JP3412721B2 - Refrigerator oil and fluid composition for refrigerator - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to refrigerating machine oil (lubricating oil for refrigerating machine), fluid composition for refrigerating machine, refrigerating machine, and method for lubricating cooling system. More specifically, the present invention relates to a refrigerating machine oil containing a hydrocarbon compound having a specific structure, useful as a hydrofluorocarbon (HFC) refrigerant, a refrigerating machine fluid composition containing the refrigerating machine oil, and a refrigerator machine. The present invention relates to a refrigerating machine using a fluid composition as a circulating fluid, and a method of lubricating a cooling system using hydrofluorocarbon (HFC) as a refrigerant, which is carried out using the refrigerating machine oil as a lubricating oil.

[0002]

2. Description of the Related Art Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), which have been conventionally used as refrigerants for refrigeration equipment, are subject to regulation due to the problem of ozone layer depletion in recent years, and instead of these, hydrofluorocarbons ( HFC) is being used as a refrigerant.

On the other hand, compatibility with the refrigerant is one of the important performance requirements of refrigerating machine oil. Hydrocarbon oils such as mineral oils and alkylbenzenes have been used as refrigerating machine oils for CFCs and HCFCs, but HFCs are almost incompatible with mineral oils and alkylbenzenes. Therefore, as refrigerating machine oils for HFC refrigerants, oxygen-containing oils such as polyalkylene glycol (PAG) and esters that are compatible with HFC have been studied or used. For example, regarding PAG, U.S. Pat. No. 4,755,316, JP-A-1-198694,
No. 1-256594, No. 1-259093, No. 1-
No. 259094, No. 1-259095, No. 1-274.
No. 191, No. 2-43290, No. 2-55791,
No. 2-84491, etc., and regarding esters, Japanese Patent Publication No. 3-505602 and Japanese Patent Laid-Open No. 3-8889.
No. 2, No. 2-128991, No. 3-128992,
No. 3-200895, No. 3-227397, No. 4-
No. 20597, No. 4-72390, No. 4-21859.
2 and 4-2499593.

However, PAG has high hygroscopicity and poor electrical insulation. Also, ester oil is
It may undergo hydrolysis and generate an acid, and various inconveniences are expected to occur. Further, these oxygen-containing oils are hydrocarbon oil / CFC, or hydrocarbon oil /
It has a big problem that lubricity is inferior to that of the HCFC system.

On the other hand, JP-A-5-157379 describes a refrigeration system for HFC-134a refrigerant using a refrigerating machine oil that is incompatible with the refrigerant, and as an oil that is incompatible with such refrigerant, it has excellent electrical insulation. Chemically stable and chemically stable mineral oils, hydrocarbon oils such as poly-α-olefins and alkylbenzenes are mentioned. However, HFC-
When used as a refrigerating machine oil for 134a, the two are incompatible with each other, and thus a special devise on the system side is required.

As described above, the oxygen-containing oil and the hydrocarbon oil generally have contradictory performances, and it has not been possible to develop a refrigerating machine oil for an HFC refrigerant which has both characteristics.

[0007]

DISCLOSURE OF THE INVENTION The present invention relates to a refrigerating machine oil which is compatible with an HFC refrigerant and which satisfies various requirements such as hydrolysis stability, electric insulation and lubricity, and the refrigerating machine oil and the HFC refrigerant. An object of the present invention is to provide a fluid composition for a refrigerator containing It is another object of the present invention to provide a refrigerating machine using the refrigerating machine fluid composition as a circulating fluid, and a cooling system lubricating method using HFC using the refrigerating machine oil as a lubricating oil as a refrigerant. .

[0008]

[Means for Solving the Problems] As a result of intensive studies conducted by the present inventors to develop a refrigerating machine oil having both compatibility and various other performances, a hydrocarbon compound having a specific structure is found to be HFC. The inventors have found that they are compatible with a refrigerant and satisfy other required performances, and have completed the present invention.

That is, the present invention relates to the general formula (1)

[0010]

[Chemical 5] [In the above formula (1), R represents an alkylene group having 1 to 8 carbon atoms or an alkenylene group, and R ¹ , R ² , R ³ and R
⁴ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R, R ¹ , R
² , the total carbon number of R ³ and R ⁴ is 1 to 8], and a refrigerating machine oil for a hydrofluorocarbon refrigerant is provided.

The present invention also provides [I] a hydrofluorocarbon refrigerant, and [II] a general formula (1).

[0012]

[Chemical 6] [In the above formula (1), R represents an alkylene group having 1 to 8 carbon atoms or an alkenylene group, and R ¹ , R ² , R ³ and R
⁴ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R, R ¹ , R
The total number of carbon atoms of ² , R ³ and R ⁴ is 1 to 8], and a fluid composition for a refrigerator is provided.

Furthermore, the present invention provides [I] a hydrofluorocarbon refrigerant, and [II] a general formula (1).

[0014]

[Chemical 7] [In the above formula (1), R represents an alkylene group having 1 to 8 carbon atoms or an alkenylene group, and R ¹ , R ² , R ³ and R
⁴ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R, R ¹ , R
² , the total carbon number of R ³ and R ⁴ is 1 to 8], a refrigerating machine using a fluid composition for a refrigerator containing a hydrocarbon compound represented by the formula, and a general formula (1)

[0015]

[Chemical 8] [In the above formula (1), R represents an alkylene group having 1 to 8 carbon atoms or an alkenylene group, and R ¹ , R ² , R ³ and R
⁴ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R, R ¹ , R
² , the total number of carbon atoms of R ³ and R ⁴ is 1 to 8], a refrigerating machine oil containing a hydrocarbon compound represented by A lubrication method is provided.

The contents of the present invention will be described in detail below.

The refrigerating machine oil of the present invention has the general formula (1):

[0018]

[Chemical 9] [In the above formula (1), R represents an alkylene group having 1 to 8 carbon atoms or an alkenylene group, and R ¹ , R ² , R ³ and R
⁴ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R, R ¹ , R
² , the total carbon number of R ³ and R ⁴ is 1 to 8]. When R in the formula (1) is an alkylene group having 9 or more carbon atoms or an alkenylene group, at least one of R ¹ , R ² , R ³ and R ⁴ is an alkyl group having 5 or more carbon atoms, and R, R
^When the total carbon number of ¹ , R ² , R ³ and R ⁴ is 9 or more, the compatibility of the hydrocarbon compound with the HFC refrigerant is poor, which is not preferable.

R in the hydrocarbon compound of the formula (1) represents an alkylene group having 1 to 8 carbon atoms or an alkenylene group.

