Refrigerator oil composition and mixed composition for refrigerators

Abstract

Through a refrigerant and the refrigerant comprising a component selected from the following general formula (1) C x F y H z ...(1) [In the aforementioned general formula (1), x is 2 to 6, y is 1 to 11, and z is an integer from 1 to 11, and the molecule has one or more carbon-carbon unsaturated bonds.] A refrigeration oil composition comprising one or more unsaturated fluorinated hydrocarbon compounds, and the refrigeration oil composition containing an epoxy compound (B) and a base oil (A) selected from polyalkylene glycols, polyvinyl ethers, copolymers of poly(oxy)alkylene glycols or their monoethers with polyvinyl ethers, and polyol esters, and the aforementioned epoxy compound (B) satisfies the following conditions (B1) and (B2), thereby providing a refrigeration oil composition that can effectively suppress the rise in acid value even when the ratio of unsaturated fluorinated hydrocarbon compounds (HFO) in the refrigerant is increased. (B1) The molecule has at least one divalent group represented by the following formula (1). (B2) The molecule has at least one ester group.

Description

Technical Field

[0001] This invention relates to refrigeration oil compositions and blended compositions for refrigeration equipment.

[0002] It should be noted that, in this specification, "mixed composition for refrigeration machines" refers to a composition obtained by mixing "refrigeration oil composition" with "refrigerant". Background Technology

[0003] A refrigeration unit, such as a compression refrigeration unit, typically includes at least a compressor, a condenser, an expansion mechanism (e.g., an expansion valve), and an evaporator, and has a structure that allows the refrigeration unit to circulate a mixed composition within a closed system.

[0004] As refrigerants used in compressor-type refrigerators and other refrigeration equipment, environmentally friendly fluorinated hydrocarbon compounds are gradually replacing the previously commonly used hydrochlorofluorocarbons (HCFCs). These fluorinated hydrocarbon compounds are increasingly being used as saturated fluorinated hydrocarbon compounds (Hydro-Fluoro-Carbon; hereinafter also referred to as "HFCs") such as 1,1,1,2-tetrafluoroethane (R134a), difluoromethane (R32), and 1,1-difluoroethane (R152a).

[0005] In addition, the use of unsaturated fluorinated hydrocarbon compounds (Hydro-Fluoro-Olefin; hereinafter also referred to as "HFO") such as 1,3,3,3-tetrafluoropropylene (R1234ze), 2,3,3,3-tetrafluoropropylene (R1234yf) and 1,2,3,3-tetrafluoropropylene (R1234ye) with low global warming potential (GWP) was also investigated (see, for example, Patent Document 1).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Publication No. 2006-503961 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] However, while unsaturated fluorinated hydrocarbons (HFOs) have the advantage of low global warming potential (GWP), they also have the disadvantage of poor thermal stability at high temperatures compared to saturated fluorinated hydrocarbons (HFCs). Therefore, an issue arises where increasing the content of unsaturated fluorinated hydrocarbons (HFOs) in the refrigerant can easily lead to an increase in the acid value of the refrigeration oil composition.

[0011] Furthermore, in recent years, refrigeration units have become increasingly compact and high-performance, resulting in more stringent operating conditions. Therefore, the quality requirements for refrigeration oil compositions are higher than ever before. For example, with the compact design of refrigeration units, the amount of refrigeration oil composition used within the machine is gradually decreasing. On the other hand, the increased frictional heat from the compressor's sliding parts due to the harsher operating conditions can easily lead to localized high temperatures. If the refrigeration oil composition is exposed to such areas, the acid value of the refrigeration oil composition is more likely to rise.

[0012] Therefore, it is desirable to create a refrigeration oil composition that can effectively suppress the rise in acid value even when the content of unsaturated fluorinated hydrocarbons (HFO) in the refrigerant is increased.

[0013] The present invention was made in view of this expectation, and its objective is to provide a refrigeration oil composition that can effectively suppress the rise of acid value even when the content of unsaturated fluorinated hydrocarbon compounds (HFO) in the refrigerant is increased, and a refrigeration blend composition containing the refrigeration oil composition.

[0014] means for solving problems

[0015] The inventors conducted in-depth research to solve the aforementioned problems. The results showed that a refrigeration oil composition containing a specific epoxy compound can solve these problems, thus completing this invention.

[0016] That is, the present invention relates to the following [1] to [3].

[0017] [1] A refrigeration oil composition for use in a refrigerant comprising one or more unsaturated fluorinated hydrocarbon compounds selected from compounds represented by the following general formula (1).

[0018] C x F y H z ···(1)

[0019] [In the aforementioned general formula (1), x is an integer from 2 to 6, y is an integer from 1 to 11, and z is an integer from 1 to 11, and the molecule has more than one carbon-carbon unsaturated bond.]

[0020] The refrigeration oil composition contains an epoxy compound (B) and a base oil (A) selected from polyalkylene glycols, polyvinyl ethers, copolymers of poly(oxy)alkylene glycols or their monoethers with polyvinyl ethers, and polyol esters.

[0021] The aforementioned epoxy compound (B) satisfies the following conditions (B1) and (B2).

[0022] (B1) The molecule has at least one divalent group as shown in formula (1) below.

[0023] [Chemistry 1]

[0024]

[0025] (B2) The molecule has at least one ester group.

[0026] [2] A mixed composition for refrigeration machines, comprising a refrigerant and the refrigeration oil composition described in [1], wherein the refrigerant comprises one or more unsaturated fluorinated hydrocarbon compounds selected from compounds represented by the following general formula (1).

[0027] C x F y H z ···(1)

[0028] [In the aforementioned general formula (1), x is an integer from 2 to 6, y is an integer from 1 to 11, and z is an integer from 1 to 11, and the molecule has more than one carbon-carbon unsaturated bond.]

[0029] [3] A method for manufacturing a refrigeration oil composition, which is a method for manufacturing a refrigeration oil composition for a refrigerant, said refrigerant comprising one or more unsaturated fluorinated hydrocarbon compounds selected from compounds represented by the following general formula (1).

[0030] C x F y H z ···(1)

[0031] [In the aforementioned general formula (1), x is an integer from 2 to 6, y is an integer from 1 to 11, and z is an integer from 1 to 11, and the molecule has more than one carbon-carbon unsaturated bond.]

[0032] The manufacturing method includes:

[0033] The process of mixing epoxy compound (B) with base oil (A) selected from polyalkylene glycols, polyvinyl ethers, copolymers of poly(oxy)alkylene glycols or their monoethers with polyvinyl ethers, and polyol esters.

[0034] The aforementioned epoxy compound (B) satisfies the following conditions (B1) and (B2).

[0035] (B1) The molecule has at least one divalent group as shown in formula (1) below.

[0036] [Chemistry 2]

[0037]

[0038] (B2) The molecule has at least one ester group.

[0039] Invention Effects

[0040] According to the present invention, a refrigeration oil composition that can effectively suppress the rise in acid value even when the content of unsaturated fluorinated hydrocarbon compounds (HFO) in the refrigerant is increased, and a refrigeration blend composition containing the refrigeration oil composition can be provided. Detailed Implementation

[0041] The upper and lower limits of the numerical ranges described in this specification can be combined arbitrarily. For example, if the numerical ranges are described as "A~B" and "C~D", the numerical ranges of "A~D" and "C~B" also fall within the scope of this invention.

[0042] In addition, the numerical range “lower limit to upper limit” described in this specification means above the lower limit and below the upper limit unless otherwise specified.

[0043] Furthermore, in this specification, the numerical values ​​of the embodiments are numerical values ​​that can be used as upper or lower limits.

[0044] [Form of Refrigeration Oil Composition]

[0045] The refrigeration oil composition of this embodiment is a refrigeration oil composition for a refrigerant, wherein the refrigerant comprises one or more unsaturated fluorinated hydrocarbon compounds selected from the compounds shown in the following general formula (1).

[0046] C x F y H z ···(1)

[0047] [In the aforementioned general formula (1), x is an integer from 2 to 6, y is an integer from 1 to 11, and z is an integer from 1 to 11, and the molecule has more than one carbon-carbon unsaturated bond.]

[0048] The refrigeration oil composition of this embodiment contains a base oil (A) and an epoxy compound (B). Furthermore, the epoxy compound (B) satisfies the following conditions (B1) and (B2).

[0049] (B1) The molecule has at least one divalent group as shown in formula (1) below.

[0050] [Chemistry 3]

[0051]

[0052] (B2) The molecule has at least one ester group.

[0053] Based on the consideration that one of the reasons why the acid value of the refrigeration oil composition tends to rise when the content of unsaturated fluorinated hydrocarbons (HFO) in the refrigerant increases is the fluorine component produced by the decomposition of unsaturated fluorinated hydrocarbons (HFO) under high temperature conditions, the inventors have conducted various studies.

[0054] The results showed that refrigeration oil compositions containing epoxy compounds (B) that meet specific conditions can suppress the increase in fluorine concentration in the refrigeration oil composition caused by fluorine components generated by the decomposition of unsaturated fluorinated hydrocarbon compounds (HFO) under high temperature conditions, and can suppress the increase in acid value of the refrigeration oil composition.

[0055] The mechanism by which the present invention achieves its effects is speculated as follows.

[0056] That is, compared with epoxy compounds containing epoxy groups at the molecule's ends, the aforementioned epoxy compound (B), which has epoxy groups inside the molecule, is less prone to decomposing unsaturated fluorinated hydrocarbon compounds (HFO). Therefore, it is less likely to produce fluorine components (such as hydrofluoric acid) that would otherwise be generated, especially under high-temperature conditions due to the decomposition of unsaturated fluorinated hydrocarbon compounds (HFO). Furthermore, any trace amounts of fluorine that have already been generated react with the epoxy groups in epoxy compound (B) and are captured into epoxy compound (B).

[0057] It can be inferred that by using epoxy compounds (B), HFO is not easily decomposed. As a result, the dissolution of fluorine components into the refrigeration oil composition is suppressed, and the dissolved fluorine components can be captured. Therefore, the increase in acid value of the refrigeration oil composition can be suppressed.

[0058] It should be noted that in the following description, “base oil (A)” and “epoxide compound (B)” will also be referred to as “component (A)” and “component (B)”, respectively.

[0059] The refrigeration oil composition of this embodiment may consist only of component (A) and component (B), or may contain other components besides component (A) and component (B) without impairing the effects of the present invention.

[0060] In the refrigeration oil composition of this embodiment, the total content of component (A) and component (B) is preferably 80% to 100% by mass, more preferably 85% to 100% by mass, and even more preferably 90% to 100% by mass, based on the total amount (100% by mass) of the refrigeration oil composition.

[0061] The components contained in the refrigeration oil composition of this embodiment will be described in detail below.

[0062] <Base Oil (A)>

[0063] The refrigeration oil composition of this embodiment contains base oil (A).

[0064] In the refrigeration oil composition of this embodiment, from the viewpoint of long-term stability required for a refrigeration oil composition, the content of base oil (A), based on the total amount of the refrigeration oil composition (100% by mass), is preferably 85.0% by mass or more, more preferably 90.0% by mass or more, and even more preferably 92.0% by mass or more. Furthermore, from the viewpoint of easily ensuring the content of epoxy compound (B) in the refrigeration oil composition, and consequently easily ensuring the content of additives other than epoxy compound (B), it is preferably 99.0% by mass or less, more preferably 98.5% by mass or less, and even more preferably 98.0% by mass or less.

[0065] The upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 85.0% to 99.0% by mass, more preferably 90.0% to 98.5% by mass, and even more preferably 92.0% to 98.0% by mass.

[0066] As base oil (A), base oils commonly used in refrigeration oil compositions may be used without particular limitation. For example, one or more types selected from synthetic oils and mineral oils may be used as base oil (A).

[0067] Here, in the refrigeration oil composition of this embodiment, from the viewpoint of the solubility of the epoxy compound (B), the base oil (A) is preferably a synthetic oil.

[0068] In addition, from the viewpoint of improving the thermal stability of the refrigeration oil composition, the base oil (A) preferably contains one or more base oils selected from polyalkylene glycols (hereinafter also referred to as "PAG"), polyvinyl ethers (hereinafter also referred to as "PVE"), copolymers of poly(oxy)alkylene glycols or their monoethers with polyvinyl ethers (hereinafter also referred to as "ECP"), and polyol esters (hereinafter also referred to as "POE") (hereinafter also referred to as "base oil (A1)").

[0069] Furthermore, from the viewpoints of improving compatibility with refrigerants, improving hydrolysis resistance, and further improving the thermal stability of the refrigeration oil composition, the base oil (A) more preferably contains one or more base oils selected from PAG and PVE (hereinafter also referred to as "base oil (A2)").

[0070] The following provides a detailed explanation of PAG, PVE, ECP, and POE.

[0071] (Polyalkylene glycols (PAGs))

[0072] As a PAG, a PAG used as a base oil in a refrigeration oil composition may be used without particular limitation, preferably a polymer (A-1) represented by the following general formula (A-1).

