JPH0873880A - Refrigerator oil composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition, excellent in contamination resistance, capable of preventing sludges or metallic corrosion from occurring in a freezing cycle and useful for car air conditioners, etc., by blending a base oil with a specific oxazoline compound. CONSTITUTION: This composition is obtained by blending (A) a base oil comprising an organic compound, containing oxygen and having 1-50cst kinematic viscosity at 100 deg.C with (B) preferably 0.01-10wt.%, especially 0.05-3wt.% oxazoline compound of formula I (R<1> is a 3-18C alkyl or alkenyl; R<2> and R<3> are each H or a 1-5C alkyl). Furthermore, the component (A) is, e.g. any one or more of polyalkylene glycols of formula II [R<4> and R<6> are each H, a 1-10C alkyl or an acyl; R<5> is a 2-4C alkyl; (n) is 1-6; (m) is a number so as to provide 6-80 average value of (m)×(n)], polyesters, polyol esters, polycarbonates and polyvinyl ethers. An antioxidant, an extreme pressure agent or a flurocarbon refrigerant containing hydrogen is preferably further contained therein.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a refrigerator oil composition,
More specifically, the present invention relates to a refrigerating machine oil composition for hydrogen-containing CFC refrigerant, which has excellent contamination resistance and can prevent sludge and metal corrosion from occurring in the refrigeration cycle.

[0002]

2. Description of the Related Art Conventionally, in a compression type refrigeration cycle consisting of a compressor, a condenser, an expansion valve and an evaporator, dichlorodifluoromethane (R-12) or chlorodifluoromethane (R-22) as a refrigerant is fluorinated. Hydrocarbon-based CFC compounds have been used, and in combination with them, various oil solutions having no problems have been produced and used. However, it is feared that these freon compounds, which have been used as refrigerants in the past, may destroy the ozone layer and cause environmental pollution problems when released into the atmosphere. Recently, 1,1,1,2-tetrafluoroethane (R-134), which can be used as a substitute from the viewpoint of environmental pollution countermeasures.
a) and other fluorinated hydrocarbons (or chlorinated fluorinated hydrocarbons) have been developed, and already R-134a, 1,
Various so-called CFC alternatives, such as hydrogen-containing CFC refrigerants such as 1,2,2-tetrafluoroethane (R-134), which are less likely to cause environmental pollution, have been on the market. This new CFC-based alternative refrigerant has different properties from conventional CFC-based refrigerants, and as a refrigerating machine oil used together with it, a specific polyalkylene glycol, polyester, polyol ester, polycarbonate, polyvinyl ether or the like is used as a base oil. , To improve the stability of refrigerating machine oil, antioxidant, extreme pressure agent, defoaming agent,
A mixture of various additives such as a hydrolysis inhibitor is used.

[0003]

However, even if a refrigerating machine oil suitable for an alternative CFC-based refrigerant as described above is used, various mineral oil-based oil agents such as cutting oil, which are used during refrigeration system manufacturing, are used. Press oil, rust preventive oil, cleaning oil, etc. often remain in the system as contaminants. In such cases, these contaminants are insoluble in hydrogen-containing CFCs and deteriorate early, resulting in metal corrosion and system corrosion. There was a problem of causing sludge. Under the circumstances, the present invention has developed a refrigerating machine oil for hydrogen-containing CFC refrigerants having high contamination resistance in view of the fact that the causes of metal corrosion and sludge are mainly due to the above-mentioned contaminants remaining in the refrigeration system. The purpose is to do.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a specific oxazoline compound reacts with a contaminant deterioration product to render it harmless to metal corrosion. In addition, it was found that the formation of sludge was suppressed. The present invention has been completed based on such findings. That is, the present invention provides (1) 10
A refrigerating machine oil composition prepared by blending a base oil composed of an oxygen-containing organic compound having a kinematic viscosity at 0 ° C of 1 to 50 cSt with an oxazoline compound represented by the following general formula (I):

[0005]

Embedded image

In the formula, R ¹ represents an alkyl group or an alkenyl group having a linear or side chain having 3 to 18 carbon atoms,
R ² and R ³ each represent a hydrogen atom or a straight-chain or side-chain alkyl group having 1 to 5 carbon atoms. (2) The refrigerating machine oil composition according to (1) above, wherein the oxygen-containing organic compound is at least one selected from the group consisting of polyalkylene glycol, polyester, polyol ester, polycarbonate and polyvinyl ether, (3) general formula ( I) the oxazoline compound represented by 0.01 to 1
The refrigerating machine oil composition according to (1) above, which is blended in an amount of 0% by weight, and (4) above, further comprising an antioxidant and / or an extreme pressure agent. The refrigerating machine oil composition according to (1) above, and (5) further containing a hydrogen-containing CFC refrigerant.

The present invention will be described in more detail below. The refrigerator oil composition of the present invention contains the oxazoline compound represented by the general formula (I) as described above. In the general formula (I), R ¹ is an alkyl group or an alkenyl group having a linear or side chain having 3 to 18 carbon atoms, preferably an alkyl group having a linear or side chain having 5 to 18 carbon atoms or An alkenyl group, and more preferably a linear or side-chain alkyl group having 7 to 15 carbon atoms. If R ¹ has more than 18 carbon atoms, the solubility of the compound in the hydrogen-containing CFC refrigerant is lowered, and if the carbon number is less than 3, it is not practical because the boiling point is low.