Specific examples of such R include a methylene group; a methylmethylene group (ethylidene group);
C2 alkylene group such as ethylene group; ethylmethylene group (propylidene group), dimethylmethylene group (isopropylidene group), methylethylene group (propylene group),
C3 alkylene group such as trimethylene group; n-propylmethylene group (butylidene group), isopropylmethylene group (isobutylidene group), ethylmethylmethylene group,
Ethyl ethylene group, 1,1-dimethyl ethylene group, 1,
2-dimethylethylene group, 1-methyltrimethylene group,
C4 alkylene group such as 2-methyltrimethylene group and tetramethylene group; n-butylmethylene group (pentylidene group), sec-butylmethylene group, isobutylmethylene group (isopentylidene group), tert-butylmethylene group , N-propylmethylmethylene group, isopropylmethylmethylene group, diethylmethylene group, n-propylethylene group, isopropylethylene group, 1-ethyl-1
-Methylethylene group, 1-ethyl-2-methylethylene group, trimethylethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group , 1,3
An alkylene group having 5 carbon atoms such as dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, pentamethylene group; n-pentylmethylene group (hexylidene group) ,
(1-methylbutyl) methylene group, isopentylmethylene group (isopentylidene group), (1,2-dimethylpropyl) methylene group, n-butylmethylmethylene group, isobutylmethylmethylene group, ethyl-n-propylmethylene group, Ethyl isopropyl methylene group, butyl ethylene group, isobutyl methylene group, 1- (n-propyl) -1
-Methylethylene group, 1- (n-propyl) -2-methylethylene group, 1-isopropyl-1-methylethylene group, 1-isopropyl-2-methylethylene group, 1,2
-Diethylethylene group, 1-ethyl-2,2-dimethylethylene group, tetramethylethylene group, 1-n-propyltrimethylene group, 2-n-propyltrimethylene group,
1-isopropyltrimethylene group, 2-isopropyltrimethylene group, 1-ethyl-3-methyltrimethylene group, 1-ethyl-2-methyltrimethylene group, 1,1,
2-trimethyltrimethylene group, 1,1,3-trimethyltrimethylene group, 1-ethyltetramethylene group, 1,
1-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 1,4-dimethyltetramethylene group,
C2-C6 alkylene groups such as 2,2-dimethyltetramethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, and hexamethylene group (all C6
(Including isomers of alkylene groups); n-hexylmethylene group (heptylidene group), n-pentylethylene group (heptylene group) and other alkylene groups having 7 carbon atoms (all isomers of alkylene groups having 7 carbon atoms C8 alkylene groups such as n-heptylmethylene group (octylidene group) and n-hexylethylene group (octylene group) (including isomers of all C8 alkylene groups); vinylidene group, ethenylene An alkenylene group having 2 carbon atoms such as a group (vinylene group); a propenylene group, a methyleneethylene group,
C3 alkenylene groups such as methylethenylene group, 1-propenylidene group and 2-propenylidene group; C4 alkenylene groups such as 3-methylpropenylene group (all isomers of C4 alkenylene groups Including); 1-
Methyl-3-methylene trimethylene group, 3-ethylpropenylene group, 1,3-dimethylpropenylene group, 2,3
-C5 alkenylene groups such as dimethylpropenylene group and 3,3-dimethylpropenylene group (including all isomers of C5 alkenylene groups); 1,1-dimethyl-3-methylenetrimethylene group , 1-ethyl-3-methylene trimethylene group, 3-ethyl-1-methylpropenylene group, 3-ethyl-2-methylpropenylene group,
1,3,3-trimethylpropenylene group, 2,3,3-
C6 alkenylene group such as trimethylpropenylene group (including all isomers of C6 alkenylene group); C7 alkenylene group such as heptenylene group (all isomers of C7 alkenylene group) , Etc.); C8 alkenylene groups such as octenylene groups (including all isomers of C8 alkenylene groups); and the like.

Of these, an alkylene group having 1 to 6 carbon atoms and an alkenylene group are preferable, and particularly preferable are methylene group, methylmethylene group (ethylidene group), ethylene group, ethylmethylene group (propylidene group) and dimethylmethylene. C1-C3 alkylene groups such as group (isopropylidene group), methylethylene group (propylene group), trimethylene group; vinylidene group, ethenylene group (vinylene group), propenylene group, methyleneethylene group, methylethenylene group, 1-propenylidene group, 2
An alkenylene group having 2 to 3 carbon atoms such as a propenylidene group; an alkylene group having 4 to 6 carbon atoms, 1-methyltrimethylene group, 1-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 1, 2-dimethyltrimethylene group, 1,3-dimethyltrimethylene group, 1-ethyl-3
-Methyltrimethylene group, 1-ethyl-2-methyltrimethylene group, 1,1,2-trimethyltrimethylene group,
1,1,3-trimethyltrimethylene group; and, among alkenylene groups having 4 to 6 carbon atoms, 3-methylpropenylene group, 1-methyl-3-methylenetrimethylene group, 3-
Ethylpropenylene group, 1,3-dimethylpropenylene group, 2,3-dimethylpropenylene group, 3,3-dimethylpropenylene group, 1,1-dimethyl-3-methylenetrimethylene group, 1-ethyl-3 -Methylene trimethylene group, 3-ethyl-1-methylpropenylene group, 3-ethyl-2-methylpropenylene group, 1,3,3-trimethylpropenylene group, 2,3,3-trimethylpropenylene group; Etc.

Further, R in the hydrocarbon compound of the formula (1) is
¹ , R ² , R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having 1 to 4 carbon atoms here include a methyl group, an ethyl group and n-
Propyl group, isopropyl group, n-butyl group, sec-
Examples thereof include a butyl group, an isobutyl group and a tert-butyl group.

Further, the total carbon number of R, R ¹ , R ² , R ³ and R ⁴ in the hydrocarbon compound of the formula (1) is 1-8.
And preferably 1 to 6.

Specific examples of the hydrocarbon compound represented by the formula (1) according to the present invention include diphenylmethane, phenyltolylmethane, phenylxylylmethane,
Ditolylmethane, tolylxylylmethane, dixylylmethane, (ethylphenyl) phenylmethane, (ethylphenyl) tolylmethane, (ethylmethylphenyl) phenylmethane, (ethylphenyl) xylylmethane, (ethylmethylphenyl) tolylmethane, (ethylmethylphenyl) xylylmethane, (Diethylphenyl) phenylmethane, bis (ethylphenyl) methane, (diethylphenyl) tolylmethane, (ethylmethylphenyl)
(Ethylphenyl) methane, phenyl (n-propylphenyl) methane, phenyl (isopropylphenyl) methane, (n-propylphenyl) tolylmethane, (isopropylphenyl) tolylmethane, (methyl-n-propylphenyl) phenylmethane, (methylisopropyl) (Phenyl) phenylmethane, (methyl-n-propylphenyl) tolylmethane, (methylisopropylphenyl) tolylmethane, (n-propylphenyl) xylylmethane, (isopropylphenyl) xylylmethane,
(Ethyl-n-propylphenyl) phenylmethane,
(Ethylisopropylphenyl) phenylmethane, (ethylphenyl) (n-propylphenyl) methane, (ethylphenyl) (isopropylphenyl) methane, (n
-Butylphenyl) phenylmethane, (isobutylphenyl) phenylmethane, (sec-butylphenyl) phenylmethane, (tert-butylphenyl) phenylmethane, (n-butylmethylphenyl) phenylmethane, (isobutylmethylphenyl) phenylmethane,
(Sec-butylmethylphenyl) phenylmethane,
(Tert-butylmethylphenyl) phenylmethane,
Hydrocarbon compounds having a methylene group such as (n-butylphenyl) tolylmethane, (isobutylphenyl) tolylmethane, (sec-butylphenyl) tolylmethane, and (tert-butylphenyl) tolylmethane;

1,1-diphenylethane, 1-phenyl-1-tolylethane, 1-phenyl-1-xylylethane, 1,1-ditolylethane, 1-tolyl-1-xylylethane, 1,1-dixylylethane, 1- (ethyl Phenyl) -1-phenylethane, 1- (ethylphenyl) -1-tolylethane, 1- (ethylmethylphenyl) -1-phenylethane, 1- (ethylphenyl)-
1-xylylethane, 1- (ethylmethylphenyl)-
1-tolylethane, 1- (diethylphenyl) -1-phenylethane, 1,1-bis (ethylphenyl) ethane, 1-phenyl-1- (n-propylphenyl) ethane, 1-phenyl-1- (isopropylphenyl ) Ethane, 1- (n-propylphenyl) -1-tolylethane, 1- (isopropylphenyl) -1-tolylethane, 1- (methyl-n-propylphenyl) -1-phenylethane, 1- (methylisopropylphenyl) -1
-Phenylethane, 1- (n-butylphenyl) -1-
Phenylethane, 1- (isobutylphenyl) -1-phenylethane, 1- (sec-butylphenyl) -1-
Phenylethane, 1- (tert-butylphenyl)-
A hydrocarbon compound having a methylmethylene group (ethylidene group) such as 1-phenylethane;