[0073] R 13a -[(OR 14a ) p -OR 15a ] q (A-1)

[0074] It should be noted that when the base oil (A) contains PAG, PAG can be used alone or in combination with two or more types.

[0075] In the above general formula (A-1), R 13a R represents a hydrogen atom, a monovalent hydrocarbon group with 1 to 10 carbon atoms, an acyl group with 2 to 10 carbon atoms, a divalent to hexavalent hydrocarbon group with 1 to 10 carbon atoms, or a heterocyclic group with 3 to 10 substituted or unsubstituted cyclic atoms. 14a R represents an alkylene group having 2 to 4 carbon atoms. 15a It represents a hydrogen atom, a monovalent hydrocarbon group with 1 to 10 carbon atoms, an acyl group with 2 to 10 carbon atoms, or a heterocyclic group with 3 to 10 substituted or unsubstituted cyclic atoms.

[0076] Examples of substituents that can be optionally present in a heterocyclic group include alkyl groups with 1 to 10 carbon atoms (preferably 1 to 6, more preferably 1 to 3); cycloalkyl groups with 3 to 10 cyclic carbon atoms (preferably 3 to 8, more preferably 5 or 6); aryl groups with 6 to 18 cyclic carbon atoms (preferably 6 to 12); halogen atoms (fluorine, chlorine, bromine, iodine); cyano; nitro; hydroxyl; amino, etc.

[0077] These substituents may be further replaced by any of the substituents mentioned above.

[0078] q is an integer from 1 to 6, preferably an integer from 1 to 3, and more preferably 1.

[0079] It should be noted that q is based on R in the above general formula (A-1). 13a The number of bonding sites determines the bond strength. For example, in R... 13a In the case of alkyl or acyl groups, q becomes 1, in R 13a When the group is a hydrocarbon group or a heterocyclic group and the valence of the group is 2, 3, 4, 5 or 6, q becomes 2, 3, 4, 5 or 6 respectively.

[0080] p is OR 14aThe number of repeating units is usually 1 or more, preferably p×q is a number from 6 to 80. It should be noted that the value of p is a value set appropriately to adjust the kinematic viscosity of base oil (A) at 40°C to an appropriate range. There are no particular limitations as long as the adjustment is made in a way that makes the kinematic viscosity at 40°C an appropriate range.

[0081] It should be noted that multiple R 14a They can be the same or different. Furthermore, when q is 2 or higher, multiple Rs in one molecule... 15a They can be the same, or they can be completely different.

[0082] As R 13a and R 15a The monovalent hydrocarbon groups shown above can include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, various butyl, various pentyl, various hexyl, various heptyl, various octyl, various nonyl, and various decyl; cyclopentyl, cyclohexyl, various methylcyclohexyl, various ethylcyclohexyl, various propylcyclohexyl, and various dimethylcyclohexyl; aryl groups such as phenyl, various methylphenyl, various ethylphenyl, various dimethylphenyl, various propylphenyl, various trimethylphenyl, various butylphenyl, and various naphthyl; and arylalkyl groups such as benzyl, various phenylethyl, various methylbenzyl, various phenylpropyl, and various phenylbutyl. It should be noted that the above alkyl groups can be either straight-chain or branched.

[0083] Here, "various" refers to hydrocarbon groups that are "straight-chain, branched, or cyclic." For example, "various butyl groups" refers to various butyl groups such as "n-butyl, sec-butyl, isobutyl, tert-butyl, and cyclobutyl." Furthermore, regarding groups with cyclic structures, this includes positional isomers such as ortho-, meta-, and para-isomers, and the same applies below.

[0084] From the perspective of compatibility with refrigerants, R 13a and R 15a The number of carbon atoms in the monovalent hydrocarbon group shown is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0085] R 13a and R 15a The alkyl group of the acyl group having 2 to 10 carbon atoms shown above can be any of straight-chain, branched, or cyclic. Examples of the alkyl group include the aforementioned R... 13a and R 15a The hydrocarbon groups shown are hydrocarbon groups with 1 to 9 carbon atoms.

[0086] From the perspective of compatibility with refrigerants, R 13a and R 15a The number of carbon atoms in the acyl group shown is preferably 2 to 8, more preferably 2 to 6.

[0087] As R 13a The 2- to 6-valent hydrocarbon groups shown above can be listed as derived from the above R 13a The residues obtained by further removing 1 to 5 hydrogen atoms from the monovalent hydrocarbon group shown; residues obtained by removing hydroxyl groups from polyols such as trimethylolpropane, glycerol, pentaerythritol, sorbitol, 1,2,3-trihydroxycyclohexane, and 1,3,5-trihydroxycyclohexane.

[0088] From the perspective of compatibility with refrigerants, R 13a The number of carbon atoms in the 2-6 valent acyl groups shown is preferably 2-10, more preferably 2-6.

[0089] As R 13a and R 15a The heterocyclic group shown above is preferably a heterocyclic group containing oxygen atoms or a heterocyclic group containing sulfur atoms. It should be noted that the heterocyclic group can be a saturated ring or an unsaturated ring.

[0090] Examples of the aforementioned heterocyclic groups containing oxygen atoms include saturated heterocycles containing oxygen atoms, such as ethylene oxide, 1,3-epoxypropane, tetrahydrofuran, tetrahydropyran, and epoxyhexane; and residues obtained by removing 1 to 6 hydrogen atoms from unsaturated heterocycles containing oxygen atoms, such as epoxyacetylene, furan, pyran, oxetane-heptanetriene, isobenzofuran, and isobenzopyran.

[0091] In addition, as the aforementioned heterocyclic groups containing sulfur atoms, examples include residues obtained by removing 1 to 6 hydrogen atoms from saturated heterocycles containing sulfur atoms, such as cyclothioethane, cyclothiopropane, tetrahydrothiophene, tetrahydrothioran, and cyclothiohexane, as well as unsaturated heterocycles containing sulfur atoms, such as cyclothioacetylene, thiophene, thioran, and thioheptatriene.

[0092] R 13a and R 15a The heterocyclic group shown above may optionally have a substituent, which may optionally be bonded to an oxygen atom in the above general formula (A-1). As described above, the substituent is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

[0093] From the viewpoint of compatibility with refrigerants, the number of cyclic atoms in the above-mentioned heterocyclic group is preferably 3 to 10, more preferably 3 to 6.

[0094] As R 14aThe alkylene groups shown above can be categorized as follows: alkylene groups with 2 carbon atoms, such as dimethylene (-CH2CH2-) and ethylene (-CH(CH3)-); alkylene groups with 3 carbon atoms, such as trimethylene (-CH2CH2CH2-), propylene (-CH(CH3)CH2-), propylene (-CHCH2CH3-), and isopropylene (-C(CH3)2-); and alkylene groups with 4 carbon atoms, such as tetramethylene (-CH2CH2CH2CH2-), 1-methyltrimethylene (-CH(CH3)CH2CH2-), 2-methyltrimethylene (-CH2CH(CH3)CH2-), and butylene (-C(CH3)2CH2-). Among these, R... 14a Preferably, it is propylene (-CH(CH3)CH2-).

[0095] It should be noted that in the polymer (A-1) represented by the above general formula (A-1), the content of the oxypropylene unit (-OCH(CH3)CH2-) is defined as the content of the oxyalkylene group (OR) in the polymer (A-1). 14a Based on the total amount (100 mol%), it is preferably 50 mol% or more, more preferably 65 mol% or more, and even more preferably 80 mol% or more.

[0096] Among the polymers (A-1) represented by the above general formula (A-1), it is preferably selected from one or more of the following general formulas: polyoxypropylene glycol dimethyl ether represented by general formula (A-1-i), polyoxyethylene polyoxypropylene glycol dimethyl ether represented by general formula (A-1-ii), polyoxypropylene glycol monobutyl ether represented by general formula (A-1-iii), polyoxypropylene glycol monomethyl ether represented by general formula (A-1-iv), and polyoxypropylene glycol diacetate.

[0097] [Chemistry 4]

[0098]

[0099] (In formula (A-1-i), p1 represents a number greater than 1, preferably a number between 6 and 80).

[0100] [Chemistry 5]

[0101]

[0102] (In formula (A-1-ii), p2 and p3 each independently represent numbers greater than 1, and preferably the value of p2+p3 is a number from 6 to 80).

[0103] [Chemistry 6]

[0104]

[0105] (In formula (A-1-iii), p4 represents a number greater than 1, preferably a number between 6 and 80).

[0106] [Chemistry 7]

[0107]

[0108] (In formula (A-1-iv), p5 represents a number greater than 1, preferably a number between 6 and 80.)

[0109] It should be noted that p1 in the above general formula (A-1-i), p2 and p3 in the above general formula (A-1-ii), p4 in the above general formula (A-1-iii), and p5 in the above general formula (A-1-iv) can be appropriately selected according to the kinematic viscosity required by the base oil (A).

[0110] (Polyvinyl ethers (PVE))

[0111] PVE is a polymer having one or more structural units derived from vinyl ethers, and can be used as a base oil in refrigeration oil compositions without particular limitation.

[0112] It should be noted that when the base oil (A) contains PVE, PVE can be used alone or in combination with two or more types.

[0113] From the viewpoint of compatibility with refrigerants, PVE is preferably a polymer having one or more structural units derived from vinyl ethers and having alkyl groups with 1 to 4 carbon atoms in the side chain. From the viewpoint of further improving compatibility with refrigerants, methyl or ethyl groups are preferred as the alkyl group, and methyl is more preferred.

[0114] PVE is preferably a polymer (A-2) having one or more structural units as shown in the following general formula (A-2).

[0115] [Chemistry 8]

[0116]

[0117] In equation (A-2), R 1a R 2a and R 3a Each can independently represent a hydrocarbon group with 1 to 8 hydrogen or carbon atoms. R 4a R represents a divalent hydrocarbon group with 2 to 10 carbon atoms. 5a This represents a hydrocarbon group with 1 to 10 carbon atoms. r stands for OR. 4a The number of repeating units is typically 0 to 10, preferably 0 to 5, more preferably 0 to 3, and even more preferably 0. It should be noted that multiple ORs exist in the structural unit shown in the above general formula (A-2).4a In the case of multiple ORs 4a They can be the same, or they can be completely different.

[0118] As R 1a R 2a and R 3a The hydrocarbon groups with 1 to 8 carbon atoms shown can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, various butyl, various pentyl, various hexyl, various heptyl, and various octyl; cyclopentyl, cyclohexyl, various methylcyclohexyl, various ethylcyclohexyl, and various dimethylcyclohexyl; aryl groups such as phenyl, various methylphenyl, various ethylphenyl, and various dimethylphenyl; and arylalkyl groups such as benzyl, various phenylethyl, and various methylbenzyl.

[0119] R 1a R 2a and R 3a The number of carbon atoms in the hydrocarbon group shown is preferably 1 to 6, more preferably 1 to 3.

[0120] R 1a R 2a and R 3a Each of the components is 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, and even more preferably a hydrogen atom.

[0121] As R 4a The divalent hydrocarbon groups with 2 to 10 carbon atoms shown can be categorized as follows: ethylene, 1,2-propylene, 1,3-propylene, various butylenes, various pentylenes, various hexylenes, various heptylenes, various octylenes, various nonylenes, various decylenes, etc.; divalent alicyclic groups such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, propylcyclohexane, etc.; divalent aromatic groups such as various phenylenes, various methylphenylenes, various ethylphenylenes, various dimethylphenylenes, various naphthalenes, etc.; divalent alkyl aromatic groups with monovalent bonding sites in the alkyl and aromatic portions of alkyl aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; and divalent alkyl aromatic groups with bonding sites in the alkyl portions of polyalkyl aromatic hydrocarbons such as xylene and diethylbenzene.

[0122] R 4a The hydrocarbon group shown preferably has 2 to 6 carbon atoms, more preferably 2 to 4.

[0123] R 4a Preferably, it is a divalent aliphatic group with 2 to 10 carbon atoms, and more preferably a divalent aliphatic group with 2 to 4 carbon atoms.

[0124] As R 5aThe hydrocarbon groups with 1 to 10 carbon atoms shown can be categorized as follows: alkyl groups such as methyl, ethyl, n-propyl, isopropyl, various butyl, various pentyl, various hexyl, various heptyl, various octyl, various nonyl, and various decyl; cyclopentyl, cyclohexyl, various methylcyclohexyl, various ethylcyclohexyl, various propylcyclohexyl, and various dimethylcyclohexyl; aryl groups such as phenyl, various methylphenyl, various ethylphenyl, various dimethylphenyl, various propylphenyl, various trimethylphenyl, various butylphenyl, and various naphthyl; and arylalkyl groups such as benzyl, various phenylethyl, various methylbenzyl, various phenylpropyl, and various phenylbutyl.

[0125] R 5a The hydrocarbon group shown preferably has 1 to 8 carbon atoms, more preferably 1 to 6.

[0126] From the perspective of further improving compatibility with refrigerants, R 5a Preferably, it is an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, further preferably methyl or ethyl, and even more preferably methyl.

