JPH0967589A - Working fluid composition for refrigerator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a working fluid compsn. for a refrigerator which has excellent lubricity, compatibility with a hydrofluorocarbon and other properties and, in addition, offers excellent abrasion resistance of a metal contact surface by adding a particular compd. to a particular base oil. SOLUTION: This working fluid compsn. for a refrigerator comprises: a lubricating oil compsn. comprising a base oil composed mainly of an ester, a polyalkylene glycol, or a carbonate synthetic oil or a mixture thereof and, incorporated into the base oil, an acid phosphoric ester represented by formulae I and/or II (wherein R<1> , R<2> , and R<5> represent an alkylene; R<3> , R<4> , R<6> , and R<7> represent H, a (halogenated) alkyl, an alkenyl, a (halogenated) aryl, or an aralkyl; (p), (q), and (r) are 0 to 30) and a polyamine compd. represented by formulae III and/or IV (wherein R<8> , R<9> , and R<11> represent H, an alkyl, an alkenyl, an aryl, or an aralkyl; R<12> and R<14> represent an alkylene; R<10> represents H, an alkyl, an alkenyl, an aryl, an aralkyl, or the like; or the like); and a hydrofluorocarbon.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition for a working fluid of a refrigerator. More specifically, ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a base oil containing a mixed oil thereof as a main component, a lubricating oil composition prepared by blending a specific phosphorus compound and a polyvalent amine compound, and hydrofluorocarbon. The present invention provides a composition for a working fluid of a refrigerator containing the composition.

[0002]

2. Description of the Related Art Recently, the use of dichlorodifluoromethane (CFC12), which is used in refrigerators and car coolers to protect the ozone layer, has been regulated, and it was decided that it will be prohibited by the end of 1995. In addition, subsequently, chlorodifluoromethane (HCF) used for room air conditioners, etc.
The use of C22) is about to be regulated. for that reason,
As alternatives to the CFC12 and HCFC22, various hydrofluorocarbon (HFC) -based refrigerants that do not destroy the ozone layer, such as 1,1,1,2-tetrafluoroethane (HFC134a) and difluoromethane (HFC), are used.
FC32) and pentafluoroethane (Freon 125) have been developed.

These HFC-based refrigerants are CFC12 and H
When lubricating oils such as naphthenic mineral oils, poly α-olefins, and alkylbenzenes, which have higher polarity than CFC22 and are generally used as refrigerating machine oils, are used, the compatibility between these lubricating oils and HFC refrigerants is improved. Poorly, it causes bilayer separation at low temperature. When two-layer separation occurs, oil return deteriorates, a thick oil film is attached near the condenser or evaporator as a heat exchanger to hinder heat transfer, and there are important defects such as poor lubrication and foaming at startup. Cause of. Therefore, the conventional refrigerating machine oil cannot be used as a refrigerating machine oil under these new refrigerant atmospheres. Therefore, there is a need for a lubricating oil that has good compatibility with hydrofluorocarbons.

Also, regarding lubricity, CFC12 and HCF are also available.
In C22, there was an effect that it partially decomposed to generate hydrogen chloride, and this hydrogen chloride reacted with the friction surface to form a chloride film to improve lubricity. However, HFC-based refrigerants such as pentafluoroethane, 1,1,1-trifluoroethane, difluoromethane, and 1,1,1,2-tetrafluoroethane that do not contain chlorine atoms have such effects. Because I can't expect
Refrigerating machine oil used together with this is required to have better lubricity than conventional ones.

The problem of compatibility with these hydrofluorocarbons can be solved by using an ester type lubricating oil, a polyalkylene glycol type lubricating oil or a carbonate type lubricating oil. However, it cannot be said that the lubricity, particularly the wear resistance, is sufficiently good, and compared with the conventional chlorofluorocarbon or hydrochlorofluorocarbon-naphthene mineral oil system, hydrofluorocarbon-ester lubricating oil or polyalkylene glycol lubricating oil is used. Oil and carbonate type lubricating oil systems are inferior.

In the field of working fluid for refrigerators, many methods of adding additives to refrigerator oils have been proposed as methods for improving lubricity. As a method for improving the lubricity in the coexistence of hydrofluorocarbon, there is disclosed in JP-A-2-87104.
JP, JP 3-28297 JP, JP 3-285992 JP, JP 4-28792 JP, JP 4-100894 JP, JP 5-59388 JP, JP 5-230487 JP , JP-A-6-
88086, JP-A-6-145688, JP-A-6-184582
The method of adding a phosphoric acid triester as seen in JP-A No. 4-100894 and JP-A No.
5-59388, JP-A-6-145688, JP-A-6-1845
Method of adding phosphite triester as seen in JP-A-82, also JP-A-5-230488, JP-A-5-302093
JP-A-5-302093 describes a method of adding hydrogen phosphite as disclosed in JP-A-5-302093. Furthermore,
As seen in JP-A-5-17794 and JP-A-5-230487, there is a method of adding an acidic phosphoric acid ester and a monovalent amine compound.

[0007]

As the phosphoric acid ester which can solve the above problems, phosphoric acid triester, phosphorous acid triester, hydrogen phosphite,
It has been proposed to use phosphonates and acidic phosphoric acid esters in combination with amine compounds, but if these phosphoric acid esters are simply added, ester-based, polyalkylene glycol-based or carbonate-based lubricating oils can be used as base oils. In addition, the effect of suppressing wear is insufficient. Furthermore, the addition of hydrogen phosphite and acidic phosphates has the problem of promoting the hydrolysis of these base oils. Also,
The combined use of the acidic phosphate ester and the monovalent amine compound disclosed in JP-A-5-17794 and JP-A-5-230487 was insufficient in the effect of suppressing wear.

Therefore, the object of the present invention is to provide excellent lubricity,
It is an object of the present invention to provide a composition for a working fluid of a refrigerator, which is excellent in compatibility with hydrofluorocarbons and is also excellent in wear resistance on a metal contact surface.

[0009]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that
It is possible to achieve the above object by adding an acidic phosphate ester having a specific structure and a polyvalent amine compound to a base oil mainly composed of a polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof. Heading, it came to complete this invention.

That is, the gist of the present invention is to provide a base oil containing [1] an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil of these as a main component, represented by the general formula (1) and / or (2 ) Acidic phosphate represented by

[0011]

[Chemical 7]

(In the formula, R ¹ and R ² may be the same or different and each represents a linear or branched alkylene group having 2 to 4 carbon atoms. P and q are integers of 0 to 30. R ³ and R ⁴ may be the same or different and each is a hydrogen atom, a straight chain alkyl group having 1 to 18 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, or a carbon number. A straight chain alkenyl group having 2 to 18 carbon atoms, a branched chain alkenyl group having 3 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and a halogen having 1 to 18 carbon atoms Alkyl group or a halogenated aryl group having 6 to 18 carbon atoms, provided that when p and q are both 0, R ³ and R ⁴ are not hydrogen atoms at the same time.)

[0013]

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(In the formula, R ⁵ represents a linear or branched alkylene group having 2 to 4 carbon atoms. R represents an integer of 0 to 30.
R ⁶ is a hydrogen atom, a straight chain alkyl group having 1 to 18 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, a straight chain alkenyl group having 2 to 18 carbon atoms, a branched chain having 3 to 18 carbon atoms Represents a chain alkenyl group, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, a halogenated alkyl group having 1 to 18 carbon atoms, or a halogenated aryl group having 6 to 18 carbon atoms. . R
⁷ is a straight chain alkyl group having 1 to 18 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, a straight chain alkenyl group having 2 to 18 carbon atoms, a branched chain alkenyl group having 3 to 18 carbon atoms An aryl group having 6 to 18 carbon atoms,
Aralkyl groups having 7 to 18 carbon atoms, 1 to 18 carbon atoms
And a halogenated aryl group having 6 to 18 carbon atoms. ), And a polyvalent amine compound represented by the general formula (3) and / or (4)

[0015]

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(In the formula, R ⁸ , R ⁹ and R ¹¹ may be the same or different, and are a hydrogen atom and a carbon number of 1 to 1.
A straight chain alkyl group having 8 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, a straight chain alkenyl group having 2 to 18 carbon atoms, a branched chain alkenyl group having 3 to 18 carbon atoms, and 6 to 18 carbon atoms. An aryl group having or a carbon number of 7 to 18
Represents an aralkyl group having. R ¹² represents a linear or branched alkylene group having 2 to 6 carbon atoms. R ¹⁰ is a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, or 3 to 18 carbon atoms.
A branched chain alkyl group having 2 to 18 carbon atoms, a linear alkenyl group having 2 to 18 carbon atoms, a branched chain alkenyl group having 3 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and 7 carbon atoms.
Aralkyl group having to 18, or - (R ¹³ -NH) m
-R ¹³ -NH ₂ group (R ¹³ represents a linear or branched alkylene group having 2 to 6 carbon atoms, m is an integer of from 1 to 20.)
Represents k is an integer of 1 to 4. )

[0017]

Embedded image

(In the formula, R ¹⁵ is a hydrogen atom and has 1 to 18 carbon atoms.
Having a straight chain alkyl group having 3 to 18 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, a straight chain alkenyl group having 2 to 18 carbon atoms, a branched chain alkenyl group having 3 to 18 carbon atoms, and 6 to 18 carbon atoms An aryl group, an aralkyl group having 7 to ¹⁸ carbon atoms, or a -R ¹⁶ NR ¹⁷ R ¹⁸ group (R ¹⁶ represents a linear or branched alkylene group having 2 to 6 carbon atoms. R ¹⁷ ,
R ¹⁸ is a hydrogen atom, a straight chain alkyl group having 1 to 18 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, a straight chain alkenyl group having 2 to 18 carbon atoms, an aryl having 6 to 18 carbon atoms Represents a group, an aralkyl group having 7 to 18 carbon atoms, or a branched alkenyl group having 3 to 18 carbon atoms. ) Represents. The n R ^{15 s} may be the same or different. R ¹⁴ represents a linear or branched alkylene group having 2 to 6 carbon atoms. n is an integer of 1 to 4. However, when n is 1, R ¹⁵ represents a -R ¹⁶ NR ¹⁷ R ¹⁸ group. A composition for a working fluid of a refrigerating machine, which comprises a lubricating oil composition containing the above) and hydrofluorocarbon, [2] an acidic phosphoric acid ester and a polyvalent amine compound,
Ratio of the value obtained by multiplying the amine value (mgKOH / g) of the polyvalent amine compound by the compounding weight (g) with respect to the value obtained by multiplying the acid value (mgKOH / g) of the acidic phosphoric acid ester by the compounding weight (g). The composition for a working fluid for a refrigerator according to the above [1], which is blended in an amount of 1.0 to 5.0, [3] The total of the blending amounts of the acidic phosphate ester and the polyvalent amine compound is an ester. 0.05 to 100 parts by weight of a base oil mainly composed of a synthetic oil, a polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof.
The composition for a working fluid of a refrigerator according to the above [1] or [2], which is 5.0 parts by weight.