1,2-diphenylethane, 1-phenyl-2-tolylethane, 1-phenyl-2-xylylethane, 1,2-ditolylethane, 1-tolyl-2-xylylethane, 1,2-dixylylethane, 1- (ethyl Phenyl) -2-phenylethane, 1- (ethylphenyl) -2-tolylethane, 1- (ethylmethylphenyl) -2-phenylethane, 1- (ethylphenyl)-
2-xylylethane, 1- (ethylmethylphenyl)-
2-tolylethane, 1- (diethylphenyl) -2-phenylethane, 1,2-bis (ethylphenyl) ethane, 1-phenyl-2- (n-propylphenyl) ethane, 1-phenyl-2- (isopropylphenyl) ) Ethane, 1- (n-propylphenyl) -2-tolylethane, 1- (isopropylphenyl) -2-tolylethane, 1- (methyl-n-propylphenyl) -2-phenylethane, 1- (methylisopropylphenyl) -2
-Phenylethane, 1- (n-butylphenyl) -2-
Phenylethane, 1- (isobutylphenyl) -2-phenylethane, 1- (sec-butylphenyl) -2-
Phenylethane, 1- (tert-butylphenyl)-
A hydrocarbon compound having an ethylene group such as 2-phenylethane;

1,1-diphenylpropane, 1-phenyl-1-tolylpropane, 1-phenyl-1-xylylpropane, 1,1-ditolylpropane, 1-tolyl-1
-Xylylpropane, 1- (ethylphenyl) -1-phenylpropane, 1- (ethylphenyl) -1-tolylpropane, 1- (ethylmethylphenyl) -1-phenylpropane, 1-phenyl-1- (n Hydrocarbon compounds having an ethylmethylene group (propylidene group) such as -propylphenyl) propane and 1-phenyl-1- (isopropylphenyl) propane;

1,2-diphenylpropane, 1-phenyl-2-tolylpropane, 1-phenyl-2-xylylpropane, 1,2-ditolylpropane, 1-tolyl-2
-Xylylpropane, 1- (ethylphenyl) -2-phenylpropane, 1- (ethylphenyl) -2-tolylpropane, 1- (ethylmethylphenyl) -2-phenylpropane, 1-phenyl-2- (n -Propylphenyl) propane, 1-phenyl-2- (isopropylphenyl) propane, 2-phenyl-1-tolylpropane,
2-phenyl-1-xylylpropane, 2-tolyl-1
-Xylylpropane, 2- (ethylphenyl) -1-phenylpropane, 2- (ethylphenyl) -1-tolylpropane, 2- (ethylmethylphenyl) -1-phenylpropane, 2-phenyl-1- (n -Propylphenyl) propane, 2-phenyl-1- (isopropylphenyl) propane and other methylethylene groups (propylene groups)
A hydrocarbon compound having

1,3-diphenylpropane, 1-phenyl-3-tolylpropane, 1-phenyl-3-xylylpropane, 1,3-ditolylpropane, 1-tolyl-3
-Xylylpropane, 1- (ethylphenyl) -3-phenylpropane, 1- (ethylphenyl) -3-tolylpropane, 1- (ethylmethylphenyl) -3-phenylpropane, 1-phenyl-3- (n Hydrocarbon compounds having a trimethylene group such as -propylphenyl) propane and 1-phenyl-3- (isopropylphenyl) propane;

2,2-diphenylpropane, 2-phenyl-2-tolylpropane, 2-phenyl-2-xylylpropane, 2,2-ditolylpropane, 2-tolyl-2
-Xylylpropane, 2- (ethylphenyl) -2-phenylpropane, 2- (ethylphenyl) -2-tolylpropane, 2- (ethylmethylphenyl) -2-phenylpropane, 2-phenyl-2- (n Hydrocarbon compounds having a dimethylmethylene group (isopropylidene group) such as -propylphenyl) propane and 2-phenyl-2- (isopropylphenyl) propane;

1,3-diphenylbutane, 1-phenyl-3-tolylbutane, 1-phenyl-3-xylylbutane, 1- (ethylphenyl) -3-phenylbutane,
Hydrocarbon compounds having a 1-methyltrimethylene group such as 1,3-ditolylbutane, 3-phenyl-1-tolylbutane, 3-phenyl-1-xylylbutane, 3- (ethylphenyl) -1-phenylbutane;

1,4-diphenylbutane, 1-phenyl-4-tolylbutane, 1-phenyl-4-xylylbutane, 1- (ethylphenyl) -3-phenylbutane,
Hydrocarbon compounds having a tetramethylene group such as 1,4-ditolylbutane;

2,3-diphenylbutane, 2-phenyl-3-tolylbutane, 2-phenyl-3-xylylbutane, 2- (ethylphenyl) -3-phenylbutane,
Hydrocarbon compounds having a 1,2-dimethylethylene group such as 2,3-ditolylbutane;

Hydrocarbon compounds having a 1-ethyltrimethylene group such as 1,3-diphenylpentane, 1-phenyl-3-tolylpentane and 3-phenyl-1-tolylpentane;

Hydrocarbon compounds having a 1-methyltetramethylene group such as 1,4-diphenylpentane, 1-phenyl-4-tolylpentane and 4-phenyl-1-tolylpentane;

Hydrocarbon compounds having a pentamethylene group such as 1,5-diphenylpentane and 1-phenyl-5-tolylpentane;

Hydrocarbon compounds having a 1-ethyl-2-methylethylene group such as 2,3-diphenylpentane, 2-phenyl-3-tolylpentane and 3-phenyl-2-tolylpentane;

Hydrocarbon compounds having a 1,3-dimethyltrimethylene group such as 2,4-diphenylpentane and 2-phenyl-4-tolylpentane;

2-methyl-1,3-diphenylbutane,
A hydrocarbon compound having a 1,2-dimethyltrimethylene group such as 2-methyl-1-phenyl-3-tolylbutane and 2-methyl-3-phenyl-1-tolylbutane;

3-methyl-1,3-diphenylbutane,
A hydrocarbon compound having a 1,1-dimethyltrimethylene group such as 3-methyl-1-phenyl-3-tolylbutane and 3-methyl-3-phenyl-1-tolylbutane;

2-methyl-1,4-diphenylbutane,
A hydrocarbon compound having a 2-methyltetramethylene group such as 2-methyl-1-phenyl-4-tolylbutane and 2-methyl-4-phenyl-1-tolylbutane;

2-methyl-2,3-diphenylbutane,
1,1,2 such as 2-methyl-2-phenyl-3-tolylbutane and 2-methyl-3-phenyl-2-tolylbutane
A hydrocarbon compound having a trimethylethylene group;

1,1-diphenylhexane, 1,2-diphenylhexane, 1,3-diphenylhexane, 1,
4-diphenylhexane, 1,5-diphenylhexane, 1,6-diphenylhexane, 2,2-diphenylhexane, 2,3-diphenylhexane, 2,4-diphenylhexane, 2,5-diphenylhexane, 3,3
-Diphenylhexane, 3,4-diphenylhexane,
2-methyl-1,1-diphenylpentane, 4-methyl-1,1-diphenylpentane, 2-methyl-1,2-
Diphenylpentane, 4-methyl-1,2-diphenylpentane, 2-methyl-1,3-diphenylpentane,
4-methyl-1,3-diphenylpentane, 2-methyl-1,4-diphenylpentane, 2-methyl-1,5-
Diphenylpentane, 4-methyl-2,2-diphenylpentane, 2-methyl-2,3-diphenylpentane,
2-methyl-2,4-diphenylpentane, 2-methyl-3,4-diphenylpentane, 2-methyl-2,5-
Diphenylpentane, 2-methyl-3,3-diphenylpentane, 2,3-dimethyl-1,1-diphenylbutane, 2,3-dimethyl-1,2-diphenylbutane,
2,3-dimethyl-1,3-diphenylbutane, 2,3
-Dimethyl-1,4-diphenylbutane, 2,3-dimethyl-2,3-diphenylbutane, 2-benzyl-1-
Hydrocarbon compounds having an alkylene group having 6 carbon atoms such as phenylpentane and 2-benzyl-3-methyl-1-phenylbutane;

