JPH09118890A - Synthetic lubricating oil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a synthetic lubricating oil, comprising a compound of a specific structure, excellent in compatibility with refrigerants such as a hydrofluorocarbon, hydrolytic stability, lubricity or abrasion resistance and useful as a refrigerator oil. SOLUTION: This synthetic lubricating oil comprises a compound of the formula R<1> and R<2> are each H or a 1-10C hydrocarbon group; R<3> and R<4> are each a 2-4C alkylene; R<5> is a 1-10C alkylene or alkenylene; R<6> to R<9> are each H or a 1-10C alkyl; (m) and (n) are each 0-10; 1<=[(m)+(n)]<=15} (e.g. a dimethyl etherified substance of a compound prepared by adding 2mol propylene oxide to 1mol bisphenol A) in an amount of 50-100wt.%, especially 70-100wt.% based on the total amount of the synthetic lubricating oil.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a synthetic lubricating oil,
Specifically, it relates to a synthetic lubricating oil which is particularly useful as a refrigerating machine oil containing a compound having a specific structure.

[0001]

2. Description of the Related Art Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), which have been used as refrigerants for refrigeration equipment, are now subject to regulation due to the problem of ozone depletion in recent years, and chlorine is contained instead of them. Not Hydrofluorocarbon (HF
C) 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. Although hydrocarbon oils such as mineral oils and alkylbenzenes have been used as refrigerating machine oils for CFCs and HCFCs, 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, 1-256594, 1-255993, 1-259094, 1-259095.
JP-A No. 2-274191 and JP-A 2-43290.
JP-A No. 2-55791, No. 2-84491, etc.
-505602, JP-A-3-88892,
No. 2-128991, No. 3-128992, No. 3-200895, No. 3-227397, No. 4-20597, No. 4-72390, No. 4-218592. It is described in Japanese Patent Publication No. 4-249593 and the like.

However, PAG has high hygroscopicity and poor electrical insulation. Ester oil may hydrolyze due to its structure to generate an acid, and various disadvantages are expected to occur. In addition, these oils have a serious problem that they are inferior in lubricity as compared with hydrocarbon oil / CFC or hydrocarbon oil / HCFC systems.

On the other hand, Japanese Patent Laid-Open No. 5-157379 discloses HFC-134 using refrigerating machine oil that is incompatible with the refrigerant.
a Refrigerant refrigeration system is described, and as this incompatible oil, hydrocarbon oil such as mineral oil, poly α-olefin and alkylbenzene having excellent electric insulation and low hygroscopicity, and chemically stable Listed. However, when alkylbenzene is used as a refrigerating machine oil for HFC-134a, the two are incompatible with each other, and therefore, a special device on the system side is required. As described above, the oxygen-containing oil and the hydrocarbon oil have contradictory performances, and at the present time, a refrigerating machine oil for an HFC refrigerant having both features has not been developed.

[0006]

SUMMARY OF THE INVENTION The present invention is based on the HFC-1.
It is an object of the present invention to provide a synthetic lubricating oil having excellent compatibility with various refrigerants such as 34a and satisfying various required performances such as hydrolysis stability and lubricity.

[0007]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to develop a synthetic lubricating oil having both compatibility and various other properties, the compound having a specific structure was found to be HF.
They have found that they have excellent compatibility with refrigerants such as C-134a and that they also satisfy other required performances, and have completed the present invention.

That is, the present invention has the general formula (1)

Embedded image (In the above formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; R ³ and R ⁴
Each independently represents an alkylene group having 2 to 4 carbon atoms;
R ⁵ represents an alkylene group having 1 to 10 carbon atoms or an alkenylene group; R ^{6 to} R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; m and n each independently represent 0 to 10 And an integer of m + n of 1 to 15)).

[0009]

DETAILED DESCRIPTION OF THE INVENTION The contents of the present invention will be described in detail below. The synthetic lubricating oil of the present invention has the general formula (1)

Embedded image It contains a compound represented by.

R ¹ and R ² of the compound of the above formula (1) are
Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. As the hydrocarbon group represented by R ¹ and R ² ,
Specifically, for example, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an alkylcycloalkyl group having 6 to 10 carbon atoms, and an alkyl cycloalkyl group having 6 to 10 carbon atoms. Examples thereof include an aryl group, an alkylaryl group having 7 to 10 carbon atoms, and an arylalkyl group having 7 to 10 carbon atoms.

