Refrigerating-machine oil composition and mixture composition for refrigerating machine

Abstract

Provided is a refrigerating-machine oil composition which is for use in combination with a refrigerant including an unsaturated fluorinated compound having a carbon-carbon unsaturated bond and represented by general formula (I): C2FpR4-p [in general formula (I), the R moieties each independently represent a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom and p is an integer of 1-3]. The refrigerating-machine oil composition comprises a base oil (A), an aliphatic epoxy compound (B1), an alicyclic epoxy compound (B2), and a terpene compound (C).

Description

Refrigerating machine oil composition and mixed composition for refrigerators

[0001] The present invention relates to a refrigerating machine oil composition and a mixed composition for a refrigerating machine. In this specification, the term "mixed composition for a refrigerating machine" refers to a composition obtained by mixing a "refrigerant" and a "refrigerating machine oil composition."

[0002] A refrigerator such as a compression type refrigerator generally includes at least a compressor, a condenser, an expansion mechanism (e.g., an expansion valve), and an evaporator, and has a structure in which a mixture composition for a refrigerator circulates within a sealed system.

[0003] As refrigerants used in freezers such as compression freezers, fluorocarbon compounds with lower environmental impact are increasingly being used in place of the hydrochlorofluorocarbons (HCFCs) that have been widely used in the past. Examples of fluorocarbon compounds include saturated fluorocarbon compounds (hydro-fluoro-carbons; hereinafter also referred to as "HFCs") such as 1,1,1,2-tetrafluoroethane (R134a), difluoromethane (R32), 1,1-difluoroethane (R152a), and a mixture of difluoromethane and pentafluoroethane (R410A).

[0004] The use of unsaturated fluorinated hydrocarbon compounds (hydro-fluoro-olefins; hereinafter also referred to as "HFOs"), which have a lower global warming potential (GWP) than HFCs, has also been considered. To date, propene-based HFOs such as 1,3,3,3-tetrafluoropropene (R1234ze), 2,3,3,3-tetrafluoropropene (R1234yf), and 1,2,3,3-tetrafluoropropene (R1234ye) have been the focus of much research. In recent years, ethylene-based HFOs such as trans-1,2-difluoroethylene (R1132(E)), which have a lower global warming potential (GWP) and a lower boiling point than propene-based HFOs, have also been considered (see, for example, Patent Document 1).

[0005] JP 2014-211092 A

[0006] However, although Patent Document 1 lists polyol esters, polyvinyl ethers, alkylbenzenes, and the like as refrigerating machine oils to be used with refrigerants containing ethylene-based HFOs such as trans-1,2-difluoroethylene (R1132(E)), no consideration is given at all to thermal stability and the like.

[0007] Furthermore, in recent years, the performance of refrigerators has improved, and their operating conditions have become more severe than ever before. Therefore, refrigerator oil compositions are required to have higher quality than ever before. This trend is particularly noticeable in air conditioning equipment with heating and cooling functions, and the performance required of refrigerator oil compositions is extremely strict. Specifically, thermal stability at higher temperatures is required. This is no exception even when an ethylene-based HFO such as trans-1,2-difluoroethylene (R1132(E)) is used as a refrigerant.

[0008] Therefore, an object of the present invention is to provide a refrigerating machine oil composition that can exhibit excellent thermal stability even when a refrigerant containing an ethylene-based HFO is used.

[0009] According to the present invention, the following [1] to [3] are provided: [1] A compound represented by the following general formula (I): ２ F ｐ R ４－ｐ ...(I) [In the general formula (I), each R independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and p is an integer of 1 to 3.] A refrigerator oil composition to be used together with a refrigerant containing an unsaturated fluorinated compound having a carbon-carbon unsaturated bond represented by the following general formula (I): C ２ F ｐ R ４－ｐ ...(I) [In the general formula (I), each R independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and p is an integer of 1 to 3.], and the refrigerating machine oil composition. [3] A mixed composition for a refrigerator, comprising a refrigerant containing an unsaturated fluorinated compound having a carbon-carbon unsaturated bond represented by the following general formula (I): C２ F ｐ R ４－ｐ ...(I) A method for producing a refrigerator oil composition to be used together with a refrigerant containing an unsaturated fluorinated compound having a carbon-carbon unsaturated bond represented by the general formula (I): [in the general formula (I), each R independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and p is an integer of 1 to 3], the method comprising the step of mixing a base oil (A), an aliphatic epoxy compound (B1), an alicyclic epoxy compound (B2), and a terpene compound (C).

[0010] According to the present invention, it is possible to provide a refrigerating machine oil composition that can exhibit excellent thermal stability even when a refrigerant containing an ethylene-based HFO is used.

[0011] The upper and lower limit values ​​of the numerical ranges described in this specification can be combined in any way. For example, when "A to B" and "C to D" are described as numerical ranges, the numerical ranges "A to D" and "C to B" are also included in the scope of the present invention. Furthermore, the numerical range "lower limit to upper limit" described in this specification means that the range is equal to or greater than the lower limit and equal to or less than the upper limit, unless otherwise specified. Furthermore, in this specification, the numerical values ​​in the examples are numerical values ​​that can be used as upper or lower limit values.

[0012] [Aspects of Refrigerating Machine Oil Composition of the Present Embodiment] The refrigerating machine oil composition of the present embodiment contains a base oil (A), an aliphatic epoxy compound (B1), an alicyclic epoxy compound (B2), and a terpene compound (C). The refrigerating machine oil composition of the present embodiment is used together with a refrigerant containing an unsaturated fluorinated compound having a carbon-carbon unsaturated bond represented by the following general formula (I): ２ F ｐ R ４－ｐ ... (I) [In the general formula (I), each R independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and p is an integer of 1 to 3.] In the following description, the unsaturated fluorinated compound having a carbon-carbon unsaturated bond represented by the general formula (I) will also be referred to as "unsaturated fluorinated compound (I)."

[0013] The present inventors have conducted extensive research to solve the above-mentioned problems. During the research, they found that it is more difficult to ensure the thermal stability of a refrigerating machine oil composition when an unsaturated fluorinated compound (I) is used as a refrigerant than when a propene-based HFO is used as a refrigerant, and solving the above-mentioned problems has been extremely difficult. As a result of various studies, the present inventors have found that by blending three additives, i.e., an aliphatic epoxy compound (B1), an alicyclic epoxy compound (B2), and a terpene compound (C), with a base oil (A), it is possible to provide a refrigerating machine oil composition that can exhibit extremely excellent thermal stability even when used with a refrigerant containing an unsaturated fluorinated compound (I).

[0014] In the following description, the "base oil (A)," the "aliphatic epoxy compound (B1)," the "alicyclic epoxy compound (B2)," and the "terpene compound (C)" will also be referred to as "component (A)," "component (B1)," "component (B2)," and "component (C)," respectively.

[0015] The refrigerator oil composition of this embodiment may be composed only of component (A), component (B1), component (B2), and component (C), or may further contain components other than component (A), component (B1), component (B2), and component (C). In the refrigerator oil composition of this embodiment, the total content of component (A), component (B1), component (B2), and component (C) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, still more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, based on the total amount of the refrigerator oil composition.

[0016] Hereinafter, each component contained in the refrigerator oil composition of the present embodiment will be described in detail.

[0017] <Base oil (A)> The refrigerating oil composition of this embodiment contains base oil (A). In the refrigerating oil composition of this embodiment, the content of base oil (A) is preferably 80.0 mass% or more, more preferably 85.0 mass% or more, and even more preferably 90.0 mass% or more, based on the total amount of the refrigerating oil composition, from the viewpoint of the long-term stability required of a refrigerating oil composition. Furthermore, from the viewpoint of easily ensuring the contents of components (B1), (B2), and (C) in the refrigerating oil composition and from the viewpoint of easily ensuring the contents of additives other than components (B1), (B2), and (C), the content of base oil (A) is preferably 96.6 mass% or less.

[0018] The base oil (A) can be, for example, one or more selected from the group consisting of synthetic oils and mineral oils. From the viewpoint of improving the thermal stability of the refrigerating machine oil composition, the base oil (A) preferably contains one or more base oils selected from the group consisting of polyvinyl ethers (hereinafter also referred to as "PVE"), polyalkylene glycols (hereinafter also referred to as "PAG"), polyol esters (hereinafter also referred to as "POE"), and mineral oils (hereinafter also referred to as "base oil (A1)"). From the viewpoint of further improving the thermal stability of the refrigerating machine oil composition, it is more preferable to contain one or more base oils selected from the group consisting of PVE and PAG (hereinafter also referred to as "base oil (A2)"). From the viewpoint of further improving the thermal stability of the refrigerating machine oil composition, it is even more preferable to contain PVE (hereinafter also referred to as "base oil (A3)"). PVE, PAG, POE, and mineral oil will be described in detail below.