1,1-diphenylethene, 1-phenyl-1-tolylethene, 1-phenyl-1-xylylethene, 1,1-ditolylethene, 1-tolyl-1-xylylethene, 1,1-dixylylethene, 1- (ethyl Phenyl) -1-phenylethene, 1- (ethylphenyl) -1-tolylethene, 1- (ethylmethylphenyl) -1-phenylethene, 1- (ethylphenyl)-
1-xylylethene, 1- (ethylmethylphenyl)-
1-tolylethene, 1- (diethylphenyl) -1-phenylethene, 1,1-bis (ethylphenyl) ethene, 1-phenyl-1- (n-propylphenyl) ethene, 1-phenyl-1- (isopropylphenyl ) Ethene, 1- (n-propylphenyl) -1-tolylethene, 1- (isopropylphenyl) -1-tolylethene, 1- (methyl-n-propylphenyl) -1-phenylethene, 1- (methylisopropylphenyl) -1
-Phenylethene, 1- (n-butylphenyl) -1-
Phenylethene, 1- (isobutylphenyl) -1-phenylethene, 1- (sec-butylphenyl) -1-
Phenylethene, 1- (tert-butylphenyl)-
Hydrocarbon compounds having vinylidene group such as 1-phenylethene;

1,2-diphenylethene, 1-phenyl-2-tolylethene, 1-phenyl-2-xylylethene, 1,2-ditolylethene, 1-tolyl-2-xylylethene, 1,2-dixylylethene, 1- (ethyl Phenyl) -2-phenylethene, 1- (ethylphenyl) -2-tolylethene, 1- (ethylmethylphenyl) -2-phenylethene, 1- (ethylphenyl)-
2-xylylethene, 1- (ethylmethylphenyl)-
2-tolylethene, 1- (diethylphenyl) -2-phenylethene, 1,2-bis (ethylphenyl) ethene, 1-phenyl-2- (n-propylphenyl) ethene, 1-phenyl-2- (isopropylphenyl) ) Ethene, 1- (n-propylphenyl) -2-tolylethene, 1- (isopropylphenyl) -2-tolyleethene, 1- (methyl-n-propylphenyl) -2-phenylethene, 1- (methylisopropylphenyl) -2
-Phenylethene, 1- (n-butylphenyl) -2-
Phenylethene, 1- (isobutylphenyl) -2-phenylethene, 1- (sec-butylphenyl) -2-
Phenylethene, 1- (tert-butylphenyl)-
A hydrocarbon compound having an ethenylene group (vinylene group) such as 2-phenylethene;

1,2-diphenylpropene, 1-phenyl-2-tolylpropene, 1-phenyl-2-xylylpropene, 1,2-ditolylpropene, 1-tolyl-2
-Xylylpropene, 1- (ethylphenyl) -2-phenylpropene, 1- (ethylphenyl) -2-tolylpropene, 1- (ethylmethylphenyl) -2-phenylpropene, 1-phenyl-2- (n -Propylphenyl) propene, 1-phenyl-2- (isopropylphenyl) propene, 2-phenyl-1-tolylpropene,
2-phenyl-1-xylylpropene, 2-tolyl-1
-Xylylpropene, 2- (ethylphenyl) -1-phenylpropene, 2- (ethylphenyl) -1-tolylpropene, 2- (ethylmethylphenyl) -1-phenylpropene, 2-phenyl-1- (n Hydrocarbon compounds having a methylethenylene group such as -propylphenyl) propene and 2-phenyl-1- (isopropylphenyl) propene;

1,3-diphenylpropene, 1-phenyl-3-tolylpropene, 1-phenyl-3-xylylpropene, 1,3-ditolylpropene, 1-tolyl-3
-Xylylpropene, 1- (ethylphenyl) -3-phenylpropene, 1- (ethylphenyl) -3-tolylpropene, 1- (ethylmethylphenyl) -3-phenylpropene, 1-phenyl-3- (n -Propylphenyl) propene, 1-phenyl-3- (isopropylphenyl) propene, 3-phenyl-1-tolylpropene,
3-phenyl-1-xylylpropene, 3-tolyl-1
-Xylylpropene, 3- (ethylphenyl) -1-phenylpropene, 3- (ethylphenyl) -1-tolylpropene, 3- (ethylmethylphenyl) -1-phenylpropene, 3-phenyl-1- (n Hydrocarbon compounds having a propenylene group such as -propylphenyl) propene and 3-phenyl-1- (isopropylphenyl) propene;

2,3-diphenylpropene, 2-phenyl-3-tolylpropene, 2-phenyl-3-xylylpropene, 2,3-ditolylpropene, 2-tolyl-3
-Xylylpropene, 2- (ethylphenyl) -3-phenylpropene, 2- (ethylphenyl) -3-tolylpropene, 2- (ethylmethylphenyl) -3-phenylpropene, 2-phenyl-3- (n -Propylphenyl) propene, 2-phenyl-3- (isopropylphenyl) propene, 3-phenyl-2-tolylpropene,
3-phenyl-2-xylylpropene, 3-tolyl-2
-Xylylpropene, 3- (ethylphenyl) -2-phenylpropene, 3- (ethylphenyl) -2-tolylpropene, 3- (ethylmethylphenyl) -2-phenylpropene, 3-phenyl-2- (n Hydrocarbon compounds having a methylene ethylene group such as -propylphenyl) propene and 3-phenyl-2- (isopropylphenyl) propene;

1,3-diphenylbutene, 1-phenyl-3-tolylbutene, 1-phenyl-3-xylylbutene, 1- (ethylphenyl) -3-phenylbutene,
Hydrocarbon compounds having a 3-methylpropenylene group such as 1,3-ditolylbutene, 3-phenyl-1-tolylbutene, 3-phenyl-1-xylylbutene, and 3- (ethylphenyl) -1-phenylbutene;

Hydrocarbon compounds having a 3-ethylpropenylene group such as 1,3-diphenylpentene, 1-phenyl-3-tolylpentene and 3-phenyl-1-tolylpentene;

Hydrocarbon compounds having a 1-methyl-3-methylenepropenylene group such as 2,4-diphenylpentene, 2-phenyl-4-tolylpentene and 4-phenyl-2-tolylpentene;

2,4-diphenyl-2-pentene, 2-
Phenyl-4-tolyl-2-pentene, 4-phenyl-
Hydrocarbon compounds having a 1,3-dimethylpropenylene group such as 2-tolyl-2-pentene;

2-methyl-1,3-diphenylbutene,
Hydrocarbon compounds having a 2,3-dimethylpropenylene group such as 2-methyl-1-phenyl-3-tolylbutene and 2-methyl-3-phenyl-1-tolylbutene;

3-methyl-1,3-diphenylbutene,
Hydrocarbon compounds having a 3,3-dimethylpropenylene group such as 3-methyl-1-phenyl-3-tolylbutene and 3-methyl-3-phenyl-1-tolylbutene;

2,4-diphenylhexene, 2,4-diphenyl-2-hexene, 2-methyl-1,3-diphenylpentene, 4-methyl-2,4-diphenylpentene, 4-methyl-2,4- Diphenyl-2-pentene,
Hydrocarbon compounds having an alkenylene group having 6 carbon atoms such as 2,3-dimethyl-1,3-diphenylbutene; and the like.

