JPH09227884A - Lubricating oil composition - Google Patents

Abstract

(57) Abstract: A lubricating oil composition having excellent stability is provided. SOLUTION: (a) General formula (I): Wherein, n represents an integer of 0 to 5, R _1a is CF ₂ CF ₂ H
Or H is shown; R ₂ , R ₅ , and R ₆ are the same or different and each is a monovalent aliphatic group having 1 to 100 carbon atoms, or an aliphatic group having 1 to 100 carbon atoms partially substituted with a fluorine atom. represents a _{group, R 3, R 4, R} 7 are the same or different and each a divalent aliphatic group having 1 to 100 carbon atoms, substituted partially by fluorine atoms aliphatic group having 1 to 100 carbon atoms (Provided that when R _1a is H, it has a fluorine atom in any of R ₂ , R ₅ and R ₆ ). ] A lubricating oil excellent in stability, containing at least one selected from the group consisting of a fluorine-containing lubricating oil represented by (2) and an oxygen atom-containing lubricating oil, ether oil, mineral oil, alkylbenzene oil and ester oil. Composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a lubricating oil or refrigerator oil composition having excellent stability. Also, the present invention
It relates to mixtures of these compositions with partially or fully halogenated compounds.

[0002]

2. Description of the Related Art Conventionally, as refrigerating machine oils, mineral oils such as paraffin type and naphthene type, synthetic oils such as alkylbenzene type and ester type are known. These oils are mainly used in refrigerators that use trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), chlorodifluoromethane (CFC-22), etc. as refrigerants. However, in recent years, when released into the atmosphere, chlorine-containing fully halogenated hydrocarbons such as Freon-11 and Freon-12 or chlorine-containing halogenated hydrocarbons such as Freon-22 destroy the ozone layer in the stratosphere, As a result, it has been pointed out that it has a serious adverse effect on the global ecosystem including humankind. Therefore, Freon-1
Regarding specific freons such as 1, Freon-12 and freon-22, international agreements have led to restrictions on use and production.

CH ₂ FCF ₃ (CFC-1) is a refrigerant that replaces CFC-11, CFC-12 and CFC-22.
34a), CH ₂ F ₂ (CFC-32), CHF ₂ CF
₃ (CFC-125), CHF ₃ (CFC-23), CF
Hydrogen-containing fluorohydrocarbons such as ₃ CH ₃ (CFC-143a) have been proposed. It does not damage the ozone layer, but has very low compatibility with conventional refrigeration oils. Therefore, if a conventional refrigerating machine oil is applied to a refrigerator that uses hydrogen-containing fluorohydrocarbon as a refrigerant, the durability of the compressor deteriorates and it becomes impossible to operate in a short time, or the cooling capacity and coefficient of performance of the refrigerator. Was sometimes significantly reduced.

Therefore, it is conceivable to use, as the refrigerating machine oil, a fluorine-containing oil (fluorine-based oil) which is a compound which is considered to have good compatibility with hydrogen-containing fluorohydrocarbons. As such a fluorinated refrigerating machine oil, Fomblin (Montefluos Co., Ltd.), Krytox (DuPont), Demnum (Daikin Industries, Ltd.) and the like are commercially available. The refrigerating machine oil has the following repeating units.

[0005] _{- (C (CF 3) FCF} 2 -O) - - (CF 2 CF 2 CF 2 -O) - - (C (CF 3) FCF 2 -O) n '- (CF 2 -O) m _{'In the} formula, n'and m'represent an integer of 1 or more. However, these known fluorine-based oils are not always satisfactory in terms of compatibility with the refrigerant. that is,
It is considered that these fluorinated oils do not contain hydrogen in the structure, or contain almost no hydrogen. Further, these fluorine-based oils are expensive in the monomer corresponding to the repeating unit in the structure,
Practical application involves difficulties.

Therefore, when the above-mentioned hydrogen-containing fluorohydrocarbon is used as a refrigerant, in order to improve the compatibility between the refrigerant and the refrigerating machine oil, a fluorine-containing oil containing hydrogen together with fluorine is used as the refrigerating machine oil. It is considered effective to use.

Fluorine-containing oils containing hydrogen are described in JP-A-3-205491, JP-A-3-7798 and the like.
A compound having a perfluoropolyether bond serves as a basic unit, and the monomer used as a raw material is similarly expensive. Further, since the fluorine-containing portion is basically COF-terminated, the reaction product with the hydrocarbon compound becomes an ester, which is liable to be hydrolyzed.

On the other hand, when synthesizing a compound other than an ester, it is necessary to convert the terminal --COF of the fluorine-containing compound into --CH ₂ OH by, for example, a reduction reaction, which has a drawback that the reaction has multiple steps. Further, the refrigerating machine oil to be synthesized becomes expensive, and it is difficult to put it into practical use. In addition, polyester compounds disclosed in JP-A-3-128991, JP-A-3-1799091 and the like are also said to have excellent compatibility with Freon-134a, but have high hygroscopicity, and Since it contains an ester group, it is prone to hydrolysis and has a problem in durability.

[0009]

DISCLOSURE OF THE INVENTION The present invention has good compatibility with hydrogen-containing halogenated hydrocarbons, high stability, and
An object of the present invention is to provide a lubricating oil composition suitable for use in a refrigerator using a hydrogen-containing halogenated hydrocarbon as a refrigerant.

[0010]

The present invention includes the following items 1 to 3.
Item 12. The composition according to Item 12.

Item 1. (A) General formula (I):

[0012]

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[Wherein n represents an integer of 0 to 5 and R _1a represents CF ₂ CF ₂ H or H; R ₂ , R ₅ and R ₆ are the same or different and each has a monovalent carbon number. 1 to 100 aliphatic groups,
1 to 100 carbon atoms partially substituted with fluorine atoms
Of represents an aliphatic _{group, R 3, R 4, R} 7 are the same or different and each a divalent aliphatic group having 1 to 100 carbon atoms, partially by number 1 to 100 carbon substituted by fluorine atoms It represents an aliphatic group (provided that when R _1a is H, any one of R ₂ , R ₅ and R ₆ has a fluorine atom). ] A fluorine-containing lubricating oil represented by and (b) a lubricating oil having an oxygen atom,
A lubricating oil composition having excellent stability, containing at least one selected from the group consisting of ether oil, polyoxyalkylene glycol oil, mineral oil, alkylbenzene oil and ester oil.

Item 2. (A) General formula (I):

[0015]

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[In the formula, n, R _1a and R _{2 to} R ₇ are the same as defined above. ] Fluorine-containing lubricating oil represented by and (b) at least one selected from the group consisting of oxygen-containing lubricating oil, ether oil, polyoxyalkylene glycol oil, mineral oil, alkylbenzene oil and ester oil, stable The refrigerating machine oil composition according to Item 1, which has excellent properties.

Item 3. (A) General formula (I):

[0018]

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[In the formula, n, R _1a and R _{2 to} R ₇ are the same as defined above. ] The compound and general formula (II) represented by:

[0020]

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[Wherein, m is an integer of 1 to 6, R _1b and R _1c are the same or different and represent CF ₂ CF ₂ H or H; R ₈ and R ₁₁ are the same or different and 2 Valence carbon number 1
An aliphatic group having 100 to 100 carbon atoms or a partially substituted aliphatic group having 1 to 100 carbon atoms, R ₉ and R ₁₀
Is the same or different and is a monovalent aliphatic group having 1 to 100 carbon atoms or 1 carbon atom in which a part thereof is substituted with a fluorine atom.
To 100 aliphatic groups (provided that when R _1b and R _1c are simultaneously H, a fluorine atom is contained in either R ₉ or R ₁₀ ). ] Containing at least one selected from the group consisting of a mixture of compounds represented by and (b) an oxygen atom-containing lubricating oil, ether oil, polyoxyalkylene glycol oil, mineral oil, alkylbenzene oil and ester oil, Excellent lubricating oil composition.

Item 4. (A) General formula (I):

[0023]

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[In the formula, n, R _1a and R _{2 to} R ₇ are the same as defined above. ] The compound and general formula (II) represented by:

[0025]

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[In the formula, m, R _1b , R _1c , and R _{8 to} R ₁₁ are
Same as above. ] A mixture of compounds represented by and (b) at least one selected from the group consisting of lubricating oil having an oxygen atom, ether oil, polyoxyalkylene glycol oil, mineral oil, alkylbenzene oil and ester oil,
Refrigerating machine oil composition having excellent stability.

Item 5. (A) General formula (III): R ₁₂ (OR ₁₃ ) _L (III) [wherein, L represents an integer of 1 to 20, and R ₁₂ has 6 to 6 carbon atoms.
An L-valent aromatic group of 100 is shown. R ₁₃ is CF ₂ CF ₂ H
Or H is shown; when L is 2 or more, R ₁₃ 's may be different (provided that not all R _13's are H). ] And at least one selected from the group consisting of a fluorine-containing lubricating oil represented by (b) an oxygen-containing aliphatic lubricating oil, an aliphatic ether oil, an aliphatic polyoxyalkylene glycol oil, and an aliphatic ester oil. A lubricating oil composition containing excellent stability.