Specific examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a linear or branched butyl group,
A straight-chain or branched pentyl group, a straight-chain or branched hexyl group, a straight-chain or branched heptyl group, a straight-chain or branched octyl group, a straight-chain or branched nonyl group, A straight-chain or branched decyl group and the like can be mentioned.

As the alkenyl group having 2 to 10 carbon atoms,
Specifically, for example, an ethenyl group, a linear or branched propenyl group, a linear or branched butenyl group, a linear or branched pentenyl group, a linear or branched hexenyl group, a direct Examples thereof include a linear or branched heptenyl group, a linear or branched octenyl group, a linear or branched nonenyl group, and a linear or branched decenyl group. As the cycloalkyl group having 5 to 7 carbon atoms,
Specific examples include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like.

Specific examples of the alkylcycloalkyl group having 6 to 10 carbon atoms include methylcyclopentyl group (including all substituted isomers), dimethylcyclopentyl group (including all substituted isomers), ethylcyclopentyl group. Group (including all substitution isomers), methylethylcyclopentyl group (including all substitution isomers), diethylcyclopentyl group (including all substitution isomers), methylcyclohexyl group (including all substitution isomers) , Dimethylcyclohexyl group (including all substituted isomers), ethylcyclohexyl group (including all substituted isomers), methylethylcyclohexyl group (including all substituted isomers), diethylcyclohexyl group (all substituted isomers) including),
A methylcycloheptyl group (including all substituted isomers),
Examples thereof include a dimethylcycloheptyl group (including all substituted isomers), an ethylcycloheptyl group (including all substituted isomers), a methylethylcycloheptyl group (including all substituted isomers), and the like.

Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl group and naphthyl group. Specific examples of the alkylaryl group having 7 to 10 carbon atoms include a tolyl group (including all substitution isomers), a xylyl group (including all substitution isomers), an ethylphenyl group (all substitution isomers). ), Straight-chain or branched propylphenyl groups (including all substituted isomers),
A straight-chain or branched butylphenyl group (including all substituted isomers) and the like can be mentioned.

Specific examples of the arylalkyl group having 7 to 10 carbon atoms include benzyl group, 1-phenylethyl group, 2-phenylethyl group (phenethyl group) and phenylpropyl group (isomers of propyl group). Included), phenylbutyl group (including butyl group isomers), and the like.

Among them, R ¹ and R ² have excellent compatibility with the refrigerant when the lubricating oil of the present invention is used as a refrigerating machine oil.
Is preferably a hydrocarbon group, more preferably having 1 to 6 carbon atoms.
Is an alkyl group. Furthermore, most preferably 1 carbon atom
~ 3 alkyl groups.

In the above formula (1), R ³ and R ⁴ each independently represent an alkylene group having 2 to 4 carbon atoms. Specific examples of the alkylene group represented by R ³ and R ⁴ include C ² alkylene groups such as methylmethylene group (ethylidene group) and ethylene group; ethylmethylene group (propylidene group), dimethylmethylene group (isopropylidene group). Ridene group), methylethylene group (propylene group), trimethylene group and other alkylene groups having 3 carbon atoms; n-propylmethylene group (butylidene group), isopropylmethylene group (isobutylidene group), ethylmethylmethylene group, ethylethylene group ( Butylene group), 1,1-dimethylethylene group, 1,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, alkylene group having 4 carbon atoms such as tetramethylene group, and the like, Among these, ethylene group, propylene group and butylene group are preferable.

Further, as a matter of course, as the compound represented by the formula (1) used in the present invention, as the (R ³ O) group and the (OR ⁴ ) group, only one kind of oxyalkylene group is present in the same molecule. Or may have two or more different oxyalkylene groups. Furthermore, in the case of having two or more different oxyalkylene groups, the oxyalkylene groups may be randomly copolymerized or block copolymerized.