Among the hydrocarbon compounds represented by the formula (1) according to the present invention, the total carbon number of R, R ¹ , R ² , R ³ and R ⁴ is 1 to 6, and R ¹ , R ² , R ³ and R ⁴
Is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group,
A group selected from sec-butyl groups, and at least two or more of them are hydrogen atoms are preferred. Most preferably, R is an alkylene group having 1 to 3 carbon atoms or an alkenylene group, the total carbon number of R, R ¹ , R ² , R ³ and R ⁴ is 1 to 6, and R ¹ and R ² , R ³ and R ⁴ are
Hydrogen atom, methyl group, ethyl group, isopropyl group, se
a group selected from c-butyl groups, at least two of which are hydrogen atoms, or R is an alkylene group having 4 to 6 carbon atoms or an alkenylene group, and R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms.

The most preferable hydrocarbon compound represented by the formula (1) according to the present invention is, for example, diphenylmethane, phenyltolylmethane, phenylxylylmethane, ditolylmethane or (ethylphenyl) phenylmethane. , (Ethylphenyl) tolylmethane, (ethylmethylphenyl) phenylmethane, (diethylphenyl) phenylmethane, bis (ethylphenyl) methane, phenyl (isopropylphenyl) methane, (isopropylphenyl) tolylmethane, (methylisopropylphenyl) phenylmethane, (Ethylisopropylphenyl) phenylmethane, (ethylphenyl) (isopropylphenyl) methane, (sec-butylphenyl) phenylmethane, (sec-butylmethylphenyl) phenylmethane (Sec-butylphenyl) hydrocarbon compound having a methylene group such Torirumetan;

1,1-diphenylethane, 1-phenyl-1-tolylethane, 1-phenyl-1-xylylethane, 1,1-ditolylethane, 1- (ethylphenyl)
-1-phenylethane, 1- (ethylphenyl) -1-
Trilyethane, 1- (ethylmethylphenyl) -1-phenylethane, 1- (diethylphenyl) -1-phenylethane, 1,1-bis (ethylphenyl) ethane, 1
-Phenyl-1- (isopropylphenyl) ethane, 1
-(Isopropylphenyl) -1-tolylethane, 1-
Hydrocarbon compounds having a methylmethylene group (ethylidene group) such as (methylisopropylphenyl) -1-phenylethane and 1- (sec-butylphenyl) -1-phenylethane;

1,2-diphenylethane, 1-phenyl-2-tolylethane, 1-phenyl-2-xylylethane, 1,2-ditolylethane, 1- (ethylphenyl)
-2-phenylethane, 1- (ethylphenyl) -2-
Trilyethane, 1- (ethylmethylphenyl) -2-phenylethane, 1- (diethylphenyl) -2-phenylethane, 1,2-bis (ethylphenyl) ethane, 1
-Phenyl-2- (isopropylphenyl) ethane, 1
-(Isopropylphenyl) -2-tolylethane, 1-
A hydrocarbon compound having an ethylene group such as (methylisopropylphenyl) -2-phenylethane, 1- (sec-butylphenyl) -2-phenylethane;

1,1-diphenylpropane, 1-phenyl-1-tolylpropane, 1-phenyl-1-xylylpropane, 1,1-ditolylpropane, 1- (ethylphenyl) -1-phenylpropane, 1 A hydrocarbon compound having an ethylmethylene group (propylidene group) such as-(ethylphenyl) -1-tolylpropane, 1- (ethylmethylphenyl) -1-phenylpropane, 1-phenyl-1- (isopropylphenyl) propane;

2,2-diphenylpropane, 2-phenyl-2-tolylpropane, 2-phenyl-2-xylylpropane, 2,2-ditolylpropane, 2- (ethylphenyl) -2-phenylpropane, 2 Hydrocarbon compound having dimethylmethylene group (isopropylidene group) such as-(ethylphenyl) -2-tolylpropane, 2- (ethylmethylphenyl) -2-phenylpropane, 2-phenyl-2- (isopropylphenyl) propane ;

A hydrocarbon compound having an alkenylene group having 4 carbon atoms such as 1,3-diphenylbutane;

Hydrocarbons having an alkylene group having 5 carbon atoms, such as 1,3-diphenylpentane, 2,4-diphenylpentane, 2-methyl-1,3-diphenylbutane and 3-methyl-1,3-diphenylbutane. Compound;

2,4-diphenylhexane, 2-methyl-1,3-diphenylpentane, 2-methyl-2,4-
Hydrocarbon compounds having an alkylene group having 6 carbon atoms, such as diphenylpentane and 2,3-dimethyl-1,3-diphenylbutane;

1,1-diphenylethene, 1-phenyl-1-tolylethene, 1-phenyl-1-xylylethene, 1,1-ditolylethene, 1- (ethylphenyl)
-1-Phenylethene, 1- (ethylphenyl) -1-
Trilylethene, 1- (ethylmethylphenyl) -1-phenylethene, 1- (diethylphenyl) -1-phenylethene, 1,1-bis (ethylphenyl) ethene, 1
-Phenyl-1- (isopropylphenyl) ethene, 1
-(Isopropylphenyl) -1-tolylethene, 1-
A hydrocarbon compound having a vinylidene group such as (methylisopropylphenyl) -1-phenylethene and 1- (sec-butylphenyl) -1-phenylethene;

1,2-diphenylethene, 1-phenyl-2-tolylethene, 1-phenyl-2-xylylethene, 1,2-ditolylethene, 1- (ethylphenyl)
-2-phenylethene, 1- (ethylphenyl) -2-
Trilylethene, 1- (ethylmethylphenyl) -2-phenylethene, 1- (diethylphenyl) -2-phenylethene, 1,2-bis (ethylphenyl) ethene, 1
-Phenyl-2- (isopropylphenyl) ethene, 1
-(Isopropylphenyl) -2-tolylethene, 1-
Hydrocarbon compounds having an ethenylene group (vinylene group) such as (methylisopropylphenyl) -2-phenylethene and 1- (sec-butylphenyl) -2-phenylethene;

1,2-diphenylpropene, 1-phenyl-2-tolylpropene, 1-phenyl-2-xylylpropene, 1,2-ditolylpropene, 1- (ethylphenyl) -2-phenylpropene, 1 -(Ethylphenyl) -2-tolylpropene, 1- (ethylmethylphenyl) -2-phenylpropene, 1-phenyl-2- (isopropylphenyl) propene, 2-phenyl-1-tolylpropene, 2-phenyl-1 -Xylyl propene,
2- (ethylphenyl) -1-phenylpropene, 2-
A hydrocarbon compound having a methylethenylene group, such as (ethylphenyl) -1-tolylpropene, 2- (ethylmethylphenyl) -1-phenylpropene, 2-phenyl-1- (isopropylphenyl) propene;

1,3-diphenylpropene, 1-phenyl-3-tolylpropene, 1-phenyl-3-xylylpropene, 1,3-ditolylpropene, 1- (ethylphenyl) -3-phenylpropene, 1 -(Ethylphenyl) -3-tolylpropene, 1- (ethylmethylphenyl) -3-phenylpropene, 1-phenyl-3- (isopropylphenyl) propene, 3-phenyl-1-tolylpropene, 3-phenyl-1 -Xylyl propene,
3- (ethylphenyl) -1-phenylpropene, 3-
Hydrocarbon compounds having a propenylene group such as (ethylphenyl) -1-tolylpropene, 3- (ethylmethylphenyl) -1-phenylpropene, 3-phenyl-1- (isopropylphenyl) propene;

