxylic acid salts, and petroleum sulfonic acid, dinolyl naphthalene sulfonic acid and alkylbenzene sulfonic acid for sulfonic acid salts. Na, Mg, Ca, and Ba salts of sorbitan monooleate and sorbitan monolaurate such as sorbitan monolaurate and pentaerythritol monofatty acid ester as esters, and N-phenyl-α-naphthylamine as amine Aromatic amines such as aliphatic amines, rosin amines, phosphoric acid esters such as monoesters of phosphoric acid, and salts thereof, phosphoric acid diesters and salts thereof, and phosphoric acid triesters such as triphenyl phosphate; Phosphites such as triphenyl phosphite, epoxy In the compound, aryl glycidyl ether such as phenyl glycidyl ether or alkyl glycidyl ether such as 2-ethylhexyl glycidyl ether as glycidyl ether type epoxy compound, and aromatic such as diglycidyl phthalate as glycidyl ester type epoxy compound Carboxylic acid glycidyl ester, 2-ethylhexanoic acid glycidyl ester and decanoic acid glycidyl ester saturated aliphatic carboxylic acid glycidyl ester, unsaturated aliphatic carboxylic acid glycidyl ester, epoxidized fatty acid monoester butyl epoxy stearate, Hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl and butylphenyl esters are used as nitrogen-containing heterocyclic compounds, benzotriazole, 5-methyl-1H- Benzotriazole derivatives such as various alkyl-substituted benzotriazoles such as benzotriazole, imidazole and its derivatives, benzimidazole, benzimidazole derivatives such as 2- (alkyldithio) benzimidazole, 1,3,4-thiadiazo -Lupolysulfide and the like, and other examples include zinc dialkyldithiophosphate. The above corrosion inhibitors may be used alone or as a mixture of several kinds. When these corrosion inhibitors are blended, 1) a lubricating oil composition comprising a fluorine-containing aromatic compound (A) represented by the general formula (1) of the present invention and an aromatic oil (B) or a partially substituted product thereof 2) A lubricating oil composition comprising the fluorine-containing aromatic compound represented by the general formula (2) or / and (3) of the present invention and an aromatic hydrocarbon compound (B) or a partially substituted product thereof, or 3) 0.001 to 25% by weight, preferably 0.001 to 5.0% by weight, more preferably based on the fluorine-containing aromatic compound represented by the general formula (2) or / and (3) of the present invention. It is desirable to contain in the ratio of 0.1 to 2.0% by weight. When the proportion of the corrosion inhibitor is less than 0.001% by weight, the effect on the corrosion resistance is not sufficient. On the other hand, when it exceeds 25% by weight, the characteristics of the refrigerating machine oil such as electrical insulation are adversely affected.

  Further, 1) a lubricating oil composition comprising the fluorine-containing aromatic compound (A) represented by the general formula (1) of the present invention and the aromatic oil (B), 2) the general formula (2) of the present invention or / And a lubricating oil composition comprising the fluorine-containing aromatic compound represented by (3) and the aromatic oil (B), or 3) the inclusion represented by the general formula (2) or / and (3) of the present invention. When the fluoroaromatic compound (A) is used as refrigerating machine oil, oxidation of phenols (for example, 2,6-di-tert-butyl-p-cresol) and aromatic amines (for example, α-naphthylamine) Viscosity of various polymers such as inhibitors, antifoaming agents such as silicone oil (for example, dimethylsiloxane), organosilicates, detergent dispersants such as sulfonates, phenates, and succinimides, and polymethacrylates The number improvers, can be used diesters and polyalkylene glycols, pour point modifiers, such as triglycerides, N, N'-disalicylidene-1,2-diaminoethane, with metal deactivator such as acetylacetone.

Accordingly, 1) a lubricating oil composition comprising the fluorine-containing aromatic compound (A) represented by the general formula (1) of the present invention and the aromatic oil (B), 2) the general formula (2) of the present invention or / And (3)
Or a lubricating oil composition comprising a fluorine-containing aromatic compound (A) and an aromatic oil (B) represented by the formula: 3) a fluorine-containing formula represented by the general formula (2) or / and (3) of the present invention Contains at least one additive selected from aromatic compounds and load bearing additives, corrosion inhibitors, antioxidants, metal deactivators, antifoaming agents, detergent dispersants, viscosity index improvers, and pour point improvers. Refrigerating machine oil compositions for refrigerators using fluorinated alkane-based refrigerants are promising as alternatives to refrigerants such as CFC-12 and HCFC-22 used in refrigerators, freezers, car air conditioners, room air conditioners, etc. It is extremely useful as a lubricating oil for various refrigerators using fluorinated alkane as a refrigerant.
According to another aspect of the present invention, the fluorine-containing aromatic compound represented by the general formula (2) and the general formula (3) are particularly characterized by taking the structure of the general formula (3a). A fluorine-containing aromatic compound is provided.

［Ｒ⁶ 、Ｒ⁷ 、Ｒ⁸ およびＲｆ⁶ は、それぞれ一般式（３）の中のＲ³ 、Ｒ⁴ 、Ｒ⁵ およびＲｆと同じである。但し、Ｒ⁶ Ｒ⁷ Ｒ⁸ Ｃ−基の炭素原子の数の総和は５〜２５の範囲である。］ General formula (2) is as described above. The general formula (3a) is as follows.

[R ⁶ , R ⁷ , R ⁸ and Rf ⁶ are the same as R ³ , R ⁴ , R ⁵ and Rf in the general formula (3), respectively. However, the total number of carbon atoms in the R ⁶ R ⁷ R ⁸ C— group is in the range of 5-25. ]

On the other ^{hand, R 6, R 7, R} 8 in the general formula (3a) used in the present invention are 1-20 alkyl group carbon atoms. In the general formula (3a), the total number of carbon atoms of all R ⁶ R ⁷ R ⁸ C— groups bonded to the aromatic nucleus is in the range of 5 to 25, particularly preferably 7 to 15. When the total number of carbon atoms of the R ³ 'R ⁴ ' R ⁵ 'C-group is 5 or more, it is preferable because it has an appropriate viscosity as a lubricating oil and also exhibits a low bioconcentration value. On the other hand, when the total number of carbon atoms in the R ⁶ R ⁷ R ⁸ C-group is 26 or more, the compatibility with hydrofluorocarbon refrigerants such as HFC-134a or various hydrogen atom-containing fluorine-containing ether refrigerants decreases. Moreover, since acquisition of a raw material becomes very difficult, it is not preferable.