In the above formula (1), R ⁵ has 1 to 1 carbon atoms.
10 represents an alkylene group or an alkenylene group. Specific examples of R ⁵ include a methylene group;
C2 alkylene groups such as methylmethylene group (ethylidene group) and ethylene group; ethylmethylene group (propylidene group), dimethylmethylene group (isopropylidene group),
C3 alkylene groups such as methylethylene group (propylene group) and trimethylene group; n-propylmethylene group (butylidene group), isopropylmethylene group (isobutylidene group), ethylmethylmethylene group, ethylethylene group, 1,1- C4 alkylene group such as dimethylethylene group, 1,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, tetramethylene group; n-butylmethylene group (pentylidene group), se
c-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,
C5-C5 alkylene groups such as 2-dimethyltrimethylene group, 1,3-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group and pentamethylene group N-pentylmethylene group (hexylidene group), (1-methylbutyl) methylene group, (2-methylbutyl) methylene group,
(3-methylbutyl) methylene group (isopentylidene group), (1,1-dimethylpropyl) methylene group,
(1,2-Dimethylpropyl) methylene group, n-butylmethylmethylene group, (1-methylpropyl) methylmethylene group, (2-methylpropyl) methylmethylene group, ethyl-n-propylmethylene group, ethylisopropylmethylene group , Butylethylene group, isobutylmethylene 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-trimethyltrimethyl group Methylene group, 1,1,3-trimethyltrimethylene group, 1-ethyltetramethylene group, 1,1-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 1,4-dimethyltetramethylene group, 2, 2-dimethyltetramethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, hexamethylene group, and other alkylene groups having 6 carbon atoms (including all isomers of alkylene groups having 6 carbon atoms); n- Hexylmethylene group (heptylidene group), n
An alkylene group having 7 carbon atoms such as a pentylethylene group (heptylene group) (including all isomers of an alkylene group having 7 carbon atoms); n-heptylmethylene group (octylidene group), n-hexylethylene group (octylene group) ) Etc. having 8 carbon atoms (including all isomers of alkylene groups having 8 carbon atoms); n-octylmethylene group (nonylidene group), n-heptylethylene group (nonylene group) etc. Alkylene group (including all isomers of alkylene group having 9 carbon atoms); n-nonylmethylene group (decylidene group), n-octylethylene group (decylene group) and other alkylene groups having 10 carbon atoms (all carbon numbers) (Including isomers of 10 alkylene groups); vinylidene group, ethenylene group (vinylene group), and other alkenylene groups having 2 carbon atoms; propenylene group, methyl C3 alkenylene group such as ethylene group, methylethenylene group, 1-propenylidene group, 2-propenylidene group; alkenylene group having 4 carbon atoms such as 3-methylpropenylene group (of all alkenylene groups having 4 carbon atoms) 1-methyl-3-methylene trimethylene group, 3-ethylpropenylene group, 1,
Alkylene groups having 5 carbon atoms such as 3-dimethylpropenylene group, 2,3-dimethylpropenylene group and 3,3-dimethylpropenylene group (including all isomers of alkenylene group having 5 carbon atoms); 1-dimethyl-3-methylenetrimethylene group, 1-ethyl-3-methylenetrimethylene group, 3-ethyl-1-methylpropenylene group, 3-ethyl-2-methylpropenylene group, 1,3,3- C6 alkenylene groups such as trimethylpropenylene group and 2,3,3-trimethylpropenylene group (including all isomers of C6 alkenylene group); C7 alkenylene groups such as heptenylene group ( Includes all isomers of C7 alkenylene groups); C8 alkenylene groups such as octenylene groups (all isomers of C8 alkenylene groups M); alkenylene group having 9 carbon atoms such as nonenylene group (including all isomers of alkenylene group having 9 carbon atoms); alkenylene group having 10 carbon atoms such as decenylene group (isomerization of all alkenylene groups having 10 carbon atoms) (Including the body).