[4] The ester synthetic oil comprises (a) a C 2-10 divalent to C 6 saturated aliphatic polyhydric alcohol and a C 2 to C 9 linear or branched saturated aliphatic monoalcohol. An ester obtained from a carboxylic acid or a derivative thereof,
(B) C1-C10 linear or branched saturated aliphatic 1
An ester obtained from a polyhydric alcohol and a divalent to hexavalent polycarboxylic acid having 2 to 10 carbon atoms or a derivative thereof, (c)
A C2-C10 divalent to C6 saturated aliphatic polyhydric alcohol, a C2-C9 linear or branched saturated aliphatic monocarboxylic acid or a derivative thereof, and a C2-C10 linear or An ester obtained from a branched saturated aliphatic dicarboxylic acid or a derivative thereof, and (d) 2 having 2 to 10 carbon atoms
~ Hexavalent saturated aliphatic polyhydric alcohol and 1 to 1 carbon atoms
An ester obtained from a straight-chain or branched-chain saturated aliphatic monohydric alcohol of 0 and a divalent to hexavalent polycarboxylic acid having 2 to 10 carbon atoms or a derivative thereof, and [1] to [3] The working fluid composition for a refrigerator according to any one of [1] to [3], wherein the polyalkylene glycol-based synthetic oil is represented by the general formula (5). represents a working fluid composition for refrigerating machine, A- and ^{(O- (R 19 O) v} -R 20) w (5) ( wherein, R ¹⁹ is a straight-chain or branched-chain alkylene group having 2 to 4 carbon atoms R ²⁰ represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, or an acyl group having 2 to 15 carbon atoms, A represents a hydrogen atom, a w-valent alcohol residue having 1 to 15 carbon atoms, or a carbon number Represents a w-valent phenol residue of 6 to 15. v is 1 to
The integer of 50 and w represent the integer of 1-6. However, v R ¹⁹ O, w R ²⁰ and w O- (R ¹⁹ O) v -R ²⁰
May be the same or different. [6] A composition for a working fluid of a refrigerator according to any one of the above [1] to [3], wherein the carbonate-based synthetic oil is represented by the general formula (6).

[0020]

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(In the formula, R ²¹ and R ²³ may be the same or different and each is an alkyl group having 1 to 18 carbon atoms;
Aryl group, alkylaryl group, an aralkyl group, or - represents the (R ²⁵ O) groups represented by z -R ^24. Where R
²⁴ is an alkyl group having 1 to 18 carbon atoms, an aryl group, an alkylaryl group or an aralkyl group, and R ²⁵ is 2 to 18 carbon atoms.
Of alkylene group, arylene group, alkylarylene group or aralkylene group, and z represents an integer of 1 to 100. z
The individual R ²⁵ O may be the same or different. R ²²
Is an alkylene group having 2 to 18 carbon atoms, an arylene group, an alkylarylene group or an aralkylene group, and x is 1 to 100.
And y represents an integer of 0 to 100. x R ²² O may be the same or different, and y R ²² O

[0022]

[Chemical 12]

May be the same or different. ] [7] The mixing ratio of hydrofluorocarbon and lubricating oil composition is hydrofluorocarbon / lubricating oil composition =
[1] to 50/1 to 1/20 (weight ratio)
[6] The composition for a working fluid of a refrigerator according to any one of the above.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. 1. Base oil (i) Ester-based synthetic oil The ester-based synthetic oil used in the present invention is compatible with hydrofluorocarbons, has a pour point of 0 ° C or lower, and has the general formula (1) and / or (2). ) Acidic phosphoric acid ester represented by the formula) and the general formulas (3) and / or (4)
There is no particular limitation as long as it is an ester capable of dissolving the polyvalent amine compound represented by For example, esters selected from the following groups are preferred. (A) C2-C10 divalent to hexavalent saturated aliphatic polyhydric alcohol (component-1) and C2-C9 linear or branched saturated aliphatic monocarboxylic acid or derivative thereof (component) −
2) An ester obtained from (B) C1-C10 linear or branched saturated aliphatic 1
Polyhydric alcohol (component-3) and 2-6 with 2-10 carbon atoms
An ester obtained from a divalent polycarboxylic acid or a derivative thereof (component-4). (C) C2-C10 divalent to hexavalent saturated aliphatic polyhydric alcohol (component-1) and C2-C9 linear or branched saturated aliphatic monocarboxylic acid or derivative thereof (component) −
An ester obtained from 2) and a linear or branched saturated aliphatic dicarboxylic acid having 2 to 10 carbon atoms or a derivative thereof (component-5). (D) a C2-C10 divalent to hexavalent saturated aliphatic polyhydric alcohol (Component-1) and a C1-C10 linear or branched saturated aliphatic monohydric alcohol (Component-3) And an ester obtained from a divalent to hexavalent polycarboxylic acid having 2 to 10 carbon atoms or a derivative thereof (component-4).

Regarding Component-1 The valence of the alcohol of Component-1 is 2 to 6, and preferably 2 to 4. The valence is preferably 2 or more from the viewpoint of having an appropriate viscosity, and is preferably 6 or less from the viewpoint of avoiding unnecessary viscosity and compatibility with the hydrofluorocarbon. The carbon number thereof is 2-10, preferably 2-6. The number of carbon atoms is preferably 2 or more from the viewpoint of having an appropriate viscosity, and is 1 from the viewpoint of avoiding excessive viscosity and compatibility with hydrofluorocarbons.
0 or less is preferable. Further, it is preferable not to contain an unsaturated bond from the viewpoint of heat resistance.

Specific examples of the alcohol as the component-1 include:
Hindered alcohols such as neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol, and ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-
Examples thereof include polyhydric alcohols such as butanediol, 1,6-hexanediol, glycerin, diglycerin, triglycerin, sorbitol, and mannitol. Among these, hindered alcohol is particularly excellent from the viewpoint of heat resistance.

Regarding Component-2 The carboxylic acid of Component-2 has 2 to 9 carbon atoms, preferably 5 to 9 carbon atoms. The number of carbon atoms is preferably 2 or more from the viewpoint of suppressing corrosiveness to metals, and is preferably 9 or less from the viewpoint of compatibility with hydrofluorocarbons. From the viewpoint of compatibility with hydrofluorocarbons and hydrolysis resistance, branched saturated fatty acids are more preferable than linear saturated fatty acids. On the other hand, from the viewpoint of lubricity, straight-chain saturated fatty acids are more preferable than branched-chain saturated fatty acids. In the present invention,
A suitable one is selected depending on the mode of use as a composition for a working fluid of a refrigerator. Further, from the viewpoint of heat resistance, it is more preferable not to contain an unsaturated bond.

Specific examples of the component-2 carboxylic acid include:
Valeric acid, isovaleric acid, 2-methylbutyric acid, caproic acid, enanthic acid, 2-ethylpentanoic acid, 2-methylhexanoic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, 3,5,5-trimethylhexanoic acid Etc. In addition, specific examples of the carboxylic acid derivative of the component-2 include methyl ester, ethyl ester, and acid anhydride of these carboxylic acids.

Regarding Component-3 The alcohol of Component-3 has 1 to 10 carbon atoms, preferably 5 to 9 carbon atoms. From the viewpoint of compatibility with hydrofluorocarbons, 10 or less is preferable. From the viewpoint of compatibility with hydrofluorocarbons and hydrolysis resistance, branched-chain saturated alcohols are more preferable than straight-chain saturated alcohols. From the viewpoint of lubricity, straight-chain saturated alcohols are more preferable than branched-chain saturated alcohols. In the present invention, a suitable material is selected according to the mode of use as the composition for the working fluid of the refrigerator. Also, in terms of heat resistance,
It is more preferable not to include an unsaturated bond.

Specific examples of the alcohol of component-3 include:
Hexanol, 3-methylhexanol, heptanol, 2-ethylhexanol, octanol, 3,5
Examples include 5-trimethylhexanol and nonanol.

Regarding Component-4: The carboxylic acid of Component-4 has a valence of 2 to 6, preferably 2 to 4, and more preferably 2 to 3. The valence is preferably 2 or more from the viewpoint of having an appropriate viscosity, and is preferably 6 or less from the viewpoint of avoiding unnecessary viscosity and compatibility with the hydrofluorocarbon. The carbon number thereof is 2-10, preferably 4-9. From the viewpoint of compatibility with hydrofluorocarbons, 10 or less is preferable.

Specific examples of the carboxylic acid of component-4 include:
Saturated aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and 1,2,3-
Examples thereof include saturated aliphatic tricarboxylic acids such as propanetricarboxylic acid and β-methyltricarboxylic acid, and aromatic polycarboxylic acids such as phthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid. Further, specific examples of the carboxylic acid derivative of the component-4 include methyl ester, ethyl ester, acid anhydride and the like of these carboxylic acids.