  As described above, the fluorine-containing aromatic compound (A) represented by the general formulas (2) and (3a) has excellent compatibility with various oils, low bioconcentration, high stability, and high lubricating properties. In addition to the lubricating oil for refrigerators, the magnetic recording is possible by using the oil of the general formula (2) and / or the general formula (3 ′) alone or as a mixed oil with other oils. It is useful as a high-performance lubricating oil such as medium lubricating oil, compressor oil, hydraulic oil, rolling oil, gear oil, hydraulic oil, traction drive oil, engine oil, and base oil for grease. Applications other than lubricating oils include various oil durability and lubricity modifiers, surface modifiers such as polymers, mold release agents, compatibilizing agents, and base oils for electrorheological and magnetic fluids. Can do.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples. However, the scope of the present invention is not limited to the examples.
The kinematic viscosity of the lubricating oil of the present invention can be determined by measuring the viscosity with various viscometers. As the viscometer, an E-type rotational viscometer (manufactured by Tokyo Keiki Co., Ltd.) was used.
<Synthesis Example 1>
According to (Example 54) described in JP-A-5-86382, oil [S-1] was synthesized by the following method.

Into a reaction vessel (500 ml micropombe), 68.7 g of 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A), 6.2 g of potassium hydroxide, 120 ml of dimethyl sulfoxide and 1 ml of water were placed. In order to dissolve, the reaction vessel was heated to 60 ° C. in an oil bath, and the mixture was heated and dissolved under atmospheric pressure for 5 hours. After degassing the system, the pressure was returned to normal pressure with an inert gas N ₂ . The reaction vessel was heated to 60 ° C. with an oil bath, and tetrafluoroethylene was introduced to start the reaction. Tetrafluoroethylene was supplied so that the system internal pressure (gauge pressure) was maintained at ³ to 4 kg / cm ^2, and the reaction was performed for about 5 hours.

Dimethyl sulfoxide was distilled off from the solution after the reaction at 150 ° C. at about 5 mmHg, and washed 5 times with 100 ml of pure water to obtain 130 g of colorless and transparent oil (containing 99 wt% of [S-1]). After simple distillation at a boiling point of about 150 ° C. and 0.1 to 0.3 mmHg, the product was purified using a silica gel column to isolate oil [S-1]. Infrared absorption spectrum analysis and mass spectrometry [m / e 428 (M ⁺ ), 413 (M ⁺ —CH ₃ )] confirmed that this oil [S-1] was a compound having the following structure. The kinematic viscosity of this compound at 40 ° C. was 26 cSt.

<Synthesis Example 2>
Oil [S-2] was obtained in the same manner as in Synthesis Example 1 except that chlorotrifluoroethylene was used instead of tetrafluoroethylene and the amount of water added was changed from 1 ml to 44 ml (yield 99%). .
As a result of analyzing the oil obtained by this method by gas chromatography, the purity of the target product was 99.9%. From infrared absorption spectrum analysis and mass spectrometry [m / e 460, 462 (M ⁺ ) 445, 447 (M ⁺ —CH ₃ )], it was confirmed that this oil [S-2] was a compound having the following structure: did. The kinematic viscosity of this compound at 40 ° C. was 57 cSt.

<Synthesis Example 3>
Oil [S-3] was obtained in the same manner as in Synthesis Example 1 except that the compound [G-1] shown below was used instead of bisphenol A (yield 95%). Infrared absorption spectrum analysis and mass spectrometry [m / e 470 (M ⁺ )] shown in FIG. 1 confirmed that this compound had a structure shown below. The kinematic viscosity of this compound at 40 ° C. was 109 cSt.

<Synthesis Example 4>
Oil [S-4] was obtained in the same manner as in Synthesis Example 1 except that pt-octylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of bisphenol A (yield 94%). Infrared absorption spectrum analysis and mass spectrometry [m / e 306 (M ⁺ )] shown in FIG. 2 confirmed that this compound had a structure shown below. The kinematic viscosity of this compound at 40 ° C. was 6.1 cSt.

<Synthesis Example 5>
Oil [S-5] was obtained in the same manner as in Synthesis Example 1 except that the compound [G-2] shown below was used instead of bisphenol A (yield 90%). By infrared absorption spectrum analysis and mass spectrometry [m / e 498 (M ⁺ )], it was confirmed that this compound was a compound having the structure shown in the following chemical formula 7. The kinematic viscosity of this compound at 40 ° C. was 112 cSt.

<Synthesis Example 6>
Oil [S-6] was obtained in the same manner as in Synthesis Example 1 except that the compound [G-3] shown below was used instead of bisphenol A (yield 88%). Infrared absorption spectrum analysis and mass spectrometry [m / e 498 (M ⁺ )] confirmed that this compound was a compound having the structure shown below. The kinematic viscosity of this compound at 40 ° C. was 250 cSt.

<Synthesis Example 7>
The compound [G-1] shown below is used instead of bisphenol A, chlorotrifluoroethylene is used instead of tetrafluoroethylene, and the addition amount of water is changed from 1 ml to 44 ml. The oil [S-7] was obtained in exactly the same manner (yield 95%). Infrared absorption spectrum analysis and mass spectrometry [m / e 502, 504 (M ⁺ )] confirmed that this compound was a compound having the structure shown below. The kinematic viscosity of this compound at 40 ° C. was 230 cSt.

<Synthesis Example 8>
Oil [S-8] was obtained in the same manner as in Reaction Example 1 except that 2,4-di-t-amylphenol was used in place of bisphenol A (yield 90%). Infrared absorption spectrum analysis and mass spectrometry [m / e 334 (M ⁺ )] confirmed that this compound was a compound having the structure shown below. The kinematic viscosity of this compound at 40 ° C. was 9.0 cSt.

<Synthesis Example 9>
Oil [S-9] was obtained in the same manner as in Synthesis Example 1 except that the compound [G-4] shown below was used instead of bisphenol A (yield 94%). It was confirmed by infrared absorption spectrum analysis and mass spectrometry [m / e 442 (M ⁺ )] that this compound had a structure shown below. The kinematic viscosity of this compound at 40 ° C. was 50 cSt.