[0019] (Polyvinyl ethers (PVE)) The PVE may be any polymer having one or more vinyl ether-derived structural units. When the base oil (A) contains a PVE, one PVE may be used alone, or two or more PVEs may be used in combination.

[0020] The PVE is preferably a polymer (A-1) having one or more structural units represented by the following general formula (A-1).

[0021]

[0022] In formula (A-1), R１ａ , R ２ａ and R ３ａ R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. ４ａ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. ５ａ represents a hydrocarbon group having 1 to 10 carbon atoms; r represents OR ４ａ The number of repeating units of the formula (A-1) is 0 to 10, preferably 0 to 5, more preferably 0 to 3, and even more preferably 0. ４ａ If there are multiple, multiple OR ４ａ may be the same or different.

[0023] R １ａ , R ２ａ and R ３ａ Examples of hydrocarbon groups having 1 to 8 carbon atoms represented by the formula (I) include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, and various dimethylcyclohexyl groups; aryl groups such as phenyl group, various methylphenyl groups, various ethylphenyl groups, and various dimethylphenyl groups; and arylalkyl groups such as benzyl group, various phenylethyl groups, and various methylbenzyl groups. Here, "various" refers to "linear, branched, or cyclic" hydrocarbon groups, and for example, "various butyl groups" refers to various butyl groups such as "n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, cyclobutyl group, and the like. Furthermore, with respect to groups having a cyclic structure, positional isomers such as ortho-, meta- and para-isomers are included, and the same applies hereinafter.

[0024] R １ａ , R ２ａ and R ３ａ The number of carbon atoms in the hydrocarbon group represented by R is preferably 1 to 6, and more preferably 1 to 3. １ａ , R ２ａ and R ３ａare each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0025] R ４ａ Examples of divalent hydrocarbon groups having 2 to 10 carbon atoms represented by the formula (R) include divalent aliphatic groups such as ethylene group, 1,2-propylene group, 1,3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, and various decylene groups; divalent alicyclic groups such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, and propylcyclohexane; divalent aromatic groups such as various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, and various naphthylenes; divalent alkylaromatic groups having monovalent bonding sites at the alkyl moiety and aromatic moiety of alkylaromatic hydrocarbons such as toluene, xylene, and ethylbenzene; and divalent alkylaromatic groups having a bonding site at the alkyl moiety of polyalkylaromatic hydrocarbons such as xylene and diethylbenzene. ４ａ The number of carbon atoms in the hydrocarbon group represented by R is preferably 2 to 6, and more preferably 2 to 4. ４ａ is preferably a divalent aliphatic group having 2 to 10 carbon atoms, more preferably a divalent aliphatic group having 2 to 4 carbon atoms.

[0026] R ５ａExamples of hydrocarbon groups having 1 to 10 carbon atoms represented by the formula (R) include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, and various dimethylcyclohexyl groups; aryl groups such as phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, and various naphthyl groups; and arylalkyl groups such as benzyl group, various phenylethyl groups, various methylbenzyl groups, various phenylpropyl groups, and various phenylbutyl groups. ５ａ The number of carbon atoms in the hydrocarbon group represented by R is preferably 1 to 8, more preferably 1 to 6. ５ａ From the viewpoint of further improving compatibility with the refrigerant, the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

[0027] The number of units (degree of polymerization) of the structural unit represented by the general formula (A-1) is appropriately selected depending on the kinematic viscosity required for the base oil (A). Furthermore, the polymer having the structural unit represented by the general formula (A-1) may be a homopolymer having only one type of the structural unit, or a copolymer having two or more types of the structural unit. When the polymer is a copolymer, the form of copolymerization is not particularly limited, and may be any of a block copolymer, a random copolymer, or a graft copolymer. Furthermore, the PVE may contain a polyalkylene glycol structure in its structure, but preferably does not contain a polyalkylene glycol structure.

[0028] At the terminal portion of the polymer (A-1), a monovalent group derived from a saturated hydrocarbon, ether, alcohol, ketone, amide, nitrile, etc. Among these, it is preferable that one terminal portion of the polymer (A-1) is a group represented by the following general formula (A-1-i):

[0029]

[0030] In formula (A-1-i), * indicates the bonding position to the carbon atom in the structural unit represented by general formula (A-1). ６ａ , R ７ａ and R ８ａ R each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ６ａ , R ７ａ and R ８ａ The hydrocarbon group having 1 to 8 carbon atoms represented by the formula (A-1) is R １ａ , R ２ａ and R ３ａ Examples of the hydrocarbon group having 1 to 8 carbon atoms and represented by the following formula include the same as those listed above.

[0031] In the above formula (A-1-i), R ９ａ represents a divalent hydrocarbon group having 2 to 10 carbon atoms, preferably a divalent hydrocarbon group having 2 to 6 carbon atoms, and more preferably a divalent aliphatic group having 2 to 4 carbon atoms. ９ａ and represents an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and even more preferably 0. In addition, if OR ９ａ If there are multiple, multiple OR ９ａ may be the same or different. ９ａ The divalent hydrocarbon group having 2 to 10 carbon atoms represented by the formula (A-1) is R ４ａ Examples of the divalent hydrocarbon group having 2 to 10 carbon atoms and represented by the following formula include the same as those listed above.

[0032] In formula (A-1-i), R １０ａ represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. １０ａWhen r1 in the above general formula (A-1-i) is 0, an alkyl group having 1 to 6 carbon atoms is preferable, and when r1 is 1 or more, an alkyl group having 1 to 4 carbon atoms is preferable. １０ａ The hydrocarbon group having 1 to 10 carbon atoms represented by the formula (A-1) is R ５ａ Examples of the hydrocarbon group having 1 to 10 carbon atoms and represented by the following formula include the same as those listed above.

[0033] Furthermore, when one end moiety of the polymer (A-1) is a group represented by the above general formula (A-1-i), the other end moiety is preferably any one of a group represented by the above general formula (A-1-i), a group represented by the following general formula (A-1-ii), a group represented by the following general formula (A-1-iii), and a group having an olefinically unsaturated bond.

[0034]

[0035] In formulas (A-1-ii) and (A-1-iii), R ６ａ , R ７ａ , R ８ａ , R ９ａ , R １０ａ and r1 are the same as those in the general formula (A-1-i). １１ａ , R １２ａ and r2 are each R in the general formula (A-1-i) ９ａ , R １０ａ and r1 are defined as follows.

[0036] In this embodiment, the PVE having the structural unit represented by general formula (A-1) is R １ａ , R ２ａ , and R ３ａ are all hydrogen atoms, r is 0, and R ５ａ is an ethyl group, from the viewpoint of improving solubility in refrigerants and thermal stability. １ａ , R ２ａ , and R ３ａ are all hydrogen atoms, r is 0, and R ５ａis an ethyl group; and １ａ , R ２ａ , and R ３ａ are all hydrogen atoms, r is 0, and R ５ａ is an isobutyl group. In this case, the molar ratio of the ethyl vinyl ether structural units to the isobutyl vinyl ether structural units [(ethyl vinyl ether structural units) / (isobutyl vinyl ether structural units)] is preferably 50 / 50 to 99 / 1, more preferably 70 / 30 to 99 / 1, even more preferably 75 / 25 to 95 / 5, and still more preferably 80 / 20 to 90 / 10.

[0037] (Polyalkylene glycols (PAG)) The PAG is preferably a polymer (A-2) represented by the following general formula (A-2): R １３ａ - [(OR １４ａ ) ｍ -OR １５ａ ] ｎ (A-2) When the base oil (A) contains a PAG, the PAG may be used alone or in combination of two or more.

[0038] In the above general formula (A-2), R １３ａ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, a divalent to hexavalent hydrocarbon group having 1 to 10 carbon atoms, or a substituted or unsubstituted heterocyclic group having 3 to 10 ring atoms; R １４ａ represents an alkylene group having 2 to 4 carbon atoms, and R １５ａrepresents a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted heterocyclic group having 3 to 10 ring atoms. Examples of substituents that the heterocyclic group may have include an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6, more preferably 1 to 3); a cycloalkyl group having 3 to 10 ring carbon atoms (preferably 3 to 8, more preferably 5 or 6); an aryl group having 6 to 18 ring carbon atoms (preferably 6 to 12); a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom); a cyano group; a nitro group; a hydroxy group; an amino group, and the like. These substituents may be further substituted with any of the substituents described above.