In the general formula (I), R ² and R
³ represents a hydrogen atom or an alkyl group having a straight chain or a side chain having 1 to 5 carbon atoms. If the carbon number of R ² or R ³ exceeds 5, the effect of addition decreases. In the present invention, the sum of the carbon numbers of R ² and R ³ is 8 or less, and further 6
The following is preferred. If this value exceeds 8, the effect of the present invention will be slightly inferior. In the refrigerator oil composition of the present invention, the oxazoline compound is preferably contained in an amount of 0.01 to 10% by weight, more preferably
It is contained in an amount of 0.05 to 3% by weight. The above content is 10% by weight
If it exceeds, the compatibility between the compound and the chlorofluorocarbon refrigerant decreases and the viscosity also decreases. When the content is less than 0.01% by weight, the effect of addition is hardly recognized.

The refrigerator oil composition of the present invention contains a base oil composed of an oxygen-containing organic compound. As such an oxygen-containing organic compound, at least one selected from the group consisting of polyalkylene glycol, polyester, polyol ester, polycarbonate and polyvinyl ether is preferably used. Examples of the polyalkylene glycol that can be used as the base oil in the present invention include compounds represented by the following general formula (II).

[0010]

[Chemical 3]

R in the formula^FourIs a hydrogen atom or has 1 to 1 carbon atoms
Having 0 to 6 alkyl groups, acyl groups or 2 to 6 bonding sites
Aliphatic hydrocarbon, R^FiveIs an alkylene having 2 to 4 carbon atoms
Group, R ⁶Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
Is an acyl group, n is an integer of 1 to 6, and m is an average value of m × n.
It is a number of 6 to 80.

R^FourThe alkyl group represented by is linear or branched.
It may be chain-shaped or cyclic. The alkyl group ingredient
As a body example, a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, various butyl groups, various pentyl groups, various
Hexyl group, various heptyl groups, various octyl groups, various groups
Nyl group, various decyl groups, cyclopentyl group, cyclohexyl
A sil group etc. can be mentioned. This alkyl charcoal
When the number of primes exceeds 10, the compatibility with CFC refrigerant decreases,
Phase separation may occur. Preferred alkyl group carbon
The number is 1-6. In addition, the alkyl group part of the acyl group
May be linear, branched or cyclic. The
Specific examples of the alkyl group portion of the acyl group include the above-mentioned alkyl groups.
The various groups mentioned as specific examples of the kill group are also listed.
You can If the carbon number of the acyl group exceeds 10, then
The compatibility with the refrigerant may decrease and phase separation may occur.
It The preferred acyl group has 2 to 6 carbon atoms. R^FourOver
And R⁶Are both alkyl groups or acyl groups
Has R^FourAnd R ⁶Can be the same or different
It may be.

Further, when n is 2 or more, a plurality of R ^{6 s in} one molecule may be the same or different. When R ⁴ is an aliphatic hydrocarbon group having 1 to 6 carbon atoms and having 2 to 6 bonding sites, the aliphatic hydrocarbon group may be chain-like or cyclic. Good. As the aliphatic hydrocarbon group having two bonding sites,
For example, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group,
Examples thereof include a nonylene group, a decylene group, a cyclopentylene group, a cyclohexylene group and the like. In addition, binding sites 3-6
As the aliphatic hydrocarbon group having, for example, trimethylolpropane, glycerin, pentaerythritol,
Examples thereof include a residue obtained by removing a hydroxyl group from a polyhydric alcohol such as sorbitol, 1,2,3-trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane. When the number of carbon atoms of this aliphatic hydrocarbon group exceeds 10, the compatibility with the fluorocarbon refrigerant decreases and phase separation may occur. The preferred carbon number is 2-6.

R ⁵ in the general formula (II) has 2 to 4 carbon atoms.
Examples of the oxyalkylene group of the repeating unit include an oxyethylene group, an oxypropylene group, and an oxybutylene group. The oxyalkylene groups in one molecule may be the same or may contain two or more kinds of oxyalkylene groups, but one having at least an oxypropylene unit in one molecule is preferable,
Particularly, those containing 50 mol% or more of oxypropylene units in the oxyalkylene units are preferable. In the general formula (II), n is an integer of 1 to 6 and is determined according to the number of R ⁴ binding sites. For example, when R ⁴ is an alkyl group or an acyl group, n is 1, and R ⁴ is a bonding site 2, 3, 4, 5,
And n are 2, 3, 4, 5 and 6, respectively. Further, m is m × n
Is an average value of 6 to 80, and if the average value of m × n deviates from the above range, the object of the present invention cannot be sufficiently achieved. The polyoxyalkylene glycol derivative represented by the general formula (II) includes a polyoxyalkylene glycol derivative having a hydroxyl group at the terminal, and the content of the hydroxyl group is 30 mol% based on all the terminal groups. If the ratio is as follows, even if it is contained, it can be suitably used. If the content of the hydroxyl groups exceeds 30 mol%, the hygroscopicity increases and the viscosity index decreases, which is not preferable. As the polyalkylene glycol represented by the general formula (II), any of those described in detail in JP-A No. 2-305893 can be used.