<Synthesis Example 10>
Oil [S-10] was obtained in the same manner as in Synthesis Example 1 except that the compound [G-5] shown below was used instead of bisphenol A (yield 91%). Infrared absorption spectrum analysis and mass spectrometry [m / e 456 (M ⁺ )] confirmed that this compound was a compound having the structure shown below. The kinematic viscosity of this compound at 40 ° C. was 115 cSt.

<Synthesis Example 11>
Compound [S-11] was obtained in the same manner as in Synthesis Example 1 except that compound [G-6] shown below was used instead of bisphenol A (yield 96%). Infrared absorption spectrum analysis and mass spectrometry [m / e 456 (M ⁺ )] confirmed that this compound was a compound having the structure shown below.

<Synthesis Example 12>
Oil [S-12] was obtained in the same manner as in Synthesis Example 1 except that pn-heptylphenol was used instead of bisphenol A (yield 95%). Infrared absorption spectrum analysis and mass spectrometry [m / e 292 (M ⁺ )] confirmed that this compound had a structure shown below. The kinematic viscosity of this compound at 40 ° C. was 3.1 cSt.

<Synthesis Example 13>
An oil [S-13] was obtained in the same manner as in Synthesis Example 1 except that nonylphenol was used in place of bisphenol A (yield 92%). Infrared absorption spectrum analysis and mass spectrometry [m / e 320 (M ⁺ )] confirmed that this compound was a compound having the structure shown below. The kinematic viscosity of this compound at 40 ° C. was 6.2 cSt.

<Synthesis Example 14>
An oil [S-14] was obtained in the same manner as in Synthesis Example 1 except that dodecylphenol was used instead of bisphenol A (yield 93%). Infrared absorption spectrum analysis and mass spectrometry [m / e 362 (M ⁺ )] confirmed that this compound was a compound having the structure shown below. The kinematic viscosity of this compound at 40 ° C. was 14 cSt.

<Synthesis Example 15>
The compound [G-1] shown in Synthesis Example 3 was used instead of bisphenol A, and perfluoropropyl vinyl ether (CF ₂ = CFOCF ₂ CF ₂ CF ₃ ) was used instead of tetrafluoroethylene. Synthesis Example 1 In the same manner, oil [S-15] was synthesized. However, the scale of the synthesis was carried out with a scale of 1/20 that of Synthesis Example 1. A small amount of oil [S15] was isolated from the resulting crude reaction product using a Kugel Rohr type microdistillation apparatus, and the structure was analyzed by infrared absorption spectrum and mass spectrometry [m / e 802 (M ⁺ )]. confirmed.

<Synthesis Example 16>
A small amount of oil [S-16] was isolated in the same manner as in Synthesis Example 15 except that hexafluoropropene was used in place of perfluoropropyl vinyl ether (CF ₂ = CFOCF ₂ CF ₂ CF ₃ ), and the structure was analyzed by infrared absorption spectrum and mass. It was confirmed by analysis [m / e 570, 550, 530 (M ⁺ )].

（Ｒｆａは、ＣＦ₃ ＣＦ＝ＣＦ−、又は、ＣＦ₃ ＣＨＦＣＦ₂ −である。）

(Rfa is, CF ₃ CF = CF-, or, CF ₃ CHFCF ₂ - a is.)

<Synthesis Example 17>
Oil [S-17] was obtained in the same manner as in Synthesis Example 15, except that pt-octylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of compound [G-1].
[S-17] was isolated from the crude reaction product by a Kugelrohr type microdistillation apparatus, and its structure was confirmed by infrared absorption spectrum and mass spectrometry [m / e 472 (M ⁺ )].

<Synthesis Example 18>
Synthesis example except that pt-octylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of compound [G-1] and hexafluoropropene (CF ₂ = CFCF ₃ ) was used instead of perfluoropropyl vinyl ether. In the same manner as in Example 15, oil [S-18] was obtained.
[S-18] was isolated from the crude reaction product by a Kugelrohr type microdistillation apparatus, and its structure was confirmed by infrared absorption spectrum and mass spectrometry [m / e 336, 356 (M ⁺ )].

（Ｒｆｂは、ＣＦ₃ ＣＦ＝ＣＦ−、又は、ＣＦ₃ ＣＨＦＣＦ₂ −である。）

(Rfb is, CF ₃ CF = CF-, or, CF ₃ CHFCF ₂ - a is.)

<Synthesis Example 19>
Synthesis example except that pt-octylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of compound [G-1] and chlorotrifluoroethylene (CF ₂ = CFCl) was used instead of perfluoropropyl vinyl ether. In the same manner as in Example 15, oil [S-19] was obtained. [S-19] was isolated from the crude reaction product by a Kugelrohr type microdistillation apparatus, and its structure was confirmed by infrared absorption spectrum and mass spectrometry [m / e 322, 324 (M ⁺ )].

[Example 1]
<Compatibility of fluorine-containing aromatic compound (A) and aromatic oil (B)>
Compound [S-1] obtained in Synthesis Example 1 and Allomix 20T (branched alkylbenzene having a kinematic viscosity of 14 cSt at 40 ° C.) (trade name, manufactured by Nippon Petroleum Detergent Co., Ltd.) were mixed at various ratios. The compatibility at 25 ° C. was examined. [S-1] 100 parts by weight was put into a beaker, and 1 part by weight of Amilox 20T was sequentially added to 1 part by weight until 100 parts by weight was reached. When the amount reached 100 parts by weight, the compatibility was visually evaluated.
On the other hand, 100 parts by weight of allomix 20T was put into a beaker, and [S-1] was sequentially added in the same manner as above, and the compatibility was visually evaluated.
As a result, it was found that compound [S-1] and allomix 20T were completely compatible at all mixing ratios. The results are shown in Table 1.

[Examples 2 and 3]
Instead of Aromix 20T, Alomix 22 (branched alkylbenzene having a kinematic viscosity of 31.5 cSt at 40 ° C.) (trade name, manufactured by Nippon Petroleum Detergent Co., Ltd.) or AB-SG (dynamic viscosity of 5.8 cSt at 40 ° C.) The compatibility at 25 ° C. was examined in the same manner as in Example 1 except that chain-type alkylbenzene (trade name, manufactured by Mitsubishi Yuka Co., Ltd.) was used. As a result, it was found that compound [S-1] and allomix 22 or AB-SG were completely compatible at all mixing ratios. The results are shown in Table 1.