[0039] n is an integer of 1 to 6, preferably an integer of 1 to 3, and more preferably 1. Note that n is the same as R １３ａ For example, R １３ａ When R is an alkyl group or an acyl group, n is 1, and R １３ａ is a hydrocarbon group or a heterocyclic group, and when the valence of the group is di-, tri-, tetra-, penta-, or hexa-valent, n is 2, 3, 4, 5, or 6, respectively. １４ａ The number of repeating units is 1 or more, and preferably m×n is a number from 6 to 80. The value of m is determined based on the kinematic viscosity of the base oil (A) at 100° C. of 2 to 50 mm ２ The kinematic viscosity is a value that is appropriately set so as to fall within the range of R / s, and there is no particular limitation as long as the kinematic viscosity is adjusted so as to fall within the predetermined range. １４ａ may be the same or different. When n is 2 or more, multiple R １５ａ may be the same as or different from each other.

[0040] R １３ａ and R １５ａExamples of the monovalent hydrocarbon group represented by the formula (I) include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups; cycloalkyl groups such as cyclopentyl, cyclohexyl, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, and various dimethylcyclohexyl groups; aryl groups such as phenyl, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, and various naphthyl groups; and arylalkyl groups such as benzyl, various phenylethyl groups, various methylbenzyl groups, various phenylpropyl groups, and various phenylbutyl groups. The alkyl groups may be linear or branched. R １３ａ and R １５ａ The number of carbon atoms in the monovalent hydrocarbon group represented by the formula (I) is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3, from the viewpoint of compatibility with the refrigerant.

[0041] R １３ａ and R １５ａ The hydrocarbon group portion of the acyl group having 2 to 10 carbon atoms represented by the formula (I) may be linear, branched or cyclic. １３ａ and R １５ａ Among the hydrocarbon groups represented by the formula (R), those having 1 to 9 carbon atoms are exemplified. １３ａ and R １５ａ The number of carbon atoms in the acyl group represented by the formula (I) is preferably 2 to 8, more preferably 2 to 6, from the viewpoint of compatibility with the refrigerant.

[0042] R １３ａ The divalent to hexavalent hydrocarbon group represented by the formula (I) is the same as the above-mentioned R １３ａ and residues in which hydroxyl groups have been removed from polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, sorbitol, 1,2,3-trihydroxycyclohexane, and 1,3,5-trihydroxycyclohexane.１３ａ The number of carbon atoms in the divalent to hexavalent acyl group represented by the formula (I) is preferably 2 to 10, more preferably 2 to 6, from the viewpoint of compatibility with the refrigerant.

[0043] R １３ａ and R １５ａ The heterocyclic group represented by the formula (I) is preferably an oxygen atom-containing heterocyclic group or a sulfur atom-containing heterocyclic group. The heterocyclic group may be a saturated ring or an unsaturated ring. Examples of the oxygen atom-containing heterocyclic group include residues of oxygen atom-containing saturated heterocycles such as ethylene oxide, 1,3-propylene oxide, tetrahydrofuran, tetrahydropyran, and hexamethylene oxide; and residues of oxygen atom-containing unsaturated heterocycles such as acetylene oxide, furan, pyran, oxycycloheptatriene, isobenzofuran, and isochromene, in which 1 to 6 hydrogen atoms have been removed. Examples of the sulfur atom-containing heterocyclic group include residues of sulfur atom-containing saturated heterocycles such as ethylene sulfide, trimethylene sulfide, tetrahydrothiophene, tetrahydrothiopyran, and hexamethylene sulfide; and residues of sulfur atom-containing unsaturated heterocycles such as acetylene sulfide, thiophene, thiapyran, and thiotripyridene, in which 1 to 6 hydrogen atoms have been removed.

[0044] R １３ａ and R １５ａ The heterocyclic group represented by the formula (A-1) may have a substituent, and the substituent may be bonded to the oxygen atom in the general formula (A-2). As the substituent, as described above, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred. From the viewpoint of compatibility with the refrigerant, the number of ring atoms of the heterocyclic group is preferably 3 to 10, and more preferably 3 to 6.

[0045] R １４ａ The alkylene group represented by the formula (I) is a dimethylene group (—CH ２ CH ２ -), ethylene group (-CH(CH ３ an alkylene group having 2 carbon atoms, such as a trimethylene group (—CH ２ CH ２ CH ２ -), propylene group (-CH(CH ３ ) CH２ -), propylidene group (-CHCH ２ CH ３ -), isopropylidene group (-C(CH ３ ) ２ an alkylene group having 3 carbon atoms, such as a tetramethylene group (—CH ２ CH ２ CH ２ CH ２ -), 1-methyltrimethylene group (-CH(CH ３ ) CH ２ CH ２ -), 2-methyltrimethylene group (-CH ２ CH (CH ３ ) CH ２ -), butylene group (-C(CH ３ ) ２ CH ２ Among these, alkylene groups having 4 carbon atoms such as R １４ａ Examples of the propylene group include: ３ ) CH ２ -) is preferred.

[0046] In the polymer (A-2) represented by the general formula (A-2), the oxypropylene unit (—OCH(CH ３ ) CH ２ The content of oxyalkylene (OR -) in the polymer (A-2) １４ａ ) is preferably 50 mol % or more, more preferably 65 mol % or more, and even more preferably 80 mol % or more, based on the total amount (100 mol %) of the copolymers.

[0047] Among the polymers (A-2) represented by the general formula (A-2) above, at least one selected from the group consisting of polyoxypropylene glycol dimethyl ether represented by the following general formula (A-2-i), polyoxyethylene polyoxypropylene glycol dimethyl ether represented by the following general formula (A-2-ii), and polyoxypropylene glycol monobutyl ether and polyoxypropylene glycol diacetate represented by the following general formula (A-2-iii) are preferred.

[0048] (In formula (A-2-i), m1 represents a number of 1 or more, and preferably a number of 6 to 80.)

[0049] (In formula (A-2-ii), m2 and m3 each independently represent a number of 1 or more, and preferably a number such that the value of m2+m3 is 6 to 80.)

[0050] (In formula (A-2-iii), m4 represents a number of 1 or more, and preferably a number of 6 to 80.)

[0051] Note that m1 in the general formula (A-2-i), m2 and m3 in the general formula (A-2-ii), and m4 in the general formula (A-2-iii) may be appropriately selected depending on the kinematic viscosity required for the base oil (A).

[0052] (Polyol Esters (POE)) Examples of POE include esters of diols or polyols with fatty acids. When the base oil (A) contains POE, one type of POE may be used alone, or two or more types may be used in combination. The POE is preferably an ester of a diol or a polyol having 3 to 20 hydroxyl groups with a fatty acid having 3 to 20 carbon atoms.

[0053] Examples of diols include 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, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol.

[0054] Examples of polyols include polyhydric alcohols such as trimethylolethane, trimethylolpropane, trimethylolbutane, di-(trimethylolpropane), tri-(trimethylolpropane), pentaerythritol, di-(pentaerythritol), tri-(pentaerythritol), glycerin, polyglycerin (a dimer to 20-mer of glycerin), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol-glycerin condensates, adonitol, arabitol, xylitol, and mannitol; sugars such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gentianose, and melenitose; and partially etherified products thereof, methyl glucosides (glycoside). Among these, preferred are hindered alcohols such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di-(trimethylolpropane), tri-(trimethylolpropane), pentaerythritol, di-(pentaerythritol), tri-(pentaerythritol), etc. The term "hindered alcohol" refers to an alcohol having a quaternary carbon atom bonded to four carbon atoms.

[0055] The carbon number of the fatty acid is preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, and even more preferably 8 or more, from the viewpoint of lubrication performance; and preferably 20 or less, more preferably 16 or less, even more preferably 12 or less, and even more preferably 10 or less, from the viewpoint of compatibility with the refrigerant. The carbon number of the fatty acid includes the carbon atom of the carboxy group (—COOH) possessed by the fatty acid. The fatty acid may be either a linear fatty acid or a branched fatty acid, but from the viewpoint of lubrication performance, a linear fatty acid is preferred, and from the viewpoint of hydrolysis stability, a branched fatty acid is preferred. Furthermore, the fatty acid may be either a saturated fatty acid or an unsaturated fatty acid.

[0056] Examples of fatty acids include straight-chain or branched-chain fatty acids such as isobutyric acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, and oleic acid, as well as so-called neo acids in which the α-carbon atom is quaternary. More specifically, isobutyric acid, valeric acid (n-pentanoic acid), caproic acid (n-hexanoic acid), enanthic acid (n-heptanoic acid), caprylic acid (n-octanoic acid), pelargonic acid (n-nonanoic acid), capric acid (n-decanoic acid), oleic acid (cis-9-octadecenoic acid), isopentanoic acid (3-methylbutanoic acid), 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, and the like are preferred.