[0127] The number of structural units (degree of polymerization) shown in the above general formula (A-2) is appropriately selected according to the kinematic viscosity required by the base oil (A).

[0128] Furthermore, polymers having the structural units shown in the above general formula (A-2) can be homopolymers having only one type of structural unit, or copolymers having two or more types of structural units. It should be noted that, in the case of copolymers, the copolymerization form is not particularly limited and can be any of block copolymers, random copolymers, or graft copolymers.

[0129] Monovalent groups derived from saturated hydrocarbons, ethers, alcohols, ketones, amides, nitriles, etc., can be introduced into the terminal portion of polymer (A-2). Among these, a terminal portion of polymer (A-2) is preferably a group represented by the following general formula (A-2-i).

[0130] [Chemistry 9]

[0131]

[0132] In formula (A-2-i), * indicates the position where a carbon atom in the structural unit shown in the above general formula (A-2) is bonded.

[0133] In equation (A-2-i), R 6a R 7a and R 8a Each of the groups independently represents a hydrocarbon group having 1 to 8 hydrogen atoms or carbon atoms, preferably a hydrocarbon group having 1 to 6 hydrogen atoms or carbon atoms, and more preferably an alkyl group having 1 to 3 hydrogen atoms or carbon atoms.

[0134] As R 6a R 7a and R 8a The hydrocarbon groups with 1 to 8 carbon atoms shown can be listed as R in the above general formula (A-2). 1a R 2a and R 3a The groups that are the same as the hydrocarbon groups with 1 to 8 carbon atoms shown in the examples.

[0135] In the above formula (A-2-i), R 9a It represents a divalent hydrocarbon group with 2 to 10 carbon atoms, preferably a divalent hydrocarbon group with 2 to 6 carbon atoms, and more preferably a divalent aliphatic group with 2 to 4 carbon atoms.

[0136] In the above formula (A-2-i), r1 is OR 9a The number of repeating units is typically 0 to 10, preferably 0 to 5, more preferably 0 to 3, and even more preferably 0. It should be noted that multiple ORs exist in the structural unit shown in the above general formula (A-2-i). 9a In the case of multiple ORs 9a They can be the same, or they can be completely different.

[0137] As R 9a The divalent hydrocarbon groups with 2 to 10 carbon atoms shown can be listed as R in the above general formula (A-2). 4a The groups that are the same as the divalent hydrocarbon groups with 2 to 10 carbon atoms shown in the examples.

[0138] In equation (A-2-i), R 10a The hydrocarbon group represents 1 to 10 carbon atoms, preferably a hydrocarbon group with 1 to 8 carbon atoms, and more preferably an alkyl group with 1 to 8 carbon atoms.

[0139] It should be noted that, as R 10a When r1 in the above general formula (A-2-i) is 0, it is preferably an alkyl group with 1 to 6 carbon atoms; when r1 is 1 or more, it is preferably an alkyl group with 1 to 4 carbon atoms.

[0140] As R 10a The hydrocarbon groups with 1 to 10 carbon atoms shown can be listed as R in the above general formula (A-2). 5a The groups that are the same as the hydrocarbon groups with 1 to 10 carbon atoms shown.

[0141] Furthermore, regarding polymer (A-2), when one of its terminal portions is a group represented by the general formula (A-2-i) above, the other terminal portion is preferably any one of the group represented by the general formula (A-2-i) above, the group represented by the general formula (A-2-ii) below, the group represented by the general formula (A-2-iii) below, and a group having an olefinic unsaturated bond.

[0142] [Chemistry 10]

[0143]

[0144] In equations (A-2-ii) and (A-2-iii), R 6a R 7a R 8a R 9a R 10a And r1 is the same as that specified in the above general formula (A-2-i). Additionally, in formula (A-2-ii), R... 11a R 12a r2 and r2 are respectively related to R in the above general formula (A-2-i) 9a R 10a The same rules apply as r1.

[0145] (Copolymer (ECP) of poly(oxyalkylene glycol) or its monoether with polyvinyl ether)

[0146] As a copolymer (ECP) of poly(oxy)alkylene glycol or its monoether and polyvinyl ether, it is acceptable as long as it is a copolymer having structural units derived from poly(oxy)alkylene glycol or its monoether and structural units derived from polyvinyl ether.

[0147] It should be noted that "poly(oxy)alkylene glycol" refers to both polyalkylene glycol and polyoxyalkylene glycol.

[0148] In addition, when the base oil (A) contains ECP, one type of ECP can be used alone, or two or more types can be used in combination.

[0149] The preferred ECP is a copolymer (A-3-i) represented by the following general formula (A-3-i) or a copolymer (A-3-ii) represented by the general formula (A-3-ii).

[0150] [Chemistry 11]

[0151]

[0152] In general formulas (A-3-i) and (A-3-ii), R 1c R 2c and R 3cEach can be independently represented by a hydrocarbon group consisting of 1 or more hydrogen atoms and 8 or fewer carbon atoms.

[0153] R 4c Each group independently represents a hydrocarbon group with 1 to 10 carbon atoms.

[0154] R 5c Each can be used independently to represent an alkylene group having 2 to 4 carbon atoms.

[0155] R 6c Each can independently represent a hydrogen atom, an alkyl group with 1 to 20 or fewer carbon atoms, a substituted or unsubstituted alicyclic group with 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group with 6 to 24 carbon atoms, an acyl group with 2 to 20 carbon atoms, or an oxygen-containing hydrocarbon group with 2 to 50 carbon atoms.

[0156] It should be noted that there are multiple Rs. 1c R 2c R 3c R 4c R 5c and R 6c At that time, each type of structural unit can be the same or different.

[0157] X C and Y C Each can independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group with 1 to 20 carbon atoms.

[0158] In general formulas (A-3-i) and (A-3-ii), v represents OR. 5c The average number of units shown represents a number greater than 1, preferably a number between 1 and 50. Multiple ORs exist. 5c At that time, multiple ORs 5c They can be the same or different. It should be noted that "OR"... 5c "" indicates a structural unit derived from poly(oxy)alkylene glycol or its monoether.

[0159] In the general formula (A-3-i), u represents a number greater than or equal to 0, preferably a number between 0 and 50, and w represents a number greater than or equal to 1, preferably a number between 1 and 50.

[0160] In the general formula (A-3-ii), x and y each independently represent a number greater than 1, preferably a number from 1 to 50.

[0161] It should be noted that the values ​​of v, u, w, x, and y mentioned above can be adjusted according to the hydroxyl value required by the base oil (A), and there are no special restrictions.

[0162] It should be noted that the copolymerization form of copolymers (A-3-i) and (A-3-ii) is not particularly limited; it can be a block copolymer, a random copolymer, or a graft copolymer.

[0163] Regarding what can be used as R 1c R 2c and R 3c The hydrocarbon groups selected, with 1 to 8 carbon atoms, can be listed as R in the general formula (A-1). 1a R 2a and R 3a The selected group consists of monovalent hydrocarbon groups with 1 to 8 carbon atoms.

[0164] Regarding what can be used as R 1c R 2c and R 3c The number of carbon atoms in the aforementioned hydrocarbon group is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 3.

[0165] As R 1c R 2c and R 3c Each of them is preferably an alkyl group having 1 to 8 hydrogen atoms or carbon atoms, more preferably an alkyl group having 1 to 6 hydrogen atoms or carbon atoms, and even more preferably an alkyl group having 1 to 3 hydrogen atoms or carbon atoms.

[0166] In addition, R is preferred. 1c R 2c and R 3c At least one of them is a hydrogen atom, more preferably R 1c R 2c and R 3c It consists entirely of hydrogen atoms.

[0167] Regarding what can be used as R 4c The hydrocarbon groups selected, with 1 to 10 carbon atoms, can be listed as R in the general formula (A-2). 5a The selected group consists of hydrocarbon groups with 1 to 10 carbon atoms.

[0168] Regarding what can be used as R 4c The number of carbon atoms in the aforementioned hydrocarbon group is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4.

[0169] Regarding what can be used as R 5c The aforementioned alkylene groups selected can be listed as R in general formula (A-1). 14a The selected group having the same alkylene group with 2 or more but less than 4 carbon atoms is preferably propylene (-CH(CH3)CH2-).

[0170] It should be noted that in copolymers (A-3-i) or (A-3-ii), the content of oxypropylene units (-OCH(CH3)CH2-) is defined as the structural units in copolymers (A-3-i) or (A-3-ii) derived from poly(oxy)alkylene glycols or their monoethers, i.e., oxyalkylene (OR) 5c Based on the total amount (100 mol%), it is preferably 50 mol% or more and 100 mol% or less, more preferably 65 mol% or more and 100 mol% or less, and even more preferably 80 mol% or more and 100 mol% or less.

[0171] Regarding what can be used as R 6c Alkyl groups with 1 to 20 carbon atoms can be exemplified by methyl, ethyl, various propyl, various butyl, various pentyl, various hexyl, various heptyl, various octyl, various nonyl, various decyl, etc.

[0172] The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0173] Regarding what can be used as R 6c The alicyclic groups selected for cyclization with 3 to 20 carbon atoms include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

[0174] The number of cyclic carbon atoms in the alicyclic group is preferably 3 to 10, more preferably 3 to 8, and even more preferably 3 to 6.

[0175] It should be noted that the alicyclic group may optionally have the aforementioned substituents, and the preferred substituent is an alkyl group.

[0176] Regarding what can be used as R 6c The aromatic groups selected for cyclic formation with 6 to 24 carbon atoms can be exemplified by phenyl, naphthyl, anthraceneyl, phenanthrene, etc.

[0177] The number of cyclic carbon atoms in the aromatic group is preferably 6 to 18, more preferably 6 to 12.

[0178] It should be noted that the aromatic group may optionally have the aforementioned substituents, preferably alkyl groups.

[0179] Regarding what can be used as R 6c The acyl groups selected for cyclization with 2 to 20 carbon atoms can be exemplified by acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, neovaleryl, benzoyl, tolueneyl, etc.

[0180] The number of carbon atoms in the acyl group is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6.

[0181] Regarding what can be used as R 6c Examples of oxygen-containing hydrocarbon groups with 2 to 50 carbon atoms include methoxymethyl, methoxyethyl, methoxypropyl, 1,1-dimethoxypropyl, 1,2-dimethoxypropyl, ethoxypropyl, (2-methoxyethoxy)propyl, and (1-methyl-2-methoxy)propyl.

[0182] The number of carbon atoms in the carbon-containing hydrocarbon group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0183] Regarding X C Y C Examples of hydrocarbon groups with 1 to 20 carbon atoms include alkyl groups with 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3), substituted or unsubstituted cycloalkyl groups with 3 to 20 carbon atoms (preferably 3 to 10, more preferably 3 to 8, and even more preferably 3 to 6), substituted or unsubstituted phenyl groups, substituted or unsubstituted naphthyl groups, and arylalkyl groups with 7 to 20 carbon atoms (preferably 7 to 13).

[0184] (Polyol esters (POE))

[0185] Examples of POEs include esters of glycols or polyhydroxy compounds with fatty acids. It should be noted that when a base oil (A) contains POEs, one type of POE may be used alone, or two or more may be used in combination.

[0186] POE is preferably an ester of a diol or a polyhydroxy compound with 3 to 20 hydroxyl groups and a fatty acid with 3 to 20 carbon atoms.

[0187] 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, neopentanediol, 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.

[0188] Examples of polyhydroxy compounds include trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, polyglycerol (2-20 polymers of glycerol), 1,3,5-pentanetriol, sorbitol, dehydrated sorbitol, sorbitol glycerol condensate, calendula alcohol, arabinitol, xylitol, mannitol, and other polyols; xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbitol, cellobiose, maltose, isomaltose, trehalose, sucrose, metriose, gentiotriose, mesentylose, pinetriose, and other sugars; as well as their partial etherifications, methyl glucosides (glycosides), etc.

[0189] Among these, hindered alcohols such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, dipentaerythritol, and tripentaerythritol are preferred. It should be noted that hindered alcohols refer to alcohols having a quaternary carbon atom bonded to four carbon atoms.

[0190] From the viewpoint of lubrication performance, the number of carbon atoms in fatty acids is preferably 3 or more, more preferably 4 or more, further preferably 5 or more, and even more preferably 8 or more. In addition, from the viewpoint of compatibility with refrigerants, it is preferably 20 or less, more preferably 16 or less, further preferably 12 or less, and even more preferably 10 or less.

[0191] It should be noted that the number of carbon atoms in the fatty acids mentioned above also includes the carbon atoms of the carboxyl group (-COOH) present in the fatty acid.

[0192] Furthermore, the fatty acid can be either a straight-chain fatty acid or a branched-chain fatty acid. From the viewpoint of lubrication performance, a straight-chain fatty acid is preferred, while from the viewpoint of hydrolytic stability, a branched-chain fatty acid is preferred. Moreover, the fatty acid can be either a saturated fatty acid or an unsaturated fatty acid.