[Comparative Examples 1 and 2]
SUNISO3GS (Naphthenic mineral oil with a kinematic viscosity of 30 cSt at 40 ° C) (trade name, manufactured by Nippon San Oil Co., Ltd.) or liquid paraffin (paraffin with a kinematic viscosity of 40 cSt at 40 ° C) instead of Aromix 20T (Wako Pure Chemical Industries, Ltd.) The compatibility at 25 ° C. was examined in the same manner as in Example 1 except that the reagent grade 1) was used. As a result, it was found that the compound [S-1] and SUNISO3GS or liquid paraffin were compatible only at a limited mixing ratio. The results are shown in Table 1.

以上の結果より、一般式（１）で表される含フッ素芳香族化合物は、非芳香族炭化水素系化合物とは限られた混合比でしか相溶しないのに対し、芳香族系炭化水素化合物とはあらゆる混合比でも良好な相溶性を示す事が分かる。

From the above results, the fluorine-containing aromatic compound represented by the general formula (1) is compatible only with a limited mixing ratio with the non-aromatic hydrocarbon compound, whereas the aromatic hydrocarbon compound. It can be seen that it exhibits good compatibility at any mixing ratio.

[Example 4]
<Compatibility between lubricating oil and refrigerant>
Hydrofluoroalkane of lubricating oil composition obtained by mixing compound [S-1] obtained in Synthesis Example 1 and allomix 20T at a weight ratio of compound [S-1] / allomix 20T of 80/20 The compatibility with HFC-134a (1,1,1,2 tetrafluoroethane) was examined by the following method.
First, 1.8 g of the lubricating oil composition was put in a glass tube having an internal volume of 6 ml, cooled with liquid nitrogen together with the glass tube, decompressed, and about 0.2 g of HFC-134a was introduced. After sealing the glass tube, the compatibility of the mixed oil and the hydrofluoroalkane at room temperature was judged visually. Furthermore, after cooling in a methanol refrigerant and the temperature reaches equilibrium, the compatibility between the mixed oil and the fluorinated alkane is judged visually to judge the compatibility from room temperature to the low temperature region. The temperature at which the mixed solution began to suspend was defined as the compatibility lower limit temperature. The results are shown in Table 2.
[Examples 5 and 6]
Alkene L (trade name of linear-alkylbenzene, kinematic viscosity 4.3 cSt at 40 ° C, manufactured by Nippon Petroleum) and AB-SG (trade name of linear-alkylbenzene, kinematic viscosity at 40 ° C instead of amylox 20T Was used in the same manner as in Example 4 except that 4.3 cSt, manufactured by Mitsubishi Oil Chemical Co., Ltd. was used.
Table 2 shows the results of examining the compatibility between the lubricating composition and the refrigerant composition.

[Example 7]
The compatibility of the lubricating oil composition with hydrofluoroalkane HFC-134a was examined in the same manner as in Example 4 except that the compound [S-2] obtained in Synthesis Example 2 was used instead of the compound [S-1]. The results are shown in Table 2.
[Example 8]
Table 2 shows the results of examining the compatibility of the lubricating oil composition with hydrofluoroalkane HFC-134a in the same manner as in Example 4 except that the weight ratio of Compound [S-1] / Allomix 20T was mixed at 20/80. Shown in
[Comparative Examples 3 to 5]
The results of examining the compatibility of HFC-134a with the lubricating oil composition comprising the compound [S-1] or [S-2] and various non-aromatic oils described in Table 2 in the same manner as in Example 4 are shown in Table 2. Shown in

以上の結果より、一般式（１）で表される含フッ素芳香族化合物と芳香族オイル化合物との潤滑オイル組成物は、非芳香族オイルとの潤滑オイル組成物に比べて、ＨＦＣ−１３４ａと低温領域でも良好な相溶性を示す事が分かる。

From the above results, the lubricating oil composition of the fluorine-containing aromatic compound represented by the general formula (1) and the aromatic oil compound is more HFC-134a than the lubricating oil composition of the non-aromatic oil. It can be seen that good compatibility is exhibited even at low temperatures.

[Examples 9 to 13]
Fluorinated aromatic compound [S-3] and listed in Table 3 in the same manner as in Example 1, except that compound [S-3] obtained in Synthesis Example 3 was used instead of compound [S-1]. The compatibility of this product with an aromatic oil at 25 ° C. was examined. The results are shown in Table 3.
[Comparative Example 6]
Table 3 shows the results of examining the compatibility of compound [S-3] and liquid paraffin at 25 ° C. in the same manner as in Example 1 except that compound [S-3] and liquid paraffin were used.

以上の結果より、化合物［Ｓ−３］に代表される一般式（２）で表される含フッ素芳香族化合物は、非芳香族炭化水素系化合物とは限られた混合領域でしか相溶しないのに対し、芳香族オイルとはあらゆる混合比でも良好な相溶性を示す事が分かる。

From the above results, the fluorine-containing aromatic compound represented by the general formula (2) represented by the compound [S-3] is compatible only in a limited mixed region with the non-aromatic hydrocarbon-based compound. On the other hand, it can be seen that the aromatic oil exhibits good compatibility at any mixing ratio.

[Examples 14 to 16]
Results of examining the compatibility of the lubricating oil composition comprising the compound [S-3] obtained in Synthesis Example 3 and various aromatic oils shown in Table 4 with respect to HFC-134a in the same manner as in Examples 4 to 8. Is shown in Table 4.
[Comparative Example 7]
Table 4 shows the results of examining the compatibility of HFC-134a with the lubricating oil composition comprising compound [S-3] and SUNISO3GS in the same manner as in Example 4.

From the above results, the lubricating oil composition of the fluorine-containing aromatic compound represented by the general formula (2) and the aromatic oil is more HFC- than the lubricating oil composition of the non-aromatic hydrocarbon compound.
It can be seen that good compatibility is exhibited even at a low temperature region of 134a. In addition, when Examples 6 and 8 for compound [S-1] are compared with Examples 15 and 16 for compound [S-3], the composition containing [S-3] is more effective than [S-1]. It can be seen that although it has a higher viscosity than the composition it contains, it has a much lower minimum compatible temperature with HFC-134a.