[0057] The POE may be a partial ester in which some of the hydroxyl groups of the polyol remain unesterified, or a complete ester in which all of the hydroxyl groups are esterified. The POE may be a mixture of a partial ester and a complete ester, but a complete ester is preferred.

[0058] As the POE, from the viewpoint of superior hydrolysis stability, esters of hindered alcohols such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di-(trimethylolpropane), tri-(trimethylolpropane), pentaerythritol, di-(pentaerythritol), and tri-(pentaerythritol) are preferred, esters of neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, and pentaerythritol are more preferred, and from the viewpoint of particularly superior compatibility with refrigerants and hydrolysis stability, esters of pentaerythritol are even more preferred.

[0059] Specific preferred examples of POE include diesters of neopentyl glycol and one or more fatty acids selected from the group consisting of isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; triesters of trimethylolethane and one or more fatty acids selected from the group consisting of isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; and triesters of trimethylolpropane and one or more fatty acids selected from the group consisting of isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid. triesters of one or more fatty acids selected from the group consisting of trimethylol butane and isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; triesters of trimethylol butane and one or more fatty acids selected from the group consisting of isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; tetraesters of pentaerythritol and one or more fatty acids selected from the group consisting of isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid.

[0060] The ester of two or more fatty acids may be a mixture of two or more esters of one fatty acid and a polyol. Among POEs, esters of two or more mixed fatty acids and polyols are preferred from the viewpoints of improving low-temperature properties and compatibility with refrigerants.

[0061] (Mineral Oil) Examples of mineral oils include oils obtained by atmospheric distillation of paraffinic, intermediate, or naphthenic crude oils, or by vacuum distillation of the atmospheric residual oil obtained by atmospheric distillation of crude oil, and then refining the lubricating oil fraction by one or more of solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, etc., and oils produced by isomerizing mineral oil waxes. When mineral oil is contained in base oil (A), one mineral oil may be used alone, or two or more mineral oils may be used in combination.

[0062] (Preferred Aspect of Base Oil (A)) In the refrigerator oil composition of this embodiment, the main component of the base oil (A) is preferably the base oil (A1) described above, more preferably the base oil (A2) described above, and even more preferably the base oil (A3) described above. In this specification, "main component" means the component with the highest content. The content of the base oil (A1), base oil (A2), or base oil (A3) in the base oil (A) is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, even more preferably 70 to 100 mass%, still more preferably 80 to 100 mass%, and even more preferably 90 to 100 mass%, based on the total amount (100 mass%) of the base oil (A). In particular, the content of base oil (A3) (i.e., PVE) in base oil (A) is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably 70% by mass to 100% by mass, still more preferably 80% by mass to 100% by mass, even more preferably 90% by mass to 100% by mass, and even more preferably 95% by mass to 100% by mass.

[0063] (Other Base Oils) In addition to the base oil (A1), base oil (A2), or base oil (A3), the base oil (A) may further contain other base oils. Examples of other base oils include synthetic oils that do not fall under the category of the aforementioned PVE, PAG, POE, and mineral oil, such as polyesters, polycarbonates, hydrogenated α-olefin oligomers, alicyclic hydrocarbon compounds, alkylated aromatic hydrocarbon compounds, and copolymers (ECPs) of poly(oxy)alkylene glycol or its monoether with polyvinyl ether. Note that "copolymers (ECPs) of poly(oxy)alkylene glycol or its monoether with polyvinyl ether" refer to copolymers having structural units derived from poly(oxy)alkylene glycol or its monoether and structural units derived from polyvinyl ether, and "poly(oxy)alkylene glycol" refers to both polyalkylene glycol and polyoxyalkylene glycol.

[0064] The kinematic viscosity at 40°C of the base oil (A) is preferably 20 mm from the viewpoint of improving lubricating performance and sealing performance. ２ / s or more, more preferably 25 mm ２ / s or more, more preferably 30 mm ２ / s or more. From the viewpoint of improving the energy saving properties of the refrigerating machine oil composition, it is preferably 150 mm ２ / s or less, more preferably 100 mm ２ / s or less, more preferably 80 mm ２ The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, it is preferably 20 mm ２ / s~150mm ２ / s, more preferably 25 mm ２ / s ~ 100 mm ２ / s, more preferably 30 mm ２ / s~80mm ２ In this specification, the 40°C kinematic viscosity of the base oil (A) is a value measured in accordance with JIS K2283:2000.

[0065] <Aliphatic Epoxy Compound (B1)> The refrigerating oil composition of the present embodiment contains an aliphatic epoxy compound (B1). The refrigerating oil composition of the present embodiment contains an alicyclic epoxy compound (B2) and a terpene compound (C) together with the aliphatic epoxy compound (B1), and thereby exhibits excellent thermal stability.

[0066] The aliphatic epoxy compound (B1) is a compound having an aliphatic hydrocarbon group and one or more epoxy groups in one molecule, and examples thereof include compounds having a glycidyl ether group such as alkyl glycidyl ether and alkylene glycol glycidyl ether, alkyl epoxide, epoxidized soybean oil, etc. The aliphatic epoxy compound (B1) may be used alone or in combination of two or more.

[0067] Here, from the viewpoint of making it easier to improve the thermal stability of the refrigerator oil composition, the aliphatic epoxy compound (B1) preferably contains a compound having a glycidyl ether group (hereinafter also simply referred to as a "glycidyl ether compound". The content of the glycidyl ether compound is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably 70% by mass to 100% by mass, still more preferably 80% by mass to 100% by mass, even more preferably 90% by mass to 100% by mass, and even more preferably 95% by mass to 100% by mass, based on the total amount of the aliphatic epoxy compound (B1).

[0068] Examples of glycidyl ether compounds include glycidyl ethers derived from saturated or unsaturated aliphatic monoalcohols or aliphatic polyalcohols, each having preferably 4 to 30 carbon atoms, more preferably 4 to 24 carbon atoms, and even more preferably 5 to 20 carbon atoms. The aliphatic monoalcohol or aliphatic polyalcohol may have a linear structure or a branched chain. In the case of a glycidyl ether derived from an aliphatic polyalcohol, it is preferable that all of the hydroxyl groups are glycidyl etherified, from the viewpoint of the stability of the refrigerating machine oil composition and the viewpoint of suppressing an increase in the hydroxyl value. Among these, glycidyl ether compounds, particularly glycidyl ethers derived from linear or branched saturated aliphatic monoalcohols having 5 to 20 carbon atoms, are more preferred. In the above description, the number of carbon atoms in the glycidyl ether compound refers to the number of carbon atoms in the entire glycidyl ether compound, including the number of carbon atoms in the glycidyl ether group (3 carbon atoms).

[0069] More preferred glycidyl ether compounds include those represented by the following general formula (b1):

[0070] In the above general formula (b1), R １１ represents a saturated aliphatic hydrocarbon group having 1 to 27 carbon atoms. From the viewpoint of making it easier to improve the thermal stability of the refrigerator oil composition, the number of carbon atoms in the saturated aliphatic hydrocarbon group is preferably 4 to 24, more preferably 6 to 20, and even more preferably 6 to 16. R １２ represents a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms. m represents an integer of 0 to 3, and from the viewpoint of making it easier to improve the thermal stability of the refrigerator oil composition, it is preferably 0 to 2, more preferably 0 to 1, and even more preferably 0. Note that when m is 2 or more and R １２ When there are multiple R １２ Here, from the viewpoint of making it easier to improve the thermal stability of the refrigerator oil composition, R １１is preferably a branched alkyl group. Examples of glycidyl ether compounds include 2-ethylethyl glycidyl ether, 2-methylhexyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-propylhexyl glycidyl ether, 3-methylhexyl glycidyl ether, 3-ethylhexyl glycidyl ether, 3-propylhexyl glycidyl ether, isononyl glycidyl ether, caprinoyl glycidyl ether, lauryl glycidyl ether, and myristyl glycidyl ether. Among these, 2-ethylhexyl glycidyl ether is preferred.

[0071] The glycidyl ether compounds represented by the general formula (b1) may be used singly or in combination of two or more.

[0072] <Alicyclic Epoxy Compound (B2)> The refrigerating oil composition of the present embodiment contains the alicyclic epoxy compound (B2). The refrigerating oil composition of the present embodiment contains the aliphatic epoxy compound (B1) and the terpene compound (C) together with the alicyclic epoxy compound (B2), and thereby exhibits excellent thermal stability.