[0193] As fatty acids, examples include straight-chain or branched fatty acids such as isobutyric acid, propionic acid, butyric acid, valeric 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, eicosanoic acid, and oleic acid; or so-called new acids where the α-carbon atom is a quaternary carbon.

[0194] More specifically, the preferred choices are isobutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid (cis-9-octadecenoic acid), isovaleric acid (3-methylbutyric acid), 2-methylhexanoic acid, 2-ethylvaleric acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, etc.

[0195] As a POE, it can be a partial ester that remains unesterified from some of the multiple hydroxyl groups in a polyhydroxy compound, or it can be a full ester in which all hydroxyl groups have been esterified. In addition, the POE can be a mixture of partial ester and full ester, preferably a full ester.

[0196] From the viewpoint of superior hydrolytic stability, esters of hindered alcohols such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, dipentaerythritol, and tripentaerythritol are preferred as POEs. Esters of neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, and pentaerythritol are more preferred. Furthermore, from the viewpoint of particularly excellent compatibility with refrigerants and hydrolytic stability, esters of pentaerythritol are even more preferred.

[0197] Specific examples of preferred POEs include: neopentyl glycol and a diester formed with one or more fatty acids selected from isobutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, isovaleric acid, 2-methylhexanoic acid, 2-ethylvaleric acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; trimethylolethane and a triester formed with one or more fatty acids selected from isobutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, isovaleric acid, 2-methylhexanoic acid, 2-ethylvaleric acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; and trimethylolpropane and a diester formed with one or more fatty acids selected from isobutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, isovaleric acid, 2-methylhexanoic acid, 2-ethylvaleric acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; Triesters formed from one or more fatty acids selected from isobutyric acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid; triesters formed from trimethylolbutane and one or more fatty acids selected from isobutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, isovaleric acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid; tetraesters formed from pentaerythritol and one or more fatty acids selected from isobutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, isovaleric acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid, etc.

[0198] It should be noted that the ester formed with two or more fatty acids can be an ester obtained by mixing two or more polyhydroxy compounds with an ester of one fatty acid. From the viewpoint of improving low-temperature characteristics and compatibility with refrigerants, esters of two or more mixed fatty acids and polyhydroxy compounds are preferred in POEs.

[0199] (Preferred method for base oil (A))

[0200] In the refrigeration oil composition of this embodiment, from the viewpoint of long-term stability required for a refrigeration oil composition, the main component of the base oil (A) is preferably the aforementioned base oil (A1), and more preferably the aforementioned base oil (A2). It should be noted that, in this specification, "main component" refers to the component with the highest content.

[0201] The content of base oil (A1) or base oil (A2) in base oil (A) is preferably 50% to 100% by mass, more preferably 60% to 100% by mass, further preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, and even more preferably 100% by mass, based on the total amount of base oil (A) (100% by mass).

[0202] Here, the base oil (A1) is preferably PAG, PVE, ECP or POE (i.e., composed only of PAG, PVE, ECP or POE).

[0203] Therefore, the content of PAG, PVE, ECP or POE in the base oil (A) is preferably 50% to 100% by mass, more preferably 60% to 100% by mass, further preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, and even more preferably 100% by mass, based on the total amount (100% by mass) of the base oil (A).

[0204] Furthermore, from the viewpoint of the long-term stability required as a refrigeration oil composition, the base oil (A2) is preferably PAG or PVE (i.e., composed only of PAG or PVE).

[0205] Therefore, the content of PAG or PVE in the base oil (A) is preferably 50% to 100% by mass, more preferably 60% to 100% by mass, further preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, and even more preferably 100% by mass, based on the total amount (100% by mass) of the base oil (A).

[0206] (Other base oils)

[0207] The base oil (A) may further contain other base oils without impairing the effects of the present invention.

[0208] Other base oils can be selected from mineral oils and synthetic oils that are not among the aforementioned PVE, PAG, ECP and POE.

[0209] As mineral oils, examples include oils refined from lubricating oil fractions obtained by atmospheric distillation of alkane-based crude oil, intermediate-based crude oil, or cycloalkane-based crude oil, or by vacuum distillation of atmospheric residue obtained from atmospheric distillation of crude oil, and by solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, etc.; and oils manufactured by isomerizing mineral oil waxes.

[0210] It should be noted that when the base oil (A) contains mineral oil, one type of mineral oil may be used alone, or two or more types may be used in combination.

[0211] Synthetic oils that do not belong to the aforementioned PVE, PAG, ECP, and POE include, for example, polyesters, polycarbonates, hydrides of α-olefin oligomers, alicyclic hydrocarbons, alkylated aromatic hydrocarbons, and oils produced by isomerizing GTL WAX (vapor-to-liquid wax) manufactured using the Fischer-Tropsch process.

[0212] It should be noted that if the base oil (A) contains synthetic oils that are not among the aforementioned PVE, PAG, ECP and POE, the synthetic oil can be used alone or in combination with two or more.

[0213] It should be noted that, from the viewpoint of the solubility of the epoxy compound (B), the mineral oil content in the refrigeration oil composition of this embodiment is preferably low. Specifically, the mineral oil content, based on the total amount of base oil (A), is preferably 10% by mass or less, more preferably 1% by mass or less, further preferably 0.1% by mass or less, and even more preferably free of mineral oil.

[0214] (Kinematic viscosity of base oil (A) at 100°C)

[0215] From the perspective of improving lubrication performance (load resistance) and sealing performance, the kinematic viscosity of base oil (A) at 100°C is preferably 3 mm. 2 / s or higher, more preferably 4mm 2 / s or higher, preferably 5mm 2 / s or higher. Furthermore, from the viewpoint of improving compatibility with the refrigerant, 50 mm is preferred. 2 / s or less, more preferably 40mm 2 / s or less, more preferably 30mm 2 / s or less.

[0216] The upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, 3mm is preferred. 2 / s~50mm 2 / s, more preferably 4mm 2 / s~40mm 2 / s, further preferably 5mm 2 / s~30mm 2 / s.

[0217] In this specification, the kinematic viscosity of base oil (A) at 100°C is the value measured according to JIS K2283:2000.

[0218] (Hydroxy value of base oil (A))

[0219] From the viewpoint of improving the thermal stability of the refrigeration oil composition, the hydroxyl value of the base oil (A) is preferably 30 mg KOH / g or less, more preferably 25 mg KOH / g or less, and even more preferably 20 mg KOH / g or less. Additionally, it is typically 0.5 mg KOH / g or more.

[0220] In this specification, the hydroxyl value of base oil (A) is the value determined according to JIS K0070:1992 using the neutralization titration method.

[0221] (Number average molecular weight (Mn) of base oil (A))

[0222] From the viewpoint of improving lubrication performance (load resistance) and sealing performance, the number average molecular weight (Mn) of the base oil (A) is preferably 300 or more, more preferably 400 or more, and even more preferably 500 or more. Furthermore, from the viewpoint of improving compatibility with the refrigerant, it is preferably 10,000 or less, more preferably 7,000 or less, and even more preferably 5,000 or less.

[0223] The upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, 300 to 10,000 is preferred, 400 to 7,000 is more preferred, and 500 to 5,000 is even more preferred.

[0224] In this specification, the number-average molecular weight (Mn) of the base oil (A) is a value obtained using the method described in the examples below.

[0225] <Epoxy Compounds (B)>

[0226] The refrigeration oil composition of this embodiment contains an epoxy compound (B) that satisfies the following conditions (B1) and (B2).

[0227] (B1) The molecule has at least one divalent group as shown in formula (1) below.

[0228] [Chemistry 12]

[0229]

[0230] (B2) The molecule has at least one ester group.

[0231] It can be inferred that, compared to epoxy compounds with an epoxy group at the molecule's end, the group shown in formula (1) of epoxy compound (B) is less likely to decompose unsaturated fluorinated hydrocarbons (HFOs), and is less likely to produce fluorine components (such as hydrofluoric acid) generated by the decomposition of unsaturated fluorinated hydrocarbons (HFOs) under high-temperature conditions. In addition, the trace amounts of fluorine components produced react with the epoxy groups in epoxy compound (B) and are captured into epoxy compound (B). By suppressing the dissolution of fluorine components in the refrigeration oil composition through these functions, and by capturing the dissolved fluorine components, the acid value of the refrigeration oil composition can be suppressed.

[0232] If the molecular weight of the aforementioned epoxy compound (B) is 300 or more, it can moderately suppress the reactivity of the epoxy group, suppress the decomposition of unsaturated fluorinated hydrocarbon compounds, and improve its solubility in base oil. Therefore, it is preferred, and more preferably, 350 or more.

[0233] Furthermore, from the viewpoint of solubility in refrigeration oil and the formation of sludge after stability evaluation, the molecular weight of the epoxy compound (B) is preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less.

[0234] In the refrigeration oil composition of this embodiment, from the viewpoint of more easily exerting the effect of suppressing the increase of acid value in the refrigeration oil composition, the content of epoxy compound (B), based on the total amount of the refrigeration oil composition (100% by mass), is preferably 0.10% by mass or more, more preferably 0.20% by mass or more, further preferably 0.50% by mass or more, and even more preferably 1.00% by mass or more. It should be noted that there is no particular limitation on the upper limit of the content of epoxy compound (B), but from the viewpoint of obtaining an effect commensurate with the amount added, it is preferably 10.00% by mass or less, more preferably 7.00% by mass or less, and even more preferably 5.00% by mass or less.

[0235] The upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 0.10% to 10.00% by mass, more preferably 0.20% to 7.00% by mass, even more preferably 0.50% to 5.00% by mass, and even more preferably 1.00% to 5.00% by mass.

[0236] In this embodiment, the epoxy compound (B) may be selected from one or more substances that satisfy the above two conditions without particular limitation.

[0237] Specific examples of epoxide compounds (B) include epoxidized fatty acid esters, epoxidized alicyclic carboxylic acid esters, and epoxidized vegetable oils, which satisfy the above conditions (B1) and (B2).

[0238] (Epoxidized fatty acid esters)

[0239] Examples of the above-mentioned epoxidized fatty acid esters include substances obtained by epoxidizing fatty acids with 8 to 30 carbon atoms (preferably 12 to 20 carbon atoms) with esters of alcohols, phenols, or alkylphenols with 1 to 8 carbon atoms.

[0240] From the viewpoint that the epoxidized fatty acid ester described above can effectively suppress the increase in acid value of the refrigeration oil composition, the substance shown in the following general formula (1-1) is preferred.

[0241] [Chemistry 13]

[0242]

[0243] (In equation (1-1), R) 1 R is a hydrocarbon group with 4 to 20 carbon atoms. 2 For hydrocarbon groups with 1 to 10 carbon atoms, p is an integer from 1 to 3, n is an integer from 0 to 12, and m is an integer from 1 to 3. When m is 2 or more, the structures within the multiple brackets can be chosen to be the same or different from each other.

[0244] Examples of hydrocarbon groups mentioned above include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, various butyl, various pentyl, various hexyl, various heptyl, various octyl, various nonyl, and various decyl; cyclopentyl, cyclohexyl, various methylcyclohexyl, various ethylcyclohexyl, various propylcyclohexyl, and various dimethylcyclohexyl; aryl groups such as phenyl, various methylphenyl, various ethylphenyl, various dimethylphenyl, various propylphenyl, various trimethylphenyl, various butylphenyl, and various naphthyl; and arylalkyl groups such as benzyl, various phenylethyl, various methylbenzyl, various phenylpropyl, and various phenylbutyl, which contain various hydrocarbon groups with the specified number of carbon atoms.

[0245] Of the epoxidized fatty acid esters shown in (1-1) above, the preferred one is: R 1 It is an alkyl group with 5 to 12 carbon atoms, R 2 It is an alkyl group with 1 to 6 carbon atoms, p is 1, n is an integer from 1 to 10, and m is 1 or 2.

[0246] Specific examples of the aforementioned epoxidized fatty acid esters include substances obtained by epoxidizing linoleic acid, oleic acid, palmitic acid, linolenic acid or stearic acid, butyl ester, hexyl ester, 2-ethylhexyl ester, benzyl ester, cyclohexyl ester, methoxyethyl ester, octyl ester, phenyl ester or butylphenyl ester.

[0247] Commercially available examples of the aforementioned epoxidized vegetable oils include Sunshine Cyzer E-6000 manufactured by Shin Nippon Rikka Co., Ltd., and Kemi Cyzer T-5000 manufactured by Sanwa Synthetic Chemical Co., Ltd.

[0248] (Epoxidized cyclic carboxylic esters)

[0249] Examples of the above-mentioned epoxidized alicyclic carboxylic acid esters include substances obtained by epoxidation of an alicyclic carboxylic acid with 5 to 12 carbon atoms and an ester of an alcohol, phenol, or alkylphenol with 1 to 8 carbon atoms. The alicyclic carboxylic acid can be a monocarboxylic acid or a dicarboxylic acid.