Regarding Component-5 The carboxylic acid of Component-5 has 2 to 10 carbon atoms, preferably 4 to 6 carbon atoms. From the viewpoint of compatibility with hydrofluorocarbons, 10 or less is preferable. Further, from the viewpoint of heat resistance, it is more preferable not to contain an unsaturated bond.

Specific examples of the carboxylic acid of component-5 are:
The linear or branched saturated aliphatic dicarboxylic acid among the carboxylic acids mentioned in the component-4 can be mentioned, and specific examples of the carboxylic acid derivative of the component-5 include methyl ester, ethyl ester of the dicarboxylic acid, Examples thereof include acid anhydrides.

The above (a) to (d) used in the present invention.
Among the esters described above, the ester compound described in (a) is particularly preferable in consideration of the balance of required performance such as compatibility with hydrofluorocarbons, thermal stability, lubricity, and electrical insulation. Among the esters described in (a), a C2-10 divalent to C6 hindered alcohol was used as the polyhydric alcohol, and a C5-9 saturated aliphatic monocarboxylic acid was used as the monocarboxylic acid. Hindered esters are particularly preferred. As the polyhydric alcohol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol and the like are preferable. As the monocarboxylic acid, valeric acid, isovaleric acid, 2-methylbutyric acid, caproic acid, enanthic acid, 2-ethylpentanoic acid, 2-methylhexanoic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, 3,5 1,5-trimethylhexanoic acid and the like are preferable.

Specific examples of the preferable ester described in (a) include 3,5,5-trimethylhexanoic acid ester of neopentyl glycol, 2-ethylhexanoic acid ester of neopentyl glycol, and 3,5,5 of trimethylolpropane. Five-
Trimethylhexanoate, trimethylolpropane 2-methylhexanoic acid / 2-ethylpentanoic acid / 3,5,5-
Trimethylhexanoic acid mixed fatty acid ester, trimethylolpropane 2-ethylhexanoic acid ester, trimethylolpropane 2-methylhexanoic acid / 2-ethylpentanoic acid mixed fatty acid ester, pentaerythritol valeric acid / isovaleric acid / 3,5, 5-Trimethylhexanoic acid mixed fatty acid ester, pentaerythritol enanthate / 3,5,5-trimethylhexanoic acid mixed fatty acid ester,
Pentaerythritol 2-ethylhexanoic acid / 3,5,5-trimethylhexanoic acid mixed fatty acid ester, Pentaerythritol 2-methylhexanoic acid / 2-ethylpentanoic acid /
2-Ethylhexanoic acid mixed fatty acid ester, pentaerythritol caprylic acid / 3,5,5-trimethylhexanoic acid mixed fatty acid ester, pentaerythritol 2-methylhexanoic acid / 2-ethylpentanoic acid / 2-ethylhexanoic acid /
3,5,5-Trimethylhexanoic acid mixed fatty acid ester and the like can be mentioned.

The ester used in the present invention can be obtained from the above-mentioned components by a known esterification reaction or transesterification reaction which is usually carried out. That is, the above (a)
For the ester of (1), one or more alcohols of component-1 and one or more of the carboxylic acid or derivative thereof of component-2, and for the ester of (b), one or more alcohols of component-3 , The carboxylic acid of component-4 or one or more of its derivatives, the ester of (c),
From one or more of the component-1 alcohol, one or more of the component-2 carboxylic acid or derivative thereof and component-5 of the carboxylic acid or derivative thereof, and with respect to the ester of (d): From one or more alcohols of component-1 and one or more alcohols of component-3, and one or more carboxylic acids or derivatives thereof of component-4, by a known esterification reaction or transesterification reaction that is usually performed. Obtainable.

The acid value of the above-obtained ester used in the present invention is not particularly limited, but it may cause corrosion of metal materials, deterioration of wear resistance, deterioration of thermal stability, and deterioration of electric insulation. From the viewpoint of suppressing 1 mgKOH / g
The following is preferable, 0.2 mgKOH / g or less is more preferable, 0.1 mgKOH / g or less is further preferable,
0.05 mgKOH / g or less is particularly preferable.

The hydroxyl value of the ester used in the present invention is not particularly limited, but is preferably 0.1 to 50 mgKOH / g, more preferably 0.1 to 30 mgKOH / g,
0.1-20 mg KOH / g is particularly preferred. 0.1 mgKOH / g or more is preferable from the viewpoint of wear resistance, and 50 mgKOH / g or less is preferable from the viewpoint of hygroscopicity. The iodine value of the ester used in the present invention (Img / 100
Although g) is not particularly limited, it is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less, and particularly preferably 1 or less, from the viewpoint of thermal oxidation stability of the obtained lubricating oil composition. The temperature of the two-phase separation of the ester used in the present invention from the hydrofluorocarbon at a low temperature is not particularly limited, but is preferably -10 ° C or lower, more preferably -30 ° C or lower, still more preferably -50 ° C or lower. The kinematic viscosity of the ester used in the present invention at 100 ° C. is not particularly limited, but is preferably 100 mm ² / s or less from the viewpoint of compatibility with hydrofluorocarbon, and is usually 1 to 100.
mm ² / s are preferred, 1 to 30 mm ² / s is more preferable.

(Ii) Polyalkylene glycol-based synthetic oil The polyalkylene glycol-based synthetic oil used in the present invention is compatible with hydrofluorocarbons, has a pour point of 0 ° C or lower, and has the general formula (1) and / Or an acidic phosphoric acid ester represented by (2) and a general formula (3)
And / or it is not particularly limited as long as it is a polyalkylene glycol capable of dissolving the polyvalent amine compound represented by (4). For example, those represented by the following general formula (5) may be mentioned.

A- (O- (R ¹⁹ O) v -R ²⁰ ) w (5) (In the formula, R ¹⁹ represents a linear or branched alkylene group having 2 to 4 carbon atoms. R ²⁰ represents a hydrogen atom. Represents a hydrocarbon group having 1 to 15 carbon atoms or an acyl group having 2 to 15 carbon atoms, A represents a hydrogen atom, a w-valent alcohol residue having 1 to 15 carbon atoms, or a w-valent having 6 to 15 carbon atoms. Represents a phenol residue of, where v is 1 to
The integer of 50 and w represent the integer of 1-6. However, v R ¹⁹ O, w R ²⁰ and w O- (R ¹⁹ O) v -R ²⁰
May be the same or different. )

Here, R ¹⁹ is specifically an ethylene group,
Examples thereof include a propylene group, a trimethylene group, a butylene group, an isobutylene group and a tetramethylene group.

From the viewpoint of compatibility with hydrofluorocarbons, R ²⁰ preferably has 15 or less carbon atoms, and more preferably a hydrocarbon group having 1 to 10 carbon atoms or an acyl group having 2 to 9 carbon atoms.

Examples of the hydrocarbon group for R ²⁰ include the following alkyl groups, aryl groups and alkylaryl groups. Alkyl group: methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, 2-
Methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, cyclopentyl group, hexyl group, 2-methylpentyl group, 2-ethylbutyl group, 2,3-dimethylbutyl group, cyclohexyl group, 2-methylhexyl group, Octyl group, 2-ethylhexyl group, nonyl group,
3,5,5-trimethylhexyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, pentadecyl group, isopentaldecyl group.

Aryl group and alkylaryl group: phenyl group, 4-methylphenyl group, 4-ethylphenyl group, 2,4-dimethylphenyl group, 4-isopropylphenyl group, 2-propylphenyl group, 4-t-butyl group. Phenyl group, 5-isopropyl-3-methylphenyl group,
Naphthyl group, 2,4-di-t-butylphenyl group, 2-
Methylnaphthyl group, 2,6-di-t-butylphenyl group, 2,6-di-t-butyl-4-methylphenyl group,
4-nonylphenyl group and the like.

Examples of the acyl group of R ²⁰ include the following. Acetic acid, propionic acid, valeric acid, isovaleric acid, 2-methylbutyric acid, caproic acid, enanthic acid, 2-ethylpentanoic acid, 2-methylhexanoic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, 3,5,5. Acyl group of carboxylic acid such as 5-trimethylhexanoic acid, undecanoic acid and isotridecanoic acid.

The carbon number of A is preferably 15 or less from the viewpoint of compatibility with hydrofluorocarbon. Examples of the alcohol residue or the phenol residue of A include the following. Alcohol residue: methanol, ethanol, propanol, isopropanol, butanol, t-butanol,
Pentanol, 2-methylbutanol, 3-methylbutanol, 2,2-dimethylpropanol, hexanol, 2-methylpentanol, 2-ethylbutanol,
2,3-dimethylbutanol, heptanol, 2-methylhexanol, 3-cyclohexanol, octanol, 2-ethylhexanol, nonanol, 3,5,5
Alcohol residues of monohydric alcohols such as trimethylhexanol, decyl alcohol, isodecyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, isotridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol.

Alcohol residues of hindered alcohols such as neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolpropane and dipentaerythritol. Of polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, diglycerin, polyglycerin, sorbitol and mannitol. Alcohol residue.

Phenol residue: 4-methylphenol,
4-ethylphenol, 4-t-butylphenol,
2,4-di-t-butylphenol, 2,6-di-t-
Phenol residues of phenol such as butylphenol, 2,6-di-t-butyl-4-methylphenol, 4-nonylphenol and bisphenol A.

Further, v is 50 from the viewpoint of viscosity and hygroscopicity.
The following integers are preferable, and integers of 1 to 30 are more preferable. From the viewpoint of viscosity, w is preferably an integer of 6 or less, and more preferably an integer of 1 to 3.