Item 6. (A) General formula (III): R ₁₂ (OR ₁₃ ) _L (III) [In the formula, L, R ₁₂ and R ₁₃ are the same as defined above. ] At least one selected from the group consisting of a fluorine-containing lubricating oil represented by and (b) an aliphatic lubricating oil having an oxygen atom, an aliphatic ether oil, an aliphatic polyoxyalkylene glycol oil, and an aliphatic ester oil. A refrigerating machine oil composition containing excellent stability.

Item 7. (A) Of the compounds of any one of the general formulas (I) to (III) and (b) of the compounds of the general formulas (I) to (III), two other compounds not included in the above (a) A lubricating oil composition having excellent stability, containing at least two compounds selected from the group consisting of a compound, a lubricating oil having an oxygen atom, an ether oil, a polyoxyalkylene glycol oil, an ester oil, a mineral oil, and an alkylbenzene oil.

Item 8. (A) One compound of any one of the general formulas (I) to (III) and (b) Two other compounds not included in the above (a), a lubricating oil having an oxygen atom, an ether oil and a polyoxy compound. A refrigerating machine oil composition having excellent stability, containing at least two kinds selected from the group consisting of alkylene glycol oil, ester oil, mineral oil, and alkylbenzene oil.

Item 9. Item 9. A lubricating oil composition containing the composition according to any one of Items 1 to 8 and an additive.

Item 10. Item 10. A refrigerating machine oil composition containing the composition according to any one of Items 1 to 8 and an additive.

Item 11. (A) 1 partially or completely substituted with at least one atom of chlorine or fluorine
Saturated hydrocarbon having 5 to 5 carbon atoms and having a standard boiling point in the range of -80 ° C to + 50 ° C, and (b) items 2, 4;
A refrigerator working fluid composition containing the composition according to any one of 6, 8, and 10.

Item 12. The component (a) is HFC-1
34a (1,1,1,2-tetrafluoroethane), H
FC-134 (1,1,2,2-tetrafluoroethane), HFC-32 (difluoromethane), HFC-1
Item 12. The composition according to Item 11, which is at least one compound selected from the group consisting of 25 (1,1,1,2,2-pentafluoroethane).

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION In the lubricating oil composition and the refrigerator oil composition of the present invention, at least one of (1) a lubricating oil having an oxygen atom, an ether oil, a polyoxyalkylene glycol oil, an ester oil, a mineral oil and an alkylbenzene oil is used. Seed and
(2) The ratio of the at least one fluorine-containing lubricating oil of the general formulas (I) and (II) is not particularly limited, but the total of (1) and (2) is 100% by weight, and (2) is Usually 1 ppm to 99
% By weight; preferably 5 ppm to 80% by weight; more preferably 10 ppm to 50% by weight.

Further, (3) at least one of an aliphatic lubricating oil having an oxygen atom, an aliphatic ether oil, an aliphatic polyoxyalkylene glycol oil, and an aliphatic ester oil,
(4) The ratio of the fluorine-containing lubricating oil of the general formula (III) is not particularly limited, but the total of (3) and (4) is 100% by weight,
(4) is usually 1 ppm to 99% by weight; preferably 5 ppm
~ 90 wt%; more preferably 10 ppm to 80 wt%
It is.

On the other hand, (ii) any one of the fluorine-containing lubricating oils of the general formulas (I) to (III), and (ii) another fluorine-containing lubricating oil of the general formulas (I) to (III), When at least two kinds selected from the group consisting of oxygen-containing lubricating oils, ether oils, polyoxyalkylene glycol oils, ester oils, mineral oils and alkylbenzene oils are mixed, the ratio is not particularly limited, but (i) and ( (i) is 10 ppm to 99.99%, preferably 50 ppm to 99%, more preferably 100 pp, with the total of ii) being 100% by weight.
m to 95%.

In the present invention, the content ratio (weight ratio) of the compound (I) to the compound (II) is not particularly limited, but is usually 1 ppm to 100% by weight; preferably 5 ppm.
-80% by weight; more preferably 10 ppm-60% by weight; particularly preferably 1% -30% by weight.

Since the compound of the general formula (I) and the compound of the general formula (II) can be simultaneously produced, the compound of the general formula (II) is preferable as the substance to be mixed with the compound of the general formula (I). Compounds other than II) may be mixed.

The monovalent aliphatic group having 1 to 100 carbon atoms represented by R ₂ , R ₅ , R ₆ , R ₉ and R ₁₀ may have an oxygen atom or an unsaturated bond, and may be methyl. , Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-
Alkyl groups such as butyl and t-butyl; alkenyl groups such as vinyl, allyl and 3-butenyl; hydroxymethyl, 2-hydroxyethyl, 1-hydroxypropyl,
Examples thereof include hydroxyalkyl groups such as 2-hydroxypropyl and 3-hydroxypropyl. The number of carbon atoms of the aliphatic group is 1 to 100, preferably 1 to 1
0, more preferably 1-6, especially 1-4.

The aliphatic group having 1 to 100 carbon atoms represented by R ₃ , R ₄ , R ₇ , R ₈ and R ₁₁ may have an oxygen atom or an unsaturated bond, for example, methylene, Alkylene groups such as ethylene, propylene and butylene; General formula (A): —CH ₂ — (OCH ₂ CH ₂ ) _x — (A) [In the formula, x represents an integer of 1 to 30. Compounds represented by]; formula _{(B): -CH 2 - (} OCHMeCH 2) y - (B) wherein, y is an integer of 1 to 30. Me represents a methyl group. ] The compound represented by these; etc. are mentioned.

The fluorine-substituted aliphatic group having 1 to 100 carbon atoms represented by R ₂ , R ₅ , R ₆ , R ₉ and R ₁₀ may have an oxygen atom or an unsaturated bond, for example, fluoro. Fluorine-substituted alkyl groups such as methyl, difluoromethyl, fluoroethyl and fluoropropyl; fluorine-substituted alkoxyalkyl groups such as CH ₂ OCF ₂ CF ₂ H; and the like.

Examples of the fluorine-substituted aliphatic group having 1 to 100 carbon atoms represented by R ₃ , R ₄ , R ₇ , R ₈ and R ₁₁ include fluorine-substituted alkylene groups such as fluoromethylene and fluoroethylene. .

The aromatic group represented by R ₁₂ may have an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, a fluorine atom, an unsaturated bond, etc., and has a plurality of aromatic nuclei. Well, for example

[0045]

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The present invention is not limited to the above examples.

Examples of the substituent bound to the aromatic nucleus in R ₁₂ include the following substituents, but the present invention is not limited thereto: —CH ₃ , —CH ₂ CH ₃ ,
_{-CH (CH 3) 2, -C} (CH 3) 3, - (C 2 H 4) na H (na = 2~10), - (C 3 H 6) nb H (nb = 1~10), _{-C (CH 3) 2 CH 2} C (CH 3) 2 CH 3, -C (C
_{H 3) 2 CH 2 CH 3} , -CH (CH 3) C nc H 2nc + 1 (nc = 1~20), -C (CH 3) 2 C nd H 2nd + 1 (nd = 1~20),

[0048]

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--CH ₂ --CH = CH ₂ , --CH ₂ CH _2-
CH = CH _2, cyclohexyl, -OH, -SH, -C
_{N, -NO 2, -F, -Cl} , -CH 2 OH, -CH 2
_{CH 2 Cl, -OCH 3, -O} (CH 2) 7 CH 3, -OC
_{H 2 CH 2 OCH 3, -} (OCH 2 CH 2) 20 -OC
_{4 H 9, - (OC 3} H 6) 10-15 -OCH 2 CH 3, - (OC
_{H 2 CH 2 CH 2 CH 2} ) 2 -OCH 2 CH 2 CH 2 CH 3, -
_{OCH 2 CH 2 OCH 2 CH 2} OCH 3, -COCH 3, -C
_{OC 8 H 17, CH 3 (} CH 2) 16 COO -, - OCOC
_{H 3, -OCOCH (CH 3)} (CH 2) 3 CH 3, -CO
_{OCH 3, -COOCH (CH 3)} 2, -CONH 2, -C
_{ON (C 4 H 9) 2} , - succinimide, CH ₃ (CH _{2) 7
CH = CH (CH 2) 7} COO -, - S-C 4 H 9, -SO
_{2 N (Me) 2, -NHSO} 2 CH 3, -SO-CH 3, -
SO ₂ C ₆ H ₁₃ ,

[0050]

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--CH ₂ OCH ₂ CH ₃ , --CH (CH ₃ )-
_{O- (CH 2 CH 2 O)} 5 -CH 3, -CH 2 COCH 3, -
_{CH 2 OCOCH 3, -CH 2 N} (Me) 2, -CH 2 -O
-P (= O) (OEt) 2, -CF 3, -CF 2 CF 2 CF
_{3, -CH 2 CH 2 CF 3} , -C (CH 3) (CF 2 CHFC
_{F 3) C 6 H 13,} -C (CH 3) 2 CF 2 CHFCF 3, -O
_{CH 2 CH 2 OCH 2 CH 2} OCH 2 CH 2 CF 3, -COC
_{F 3, -SO 2 CF 2 CF} 2 CF 3, -NHSO 2 CF 2 C
_{F 3, -CH 2 OCH (CF} 3) 2, -COOCH 2 CF 3,
Specific examples of R ₁₂ containing the above-mentioned substituents and linking groups include the following, but the present invention is not limited thereto.