[0250] From the viewpoint that the epoxidized cyclic carboxylic acid ester described above can effectively suppress the increase in acid value of the refrigeration oil composition, the substance shown in the following general formula (1-2) is preferred.

[0251] [Chemistry 14]

[0252]

[0253] (In equation (1-2), R) 3 and R 4 Each group is an independent hydrocarbon group with 4 to 20 carbon atoms.

[0254] As specific examples of the aforementioned hydrocarbon groups, groups whose number of carbon atoms in the hydrocarbon groups listed as hydrocarbon groups in formula (1-1) conform to the specified number can be given.

[0255] In the epoxidized cyclocarboxylic esters shown in (1-2) above, R 3 and R 4 Each is preferably an alkyl group having 6 to 12 carbon atoms.

[0256] As a specific example of the aforementioned epoxidized cyclocarboxylic acid esters, epoxidized cyclocarboxylic acid esters can be listed, and more specifically, 4,5-epoxycyclohexane-1,2-dicarboxylic acid di(2-ethylhexyl) ester can be listed.

[0257] Commercially available products of the aforementioned epoxidized cyclic carboxylic esters include, for example, Sanso Saizer E-PS manufactured by Shin Nippon Rikka Co., Ltd.

[0258] (Epoxidized vegetable oil)

[0259] Examples of epoxidized vegetable oils include substances obtained by epoxidizing vegetable oils such as soybean oil, linseed oil, rice bran oil, and cottonseed oil.

[0260] From the viewpoint of effectively suppressing the increase in acid value of the refrigeration oil composition, the epoxidized vegetable oil described above is preferably a substance having a group shown in the following general formula (1-3). More specifically, it is preferably a glycerol ester having one or more groups shown in the following general formula (1-3), more preferably a triglyceride having one or more groups shown in the following general formula (1-3), and even more preferably a triglyceride having two or more groups shown in the following general formula (1-3).

[0261] [Chemistry 15]

[0262]

[0263] (In equation (1-3), R) 1 For hydrocarbon groups with 4 to 20 carbon atoms, p is an integer from 1 to 3, n is an integer from 0 to 12, and m is an integer from 1 to 3. When m is 2 or more, the structures within the multiple brackets can be chosen to be the same or different from each other.

[0264] The above R 1 The details are the same as those in equation (1-1) above.

[0265] Of the groups shown in (1-3) above, the preferred one is: R 1 It is an alkyl group with 5 to 12 carbon atoms, p is 1, n is an integer from 1 to 10, and m is 1 or 2.

[0266] Commercially available products of the above-mentioned epoxidized vegetable oil include Semense E-2000H manufactured by Shinnippon Rika Co., Ltd.; Semense SE-80, Semense SE-100 and Semen manufactured by Sanwa Synthetic Chemical Co., Ltd.サイザーT-3000N, ケミサイザーLE-3000, ケミサイザーT-2000; Japan Nifter 510R manufactured by Oil Co., Ltd.; Ameraser O-180A manufactured by ADEKA, etc.

[0267] <Glycidyl ether compound (C)>

[0268] The refrigeration oil composition of this embodiment may also contain glycidyl ether compound (C).

[0269] Examples of glycidyl ether compounds (C) include aliphatic monools or aliphatic polyols, typically having 3 to 30 carbon atoms, preferably 4 to 24, and more preferably 6 to 16; or glycidyl ethers derived from aromatic compounds containing one or more hydroxyl groups. The aliphatic monools or aliphatic polyols can be linear, branched, or cyclic, and can be saturated or unsaturated, with saturated aliphatic monools being preferred.

[0270] It should be noted that, in the case of aliphatic polyols and aromatic compounds containing two or more hydroxyl groups, from the viewpoint of the stability of the refrigeration oil composition, it is preferable that all hydroxyl groups are glycidyl etherified.

[0271] Examples of glycidyl ether compounds include phenyl glycidyl ether, alkyl glycidyl ether, and alkylene glycol glycidyl ether. Among these, glycidyl ethers derived from saturated aliphatic monools with 6 to 16 carbon atoms (i.e., alkyl glycidyl ethers with 6 to 16 carbon atoms in the alkyl group) are particularly preferred. Examples of such glycidyl ethers include 2-ethylhexyl glycidyl ether, isononyl glycidyl ether, decyl glycidyl ether, lauryl glycidyl ether, and myristyl glycidyl ether, with 2-ethylhexyl glycidyl ether being the most preferred. By using alkyl glycidyl ethers such as 2-ethylhexyl glycidyl ether, it is easier to appropriately prevent the acid value of the refrigeration oil composition from increasing and to improve its oxidative stability at high temperatures.

[0272] The content of glycidyl ether compound (C) is preferably 0.10 to 10.00% by mass, based on the total amount of the refrigeration oil composition. By setting the content of glycidyl ether compound (C) to 0.10% by mass or more, acids in the refrigeration oil composition are appropriately captured, effectively preventing the acid value of the refrigeration oil composition from rising and easily improving high-temperature stability. Furthermore, setting it to 10.00% by mass or less allows for an effect consistent with the content.

[0273] Furthermore, the content of glycidyl ether compound (C) is more preferably 0.4% by mass or more, and even more preferably 0.5% by mass or more. More preferably, it is 5% by mass or less, even more preferably 4% by mass or less, and even more preferably 3% by mass or less. These upper and lower limits of the numerical range can be combined arbitrarily. Specifically, it is more preferably 0.4% to 5% by mass, even more preferably 0.5% to 4% by mass, and even more preferably 0.5% to 3% by mass. It should be noted that glycidyl ether compound (C) can be used alone or in combination with two or more compounds.

[0274] <Ratio of epoxide compound (B) to glycidyl ether compound (C)>

[0275] In the refrigeration oil composition of this embodiment, from the viewpoint that it is easier to exert the effects of the present invention, the content ratio of epoxy compound (B) to glycidyl ether compound (C) [(B) / (C)] is preferably 0.050 or more by mass, more preferably 0.10 or more, and even more preferably 0.20 or more. In addition, it is preferably 5.0 or less, more preferably 3.5 or less, and even more preferably 2.5 or less.

[0276] The upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, the range is preferably 0.050 to 5.0, more preferably 0.10 to 3.5, and even more preferably 0.20 to 2.5.

[0277] <Other Additives>

[0278] The refrigeration oil composition of this embodiment may further contain other additives besides the above-described components (A), (B) and (C) without impairing the effects of the present invention.

[0279] Other additives may include one or more selected from antioxidants, stabilizers, extreme pressure agents, and defoamers.

[0280] The total content of these additives, based on the total amount (100% by mass) of the refrigeration oil composition, is preferably 0% to 10% by mass, more preferably 0.01% to 5% by mass, and even more preferably 0.1% to 3% by mass.

[0281] (Antioxidants)

[0282] As antioxidants, one or more selected from phenolic antioxidants and amine antioxidants are preferred.

[0283] 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).

[0284] Examples of amine-based antioxidants include phenyl-α-naphthylamine and N,N'-diphenyl-p-phenylenediamine.

[0285] Among these, phenolic antioxidants are preferred, and among phenolic antioxidants, 2,6-di-tert-butyl-p-cresol (DBPC) is preferred.

[0286] From the viewpoint of stability and antioxidant performance, the antioxidant content, based on the total amount (100% by mass) of the refrigeration oil composition, is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. Furthermore, it is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0287] The upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 0.01% to 5% by mass, more preferably 0.05% to 3% by mass, and even more preferably 0.1% to 1% by mass.

[0288] (Stabilizer)

[0289] Examples of stabilizers include aliphatic unsaturated compounds and terpenes with double bonds.

[0290] As the aforementioned aliphatic unsaturated compounds, unsaturated hydrocarbons are preferred, specifically alkenes, dienes, trienes, and other polyenes. From the viewpoint of oxygen reactivity, α-olefins such as 1-tetradecene, 1-hexadecene, and 1-octadecene are preferred as alkenes.

[0291] As for aliphatic unsaturated compounds other than those mentioned above, from the viewpoint of reactivity with oxygen, compounds with the molecular formula C are preferred. 20 H 30 O represents unsaturated aliphatic alcohols with conjugated double bonds, such as vitamin A ((2E,4E,6E,8E)-3,7-dimethyl-9-(2,6,6-trimethylcyclohexen-1-yl)non-2,4,6,8-tetraen-1-ol).

[0292] As terpenes containing double bonds, terpene hydrocarbons containing double bonds are preferred, and from the viewpoint of reactivity with oxygen, α-pinene, β-pinene, and α-farnesene (C) are more preferred. 15 H 24 3,7,11-trimethyldodec-1,3,6,10-tetraene) and β-farnesene (C 15 H 24 (7,11-Dimethyl-3-methyldodec-1,6,10-triene).

[0293] Stabilizers can be used alone or in combination of two or more.

[0294] (Extreme pressure agent)

[0295] The preferred extreme pressure agents are phosphorus-based extreme pressure agents, carboxylic acid metal salts, and sulfur-based extreme pressure agents.

[0296] Examples of phosphorus-based extreme pressure agents include phosphate esters, acid phosphate esters, phosphites, acid phosphites, and their amine salts.

[0297] From the viewpoint of improving extreme pressure and triboelectric properties, one or more of the following are preferred: tricresyl phosphate (TCP), trithiophene phosphate, tri(nonylphenyl) phosphite, dioleenyl hydrogen phosphite, and 2-ethylhexyl diphenyl phosphite, with tricresyl phosphate (TCP) being more preferred.

[0298] Examples of metal salts of carboxylic acids include, for example, metal salts of carboxylic acids having 3 to 60 carbon atoms (preferably 3 to 30).

[0299] Among these, one or more are preferably selected from fatty acids having 12 to 30 carbon atoms and metal salts of dicarboxylic acids having 3 to 30 carbon atoms.

[0300] Furthermore, the metals constituting the metal salt are preferably alkali metals and alkaline earth metals, and more preferably alkali metals.

[0301] Examples of sulfur-based extreme pressure agents include sulfurized oils, sulfurized fatty acids, sulfurized esters, sulfurized alkenes, dialkyl polysulfides, thiocarbamates, thioterpenes, and dialkyl thiodipropionates.

[0302] From the viewpoint of lubrication and stability, the content of extreme pressure agent, based on the total amount (100% by mass) of the refrigeration oil composition, is preferably 0.001 to 5% by mass, more preferably 0.005 to 3% by mass.

[0303] (Defoamer)

[0304] Examples of defoamers include silicone oil and fluorinated silicone oil, among others.

[0305] [Method for manufacturing refrigeration oil composition]

[0306] There are no particular limitations on the method for manufacturing the above-mentioned refrigeration oil composition.

[0307] For example, the method for manufacturing the refrigeration oil composition of this embodiment is a method for manufacturing a refrigeration oil composition for a refrigerant, wherein the refrigerant comprises one or more unsaturated fluorinated hydrocarbon compounds selected from the compounds shown in the following general formula (1).

[0308] C x F y H z ···(1)

[0309] [In the aforementioned general formula (1), x is an integer from 2 to 6, y is an integer from 1 to 11, and z is an integer from 1 to 11, and the molecule has more than one carbon-carbon unsaturated bond.]

[0310] The manufacturing method includes a step of mixing base oil (A) with an epoxy compound (B).

[0311] The aforementioned epoxy compound (B) satisfies the following conditions (B1) and (B2).

[0312] (B1) The molecule has at least one ethylene oxide-2,3-diyl group.

[0313] (B2) The molecule has at least one ester group.

[0314] There are no particular limitations on the method for mixing the above-mentioned components. For example, a method that includes the step of compounding epoxy compound (B) into base oil (A) can be used. Glycidyl ether compound (C) and other additives can be compounded into base oil (A) simultaneously with epoxy compound (B), or they can be compounded separately. It should be noted that the components can be compounded after preparing a solution (dispersion) by adding diluent oil, etc. Preferably, after compounding the components, they are stirred using a known method to achieve uniform dispersion.

[0315] [Physical Properties of Refrigeration Oil Compositions]

[0316] In this embodiment, the autoclave properties of the refrigeration oil composition as described in the later embodiments are as follows.

[0317] <Acid Value>

[0318] The acid value of the refrigeration oil composition after the autoclave test described in the following examples is preferably 0.15 mg KOH / g or less, more preferably 0.10 mg KOH / g or less.

[0319] Fluoride content

[0320] The amount of fluorine in the refrigeration oil composition after the autoclave test described in the following examples is preferably 15 ppm by mass or less, more preferably 10 ppm by mass or less, and even more preferably 7 ppm by mass or less, based on the total amount of the refrigeration oil composition.

[0321] [Mixed Composition for Refrigeration Equipment]

[0322] The above-mentioned refrigeration oil composition is mixed with a refrigerant to be used as a mixed composition for refrigeration machines.

[0323] That is, the refrigeration oil composition contains the above-mentioned refrigeration oil composition and refrigerant.

[0324] The following section explains the refrigerant.