[0073] The alicyclic epoxy compound (B2) is a compound having an alicyclic hydrocarbon group and one or more epoxy groups in one molecule, and preferred examples thereof include compounds represented by the following general formula (b2):

[0074]

[0075] In general formula (b2), the alicyclic ring represented by a substantially circular shape is a cycloalkane skeleton having 5 to 12 ring carbon atoms or a cycloalkene skeleton having 5 to 12 ring carbon atoms. Here, from the viewpoint of making it easier to improve the thermal stability of the refrigerating oil composition, the alicyclic ring is preferably a cycloalkane skeleton having 5 to 10 ring carbon atoms or a cycloalkene skeleton having 5 to 10 ring carbon atoms, more preferably a cycloalkane skeleton having 5 to 8 ring carbon atoms or a cycloalkene skeleton having 5 to 8 ring carbon atoms, even more preferably a cyclohexane skeleton or a cyclohexene skeleton, and still more preferably a cyclohexane skeleton. That is, the alicyclic epoxy compound (B2) preferably contains a compound having a cyclohexane skeleton. The content of the compound having a cyclohexane skeleton is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably 70% by mass to 100% by mass, still more preferably 80% by mass to 100% by mass, still more preferably 90% by mass to 100% by mass, and even more preferably 95% by mass to 100% by mass, based on the total amount of the alicyclic epoxy compound (B2).

[0076] In general formula (b2), R ２１ is an aliphatic hydrocarbon group having a linear or branched olefin structure and having 2 to 10 carbon atoms, such as a vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 1,2-dimethyl-3-pentenyl group, and 1,2-dimethyl-4-pentenyl group. The aliphatic hydrocarbon group may have one or more ether bonds, but is preferably an aliphatic hydrocarbon group without an ether bond. The aliphatic hydrocarbon group may be either a substituted or unsubstituted aliphatic hydrocarbon group, but is preferably an unsubstituted aliphatic hydrocarbon group. When the aliphatic hydrocarbon group has a substituent, examples of the substituent include a halogen atom, a hydroxy group, an alkoxy group, an amino group, an imino group, an amide group, and a carboxyl group. When the aliphatic hydrocarbon group has multiple substituents, these multiple substituents may be the same or different.

[0077] In general formula (b2), n is 0 or 1.

[0078] In the general formula (b2), when n is 1, from the viewpoint of making it easier to improve the thermal stability of the refrigerator oil composition, R ２１ is preferably an aliphatic hydrocarbon group having a linear olefin structure, more preferably an aliphatic hydrocarbon group having a linear α-olefin structure. In addition, when n is 1 in the general formula (b2), from the viewpoint of further improving the thermal stability of the refrigerating machine oil composition, R ２１ has preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms. Therefore, in general formula (b2), when n is 1, R ２１ is a vinyl group, an allyl group, a 3-butenyl group, a 4-pentenyl group, a 5-hexenyl group, and the like, and is preferably a vinyl group or an allyl group, and more preferably a vinyl group. When the alicyclic ring is a cyclohexane ring (i.e., when the cyclohexane skeleton containing an epoxy group is a 1,2-epoxycyclohexane skeleton), R ２１ is preferably attached to the 4-position of the cyclohexane ring.

[0079] In general formula (b2), R ２２ is R in the alicyclic ring ２１ The substituent is a substituent other than a group. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms, a halogen atom, a hydroxy group, an alkoxy group, an amino group, an imino group, an amide group, and a carboxyl group. q is an integer of 0 or more. When q is 2 or more, a plurality of R ２２ may be the same or different. Here, q is preferably 0 from the viewpoint of making it easier to improve the thermal stability of the refrigerator oil composition.

[0080] The compound having a cyclohexane skeleton is preferably at least one selected from the group consisting of 1,2-epoxy-4-vinylcyclohexane and 1,2-epoxycyclohexane.

[0081] The compound having a cyclohexane skeleton may be used alone or in combination of two or more.

[0082] <Terpene Compound (C)> The refrigerating oil composition of the present embodiment contains a terpene compound (C). The refrigerating oil composition of the present embodiment contains an aliphatic epoxy compound (B1) and an alicyclic epoxy compound (B2) together with the terpene compound (C), and thereby exhibits excellent thermal stability.

[0083] The terpene compound (C) is preferably, for example, a monoterpene compound. Examples of the monoterpene compound include pinene compounds such as α-pinene and β-pinene; terpinene compounds such as α-terpinene and γ-terpinene; monocyclic monoterpene compounds such as d-limonene and l-limonene; and limonene oxide. Among these, the terpene compound (C) preferably contains one or more compounds selected from the group consisting of pinene compounds and terpinene compounds, and more preferably contains one or more compounds selected from the group consisting of β-pinene and γ-terpinene. The content of one or more compounds selected from the group consisting of pinene compounds and terpinene compounds (preferably one or more compounds selected from the group consisting of β-pinene and γ-terpinene) is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, even more preferably 70% by mass to 100% by mass, still more preferably 80% by mass to 100% by mass, even more preferably 90% by mass to 100% by mass, and even more preferably 95% by mass to 100% by mass, based on the total amount of the terpene compound (C).

[0084] The terpene compound (C) may be used alone or in combination of two or more.

[0085] <Total Content of Component (B1), Component (B2), and Component (C)> In the refrigerating oil composition of this embodiment, from the viewpoint of improving the thermal stability of the refrigerating oil composition, the total content of the aliphatic epoxy compound (B1), the alicyclic epoxy compound (B2), and the terpene compound (C) is preferably 3.0 mass% or more, more preferably 4.0 mass% or more, and even more preferably 5.0 mass% or more, based on the total amount of the refrigerating oil composition. Furthermore, from the viewpoint of ensuring the thermal stability of the refrigerating oil composition with an appropriate addition amount, the total content is preferably 10 mass% or less, more preferably 9.0 mass% or less, and even more preferably 8.0 mass% or less. The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, the total content is preferably 3.0 mass% to 10 mass%, more preferably 4.0 mass% to 9.0 mass%, and even more preferably 5.0 mass% to 8.0 mass%.

[0086] <Content of Component (B1)> In the refrigerating oil composition of this embodiment, from the viewpoint of improving the thermal stability of the refrigerating oil composition, the content of the aliphatic epoxy compound (B1) is preferably 0.5 mass% or more, more preferably 0.7 mass% or more, and even more preferably 0.8 mass% or more, based on the total amount of the refrigerating oil composition. Furthermore, from the viewpoint of ensuring the thermal stability of the refrigerating oil composition with an appropriate addition amount, the content is preferably 4.0 mass% or less, more preferably 3.5 mass% or less, and even more preferably 3.0 mass% or less. The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, the content is preferably 0.5 mass% to 4.0 mass%, more preferably 0.7 mass% to 3.5 mass%, and even more preferably 0.8 mass% to 3.0 mass%.

[0087] <Content of Component (B2)> In the refrigerator oil composition of this embodiment, from the viewpoint of improving the thermal stability of the refrigerator oil composition, the content of the alicyclic epoxy compound (B2) is preferably 0.5 mass% or more, more preferably 1.0 mass% or more, even more preferably 1.5 mass% or more, still more preferably 2.0 mass% or more, and even more preferably 2.5 mass% or more, based on the total amount of the refrigerator oil composition. Furthermore, from the viewpoint of ensuring the thermal stability of the refrigerator oil composition with an appropriate addition amount, the content is preferably 5.0 mass% or less, more preferably 4.8 mass% or less, even more preferably 4.6 mass% or less, still more preferably 4.4 mass% or less, and even more preferably 4.2 mass% or less. The upper and lower limits of these numerical ranges can be combined in any desired manner. Specifically, it is preferably 0.5% by mass to 5.0% by mass, more preferably 1.0% by mass to 4.8% by mass, even more preferably 1.5% by mass to 4.6% by mass, still more preferably 2.0% by mass to 4.4% by mass, and even more preferably 2.5% by mass to 4.2% by mass.

[0088] <Content of Component (C)> In the refrigerator oil composition of this embodiment, from the viewpoint of improving the thermal stability of the refrigerator oil composition, the content of the terpene compound (C) is preferably 0.5 mass% or more, more preferably 0.8 mass% or more, and even more preferably 1.0 mass% or more, based on the total amount of the refrigerator oil composition. Furthermore, from the viewpoint of ensuring the thermal stability of the refrigerator oil composition with an appropriate addition amount, the content is preferably 3.0 mass% or less, more preferably 2.5 mass% or less, and even more preferably 2.0 mass% or less. The upper and lower limits of these numerical ranges can be arbitrarily combined. Specifically, the content is preferably 0.5 mass% to 3.0 mass%, more preferably 0.8 mass% to 2.5 mass%, and even more preferably 1.0 mass% to 2.0 mass%.