[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

[Chemical 21]

[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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The various highly stable compositions of the present invention include thickeners, viscosity index improvers, detergent dispersants, extreme pressure additives, antiwear agents, oiliness improvers, rust preventives, antioxidants, At least one kind of various additives to be added to ordinary lubricating oils such as a corrosion inhibitor, an antifoaming agent, an emulsifier, a water separating agent, a pour point depressant, a metal deactivator and an anti-corrosion agent is usually used. It can be added in an amount and used. Further, as these additives, a fluorine-containing additive may be used, and various aliphatic or aromatic fluorine-containing additives may be used.

The amount of the additive to be added may be a commonly used amount and is not particularly limited, but is usually 0.1 ppm to 95.
% By weight, preferably 1 ppm to 90% by weight.

The saturated hydrocarbon having a standard boiling point in the range of -80 to + 50 ° C. and having 1 to 5 carbon atoms substituted by at least one chlorine atom or fluorine atom used in the present invention is HFC134a. (1,1,1,2-tetrafluoroethane), HFC134 (1,1,2,2-tetrafluoroethane), HFC32 (difluoromethane), HFC125 (pentafluoroethane), HFC
23 (trifluoromethane), HFC143a (1,
1,1-trifluoroethane), HFC152a (1,
1-difluoroethane), HFC227ea (1,1,
1,2,3,3,3-heptafluoropropane), HF
C227ca (1,1,1,2,2,3,3- _{heptafluoropropane), CF 3 CH 2 CF 3} , CF 3 CHFCH
F ₂ , CF ₃ CF ₂ CH ₂ F, CF ₂ HCF ₂ CHF ₂ , CF ₃
CH ₂ CHF ₂ , CF ₃ CF ₂ CH ₃ , CF ₂ HCF ₂ CH
₂ F, CF ₃ CF ₂ CH ₃ , CF ₃ CHFCHFCF ₃ , CF
₃ CHFCHFCF ₂ CF ₃ tetrafluoromethane, such as fluoride ethane, fluoride propane, includes various lower fluoride alkanes such as fluorinated butane, but not limited thereto.

The weight ratio of total amount of refrigerant / total amount of lubricating oil in the refrigeration system is usually in the range of 99/1 to 1/99, preferably 99/1 to 10/90, and particularly preferably 99.
The range is / 1 to 20/80.

The ether oil used in the present invention has the general formula (C)

[0068]

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[Wherein, R _{14 to} R ₁₉ are the same or different and each represents a hydrogen atom, a hydroxy group, an aromatic group or a carbon number of 1
~ 100 aliphatic groups. n1 shows the integer of 1-20. However, when n1 is 2 or more, R _{15 of} each repeating unit is
To R ₁₈ may be the same or different. ] As the aromatic group represented by R _{14 to} R ₁₉ , a phenyl group,
Various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups, and other aryl groups, benzyl groups, various phenylethyl groups, various methylbenzyl groups , Arylphenyl groups such as various phenylpropyl groups and various phenylbutyl groups.

The aliphatic group having 1 to 100 carbon atoms represented by R _{14 to} R ₁₉ may have an oxygen atom or an unsaturated bond, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, alkyl groups such as various decyl groups, cyclopentyl groups,
Cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, various dimethylcyclohexyl groups, and other cycloalkyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, various butynyl groups, various pentenyl groups, various Alkenyl groups such as hexenyl group, various heptenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, 2,
Examples thereof include a 5-dioxa-3-methylhexanyl group.

[0071] In _{addition, - (R 20 O) x1} R 21 - (OR 22) in _y1 R ₂₃ [wherein, x1, y1 both is an integer of 1 to 30.
R ₂₀ and R ₂₂ are divalent aliphatic groups or alicyclic hydrocarbons having 2
The alicyclic group, the aromatic hydrocarbon group, and the alkyl aromatic group each having a single bonding site are shown. R ₂₁ and R ₂₃ have 1 to 10 carbon atoms
Represents an aliphatic group or an aromatic group having 6 to 30 carbon atoms.
However, when x1 and y1 are 2 or more, R ₂₀ and R ₂₂ may be the same or different. ] The compound represented by this is mentioned.

Examples of the divalent aliphatic group represented by R ₂₀ and R ₂₂ include ethylene group, 1-methylethylene group, ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, n-propylethylene group, isopropylethylene group, 1-ethyl-2-methylethylene group, 1-
Ethyl-1-methylethylene group, trimethylene group, tetramethylene group, pentamethylene group, (methoxymethyl)
Ethylene group, (ethoxymethyl) ethylene group, (methoxyethyl) ethylene group, 1-methoxymethyl-2-methylethylene group, 1,2-bis (methoxymethyl) ethylene group, 1,1-bis (methoxymethyl) ethylene Base,
(Ethoxyethyl) ethylene group, 1,2-bis (ethoxyethyl) ethylene group, 1,1-bis (ethoxyethyl) ethylene group, 2-methoxy-1,3-propylene group, phenylethylene group, 1,2- Propylene group, 2-
Examples thereof include phenyl-1,2-propylene group, 1,3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, and various decylene groups.

Examples of the alicyclic group having two bonding sites on the alicyclic hydrocarbon include cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane and propylcyclohexane.

Examples of the aromatic hydrocarbon group include divalent aromatic hydrocarbon groups such as various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups and various naphthylene groups.

Examples of the alkyl aromatic group include an alkyl aromatic group such as toluene, xylene, and ethylbenzene, and an alkyl aromatic group having a monovalent bond site on the aromatic moiety, and a polyalkyl such as xylene and diethylbenzene. Examples thereof include an alkyl aromatic group having a binding site in the alkyl portion of an aromatic hydrocarbon.

The aliphatic group having 1 to 10 carbon atoms represented by R ₂₁ and R ₂₃ may have an oxygen atom or an unsaturated bond,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups,
Alkyl groups such as decyl, cyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl,
Cycloalkyl groups such as various dimethylcyclohexyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, various butynyl groups, various pentenyl groups, various hexenyl groups, various heptenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups And alkenyl groups and the like.

As the aromatic group represented by R ₂₁ and R ₂₃ ,
Phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups and other aryl groups, benzyl groups, various phenylethyl groups, various Examples thereof include arylalkyl groups such as methylbenzyl group, various phenylpropyl groups, and various phenylbutyl groups.

The polyoxyalkylene glycol oil in the present invention has the general formula (F) R ₂₄ O- (R ₂₅ O) _z -R ₂₆ (F) [wherein z represents an integer of 1 to 20]. R ₂₄ and R ₂₆ are
A hydrogen atom, an aromatic group or an aliphatic group having 1 to 100 carbon atoms is shown. R ₂₅ is a divalent aromatic group or a carbon number of 1 to 10
0 represents a divalent aliphatic group. However, when z is 2 or more, R _{25 s} may be the same or different. ]
The compound represented by these is mentioned.

As the aromatic group represented by R ₂₄ and R ₂₆ ,
Phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups and other aryl groups, benzyl groups, various phenylethyl groups, various Examples thereof include arylalkyl groups such as methylbenzyl group, various phenylpropyl groups, and various phenylbutyl groups.

The aliphatic group having 1 to 100 carbon atoms represented by R ₂₄ and R ₂₆ may have an oxygen atom or an unsaturated bond, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, alkyl groups such as various decyl groups, cyclopentyl groups,
Cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, various dimethylcyclohexyl groups, and other cycloalkyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, various butynyl groups, various pentenyl groups, various Alkenyl groups such as hexenyl group, various heptenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, 2,
Examples thereof include a 5-dioxa-3-methylhexanyl group.

[0081] In _{addition, - (R 20 O) x1} R 21 - (OR 22) in _y1 R ₂₃ [wherein, x1, y1 both is an integer of 1 to 30.
R ₂₀ and R ₂₂ are divalent aliphatic groups or alicyclic hydrocarbons having 2
The alicyclic group, the aromatic hydrocarbon group, and the alkyl aromatic group each having a single bonding site are shown. R ₂₁ and R ₂₃ have 1 to 10 carbon atoms
Represents an aliphatic group or an aromatic group having 6 to 30 carbon atoms.
However, when x1 and y1 are 2 or more, R ₂₀ and R ₂₂ may be the same or different. ] The compound represented by this is mentioned.