[Examples 17 to 20]
The results of examining the compatibility of the lubricating oil composition composed of the compound [S-4] obtained in Synthesis Example 4 and various aromatic oils shown in Table 5 with respect to HFC-134a in the same manner as in Examples 4-8. Table 5 shows.
[Comparative Example 8]
Table 5 shows the results of examining the compatibility of HFC-134a with the lubricating oil composition comprising the compound [S-4] and SUNISO3GS in the same manner as in Example 8.

以上の結果より、化合物［Ｓ−４］で表される含フッ素芳香族化合物と芳香族オイルとの潤滑オイル組成物は、非芳香族炭化水素系化合物との潤滑オイル組成物に比べて、ＨＦＣ−１３４ａと低温領域でも良好な相溶性を示す事が分かる。

From the above results, the lubricating oil composition of the fluorine-containing aromatic compound represented by the compound [S-4] and the aromatic oil is more HFC than the lubricating oil composition of the non-aromatic hydrocarbon compound. It can be seen that good compatibility is exhibited even at a low temperature region of -134a.

[Examples 21 to 24]
Mixed refrigerant HFC-32 / HFC-125 / HFC-134a (30/10/60 wt%) of a lubricating oil composition obtained by mixing compound [S-3] and allomix 20T at various ratios shown in Table 6 Table 6 shows the results obtained by examining the compatibility with) in the same manner as in Example 4.

以上の結果より、一般式（２）で表される含フッ素芳香族化合物と芳香族オイルとを各種の割合で混合して得られる潤滑オイル組成物は、混合冷媒ＨＦＣ−３２／ＨＦＣ−１２５／ＨＦＣ−１３４ａ（３０／１０／６０ｗｔ％）と低温領域でも良好な相溶性を示す事が分かる。

From the above results, the lubricating oil composition obtained by mixing the fluorine-containing aromatic compound represented by the general formula (2) and the aromatic oil at various ratios is a mixed refrigerant HFC-32 / HFC-125 / It can be seen that HFC-134a (30/10/60 wt%) exhibits good compatibility even at low temperatures.

[Examples 25, 26, and 27]
Mixed refrigerant HFC-143a / HFC-134a / HFC of lubricating oil composition obtained by mixing compound [S-3] and allomix 20T at a weight ratio of 80/20 of compound [S-3] / allomix 20T Table 7 shows the results obtained by examining the compatibility with −125 (52/4/44 wt%) in the same manner as in Example 4 by mixing the lubricating oil composition and the mixed refrigerant at various ratios shown in Table 7.

以上の結果より、一般式（２）で表される含フッ素芳香族化合物と芳香族オイルとの潤滑オイル組成物は、混合冷媒ＨＦＣ−１４３ａ／ＨＦＣ−１３４ａ／ＨＦＣ−１２５（５２／４／４４ｗｔ％）と種々の混合比においても低温領域で良好な相溶性を示す事が分かる。

From the above results, the lubricating oil composition of the fluorine-containing aromatic compound represented by the general formula (2) and the aromatic oil is mixed refrigerant HFC-143a / HFC-134a / HFC-125 (52/4/44 wt. %) And various mixing ratios show good compatibility at low temperatures.

[Example 28]
Mixed refrigerant HFC-32 / HFC-125 / HFC of lubricating oil composition obtained by mixing compound [S-3] and allomix 20T at a weight ratio of compound [S-3] / allomix 20T of 80/20 The compatibility with -134a is the same as in Example 4 except that the mixed refrigerant HFC-32 / HFC-125 / HFC-134a (weight ratio 23/25/52) is used as the hydrofluoroalkane instead of HFC-134a. I investigated. As a result, the HFC-32 / HFC-125 / HFC-134a mixed refrigerant was compatible at room temperature, and the compatibility lower limit temperature was -70 ° C.

[Example 29]
Mixed refrigerant HFC-32 / HFC-125 / HFC of lubricating oil composition obtained by mixing compound [S-4] and allomix 20T at a weight ratio of compound [S-4] / allomix 20T of 80/20 The compatibility with -134a is the same as in Example 4 except that the mixed refrigerant HFC-32 / HFC-125 / HFC-134a (weight ratio 30/10/60) is used as the hydrofluoroalkane instead of HFC-134a. I investigated. The result was compatible with the HFC-32 / HFC-125 / HFC-134a mixed refrigerant at room temperature, and remained compatible even when cooled to -78 ° C.

[Example 30]
A mixed refrigerant HFC- of a lubricating oil composition obtained by mixing the compound [S-5] obtained in Synthesis Example 5 and the allomix 20T at a weight ratio of 80/20 of the compound [S-5] / allomix 20T. Compatibility with 32 / HFC-125 / HFC-134a, except mixed refrigerant HFC-32 / HFC-125 / HFC-134a (weight ratio 30/10/60) instead of HFC-134a as hydrofluoroalkane Were examined in the same manner as in Example 4. The results were compatible with the HFC-32 / HFC-125 / HFC-134a mixed refrigerant at room temperature and remained compatible even when cooled to -50 ° C.

[Example 31]
Alkene 56N (branched alkylbenzene from Nippon Petroleum Detergent Co., Ltd. (kinematic viscosity 5.8 cSt at 40 ° C.) and Alomix 22 (branched alkylbenzene from Japan Petroleum Detergent Co., Ltd. (kinematic viscosity 29 cSt at 40 ° C.)) Oil mixed at a weight ratio of 45/55 (kinematic viscosity at 40 ° C. 14 cSt) and compound [S-3] were mixed at a weight ratio of compound [S-3] / aromatic oil of 80/20. The compatibility of the resulting lubricating oil composition with HFC-134a was examined in the same manner as in Example 4 except that the mixing ratio of lubricating oil composition / HFC-134a was changed to 70/30 by weight. The results were well compatible at room temperature, and the compatibility minimum temperature was -50 ° C.

[Examples 32-35]
The compatibility of the mixed refrigerant HFC-32 / HFC-125 / HFC-134a of the lubricating oil composition comprising the compound [S-3] and various aromatic oils described in Table 8 is HFC-134a as hydrofluoroalkane. Instead, a mixed refrigerant HFC-32 / HFC-125 / HFC-134a (weight ratio 30/10/60) was used in the same manner as in Example 4 except that it was used. The results are shown in Table 8.