Examples of the polyester that can be used as the base oil include aliphatic polyester derivatives having a structural unit represented by the following general formula (III) and having a molecular weight of 300 to 2,000.

[0016]

[Chemical 4]

[R ⁷ represents an alkylene group having 1 to 10 carbon atoms, and R ⁸ represents an alkylene group having 2 to 10 carbon atoms or an oxaalkylene group having 4 to 20 carbon atoms. R ⁷ in the general formula (III) represents an alkylene group having 1 to 10 carbon atoms. Specifically, methylene group, ethylene group, propylene group, ethylmethylene group, 1,1-dimethylethylene, 1, 2, -dimethylethylene group, n-butylethylene group, isobutylethylene group, 1-ethyl-2-methylethylene group, 1-ethyl-1-methylethylene group, trimethylene group, tetramethylene group, pentamethylene group and the like. However, an alkylene group having 6 or less carbon atoms is preferable. R ⁸ represents an alkylene group having 2 to 10 carbon atoms or an oxaalkylene group having 4 to 20 carbon atoms.
The alkylene group is specifically a specific example of R ⁷ (provided that
(Excluding methylene group), preferably having 2 carbon atoms
To 6 are alkylene groups, and the oxaalkylene group is specifically a 3-oxa-1,5-pentylene group; 3,6-
Dioxa-1,8-octylene group; 3,6,9-trioxa-1,11-undecylene group; 3-oxa-1,4
-Dimethyl-1,5-pentylene group; 3,6-dioxa-1,4,7-trimethyl-1,8-octylene group;
3,6,9-trioxa-1,4,7,10-tetramethyl-1,11-undecylene group; 3-oxa-1,4
-Diethyl-1,5-pentylene group; 3,6-dioxa-1,4,7-triethyl-1,8-octylene group;
3,6,9-trioxa-1,4,7,10-tetraethyl-1,11-undecylene group; 3-oxa-1,
1,4,4-tetramethyl-1,5-pentylene group;
3,6-Dioxa-1,1,4,4,7,7-hexamethyl-1,8-octylene group; 3,6,9-trioxa-1,1,4,4,7,7,10,10 -Octamethyl-1,1,1-undecylene group; 3-oxa-1,2,
4,5-Tetramethyl-1,5-pentylene group; 3,6
-Dioxa-1,2,4,5,7,8-hexamethyl-
1,8-octylene group; 3,6,9-trioxa-1,
2,4,5,7,8,10,11-octamethyl-1,
1,1-undecylene group; 3-oxa-1-methyl-
1,5-pentylene group; 3-oxa-1-ethyl-1,
5-pentylene group; 3-oxa-1,2-dimethyl-
1,5-Pentylene group; 3-oxa-1-methyl-4-
Ethyl-1,5-pentylene group; 4-oxa-2,2,
6,6-Tetramethyl-1,7-heptylene group; 4,8
-Dioxa-2,2,6,6,10,10-hexamethyl-1,11-undecylene group. In addition, R ⁷ and R
⁸ may be the same or different. Further, a plurality of R ⁷ and R ⁸ forming the above structural unit may be the same or different.

Further, the aliphatic polyester derivative represented by the general formula (III) has a molecular weight of 300 (measured by gel permeation chromatography (GPC)).
~ 2000 is required. Where the molecular weight is 3
If it is less than 00, the kinematic viscosity is too small, and it is 2000
If it exceeds, it becomes waxy, and all are unsuitable as refrigerating machine oil. As such a polyester, any of those described in detail in WO91 / 07479 can be used.

Examples of the polyol ester used as the base oil include at least one carboxylic acid ester of a polyhydric hydroxy compound having at least two hydroxyl groups, and are represented by the following general formula (IV). One is used. R [OC-O-R ^9] _n (IV) wherein, R is a hydrocarbyl group, R ⁹ is independently a hydrogen atom, a straight chain lower hydrocarbyl group, the hydrocarbyl group of the branched or 8 carbon atoms, 22 straight chain hydrocarbyl groups, provided that at least one R ⁹ group is a hydrogen atom, a lower straight chain hydrocarbyl group or a branched chain hydrocarbyl group, or a carboxylic acid-containing hydrocarbyl group or a carboxylic acid ester-containing group. Is a hydrocarbyl group and n is a number of at least 2.

The above-mentioned carboxylic acid ester is formed by the reaction of one or more carboxylic acids or their lower esters (eg, methyl ester, ethyl ester, etc.) with a polyvalent hydroxy compound containing at least two hydroxyl groups. It is a thing. This polyhydric hydroxy compound is represented by the following general formula (V). R (OH) _n (V) where R is a hydrocarbyl group and n is a number of at least 2. Examples of the carboxylic acid used when preparing the carboxylic acid ester include those represented by the following general formula: R ⁹ COOH (VI) where R ⁹ is a hydrogen atom or a straight chain lower A mixture of one or both of a hydrocarbyl group, a branched hydrocarbyl group, or a linear lower hydrocarbyl group and a branched hydrocarbyl group, and a linear hydrocarbyl group having 8 to 22 carbon atoms, or a carboxylic acid or It is a hydrocarbyl group containing a carboxylic acid ester. For such polyol ester, see Table 3-50560.
Any of those described in detail in Japanese Patent Publication No. 2 can be used.