Examples of the divalent aliphatic group represented by R ₂₀ and R ₂₂ include ethylene group, 1-methylethylene group, ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, n-propylethylene group, isopropylethylene group, 1-ethyl-2-methylethylene group, 1-
Ethyl-1-methylethylene group, trimethylene group, tetramethylene group, pentamethylene group, (methoxymethyl)
Ethylene group, (ethoxymethyl) ethylene group, (methoxyethyl) ethylene group, 1-methoxymethyl-2-methylethylene group, 1,2-bis (methoxymethyl) ethylene group, 1,1-bis (methoxymethyl) ethylene Base,
(Ethoxyethyl) ethylene group, 1,2-bis (ethoxyethyl) ethylene group, 1,1-bis (ethoxyethyl) ethylene group, 2-methoxy-1,3-propylene group, phenylethylene group, 1,2- Propylene group, 2-
Examples thereof include phenyl-1,2-propylene group, 1,3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, and various decylene groups.

Examples of the alicyclic group having two bonding sites on the alicyclic hydrocarbon include cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane and propylcyclohexane.

Examples of the aromatic hydrocarbon group include divalent aromatic hydrocarbon groups such as various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups and various naphthylene groups.

Examples of the alkyl aromatic group include alkyl aromatic groups such as toluene, xylene and ethylbenzene, and alkyl aromatic groups each having a monovalent bonding site on the aromatic moiety, and polyalkyl such as xylene and diethylbenzene. Examples thereof include an alkyl aromatic group having a binding site in the alkyl portion of an aromatic hydrocarbon.

The aliphatic group having 1 to 10 carbon atoms represented by R ₂₁ and R ₂₃ may have an oxygen atom or an unsaturated bond,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups,
Alkyl groups such as decyl, cyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl,
Cycloalkyl groups such as various dimethylcyclohexyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, various butynyl groups, various pentenyl groups, various hexenyl groups, various heptenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups And alkenyl groups and the like.

As the aromatic group represented by R ₂₁ and R ₂₃ ,
Phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups and other aryl groups, benzyl groups, various phenylethyl groups, various Examples thereof include arylalkyl groups such as methylbenzyl group, various phenylpropyl groups, and various phenylbutyl groups.

R ₂₅ is ethylene group, 1-methylethylene group, ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, n-propylethylene group, isopropylethylene group, 1- Ethyl-2-methylethylene group, 1-ethyl-1-methylethylene group,
Trimethylene group, tetramethylene group, pentamethylene group, (methoxymethyl) ethylene group, (ethoxymethyl) ethylene group, (methoxyethyl) ethylene group, 1-
Methoxymethyl-2-methylethylene group, 1,2-bis (methoxymethyl) ethylene group, 1,1-bis (methoxymethyl) ethylene group, (ethoxyethyl) ethylene group, 1,2-bis (ethoxyethyl) ethylene Base 1,
1-bis (ethoxyethyl) ethylene group, 2-methoxy-1,3-propylene group, phenylethylene group, 1,2
-Propylene group, 2-phenyl-1,2-propylene group, 1,3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, various decylene groups, etc. Divalent aliphatic group; cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane,
An alicyclic group having two bonding sites on an alicyclic hydrocarbon such as propylcyclohexane; divalent aromatics such as various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, various naphthylene groups Group hydrocarbon group; alkylaromatic group having monovalent bonding sites on the alkyl and aromatic moieties of an alkylaromatic hydrocarbon such as toluene, xylene, and ethylbenzene,
An alkylaromatic group such as an alkylaromatic group having a bonding site at the alkyl portion of a polyalkylaromatic hydrocarbon such as xylene or diethylbenzene; or the general formula (G)

[0089]

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[In the formula, R ₂₇ , R ₂₈ , R ₂₉ , and R ₃₀ represent a hydrogen atom, an aromatic group, or an aliphatic group having 1 to 100 carbon atoms. ] The group represented by this is mentioned.

As the aromatic group represented by R _{27 to} R ₃₀ ,
Phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups and other aryl groups, benzyl groups, various phenylethyl groups, various Examples thereof include arylalkyl groups such as methylbenzyl group, various phenylpropyl groups, and various phenylbutyl groups.

The C 1-100 aliphatic group represented by R _{27 to} R ₃₀ may have an oxygen atom or an unsaturated bond, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, alkyl groups such as various decyl groups, cyclopentyl groups,
Cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, various dimethylcyclohexyl groups, and other cycloalkyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, various butynyl groups, various pentenyl groups, various Alkenyl groups such as hexenyl group, various heptenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, 2,
Examples thereof include a 5-dioxa-3-methylhexanyl group.

[0093] In _{addition, - (R 20 O) x1} R 21 - (OR 22) in _y1 R ₂₃ [wherein, x1, y1 both is an integer of 1 to 30.
R ₂₀ and R ₂₂ are divalent aliphatic groups or alicyclic hydrocarbons having 2
The alicyclic group, the aromatic hydrocarbon group, and the alkyl aromatic group each having a single bonding site are shown. R ₂₁ and R ₂₃ have 1 to 10 carbon atoms
Represents an aliphatic group or an aromatic group having 6 to 30 carbon atoms.
However, when x1 and y1 are 2 or more, R ₂₀ and R ₂₂ may be the same or different. ] The compound represented by this is mentioned.

Examples of the divalent aliphatic group represented by R ₂₀ and R ₂₂ include ethylene group, 1-methylethylene group, ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, n-propylethylene group, isopropylethylene group, 1-ethyl-2-methylethylene group, 1-
Ethyl-1-methylethylene group, trimethylene group, tetramethylene group, pentamethylene group, (methoxymethyl)
Ethylene group, (ethoxymethyl) ethylene group, (methoxyethyl) ethylene group, 1-methoxymethyl-2-methylethylene group, 1,2-bis (methoxymethyl) ethylene group, 1,1-bis (methoxymethyl) ethylene Base,
(Ethoxyethyl) ethylene group, 1,2-bis (ethoxyethyl) ethylene group, 1,1-bis (ethoxyethyl) ethylene group, 2-methoxy-1,3-propylene group, phenylethylene group, 1,2- Propylene group, 2-
Examples thereof include phenyl-1,2-propylene group, 1,3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, and various decylene groups.

Examples of the alicyclic group having two bonding sites on the alicyclic hydrocarbon include cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane and propylcyclohexane.

Examples of the aromatic hydrocarbon group include divalent aromatic hydrocarbon groups such as various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups and various naphthylene groups.

Examples of the alkylaromatic group include alkylaromatic groups having monovalent bonding sites on the alkyl moiety and aromatic moiety of an alkylaromatic hydrocarbon such as toluene, xylene and ethylbenzene, and polyalkyl such as xylene and diethylbenzene. Examples thereof include an alkyl aromatic group having a binding site in the alkyl portion of an aromatic hydrocarbon.

The aliphatic group having 1 to 10 carbon atoms represented by R ₂₁ and R ₂₃ may have an oxygen atom or an unsaturated bond,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups,
Alkyl groups such as decyl, cyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl,
Cycloalkyl groups such as various dimethylcyclohexyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, various butynyl groups, various pentenyl groups, various hexenyl groups, various heptenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups And alkenyl groups and the like.

As the aromatic group represented by R ₂₁ and R ₂₃ ,
Phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups and other aryl groups, benzyl groups, various phenylethyl groups, various Examples thereof include arylalkyl groups such as methylbenzyl group, various phenylpropyl groups, and various phenylbutyl groups.

The ester oil used in the present invention includes:
Formula _{(H) R 31 (OC =} OR 32) p (H) wherein, p is an integer of 1-20. R ₃₁ has 1 carbon atom
~ 100 aliphatic groups. R ₃₂ independently has 1 carbon atom
~ 100 aliphatic or aromatic groups. Where p
When is 2 or more, R _{32 s} may be the same or different. ] The compound represented by this is mentioned.

Preferred groups represented by R ₃₁ —OH include pentaerythritol, dipentaerythritol,
Examples include tripentaerythritol, trimethylolethane, trimethylolpropane, and neopentyl glycol.

R ₃₁ is a hydroxyl group-containing hydrocarbon group remaining after removing some of the hydroxyl groups from pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolethane, trimethylolpropane or neopentyl glycol.

Examples of the aromatic group represented by R ₃₂ include a phenyl group, various methylphenyl groups, various ethylphenyl groups,
Various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups, and other aryl groups, benzyl groups, various phenylethyl groups, various methylbenzyl groups, various phenylpropyl groups, various phenylbutyl groups And other arylalkyl groups.

The aliphatic group having 1 to 100 carbon atoms represented by R ₃₂ may have an oxygen atom or an unsaturated bond, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or an n group.
-Butyl group, isobutyl group, sec-butyl group, ter
Alkyl groups such as t-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propyls Cycloalkyl groups such as cyclohexyl group, various dimethylcyclohexyl groups, vinyl group, allyl group, propenyl group, isopropenyl group, various butynyl groups, various pentenyl groups, various hexenyl groups, various heptenyl groups, various octenyl groups, various nonenyl groups,
Examples thereof include alkenyl groups such as various decenyl groups and 2,5-dioxa-3-methylhexanyl group. Carbon number 1
Alkyl group having a straight-chain or branched having 1 to 30, a polyester group, the general formula (J), (K) - (R 33 O) x R 34 (J) - (OR 35) y R 36 (K) [ In the formula, x and y are the same as above. R ₃₃ and R ₃₅ represent a divalent aliphatic group, an alicyclic group having two bonding sites for an alicyclic hydrocarbon, an aromatic hydrocarbon group or an alkylaromatic group.
R ₃₄ and R ₃₆ represent an aliphatic group having 1 to 30 carbon atoms or an aromatic group. ] As the aromatic group represented by R ₃₄ and R ₃₆ , a phenyl group,
Aryl groups such as various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups, benzyl groups, various phenylethyl groups, various methylbenzyl groups , Arylphenyl groups such as various phenylpropyl groups and various phenylbutyl groups.