These polyalkylene glycols can be produced, for example, as follows. By reacting water or alcohol with alkylene oxide under an alkaline catalyst such as NaOH or KOH, a monoalkyl ether type polyalkylene glycol or glycol type polyalkylene glycol can be obtained. Further, the terminal hydroxyl group is alkylated with an alkyl halide using an alkali metal as a catalyst, and is also acylated by reacting with a carboxylic acid or its methyl ester, ethyl ester, or acid anhydride to obtain a dialkyl ether type polyalkylene glycol or An ester ether type polyalkylene glycol can be obtained.

The acid value of the polyalkylene glycol obtained as described above, which is used in the present invention, has a viewpoint of suppressing corrosion of metal materials, deterioration of abrasion resistance, deterioration of thermal stability, and deterioration of electric insulation. To 1 mgKOH / g or less are preferable, 0.2 mgKOH / g or less are more preferable, and 0.
1 mgKOH / g or less is more preferable, 0.05 mg
KOH / g or less is particularly preferable.

The temperature of the two-phase separation of the polyalkylene glycol used in the present invention from the hydrofluorocarbon at a low temperature is preferably -10 ° C or lower, more preferably -30 ° C or lower, and particularly preferably -50 ° C or lower. The two-phase separation temperature at high temperature is preferably 60 ° C or higher, more preferably 80 ° C or higher, and even more preferably 100 ° C or higher. Also,
100 of the polyalkylene glycol used in the present invention
Kinematic viscosity at ℃ is preferably not more than 100 mm ² / s from the viewpoint of compatibility with hydrofluorocarbons, usually preferably ^{1~100mm 2 / s, 1~30mm 2 /} s
Is more preferred.

(Iii) Carbonate Synthetic Oil The carbonate synthetic oil used in the present invention is compatible with hydrofluorocarbon and has a pour point of 0.
If it is a carbonate having a temperature equal to or lower than 0 ° C. and dissolving the acidic phosphoric acid ester represented by the general formula (1) and / or (2) and the polyvalent amine represented by the general formula (3) and / or (4), It is not particularly limited. For example, those represented by the following general formula (6) are listed.

[0055]

Embedded image

(In the formula, R ²¹ and R ²³ may be the same or different and each is an alkyl group having 1 to 18 carbon atoms;
Aryl group, alkylaryl group, an aralkyl group, or - represents the (R ²⁵ O) groups represented by z -R ^24. Where R
²⁴ is an alkyl group having 1 to 18 carbon atoms, an aryl group, an alkylaryl group or an aralkyl group, and R ²⁵ is 2 to 18 carbon atoms.
Of alkylene group, arylene group, alkylarylene group or aralkylene group, and z represents an integer of 1 to 100. z
The individual R ²⁵ O may be the same or different. R ²²
Is an alkylene group having 2 to 18 carbon atoms, an arylene group, an alkylarylene group or an aralkylene group, and x is 1 to 100.
And y represents an integer of 0 to 100. x R ²² O may be the same or different, and y R ²² O

[0057]

Embedded image

May be the same or different. )

R ²¹ and R ²³ are an alkyl group having 1 to 18 carbon atoms, an aryl group, an alkylaryl group, an aralkyl group,
Alternatively, it is a group represented by — (R ²⁵ O) z —R ²⁴ , and R ²⁴ is an alkyl group having 1 to 18 carbon atoms, an aryl group, an alkylaryl group or an aralkyl group. Here, from the viewpoint of compatibility with hydrofluorocarbons, R ²¹ , R ²³ , R ²⁴
The number of carbon atoms of is preferably 18 or less, more preferably 1 to 1
0. Specific examples include the following.

Alkyl group: In addition to the alkyl group mentioned for R ²⁰ , the following can be mentioned. Hexadecyl group, 1-methylpentadecyl group, isopentadecyl group, octadecyl group, 2-heptylundecyl group, isostearyl group and the like. Aryl group and alkylaryl group: 2,4,6-tri-t-butylphenyl group and the like in addition to those listed for R ²⁰ . Aralkyl group: benzyl group, 4-methylbenzyl group, phenethyl group, sec-phenethyl group, 3,5-dimethylbenzyl group, 4-ethylbenzyl group, 3-phenylpropyl group, 4-isopropylbenzyl group, 4-butylbenzyl Group, 4-t-butylbenzyl group, 1,1-dimethyl-3-phenylpropyl group, 5-phenylpentyl group,
Naphthylmethyl group, naphthylethyl group, 6-phenylhexyl group and the like.

R ²² and R ²⁵ are an alkylene group having 2 to 18 carbon atoms, an arylene group, an alkylarylene group or an aralkylene group. From the viewpoint of compatibility with hydrofluorocarbons, the carbon number is preferably 18 or less, more preferably 2 to 10. Specific examples include the following.

Examples of the alkylene group include alcohol residues of dihydric alcohols shown below. Ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,
5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,4-
Cyclohexanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 1 , 2-decanediol, 1,10-decanediol, 1,2-dodecanediol, 1,2-hexadecanediol, 1,2-octadecanediol and the like.

Examples of the arylene group, alkylarylene group and aralkylene group include the following divalent phenol or alcohol residues. Catechol, resorcin, 2-hydroxybenzyl alcohol, 4-methylcatechol, 2-methylresorcinol, 1,4-
Benzene dimethanol, 4-ethyl resorcinol, 1
-Phenyl-1,2-ethanediol, 2-phenyl-
1,2-propanediol, 4-t-butylcatechol, 4-hexylresorcinol, 3,5-di-t-butylcatechol, 4-dodecylresorcinol and the like.

Z represents an integer of 1 to 100, preferably an integer of 1 to 50, and more preferably an integer of 1 to 30. From the viewpoint of viscosity and hygroscopicity, z is preferably 100 or less. x represents an integer of 1 to 100, preferably an integer of 1 to 50, and more preferably an integer of 1 to 30. From the viewpoint of viscosity and hygroscopicity, x is preferably 100 or less. y represents an integer of 0 to 100, preferably an integer of 1 to 50, and more preferably an integer of 1 to 30. From the viewpoint of viscosity and hygroscopicity, y is preferably 100 or less.

These carbonates are generally monovalent and / or
Alternatively, it can be obtained by a transesterification reaction of one or more dihydric alcohols or phenols with a carbonic acid ester such as dimethyl carbonate or diethyl carbonate.

The acid value of the above-obtained carbonate used in the present invention is 1 mgKOH from the viewpoint of suppressing corrosion of metal materials, deterioration of wear resistance, deterioration of thermal stability, and deterioration of electric insulation. / G or less is preferable,
0.2 mgKOH / g or less is more preferable, and 0.1 mg
KOH / g or less is more preferable, 0.05 mg KOH
/ G or less is particularly preferable. Further, the two-phase separation temperature of the carbonate used in the present invention at a low temperature from the hydrofluorocarbon is preferably 0 ° C or lower, more preferably -10 ° C or lower, and particularly preferably -30 ° C or lower. Furthermore, the kinematic viscosity of the carbonate used in the present invention at 100 ° C. is not particularly limited, but 100 mm ² / s or less is preferable from the viewpoint of compatibility with hydrofluorocarbon,
Is usually preferably 1~100mm ² / s, 1~30mm ²
/ S is more preferable.

(Iv) Mixed Oil In the mixed oil of ester type, polyalkylene glycol type and carbonate type synthetic oils used in the present invention,
It is desirable that the two-phase separation temperature at low temperature with the hydrofluorocarbon is low, preferably -10 ° C or lower, more preferably -30 ° C or lower, and particularly preferably -50 ° C or lower.

Further, it is desirable that the two-phase separation temperature at a high temperature is high, preferably 60 ° C. or higher, more preferably 80.
C. or higher, particularly preferably 100.degree. C. or higher. The mixing ratio of the ester-based, polyalkylene glycol-based, and carbonate-based synthetic oils is not particularly limited as long as it does not impair the compatibility with hydrofluorocarbon. Also in the mixed oil, the kinematic viscosity at 100 ° C. is preferably 100 mm ² / s or less from the viewpoint of compatibility with hydrofluorocarbon, and is usually 1 to 100 m.
m ² / s is preferable, and 1 to 30 mm ² / s is more preferable.

The ester-based, polyalkylene glycol-based or carbonate-based synthetic oils or their mixed oils used in the present invention may be mineral oils, poly-α-olefins and alkylbenzenes as long as the compatibility with hydrofluorocarbons is not impaired. Further, esters other than the above and synthetic oils such as polyalkylene glycol, carbonate, perfluoropolyether, and phosphoric acid ester may be further mixed. Specific examples are described in "New Edition Physical Chemistry of Lubrication" (Koushobo), "Basics and Applications of Lubricating Oils" (Corona).

2. Regarding acidic phosphate ester The acidic phosphate ester used in the present invention is represented by the general formula (1) and / or (2).

[0071]

[Chemical 15]

(In the formula, R ¹ and R ² may be the same or different and each represents a linear or branched alkylene group having 2 to 4 carbon atoms. P and q are integers of 0 to 30. R ³ and R ⁴ may be the same or different and each is a hydrogen atom, a straight chain alkyl group having 1 to 18 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, or a carbon number. A straight chain alkenyl group having 2 to 18 carbon atoms, a branched chain alkenyl group having 3 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and a halogen having 1 to 18 carbon atoms Alkyl group or a halogenated aryl group having 6 to 18 carbon atoms, provided that when p and q are both 0, R ³ and R ⁴ are not hydrogen atoms at the same time.)