Examples of the polycarbonate which can be used as the base oil include polycarbonate derivatives having a structural unit represented by the following general formula (VII) and having a molecular weight of 300 to 3000.

[0022]

[Chemical 5]

[In the formula, R ^{10 to} R ¹³ are each a hydrogen atom,
An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms is shown. However, R ¹⁰
Except when all of R ¹³ are hydrogen atoms. n is 2-10
Indicates an integer. In the formula, R ^{10 to} R ¹³ are each a hydrogen atom or a carbon number of 1 to 6.
Alkyl groups (for example, methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups), aryl groups having 6 to 10 carbon atoms (phenyl group, tolyl group, xylyl group) , Ethylphenyl group, cumenyl group, naphthyl group, etc.), arylalkyl group having 7 to 10 carbon atoms (benzyl group, α-phenylethyl group, β-phenylethyl group, etc.) or 2 to 6 carbon atoms
Shows an alkoxyalkyl group of (methoxymethyl group, methoxyethyl group, ethoxymethyl group, etc.). Of which
Particularly preferred is one in which any one of R ^{10 to} R ¹³ is an alkyl group such as a methyl group or an ethyl group and the rest is hydrogen.

In the general formula (VII), n is 2 to
10, preferably 2 to 4. If n is less than 2, it is not suitable as a refrigerating machine oil because of its low boiling point. Conversely 10
If it exceeds, the solubility with the Freon refrigerant will be insufficient. Furthermore, the polycarbonate derivative having the structural unit of the general formula (VII) has a molecular weight (weight average molecular weight) of 300 to 3000, preferably 400 to 1500.
Is. If the molecular weight is less than 300, the kinematic viscosity is too small to be suitable for a lubricating oil, while if it exceeds 3,000, it becomes waxy and difficult to use as a lubricating oil. The above polycarbonate derivative can be produced by various methods, but is usually produced using a carbonic acid ester-forming derivative such as carbonic acid diester or phosgene and an aliphatic dihydric alcohol as raw materials. In order to produce the polycarbonate derivative used in the present invention using these, it is sufficient to follow the usual production method of polycarbonate,
Generally, transesterification or phosgene method may be used. As the polycarbonate derivative, any of those described in detail in JP-A-3-217495 can be used.

In the present invention, a specific glycol ether carbonate represented by the following general formula (VIII) can be used as the base oil.

[0026]

[Chemical 6]

However, in the above general formula (VIII), R
¹⁴ and R ¹⁵ are groups selected from the group consisting of aliphatic, alicyclic, aromatic, and araliphatic hydrocarbon groups each having 1 to 20 carbon atoms. Here, specific examples of the aliphatic hydrocarbon group represented by R ¹⁴ and R ¹⁵ include methyl group, ethyl group, propyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group. Group, pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group , N-
Undecyl group, isoundecyl group, n-dodecyl group, isododecyl group, n-tridecyl group, isotridecyl group,
n-tetradecyl group, isotetradecyl group, n-pentadecyl group, isopentadecyl group, n-hexadecyl group,
Isohexadecyl group, n-heptadecyl group, isoheptadecyl group, n-octadecyl group, isooctadecyl group,
Examples thereof include an n-nonyldecyl group, an isononyldecyl group, an n-aicosanyl group and an isoaicosanyl group.

Specific examples of the alicyclic hydrocarbon group represented by R ¹⁴ and R ¹⁵ include cyclohexyl group, 1-cyclohexenyl group, methylcyclohexyl group, dimethylcyclohexyl group and decahydronaphthyl group. Group, tricyclodecanyl group and the like.
Further, specific examples of the aromatic hydrocarbon group represented by each of R ¹⁴ and R ¹⁵ include phenyl group, o-tolyl group, p-tolyl group, m-tolyl group and 2,4-xylyl group. , Mesityl group, benzyl group, phenethyl group, 1-phenylethyl group, 1-methyl-1-phenylethyl group, p
-Methylbenzyl group, styryl group, cinnamyl group, 1-
Examples thereof include a naphthyl group. Furthermore, R
Specific examples of the aromatic-aliphatic hydrocarbon group represented by each of ¹⁴ and R ¹⁵ include a benzyl group, a methylbenzyl group, a β-phenylethyl group and the like.

In the above general formula (VIII), R ¹⁶
And R ¹⁷ are each a group selected from the group consisting of an ethylene group and an isopropylene group. Further, in the general formula (VIII), m is an integer of 2 to 100,
n is an integer of 0-100. The general formula (VI
The glycol ether carbonate represented by II) can be produced, for example, by transesterifying a polyalkylene glycol monoalkyl ether in the presence of a carbonic acid ester of an alcohol having a relatively low boiling point. As the glycol ether carbonate, any of those described in detail in JP-A-3-149295 can be used.