The aliphatic group having 1 to 30 carbon atoms represented by R ₃₄ and R ₃₆ may have an oxygen atom or an unsaturated bond,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups,
Alkyl groups such as decyl, cyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl,
Cycloalkyl groups such as various dimethylcyclohexyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, various butynyl groups, various pentenyl groups, various hexenyl groups, various heptenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups And alkenyl groups and the like.

Further, R ₃₃ and R ₃₅ are ethylene groups,
1-methylethylene group, ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, n-
Propylethylene group, isopropylethylene group, 1-ethyl-2-methylethylene group, 1-ethyl-1-methylethylene group, trimethylene group, tetramethylene group, pentamethylene group, (methoxymethyl) ethylene group, (ethoxymethyl) Ethylene group, (methoxyethyl) ethylene group, 1-methoxymethyl-2-methylethylene group, 1,
2-bis (methoxymethyl) ethylene group, 1,1-bis (methoxymethyl) ethylene group, (ethoxyethyl) ethylene group, 1,2-bis (ethoxyethyl) ethylene group, 1,1-bis (ethoxyethyl) Ethylene group, 2-
Methoxy-1,3-propylene group, phenylethylene group, 1,2-propylene group, 2-phenyl-1,2-propylene group, 1,3-propylene group, various butylene groups,
Divalent aliphatic groups such as various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, various decylene groups; cycloaliphatic groups such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane and propylcyclohexane 2 for hydrocarbons
Alicyclic groups having individual bonding sites; various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, various naphthylene groups and other divalent aromatic hydrocarbon groups; toluene, xylene, ethylbenzene, etc. Alkyl Group Having Monovalent Bonding Sites on the Alkyl and Aromatic Moieties of Alkyl, and Alkyl Aromatic Groups Having Bonding Sites on the Alkyl Part of Polyalkyl Aromatic Hydrocarbons such as Xylene and Diethylbenzene Alkyl aromatic groups such as

The aliphatic ether oil used in the present invention is represented by the general formula (L)

[0108]

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[In the formula, R _{37 to} R ₄₂ are the same or different and each represents a hydrogen atom, a hydroxy group or an aliphatic group having 1 to 100 carbon atoms. n ₂ is an integer of 1-20. However,
When n ₂ is 2 or more, R _{38 to} R ₄₁ of each repeating unit may be the same or different. The C 1-100 aliphatic group represented by R _{37 to} R ₄₂ may have an oxygen atom or an unsaturated bond, and may be a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various Alkyl group such as decyl, cyclopentyl group, cyclohexyl group,
Various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, cycloalkyl groups such as various dimethylcyclohexyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, various butynyl groups, various pentenyl groups, various hexenyl groups, Alkenyl groups such as various heptenyl groups, various octenyl groups, various nonenyl groups and various decenyl groups, 2,5-dioxa-3-
Examples thereof include a methylhexanyl group.

[0110] In _{addition, - (R 43 O) x2} R 44 - (OR 45) y2 R 46 wherein, x2, y2 are both an integer of 1 to 30.
R ₄₃ and R ₄₅ are divalent aliphatic groups or alicyclic hydrocarbons with 2
An alicyclic group having 4 bonding sites is shown. R ₄₄ and R ₄₆ are
An aliphatic group having 1 to 10 carbon atoms is shown. ] The compound represented by this is mentioned.

Examples of the divalent aliphatic group represented by R ₄₃ and R ₄₅ include ethylene group, 1-methylethylene group, ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, n-propylethylene group, isopropylethylene group, 1-ethyl-2-methylethylene group, 1-
Ethyl-1-methylethylene group, trimethylene group, tetramethylene group, pentamethylene group, (methoxymethyl)
Ethylene group, (ethoxymethyl) ethylene group, (methoxyethyl) ethylene group, 1-methoxymethyl-2-methylethylene group, 1,2-bis (methoxymethyl) ethylene group, 1,1-bis (methoxymethyl) ethylene Base,
(Ethoxyethyl) ethylene group, 1,2-bis (ethoxyethyl) ethylene group, 1,1-bis (ethoxyethyl) ethylene group, 2-methoxy-1,3-propylene group, 1,2-propylene group, 1 , 3-propylene group, various butylene groups, various pentylene groups, various hexylene groups,
Examples include various heptylene groups, various octylene groups, various nonylene groups, and various decylene groups.

Examples of the alicyclic group having two bonding sites on the alicyclic hydrocarbon include cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane and propylcyclohexane.

The aliphatic group having 1 to 10 carbon atoms represented by R ₄₄ and R ₄₆ may have an oxygen atom or an unsaturated bond,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups,
Alkyl groups such as decyl, cyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl,
Cycloalkyl groups such as various dimethylcyclohexyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, various butynyl groups, various pentenyl groups, various hexenyl groups, various heptenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups And alkenyl groups and the like.

The aliphatic polyoxyalkylene glycol oil in the present invention has a general formula (M) R ₄₇ O- (R ₄₈ O) _{z 1} -R ₄₉ (M) [wherein z 1 represents an integer of 1 to 20]. . R ₄₇ and R ₄₉ are
A hydrogen atom or an aliphatic group having 1 to 100 carbon atoms is shown. R
₄₈ represents a divalent aliphatic group having 1 to 100 carbon atoms. However, when z1 is 2 or more, R ₄₈ may be the same or different. ] The compound represented by this is mentioned.

The aliphatic group having 1 to 100 carbon atoms represented by R ₄₇ and R ₄₉ may have an oxygen atom or an unsaturated bond, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, alkyl groups such as various decyl groups, cyclopentyl groups,
Cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, various dimethylcyclohexyl groups, and other cycloalkyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, various butynyl groups, various pentenyl groups, various Alkenyl groups such as hexenyl group, various heptenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, 2,
Examples thereof include a 5-dioxa-3-methylhexanyl group.

[0116] In _{addition, - (R 43 O) x2} R 44 - (OR 45) y2 R 46 wherein, x2, y2 are both an integer of 1 to 30.
R ₄₃ and R ₄₅ represent a divalent aliphatic group or an alicyclic group having two bonding sites on the alicyclic hydrocarbon. R ₄₄ , R
₄₆ represents an aliphatic group having 1 to 10 carbon atoms. Where x
When 2 and y2 are 2 or more, R ₄₃ and R ₄₅ may be the same or different. ] The compound represented by this is mentioned.

Examples of the divalent aliphatic group represented by R ₄₃ and R ₄₅ include ethylene group, 1-methylethylene group, ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, n-propylethylene group, isopropylethylene group, 1-ethyl-2-methylethylene group, 1-
Ethyl-1-methylethylene group, trimethylene group, tetramethylene group, pentamethylene group, (methoxymethyl)
Ethylene group, (ethoxymethyl) ethylene group, (methoxyethyl) ethylene group, 1-methoxymethyl-2-methylethylene group, 1,2-bis (methoxymethyl) ethylene group, 1,1-bis (methoxymethyl) ethylene Base,
(Ethoxyethyl) ethylene group, 1,2-bis (ethoxyethyl) ethylene group, 1,1-bis (ethoxyethyl) ethylene group, 2-methoxy-1,3-propylene group, 1,2-propylene group, 1 , 3-propylene group, various butylene groups, various pentylene groups, various hexylene groups,
Examples include various heptylene groups, various octylene groups, various nonylene groups, and various decylene groups.

Examples of the alicyclic group having two bonding sites on the alicyclic hydrocarbon include cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane and propylcyclohexane.

The aliphatic group having 1 to 10 carbon atoms represented by R ₄₄ and R ₄₆ may have an oxygen atom or an unsaturated bond,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups,
Alkyl groups such as decyl, cyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl,
Cycloalkyl groups such as various dimethylcyclohexyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, various butynyl groups, various pentenyl groups, various hexenyl groups, various heptenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups And alkenyl groups and the like.

R ₄₈ is an ethylene group, 1-methylethylene group, ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, n-propylethylene group, isopropylethylene group, 1- Ethyl-2-methylethylene group, 1-ethyl-1-methylethylene group,
Trimethylene group, tetramethylene group, pentamethylene group, (methoxymethyl) ethylene group, (ethoxymethyl) ethylene group, (methoxyethyl) ethylene group, 1-
Methoxymethyl-2-methylethylene group, 1,2-bis (methoxymethyl) ethylene group, 1,1-bis (methoxymethyl) ethylene group, (ethoxyethyl) ethylene group, 1,2-bis (ethoxyethyl) ethylene Base 1,
1-bis (ethoxyethyl) ethylene group, 2-methoxy-1,3-propylene group, 1,2-propylene group, 1,
3-Propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, various decylene groups, and other divalent aliphatic groups; cyclohexane, methylcyclohexane, ethylcyclohexane, dimethyl An alicyclic group having two bonding sites on an alicyclic hydrocarbon such as cyclohexane or propylcyclohexane; or a general formula (N)

[0121]

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[In the formula, R ₅₀ , R ₅₁ , R ₅₂ , and R ₅₃ represent a hydrogen atom or an aliphatic group having 1 to 100 carbon atoms. ] The group represented by this is mentioned.