2,3-diphenylpropene, 2-phenyl-3-tolylpropene, 2-phenyl-3-xylylpropene, 2,3-ditolylpropene, 2- (ethylphenyl) -3-phenylpropene, 2 -(Ethylphenyl) -3-tolylpropene, 2- (ethylmethylphenyl) -3-phenylpropene, 2-phenyl-3- (isopropylphenyl) propene, 3-phenyl-2-tolylpropene, 3-phenyl-2 -Xylyl propene,
3- (ethylphenyl) -2-phenylpropene, 3-
Hydrocarbon compounds having a methylene ethylene group such as (ethylphenyl) -2-tolylpropene, 3- (ethylmethylphenyl) -2-phenylpropene, 3-phenyl-2- (isopropylphenyl) propene;

A hydrocarbon compound having an alkenylene group having 4 carbon atoms such as 1,3-diphenylbutene;

1,3-diphenylpentene, 2,4-diphenylpentene, 2,4-diphenyl-2-pentene, 2-methyl-1,3-diphenylbutene, 3-methyl-1,3-diphenylbutene, etc. A hydrocarbon compound having an alkenylene group having 5 carbon atoms;

2,4-diphenylhexene, 2,4-diphenyl-2-hexene, 2-methyl-1,3-diphenylpentene, 4-methyl-2,4-diphenylpentene, 4-methyl-2,4- Diphenyl-2-pentene,
A hydrocarbon compound having an alkenylene group having 6 carbon atoms such as 2,3-dimethyl-1,3-diphenylbutene; and the like.

The method for producing the hydrocarbon compound according to the present invention is arbitrary and can be produced by various known methods. Some examples are shown below.

The hydrocarbon compound according to the present invention can be obtained by adding styrenes such as styrene, α-, β-methylstyrene and ethylstyrene to alkylbenzene in the presence of an acid catalyst. As the acid catalyst, there can be used mineral acids such as sulfuric acid and phosphoric acid, solid acid substances such as acid clay and activated clay, and Friedel-Crafts catalyst which is a metal halide.

The hydrocarbon compound according to the present invention can also be produced by the polymerization reaction of the above styrenes in the presence of a suitable acid catalyst. At this time, a single styrene compound may be used, or two or more styrene compounds may be used for copolymerization. Acid catalysts include mineral acids such as sulfuric acid and phosphoric acid,
Solid acid substances such as acid clay and activated clay, and Friedel-Crafts catalyst which is a metal halide can be used. Usually, the hydrocarbon compound obtained by this method is a compound in which two benzene rings are bonded by an alkenylene group, but it may be used as it is in the present invention, and the hydrogenation of the alkenylene group may be carried out in the presence of a suitable catalyst. You may use the compound which processed and converted the alkenylene group into the alkylene group.

Regarding the alkylation of aromatic compounds, the Friedel-Crafts reaction of chloride is well known, but the hydrocarbon compound according to the present invention can also be produced by this method. For example, a hydrocarbon compound according to the present invention can be obtained by reacting an alkylbenzene having a chlorinated side chain alkyl group with benzene or an alkylbenzene in the presence of a suitable Friedel-Crafts catalyst such as a metal halide. In addition, a method of coupling a dihalogenated alkane with benzene or an alkylbenzene in the presence of a suitable Friedel-Crafts catalyst such as a metal halide is also included.

The hydrocarbon compound according to the present invention has R
It may be produced by the above method using alkylbenzene having an alkyl group represented by ^{1 to} R ⁴ , or the alkyl group may be added to the hydrocarbon compound produced by the above method by various methods. Even manufactured.

The hydrocarbon compound according to the present invention may be not only a compound having a single structure but also a mixture of compounds having different structures as long as it satisfies the general formula (1).

The viscosity of the above compound contained in the refrigerator oil of the present invention is not particularly limited, but the preferred kinematic viscosity is 40 ° C.
² to 30 mm ² / s, more preferably 2.3 to 20
mm ² / s, 3 to 1 for improving wear resistance
It is preferably 5 mm ² / s.

The refrigerator oil of the present invention has the general formula (1)
Although the hydrocarbon compound represented by may be used alone, in order to adjust the viscosity and the like when used as a refrigerating machine oil, other aromatic hydrocarbon compounds may be added, if necessary, within the above viscosity range. The content of the refrigerating machine oil may be 20 wt% or less based on the total amount of refrigerating machine oil so as not to exceed the limit. Specific examples of such an aromatic hydrocarbon compound include:

[0081]

[Chemical 10]

[0082]

[Chemical 11]

[0083]

[Chemical 12]

[0084]

[Chemical 13] [In the above formulas (2) to (5), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and may be the same or different in the same molecule] and the like. In addition, as a matter of course, these aromatic hydrocarbon compounds may be contained as a by-product in the production of the hydrocarbon compound of the formula (1) according to the present invention, or the aromatic hydrocarbon compound according to the present invention ( It may be used separately added to the hydrocarbon compound of 1).

The refrigerating machine oil according to the present invention contains the above-mentioned compound, and HF is contained even in a state where no additive is added.
It can be suitably used as a refrigerating machine oil for C refrigerant,
It is also possible to use it in a form in which various additives are blended if necessary.

In order to further improve the wear resistance and load bearing capacity of the refrigerating machine oil of the present invention, phosphoric acid ester, acidic phosphoric acid ester, amine salt of acidic phosphoric acid ester, chlorinated phosphoric acid ester and phosphorous acid ester. At least one phosphorus compound selected from the group consisting of can be blended.

These phosphorus compounds are esters of phosphoric acid or phosphorous acid with alkanols or polyether type alcohols or derivatives thereof. Specifically, for example,
As the phosphoric acid ester, tributyl phosphate, tripentyl phosphate, trihexyl phosphate,
Triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate, tritridecyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, tri Octadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate and the like can be mentioned. Examples of the acidic phosphate ester include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, and monododecyl. Acid Phosphate, Monotridecyl Acid Phosphate, Monotetradecyl Acid Phosphate, Monopentadecyl Acid Phosphate, Monohexadecyl Acid Phosphate, Monoheptadecyl Acid Phosphate, Monooctadecyl Acid Phosphate, Monooleyl Acid Phosphate, Dibutyl Acid Phosphate, Dipentyl Acid Phosphate , Dihexyl reed Dohosufeto, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid phosphate, diundecyl acid phosphate, didodecyl acid phosphate,
Examples thereof include ditridecyl acid phosphate, ditetradecyl acid phosphate, dipentadecyl acid phosphate, dihexadecyl acid phosphate, diheptadecyl acid phosphate, dioctadecyl acid phosphate, dioleyl acid phosphate and the like. As the amine salt of acidic phosphoric acid ester,
The acidic phosphoric acid ester methylamine, ethylamine, propylamine, butylamine, pentylamine,
Hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine,
Diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine,
Examples thereof include salts with amines such as triheptylamine and trioctylamine. As the chlorinated phosphate ester,
Examples thereof include tris-dichloropropyl phosphate, tris-chloroethyl phosphate, tris-chlorophenyl phosphate, polyoxyalkylene-bis [di (chloroalkyl)] phosphate and the like. Examples of the phosphite include dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite, diundecyl phosphite, didodecyl phosphite, dioleyl. Phosphite, diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl phosphite Examples include phyto, tridodecyl phosphite, trioleyl phosphite, triphenyl phosphite, tricresyl phosphite, and the like. Also, a mixture of these can be used.

When these phosphorus compounds are blended with the refrigerating machine oil of the present invention, the blending amount is arbitrary, but usually the refrigerating machine oil total amount standard (the hydrocarbon compound according to the present invention, if necessary, the general formula (2 )-(5) aromatic compound, and the total amount of all compounding additives) based on the content of 0.01-5.
It is desirable to add an amount of 0% by weight, more preferably 0.02 to 3.0% by weight.