Further, in the present invention, it is also possible to use a carbonic acid ester represented by the following general formula (IX) as the base oil.

[0031]

[Chemical 7]

[0032] wherein, R ¹⁸ and R ¹⁹ may be the same or different, each represent an alkyl group or a divalent alcohol residue having 2 to 12 carbon atoms having 1 to 15 carbon atoms, R ²⁰
Represents an alkylene group having 2 to 12 carbon atoms, and n is 0 to 30
Indicates an integer. In the above formula, R ¹⁸ and R ¹⁹ may be the same or different and each has 1 to 15 carbon atoms, preferably 2 to 9 carbon atoms.
An alkyl group of 2 to 12 carbon atoms, preferably 2 to 9 carbon atoms
Shows a dihydric alcohol residue, R ²⁰ is 2 to 12 carbon atoms,
Preferably 2-9 alkylene groups are shown, and n is 0-3.
0, preferably an integer of 1 to 30 is shown. It is not preferable to use a carbonic acid ester that does not satisfy the above conditions, because various properties such as compatibility with a fluorocarbon refrigerant are poor. R ¹⁸ and R
Specific examples of the alkyl group having 1 to 15 carbon atoms represented by each of ¹⁹ include a methyl group, an ethyl group, an n-propyl group,
n-butyl group, n-pentyl group, n-hexyl group, n-
Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, iso-propyl group, iso- Butyl group, tert-butyl group, iso-pentyl group, iso-hexyl group, iso-heptyl group, iso-octyl group, iso-nonyl group, iso-decyl group, iso-undecyl group, iso-dodecyl group, iso- Examples thereof include tridecyl group, iso-tetradecyl group, iso-pentadecyl group and the like. Further, as the dihydric alcohol residue having 2 to 12 carbon atoms, specifically, ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2- Methyl-1,3-propanediol, 1,5-
Pentanediol, neopentyl glycol, 1,6
-Hexanediol, 2-ethyl-2-methyl-1,3
-Propanediol, 1,7-heptanediol, 2-
Methyl-2-propyl-1,3-propanediol,
2,2-diethyl-1,3-propanediol, 1,8
-Octanediol, 1,9-nonanediol, 1,1
0-decanediol, 1,11-undecanediol,
Examples thereof include residues such as 1,12-dodecanediol.

Further, as the alkylene group having 2 to 12 carbon atoms represented by R ²⁰ , specifically, ethylene group, trimethylene group, propylene group, tetramethylene group, butylene group, 2-methyl-trimethylene group, Pentamethylene group, 2,2-dimethyltrimethylene group, hexamethylene group, 2-ethyl 2-methyltrimethylene group, heptamethylene group, 2-methyl-2-propyltrimethylene group,
2,2-diethyltrimethylene group, octamethylene group,
Examples thereof include those having a linear structure or a branched structure such as a nonamethylene group, a decamethylene group, an undecamethylene group and a dodecamethylene group. Although the molecular weight of the carbonate ester is not particularly limited, those having a number average molecular weight of 200 to 3000 are preferably used, and a number average molecular weight of 300 to 200 is preferably used from the viewpoint of further improving the sealing property of the compressor.
Those of 0 are more preferably used. As the carbonate ester, any of those described in detail in JP-A-4-63893 can be used.

The polyvinyl ether which can be used as the base oil in the present invention includes a polyvinyl ether compound (1) having a constitutional unit represented by the following general formula (X).

[0035]

Embedded image

[In the formula, R ²¹ , R ²² and R ²³ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R ²⁴ is a carbon number. A divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent ether bond oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, and R ²⁵ has 1 to 10 carbon atoms.
20 hydrocarbon groups, m represents a number having an average value of 0 to 10, R ^{21 to} R ²⁵ may be the same or different for each constitutional unit, and when R ²⁴ O is plural. Has
A plurality of R ²⁴ O may be the same or different. ] Further, (a) a structural unit represented by the above general formula (X),
(B) A polyvinyl ether compound (2) composed of a block or random copolymer having a structural unit represented by the following general formula (XI) may also be used.

[0037]

[Chemical 9]

[In the formula, R ^{26 to} R ²⁹ each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different, and R ^{26 to} R ²⁹ have the same structure. The units may be the same or different. Further, in the present invention, (A) a polyvinyl ether compound (1) having a structural unit represented by the general formula (X), and (B) (a) a structural unit represented by the general formula (X). It is also possible to use a mixture (3) of the polyvinyl ether compound (2) composed of a block or random copolymer having (b) a structural unit represented by the general formula (XI).

R in the above general formula (X)^{twenty one}, R^{twenty two}as well as
R^{twenty three}Are each a hydrogen atom or 1 to 8 carbon atoms, preferably
1 to 4 hydrocarbon groups, which may be identical to each other
It may be different. Here, the hydrocarbon group is specifically
Is 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
Group, various heptyl groups, alkyl groups of various octyl groups,
Clopentyl group, cyclohexyl group, various methylcyclo
Hexyl group, various ethylcyclohexyl groups, various dimethys
Cycloalkyl group such as cyclohexyl group, phenyl
Groups, various methylphenyl groups, various ethylphenyl groups, each
Species Dimethylphenyl group aryl group, benzyl group, various
Aryl group of phenylethyl group and various methylbenzyl groups
Represents a alkyl group. In addition, these R ^{twenty one}, R^{twenty two}, R^{twenty three}age
Especially, a hydrogen atom is preferable.