Among them, R ⁵ is preferably an alkylene group having 1 to 6 carbon atoms, and is particularly preferable because it has excellent compatibility with a refrigerant when the lubricating oil of the present invention is used as a refrigerating machine oil. , Methylene group, methylmethylene group (ethylidene group), ethylene group, ethylmethylene group (propylidene group), dimethylmethylene group (isopropylidene group), methylethylene group (propylene group),
C3-C3 alkylene groups such as trimethylene group; Among C4-C6 alkylene groups, n-propylmethylene group (butylidene group), isopropylmethylene group (isobutylidene group), ethylmethylmethylene group, n-butyl Methylene group (pentylidene group), sec-butylmethylene group, isobutylmethylene group (isopentylidene group), t
ert-butylmethylene group, n-propylmethylmethylene group, isopropylmethylmethylene group, diethylmethylene group, n-pentylmethylene group (hexylidene group),
(1-Methylbutyl) methylene group, (2-methylbutyl) methylene group, (3-methylbutyl) methylene group (isopentylidene group), (1,1-dimethylpropyl) methylene group, (1,2-dimethylpropyl) methylene Base,
n-butylmethylmethylene group, (1-methylpropyl)
Examples thereof include a methylmethylene group, a (2-methylpropyl) methylmethylene group, an ethyl-n-propylmethylene group, and an ethylisopropylmethylene group.

In the above formula (1), R ^{6 to} R ⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group represented by R ^{6 to} R ⁹ include a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, straight-chain or branched butyl group, straight-chain or branched pentyl group, straight-chain or branched hexyl group, straight-chain or branched heptyl group, straight-chain or branched Examples include an octyl group, a linear or branched nonyl group, a linear or branched decyl group,
When the lubricating oil of the present invention is used as a refrigerating machine oil, one having a branch is preferable from the viewpoint of compatibility with the refrigerant. Further, among these, as R ^{6 to} R ⁹ , when the lubricating oil of the present invention is used as a refrigerating machine oil, it is excellent in compatibility with a refrigerant, and therefore, a hydrogen atom or a branched alkyl group having 1 to 6 carbon atoms. A group is preferable, and a hydrogen atom is more preferable.

In the above formula (1), m and n are each independently an integer of 0 to 10, preferably 0 to 8, and more preferably 0 to 6, and m + n representing the total degree of polymerization is 1.
It shows the integer so that it becomes -15, preferably 1-10.

Further, in the above formula (1), the substitution positions of the (R ³ O) group, the (OR ⁴ ) group and the R ⁵ group which are bonded to the benzene ring are arbitrary, but these are bonded to the para-position to each other. It is preferable that

Preferred examples of the compound represented by the formula (1) used in the present invention include those represented by the following general formula (2).

Embedded image (In the above formula (2), R ^{1 to} R ⁴ , R ^{6 to} R ⁹ , m and n
Are the same as in formula (1); R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the total carbon number of R ¹⁰ and R ¹¹ is 0 to 0;
5)

In the above formula (2), R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group represented by R ¹⁰ and R ¹¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a linear or branched butyl group, and a linear or branched pentyl. Groups and the like. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable as R ¹⁰ and R ¹¹ . Also, R
The total carbon number of ¹⁰ and R ¹¹ is 0 to 5.

The compound represented by the formula (1) in the present invention is not only a compound having a single structure but also a mixture of compounds having different structures as long as it satisfies the above general formula. Is also good. Further, when a mixture of different compounds represented by the formula (1) is used as described above, the average value of m + n in the total amount of the compounds represented by the formula (1) is 1 from the viewpoint of excellent electrical properties of the lubricating oil. It is preferably -5.

The method for producing the compound used in the present invention is arbitrary and can be produced by various methods. For example, a bisphenol compound is polymerized with an alkylene oxide to be etherified if necessary. Examples of this include hydrocarbon halides having 1 to 30 carbon atoms and olefins having 2 to 30 carbon atoms, sulfuric acid, phosphoric acid, silicotungstic acid,
Method of adding to a benzene ring in the presence of a mineral acid such as hydrofluoric acid, a solid acidic substance such as acid clay and activated clay, and an acid catalyst such as Friedel-Crafts catalyst which is a metal halide such as aluminum chloride and zinc chloride Etc.

It should be noted that the equation (1) is obtained by the above method and the like.
When the compound represented by is produced, a compound having a total degree of polymerization of 0 (a compound having n + m of 0) may be contained as an impurity. The compound having a total degree of polymerization of 0 is inferior in fluidity to the compound represented by the formula (1) and is not preferable. Therefore, it is preferable not to include a compound having a total degree of polymerization of 0, and even in the case where the compound having a total degree of polymerization of 0 is included, the compound represented by the formula (1) has a compound of the formula (1) and a total degree of polymerization of 0.
It is necessary that the content of the compound is 85% by mass or more, preferably 90% by mass or more, based on the total amount of the compound.