The aliphatic group having 1 to 100 carbon atoms represented by R _{50 to} R ₅₃ may have an oxygen atom or an unsaturated bond, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, alkyl groups such as various decyl groups, cyclopentyl groups,
Cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, various dimethylcyclohexyl groups, and other cycloalkyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, various butynyl groups, various pentenyl groups, various Alkenyl groups such as hexenyl group, various heptenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, 2,
Examples thereof include a 5-dioxa-3-methylhexanyl group.

[0124] In _{addition, - (R 43 O) x2} R 44 - (OR 45) y2 R 46 wherein, x2, y2 are both an integer of 1 to 30.
R ₄₃ and R ₄₅ are divalent aliphatic groups or alicyclic hydrocarbons with 2
An alicyclic group having 4 bonding sites is shown. R ₄₄ and R ₄₆ are
An aliphatic group having 1 to 10 carbon atoms is shown. However, x2, y2
When is 2 or more, R ₄₃ and R ₄₅ may be the same or different. ] The compound represented by this is mentioned.

Examples of the divalent aliphatic group represented by R ₄₃ and R ₄₅ include ethylene group, 1-methylethylene group, ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, n-propylethylene group, isopropylethylene group, 1-ethyl-2-methylethylene group, 1-
Ethyl-1-methylethylene group, trimethylene group, tetramethylene group, pentamethylene group, (methoxymethyl)
Ethylene group, (ethoxymethyl) ethylene group, (methoxyethyl) ethylene group, 1-methoxymethyl-2-methylethylene group, 1,2-bis (methoxymethyl) ethylene group, 1,1-bis (methoxymethyl) ethylene Base,
(Ethoxyethyl) ethylene group, 1,2-bis (ethoxyethyl) ethylene group, 1,1-bis (ethoxyethyl) ethylene group, 2-methoxy-1,3-propylene group, 1,2-propylene group, 1 , 3-propylene group, various butylene groups, various pentylene groups, various hexylene groups,
Examples include various heptylene groups, various octylene groups, various nonylene groups, and various decylene groups.

Examples of the alicyclic group having two bonding sites on the alicyclic hydrocarbon include cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane and propylcyclohexane.

The aliphatic group having 1 to 10 carbon atoms represented by R ₄₄ and R ₄₆ may have an oxygen atom or an unsaturated bond,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups,
Alkyl groups such as decyl, cyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, propylcyclohexyl,
Cycloalkyl groups such as various dimethylcyclohexyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, various butynyl groups, various pentenyl groups, various hexenyl groups, various heptenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups And alkenyl groups and the like.

The aliphatic ester oil used in the present invention has the general formula (O) R ₅₄ (OC = OR ₅₅ ) _p1 (O) [wherein p1 represents an integer of 1 to 20]. R ₅₄ represents an aliphatic group having 1 to 100 carbon atoms. R ₅₅ independently represents an aliphatic group having 1 to 100 carbon atoms. However, when p1 is 2 or more, R ₅₅ may be the same or different. ] The compound represented by this is mentioned.

Preferred groups represented by R ₅₄ —OH include pentaerythritol, dipentaerythritol,
Examples include tripentaerythritol, trimethylolethane, trimethylolpropane, and neopentyl glycol.

R ₅₄ is a hydroxyl group-containing hydrocarbon group remaining after removing some of the hydroxyl groups from pentaerythritol, dipentaerythritol, tripentaerythritol, trimethylolethane, trimethylolpropane or neopentyl glycol.

The aliphatic group having 1 to 100 carbon atoms represented by R ₅₅ may have an oxygen atom or an unsaturated bond, and may be methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, isobutyl group, sec-butyl group, ter
Alkyl groups such as t-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propyl Cycloalkyl groups such as cyclohexyl group, various dimethylcyclohexyl groups, vinyl group, allyl group, propenyl group, isopropenyl group, various butynyl groups, various pentenyl groups, various hexenyl groups, various heptenyl groups, various octenyl groups, various nonenyl groups,
Examples thereof include alkenyl groups such as various decenyl groups and 2,5-dioxa-3-methylhexanyl group. further,
A linear or branched alkyl group having 11 to 30 carbon atoms,
Polyester group, the general formula (P), (Q) - (R 56 O) x2 R 57 (P) - (OR 58) y2 R 59 (Q) wherein, x2, y2 are as defined above. R ₅₆ and R _{58 each} represent a divalent aliphatic group or an alicyclic group having two bonding sites on the alicyclic hydrocarbon. R ₅₇ and R ₅₉ represent an aliphatic group having 1 to 30 carbon atoms. However, when x2 and y2 are 2 or more, R
₅₆ and R ₅₈ may be the same or different. The aliphatic group having 1 to 30 carbon atoms represented by R ₅₇ and R ₅₉ may have an oxygen atom or an unsaturated bond, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- Butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, alkyl groups such as various decyl groups, cyclopentyl groups, cyclohexyl groups, various Cycloalkyl groups such as methylcyclohexyl group, various ethylcyclohexyl groups, various propylcyclohexyl groups, various dimethylcyclohexyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, various butynyl groups, various pentenyl groups, various hexenyl groups, various Such as heptenyl group, various octenyl groups, various nonenyl groups, various decenyl groups, etc. Such as alkenyl group, and the like.

Further, as R ₅₆ and R ₅₈ , an ethylene group,
1-methylethylene group, ethylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, n-
Propylethylene group, isopropylethylene group, 1-ethyl-2-methylethylene group, 1-ethyl-1-methylethylene group, trimethylene group, tetramethylene group, pentamethylene group, (methoxymethyl) ethylene group, (ethoxymethyl) Ethylene group, (methoxyethyl) ethylene group, 1-methoxymethyl-2-methylethylene group, 1,
2-bis (methoxymethyl) ethylene group, 1,1-bis (methoxymethyl) ethylene group, (ethoxyethyl) ethylene group, 1,2-bis (ethoxyethyl) ethylene group, 1,1-bis (ethoxyethyl) Ethylene group, 2-
Methoxy-1,3-propylene group, 1,2-propylene group, 1,3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, various decylene groups Divalent aliphatic groups such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane,
And alicyclic groups having two bonding sites on an alicyclic hydrocarbon such as propylcyclohexane; and the like.

[0133]

The composition lubricating oil of the present invention has the following effects.

The lubricating oil composition of the present invention contains the lubricating oil alone or CFC12 or HCFC2 because of the problem of ozone layer protection.
Fluorinated alkanes, which are promising substitutes for chlorine atom-containing refrigerants such as 2, preferably hydrofluoroalkanes such as hydrofluoroethane, and more preferably HFC-134.
Even in a refrigerant system using a, HFC-32, HFC-125, etc. as a refrigerant, the lubricating performance and durability (capillary clogging etc.) are excellent. Also,
The lubricating oil composition of the present invention has high thermal stability even when the lubricating oil is used alone or in the presence of a refrigerant.

[0135]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples.

Example 1 A 200 ml autoclave was charged with pentaerythritol (2
0 g), KOH (1.9 g) and DMSO (60 ml)
Was added thereto, the atmosphere was replaced with nitrogen, the pressure was reduced, and tetrafluoroethylene (60 g) was charged. Each time tetrafluoroethylene was consumed, 10 g of it was introduced, and the reaction was carried out at 80 ° C. for 18 hours. After completion of the reaction, the mixture was extracted with HCFC141b and washed with water, 1N-HCl aqueous solution and saturated saline.
The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure at 50 ° C to obtain an oily compound (Oil A) (63).
g).

The obtained oil A is a compound a corresponding to n = 0 in the general formula (I):

[0138]

Embedded image

[0139] and containing _{C (CH 2 OCF 2 CF 2} H) 4, the weight ratio of the compound _{a / C (CH 2 OCF 2} CF 2 H) 4 was 4/96.

Example 2 A 1 L autoclave was charged with dipentaerythritol (150
g), KOH (39 g) and DMSO (450 ml) were added, the atmosphere was replaced with nitrogen and the pressure was reduced, and tetrafluoroethylene (3
55 g) was charged. An additional 70 g of tetrafluoroethylene was introduced each time it was consumed, and the reaction was carried out at 80 ° C. for 39 hours. After the reaction, extract with HCFC141b,
It was washed with water, 1N-HCl aqueous solution, and saturated saline. The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure at 50 ° C to obtain an oily compound (Oil B) (435).
g). The obtained oil B is a compound corresponding to the case where n = 1 in the general formula (I), and the compound (b) and the compound (c):

[0141]

Embedded image

The compound (b) / compound (c) had a weight ratio of 33/67.