表８の結果より、一般式（２）で表される含フッ素芳香族化合物と分枝型アルキルベンゼンとの潤滑オイル組成物は、直鎖型アルキルベンゼンとの潤滑オイル組成物に比べて、混合冷媒ＨＦＣ−３２／ＨＦＣ−１２５／ＨＦＣ−１３４ａとより低い温度領域でも良好な相溶性を示す事が分かる。

From the results of Table 8, the lubricating oil composition of the fluorine-containing aromatic compound represented by the general formula (2) and the branched alkylbenzene is more mixed refrigerant HFC than the lubricating oil composition of the linear alkylbenzene. It can be seen that good compatibility is exhibited even at a lower temperature range of −32 / HFC-125 / HFC-134a.

[Example 36]
Compound [S-3] and alkyl diphenyl ether (kinematic viscosity at 40 ° C. 15 cSt) (LB-15, manufactured by Matsumura Oil Research Co., Ltd.) were mixed at a weight ratio of 82/18 of compound [S-3] / alkyl diphenyl ether. The lubricating oil composition thus obtained was examined for compatibility with HFC-134a in the same manner as in Example 4 by mixing the lubricating oil composition and HFC-134a at a weight ratio of 70/30. As a result, it was compatible with HFC-134a at room temperature, and the minimum compatibility temperature was -42 ° C.

[Reference Example 1 and Examples 37 to 41]
The compatibility of the compounds [S-1], [S-3], and [S-4] with various fluorine-containing ether refrigerants shown in Table 9 is as follows. Mixed and examined as in Example 4. The results are shown in Table 9.
[Comparative Examples 9 to 13]
The compatibility of perfluoropolyether (kinematic viscosity at 40 ° C. 27 cSt) (Nippon Montedison Co., Ltd. Fomblin Y-06) and mineral oil (Nihon Sun Sekiyu Co., Ltd. SUNISO 3GS) with fluorine-containing ether-based refrigerants was determined as a lubricating oil. And a fluorine-containing ether refrigerant were mixed at a weight ratio of 10/90 and examined in the same manner as in Example 4. The results are shown in Table 9.

表９の結果より、パーフルオロポリエーテルや鉱油は水素含有含フッ素エーテル系冷媒との相溶性が不良であるのに対し、一般式（１）で表される含フッ素芳香族化合物は、各種の含フッ素エーテル系冷媒とより低い温度領域でも良好な相溶性を示す事が分かる。

From the results in Table 9, perfluoropolyether and mineral oil have poor compatibility with the hydrogen-containing fluorine-containing ether refrigerant, whereas the fluorine-containing aromatic compound represented by the general formula (1) It can be seen that good compatibility with the fluorine-containing ether refrigerant is obtained even at a lower temperature range.

[Examples 42 and 43]
The lubricating oil composition comprising the compound [S-3] and the aromatic oil described in Table 10 is compatible with various fluorine-containing ether refrigerants, and the lubricating oil composition and the fluorine-containing ether refrigerant are in a weight ratio of 70/30. Mixed and examined as in Example 4. The results are shown in Table 10.
[Comparative Examples 14 and 15]
The compatibility of perfluoropolyether (kinematic viscosity at 40 ° C. 27 cSt) (Nippon Montedison Co., Ltd. Fomblin Y-06) and mineral oil (Nihon Sun Sekiyu Co., Ltd. SUNISO 3GS) with fluorine-containing ether-based refrigerants was determined as a lubricating oil. And a fluorine-containing ether refrigerant were mixed at a weight ratio of 70/30 and examined in the same manner as in Example 4. The results are shown in Table 10.

表１０の結果より、パーフルオロポリエーテルや鉱油は水素含有含フッ素エーテル系冷媒との相溶性が不良であるのに対し、一般式（１）で表される含フッ素芳香族化合物と芳香族オイルからなる潤滑オイル組成物は、各種の含フッ素エーテル系冷媒とより低い温度領域でも良好な相溶性を示す事が分かる。

From the results of Table 10, perfluoropolyether and mineral oil have poor compatibility with hydrogen-containing fluorine-containing ether refrigerants, whereas fluorine-containing aromatic compounds and aromatic oils represented by general formula (1) It can be seen that the lubricating oil composition consisting of the above shows good compatibility with various fluorine-containing ether refrigerants even in a lower temperature range.

[Examples 44 to 47]
<Pour point test>
Table 11 shows the results of measuring the pour points of various lubricating oils or lubricating oil compositions described in Table 11 by a method according to the pour point test method of JIS K2269-1987.

以上の結果から、一般式（１）の含フッ素芳香族化合物に芳香族オイルを混合することにより、低温流動性が著しく改善されたことは明らかである。

From the above results, it is clear that the low-temperature fluidity was remarkably improved by mixing the aromatic oil with the fluorine-containing aromatic compound of the general formula (1).

[Examples 48 to 51]
<Water absorption test>
The lubricating oil composition of the compound [S-3] or the lubricating oil composition comprising the compound [S-3] and various aromatic oils described in Table 12 is kept static in a constant temperature and humidity chamber at 25 ° C. and a relative humidity of 70%. Table 12 shows the results of measuring the equilibrium moisture content of the oil with a Karl Fischer moisture meter.
[Comparative Example 16]
Table 12 shows the results of measuring the equilibrium water absorption of the lubricating oil composition comprising the compound [S-3] and an ester oil (kinematic viscosity 32 cSt at 40 ° C. of pentaerythritol fatty acid ester) in the same manner as in Example 49.

以上の結果から、一般式（２）の含フッ素芳香族化合物に芳香族オイルを混合すると、吸湿性が著しく低減される事が分かる。

From the above results, it is understood that the hygroscopicity is remarkably reduced when the aromatic oil is mixed with the fluorine-containing aromatic compound of the general formula (2).

[Examples 52 and 53]
Table 13 shows the results of measuring the equilibrium water absorption of the compound [S-4] and the compound [S-8] in the same manner as in Example 48.
[Comparative Example 17]
Table 13 shows the results of measurement of the equilibrium water absorption of ester oil (pentaerythritol fatty acid ester 40 ° C. kinematic viscosity 32 cSt) in the same manner as in Example 49. From the above results, it can be seen that the fluorine-containing aromatic compound of the general formula (3) exhibits low hygroscopicity.

[Examples 54 to 56]
<Electrical characteristics>
The specific volume resistivity of the lubricating oil composition consisting of the lubricating oil of compound [S-3] or the aromatic oil listed in Table 14 and compound [S-3] conforms to JIS C2101 (electrical insulation oil test). It was measured by the method. The results are shown in Table 14.