[0325] <Refriger>

[0326] The refrigerant used in this embodiment is a refrigerant containing one or more unsaturated fluorinated hydrocarbon compounds selected from the compounds shown in the following general formula (1).

[0327] C x F y H z ···(1)

[0328] [In the aforementioned general formula (1), x is 2 to 6, y is 1 to 11, and z is an integer from 1 to 11, and the molecule has more than one carbon-carbon unsaturated bond].

[0329] The above general formula (1) represents the types and numbers of elements in a molecule. Specifically, it represents unsaturated fluorinated hydrocarbon compounds with 2 to 6 carbon atoms (C). Unsaturated fluorinated hydrocarbon compounds with 2 to 6 carbon atoms possess the physical and chemical properties required for refrigerants, such as boiling point, freezing point, and latent heat of vaporization.

[0330] In the above general formula (1), C is used. x The x carbon atoms represent unsaturated bonds such as carbon-carbon single bonds and carbon-carbon double bonds. From a stability perspective, carbon-carbon unsaturated bonds are preferably carbon-carbon double bonds, and unsaturated fluorinated hydrocarbon compounds preferably have more than one carbon-carbon double bond or other unsaturated bond in the molecule, with the number preferably being 1. That is, using C... x At least one of the bonding configurations of the x carbon atoms represented is preferably a carbon-carbon double bond.

[0331] As examples of the aforementioned unsaturated fluorinated hydrocarbon compounds, fluorides of linear or branched chain alkenes having 2 to 6 carbon atoms or cyclic alkenes having 4 to 6 carbon atoms are preferred.

[0332] Specifically, examples include fluorides of ethylene with 1 to 3 fluorine atoms, fluorides of propylene with 1 to 5 fluorine atoms, fluorides of butene with 1 to 7 fluorine atoms, fluorides of pentene with 1 to 9 fluorine atoms, fluorides of hexene with 1 to 11 fluorine atoms, fluorides of cyclobutene with 1 to 5 fluorine atoms, fluorides of cyclopentene with 1 to 7 fluorine atoms, and fluorides of cyclohexene with 1 to 9 fluorine atoms.

[0333] Among these, fluorinated propylene is preferred, and propylene with 3 to 5 fluorine atoms is more preferred. Specifically, it is preferred to be one or more selected from 1,3,3,3-tetrafluoropropylene (R1234ze), 2,3,3,3-tetrafluoropropylene (R1234yf), and 1,2,3,3-tetrafluoropropylene (R1234ye), and 2,3,3,3-tetrafluoropropylene (R1234yf) is more preferred.

[0334] The aforementioned unsaturated fluorinated hydrocarbon compounds can be used alone or in combination of two or more. Therefore, it is possible to use only one of the following: 1,3,3,3-tetrafluoropropene (R1234ze), 2,3,3,3-tetrafluoropropene (R1234yf), and 1,2,3,3-tetrafluoropropene (R1234ye).

[0335] (Other refrigerants)

[0336] In this embodiment, the refrigerant may be a mixed refrigerant that includes the unsaturated fluorinated hydrocarbon compound shown in the above general formula (1) and, as needed, other compounds, such as saturated fluorinated hydrocarbon compounds.

[0337] As a saturated fluorinated hydrocarbon compound, a fluoride of an alkane having 1 to 4 carbon atoms is preferred, a fluoride of an alkane having 1 to 3 carbon atoms is more preferred, and a fluoride of an alkane (methane or ethane) having 1 or 2 carbon atoms is even more preferred. Examples of such fluorides of methane or ethane 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 which difluoromethane and 1,1,1,2,2-pentafluoroethane are preferred.

[0338] These saturated fluorinated hydrocarbon compounds can be used alone or in combination of two or more.

[0339] In addition, refrigerants can include natural refrigerants. Examples of natural refrigerants include hydrocarbon refrigerants (HC), carbon dioxide (CO2, carbon dioxide gas), and ammonia. These natural refrigerants can be used alone or in combination of two or more.

[0340] As the aforementioned hydrocarbon-based refrigerant, hydrocarbons with 1 or more but less than 8 carbon atoms are preferred, hydrocarbons with 1 or more but less than 5 carbon atoms are more preferred, and hydrocarbons with 3 or more but less than 5 carbon atoms are even more preferred. If the number of carbon atoms is 8 or less, the boiling point of the refrigerant will not be too high, making it a preferred refrigerant. As this hydrocarbon-based refrigerant, one or more can be selected from methane, ethane, ethylene, propane (R290), cyclopropane, propylene, n-butane, isobutane (R600a), 2-methylbutane, n-pentane, isopentane, cyclopentaneisobutane, and n-hexane. One of these can be used alone, or two or more can be used in combination.

[0341] (The content of unsaturated fluorinated hydrocarbon compounds in the refrigerant)

[0342] In this embodiment, the refrigerant comprises the unsaturated fluorinated hydrocarbon compound represented by the above general formula (1).

[0343] The content of the unsaturated fluorinated hydrocarbon compound shown in the above general formula (1) is preferably 50% to 100% by mass, more preferably 60% to 100% by mass, further preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, and even more preferably 100% by mass, based on the total amount of refrigerant.

[0344] The refrigeration oil composition of this embodiment exhibits excellent performance in suppressing acid value increases, even with refrigerants containing such a high content of unsaturated fluorinated hydrocarbon compounds.

[0345] (Amount of refrigerant and refrigeration oil composition)

[0346] In the refrigeration oil mixture of this embodiment, the amounts of refrigerant and refrigeration oil composition are preferably 1 / 99 to 90 / 10, more preferably 5 / 95 to 70 / 30, based on the mass ratio of refrigeration oil composition to refrigerant [(refrigeration oil composition) / (refrigerant)]. Setting the mass ratio of refrigeration oil composition to refrigerant within this range allows for good lubricity and suitable refrigeration capacity in the refrigeration unit.

[0347] [Uses of Refrigeration Oil Compositions and Refrigeration Mixtures]

[0348] The above-mentioned refrigeration oil composition and refrigeration blend composition are preferably used in, for example, air conditioners, refrigerators, vending machines, display cases, refrigeration systems, hot water supply systems, or heating systems. It should be noted that, as for air conditioners, examples include open-type automotive air conditioners, electric vehicle air conditioners, and gas-fired heat pump (GHP) air conditioners.

[0349] [One aspect of the present invention provided]

[0350] In one aspect of the present invention, the following [1] to

[11] are provided.

[0351] [1] A refrigeration oil composition for use in a refrigerant comprising one or more unsaturated fluorinated hydrocarbon compounds selected from compounds represented by the following general formula (1).

[0352] C x F y H z ···(1)

[0353] [In the aforementioned general formula (1), x is an integer from 2 to 6, y is an integer from 1 to 11, and z is an integer from 1 to 11, and the molecule has more than one carbon-carbon unsaturated bond.]

[0354] The refrigeration oil composition contains an epoxy compound (B) and a base oil (A) selected from polyalkylene glycols, polyvinyl ethers, copolymers of poly(oxy)alkylene glycols or their monoethers with polyvinyl ethers, and polyol esters.

[0355] The aforementioned epoxy compound (B) satisfies the following conditions (B1) and (B2).

[0356] (B1) The molecule has at least one divalent group as shown in formula (1) below.

[0357] [Chemistry 16]

[0358]

[0359] (B2) The molecule has at least one ester group.

[0360] [2] The refrigeration oil composition according to [1], wherein the molecular weight of the aforementioned epoxy compound (B) is 300 or more.

[0361] [3] The refrigeration oil composition according to [1] or [2], wherein the content of the aforementioned epoxy compound (B) is 0.10% by mass or more based on the total amount of the aforementioned refrigeration oil composition.

[0362] [4] The refrigeration oil composition according to any one of [1] to [3], wherein the aforementioned epoxide compound (B) is selected from one or more of epoxidized fatty acid esters, epoxidized lipocyclic carboxylic esters and epoxidized vegetable oils.

[0363] [5] The refrigeration oil composition according to [4], wherein the aforementioned epoxidized fatty acid ester is represented by the following general formula (1-1).

[0364] [Chemistry 17]

[0365]

[0366] (In equation (1-1), R) 1 R is a hydrocarbon group with 4 to 20 carbon atoms. 2 For hydrocarbon groups with 1 to 10 carbon atoms, p is an integer from 1 to 3, n is an integer from 0 to 12, and m is an integer from 1 to 3. When m is 2 or more, the structures within the multiple brackets can be chosen to be the same or different from each other.

[0367] [6] The refrigeration oil composition according to [4], wherein the aforementioned epoxidized cyclocarboxylic acid ester is represented by the following general formula (1-2).

[0368] [Chemistry 18]

[0369]

[0370] (In equation (1-2), R) 3 and R 4 Each group is an independent hydrocarbon group with 4 to 20 carbon atoms.

[0371] [7] The refrigeration oil composition according to [4], wherein the aforementioned epoxidized vegetable oil is selected from one or more of epoxidized soybean oil, epoxidized linseed oil, epoxidized rice bran oil and epoxidized cottonseed oil.

[0372] [8] The refrigeration oil composition according to any one of [1] to [7] further contains a glycidyl ether compound (C).

[0373] [9] The refrigeration oil composition according to [8], wherein the content ratio of the aforementioned epoxy compound (B) to the aforementioned glycidyl ether compound (C) [(B) / (C)] is 0.050 or more and 5.0 or less by mass.

[0374]

[10] The refrigeration oil composition according to any one of [1] to [9] further contains one or more additives selected from antioxidants, stabilizers, extreme pressure agents and defoamers.

[0375]

[11] The refrigeration oil composition according to any one of [1] to

[10] , wherein the aforementioned unsaturated fluorinated hydrocarbon compound comprises one or more selected from R1234ze, R1234yf and R1234ye.

[0376]

[12] The refrigeration oil composition according to any one of [1] to

[11] , wherein the aforementioned refrigerant consists only of the aforementioned unsaturated fluorinated hydrocarbon compounds.

[0377]

[13] A refrigeration machine mixture comprising a refrigerant and a refrigeration oil composition as described in any one of [1] to

[12] , wherein the refrigerant comprises one or more unsaturated fluorinated hydrocarbon compounds selected from compounds represented by the following general formula (1).

[0378] C x F y H z ···(1)

[0379] [In the aforementioned general formula (1), x is an integer from 2 to 6, y is an integer from 1 to 11, and z is an integer from 1 to 11, and the molecule has more than one carbon-carbon unsaturated bond.]

[0380]

[14] A method for manufacturing a refrigeration oil composition, which is a method for manufacturing a refrigeration oil composition for a refrigerant, said refrigerant comprising one or more unsaturated fluorinated hydrocarbon compounds selected from compounds represented by the following general formula (1).

[0381] Cx F y H z ···(1)

[0382] [In the aforementioned general formula (1), x is an integer from 2 to 6, y is an integer from 1 to 11, and z is an integer from 1 to 11, and the molecule has more than one carbon-carbon unsaturated bond.]

[0383] The manufacturing method includes a step of mixing an epoxy compound (B) with a base oil (A) selected from polyalkylene glycols, polyvinyl ethers, copolymers of poly(oxy)alkylene glycols or their monoethers with polyvinyl ethers, and polyol esters.

[0384] The aforementioned epoxy compound (B) satisfies the following conditions (B1) and (B2).

[0385] (B1) The molecule has at least one divalent group as shown in formula (1) below.

[0386] [Chemistry 19]

[0387]

[0388] (B2) The molecule has at least one ester group.

[0389] Example

[0390] The present invention will be specifically described using the following embodiments. However, the present invention is not limited to the following embodiments.

[0391] [Methods for determining various physical properties]

[0392] The properties of the raw materials used in each embodiment and each comparative example, as well as the properties of the refrigeration oil compositions in each embodiment and each comparative example, were determined according to the following procedures.

[0393] (1) Kinematic viscosity at 100℃

[0394] The kinematic viscosity of base oil (A) at 100°C was determined according to JIS K2283:2000.

[0395] (2) Hydroxyl value

[0396] The determination was performed according to JIS K0070:1992 for base oil (A) using neutralization titration.

[0397] (3) Number-average molecular weight (Mn)

[0398] The number-average molecular weight (Mn) of the base oil (A) was determined using gel permeation chromatography (GPC).

[0399] Regarding GPC, the column used was a column obtained by sequentially connecting two "TSKgel Super Multipore HZ-M" columns manufactured by Tosoh Corporation. Tetrahydrofuran was used as the eluent, and a refractive index detector (RI detector) was used for measurement. Polystyrene was used as the standard sample to determine the number-average molecular weight (Mn).

[0400] [Details of the components used in the preparation of refrigeration oil compositions]

[0401] Details of the components used to prepare the refrigeration oil composition are as follows.