[0089] <Mass Ratio of Component (B2) to Component (B1)> In the refrigerator oil composition of the present embodiment, from the viewpoint of making it easier to improve the thermal stability of the refrigerator oil composition, the mass ratio of the alicyclic epoxy compound (B2) to the aliphatic epoxy compound (B1) [(B2) / (B1)] is preferably 0.40 to 5.0, more preferably 0.45 to 4.0, and even more preferably 0.50 to 3.0.

[0090] <Mass Ratio of Component (C) to Component (B1) and Component (B2)> In the refrigerator oil composition of the present embodiment, from the viewpoint of making it easier to improve the thermal stability of the refrigerator oil composition, the mass ratio of the terpene compound to the aliphatic epoxy compound (B1) and the alicyclic epoxy compound (B2), [(C) / {(B1)+(B2)}], is preferably 0.20 to 0.80, more preferably 0.25 to 0.55, and even more preferably 0.30 to 0.40.

[0091] <Additives> The refrigerator oil composition of this embodiment may further contain additives (hereinafter also referred to as "other additives"). From the viewpoint of improving the stability of the refrigerator oil composition, the other additives preferably include one or more selected from the group consisting of antioxidants, extreme pressure agents, oiliness improvers, copper deactivators, rust inhibitors, antifoaming agents, and viscosity index improvers, and more preferably include at least an antioxidant, an extreme pressure agent, and an antifoaming agent. The total content of the other additives is preferably 0 to 10% by mass, more preferably 0.01 to 8.0% by mass, even more preferably 0.1 to 5.0% by mass, and still more preferably 0.5 to 3.0% by mass, based on the total amount of the refrigerator oil composition.

[0092] (Antioxidant) The antioxidant is preferably one or more selected from the group consisting of phenolic antioxidants and amine-based antioxidants. Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol (DBPC), 2,6-di-tert-butyl-4-ethylphenol, and 2,2'-methylenebis(4-methyl-6-tert-butylphenol). Examples of amine-based antioxidants include phenyl-α-naphthylamine and N,N'-diphenyl-p-phenylenediamine. Of these, 2,6-di-tert-butyl-p-cresol (DBPC) is preferred.

[0093] (Extreme Pressure Agents) Examples of extreme pressure agents include phosphorus-based extreme pressure agents, metal salts of carboxylic acids, and sulfur-based extreme pressure agents. Examples of phosphorus-based extreme pressure agents include phosphate esters, acidic phosphate esters, phosphites, acidic phosphites, and amine salts thereof. Specific examples include tricresyl phosphate (TCP), triphenyl phosphate, tri(nonylphenyl)phosphite, dioleylhydrogen phosphite, and 2-ethylhexyldiphenyl phosphite. Examples of metal salts of carboxylic acids include metal salts of carboxylic acids having 3 to 60 carbon atoms (preferably 3 to 30 carbon atoms). Among these, one or more selected from the group consisting of metal salts of fatty acids having 12 to 30 carbon atoms and metal salts of dicarboxylic acids having 3 to 30 carbon atoms are preferred. As the metal constituting the metal salt, alkali metals and alkaline earth metals are preferred, and alkali metals are more preferred. Examples of sulfur-based extreme pressure agents include sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, sulfurized olefins, dihydrocarbyl polysulfides, thiocarbamates, thioterpenes, dialkylthiodipropionates, etc. Among these, tricresyl phosphate (TCP) is preferred.

[0094] (Oilability Improver) Examples of the oiliness improver include saturated or unsaturated aliphatic monocarboxylic acids such as stearic acid and oleic acid; polymerized fatty acids such as dimer acid and hydrogenated dimer acid; hydroxy fatty acids such as ricinoleic acid and 12-hydroxystearic acid; saturated or unsaturated aliphatic monoalcohols such as lauryl alcohol and oleyl alcohol; saturated or unsaturated aliphatic monoamines such as stearylamine and oleylamine; saturated or unsaturated aliphatic monocarboxylic acid amides such as lauric acid amide and oleic acid amide; partial esters of polyhydric alcohols such as glycerin and sorbitol with saturated or unsaturated aliphatic monocarboxylic acids; and the like.

[0095] (Copper Deactivator) Examples of copper deactivators include N-[N,N'-dialkyl (alkyl group having 3 to 12 carbon atoms) aminomethyl] triazole.

[0096] (Rust inhibitor) Examples of the rust inhibitor include metal sulfonates, aliphatic amines, organic phosphites, organic phosphates, organic metal sulfonates, organic metal phosphates, alkenyl succinates, and polyhydric alcohol esters.

[0097] (Antifoaming Agent) Examples of the antifoaming agent include silicone-based antifoaming agents such as silicone oil and fluorinated silicone oil.

[0098] (Viscosity Index Improver) Examples of viscosity index improvers include polymethacrylate, polyisobutylene, ethylene-propylene copolymer, and hydrogenated styrene-diene copolymer.

[0099] [Physical Properties of Refrigerator Oil Composition] In the present embodiment, the acid value of the refrigerator oil composition after an autoclave test described in the examples below is preferably 0.20 mgKOH / g or less, more preferably 0.16 mgKOH / g or less, and even more preferably 0.12 mgKOH / g or less.

[0100] [Method for producing refrigerating machine oil composition] The method for producing the above-mentioned refrigerating machine oil composition is not particularly limited. For example, the method for producing the refrigerating machine oil composition of this embodiment includes a method for producing a refrigerating machine oil composition containing a refrigerating machine oil having a hydroxyl group represented by the following general formula (I): ２ F ｐ R ４－ｐ...(I) [In the general formula (I), each R independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and p is an integer of 1 to 3.] A method for producing a refrigerating oil composition to be used with a refrigerant containing an unsaturated fluorinated compound having a carbon-carbon unsaturated bond, the method comprising the step of mixing a base oil (A), an aliphatic epoxy compound (B1), an alicyclic epoxy compound (B2), and a terpene compound (C). The method for mixing the above components is not particularly limited, and examples include a method comprising the step of blending the aliphatic epoxy compound (B1), the alicyclic epoxy compound (B2), and the terpene compound (C) with the base oil (A). The aliphatic epoxy compound (B1), the alicyclic epoxy compound (B2), and the terpene compound (C) may be blended into the base oil (A) simultaneously or separately. The same applies to other components. Note that each component may be blended after being prepared in the form of a solution (dispersion) by adding a diluent oil or the like. After blending the components, it is preferable to stir them by a known method to disperse them uniformly.

[0101] [Uses of Refrigerating Machine Oil Composition] More specifically, the refrigerating machine oil composition of this embodiment is used in a refrigerator having a refrigeration cycle essentially comprising a compressor, a condenser, an expansion mechanism (such as an expansion valve), and an evaporator, or a compressor, a condenser, an expansion mechanism, a dryer, and an evaporator. The refrigerating machine oil composition of this embodiment is preferably used, for example, to lubricate sliding parts provided in a compressor or the like. Accordingly, the present invention also provides a lubrication method using the refrigerating machine oil composition of this embodiment for lubricating parts inside a refrigerator. The refrigerating machine oil composition of this embodiment can also be used in, for example, air conditioners, refrigerators, vending machines, showcases, refrigeration systems, hot water supply systems, or heating systems. Examples of air conditioners include car air conditioners such as open-type car air conditioners and electric car air conditioners; gas heat pump (GHP) air conditioners; and the like. Since the refrigerating machine oil composition of this embodiment exhibits excellent thermal stability under extremely severe autoclave test conditions, as will be shown in the examples described below, it is particularly preferable to use it in air conditioning equipment that performs both heating and cooling operations.

[0102] [Mixed Composition for Refrigerators] The mixed composition for refrigerators of the present embodiment is a mixed composition for refrigerators containing a refrigerant and the refrigerating machine oil composition of the present embodiment.

[0103] <Refrigerant> The refrigerating machine oil composition of the present embodiment is used for a refrigerant, and contains an unsaturated fluorinated compound having a carbon-carbon unsaturated bond represented by the following general formula (I): ２ F ｐ R ４－ｐ (I) In the general formula (I), R each independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, but from an environmental viewpoint, a hydrogen atom is preferred. Furthermore, p is an integer of 1 to 3, preferably 2 or 3. When a plurality of Rs are present, the plurality of Rs may be the same or different. However, in this embodiment, when a plurality of Rs are present, the plurality of Rs are preferably the same. The unsaturated fluorinated compound (I) may be used alone or in combination of two or more.