Example 3 Toluene (1000 g), ethanol (304 g) and boron trifluoride diethyl ether complex (7.8 g) were placed in a four-necked flask (5 L). While cooling in an ice-water bath, while maintaining the internal temperature at approximately 25 ° C, ethyl vinyl ether (3
284 g) was added dropwise over 4.5 hours. After dropping 5
After stirring for 1 minute, the reaction mixture was transferred to a washing tank, washed with 5% by weight aqueous sodium hydroxide solution (1100 ml) three times, and further washed with water (1100 ml) three times. The solvent and unreacted raw materials were removed under reduced pressure to obtain a crude product (3250 g). Next, the crude product (600 g), hexane (600 g), and Raney Ni were placed in an SUS316 autoclave (2 L).
(18g) and zeolite (18g) were added. Hydrogen was introduced into the autoclave and the hydrogen pressure (20 kg / c
m ² ), and after stirring for 30 minutes, the pressure was released. After repeating this operation two more times, the hydrogen pressure was changed to 50 kg / cm ²
And was stirred at 140 ° C. for 2 hours. Hydrogen was added as it was consumed. After completion of the reaction, the reaction solution was cooled to room temperature, depressurized to normal pressure and allowed to stand for 1 hour, and the reaction solution was removed by decantation. The catalyst was washed twice with hexane (100 ml), the washing solution was combined with the reaction solution, and filtered. Further, after washing with a 5 wt% sodium hydroxide aqueous solution (500 ml) three times and with distilled water (500 ml) five times,
Hexane and the like were removed under reduced pressure to obtain 432 g of an oily compound (Oil C).

Example 4 Toluene (1000 g), acetaldehyde diethyl acetal (450 g) and boron trifluoride diethyl ether complex (4.5 g) were placed in a four-necked flask (5 L). While cooling in an ice-water bath, ethyl vinyl ether (3200 g) was added dropwise over 4 hours and 10 minutes while maintaining the internal temperature at about 25 ° C. After completion of dropping, the mixture was stirred for 5 minutes, the reaction mixture was transferred to a washing tank, and a 5 wt% sodium hydroxide aqueous solution (1
000 ml) three times, and then water (1000 ml)
And washed three times. The solvent and unreacted raw materials were removed under reduced pressure to obtain a crude product (3320 g). Next, SUS316
The crude product (600 g), hexane (600 g), Raney Ni (18 g) and zeolite (18 g) were added to an autoclave (2 L). Hydrogen was introduced into the autoclave to adjust the pressure to hydrogen (20 kg / cm ² ), stirred for 30 minutes, and then depressurized. After repeating this operation two more times,
The hydrogen pressure was set to 50 kg / cm ² , and the mixture was stirred at 140 ° C. for 2 hours. Hydrogen was added as it was consumed. After completion of the reaction, the reaction solution was cooled to room temperature, depressurized to normal pressure and allowed to stand for 1 hour, and the reaction solution was removed by decantation. The catalyst was washed twice with hexane (100 ml), the washing solution was combined with the reaction solution, and filtered. Further, it was washed three times with a 5 wt% sodium hydroxide aqueous solution (500 ml), and distilled water (500 m
After washing 5 times with 1), hexane and the like were removed under reduced pressure to obtain 425 g of an oily compound (Oil D).

Example 5 A four-necked flask (500 ml) was charged with toluene (50 g),
Isobutyl alcohol (11 g) and boron trifluoride diethyl ether complex (0.5 g) were added. Isobutyl vinyl ether (100 g) was added dropwise over 55 minutes while keeping the internal temperature at about 30 ° C. while cooling with an ice-water bath. After completion of dropping, the mixture was stirred for 5 minutes, and the reaction mixture was transferred to a washing tank and
It was washed with a weight% sodium hydroxide aqueous solution (100 ml) three times, and further with water (150 ml) three times. The solvent and unreacted raw materials were removed under reduced pressure to obtain a crude product (101 g)
I got Next, SUS316 autoclave (1L)
Crude product (90g), hexane (300g), Raney N
i (4.8 g) and zeolite (4.8 g) were added.
Hydrogen was introduced into the autoclave and the hydrogen pressure (20 kg /
cm ² ), and after stirring for 30 minutes, the pressure was released. After repeating this operation two more times, the hydrogen pressure was changed to 50 kg / cm.
^It was set to ² and stirred at 140 ° C. for 2 hours. Hydrogen was added as it was consumed. After completion of the reaction, the reaction solution was cooled to room temperature, depressurized to normal pressure and allowed to stand for 1 hour, and the reaction solution was removed by decantation. The catalyst was washed twice with hexane (30 ml), the washing liquid was combined with the reaction liquid, and filtered. Further, after washing with a 5 wt% sodium hydroxide aqueous solution (100 ml) three times and with distilled water (150 ml) five times,
Hexane and the like were removed under reduced pressure to obtain 79 g of an oily compound (Oil E).

Example 6 A four-necked flask (500 ml) was charged with toluene (50 g),
Acetaldehyde diethyl acetal (17.7 g) and boron trifluoride diethyl ether complex (1.5 g)
Was put. While cooling in an ice-water bath, ethyl vinyl ether (43 g) and isopropyl vinyl ether (65 g) were added dropwise over 50 minutes while maintaining the internal temperature at about 30 ° C. After completion of dropping, the mixture was stirred for 5 minutes, transferred to a washing tank, washed 3 times with a 5 wt% aqueous sodium hydroxide solution (100 ml), and further washed 3 times with water (150 ml).
The solvent and unreacted raw materials were removed under reduced pressure to obtain a crude product (11
5 g) were obtained. Next, the crude product (110 g) and hexane (300 g) were placed in an SUS316 autoclave (1 L).
g), Raney Ni (5.5 g) and zeolite (5.5)
g) was added. Hydrogen was introduced into the autoclave to adjust the pressure to hydrogen (20 kg / cm ² ), stirred for 30 minutes, and then depressurized. After repeating this operation twice more, the hydrogen pressure was set to 50 kg / cm ² and the mixture was stirred at 140 ° C. for 2 hours. Hydrogen was added as it was consumed. After completion of the reaction, the reaction solution was cooled to room temperature, depressurized to normal pressure and allowed to stand for 1 hour, and the reaction solution was removed by decantation. The catalyst was hexane (30
ml) and washed twice, and the washings were combined with the reaction solution and filtered. Furthermore, a 5 wt% sodium hydroxide aqueous solution (1
(00 ml) three times and distilled water (150 ml) five times, and then hexane and the like were removed under reduced pressure to obtain 95 g of an oily compound (Oil F).

Example 7 Pentaerythritol (1090 g) and n were placed in a flask (5 L) equipped with a Dean-Stark tube and a cooling tube.
-Hexanoic acid (3900 g) was added and the temperature was raised with stirring. When the temperature of the solution reached 200 ° C., it was held for 3 hours, further heated to 220 ° C., and then held for 10 hours. After completion of the reaction, the reaction solution was cooled to 150 ° C., and most of unreacted n-hexanoic acid was recovered under reduced pressure. The remaining liquid was dissolved in hexane (2 L), and then washed 3 times with a 3 wt% sodium hydroxide aqueous solution (1500 ml), and further washed with water (1500 ml) 3 times. Ion exchange resin (800 g) was added to the washed hexane, and the mixture was stirred for 3 hours. After filtering off the ion exchange resin, hexane was distilled off under reduced pressure to obtain 3250 g of an oily compound (Oil G).

Example 8 The oil C (900 g) obtained in Example 3 was added to the oil B (100 g) obtained in Example 2 to obtain 1000 g of an oil mixture (oil H).

Example 9 The oil D (950 g) obtained in Example 4 was added to the oil B (50 g) obtained in Example 2 to obtain 1000 g of an oil mixture (Oil I).

Example 10 Oil E (990 g) obtained in Example 5 was added to oil B (10 g) obtained in Example 2 to obtain 1000 g of an oil mixture (Oil J).

Example 11 The oil F (900 g) obtained in Example 6 was added to the oil B (100 g) obtained in Example 2 to obtain 1000 g of an oil mixture (oil K).

Example 12 Oil G (900 g) obtained in Example 7 was added to oil B (100 g) obtained in Example 2 to obtain 1000 g of an oil mixture (oil L).

Example 13 Oil F (900 g) obtained in Example 6 was added to oil A (100 g) obtained in Example 1 to obtain 1000 g of an oil mixture (Oil M).

Example 14 The oil B (80 g) obtained in Example 2 and the oil F (900 g) obtained in Example 6 were added to the oil A (20 g) obtained in Example 1 to give an oil. Mixture (oil N)
1000 g were obtained.