[0073]

Embedded image

(In the formula, R ⁵ represents a linear or branched alkylene group having 2 to 4 carbon atoms. R represents an integer of 0 to 30.
R ⁶ is a hydrogen atom, a straight chain alkyl group having 1 to 18 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, a straight chain alkenyl group having 2 to 18 carbon atoms, a branched chain having 3 to 18 carbon atoms Represents a chain alkenyl group, an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, a halogenated alkyl group having 1 to 18 carbon atoms, or a halogenated aryl group having 6 to 18 carbon atoms. . R
⁷ is a straight chain alkyl group having 1 to 18 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, a straight chain alkenyl group having 2 to 18 carbon atoms, a branched chain alkenyl group having 3 to 18 carbon atoms An aryl group having 6 to 18 carbon atoms,
Aralkyl groups having 7 to 18 carbon atoms, 1 to 18 carbon atoms
And a halogenated aryl group having 6 to 18 carbon atoms. )

(I) R ³ , R ⁴ , R ⁶ and R ⁷ Of the groups represented by R ³ , R ⁴ , R ⁶ and R ⁷ , a linear or branched alkyl group, a linear or branched alkenyl group The carbon number of the group, the aryl group, the aralkyl group, the halogenated alkyl group and the halogenated aryl group is 18 or less from the viewpoint of compatibility with hydrofluorocarbon.

Examples of the linear alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group,
Examples thereof include a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group and an octadecyl group. Carbon number 3-18
Examples of the branched chain alkyl group having R ²⁰ , R ²¹ ,
The same groups as the alkyl groups mentioned for R ²³ and R ²⁴ can be mentioned. Examples of the linear alkenyl group having 2 to 18 carbon atoms include a propenyl group, a 2-decenyl group, a 9-decenyl group,
9-undecenyl group, 10-undecenyl group, 2-dodecenyl group, 3-dodecenyl group, 2-tridecenyl group, 4
-Tetradecenyl group, 9-tetradecenyl group, 9-pentadecenyl group, 9-hexadecenyl group, 9-heptadecenyl group, 9-octadecenyl group and the like.

Examples of the branched chain alkenyl group having 3 to 18 carbon atoms include isopropenyl group, 3-methyl-2-nonenyl group, 2,4-dimethyl-2-decenyl group, 2-methyl-9-heptadecenyl group and the like. Is mentioned. Carbon number 6 ~
Examples of the aryl group and alkylaryl group having 18 include a 2,4-di-t-pentyl group and a 4-dodecylphenyl group in addition to those described for R ²⁰ . 7 carbons
Examples of the aralkyl group having 18 include R ²¹ , R ²³ and R ^24.
The same as the ones listed in. 1 to 1 carbon atoms
Examples of the halogen atom of the halogenated alkyl group having 8 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with chlorine being preferable. Specific examples of the halogenated alkyl group include a β-chloroethyl group and a 2,3-dichloropropyl group. Examples of the halogen atom of the halogenated aryl group having 6 to 18 carbon atoms include fluorine, chlorine, bromine, and iodine atoms, and chlorine is preferable. Specific examples of the halogenated aryl group include a monochlorophenyl group, a dichlorophenyl group, a monochloro-4-methylphenyl group, a dichloro-4-methylphenyl group and the like.

(Ii) R ¹ , R ² and R ⁵ R ¹ , R ² and R ⁵ represent a straight chain or branched chain alkylene group having 2 to 4 carbon atoms, and a straight chain having 2 to 4 carbon atoms. Alternatively, examples of the branched alkylene group include an ethylene group, a propylene group, a trimethylene group, a butylene group, an isobutylene group, and a tetramethylene group. p, q, and r represent an integer of 0 to 30, preferably 0 to 20, and more preferably 0 to 10. p, q and r may be the same or different. Here, when p, q, and r are large, the phosphorus concentration decreases, and the effect of addition decreases, so p, q, and r are preferably integers of 30 or less.

Therefore, specific examples of the acidic phosphoric acid ester preferably used in the present invention include monobutyl acid phosphate, dibutyl acid phosphate, sesquibutyl acid phosphate, sesquipropyl acid phosphate, di2-ethylhexyl acid phosphate. Phosphate, 2-ethylhexyl mono-2-ethylhexyl phosphonate, sesqui-3-methyl-2
-Nonenyl acid phosphate, sesquioctadecyl acid phosphate, sesquioctadecenyl acid phosphate, sesquiethylene glycol acid phosphate, sesqui 4-methylphenyl acid phosphate, sesqui β-chloroethyl acid phosphate, sesqui 4- Examples thereof include chlorophenyl acid phosphate, sesquiethyl acid phosphate, sesquibutoxyethyl acid phosphate, sesquiisopropyl acid phosphate, sesquiisodecyl acid phosphate, sesquilauryl acid phosphate.

Among the acidic phosphoric acid esters represented by the general formulas (1) and / or (2), straight chain or branched chain alkyl groups, straight chain or branched chain alkenyl groups, aryl groups,
Alternatively, the acidic phosphoric acid ester having an aralkyl group is obtained by a reaction of a linear or branched alkyl alcohol, a linear or branched alkenyl alcohol, an aryl alcohol, or an aralkyl alcohol with phosphoric anhydride (P ₂ O ₅ ). At this time, the reaction can be carried out in the presence of water, orthophosphoric acid or polyphosphoric acid to obtain a high yield. The halogenated alkyl group and the halogenated aryl group can be obtained by substituting the halogen atom of the alkyl group or aryl group of the corresponding acidic phosphoric acid ester with halogen. The acidic phosphoric acid ester containing a linear or branched oxyalkylene group can be obtained by an esterification reaction with oxyalkylene glycol or an alkylene oxide addition reaction. In addition, in this invention, the said acidic phosphoric acid ester may be used individually and may use 2 or more types of acidic phosphoric acid ester.

3. Amine Compound The polyvalent amine compound used in the present invention is represented by the following general formula (3) and / or (4).

[0082]

Embedded image

(In the formula, R ⁸ , R ⁹ and R ¹¹ may be the same or different, and are a hydrogen atom and a carbon number of 1 to 1.
A straight chain alkyl group having 8 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, a straight chain alkenyl group having 2 to 18 carbon atoms, a branched chain alkenyl group having 3 to 18 carbon atoms, and 6 to 18 carbon atoms. An aryl group having or a carbon number of 7 to 18
Represents an aralkyl group having. R ¹² represents a linear or branched alkylene group having 2 to 6 carbon atoms. R ¹⁰ is a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, or 3 to 18 carbon atoms.
A branched chain alkyl group having 2 to 18 carbon atoms, a linear alkenyl group having 2 to 18 carbon atoms, a branched chain alkenyl group having 3 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and 7 carbon atoms.
Aralkyl group having to 18, or - (R ¹³ -NH) m
-R ¹³ -NH ₂ group (R ¹³ represents a linear or branched alkylene group having 2 to 6 carbon atoms, m is an integer of from 1 to 20.)
Represents k is an integer of 1 to 4. )

[0084]

Embedded image

(In the formula, R ¹⁵ is a hydrogen atom and has 1 to 18 carbon atoms.
Having a straight chain alkyl group having 3 to 18 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, a straight chain alkenyl group having 2 to 18 carbon atoms, a branched chain alkenyl group having 3 to 18 carbon atoms, and 6 to 18 carbon atoms An aryl group, an aralkyl group having 7 to ¹⁸ carbon atoms, or a -R ¹⁶ NR ¹⁷ R ¹⁸ group (R ¹⁶ represents a linear or branched alkylene group having 2 to 6 carbon atoms. R ¹⁷ ,
R ¹⁸ is a hydrogen atom, a straight chain alkyl group having 1 to 18 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, a straight chain alkenyl group having 2 to 18 carbon atoms, an aryl having 6 to 18 carbon atoms Represents a group, an aralkyl group having 7 to 18 carbon atoms, or a branched alkenyl group having 3 to 18 carbon atoms. ) Represents. The n R ^{15 s} may be the same or different. R ¹⁴ represents a linear or branched alkylene group having 2 to 6 carbon atoms. n is an integer of 1 to 4. However, when n is 1, R ¹⁵ represents a -R ¹⁶ NR ¹⁷ R ¹⁸ group. )

(I) R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹⁵
Regarding, the number of carbon atoms of the hydrocarbon group represented by R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹⁵ is preferably 18 or less from the viewpoint of compatibility with hydrofluorocarbon. Linear alkyl group having 1 to 18 carbon atoms, branched chain alkyl group having 3 to 18 carbon atoms, linear alkenyl group having 2 to 18 carbon atoms, branched chain alkenyl group having 3 to 18 carbon atoms, carbon number 6-18
Specific examples of the aryl group having R and the aralkyl group having 7 to 18 carbon atoms include R ³ , R ⁴ , R ⁶ and R ^7.
The same as the ones listed in.

(Ii) About R ¹⁷ and R ¹⁸ The carbon number of the linear or branched alkyl group, linear or branched alkenyl group, aryl group or aralkyl group represented by R ¹⁷ and R ¹⁸ is that of hydrofluorocarbon. 18 or less is preferable from the viewpoint of compatibility. Linear alkyl group having 1 to 18 carbon atoms, branched alkyl group having 3 to 18 carbon atoms, linear alkenyl group having 2 to 18 carbon atoms, aryl group having 6 to 18 carbon atoms, 7 to 7 carbon atoms Specific examples of the aralkyl group having 18 or the branched alkenyl group having ^{3 to} 18 carbon atoms include R ³ , R ⁴ , R ⁶ and R.
^The same as those listed in 7.

[0088] ^{(iii) R 12, R 13} , the R ¹⁴ and R ¹⁶ R ^12, R ^13, R ¹⁴ and the carbon number of the straight-chain or branched alkylene group for R ¹⁶ is, in view of compatibility with hydrofluorocarbons To 6 or less are preferable. Specific examples of the linear or branched alkylene group having 2 to 6 carbon atoms include R ¹ and R ²
In addition to those exemplified for R ⁵ and R ⁵ , a pentamethylene group, a hexamethylene group and the like can be mentioned. k and n are integers of 1 to 4, more preferably 1 to 2 and m is 1 to 20.
Is more preferable, but 1 to 10 is more preferable, and 1 to 5 is further preferable.