[0104] The unsaturated fluorinated compound (I) is a fluorine-containing ethylene compound having one carbon-carbon unsaturated bond and 1 to 3 (preferably 2 or 3) fluorine atoms. As the unsaturated fluorinated compound (I), from the viewpoint of obtaining a refrigerant with a low global warming potential (GWP), one or more selected from monofluoroethylene (R1141), 1,1,2-trifluoroethylene (R1123), 1,1-difluoroethylene (R1132a), cis-1,2-difluoroethylene (R1132(Z)), and trans-1,2-difluoroethylene (R1132(E)) are preferred, one or more selected from 1,1,2-trifluoroethylene (R1123), 1,1-difluoroethylene (R1132a), cis-1,2-difluoroethylene (R1132(Z)), and trans-1,2-difluoroethylene (R1132(E)) are more preferred, and trans-1,2-difluoroethylene (R1132(E)) is even more preferred. That is, the refrigerant used in the refrigerator oil composition of this embodiment preferably contains one or more selected from monofluoroethylene (R1141), 1,1,2-trifluoroethylene (R1123), 1,1-difluoroethylene (R1132a), cis-1,2-difluoroethylene (R1132(Z)), and trans-1,2-difluoroethylene (R1132(E)), more preferably contains one or more selected from 1,1,2-trifluoroethylene (R1123), 1,1-difluoroethylene (R1132a), cis-1,2-difluoroethylene (R1132(Z)), and trans-1,2-difluoroethylene (R1132(E)), and even more preferably contains trans-1,2-difluoroethylene (R1132(E)).

[0105] The refrigerating machine oil composition of the present embodiment preferably further contains, together with the unsaturated fluorinated compound (I), one or more refrigerants selected from the group consisting of unsaturated fluorohydrocarbon refrigerants having 3 or more carbon atoms, saturated fluorohydrocarbon refrigerants, and natural refrigerants. Each refrigerant will be described below.

[0106] (Unsaturated Fluorinated Hydrocarbon Refrigerant Having 3 or More Carbon Atoms) Examples of unsaturated fluorocarbon compounds having 3 or more carbon atoms include those having a carbon-carbon double bond, such as fluorinated linear or branched chain olefins having 3 to 6 carbon atoms and cyclic olefins having 4 to 6 carbon atoms. More specific examples include propene having 1 to 5 fluorine atoms introduced, butene having 1 to 7 fluorine atoms introduced, pentene having 1 to 9 fluorine atoms introduced, hexene having 1 to 11 fluorine atoms introduced, cyclobutene having 1 to 5 fluorine atoms introduced, cyclopentene having 1 to 7 fluorine atoms introduced, and cyclohexene having 1 to 9 fluorine atoms introduced. Of these unsaturated fluorocarbon compounds, fluorides of propene are preferred, propene having 3 to 5 fluorine atoms introduced is more preferred, and propene having 4 fluorine atoms introduced is even more preferred. Specifically, preferred compounds include 1,3,3,3-tetrafluoropropene (R1234ze), 1,2,3,3-tetrafluoropropene (R1234ye), and 2,3,3,3-tetrafluoropropene (R1234yf). Among these, 2,3,3,3-tetrafluoropropene (R1234yf) is preferred.

[0107] (Saturated Fluorinated Hydrocarbon Refrigerant) The saturated fluorohydrocarbon compound is preferably a fluoride of an alkane having 1 to 4 carbon atoms, more preferably a fluoride of an alkane having 1 to 3 carbon atoms, and even more preferably a fluoride of an alkane (methane or ethane) having 1 or 2 carbon atoms. Examples of the methane or ethane fluoride include trifluoromethane (R23), difluoromethane (R32), 1,1-difluoroethane (R152a), 1,1,1-trifluoroethane (R143a), 1,1,2-trifluoroethane (R143), 1,1,1,2-tetrafluoroethane (R134a), 1,1,2,2-tetrafluoroethane (R134), and 1,1,1,2,2-pentafluoroethane (R125). Among these, one or more selected from the group consisting of difluoromethane (R32) and 1,1-difluoroethane (R152a) are preferred.

[0108] (Natural refrigerants) Natural refrigerants include hydrocarbon refrigerants (HC), carbon dioxide (CO ２ ) and ammonia, and preferably a hydrocarbon-based refrigerant. As the hydrocarbon-based refrigerant, a hydrocarbon having 1 to 8 carbon atoms is preferred, a hydrocarbon having 1 to 5 carbon atoms is more preferred, and a hydrocarbon having 3 to 5 carbon atoms is even more preferred. When the carbon number is 8 or less, the boiling point of the refrigerant does not become too high, and this is preferable as a refrigerant. Examples of the hydrocarbon-based refrigerant include methane, ethane, ethylene, propane (R290), cyclopropane, propylene, n-butane, isobutane (R600a), 2-methylbutane, n-pentane, neopentane, cyclopentane, and normal butane. One hydrocarbon-based refrigerant may be used alone, or two or more hydrocarbon refrigerants may be used in combination.

[0109] (Preferred Aspect of Refrigerant) The refrigerant used in the refrigerating machine oil composition of this embodiment has a content of unsaturated fluorinated compound (I) (preferably R1132(E)) of preferably 1 to 100% by mass, more preferably 5 to 50% by mass, and even more preferably 10 to 30% by mass, based on the total amount of the refrigerant. Here, when the refrigerant used in the refrigerating machine oil composition of this embodiment contains a refrigerant other than the unsaturated fluorinated compound (I), the other refrigerant is preferably one or more selected from the group consisting of unsaturated fluorohydrocarbon refrigerants and saturated fluorohydrocarbon refrigerants having 3 or more carbon atoms, more preferably an unsaturated fluorohydrocarbon refrigerant or saturated fluorohydrocarbon refrigerant having 3 or more carbon atoms, and even more preferably an unsaturated fluorohydrocarbon refrigerant having 3 or more carbon atoms. The unsaturated fluorohydrocarbon refrigerant having 3 or more carbon atoms is preferably one or more selected from the group consisting of 1,3,3,3-tetrafluoropropene (R1234ze), 1,2,3,3-tetrafluoropropene (R1234ye), and 2,3,3,3-tetrafluoropropene (R1234yf), and more preferably 2,3,3,3-tetrafluoropropene (R1234yf). A preferred example of a mixed refrigerant of R1132(E) and R1234yf is R474A. The saturated fluorohydrocarbon refrigerant is one or more selected from the group consisting of trifluoromethane (R23), difluoromethane (R32), 1,1-difluoroethane (R152a), 1,1,1-trifluoroethane (R143a), 1,1,2-trifluoroethane (R143), 1,1,1,2-tetrafluoroethane (R134a), 1,1,2,2-tetrafluoroethane (R134), and 1,1,1,2,2-pentafluoroethane (R125), and more preferably one or more selected from the group consisting of difluoromethane (R32) and 1,1-difluoroethane (R152a).

[0110] (Mixing ratio of refrigerant and refrigerant oil composition) In the mixed composition for a refrigerator of this embodiment, the mixing ratio of the refrigerant oil composition to the refrigerant [refrigerant oil composition / refrigerant] is preferably 1 / 99 to 90 / 10 by mass, and more preferably 5 / 95 to 70 / 30. When the mixing ratio of the refrigerant oil composition to the refrigerant is within this range, lubricity and suitable refrigeration capacity in the refrigerator can be obtained.

[0111] [An aspect of the present invention provided] In one aspect of the present invention, the following [1] to

[13] are provided. [1] A compound represented by the following general formula (I): ２ F ｐ R ４－ｐ...(I) A refrigerator oil composition used with a refrigerant containing an unsaturated fluorinated compound having a carbon-carbon unsaturated bond represented by the following general formula (I): [In the general formula (I), each R independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and p is an integer of 1 to 3.], the refrigerator oil composition comprising: a base oil (A), an aliphatic epoxy compound (B1), an alicyclic epoxy compound (B2), and a terpene compound (C). [2] The refrigerator oil composition according to the above [1], wherein R in the general formula (I) is a hydrogen atom. [3] The refrigerator oil composition according to the above [1] or [2], wherein the refrigerant contains, as the unsaturated fluorinated compound, one or more selected from the group consisting of R1123, R1132a, R1132(Z), and R1132(E). [4] The refrigerator oil composition according to any one of [1] to [3] above, wherein the refrigerant comprises R1132(E) as the unsaturated fluorinated compound. [5] The refrigerator oil composition according to any one of [1] to [4] above, wherein the refrigerant further comprises one or more refrigerants selected from the group consisting of unsaturated fluorohydrocarbon refrigerants having 3 or more carbon atoms, saturated fluorohydrocarbon refrigerants, and natural refrigerants. [6] The refrigerator oil composition according to any one of [1] to [5] above, wherein the aliphatic epoxy compound (B1) comprises a compound having a glycidyl ether group. [7] The refrigerator oil composition according to any one of [1] to [6] above, wherein the alicyclic epoxy compound (B2) comprises a compound having a cyclohexane skeleton. [8] The refrigerator oil composition according to any one of [1] to [7] above, wherein the terpene compound (C) comprises one or more terpene compounds selected from the group consisting of pinene compounds and terpinene compounds. [9] The refrigerator oil composition according to any one of the above [1] to [8], wherein the total content of the aliphatic epoxy compound (B1), the alicyclic epoxy compound (B2), and the terpene compound (C) is 3.0 mass % to 10 mass % based on the total amount of the refrigerator oil composition.