On the other hand, R ²⁴ in the general formula (X) has 1 carbon atom.
-10, preferably a divalent hydrocarbon group having 2 to 10 carbon atoms or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, wherein a divalent hydrocarbon group having 1 to 10 carbon atoms is shown. And methylene group; ethylene 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; divalent aliphatic groups of various decylene groups, cyclohexane; methylcyclohexane A cycloaliphatic group such as ethylcyclohexane; dimethylcyclohexane; propylcyclohexane having two bond sites, various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, various naphthylenes Groups such as divalent aromatic hydrocarbon groups, toluene; xylene; alkyl aromatic groups such as ethylbenzene having alkyl groups and aromatic moieties each having a monovalent bonding site, xylene; diethylbenzene, etc. Polyalkyl aromatic carbonization It is an alkyl aromatic group having a bonding site in the alkyl group moiety of the unit. Of these, an aliphatic group having 2 to 4 carbon atoms is particularly preferable. Specific examples of the divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms include methoxymethylene group; methoxyethylene group; methoxymethylethylene group; 1,1-bismethoxymethylethylene group; -Bismethoxymethylethylene group; ethoxymethylethylene group; (2-methoxyethoxy) methylethylene group; (1-methyl-2-methoxy) methylethylene group and the like can be preferably mentioned. In addition, m in General formula (X) shows the repeating number of R < ²⁴ > O, and the average value is 0-10, Preferably it is the number of the range of 0-5. When there are plural R ²⁴ O, plural R ²⁴ O
²⁴ O may be the same or different.

Further, R ²⁵ in the general formula (X) represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. The hydrocarbon group is specifically a methyl group, an 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 of various decyl groups, cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups , Various ethylcyclohexyl groups, various propylcyclohexyl groups, various cycloalkyl groups such as dimethylcyclohexyl groups, phenyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various Butylphenyl group, aryl groups such as various naphthyl groups, benzyl group, various phenylethyl groups, various methylbenzyl groups, various phenylpropyl groups,
The arylalkyl groups of various phenylbutyl groups are shown. The R ^{21 to} R ²⁵ may be the same or different for each structural unit.

Polyvinyl ether compound (1)
Is preferably one having a carbon / oxygen molar ratio in the range of 4.2 to 7.0. If this molar ratio is less than 4.2, the hygroscopicity is high, and if it exceeds 7.0, the compatibility with CFCs may decrease. In the general formula (XI), R ^{26 to} R ²⁹ are each
Each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. Here, as the hydrocarbon group having 1 to 20 carbon atoms, the same ones as exemplified in the description of R ²⁵ in the above general formula (X) can be mentioned. Note that R ^{26 to} R ²⁹ may be the same or different for each structural unit.

The polyvinyl ether compound (2) comprising a block or random copolymer having the structural unit represented by the general formula (X) and the structural unit represented by the general formula (XI) has Those having an oxygen molar ratio in the range of 4.2 to 7.0 are preferably used. If the molar ratio is less than 4.2, the hygroscopicity is high, and if it exceeds 7.0, the compatibility with CFC may be lowered. Further in the present invention,
(A) The polyvinyl ether compound (1) and (B)
A mixture with the polyvinyl ether compound (2) can also be used. The polyvinyl ether compounds (1) and (2) used in the present invention are the polymerization of the corresponding vinyl ether monomers, and the copolymerization of the corresponding hydrocarbon monomer having an olefinic double bond with the corresponding vinyl ether monomer. Can be manufactured by.

The polyvinyl ether compound used in the present invention has the following terminal structure, that is, one of the terminals has the general formula (XII) or (XIII).

[0045]

[Chemical 10]

[0046] wherein, R ^30, R ³¹ and R ³² each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ^30,
R ³¹ and R ³² may be the same or different from each other,
R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ may be the same or different from each other. . R ³³ is a divalent hydrocarbon group having 1 to 10 carbon atoms or 2 to 20 carbon atoms.
A divalent ether-bonded oxygen-containing hydrocarbon group, R ³⁴ is a hydrocarbon group having 1 to 20 carbon atoms, n is a number having an average value of 0 to 10, and when R ³³ O is plural, plural R ³³ O are plural. R ³³ O may be the same or different. ] And the remaining terminal is represented by the general formula (XIV) or (XV)

[0047]

[Chemical 11]

[0048] wherein, R ^39, R ⁴⁰ and R ⁴¹ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ^39,
R ⁴⁰ and R ⁴¹ may be the same or different from each other,
R ^44, R ^45, R ⁴⁶ and R ⁴⁷ each represent a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 20, R ^44, R ^45, R ⁴⁶ and R ⁴⁷ may be the same with or different from each other . R ⁴² is a divalent hydrocarbon group having 1 to 10 carbon atoms or 2 to 20 carbon atoms.
A divalent ether-bonded oxygen-containing hydrocarbon group, R ⁴³ is a hydrocarbon group having 1 to 20 carbon atoms, p is a number having an average value of 0 to 10, and when R ⁴² O is plural, plural R ⁴² O are plural. R ⁴² O in may be the same or different. ] Having a structure represented by, and one end thereof is represented by the general formula (XIV) or (XV), and the remaining end is represented by the general formula (XVI)