The polyvalent amine compound used in the present invention is
Direct cyano cyanation of butadiene, reaction of ethylene dichloride with ammonia, cyanoethylation of primary amines,
It can be obtained by introducing a methyl group into the primary polyvalent amine by a reductive methylation method. Therefore, specific examples of the polyvalent amine compound include dibutylaminopropylamine, tetramethylhexamethylenediamine, tetramethylpropylenediamine, pentamethyldiethylenetriamine, 1,2-diaminopropane, methylaminopropylamine, pentamethyldiethylenetriamine, Methyliminobispropylamine, N-cyclohexyl-
1,3-propylenediamine, trimethylaminoethylpiperazine, 1,4-bisaminopropylpiperazine,
Tris (dimethylaminopropyl) hexahydro-S-
Examples thereof include triazine and N-methylhomopiperazine. In the present invention, the polyvalent amine compound may be used alone or as a mixture of two or more polyvalent amine compounds.

4. Lubricating Oil Composition and Composition for Refrigerator Working Fluid (1) Lubricating Oil Composition of the Present Invention The lubricating oil composition of the present invention comprises an acidic phosphoric acid ester and a polyvalent amine compound as described above as an ester-based polyalkylene. It is obtained by blending a glycol-based or carbonate-based synthetic oil or a base oil whose main component is an oil mixture thereof. Here, the acidic phosphoric acid ester and the polyvalent amine compound are ester-based, polyalkylene glycol-based or carbonate-based synthetic oil, or a base oil mainly composed of a mixed oil thereof, and a method of separately blending each, There is a method of preliminarily neutralizing the acidic phosphoric acid ester and the polyvalent amine compound and then blending with the base oil, and any method may be used.

When neutralizing the acidic phosphoric acid ester and the polyvalent amine compound, the acid value of the acidic phosphoric acid ester (mgKOH
/ G) and amine value of polyvalent amine compound (mgKOH
/ G) respectively, by adjusting the blending weight of each component, the amine value (mgKOH / blending weight) of the polyvalent amine compound as an absolute amount with respect to the acid value (mgKOH / blending weight) as an absolute amount. The ratio (i.e., theoretically, the ratio of gram equivalents) is preferably 1.0 to 5.0. A more preferable range of this ratio is 1.0 to 3.
It is 0, and a particularly preferable range is 1.0 to 1.5.
That is, this ratio is preferably 1.0 or more from the viewpoint of suppressing corrosive wear due to excess acidic phosphate and hydrolysis of ester synthetic oil and the like, and from the viewpoint of suppressing corrosive wear and coloration due to excess polyvalent amine compound. , 5.0 or less is preferable.

For the same reason, the compounding ratio when the acidic phosphoric acid ester and the polyvalent amine compound are separately compounded is the ratio of amine value / acid value as the absolute amount of the polyvalent amine compound to the acidic phosphoric acid ester. Is preferably 1.0 to 5.0.

The amount of the acidic phosphoric acid ester and the polyvalent amine compound to be added to the base oil is sufficient to suppress abrasion at least while the composition for a refrigerator working fluid of the present invention is in contact with a metal surface. The amount is not particularly limited as long as it is an amount, but preferably, the total amount of the acidic phosphate ester and the polyvalent amine compound added is 100% by weight with respect to 100 parts by weight of the base oil.
05 to 5.0 parts by weight. The total amount of this compound is more preferably 0.3 to 3.0 parts by weight, and particularly preferably 0.5 to 2.0 parts by weight. From the viewpoint of obtaining the desired effect of suppressing wear, the total content is preferably 0.05 parts by weight or more, and 5.0 from the viewpoint of compatibility with hydrofluorocarbons and volume resistivity which is a required characteristic of refrigerating machine oil.
It is preferably at most part by weight. Further, even if the amount exceeds 5.0 parts by weight, the effect of suppressing wear wears off, which is economically disadvantageous.

The following additives may be appropriately added to the lubricating oil composition of the present invention. (I) An additive for removing water may be added to the lubricating oil composition of the present invention. When water coexists, the base oil ester or carbonate is hydrolyzed, and carboxylic acid may be generated to clog the capillary tube or the like.
Further, there is a possibility that non-condensable CO ₂ is generated and the refrigerating capacity is lowered. Further, the PET film or the like as an insulating material may be hydrolyzed to form a PET oligomer, which may clog the capillary tube or the like. Examples of the additive for removing water include compounds having an epoxy group, and additives such as orthoester, acetal (ketal), and carbodiimide.

Examples of the compound having an epoxy group include
It has 4 to 60 carbon atoms, preferably 5 to 25 carbon atoms. Specifically, glycidyl ethers such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl glycol diglycidyl ether, glycidyl esters such as adipic acid glycidyl ester, 2-ethylhexanoic acid glycidyl ester, and epoxidized stearic acid. Examples thereof include epoxidized fatty acid monoesters such as methyl, and epoxidized vegetable oils such as epoxidized soybean oil.

Further, 1,2-epoxycyclohexane, 1,2-epoxycyclopentane and bis (3,4-
Epoxy cyclohexylmethyl) adipate, 3,4-
Other examples include alicyclic epoxy compounds such as epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.

In the present invention, these epoxy group-containing compounds may be used alone or in combination of two or more kinds. The amount added is usually 0.05 to 100 parts by weight of a base oil containing an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof as a main component.
The amount is 2.0 parts by weight, preferably 0.1 to 1.5 parts by weight, and more preferably 0.1 to 1.0 parts by weight.

Examples of the orthoester used in the present invention include compounds described in JP-A-6-17073. The amount of orthoester added is usually 0.01 to 100 parts by weight, preferably 0 to 100 parts by weight of a base oil containing an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof as a main component. .05 to 30 parts by weight.

Examples of the acetal or ketal used in the present invention include the compounds described in JP-A-6-17073. The addition amount of acetal or ketal is usually 0,0 based on 100 parts by weight of a base oil containing an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof as a main component.
The amount is 01 to 100 parts by weight, preferably 0.05 to 30 parts by weight.

Examples of the carbodiimide used in the present invention include those represented by the following general formula (7). ^{R 26 -N = C = N-} R 27 (7) ( wherein, R ²⁶ and R ²⁷ .R ²⁶ and R ²⁷ represents a hydrocarbon group having 1 to 18 carbon atoms may be the same or different. The carbon number of R ²⁶ and R ²⁷ is more preferably 1-12. Specific examples of R ²⁶ and R ²⁷ are the same as those listed for R ²⁴ .

Specific examples of the carbodiimide include 1,3-diisopropylcarbodiimide and 1,3-diisopropylcarbodiimide.
Di-t-butyl-carbodiimide, 1,3-dicyclohexylcarbodiimide, 1,3-di-p-tolylcarbodiimide, 1,3-bis- (2,6-diisopropylphenyl) carbodiimide and the like. The amount of carbodiimide added is usually 0.01 to 10 parts by weight, preferably 0.05 to 100 parts by weight of a base oil containing an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof as a main component. ~ 5 parts by weight.

(Ii) Further, a benzotriazole and / or a benzotriazole derivative for protecting the metal surface is added as an additive to the lubricating oil composition of the present invention for the purpose of preventing metal corrosion due to carboxylic acid or the like. Alternatively, a phenolic compound having a radical trapping ability for improving thermal stability or a metal deactivator having a chelating ability may be added.

Benzotriazole used in the present invention,
A benzotriazole derivative is disclosed in JP-A-5-209.
Examples thereof include compounds described in Japanese Patent No. 171. Although not particularly limited, benzotriazole, 5-methyl-1H-benzotriazole and the like are preferable. The addition amount of the benzotriazole and / or benzotriazole derivative used in the present invention is 100 parts by weight of a base oil containing an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof as a main component. , Usually 0.001-0.1
Parts by weight, preferably 0.003 to 0.03 parts by weight.

The phenolic compound having a radical trapping ability used in the present invention is described in JP-A-6-17073. Although not particularly limited, preferably 2,6-di-t-butylphenol, 2,6
6-di-t-butyl-4-methylphenol, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4 '
-Isopropylidene bisphenol, 2,6-di-t-butyl-4-ethylphenol and the like can be mentioned. The amount of the phenolic compound added is usually 0.05 to 2.0 parts by weight with respect to 100 parts by weight of a base oil containing an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof as a main component. Yes, preferably 0.05-
0.5 parts by weight.

The metal deactivator used in the present invention preferably has a chelating ability, and examples thereof include compounds described in JP-A-5-209171. Although not particularly limited, preferably N, N'-disalicylidene-1,2-diaminoethane, N, N'-disalicylidene-1,2-diaminopropane, acetylacetone, acetoacetic acid ester, alizarin, quinizarin, etc. Can be mentioned. The addition amount of the metal deactivator used in the present invention is as follows: a base oil 1 containing an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof as a main component.
0.001 to 2.0 parts by weight with respect to 00 parts by weight,
It is preferably 0.003 to 0.5 part by weight.

(Iii) In addition, various additional additives which are usually used can be used in the lubricating oil composition of the present invention, if necessary. These include antioxidants, extreme pressure agents,
Lubricating oil additives such as oiliness improvers, defoamers, detergent dispersants, viscosity index improvers, rust preventives and demulsifiers can be added. For example, as the antioxidant, in addition to the above-described phenolic antioxidant, p, p-dioctylphenylamine, monooctyldiphenylamine, phenothiazine,
3,7-Dioctylphenothiazine, phenyl-1-naphthylamine, phenyl-2-naphthylamine, alkylphenyl-1-naphthylamine, alkylphenyl-
Examples thereof include amine-based antioxidants such as 2-naphthylamine, sulfur-based antioxidants such as alkyldisulfide, thiodipropionic acid ester and benzothiazole, zinc dialkyldithiophosphate, zinc diaryldithiophosphate. The amount added is 0.05 with respect to 100 parts by weight of a base oil containing an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof as a main component.
To 2.0 parts by weight.