In the present invention, the viscosity and molecular weight of the above compound are not particularly limited, but when used as a general lubricating oil, the lubricity is excellent, and particularly when used as a refrigerating machine oil, the sealing property of the compressor is further improved. Therefore, the kinematic viscosity at 40 ° C. is ² to 1000 mm ² / s, preferably 3
It is desirable that it is 800 mm ² / s. The number average molecular weight is 250 to 2000, preferably 300 to 100.
It is preferably 0.

The content of the compound represented by the general formula (1) in the synthetic lubricating oil of the present invention is arbitrary, but preferably the total amount of the synthetic lubricating oil (the compound represented by the formula (1) and the necessary amount). 5 based on the total amount of other base oils used accordingly.
0 to 100% by mass, and more preferably 70 to 100% by mass. Further, as the synthetic lubricating oil of the present invention, in order to adjust the viscosity, the lubricity, etc., various other lubricating base oils may be added as needed on the basis of the total amount of the synthetic lubricating oil.
You may contain 0 mass% or less, preferably 30 mass% or less. Exemplifying these base oils, as mineral oil, a lubricating oil fraction obtained by distilling crude oil under atmospheric pressure and vacuum distillation, solvent degassing, solvent extraction, hydrocracking, solvent dewaxing,
Base oils of paraffin type, naphthene type, etc., which are refined by appropriately combining purification treatments such as catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment can be used. Further, as the synthetic oil, for example, poly α-olefin (polybutene, 1-octene oligomer, 1-decene oligomer, etc.), alkylbenzene, alkylnaphthalene, diester (ditolyldecyl glutarate, di2-ethylhexyl adipate, diisodecyl adipate, Ditridecyl adipate, di2
-Ethylhexyl sebacate etc.), polyol ester (neopentyl type polyol ester such as pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate, trimethylolpropane pelargonate, trimethylolpropane hexanoate etc.),
Complex ester of monool and diol with monocarboxylic acid and dicarboxylic acid, complex ester of neopentyl type polyol with monocarboxylic acid and dicarboxylic acid, polyglycol (polyoxyalkylene glycol, polyoxyalkylene glycol monoether, polyoxyalkylene glycol Diethers, polyoxyalkylene glycol glycerol esters, etc.), polyphenyl ethers, silicone oils, or mixtures of two or more thereof can be used.

The synthetic lubricating oil of the present invention can be preferably used as a refrigerating machine oil even in a state where no additives are added, but it can also be used in a form in which various additives are blended if necessary.

When the synthetic lubricating oil of the present invention is used as a refrigerating machine oil, in order to further improve its wear resistance and load resistance to a refrigerating machine, a phosphoric acid ester, an acidic phosphoric acid ester, or an amine salt of an acidic phosphoric acid ester is used. At least one phosphorus compound selected from the group consisting of chlorinated phosphoric acid ester and phosphorous acid ester can be blended. These phosphorus compounds are esters of phosphoric acid or phosphorous acid with alkanols, polyether type alcohols, or derivatives of such esters.

Specific examples of the phosphoric acid ester include 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, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, cresyl diphenyl phosphate ,
Examples include xylyl diphenyl phosphate and the like. 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 Acid Phosphate, Diheptyl Acid Phosphate, Dioctyl Acid Phosphate, Dinonyl Acid Phosphate, Didecyl Acid Phosphate, Diundecyl Acid Phosphate, Didodecyl Acid Phosphate, Ditridecyl Acid Phosphate, Ditetradecyl Acid Phosphate, Dipentadecyl Acid Phosphate, Dipentadecyl Acid Phosphate Dihexadecyl acid phosphate, diheptadecyl acid phosphate,
Dioctadecyl acid phosphate, dioleyl acid phosphate and the like can be mentioned. The amine salt of acidic phosphoric acid ester includes methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine of the acidic phosphoric acid ester. Examples thereof include salts with amines such as dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine and trioctylamine. Examples of the chlorinated phosphoric acid ester 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 Fight, tridodecyl phosphite,
Examples include trioleyl phosphite, triphenyl phosphite, tricresyl phosphite, and the like. Also,
Mixtures of these can also be used.