以上の結果から、一般式（２）の含フッ素芳香族化合物と芳香族オイルからなる潤滑オイル組成物は吸湿に起因する電気抵抗の低下が小さい事が分かる。

From the above results, it can be seen that the lubricating oil composition comprising the fluorine-containing aromatic compound of the general formula (2) and the aromatic oil has a small decrease in electrical resistance due to moisture absorption.

[Example 57]
<Bioconcentration>
The test method is stipulated in “Test Method for New Chemical Substances” (Environmental Maintenance No. 5, Yakuhaku No. 615, 49 Base No. 392, July 13, 1974). Concentration Test of Chemical Substances> and “OECD Guidelines for Testing
'305C, Bioaccumulation: Degree of Bioconcentration in Fish' as defined in “of Chemicals” (May 12, 1981).

As a specific test method, an exposure test was first performed using test water in which the concentration of the compound [S-3] was set to 0.01 mg / L and normal carp after acclimation, and exposures 2, 4 The concentration ratio of the compound [S-3] collected after a week, concentrated in vivo by high performance liquid chromatography analysis after fragmentation, homogenization, and centrifugation was measured. The results are shown in Table 15.
[Reference Examples 2 and 3]
In the same manner as in Example 57, compounds [S-9] and [S-1] were also subjected to a bioconcentration test. The results are shown in Table 15.

表１５から、一般式（１）で表される本発明の化合物の中でも、一般式（２）で表される化合物は特に生物濃縮性が低いことが分かる。

From Table 15, it can be seen that among the compounds of the present invention represented by the general formula (1), the compound represented by the general formula (2) has a particularly low bioconcentration property.

[Example 58]
In the same manner as in Example 57, the bioconcentration test was performed on the compound [S-4]. As a result, it was found that the concentration ratio of the compound [S-4] reached an equilibrium value of 2260 times in the fourth week. From the above, it can be said that the bioconcentration property of the compound [S-4] is low.
[Examples 59 and 60]
The heat resistance of the fluorinated aromatic compound was evaluated by the following method. That is, compound [S-3] or compound [S-6] was placed in a 0.5 ml test tube, heated at 175 ° C. for 19 hours under air, and then analyzed for the presence of thermal decomposition products by gas chromatography. The results are shown in Table 16.
[Reference Examples 4 and 5]
In the same manner as in Example 59, the heat resistance of the compounds [S-10] and [S-11] was also evaluated. The results are shown in Table 16.

表１６から、一般式（１）で表される本発明の化合物の中でも、一般式（２）で表される含フッ素芳香族化合物は特に高い熱安定性を示す事が分かる。

From Table 16, it can be seen that among the compounds of the present invention represented by the general formula (1), the fluorine-containing aromatic compound represented by the general formula (2) exhibits particularly high thermal stability.

[Examples 61 and 62]
In the same manner as in Example 59, the heat resistance of the compounds [S-4] and [S-8] was also evaluated. The results are shown in Table 17.
[Reference Examples 6 to 8]
In the same manner as in Example 59, the heat resistance of the compounds [S-12], [S-13], and [S-14] was also evaluated. The results are shown in Table 17. [[S-13] and [S-14] are alkylphenol-derived substances synthesized from propylene oligomers, and the structure of the alkyl group bonded to the aromatic ring is a secondary alkyl group structure or a tertiary alkyl group. It is a mixture of structures. ]

表１７から、一般式（１）で表される本発明の化合物の中でも、一般式（３）で表される含フッ素芳香族化合物は特に高い熱安定性を示す事が分かる。

From Table 17, it can be seen that among the compounds of the present invention represented by the general formula (1), the fluorine-containing aromatic compound represented by the general formula (3) exhibits particularly high thermal stability.

[Examples 63, 64, 65]
<Lubrication characteristics test> (Falex test)
The wear amount of the lubricating oil or lubricating oil composition described in Table 18 was measured under the following conditions. First, refrigerant gas (HFC-134a) is blown into the oil to be measured at a blow rate of about 10 L / hr for about 15 minutes. Further, under the condition of an oil temperature of 25 ° C. at the start of the test under refrigerant gas blowing, the load was applied for 200 minutes with a load of 200 pounds, then the load was increased to 500 pounds and the operation was continued for 2 hours while maintaining 500 pounds. The change in weight of the test piece before and after the test was measured and used as the amount of wear. The results are shown in Table 18.

[Examples 66 to 70]
Various additives were added to the lubricating oil or lubricating oil composition described in Table 17, and the amount of wear was measured in the same manner as in Example 63. The results are shown in Table 18.
[Comparative Examples 18 and 19]
The wear amount of ALOMIX 20T and SUNISO3GS was measured by the same method as in Example 63. The results are shown in Table 18.

表１８から明らかなように、一般式（２）で表される含フッ素芳香族化合物と芳香族炭化水素系化合物からなる潤滑オイル組成物は、芳香族炭化水素化合物のみならず含フッ素芳香族化合物と比較しても優れた耐摩耗性を示す事が分かる。

As is apparent from Table 18, the lubricating oil composition comprising the fluorine-containing aromatic compound represented by the general formula (2) and the aromatic hydrocarbon-based compound is not only an aromatic hydrocarbon compound but also a fluorine-containing aromatic compound. It can be seen that excellent wear resistance is exhibited even when compared with.

[Examples 71 to 74]
0.6 ml of various lubricating oils or lubricating oil compositions described in Table 19 that were absorbed in the same manner as in Example 48 were placed in a glass tube, and 0.6 ml of HFC-134a was used as a liquid.
l, 2 ml of air as gas, and iron, copper, and aluminum test pieces were added and sealed. After the refrigerant composition was heated at 175 ° C. for 10 days, the hue change of the refrigerant composition and the surface of the metal piece were observed. As a result, almost no change was observed in both the hue and the metal surface state of the refrigerant composition of the present invention. It was. Further, gas chromatography analysis (GC analysis) of the lubricating oil or lubricating oil composition after the evaluation was performed. As a result, no decomposition product was found in the lubricating oil or lubricating oil composition of the present invention. It was also found that the discoloration of the copper surface, which was slightly observed with the fluorine-containing aromatic compound alone, was improved by mixing the aromatic compound. The results are summarized in Table 19.