[0402] <Base Oil (A)>

[0403] • "PVE1": Polyvinyl ether (a copolymer of polyethyl vinyl ether (PEVE) and polyisobutyl vinyl ether (PIBVE), copolymer ratio (PEVE / PIBVE) = 9 / 1 (molar ratio)), kinematic viscosity at 100°C = 8.4 mm. 2 / s, hydroxyl value = 1 mgKOH / g, number-average molecular weight = 940

[0404] • “PVE2”: Polyethyl vinyl ether, kinematic viscosity at 100°C = 8.6 mm 2 / s, hydroxyl value = 1 mgKOH / g, number-average molecular weight = 1100

[0405] • "PAG": Polyoxypropylene glycol, kinematic viscosity at 100°C = 10.3 mm 2 / s, hydroxyl value = 6 mg KOH / g, number-average molecular weight = 1,020

[0406] • "ECP": Copolymer of polypropylene glycol (PPG) and polyethyl vinyl ether (PEV) (PPG / PEV = 5 / 5 (molar ratio)), kinematic viscosity at 100°C = 10.5 mm. 2 / s, hydroxyl value = 1 mgKOH / g, number-average molecular weight = 870

[0407] • "POE": An ester of pentaerythritol with a mixture of octanoic acid (C8 acid) and nonanoic acid (C9 acid) (C8 acid / C9 acid = 1 / 1.1 (molar ratio)), kinematic viscosity at 100°C = 8.5 mm. 2 / s, hydroxyl value = 1 mgKOH / g, number-average molecular weight = 670

[0408] <Epoxy Compounds (B)>

[0409] • "Epoxide Compound 1": Epoxidized soybean oil as shown in the following formula, molecular weight: 933, Sansocer E-2000H (manufactured by Shin Nippon Rikka Co., Ltd.)

[0410] [Chemistry 20]

[0411]

[0412] • "Epoxy Compound 2": Epoxidized soybean oil, molecular weight: 947, New Cyclone 510R (manufactured by Nippon Oil Company)

[0413] [Chemistry 21]

[0414]

[0415] • "Epoxy Compound 3": Epoxidized soybean oil, Kemi-Syzer SE-100 (manufactured by Sanwa Synthetic Chemical Co., Ltd.)

[0416] • "Epoxy Compound 4": Epoxidized linseed oil, ADEKA Silica O-180A (manufactured by ADEKA Corporation)

[0417] • "Epoxy Compound 5": Epoxidized rice oil ((C 17 H 33 OCO)3O3C3H5), molecular weight: 933, Kemi-Syzer SE-80 (manufactured by Sanwa Synthetic Chemicals Co., Ltd.)

[0418] • "Epoxy Compound 6": An epoxidized fatty acid ester as shown in the following formula, molecular weight: 411, Sansocer E-6000 (manufactured by Shin Nippon Rikka Co., Ltd.)

[0419] [Chemistry 22]

[0420]

[0421] • "Epoxy Compound 7": An epoxide cyclic carboxylic acid ester as shown in the following formula, molecular weight: 411, サンソサイザーE-PS (manufactured by Shin Nippon Rika Co., Ltd.)

[0422] [Chemistry 23]

[0423]

[0424] • "Epoxy Compound 8": Epoxidized fatty acid ester (C 17 H 33 OCOOC8H 17 ), molecular weight: 411, ケミサイザーT-5000 (manufactured by Sanwa Synthetic Chemical Co., Ltd.)

[0425] • "Epoxy Compound 9": Epoxidized fatty acid ester (C 22 H 42 O3), molecular weight: 355, Kemi-Syzer T-3000N (manufactured by Sanwa Synthetic Chemicals Co., Ltd.)

[0426] • "Epoxy Compound 10": Epoxidized fatty acid ester (C 22 H 44 O4), molecular weight: 371, Kemi-Syzer LE-3000 (manufactured by Sanwa Synthetic Chemicals Co., Ltd.)

[0427] • "Epoxy Compound 11": Epoxidized fatty acid ester (C 19 H 36 O3), molecular weight: 312, ケミサイザーT-2000 (manufactured by Sanwa Synthetic Chemical Co., Ltd.)

[0428] <Epoxidized Alpha-Olefins>

[0429] • "Epoxidized α-olefin 1": A mixture of C12 and C14 epoxidized α-olefins

[0430] • "Epoxidized α-olefin 2": C16 epoxidized α-olefin

[0431] <Glycidyl ether compound (C)>

[0432] 2-Ethylhexyl glycidyl ether is used as the glycidyl ether compound (C).

[0433] <Other Additives>

[0434] • Antioxidant: Di-tert-butyl-p-cresol (DBPC)

[0435] Stabilizer: β-pinene

[0436] Other: Extreme pressure agents (tricresyl phosphate), silicone-based defoamers

[0437] [Examples 1-34, Comparative Examples 1-16]

[0438] The above-mentioned components were mixed to prepare the refrigeration oil compositions with the compositions shown in Tables 1 to 3, and the autoclave tests described below were performed.

[0439] It should be noted that the numerical units for the blending composition in Tables 1 to 3 are "mass %".

[0440] <Autoclave Test>

[0441] The procedure was performed according to Annex C of JIS K2211:2009. Specifically, a refrigeration mixture (with a moisture content of 2,000 ppm) obtained by mixing 30 g of the refrigeration oil compositions of Examples 1-34 and Comparative Examples 1-16 with 30 g of R1234yf, and a metal catalyst composed of iron, copper, and aluminum were sealed into a 200 mL autoclave. Then, after evacuation, the mixture was kept at 175°C for 336 hours, and the appearance of the oil and catalyst (presence or absence of deterioration) and the presence or absence of precipitates (if precipitates were present, their color was observed visually) were observed.

[0442] It should be noted that the appearance of the oil is evaluated according to the ASTM color standard. Samples with a value below 0.5 (L0.5) are judged to have a good appearance, while samples with a value above 0.5 (L1.0, L1.5, etc.) are judged to have a poor appearance.

[0443] In addition, the acid value and fluorine content of the refrigeration oil composition were evaluated using the methods described below.

[0444] (Evaluation of the acid value of the refrigeration oil composition)

[0445] The determination was performed according to JIS K2501:2003 using the indicator photometric titration method (refer to Annex 1 of the JIS standard mentioned above).

[0446] (Evaluation of the fluoride content in refrigeration oil compositions)

[0447] The fluoride content in the refrigeration oil composition is determined as follows: The refrigerant is separated from the refrigeration oil mixture after autoclave testing, and the fluoride ions (F ions) in the refrigeration oil composition are detected according to JIS K 0127:2013 (General Rules for Ion Chromatography). - ).

[0448] [Table 1]

[0449]

[0450] [Table 2]

[0451]

[0452] [Table 3]

[0453]

[0454] [Table 4]

[0455]

[0456] Based on Tables 1-3, the following conclusions can be drawn.

[0457] It can be seen that the refrigeration oil compositions of Examples 1 to 34 containing epoxy compound (B) have an excellent effect on suppressing the increase of acid value of the refrigeration oil compositions after the autoclave test, and the amount of fluorine in the refrigeration oil compositions after the test is also low.

[0458] In particular, it can be seen that, compared with the refrigeration oil composition of Comparative Example 3 which contains 3.00% by mass of epoxidized α-olefin, the refrigeration oil compositions of Examples 3, 6, 9, 13 and 14 which contain the same amount of epoxy compound (B) are extremely effective in suppressing the increase of acid value of the refrigeration oil compositions after autoclave testing, and the amount of fluorine in the refrigeration oil compositions after testing is also low.

[0459] Based on the above results, it can be inferred that: by inhibiting the decomposition of refrigerant through epoxy compounds (B), and capturing the fluorine (F) dissolved into the refrigeration oil composition due to refrigerant decomposition, - ), reducing the amount of fluorine (F) in the refrigeration oil composition. - The amount of [amount] helps to suppress the rise in acid value of the refrigeration oil composition.

Claims

1. A refrigerant oil composition for a refrigerant comprising one or more unsaturated fluorinated hydrocarbon compounds selected from compounds represented by the following general formula (1'), x is an integer of 2 to 6, y is an integer of 1 to 11, and z is an integer of 1 to 11, and the compound has one or more carbon-carbon unsaturated bonds in the molecule, C x F y H z ... (1') the refrigerant oil composition comprising an epoxy compound (B), a base oil (A) selected from polyalkylene glycols, polyvinyl ethers, copolymers of poly(oxy)alkylene glycol or monoether thereof and polyvinyl ether, and polyol esters, and a glycidyl ether compound (C), the epoxy compound (B) satisfies the following conditions (B1) and (B2), and the epoxy compound (B) is one or more selected from epoxidized fatty acid esters represented by the following general formula (1-1), epoxidized alicyclic carboxylic acid esters represented by the following general formula (1-2), and epoxidized vegetable oils selected from one or more of epoxidized soybean oil, epoxidized linseed oil, epoxidized rice bran oil, and epoxidized cottonseed oil, (B1) has at least one divalent group represented by the following formula (1) in the molecule, (B2) has at least one ester group in the molecule, the content of the base oil (A) is 85.0 mass% or more and 99.0 mass% or less based on the total amount of the refrigerant oil composition. In formula (1-1), R 1 is a hydrocarbon group having 4 to 20 carbon atoms, R 2 is a hydrocarbon group having 1 to 10 carbon atoms, p is an integer of 1 to 3, n is an integer of 0 to 12, m is an integer of 1 to 3, and when m is 2 or more, the structures within the brackets present are optionally the same or different from each other, In formula (1-2), R 3 and R 4 each independently is a hydrocarbon group having 4 to 20 carbon atoms.

2. The refrigerant oil composition according to claim 1, wherein, the polyalkylene glycols are polymers (A-1) represented by the following general formula (A-1), 3. The refrigerant oil composition according to claim 1 or 2, wherein, the polymers (A-1) are one or more selected from polyoxypropylene glycol dimethyl ether represented by the following general formula (A-1-i), polyoxyethylene polyoxypropylene glycol dimethyl ether represented by the following general formula (A-1-ii), polyoxypropylene glycol monobutyl ether represented by the following general formula (A-1-iii), polyoxypropylene glycol monomethyl ether represented by the following general formula (A-1-iv), and polyoxypropylene glycol diacetate, R 13a -[(OR 14a )p-OR 15a ]q (A-1) In General Formula (A-1) above, 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-forming atoms, R 14a represents an alkylene group having 2 to 4 carbon atoms, R 15a represents 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-forming atoms.

4. The refrigerant oil composition according to claim 3, wherein, in formula (A-1-i), p1 represents one or more numbers, in formula (A-1-ii), p2 and p3 each independently represent one or more numbers, in formula (A-1-iii), p4 represents one or more numbers, in formula (A-1-iv), p5 represents one or more numbers. the polyvinyl ethers are polymers having one or more structural units derived from a vinyl ether and having an alkyl group having 1 to 4 carbon atoms in a side chain.

5. The refrigerant oil composition according to claim 1 or 2, wherein, the polyvinyl ethers are polymers (A-2) having one or more structural units represented by the following general formula (A-2), 6. The refrigerant oil composition according to claim 5, wherein, one end portion of the polymers (A-2) is a group represented by the following general formula (A-2-i), In formula (A-2), R 1a , R 2a , and R 3a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R 4a represents a divalent hydrocarbon group having 2 to 10 carbon atoms, R 5a represents a hydrocarbon group having 1 to 10 carbon atoms, and r is the number of repeating units of OR 4a , and is 0 to 10. In the case where a plurality of OR 4a are present in the structural unit represented by the above general formula (A-2), the plurality of OR 4a may be the same or different from each other.

7. The refrigerant oil composition according to claim 6, wherein, one end portion of the polymers (A-2) is a group represented by the above general formula (A-2-i), and the other end portion is any one of a group represented by the above general formula (A-2-i), a group represented by the following general formula (A-2-ii), a group represented by the following general formula (A-2-iii), and a group having an ethylenic unsaturated bond, In formula (A-2-i), * indicates the position where a carbon atom in the structural unit shown in the general formula (A-2) is bonded, and R 6a R 7a and R 8a Each can independently represent a hydrogen atom or a hydrocarbon group with 1 to 8 carbon atoms, R 9a R1 represents a divalent hydrocarbon group with 2 to 10 carbon atoms, where R1 is OR 9a The number of repeating units is 0 to 10, and there are multiple ORs in the structural unit shown in the above general formula (A-2-i). 9a In the case of multiple ORs 9a They can be the same or different, R 10a Represents hydrocarbon groups with 1 to 10 carbon atoms.

8. The refrigerant oil composition according to claim 7, wherein, the copolymers of poly(oxy)alkylene glycol or monoether thereof and polyvinyl ether are copolymers having structural units derived from poly(oxy)alkylene glycol or monoether thereof and structural units derived from polyvinyl ether. In formulae (A-2-ii) and (A-2-iii), R 6a , R 7a , R 8a , R 9a , R 10a and r1 are the same as R 6a , R 7a , R 8a , R 9a , R 10a , and r1 in the above general formula (A-2-i), In formula (A-2-ii), R 11a , R 12a and r2 are the same as the definitions of R 9a , R 10a and r1 in the above general formula (A-2-i), respectively.