When these phosphorus compounds are compounded in the synthetic lubricating oil of the present invention, the compounding amount thereof is arbitrary, but usually, the synthetic lubricating oil composition total amount standard (the compound represented by the formula (1),
The content thereof is 0.01 to 5.0% by mass, more preferably 0.02 to 3.0% by mass, based on the total amount of other base oils and total compounding additives used as necessary. It is desirable to mix the amount.

When the synthetic lubricating oil of the present invention is used as a refrigerating machine oil, in order to further improve its stability, a phenyl glycidyl ether type epoxy compound, an alkyl glycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, an aryl oxirane At least one epoxy compound selected from the group consisting of a compound, an alkyloxirane compound, an alicyclic epoxy compound, an epoxidized fatty acid monoester, and an epoxidized vegetable oil 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 examples are glycidyl 2,2-dimethyloctanoate, glycidyl benzoate, Examples thereof include glycidyl acrylate and glycidyl methacrylate. Specific examples of the aryloxirane include 1,2-
Examples thereof include epoxy styrene and alkyl-1,2-epoxy styrene.

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. Especially epoxy stearic acid butyl, hexyl, benzyl,
Cyclohexyl, methoxyethyl, octyl, phenyl and butylphenyl esters 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, glycidyl ester type epoxy compounds and epoxidized fatty acid monoesters. Among them, phenyl glycidyl ether type epoxy compounds and glycidyl ester type epoxy compounds are more preferable, and phenyl glycidyl ether, butyl phenyl glycidyl ether or alkyl glycidyl ester or a mixture thereof is particularly preferable.

When these epoxy compounds are compounded in the synthetic lubricating oil of the present invention, the compounding amount thereof is optional, but usually, the total amount of the synthetic lubricating oil composition (the compound represented by the formula (1), The content is 0.1 to 5.0% by mass based on the total amount of other base oils and all compounding additives used accordingly.
More preferably, it is desirable that the amount be 0.2 to 2.0% by mass. Moreover, it is needless to say that two or more kinds of the above phosphorus compound and epoxy compound may be used in combination.

Further, in order to further improve the performance of the synthetic lubricating oil of the present invention, a conventionally known lubricating oil additive, for example, di-tert-butyl-, may be used, if necessary.
Phenolic compounds such as p-cresol and bisphenol A,
Amine-based antioxidants such as phenyl-α-naphthylamine and N, N-di (2-naphthyl) -p-phenylenediamine, antiwear agents such as zinc dithiophosphate, extreme pressures of chlorinated paraffins and sulfur compounds Agents, oiliness agents such as fatty acids, antifoaming agents such as silicones, metal deactivators such as benzotriazole, viscosity index improvers, pour point depressants, detergent dispersants and the like, alone or in combination of several kinds. It is also possible to mix. The total compounding amount of these additives is
Usually, 10% by mass or less, preferably 5% by mass, based on the total amount of the synthetic lubricating oil composition (based on the total amount of the compound represented by the formula (1), other base oil used as needed, and all compounding additives). It is the following.

Examples of the refrigerant used when the synthetic lubricating oil of the present invention is used as a refrigerating machine oil include hydrofluorocarbon (HFC), hydrochlorofluorocarbon (HCFC), chlorofluorocarbon (CFC) and ammonia. Among these, hydrogen-containing CFCs such as HFC and HCFC and ammonia are preferable, and HFC and ammonia are more preferable from the viewpoint of environmental problems.

Examples of the hydrofluorocarbon (HFC) refrigerant 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 a mixture of two or more of these. These refrigerants are appropriately selected depending on the application and the required performance, and for example, HFC-13
4a alone; HFC-125 alone; or HFC-13
4a / HFC-32 = 60-80 mass% / 40-20 mass% mixture; HFC-32 / HFC-125 = 40-
70% by mass / 60-30% by mass mixture; HFC-12
5 / HFC-143a = 40-60 mass% / 60-40
Mass% mixture; HFC-134a / HFC-32 / H
FC-125 = 60% by mass / 30% by mass / 10% by mass mixture, HFC-134a / HFC-32 / HFC-1
25 = 40-70 mass% / 15-35 mass% / 5-40
Mass% mixture; HFC-125 / HFC-134a /
HFC-143a = 35-55 mass% / 1-15 mass%
A preferable example is a mixture of / 40 to 60% by mass.