[0049]

[Chemical 12]

[In the formula, R ⁴⁸ , R ⁴⁹ and R ⁵⁰ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different from each other. ] The one having a structure represented by

Of such a polyvinyl ether compound
Among them, the following are especially the refrigerator oil compositions of the present invention.
It is suitable as the main component. (1) One of the terminals is represented by the general formula (XII) or (XIII).
And the remaining end is represented by the general formula (XIV) or (XV).
R in the general formula (X)^{twenty one}, R ^{twenty two}as well as
R^{twenty three}Are both hydrogen atoms, m is a number from 0 to 4, R^{twenty four}Has 2 carbon atoms
~ 4 divalent hydrocarbon groups and R^{twenty five}Is a C1-C20 charcoal
Those that are hydrogenated groups. (2) having only the structural unit represented by the general formula (X)
And one of its terminals is represented by the general formula (XII),
And the remaining terminal has a structure represented by the general formula (XIV),
R in the general formula (X)^{twenty one}, R^{twenty two}And R^{twenty three}Together with hydrogen
Child, m is a number from 0 to 4, R^{twenty four}Is a divalent carbonization having 2 to 4 carbon atoms
Hydrogen radical and R^{twenty five}Is a hydrocarbon group having 1 to 20 carbon atoms
of. (3) One terminal is represented by the general formula (XII) or (XIII).
And the remaining end has a structure represented by the general formula (XVI)
R in the general formula (X)^{twenty one}, R^{twenty two}And R^{twenty three}Together
Hydrogen atom, m is a number from 0 to 4, R^{twenty four}Is divalent with 2 to 4 carbon atoms
Hydrocarbon groups and R^{twenty five}Is a hydrocarbon group having 1 to 20 carbon atoms
some stuff. (4) having only the structural unit represented by the general formula (X)
And one of its terminals is represented by the general formula (XII),
And the remaining end has a structure represented by general formula (XIII)
R in the general formula (X)^{twenty one}, R^{twenty two}And R^{twenty three}Together with water
Elementary atom, m is a number from 0 to 4, R^{twenty four}Is a C2-C4 divalent
Hydrocarbon group and R^{twenty five}Is a divalent hydrocarbon having 1 to 20 carbon atoms
Group and R^{twenty five}Is a hydrocarbon group having 1 to 20 carbon atoms.

Further, in the present invention, the above general formula (X)
With a structural unit represented by the general formula (XII) at one end and the following general formula (XVII) at the other end.
A polyvinyl ether compound having a structure represented by can also be used.

[0053]

[Chemical 13]

(In the formula, R ⁵¹ , R ⁵² and R ⁵³ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R ⁵⁴ And R ⁵⁵ each represent a divalent hydrocarbon group having 2 to 10 carbon atoms, which may be the same or different from each other, and R ⁵⁵ and R ⁵⁶ are each a hydrocarbon group having 1 to 10 carbon atoms. , They may be the same or different from each other, q and r each represent an average value of 0 to 10, and they may be the same or different from each other, and a plurality of it is more R ⁵⁴ O if there are R ⁵⁴ O may be the same or different and when there are a plurality of R ⁵⁶ O is a plurality of R ⁵⁶ O are independently identical or different May be.)

Further, in the present invention, the following general formula (XVII
I) or (XIX), which is a structural unit represented by the general formula (XX) or (XXI), having a weight average molecular weight of 300 to 1200 and having a structure represented by the following general formula (XX) or (XXI). It is also possible to use a polyvinyl ether compound composed of a homopolymer or a copolymer.

[0056]

Embedded image

(In the formula, R ⁵⁸ represents an alkyl group having 1 to 3 carbon atoms, R ⁵⁹ represents a hydrocarbon group having 1 to 8 carbon atoms, R ⁶⁰
Indicates either R ⁵⁸ or R ⁵⁹ . ) In the present invention, it has a structural unit represented by the general formula (X), does not contain an unsaturated bond, an acetal and an aldehyde structure in the molecule, and has a weight average molecular weight of 300.
It is also possible to use polyvinyl ether compounds of up to 3000. Regarding the above-mentioned polyvinyl ether compound, JP-A-6-128578 or Japanese Patent Application No. 5-1
No. 25649, Japanese Patent Application No. 5-125650, Japanese Patent Application No. 5-
Any of the details described in each of the specifications of No. 303736 can be used.

As the oxygen-containing organic compound used as the base oil, those having a kinematic viscosity at 100 ° C. of 1 to 50 cSt, preferably 1.5 to 30 cSt are preferably used. If the kinematic viscosity exceeds 50 cSt, the efficiency of the refrigerating machine decreases, and if it is less than 1 cSt, the lubricity becomes insufficient, which is not preferable. In the present invention, polyvinyl ether is preferably used as the oxygen-containing organic compound for the reason that the effect of the addition of the oxazoline compound is little changed with time. The base oil comprising the above oxygen-containing organic compound is preferably 50 to 50 in the refrigerator oil composition of the present invention.
99.99% by weight, more preferably 80 to 99.5% by weight. When the content of the base oil is less than 50% by weight, it may not be possible to expect improvement in compatibility with CFCs due to the oxygen-containing organic compound.