As the extreme pressure agent and oiliness improver, for example, zinc compounds such as zinc dialkyldithiophosphate and zinc diaryldithiophosphate, thiodipropionic acid ester, dialkyl sulfide, dibenzyl sulfide, dialkyl polysulfide, alkyl can be used. Sulfur compounds such as mercaptan, dibenzothiophene and 2,2'-dithiobis (benzothiazole), chlorine compounds such as chlorinated paraffin, molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum compounds such as molybdenum disulfide, perfluoroalkyl polyethers and ,
Examples include trifluorochloroethylene polymer, fluorine compounds such as fluorinated graphite, silicon compounds such as fatty acid-modified silicone, and graphite. The amount of addition is 0.05 to 10 parts by weight with respect to 100 parts by weight of a base oil containing an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof as a main component.

As the defoaming agent, silicone oil such as dimethylpolysiloxane and organosilicates such as diethyl silicate are used. The addition amount thereof is 0.0005 to 1 part by weight based on 100 parts by weight of a base oil containing an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof as a main component.

The detergents and dispersants used are sulfonates, phenates, salicylates, phosphonates, polybutenyl succinimides, polybutenyl succinates and the like. The added amount is 0.05 to 10 parts by weight with respect to 100 parts by weight of a base oil containing an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof as a main component.

As the rust preventive agent and the demulsifier, known ones usually used as lubricating oil additives can be mentioned. The addition amount thereof is 0.01 to 5 parts by weight with respect to 100 parts by weight of a base oil containing an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof as a main component.

In addition, an additive such as an organic tin compound or a boron compound which stabilizes the chlorofluorocarbon refrigerant may be added. The amount of addition thereof is 0.001 to 10 parts by weight based on 100 parts by weight of a base oil containing an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof as a main component.

(2) Refrigerator Working Fluid Composition of the Present Invention The mixing ratio of the hydrofluorocarbon and the lubricating oil composition in the refrigerator working fluid composition of the present invention is not particularly limited, Hydrofluorocarbon / lubricant composition = 50/1 to 1/20 (weight ratio) is preferable, and 10/1 to 1/5 (weight ratio) is more preferable. From the viewpoint of obtaining sufficient refrigerating capacity, hydrofluorocarbon /
The ratio of the lubricating oil composition is preferably higher than 1/20, and the ratio of the hydrofulcarbon is preferably higher than 50/1 from the viewpoint of optimizing the viscosity of the working fluid composition for a refrigerator. Is preferred.

The hydrofluorocarbon used here is not particularly limited as long as it is usually used for refrigerating machine oil, but preferably difluoromethane (HFC3
2) 1,1-difluoroethane (HFC152a),
1, 1, 1-trifluoroethane (HFC143a),
1, 1, 1, 2-tetrafluoroethane (HFC134
a) 1,1,1,2,2-tetrafluoroethane (HFC
134), pentafluoroethane (HFC125) and the like, with 1,1,1,2-tetrafluoroethane, difluoromethane, pentafluoroethane, and 1,1,1-trifluoroethane being particularly preferred. These hydrofluorocarbons may be used alone or in combination of two or more kinds.

[0114]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. Table 1 shows the acid value of the acidic phosphoric acid ester and the amine value of the polyvalent amine compound used in the following examples, and the mixing amount at the time of preparation and the amine value / acid value ratio. Further, a mixture of the acidic phosphoric acid ester and the polyvalent amine compound prepared as shown in Table 1 was blended as shown in Tables 2 and 3 to obtain a lubricating oil composition. The base oils A to I used here are as shown below.

Base oil A: ester of pentaerythritol (1.0 mol) and 2-ethylhexanoic acid (1.93 mol) and 3,5,5-trimethylhexanoic acid (2.07 mol) Viscosity at 40 ° C. (hereinafter abbreviated as Vis 40) ) 70.2
mm ² / s Viscosity at 100 ° C (hereinafter abbreviated as Vis 100) 8.
63mm ² / s Acid value 0.01mgKOH / g Hydroxyl value 2.4mgKOH / g

Base oil B: pentaerythritol (1.0 mol), 2-methylhexanoic acid (1.88 mol), 2-ethylpentanoic acid
(0.46 mol) of 2-ethylhexanoic ester Vis acid (1.66 ^{mol) 40: 30.9mm 2 / s Vis} 100: 5.21mm 2 / s acid value 0.01 mg / g hydroxyl value 1.1mgKOH / g

Base oil C: trimethylolpropane (1.0 mol)
And ester of 3,5,5-trimethylhexanoic acid (3.0 mol) Vis 40: 51.9mm ² / s Vis 100: 7.13mm ² / s Acid value 0.01mgKOH / g Hydroxyl value 0.89mgKOH / g

Base oil D: ester of pentaerythritol (1.0 mol) with n-heptanoic acid (1.37 mol) and 3,5,5-trimethylhexanoic acid (2.63 mol) Vis 40: 56.4 mm ² / s Vis 100: 8.08 mm ² / s Acid value 0.01 mgKOH / g Hydroxyl value 1.8 mgKOH / g

Base oil E: neopentyl glycol (1.0 mol)
And ester of glutaric acid (0.5 mol) and 2-methylhexanoic acid (1.0 mol) Vis 40: 31.3mm ² / s Vis 100: 5.82mm ² / s Acid value 0.02mgKOH / g Hydroxyl value 1.2mgKOH / g

Base oil F: neopentyl glycol (0.5 mol)
And 2-methyl ester of hexanol (1.0 mol) glutaric acid (1.0 ^{mol) Vis 40: 25.5mm 2 / s} Vis 100: 5.45mm 2 / s acid value 0.02 mg KOH / g hydroxyl value 2.5 mg KOH / g

Base oil G: poly (oxyethyleneoxypropylene) glycol monobutyl ether (Newpol 50HB-100, manufactured by Sanyo Chemical Industries, Ltd.) Vis 40: 20.3 mm ² / s Vis 100: 4.83 mm ² / s Acid value 0.03mgKOH / g Hydroxyl value 104mgKOH / g

Base oil H: Polyoxypropylene glycol dihexanate Vis 40: 17.2 mm ² / s Vis 100: 3.86 mm ² / s Acid value 0.02 mgKOH / g Hydroxyl value 1.2 mgKOH / g

Base oil I: Carbonate of dimethyl carbonate (1.0 mol) and 3-methyl-1,5-pentanediol (0.6 mol) and 3-methylhexanol (0.8 mol) Vis 40: 31.6 mm ² / s Vis 100 : 5.93 mm ² / s Acid value 0.02 mg KOH / g Hydroxyl value 0.54 mg KOH / g The viscosity of the above base oil was measured according to JIS K-2283. The acid value and the hydroxyl value are JIS K-2.
501.

Example 1 In order to examine the wear resistance of the product of the present invention, a Falex test according to ASTM D 2670-81 was conducted. V block was added to the lubricating oil composition in which the preparations of the acidic phosphoric acid ester and the polyvalent amine compound shown in Table 1 were added in the compounding amounts shown in Tables 2 and 3 to 100 parts by weight of the base oils A to I. Soak the pins, 1, 1, 1,
While blowing 2-tetrafluoroethane at 10 liters / hr, the temperature was rotated at 80 ° C. for 10 minutes without load,
Then, after preliminarily rotating at 200 lb for 5 minutes, it was operated at 300 lb for 3 hours, and the abrasion amount of the V block and the pin after the operation was examined.
The results are shown in Tables 2 and 3.

As comparative products, base oils A to I to which the acidic phosphate ester and polyvalent amine compound in the present invention are not added, or base oil A in which a preparation a is blended in a smaller amount than a predetermined amount,
Base oil A with tricresyl phosphate (TCP), tri-2-ethylhexyl phosphate (TOP), triphenyl phosphite (TPPA), di2-ethylhexyl hydrogen phosphite (DOHP), 2-
Ethylhexyl phosphonate di-2-ethylhexyl (DOPO), di-2-ethylhexyl acid phosphate (D2EHAP), dibutylaminopropylamine (DBAPA) and comparative preparations 1 and 2 shown in Table 4,
The one to which 3 was added was used. From Table 2, the products of the present invention 1 to 3
The wear amount of No. 2 was 4.0 to 9.9 mg, which showed excellent wear resistance. From Table 3, the wear amount of comparative products 1 to 20 is 1
It was found to be 1.7 to 29.8 mg, which was inferior to the wear resistance property of the present invention. Even when compared with the examples using monovalent amines shown in Table 4 (Comparative products 16, 19, 20), the difference was remarkable.

[0126]

[Table 1]

[0127]

[Table 2]

[0128]

[Table 3]

[0129]

[Table 4]

Example 2 In order to investigate the compatibility of the products 1 to 32 of the present invention with hydrofluorocarbons, the lubricating oil compositions shown in Table 5 and 1,1,1
1,2-tetrafluoroethane from 10/90 to 50/5
The mixture was mixed at a weight ratio of 0 (lubricating oil composition / 1,1,1,2-tetrafluoroethane), and the two-phase separation temperature at low temperature was measured. Table 5 shows the results. As can be seen from Table 5, the products of the present invention have excellent compatibility with hydrofluorocarbons.
Further, when the blending amount of the acidic phosphate ester and the polyvalent amine mixture in the present invention in the lubricating oil composition exceeds 5 parts by weight (Comparative Product 21), the compatibility becomes poor.