More specifically, HFC-134a / H
FC-32 = 70/30 wt% mixture; HFC-32
/ HFC-125 = 60/40 mass% mixture; HFC
-32 / HFC-125 = 50/50 mass% mixture (R410A; Allied Signal, Genetro)
nAZ-20); HFC-32 / HFC-125 = 45
/ 55 mass% mixture (R410B; DuPont S
UVA AC9100); HFC-125 / HFC-1
43a = 50/50 mass% mixture (R507C; Genetron AZ-50 manufactured by Allied Signal Co.);
HFC-32 / HFC-125 / HFC-134a = 3
0/10/60 wt% mixture; HFC-32 / HFC
-125 / HFC-134a = 23/25/52 mass%
Mixture (R407C; DuPont SUVA AC
9000); HFC-125 / HFC-134a / HF
C-143a = 44/4/52 mass% mixture (R40
4A; DuPont SUVA HP-62) and the like.

When the synthetic lubricating oil according to the present invention is used as a refrigerating machine oil, it usually exists in the form of a refrigerating machine fluid composition mixed with the above-mentioned refrigerant in the refrigerating machine. The blending ratio of the synthetic lubricating oil and the refrigerant in this composition is arbitrary, but is usually 1 to 500 parts by weight, preferably 2 to 400 parts by weight, relative to 100 parts by weight of the refrigerant.

The synthetic lubricating oil of the present invention is particularly preferably used as a refrigerating machine oil for an air conditioner or a refrigerator having a reciprocating or rotating hermetic compressor because of its excellent electric characteristics and low hygroscopicity. Further, it is particularly preferably used for a vehicle air conditioner, a dehumidifier, a freezer, a refrigerating / freezing warehouse, a vending machine, a showcase, a cooling device for a chemical plant and the like. Further, it is also preferably used for those having a centrifugal compressor. Further, the synthetic lubricating oil of the present invention is not only used as a refrigerating machine oil, but also as an engine oil, a gear oil, a hydraulic oil, a metal working oil,
It is also preferably used as other industrial lubricating oil.

[0050]

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.

Examples 1 to 5 and Comparative Examples 1 to 3 The sample oils used in Examples and Comparative Examples are shown below. Example 1: Bisphenol A represented by the following formula (3)
The compound obtained by adding 2 mol of propylene oxide to 1 mol of (2,2-bis (4′-hydroxyphenyl) propane) was further dimethyl etherified. The obtained sample oil has n and m of 0 to 4 and a total degree of polymerization (n
+ M) was a mixture of compounds 0-6. Further, the compound having a total degree of polymerization of 1 to 6 was contained in an amount of 93.7% by mass based on the total amount of the mixture of the compound having a degree of total polymerization of 0 and the compound having a degree of total polymerization of 1 to 6.

[0052]

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Example 2: The compound obtained by adding 5 mol of propylene oxide to 1 mol of bisphenol A was further dimethyl etherified. The obtained sample oil was a mixture of compounds having n and m of 0 to 8 and a total degree of polymerization (n + m) of 0 to 9. Further, the compound having a total degree of polymerization of 1 to 9 was contained in an amount of 96.2% by mass based on the total amount of the mixture of the compound having a degree of total polymerization of 0 and the compound having a degree of total polymerization of 1 to 9.

Example 3: The compound obtained by adding 4 mol of ethylene oxide to 1 mol of bisphenol A was further dimethyl etherified. The obtained sample oil was a mixture of compounds having n and m of 0 to 7 and a total degree of polymerization (n + m) of 0 to 8. Further, the compound having a total degree of polymerization of 1 to 8 was contained in an amount of 95.2% by mass based on the total amount of the mixture of the compound having a degree of total polymerization of 0 and the compound having a degree of total polymerization of 1 to 8.