The refrigerating machine oil composition of the present invention comprises the above base oil blended with the oxazoline compound represented by the general formula (I). If necessary, various additives may be blended. You can Such additives include antioxidants such as phenolic antioxidants, extreme pressure agents such as phosphorus extreme pressure agents, other antiwear additives, chlorine scavengers, metal deactivators, defoamers, detergents. Additives usually used in refrigerating machine oils such as a dispersant, a viscosity index improver, a rust preventive, and a corrosion inhibitor can be appropriately added. In the present invention, such additives can be incorporated in the composition, for example, in an amount of 0.01 to 10.0% by weight because of their unique effects.

Various examples of the hydrogen-containing CFC refrigerant used in the refrigerator to which the refrigerator oil composition of the present invention is applied include, but are not limited to, 1,1,1,2-tetrafluoroethane (R-134a) and Starting with 1,1,2,2-tetrafluoroethane (R-134), 1,1-difluoroethane (R-152a), pentafluoroethane (R-
125), trifluoromethane (R-23), difluoromethane (R-32) and the like.

[0061]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Examples 1 to 28 and Comparative Examples 1 to 15 Refrigerating machine oil compositions were prepared as shown in Table 1 and the following tests were conducted to evaluate discoloration of oil, sludge generation and metal corrosion. The results are shown in Table 2. Shield glass tube Put Fe / Cu / Al catalyst into a test glass tube and add R134a /
Fill with oil / air = 1 g / 4 ml / 10 torr and seal the tube. After holding at 200 ° C. for 10 days, it was allowed to cool to room temperature, and the oil appearance, metal corrosion, and sludge generation state were evaluated.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

Base oil 1: Polyol ester (ester of pentaerythritol and mixed fatty acid having 7 and 8 carbon atoms) (viscosity 56.0
3 cSt: 40 ° C.) 2: Both ends modified polypropylene glycol (dimethyl polypropylene glycol) (viscosity 3.08 cSt: 40
3. Polycarbonate (polypropylene glycol dimethyl carbonate) (viscosity 31.05 cSt: 40 ° C.) 4: polyvinyl ether (polyethyl vinyl ether hydride) (viscosity 30.03 cSt: 40 ° C.) 5: polyvinyl ether (ethyl / isobutyl vinyl ether) Hydrogenated polymer) (Viscosity 57.15 cSt: 4
0 ° C.) · oxazoline compound ^{1: R 1: n-C} 7, R 2 and R ^3: methyl ^{2: R 1: n-C} 14, R 2 and R ^3: methyl 3: R ^1: iso -C ₈ , R ² and R ³ : methyl group 4: R ¹ : iso-C ₁₂ , R ² and R ³ : methyl group 5: R ¹ : iso-C ₉ , R ² : H, R ³ : isopropyl group 6: _{^{R 1: n-C 22,}} R 2 and R ^3: methyl ^{7: R 1: n-C} 14, R 2 and R ^3: iso -C ₈ · antioxidant DBPC (2,6-di -t- Butylmethylphenol) ・ Extreme pressure agent TCP (tricresyl phosphate) ・ Contamination Cutting oil (1%) + Press oil (1%) + Anticorrosion oil (1%) +
Cleaning oil (remainder)

[0067]

As described in detail above, according to the present invention, by adding a specific oxazoline compound,
It is possible to obtain a refrigerating machine oil composition for hydrogen-containing CFC refrigerant, which is capable of deteriorating contaminant deterioration products against metal corrosion and suppressing the generation of sludge, and which is excellent in contamination resistance which has never been obtained. Therefore, the refrigerating machine oil composition of the present invention is particularly effective when used in car air conditioners, room air conditioners, refrigerators, etc., and its industrial utility value is extremely high.

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Claims (5)

[Claims] 1. A kinematic viscosity at 100 ° C. of 1 to 50 cS.
A base oil composed of an oxygen-containing organic compound of t is added to the following general formula (I)
A refrigerating machine oil composition containing an oxazoline compound represented by: Embedded image In the formula, R ¹ represents an alkyl group or an alkenyl group having a linear or side chain having ^{3 to} 18 carbon atoms, and R ² and R ³
Each represents a hydrogen atom or an alkyl group having a straight chain or a side chain having 1 to 5 carbon atoms. 2. The refrigerator oil composition according to claim 1, wherein the oxygen-containing organic compound is at least one selected from the group consisting of polyalkylene glycols, polyesters, polyol esters, polycarbonates and polyvinyl ethers. 3. The refrigerating machine oil composition according to claim 1, wherein the oxazoline compound represented by the general formula (I) is blended in an amount of 0.01 to 10% by weight. 4. The refrigerating machine oil composition according to claim 1, further comprising an antioxidant and / or an extreme pressure agent. 5. The refrigerating machine oil composition according to claim 1, further comprising a hydrogen-containing CFC refrigerant.