[0131]

[Table 5]

Example 3 In order to investigate the thermal stability of the compositions of the products 1 to 32 of the present invention, a shield tube test was conducted under the following conditions. That is,
The water concentration is 10 ppm or less and the acid value is 0.03 (mg
KOH / g) The lubricating oil composition 1 shown in Table 6 adjusted to the following.
0 g, and 1,1,1,2-tetrafluoroethane 5 g
Was taken into a glass tube, and iron, copper, and aluminum were added as a catalyst to seal the tube. After maintaining at 175 ° C for 14 days, 1.
Check the appearance of 1,1,2-tetrafluoroethane and the lubricating oil composition and the presence or absence of deposits, and open the sealed tube to make the 1,1,2
After removing the 1,2-tetrafluoroethane, the acid number of the oil was investigated. As a result, as shown in Table 6, in any of the invention products, the appearance was good, there were no precipitates, and
The acid value was 0.03 (mgKOH / g) or less, and no increase was observed. Therefore, it was found that the thermal stability of the product of the present invention was good.

[0133]

[Table 6]

[0134]

Industrial Applicability According to the present invention, it is possible to provide a composition for a working fluid of a refrigerator, which has excellent lubricity, compatibility with hydrofluorocarbons, and the like, and which can reduce the amount of wear on a metal contact surface. became.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C10M 137: 04 137: 12 133: 06 133: 40) C10N 30:06 40:30 (72) Invention Person Hiroyasu Togashi, 1334 Minato Minato, Wakayama City, Kao Corporation Research Laboratory (72) Inventor Toshiya Hagiwara, 1334 Minato Minato, Wakayama City, Kao Corporation

Claims (7)

[Claims] 1. A base oil containing an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof as a main component, and an acidic phosphoric acid ester represented by the general formula (1) and / or (2). , [Chemical 1] (In formula, R < ¹ > and R < ² > may be same or different and represents a C2-C4 linear or branched alkylene group. P and q represent the integer of 0-30. R ³ and R
⁴ may be the same or different, and is a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, or 3 carbon atoms.
A branched alkyl group having -18, a linear alkenyl group having 2-18 carbons, a branched alkenyl group having 3-18 carbons, an aryl group having 6-18 carbons, and 7-18 carbons. It represents an aralkyl group, a halogenated alkyl group having 1 to 18 carbon atoms, or a halogenated aryl group having 6 to 18 carbon atoms. However, when p and q are both 0, R ³ and R ⁴ are not hydrogen atoms at the same time. ) (In the formula, R ⁵ represents a linear or branched alkylene group having 2 to 4 carbon atoms. R represents an integer of 0 to 30. R ⁶ represents a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms. , Carbon number 3
A branched alkyl group having -18, a linear alkenyl group having 2-18 carbons, a branched alkenyl group having 3-18 carbons, an aryl group having 6-18 carbons, and 7-18 carbons. It represents an aralkyl group, a halogenated alkyl group having 1 to 18 carbon atoms, or a halogenated aryl group having 6 to 18 carbon atoms. R ⁷ has 1 to 1 carbon atoms
A straight chain alkyl group having 18, a branched chain alkyl group having 3 to 18 carbon atoms, a straight chain alkenyl group having 2 to 18 carbon atoms, a branched chain alkenyl group having 3 to 18 carbon atoms,
It represents an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, a halogenated alkyl group having 1 to 18 carbon atoms, or a halogenated aryl group having 6 to 18 carbon atoms. ), And a polyvalent amine compound represented by the general formula (3) and / or (4): (In the formula, R ⁸ , R ⁹ and R ¹¹ may be the same or different and each is a hydrogen atom, a straight chain alkyl group having 1 to 18 carbon atoms, or a branched chain alkyl group having 3 to 18 carbon atoms. Group, linear alkenyl group having 2 to 18 carbon atoms, branched chain alkenyl group having 3 to 18 carbon atoms, 6 to 18 carbon atoms
Or an aralkyl group having 7 to 18 carbon atoms. R ¹² represents a linear or branched alkylene group having 2 to 6 carbon atoms. R ¹⁰ is a hydrogen atom, having 1 to 18 carbon atoms
Having a straight chain alkyl group having 3 to 18 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, a straight chain alkenyl group having 2 to 18 carbon atoms, a branched chain alkenyl group having 3 to 18 carbon atoms, and 6 to 18 carbon atoms aryl group, an aralkyl group having 7 to 18 carbon atoms, or ^{- (R 13 -NH) m -R} 13 -NH
₂ groups (R ¹³ represents a linear or branched alkylene group having 2 to 6 carbon atoms, and m is an integer of 1 to 20). k is an integer of 1 to 4. ) [Chemical 4] (In the formula, R ¹⁵ is a hydrogen atom, a straight chain alkyl group having 1 to 18 carbon atoms, a branched chain alkyl group having 3 to 18 carbon atoms, a straight chain alkenyl group having 2 to 18 carbon atoms, and 3 to 3 carbon atoms. A branched alkenyl group having 18 carbon atoms, 6-18
Having an aryl group having from 7 to ¹⁸ carbon atoms, an aralkyl group having from 7 to ¹⁸ carbon atoms, or a -R ¹⁶ NR ¹⁷ R ¹⁸ group (R ¹⁶ represents a linear or branched alkylene group having from 2 to 6 carbon atoms. R ¹⁷ and R ¹⁸ are Hydrogen atom, straight chain alkyl group having 1 to 18 carbon atoms, branched chain alkyl group having 3 to 18 carbon atoms, straight chain alkenyl group having 2 to 18 carbon atoms, aryl group having 6 to 18 carbon atoms, carbon Represents an aralkyl group having 7 to 18 or a branched alkenyl group having 3 to 18 carbon atoms. The n R ^{15 s} may be the same or different. R ¹⁴
Represents a linear or branched alkylene group having 2 to 6 carbon atoms.
n is an integer of 1 to 4. However, when n is 1, R ¹⁵ represents a -R ¹⁶ NR ¹⁷ R ¹⁸ group. A composition for a working fluid of a refrigerator, which comprises a lubricating oil composition containing the above) and hydrofluorocarbon. 2. The amine value (mgKOH) of the polyvalent amine compound with respect to the value obtained by multiplying the acid value (mgKOH / g) of the acid phosphate ester by the compounding weight (g) of the acid phosphate ester and the polyvalent amine compound. / G) and its blended weight (g)
The composition for a working fluid of a refrigerator according to claim 1, which is blended in an amount of 1.0 to 5.0 at a ratio of a value multiplied by. 3. The total amount of the acidic phosphate ester and the polyvalent amine compound compounded is 100 parts by weight of a base oil containing an ester-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof as a main component. 0.05
The composition for working fluid of a refrigerator according to claim 1 or 2, wherein the composition is from 5.0 to 5.0 parts by weight. 4. The ester-based synthetic oil comprises (a) a carbon number of 2 to
Ester obtained from 10 divalent to 6-valent saturated aliphatic polyhydric alcohol and a linear or branched saturated aliphatic monocarboxylic acid having 2 to 9 carbon atoms or a derivative thereof, (b) having 1 carbon atom
An ester obtained from a linear or branched saturated aliphatic monohydric alcohol having 10 to 10 and a divalent to hexavalent polycarboxylic acid having 2 to 10 carbon atoms or a derivative thereof, (c) having 2 to 1 carbon atoms
0 to 6-valent saturated aliphatic polyhydric alcohol and 2 carbon atoms
To a linear or branched saturated aliphatic monocarboxylic acid or a derivative thereof and a linear or branched saturated aliphatic dicarboxylic acid having a carbon number of 2 to 10 or a derivative thereof, and (d) carbon A divalent to hexavalent saturated aliphatic polyhydric alcohol having 2 to 10 carbon atoms and a linear or branched saturated aliphatic monohydric alcohol having 1 to 10 carbon atoms, and 2 to 10 carbon atoms
The composition for a working fluid of a refrigerator according to any one of claims 1 to 3, which is selected from the group consisting of an ester obtained from the divalent to hexavalent polycarboxylic acid or a derivative thereof. 5. A polyalkylene glycol-based synthetic oil,
The composition for refrigerator working fluid according to any one of claims 1 to 3, which is represented by the general formula (5). ^{A- (O- (R 19 O)} v -R 20) w (5) ( wherein, .R ²⁰ R ¹⁹ is representative of a linear or branched alkylene group having 2 to 4 carbon atoms is a hydrogen atom, the number of carbon atoms It represents a hydrocarbon group having 1 to 15 or an acyl group having 2 to 15 carbon atoms, A is a hydrogen atom, a w-valent alcohol residue having 1 to 15 carbon atoms, or a w-valent phenol residue having 6 to 15 carbon atoms. Represents a group, and v is 1 to
The integer of 50 and w represent the integer of 1-6. However, v R ¹⁹ O, w R ²⁰ and w O- (R ¹⁹ O) v -R ²⁰
May be the same or different. ) 6. A carbonate-based synthetic oil has the general formula (6):
The composition for a working fluid of a refrigerator according to any one of claims 1 to 3, represented by: Embedded image (In the formula, R ²¹ and R ²³ may be the same or different, and are an alkyl group having 1 to 18 carbon atoms, an aryl group,
Alkylaryl group, an aralkyl group, or - (R ²⁵ O)
It represents a group represented by z -R ^24. However, R ²⁴ has 1 carbon atom
To 18 alkyl group, aryl group, alkylaryl group or aralkyl group, R ²⁵ represents an alkylene group having 2 to 18 carbon atoms, arylene group, alkylarylene group or aralkylene group, and z represents an integer of 1 to 100. The z R ²⁵ O may be the same or different. R ²² has 2 to 2 carbon atoms
18, an alkylene group, an arylene group, an alkylarylene group, or an aralkylene group, x represents an integer of 1 to 100, and y represents an integer of 0 to 100. x R ²² O may be the same or different, and y R ²² O May be the same or different. ) 7. The mixing ratio of hydrofluorocarbon and lubricating oil composition is hydrofluorocarbon / lubricating oil composition = 50/1 to 1/20 (weight ratio).
The composition for a working fluid of a refrigerator according to any one of claims.