[Comparative Example 20]
The ester oil (pentaerythritol fatty acid ester 40 ° C. kinematic viscosity 32 cSt) absorbed in Comparative Example 17 was evaluated for heat resistance and hydrolysis resistance in the same manner as in Example 71. A hydrolyzate was observed. The results are shown in Table 19. From Table 19, it can be seen that the refrigerant composition comprising the various lubricating oils or lubricating oil compositions of the present invention exhibits sufficient heat resistance and hydrolysis resistance.

[Examples 75 to 77]
Evaluation of thermal resistance of various lubricating oils or lubricating oil compositions described in Table 20 was carried out under the conditions more severe than Example 71, that is, the conditions of heating at 200 ° C. for 14 days, and by the same method as in Reference Example 28. did. The results are summarized in Table 20. It can be seen from Table 20 that benzotriazole and 2-ethylhexyl glycidyl ether, which are corrosion inhibitors, are effective in preventing discoloration of the metal surface.

[Example 78]
<Compatibility of the mixture of (A) compound and HFC-134a>
As (A), the compatibility of [S-15] obtained in Synthesis Example 15 and HFC-134a as a refrigerant was evaluated by the following method.
1.8 g of [S-15] was put into a glass tube having a volume of 6 ml, and the whole glass tube was cooled with liquid nitrogen and decompressed, and then about 0.2 g of HFC-134a was introduced. After sealing the glass tube, the compatibility of [S-15] and HFC-134a at 0 ° C. was visually determined.
[S-15] became a homogeneous compatible mixture with HFC-134a.
[Examples 79 to 82]
Similarly to Example 78, [S-16] to [S-19] obtained in Synthesis Examples 16 to 19 were similarly tested for compatibility with HFC-134a at 0 ° C.
As a result, a uniform compatible mixture was obtained at all mixing ratios.

[Example 83]
<Compatibility of mixture of lubricating oil composition and HFC-134a>
Compound [S-15] was mixed with ethylbenzene at a weight ratio of [S-15] / ethylbenzene of 80/20 to obtain a lubricating oil composition.
The obtained oil composition was judged for compatibility with HFC-134a in the same manner as in Example 82.
As a result, a uniform compatible mixture was obtained at all mixing ratios.

[Examples 84 to 87]
In Example 83, [S-16] to [S-19] were used in place of the compound [S-15], respectively, and the mixing ratio was set to a weight ratio of the compound / HFC-134a to 70/30. Similarly, the compatibility between the oil composition and HFC-134a was determined.
As a result, a uniform compatible mixture was obtained at the above mixing ratio.

[Example 88]
Mixed lubricant HFC-32 / HFC of lubricating oil composition (59 cSt / 40 ° C.) obtained by mixing compound [S-3] and compound [E-1] (18 cSt / 40 ° C.) at a weight ratio of 80/20 -Use of mixed refrigerant HFC32 / HFC125 / HFC134a (weight ratio 30/10/60) instead of HFC-134a with a compatibility with -125 / HFC134a as hydrofluoroalkane, and a lubricating oil composition and mixed refrigerant in a weight ratio of 70 The mixture was mixed in the same manner as in Example 4. As a result, it was well compatible at room temperature and remained uniform even at -30 ° C.

[Example 89]
Mixed refrigerant HFC-32 / HFC of a lubricating oil composition (80 cSt / 40 ° C.) obtained by mixing compound [S-3] and compound [E-2] (46 cSt / 40 ° C.) at a weight ratio of 80/20 A mixed refrigerant HFC32 / HFC-125 / HFC-134a (weight ratio 30/10/60) is used instead of HFC-134a as a hydrofluoroalkane having compatibility with -125 / HFC-134a, and a lubricating oil composition The mixed refrigerant was mixed at a weight ratio of 70/30 and examined in the same manner as in Example 4. As a result, it was well compatible at room temperature and remained uniform even at -30 ° C.

[Comparative Examples 21 to 25]
<Compatibility of perfluoropolyether and aromatic oil (B)>
As a result of examining the compatibility at 25 ° C. between various perfluoropolyethers 1) to 5) shown below at 25 ° C. in the same manner as in Example 1, various perfluoropolyethers and allomix 20T were perfluorocarbons. It was found that the mixture was not compatible with any of the polyether / allomix 20T weight ratios of 80/20, 50/50, and 20/80.

1) Fomblin Y-60:
Mn = 1800 (manufactured by Montefluos)
2) Fomblin Y-25:
Mn = 3000 (manufactured by Montefluos)
3) Fomblin Y-45:
Mn = 4100 (manufactured by Montefluos)
1) 2) 3)

4) KRYTOX 143AY:
Mn = 3000 (manufactured by Du Pont)

5) DENNUM S-20:
Mn = 2700 (manufactured by Daikin Industries, Ltd.)

The present invention relates to a lubricating oil composition.
More specifically, the present invention relates to a lubricating oil composition for a refrigerator suitable for a refrigeration system using a fluorinated alkane, a hydrogen-containing fluorine-containing ether compound, or a mixture thereof as a refrigerant.

The absorption spectrum of the oil obtained in Synthesis Example 3 is shown. The absorption spectrum of the oil obtained in Synthesis Example 4 is shown.

Claims (5)

A fluorine-containing aromatic compound represented by the general formula (2).

(However, R ^1, R ² are each a hydrogen atom, an alkyl group having 1 to 19 carbon atoms, the total number of carbon atoms of R ^1, R ² is 4 to 19 .Rf is 1-4 fluorine ( It is a fluoroalkyl group or a fluoroalkenyl group having 1 to 25 carbon atoms in which an atom may be substituted with a chlorine atom .) The fluorine-containing aromatic compound according to claim 1 , wherein Rf is a fluoroalkyl group or a fluoroalkenyl group having 1 to 10 carbon atoms.   The fluorine-containing aromatic compound according to claim 1, wherein Rf is a fluoroalkyl group having 2 to 25 carbon atoms and containing 1 to 7 ether bonds in the main chain.   The fluorine-containing aromatic compound according to claim 1, wherein Rf is a fluorine atom-containing group substituted with a chlorine atom within a range of 1 to 4. Rf number 1-3 fluoroalkyl group having a _{carbon, -CF = CFCF 3, -CF 2} CFClH, -CF = CFCl and,

The fluorine-containing aromatic compound according to claim 1, which is a monovalent group selected from:

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