Example 4: Bisphenol compound represented by the following formula (4) (1,1-bis (2'-methyl-4'-
Hydroxy-5'-t-butylphenyl) butane) 1 m
The compound obtained by adding 5 mol of propylene oxide to ol was further dimethyl etherified. The obtained sample oil has n and m of 0 to 8 and a total degree of polymerization (n + m) of 0.
Was a mixture of -9 compounds. Also, the total degree of polymerization is 1 to
The compound No. 9 was contained in an amount of 96.8% by mass based on the total amount of the mixture of the compound having the total polymerization degree of 0 and the compound having the total polymerization degree of 1 to 9.

[0056]

[Chemical 6]

Example 5: A compound obtained by adding 4 mol of propylene oxide to 1 mol of a bisphenol compound represented by the following formula (5) (bis (4'-hydroxyphenyl) methane) was further dimethyl etherified. The obtained sample oil has n and m of 0 to 7 and a total degree of polymerization (n
+ M) was a mixture of compounds 0-8. Further, the compound having a total degree of polymerization of 1 to 8 was contained in an amount of 94.8% by mass based on the total amount of the mixture of the compound having a total degree of polymerization of 0 and the compound having a total degree of polymerization of 1 to 8.

[0058]

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Comparative Example 1: Branched alkylbenzene (number average molecular weight 260). Comparative Example 2: Tetraester of pentaerythritol and 2-ethylhexanoic acid. Comparative Example 3: Polypropylene glycol monobutyl ether (number average molecular weight 690).

Test Example For the sample oils of these Examples and Comparative Examples, the refrigerant (H
The compatibility with FC-134a), hydrolysis stability, and abrasion resistance (lubricity) were evaluated. The results are shown in Table 1. 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. Further, each sample oil 2.
The low temperature side two-layer separation temperature was similarly measured for the composition containing 5 g (oil content 5%).

(2) Hydrolysis stability 150 g of sample oil and 0.15 g of water were placed in a 200 ml heat-resistant glass test tube, and copper wire, iron wire and aluminum wire (1 mmφ × 100 mm) were used as deterioration promoting catalysts, respectively.
Put 0 each and put it in a stainless steel autoclave for N
It was heat-deteriorated at 175 ° C. in ₂ atmosphere for 168 hours. After the test, the total acid value of the sample oil was measured.

(3) Abrasion resistance (lubricity) Using a rolling piston type compressor, 70 g of each sample oil and refrigerant (HFC-134) of Examples and Comparative Examples.
a) Filling with 50 g, operating for 1000 hours under the conditions of discharge pressure 16 kgf / cm ² G, suction pressure 0 kgf / cm ² G, rotation speed 3000 rpm, test temperature 160 ° C., surface of sliding surface of vane after test The roughness was measured.

[0064]

[Table 1]

As is clear from the results shown in Table 1, Example 1
The refrigerating machine oils Nos. 5 to 5 have good compatibility with the HFC refrigerant and have excellent hydrolysis stability and abrasion resistance. On the other hand, the refrigerating machine oil of Comparative Example 1 has excellent hydrolysis stability and wear resistance, but has almost no compatibility with the HFC refrigerant. The refrigerating machine oil of Comparative Example 2 has excellent compatibility with the HFC refrigerant, but has poor hydrolysis stability and wear resistance. In addition, it is clear that the refrigerating machine oil of Comparative Example 3 has poor compatibility with the HFC refrigerant and hydrolysis stability, but inferior wear resistance.

[0066]

As described above, the synthetic lubricating oil of the present invention is excellent in compatibility with a refrigerant such as HFC-134a and has various required performances such as hydrolysis stability and lubricity with a refrigeration compressor. Therefore, it is particularly useful as a refrigerating machine oil.

Claims (1)

[Claims] 1. A compound represented by the general formula (1): (In the above formula, R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; R ³ and R ⁴
Each independently represents an alkylene group having 2 to 4 carbon atoms;
R ⁵ represents an alkylene group having 1 to 10 carbon atoms or an alkenylene group; R ^{6 to} R ⁹ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; m and n each independently represent 0 to 10 Which is an integer of 1 and m + n is an integer of 1 to 15).