Further, in the refrigerating machine oil of the present invention, in order to further improve its stability, phenylglycidyl ether type epoxy compound alkyl glycidyl ether type epoxy compound glycidyl ester type epoxy compound allyloxirane compound alkyloxirane compound alicyclic epoxy compound Epoxidized fatty acid monoester At least one epoxy compound selected from the group consisting of epoxidized vegetable oils can be blended.

Specific examples of the phenylglycidyl ether type epoxy compound include phenylglycidyl ether and alkylphenylglycidyl ether. The alkylphenyl glycidyl ether as used herein has 1 to 3 alkyl groups having 1 to 13 carbon atoms, and particularly has 1 alkyl group having 4 to 10 carbon atoms, for example, n-butylphenyl glycidyl ether. , Isobutylphenyl glycidyl ether, sec
-Butyl phenyl glycidyl ether, tert-butyl phenyl glycidyl ether, pentyl phenyl glycidyl ether, hexyl phenyl glycidyl ether, heptyl phenyl glycidyl ether, octyl phenyl glycidyl ether, nonyl phenyl glycidyl ether, decyl phenyl glycidyl ether, etc. can be illustrated.

Specific examples of the alkyl glycidyl ether type epoxy compound include decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl glycol diester. Glycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether,
Examples thereof include 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol monoglycidyl ether, and polyalkylene glycol diglycidyl ether.

Specific examples of the glycidyl ester type epoxy compound include phenyl glycidyl ester, alkyl glycidyl ester, alkenyl glycidyl ester, and the like. Preferred are glycidyl 2,2-dimethyloctanoate, glycidyl benzoate, Examples thereof include glycidyl acrylate and glycidyl methacrylate.

Specific examples of allyl oxirane include 1,2-epoxystyrene and alkyl-1,2-epoxystyrene.

Specific examples of the alkyl oxirane include 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1, 2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-
Epoxy pentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,1,2-epoxyoctadecane, 2-epoxynonadecane, 1,2-
Epoxy icosane etc. can be illustrated.

Specific examples of the alicyclic epoxy compound include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis ( 3,4-epoxycyclohexylmethyl)
Adipate, exo-2,3-epoxy norbornane,
Bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (7-oxabicyclo [4.
1.0] Hept-3-yl) -spiro (1,3-dioxane-5,3 ′-[7] oxabicyclo [4.1.0]
Heptane, 4- (1'-methylepoxyethyl) -1,
2-epoxy-2-methylcyclohexane, 4-epoxyethyl-1,2-epoxycyclohexane and the like can be exemplified.

As the epoxidized fatty acid monoester, specifically, epoxidized fatty acid having 12 to 20 carbon atoms and alcohol or phenol having 1 to 8 carbon atoms,
Examples thereof include esters with alkylphenols. In particular, butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl and butylphenyl esters of epoxystearic acid are preferably used.

Specific examples of epoxidized vegetable oils include epoxy compounds of vegetable oils such as soybean oil, linseed oil and cottonseed oil.

Preferred among these epoxy compounds are phenyl glycidyl ether type epoxy compounds, phenyl glycidyl ester type epoxy compounds and epoxidized fatty acid monoesters. Among them, phenyl glycidyl ether type epoxy compounds and phenyl glycidyl ester type epoxy compounds are more preferable,
Particularly preferred are phenyl glycidyl ether, butyl phenyl glycidyl ether or alkyl glycidyl esters or mixtures thereof.

When blending these epoxy compounds with the refrigerating machine oil of the present invention, the blending amount is optional,
The content of the refrigerating machine oil is 0.1 to 0.1 (based on the total amount of the hydrocarbon compound according to the present invention, the aromatic compounds of the general formulas (2) to (5), and all the compounding additives, if necessary).
It is desirable to add such an amount that the amount is 5.0% by weight, more preferably 0.2 to 2.0% by weight.

It is needless to say that two or more kinds of the above phosphorus compound and epoxy compound may be used in combination.

Further, with respect to the refrigerating machine oil in the present invention,
In order to further enhance its performance, conventionally known refrigerating machine oil additives, such as di-tert-butyl-p, are added as needed.
-Cresol, phenol-based compounds such as bisphenol A, phenyl-α-naphthylamine, amine-based antioxidants such as N, N-di (2-naphthyl) -p-phenylenediamine, antiwear agents such as zinc dithiophosphate, Extreme pressure agents such as chlorinated paraffin and sulfur compounds, oily agents such as fatty acids,
Defoaming agents such as silicones, metal deactivators such as benzotriazole, viscosity index improvers, pour point depressants, detergent dispersants, and other additives may be used alone or in combination. . The total blending amount of these additives is usually the total amount of the refrigerating machine oil (the hydrocarbon compound according to the present invention, the aromatic compounds of the general formulas (2) to (5) as necessary, and all the blending additives). The amount is 10% by weight or less, preferably 5% by weight or less.

Examples of the hydrofluorocarbon refrigerant used in the refrigerator using the refrigerator oil (lubricating oil for refrigerator) of the present invention include hydrofluorocarbons having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms. Specifically, for example, difluoromethane (HFC-32), trifluoromethane (HFC-23), pentafluoroethane (HFC-1).
25), 1,1,2,2-tetrafluoroethane (HF
HFCs such as C-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1-trifluoroethane (HFC-143a), and 1,1-difluoroethane (HFC-152a) Or these two
Examples include a mixture of two or more species. These refrigerants are appropriately selected according to the use and the required performance, and for example, HFC-
134a alone; HFC-125 alone; HFC-134a
/ HFC-32 = 60-80% by weight / 40-20% by weight
A mixture of HFC-32 / HFC-125 = 40-70.
% / 60-30% by weight mixture; HFC-125 /
HFC-143a = 40-60 wt% / 60-40 wt% mixture; HFC-134a / HFC-32 / HFC
-125 = 60 wt% / 30 wt% / 10 wt% mixture; HFC-134a / HFC-32 / HFC-125
= 40-70 wt% / 15-35 wt% / 5-40 wt% mixture; HFC-125 / HFC-134a / HF
C-143a = 35 to 55% by weight / 1 to 15% by weight / 4
A preferable example is a mixture of 0 to 60% by weight.

The refrigerator oil of the present invention is usually present in a refrigerator in the form of a fluid composition for refrigerator mixed with the above-mentioned hydrofluorocarbon. The mixing ratio of the refrigerating machine oil and the refrigerant in the fluid composition for a refrigerating machine of the present invention is arbitrary, but usually 1 to 500 parts by weight of the refrigerating machine oil, preferably 2 to 400 parts by weight with respect to 100 parts by weight of the refrigerant.
Parts by weight.

Since the refrigerating machine oil of the present invention is compatible with the HFC refrigerant and is excellent in various required properties such as electric characteristics, hydrolysis stability, lubricity and hygroscopicity, hydrofluorocarbon is used as a refrigerant. It is particularly preferably used for refrigeration equipment (cooling system) such as an air conditioner or a refrigerator having a reciprocating or rotating hermetic compressor. In addition, the refrigerating machine oil of the present invention can be used as a refrigerating machine (cooling system) such as a vehicle air conditioner or a dehumidifier that uses hydrofluorocarbon as a refrigerant, a freezer, a refrigerating / freezing warehouse, a vending machine, a showcase, a cooling device such as a chemical plant. It is preferably used. further,
The refrigerating machine oil of the present invention is also preferably used for a refrigerating machine (cooling system) having a centrifugal compressor using hydrofluorocarbon as a refrigerant.

The lubrication method of the present invention is characterized in that various cooling systems using hydrofluorocarbon as a refrigerant are lubricated by using the refrigerating machine oil of the present invention as a lubricating oil. The specific conditions such as the specific lubricating oil supply amount are not particularly limited, and are appropriately selected according to the target cooling system.