[10] The refrigerator oil composition according to any one of the above [1] to [9], wherein the content of the alicyclic epoxy compound (B2) is 0.5 mass % to 5.0 mass % based on the total amount of the refrigerator oil composition.

[11] The refrigerator oil composition according to any one of the above items [1] to

[10] , wherein the mass ratio of the alicyclic epoxy compound (B2) to the aliphatic epoxy compound (B1) [(B2) / (B1)] is 0.40 to 5.0. ２ F ｐ R ４－ｐ ...(I) [In the general formula (I), each R independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and p is an integer of 1 to 3.], and the refrigerating machine oil composition according to any one of the above [1] to

[11] .

[13] A mixed composition for a refrigerator, comprising a refrigerant containing an unsaturated fluorinated compound having a carbon-carbon unsaturated bond represented by the following general formula (I): ２ F ｐ R ４－ｐ ...(I) A method for producing a refrigerator oil composition to be used together with a refrigerant containing an unsaturated fluorinated compound having a carbon-carbon unsaturated bond represented by the general formula (I): [in the general formula (I), each R independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and p is an integer of 1 to 3], the method comprising the step of mixing a base oil (A), an aliphatic epoxy compound (B1), an alicyclic epoxy compound (B2), and a terpene compound (C).

[0112] The present invention will be specifically described with reference to the following examples, although the present invention is not limited to the following examples.

[0113] [Methods for measuring various physical properties] The properties of the raw materials used in each example and each comparative example were measured according to the following procedures: (1) Kinematic viscosity The kinematic viscosity at 40°C was measured in accordance with JIS K2283:2000.

[0114] [Details of each component used in preparing the refrigerator oil composition] <Base oil (A)> Polyethyl vinyl ether (kinematic viscosity at 40°C: 68.4 mm ２ / s) <Aliphatic epoxy compound (B1)> 2-ethylhexyl glycidyl ether <Alicyclic epoxy compound (B2)> 1,2-epoxy-4-vinylcyclohexane 1,2-epoxy-cyclohexane <Terpene compound (C)> β-pinene γ-terpinene <Other additives> Antioxidant: 2,6-di-tert-butyl-p-cresol (DBPC) Extreme pressure agent: tricresyl phosphate (TCP) Antifoaming agent: dimethyl silicone (diluted 100 times with mineral oil)

[0115] [Examples 1 to 6, Comparative Examples 1 to 11, and Reference Example 1] Refrigerating machine oil compositions having the compositions shown in Table 1 were prepared, and their thermal stability was evaluated by the method described below. The evaluation results are shown in Table 1.

[0116] <Evaluation: Thermal Stability Test> An autoclave vessel (volume: 200 mL) was charged with Fe, Cu, and Al as catalysts, and a mixture of 30 g of refrigerant oil composition and 30 g of refrigerant was filled with 500 ppm water by mass. The air content was adjusted to 25 mL. After holding the vessel at 200°C for 5 days, the acid value (mg KOH / g) was evaluated. The acid value was measured by indicator photometric titration in accordance with JIS K2501:2003 (see Appendix 1 of the JIS standard). In Examples 1 to 6 and Comparative Examples 1 to 11, the refrigerant used in the thermal stability test was a mixed refrigerant (R474A) of R1132(E) and R1234yf (R1132(E):R1234yf = 23:77 (mass ratio)). In Reference Example 1, R1234yf was used alone.

[0117]

[0118] The following can be seen from Table 1. The refrigerating machine oil compositions of Examples 1 to 6 contain an aliphatic epoxy compound (B1), an alicyclic epoxy compound (B2), and a terpene compound (C), and therefore have excellent thermal stability. In contrast, the refrigerating machine oil compositions of Comparative Examples 1 to 11 do not contain at least one of an aliphatic epoxy compound (B1), an alicyclic epoxy compound (B2), and a terpene compound (C), and therefore have poor thermal stability. As shown in Reference Example 1, when R1234yf is used alone as the refrigerant, the refrigerating machine oil composition has excellent thermal stability even when it does not contain an alicyclic epoxy compound (B2). On the other hand, the refrigerating machine oil composition of Comparative Example 5, which has the same formulation as Reference Example 1, uses a mixed refrigerant of R1132(E) and R1234yf as the refrigerant, and in this case, it is found to have poor thermal stability. These findings demonstrate that the inclusion of R1132(E) in the refrigerant makes it difficult to ensure the thermal stability of the refrigerating machine oil composition, and that the refrigerating machine oil compositions of Examples 1 to 6 have excellent thermal stability despite such difficulties.

Claims

1. A compound represented by the following general formula (I): ２ F ｐ R ４－ｐ ...(I) A refrigerating machine oil composition to be used together with a refrigerant containing an unsaturated fluorinated compound having a carbon-carbon unsaturated bond represented by the general formula (I): [in the above general formula (I), each R independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and p is an integer of 1 to 3], the refrigerating machine oil composition comprising a base oil (A), an aliphatic epoxy compound (B1), an alicyclic epoxy compound (B2), and a terpene compound (C).

2. The refrigerator oil composition according to claim 1, wherein in said general formula (I), R is a hydrogen atom.

3. The refrigerating machine oil composition according to claim 1 or 2, wherein the refrigerant contains, as the unsaturated fluorinated compound, one or more selected from the group consisting of R1123, R1132a, R1132(Z), and R1132(E).

4. The refrigerating machine oil composition according to any one of claims 1 to 3, wherein the refrigerant contains R1132(E) as the unsaturated fluorinated compound.

5. The refrigerating machine oil composition according to any one of claims 1 to 4, wherein the refrigerant further comprises at least one selected from the group consisting of unsaturated fluorohydrocarbon refrigerants having 3 or more carbon atoms, saturated fluorohydrocarbon refrigerants, and natural refrigerants.

6. The refrigerating machine oil composition according to any one of claims 1 to 5, wherein the aliphatic epoxy compound (B1) includes a compound having a glycidyl ether group.

7. The refrigerating machine oil composition according to any one of claims 1 to 6, wherein the alicyclic epoxy compound (B2) includes a compound having a cyclohexane skeleton.

8. A refrigerator oil composition according to any one of claims 1 to 7, wherein the terpene compound (C) comprises one or more compounds selected from the group consisting of pinene compounds and terpinene compounds.

9. The refrigerating machine oil composition according to any one of claims 1 to 8, wherein a total content of the aliphatic epoxy compound (B1), the alicyclic epoxy compound (B2), and the terpene compound (C) is 3.0 mass % to 10 mass % based on a total amount of the refrigerating machine oil composition.

10. The refrigerating machine oil composition according to any one of claims 1 to 9, wherein the content of the alicyclic epoxy compound (B2) is 0.5 mass% to 5.0 mass% based on the total amount of the refrigerating machine oil composition.

11. The refrigerating machine oil composition according to any one of claims 1 to 10, wherein the mass ratio of the alicyclic epoxy compound (B2) to the aliphatic epoxy compound (B1) [(B2) / (B1)] is 0.40 to 5.

0.

12. A compound represented by the following general formula (I): ２ F ｐ R ４－ｐ ...(I) [In the general formula (I), each R independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and p is an integer of 1 to 3.], and the refrigerating machine oil composition according to any one of claims 1 to 11. A mixed composition for a refrigerator, comprising: a refrigerant containing an unsaturated fluorinated compound having a carbon-carbon unsaturated bond represented by the following general formula (I):

13. A compound represented by the following general formula (I): ２ F ｐ R ４－ｐ ...(I) [In the above general formula (I), each R independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, and p is an integer of 1 to 3.], a method for producing a refrigerating machine oil composition to be used together with a refrigerant containing an unsaturated fluorinated compound having a carbon-carbon unsaturated bond, the method comprising the step of mixing a base oil (A), an aliphatic epoxy compound (B1), an alicyclic epoxy compound (B2), and a terpene compound (C).

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