9. The refrigerant oil composition according to claim 1 or 2, wherein, ​ 10. The refrigerant oil composition according to claim 1 or 2, wherein, The poly(oxy)alkylene glycol or the mono-ether thereof and polyvinyl ether copolymer is a copolymer represented by general formula (A-3-i) or (A-3-ii), In General Formula (A-3-i) and (A-3-ii), R 1c , R 2c , and R 3c each independently represent a hydrogen atom or a hydrocarbon group having 1 or more and 8 or less carbon atoms, R 4c each independently represents a hydrocarbon group having 1 to 10 carbon atoms, R 5c each independently represents an alkylene group having 2 to 4 carbon atoms, R 6c each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 ring-forming carbon atoms, a substituted or unsubstituted aromatic group having 6 to 24 ring-forming carbon atoms, an acyl group having 2 to 20 carbon atoms, or an oxygen-containing hydrocarbon group having 2 to 50 carbon atoms, Further, there are multiple R 1c , R 2c , R 3c , R 4c , R 5c , and R 6c , each of which can be the same or different. X C and Y C each independently represents a hydrogen atom, a hydroxyl group or a hydrocarbon group having 1 to 20 carbon atoms, v in general formulae (A-3-i) and (A-3-ii) is OR 5c The average of the number of units represented by 1 or more, there are multiple OR 5c When multiple OR 5c may be the same, respectively, can be different, respectively, In general formula (A-3-i), u represents a number of 0 or more, In general formula (A-3-ii), x and y each independently represent a number of 1 or more.

11. The refrigerant oil composition according to claim 1 or 2, wherein, The polyol ester contains an ester of a diol or a polyhydric compound having a hydroxyl number of 3 to 20 and a fatty acid having a carbon number of 3 to 20.

12. The refrigerant oil composition of claim 11, wherein, The polyol ester contains an ester of a diol or a polyhydric compound having a hydroxyl number of 3 to 20 and a fatty acid having a carbon number of 3 to 20.

13. The refrigerant oil composition of claim 11, wherein, The polyhydric compound is one or more selected from the group consisting of polyhydric alcohols, saccharides, partial etherates of the polyhydric alcohols and the saccharides, and methylglucosides of the polyhydric alcohols and the saccharides.

14. The refrigerant oil composition of claim 13, wherein, The polyhydric alcohols are one or more selected from the group consisting of trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, polyglycerol, 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, and mannitol.

15. The refrigerant oil composition of claim 11, wherein, The fatty acids are one or more selected from the group consisting of isobutyric acid, propionic acid, butyric acid, valeric acid, caproic 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, eicosanoic acid, and oleic acid.

16. The refrigerant oil composition of claim 11, wherein, The polyol ester contains an ester of a hindered alcohol.

17. The refrigerant oil composition of claim 16, wherein, The hindered alcohol is one or more selected from the group consisting of neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di(trimethylolpropane), tri(trimethylolpropane), pentaerythritol, dipentaerythritol, and tripentaerythritol.

18. The refrigerant oil composition of claim 11, wherein, The polyol ester is a diester of neopentyl glycol and one or two or more fatty acids selected from the group consisting of isobutyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, isovaleric acid, 2-methylhexanoic acid, 2-ethylvaleric acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; A triester of trimethylolethane and one or two or more fatty acids selected from the group consisting of isobutyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, isovaleric acid, 2-methylhexanoic acid, 2-ethylvaleric acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; A triester of trimethylolpropane and one or two or more fatty acids selected from the group consisting of isobutyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, isovaleric acid, 2-methylhexanoic acid, 2-ethylvaleric acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; A triester of trimethylolbutane and one or two or more fatty acids selected from the group consisting of isobutyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, isovaleric acid, 2-methylhexanoic acid, 2-ethylvaleric acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid; or tetraesters of pentaerythritol with one or two or more fatty acids selected from the group consisting of isobutyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oleic acid, isovaleric acid, 2-methylhexanoic acid, 2-ethylvaleric acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid.

19. The refrigerant oil composition according to claim 1 or 2, wherein, The base oil (A) consists of the polyalkylene glycols; the polyvinyl ethers; the poly(oxy)alkylene glycol or its monoether with a polyvinyl ether; or the polyol esters.

20. The refrigerant oil composition according to claim 1 or 2, wherein, The base oil (A) has a kinematic viscosity at 100°C of 3 mm 2 / s or more and 50 mm 2 / s or less.

21. The refrigerant oil composition according to claim 1 or 2, wherein, The base oil (A) has a hydroxyl value of 0.5 mgKOH / g or more and 30 mgKOH / g or less.

22. The refrigerant oil composition according to claim 1 or 2, wherein, The base oil (A) has a number average molecular weight of 300 or more and 10,000 or less.

23. The refrigerant oil composition according to claim 1 or 2, wherein, The epoxy compound (B) has a molecular weight of 300 or more.

24. The refrigerant oil composition according to claim 1 or 2, wherein, The content of the epoxy compound (B) is 0.10% by mass or more, based on the total amount of the refrigerant oil composition.

25. The refrigerant oil composition of claim 1, wherein, The epoxydized fatty acid ester is a compound obtained by epoxydizing an ester of a fatty acid having 8 to 30 carbon atoms and an alcohol having 1 to 8 carbon atoms, a phenol, or an alkylphenol having 7 to 14 carbon atoms.

26. The refrigerant oil composition according to claim 1 or 2, wherein, The epoxydized fatty acid ester is a compound obtained by epoxydizing a butyl ester, a hexyl ester, a 2-ethylhexyl ester, a benzyl ester, a cyclohexyl ester, a methoxyethyl ester, an octyl ester, a phenyl ester, or a butylphenyl ester of linoleic acid, oleic acid, palmitic acid, linolenic acid, or stearic acid.

27. The refrigerant oil composition of claim 1, wherein, The epoxydized alicyclic carboxylic acid ester includes 4,5-epoxycyclohexane-1,2-dicarboxylic acid bis(2-ethylhexyl) ester.

28. The refrigerant oil composition of claim 1, wherein, The epoxydized vegetable oil includes a glyceride having one or more groups represented by the following general formula (1-3), In formula (1-3), R 1 is a hydrocarbon group having 4 to 20 carbon atoms, p is an integer of 1 to 3, n is an integer of 0 to 12, m is an integer of 1 to 3, and when m is 2 or more, the structures within the brackets present, are optionally the same or different from each other.

29. The refrigerant oil composition of claim 1, wherein, The glycidyl ether compound (C) includes an aliphatic monoalcohol or an aliphatic polyalcohol having 3 to 30 carbon atoms; or a glycidyl ether derived from an aromatic compound containing one or more hydroxyl groups.

30. The refrigeration compressor oil composition of claim 1 or 29, wherein, The glycidyl ether compound (C) includes one or more selected from the group consisting of a phenyl glycidyl ether, an alkyl glycidyl ether, and an alkylene glycol glycidyl ether.

31. The refrigerant oil composition of claim 30, wherein, The alkyl glycidyl ether includes one or more selected from the group consisting of a 2-ethylhexyl glycidyl ether, an isononyl glycidyl ether, a decyl glycidyl ether, a lauryl glycidyl ether, and a myristyl glycidyl ether.

32. The refrigeration oil composition of claim 1 or 29, wherein, The content of the glycidyl ether compound (C) is 0.10 to 10.00% by mass, based on the total amount of the refrigerant oil composition.

33. The refrigeration oil composition of claim 1 or 29, wherein, The content ratio (B) / (C) of the epoxy compound (B) to the glycidyl ether compound (C) is 0.050 or more and 5.0 or less, in terms of mass ratio.

34. The refrigerant oil composition according to claim 1 or 2, further containing one or more additives selected from the group consisting of an antioxidant, a stabilizer, an extreme pressure agent, and an antifoaming agent.

35. The refrigerant oil composition of claim 34, wherein, The antioxidant includes one or more selected from the group consisting of a phenol-based antioxidant and an amine-based antioxidant.

36. The refrigeration compressor oil composition of claim 34, wherein, The antioxidant includes one or more selected from the group consisting of 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-ethylphenol, and 2,2'-methylenebis(4-methyl-6-tert-butylphenol).

37. The refrigerant oil composition of claim 34, wherein, The content of the antioxidant is 0.01% by mass or more and 5% by mass or less, based on the total amount of the refrigerant oil composition.

38. The refrigerant oil composition of claim 34, wherein, The stabilizer contains one or more selected from the group consisting of aliphatic unsaturated compounds and terpenes having double bonds.

39. The refrigerant oil composition of claim 38, wherein, The terpenes having double bonds contain one or more selected from the group consisting of α-pinene, β-pinene, α-farnesene and β-farnesene.

40. The refrigerant oil composition of claim 34, wherein, The extreme pressure agent contains one or more selected from the group consisting of phosphorus-based extreme pressure agents, carboxylic acid metal salts and sulfur-based extreme pressure agents.

41. The refrigerant oil composition of claim 40, wherein, The phosphorus-based extreme pressure agent contains one or more selected from the group consisting of phosphate esters, acid phosphate esters, phosphite esters, acid phosphite esters, amine salts of phosphate esters, amine salts of acid phosphate esters, amine salts of phosphite esters and amine salts of acid phosphite esters.

42. The refrigerant oil composition of claim 40 or 41, wherein, The phosphorus-based extreme pressure agent contains one or more selected from the group consisting of tricresyl phosphate, trithiophene phosphate, tris(nonylphenyl) phosphite, diotyl hydrogen phosphite and 2-ethylhexyl diphenyl phosphite.

43. The refrigerant oil composition of claim 34, wherein, The defoaming agent contains one or more organic silicon-based defoaming agents selected from the group consisting of silicone oils and fluorinated silicone oils.

44. The refrigerant oil composition of claim 1 or 2, wherein, The unsaturated fluorinated hydrocarbon compound contains one or more selected from the group consisting of 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene and 1,2,3,3-tetrafluoropropene.

45. The refrigerant oil composition according to claim 1 or 2, wherein, The content of the unsaturated fluorinated hydrocarbon compound in the refrigerant is 50 to 100 mass% based on the total amount of the refrigerant.

46. The refrigerant oil composition of claim 1 or 2, wherein, The refrigerant consists only of the unsaturated fluorinated hydrocarbon compound.

47. A mixed composition for a refrigerator, which contains a refrigerant and the refrigerator oil composition according to any one of claims 1 to 46, the refrigerant containing one or more unsaturated fluorinated hydrocarbon compounds selected from the group consisting of compounds represented by the following general formula (1'), x is an integer of 2 to 6, y is an integer of 1 to 11, and z is an integer of 1 to 11, and the molecule has one or more carbon-carbon unsaturated bonds. C x F y H z ...(1') In the general formula (1'), x is an integer of 2 to 6, y is an integer of 1 to 11, and z is an integer of 1 to 11, and the molecule has one or more carbon-carbon unsaturated bonds.

48. The mixed composition for a refrigerator according to claim 47, wherein The amounts of the refrigerant and the refrigerator oil composition are such that the mass ratio of the refrigerator oil composition to the refrigerant, i.e., refrigerator oil composition / refrigerant, is 1 / 99 to 90 / 10.

49. A method for producing a refrigerator oil composition for a refrigerant containing one or more unsaturated fluorinated hydrocarbon compounds selected from the group consisting of compounds represented by the following general formula (1'), x is an integer of 2 to 6, y is an integer of 1 to 11, and z is an integer of 1 to 11, and the molecule has one or more carbon-carbon unsaturated bonds, C x F y H z ...(1') In the general formula (1'), x is an integer of 2 to 6, y is an integer of 1 to 11, and z is an integer of 1 to 11, and the molecule has one or more carbon-carbon unsaturated bonds, The production method includes: mixing an epoxy compound (B) with a base oil (A) selected from the group consisting of polyalkylene glycols, polyvinyl ethers, copolymers of poly(oxy)alkylene glycol or monoether thereof and polyvinyl ether, and polyol esters, and a glycidyl ether compound (C), The epoxy compound (B) satisfies the following conditions (B1) and (B2), and is one or more selected from the group consisting of epoxidized fatty acid esters represented by the following general formula (1-1), epoxidized alicyclic carboxylic acid esters represented by the following general formula (1-2) and epoxidized vegetable oils selected from the group consisting of epoxidized soybean oil, epoxidized linseed oil, epoxidized rice bran oil and epoxidized cottonseed oil, (B1) has at least one divalent group represented by the following formula (1) in the molecule, (B1) has at least one divalent group represented by the following formula (1) in the molecule, (B2) at least one ester group in the molecule, (B2) at least one ester group in the molecule, (B2) at In formula (1-1), R 1 is a hydrocarbon group having 4 to 20 carbon atoms, R 2 is a hydrocarbon group having 1 to 10 carbon atoms, p is an integer of 1 to 3, n is an integer of 0 to 12, m is an integer of 1 to 3, and when m is 2 or more, the structures within the brackets present are optionally the same or different from each other, In formula (1-2), R 3 and R 4 each independently is a hydrocarbon group having 4 to 20 carbon atoms.

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