The refrigerating machine oil of the present invention is usually circulated in the refrigerator in the form of a fluid composition for a refrigerating machine mixed with hydrofluorocarbon as described above, and the refrigerating machine of the present invention is The present invention is characterized by using the fluid composition for a refrigerator of the invention as a circulating fluid. As described above, the refrigerating machine of the present invention is not particularly limited except that the fluid composition for a refrigerating machine of the present invention is used as a circulating fluid, and its specific configuration is the same as that of the conventional various refrigerating machines described above. May be Since the refrigerating machine oil of the present invention is compatible with the HFC refrigerant, the refrigerating machine of the present invention does not require any special device for dealing with the separation of the refrigerant and the lubricating oil.

[0107]

EXAMPLES The contents of the present invention will be described more specifically below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The refrigerating machine oil (sample oil) and their kinematic viscosity used in Examples 1-6 and Comparative Examples 1-4 Examples 1-6 and Comparative Examples 1-4 are shown in Table 1.

[0108]

[Table 1] Each of the refrigerating machine oils of the above Examples and Comparative Examples was evaluated for compatibility with the refrigerant (HFC-134a), electrical characteristics (volume resistivity), hydrolysis stability, and lubricity. The obtained results are shown in Table 2. Each test was carried out by the following method.

(1) Compatibility (Two-layer separation temperature) In accordance with JIS-K-2211 4.12, the refrigerant (H
FC-134a) was mixed with 48.5 g of each sample oil of Examples and Comparative Examples (oil content 3%), and the refrigerant and the sample oil were mutually dissolved at low temperature or separated or clouded. By observing whether or not the refrigerant and the sample oil are mutually dissolved, the lower limit value (low temperature side two-layer separation temperature) was measured. In addition, 2.5% of each sample oil is added to 47.5 g of refrigerant.
The low temperature side two-layer separation temperature was similarly measured for the composition containing 5 g (oil content 5%).

(2) Electrical Characteristics (Volume Resistivity) The volume resistivity of each sample oil at 25 ° C. was measured according to JIS-C-2101.

(3) Hydrolysis stability 150 g of each sample oil and 0.15 g of water were put in a 200 ml heat-resistant glass test tube, and 10 copper wires, iron wires and aluminum wires (1 mmφ × 100 mm) were used as deterioration promoting catalysts. After the charging, each test tube was maintained at 175 ° C. for 168 hours in a stainless steel autoclave under N ₂ atmosphere to heat and deteriorate each sample oil. After this test, the total acid number of each sample oil was measured. (4) Wear resistance (wear reduction) Using a rolling piston type compressor, 70 g of each refrigerating machine oil and refrigerant (HFC-13) of the examples and comparative examples.
4a) 50 g is filled in this compressor, and the discharge pressure is 16
The surface roughness of the sliding surface of the vane of the compressor after the test was measured for 1000 hours under the conditions of kgf / cm ² G, suction pressure 0 kgf / cm ² G, rotation speed 3000 rpm, and test temperature 160 ° C.

[0112]

[Table 2] As is clear from the results of Examples and Comparative Examples shown in Table 2, the refrigerating machine oils of Examples 1 to 6 of the present invention have good compatibility with the HFC refrigerant, and further have electrical characteristics, hydrolysis stability and lubrication. It was excellent in both properties (wear resistance).

On the other hand, the refrigerating machine oils (conventional hydrocarbon oils) of Comparative Examples 1 and 2 which are alkylbenzenes.
Was excellent in electrical characteristics, hydrolysis stability and lubricity, but had almost no compatibility with the HFC refrigerant. In addition, the refrigerating machine oil (oxygen-containing oil) of Comparative Example 3, which is a tetraester of pentaerythritol and 2-ethylhexanoic acid, is excellent in compatibility with HFC refrigerant and electrical characteristics, but has hydrolysis stability and lubricity. It was inferior. Furthermore, the refrigerating machine oil (oxygen-containing oil) of Comparative Example 4, which is polypropylene glycol monobutyl ether, is HFC.
Although it has good compatibility with and hydrolytic stability, it was inferior in electrical properties and lubricity, and had problems in practical use.

[0114]

As described above, the refrigerating machine oil of the present invention containing a hydrocarbon compound having a specific structure is HF.
It is a refrigerating machine oil that is compatible with the C refrigerant and that satisfies all required performances such as hydrolysis stability, electric insulation and lubricity.

Therefore, the refrigerating machine oil of the present invention is very useful especially as a refrigerating machine oil to be used with a hydrofluorocarbon refrigerant (HFC refrigerant). By mixing the refrigerating machine oil of the present invention with the HFC refrigerant, It is possible to obtain the fluid composition for a refrigerator of the present invention which is stably compatible with each other and satisfies all the required performances such as hydrolysis stability, electric insulation and lubricity.

Further, when the refrigerating machine oil of the present invention is used, there is no fear of electric leakage even in a hermetic compressor having a structure in which the oil and the electrode come into contact with each other, and further, corrosion by an acid generated by hydrolysis of the lubricating oil is prevented. Inconvenience is also sufficiently prevented. Further, the refrigerating machine oil of the present invention can be used for a target refrigerating machine without any special measures, and furthermore, abrasion in the refrigerating machine is sufficiently prevented.

Therefore, by using the refrigerating machine oil of the present invention as a lubricating oil in a refrigerating machine (cooling system) using hydrofluorocarbon as a refrigerant, wear, electric leakage, acid corrosion, etc. in the cooling system can be prevented. The lubrication method for the cooling system of the present invention is capable of stably maintaining the operation of the cooling system for a long period of time. Further, by using the fluid composition for a refrigerator of the present invention as a circulating fluid in a refrigerating machine using hydrofluorocarbon as a refrigerant, wear in the refrigerating machine, electric leakage, corrosion for a long period of time without causing acid corrosion, etc. The refrigeration equipment of the present invention can be obtained which can be stably operated over a long period of time and which does not require any special device for dealing with the separation of the refrigerant and the lubricating oil.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-57-177096 (JP, A) JP-A-7-145100 (JP, A) UK patent application publication 2012811 (GB, A) (58) Research fields (Int.Cl. ⁷ , DB name) C10M 105/06 C10N 40:30 C09K 5/04 F25B 1/00

Claims (4)

(57) [Claims] 1. A compound represented by the general formula (1): [In the above formula (1), R represents an alkylene group having 1 to 8 carbon atoms or an alkenylene group, and R ¹ , R ² , R ³ and R
⁴ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R, R ¹ , R
² , the total carbon number of R ³ and R ⁴ is 1 to 8], a refrigerating machine oil for a hydrofluorocarbon refrigerant. 2. An [I] hydrofluorocarbon refrigerant,
And [II] General formula (1) [In the above formula (1), R represents an alkylene group having 1 to 8 carbon atoms or an alkenylene group, and R ¹ , R ² , R ³ and R
⁴ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R, R ¹ , R
² , the total carbon number of R ³ and R ⁴ is 1 to 8], a fluid composition for a refrigerator containing a hydrocarbon compound. 3. An [I] hydrofluorocarbon refrigerant,
And [II] General formula (1) [In the above formula (1), R represents an alkylene group having 1 to 8 carbon atoms or an alkenylene group, and R ¹ , R ² , R ³ and R
⁴ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R, R ¹ , R
² , the total number of carbon atoms of R ³ and R ⁴ is 1 to 8], a refrigerating machine using a fluid composition for a refrigerator containing a hydrocarbon compound as a circulating fluid. 4. A compound represented by the general formula (1): [In the above formula (1), R represents an alkylene group having 1 to 8 carbon atoms or an alkenylene group, and R ¹ , R ² , R ³ and R
⁴ may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R, R ¹ , R
² , the total number of carbon atoms of R ³ and R ⁴ is 1 to 8], a refrigerating machine oil containing a hydrocarbon compound represented by Lubrication method.