Example 15 Bisphenol A (150 g) and K were added to 1 liter of autoclave.
OH (21.7 g) and DMSO (400 ml) were added, the atmosphere was replaced with nitrogen, and the pressure was reduced to tetrafluoroethylene (14
4g) was charged. Every time tetrafluoroethylene was consumed, it was further introduced (10 g) and reacted at 80 ° C. for 14 hours. After the reaction, extract with HCFC141b,
It was washed with water, 1N-HCl aqueous solution, and saturated saline. The organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure at 50 ° C. to obtain an oily compound (Oil O) (280
g). The obtained oil O is a compound d corresponding to the general formula (III):

[0156]

Embedded image

It was. Example 16 Oil O (100 g) obtained in Example 15 and alkylbenzene oil (VG15) (100 g) Oil F (800 g) obtained in Example 6 were added to give an oily compound (Oil P) (1000 g). Obtained.

Test Example 1 Lubrication Property Test In order to verify the effect of the compounds obtained in each of Examples 3 to 16 on the lubrication property in a short time, a lubrication property test was carried out as follows. The refrigerant used is HFC-1
34a / HFC-32 / HFC-125 (52/23 /
25% by weight).

As the friction type, as shown in FIG. 1, a shell four-ball type in which three fixed balls are pressed against one rotating ball is used.
Table 1 shows the experimental conditions.

As the friction tester, a high pressure atmosphere friction and wear tester shown in FIG. 2 capable of reproducing the internal condition of the compressor was used.
The baking characteristics were evaluated. The seizure load was the load that caused a sharp increase in friction torque. Table 2 shows the results of the seizure property test.

[0161]

[Table 1] Shell 4-ball seizure test conditions Steel ball material: SUJ-2 CFC / oil: 50/50 wt% Sliding speed (rotation speed): 0.768 m / s (2000 rpm) Pressurization method: Continuous pressurization method

[0162]

[Table 2] Lubrication characteristics test results Compound Sake load (kgf) Oil H 171 Oil I 196 Oil J 203 Oil K 192 Oil L 165 Oil M 179 Oil N 190 Oil P 185 Oil C 135 Oil D 146 Oil E 151 Oil F 142 Oil G 135 Test Example 2 Actual Device Test For the compounds obtained in each Example, HFC-134a
/ HFC32 / HFC125 mixed refrigerant was tested in an actual machine to evaluate the clogging of the capillaries.

With the contamination level in the system piping set to the same level as the conventional level (R22 level), a HFC-134a / HFC32 / H was used by using a rotary piston type compressor of 3/4 horsepower.
FC125 (52/23/25 wt%) mixed refrigerant,
Continuous operation was performed under the operating conditions of Te = 5 ° C., Tc = 55 ° C., and Td = 110 ° C., and the refrigerant flow rate reduction rate after the operation between the inlet and the outlet of the system using each compound was measured. Table 3 shows the results.

[0164]

[Table 3] Capillary clogging test result Compound Operating time (hr) Capillary flow rate decrease rate (%) Oil H 1300 93 Oil I 1300 95 Oil J 1300 93 Oil K 1300 95 Oil M 1300 92 Oil N 1300 94 Oil P 1300 94 Oil C 1000 78 Oil D 1000 74 Oil E 1000 77 Oil F 1000 75

[Brief description of drawings]

FIG. 1 is a diagram showing a friction test part, a test piece shape, and dimensions in a four-ball test.

FIG. 2 is a schematic diagram of a friction and wear test under a refrigerant coexisting high pressure atmosphere.

Front page continuation (72) Inventor Eiji Sakamoto 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Works (72) Inventor Shuichi Uebata 1-1, Nishiichitsuya, Settsu-shi, Osaka Daikin Industries, Ltd. Yodogawa Factory

Claims (12)

[Claims] 1. A general formula (I): Wherein, n represents an integer of 0 to 5, R _1a is CF ₂ CF ₂ H
Or H is shown; R ₂ , R ₅ , and R ₆ are the same or different and each is a monovalent aliphatic group having 1 to 100 carbon atoms, or an aliphatic group having 1 to 100 carbon atoms partially substituted with a fluorine atom. represents a _{group, R 3, R 4, R} 7 are the same or different and each a divalent aliphatic group having 1 to 100 carbon atoms, substituted partially by fluorine atoms aliphatic group having 1 to 100 carbon atoms (Provided that when R _1a is H, it has a fluorine atom in any of R ₂ , R ₅ and R ₆ ). ] Fluorine-containing lubricating oil represented by and (b) at least one selected from the group consisting of oxygen-containing lubricating oil, ether oil, polyoxyalkylene glycol oil, mineral oil, alkylbenzene oil and ester oil, stable A lubricating oil composition with excellent properties. 2. (a) General formula (I): [In formula, n, R < _1a >, R < ₂ > -R < ₇ > is the same as the above. ] A fluorine-containing lubricating oil represented by and (b) a lubricating oil having an oxygen atom, an ether oil, a polyoxyalkylene glycol oil,
The refrigerating machine oil composition according to claim 1, comprising at least one selected from the group consisting of mineral oil, alkylbenzene oil and ester oil, and having excellent stability. (A) General formula (I): [In formula, n, R < _1a >, R < ₂ > -R < ₇ > is the same as the above. ] And a compound represented by the general formula (II): [In the formula, m represents an integer of 1 to 6, R _1b and R _1c are the same or different and represent CF ₂ CF ₂ H or H; R ₈ and R 1
₁₁ is the same or different and is a divalent aliphatic group having 1 to 100 carbon atoms or an aliphatic group having 1 to 100 carbon atoms in which a part is substituted with a fluorine atom, and R ₉ and R ₁₀ are the same or different. Differently, a monovalent aliphatic group having 1 to 100 carbon atoms or an aliphatic group having 1 to 100 carbon atoms in which a part thereof is substituted with a fluorine atom is shown (provided that R _1b and R _1c are H at the same time, Having a fluorine atom in either R ₉ or R ₁₀ . ] Containing at least one selected from the group consisting of a mixture of compounds represented by and (b) an oxygen atom-containing lubricating oil, ether oil, polyoxyalkylene glycol oil, mineral oil, alkylbenzene oil and ester oil, Excellent lubricating oil composition. (A) General formula (I): [In formula, n, R < _1a >, R < ₂ > -R < ₇ > is the same as the above. ] And a compound represented by the general formula (II): [In formula, m, R _<1b> , R _<1c> , R < ₈ > -R < ₁₁ > is the same as the above. ] Containing at least one selected from the group consisting of a mixture of compounds represented by and (b) an oxygen atom-containing lubricating oil, ether oil, polyoxyalkylene glycol oil, mineral oil, alkylbenzene oil and ester oil, Excellent refrigerator oil composition. (A) General formula (III): R ₁₂ (OR ₁₃ ) _L (III) [In the formula, L represents an integer of 1 to 20, and R ₁₂ has 6 to 6 carbon atoms.
An L-valent aromatic group of 100 is shown. R ₁₃ is CF ₂ CF ₂ H
Or H is shown; when L is 2 or more, R ₁₃ 's may be different (provided that not all R _13's are H). ] And at least one selected from the group consisting of a fluorine-containing lubricating oil represented by (b) an oxygen-containing aliphatic lubricating oil, an aliphatic ether oil, an aliphatic polyoxyalkylene glycol oil, and an aliphatic ester oil. A lubricating oil composition containing excellent stability. (A) General formula (III): R ₁₂ (OR ₁₃ ) _L (III) IN FORMULA, L, R ₁₂ AND R ₁₃ ARE THE SAME AS THE ABOVE-MENTIONED. ] At least one selected from the group consisting of a fluorine-containing lubricating oil represented by and (b) an aliphatic lubricating oil having an oxygen atom, an aliphatic ether oil, an aliphatic polyoxyalkylene glycol oil, and an aliphatic ester oil. A refrigerating machine oil composition containing excellent stability. 7. (a) Of the compounds of any one of formulas (I) to (III) and (b) the compounds of formulas (I) to (III), which are not included in the above (a). A lubricating oil composition having excellent stability, containing at least two compounds selected from the group consisting of other two compounds, an oxygen atom-containing lubricating oil, an ether oil and a polyoxyalkylene glycol oil, an ester oil, a mineral oil, and an alkylbenzene oil. Stuff. 8. (a) One compound of any one of the general formulas (I) to (III), (b) Two other compounds not included in the above (a), a lubricating oil having an oxygen atom, Ether oil and polyoxyalkylene glycol oil, ester oil, mineral oil,
A refrigerator oil composition having excellent stability, containing at least two kinds selected from the group consisting of alkylbenzene oils. 9. A lubricating oil composition containing the composition according to any one of claims 1 to 8 and an additive. 10. A refrigerating machine oil composition containing the composition according to any one of claims 1 to 8 and an additive. 11. (a) It has 1 to 5 carbon atoms partially or completely substituted with at least one atom of chlorine or fluorine, and is standard in the range of -80 ° C to + 50 ° C. Saturated hydrocarbons having different boiling points and (b) claims 2, 4, 6,
A refrigerator working fluid composition containing the composition according to any one of 8 and 10. 12. The component (a) is HFC-134a.
(1,1,1,2-tetrafluoroethane), HFC-
134 (1,1,2,2-tetrafluoroethane), H
FC-32 (difluoromethane), HFC-125
The composition according to claim 11, which is at least one compound selected from the group consisting of (1,1,1,2,2-pentafluoroethane).