JP5196823B2 - Refrigerator oil and working fluid composition for refrigerator - Google Patents

Description

  The present invention relates to a refrigerator oil and a working fluid composition for a refrigerator.

  Due to the problem of ozone layer destruction in recent years, CFC (chlorofluorocarbon) and HCFC (hydrochlorofluorocarbon), which have been used as refrigerants in conventional refrigeration and air-conditioning equipment, are subject to regulation, and HFC (hydrofluorocarbon) as a refrigerant instead. It is used.

As refrigerating machine oil for HFC refrigerant, polyalkylene glycol (refer to Patent Document 1), ester (refer to Patent Document 2), carbonate ester (refer to Patent Document 3), polyvinyl ether (compatible with HFC refrigerant) There are alkylbenzenes (see Patent Documents 5 and 6) and the like that are incompatible with the HFC refrigerant, such as Patent Document 4). In particular, in the field of car air conditioners and the like, practical application has been made by a combination of HFC-134a and the above oxygen-containing oil.
Japanese Patent Laid-Open No. 02-242888 Japanese Patent Laid-Open No. 03-200895 Japanese Patent Laid-Open No. 03-217495 Japanese Patent Laid-Open No. 06-128578 Japanese Patent Laid-Open No. 08-027478 Japanese Patent Laid-Open No. 08-027479

  In recent years, in addition to the problem of ozone layer destruction, the problem of global warming has become more serious, and a refrigerant with a low global warming potential has been demanded. Although HFC-134a has an ozone depletion potential (ODP) of 0, the global warming potential (GWP: Global. Warming Potential) is as high as 1,300.

  Then, although examination of the alternative refrigerant | coolant of HFC-134a is advanced, selecting the optimal refrigerating machine oil for every refrigerant | coolant is understood also from the example of refrigerant | coolant substitution from CFC and HCFC mentioned above to HFC. Not always easy.

  One of the factors that make it difficult to develop refrigerating machine oil due to refrigerant replacement is that refrigerating machine oil requires refrigerant compatibility in addition to basic performance as a lubricating oil.

  That is, in the refrigerant circulation system of the refrigerating and air-conditioning equipment, due to the mechanism, a part of the refrigerating machine oil in the refrigerant compressor is discharged together with the refrigerant to the circulation flow path, so that the amount of refrigerating machine oil in the refrigerant compressor is insufficient. In order to prevent poor lubrication or the like, it is important that the discharged refrigeration oil returns to the refrigerant compressor through the circulation channel (oil returnability).

  For this reason, polyalkylene glycols, esters, carbonates, polyvinyl ethers, and the like are used as refrigerating machine oils for HFC-134a, but the thermal and chemical stability of these oxygenated oils is not always sufficient.

  The present invention has been made in view of such circumstances, and includes a refrigerant having a lower global warming potential than HFC-134a, and achieves both the thermal / chemical stability of refrigerant oil and refrigerant compatibility. It is an object of the present invention to provide a working fluid composition for a refrigerator that can be used.

In order to solve the above problems, the present invention provides at least one aromatic compound selected from alkylbenzene, alkylnaphthalene, alkylbiphenyl and diphenylalkane , a tetrafluoropropene refrigerant and / or a trifluoroiodomethane refrigerant. A working fluid composition for a refrigerator is provided.

  The tetrafluoropropene refrigerant and / or the trifluoroiodomethane refrigerant contained in the working fluid composition for a refrigerator of the present invention has a lower global warming potential than HFC-134a. And, by combining such a refrigerant with an aromatic compound having an alkyl group or an alkylene group bonded to an aromatic ring, it becomes possible to achieve both the thermal and chemical stability of the refrigerating machine oil and the refrigerant compatibility. .

  The “aromatic compound having an alkyl group or an alkylene group bonded to an aromatic ring” according to the present invention includes alkylbenzene, but the working fluid composition for a refrigerator according to the present invention has a compatible system as described above. The fluid composition is fundamentally different from an incompatible fluid composition such as a combination of HFC-134a and alkylbenzene.

  The working fluid composition for a refrigerator of the present invention includes 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2,3,3,3-tetrafluoropropene (HFO-1234yf) as a tetrafluoropropene refrigerant. And at least one selected from 1,2,3,3-tetrafluoropropene (HFO-1225ye).

  According to the present invention, a working fluid composition for a refrigerator that includes a refrigerant having a global warming potential lower than that of HFC-134a and can achieve both the thermal / chemical stability of the refrigerator oil and the refrigerant compatibility. Things are provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  The working fluid composition for a refrigerator of the present invention comprises an aromatic compound having an alkyl group or an alkylene group bonded to an aromatic ring (hereinafter referred to as “the aromatic compound according to the present invention”), a tetrafluoropropene refrigerant, and And / or trifluoroiodomethane refrigerant.

  The aromatic ring of the aromatic compound according to the present invention may be monocyclic or polycyclic, and the ring may be condensed. Although the number of aromatic rings is arbitrary, Preferably it is 1-3, More preferably, it is 1 or 2. Moreover, the number of the alkyl group or alkylene group couple | bonded with the aromatic ring may be 1 or 2 or more, However, Preferably it is 1-4. The alkyl group and the alkylene group may be linear or branched, but the alkyl group is preferably branched from the viewpoint of refrigerant compatibility and stability.

  Specific preferred examples of the aromatic compound according to the present invention include alkylbenzene, alkylnaphthalene, alkylbiphenyl, diphenylalkane and the like.

The alkylbenzene is preferably the following alkylbenzene (A) and / or alkylbenzene (B) from the viewpoint of long-term reliability of the refrigeration system.
Alkylbenzene (A): an alkylbenzene having 1 to 4 alkyl groups having 1 to 19 carbon atoms and having a total carbon number of 9 to 19 (more preferably an alkyl group having 1 to 15 carbon atoms). 1 to 4 alkylbenzenes having a total carbon number of 9 to 15 alkyl groups)
Alkylbenzene (B): an alkylbenzene having 1 to 4 alkyl groups having 1 to 40 carbon atoms and having a total carbon number of 20 to 40 (more preferably an alkyl group having 1 to 30 carbon atoms). 1 to 4 alkylbenzenes having a total carbon number of 20 to 30 alkyl groups).

  Specific examples of the alkyl group having 1 to 19 carbon atoms that the alkylbenzene (A) has include, for example, a methyl group, an ethyl group, a propyl group (including all isomers), and a butyl group (including all isomers). , Pentyl group (including all isomers), hexyl group (including all isomers), heptyl group (including all isomers), octyl group (including all isomers), nonyl group (all Isomers), decyl groups (including all isomers), undecyl groups (including all isomers), dodecyl groups (including all isomers), tridecyl groups (including all isomers), Tetradecyl group (including all isomers), pentadecyl group (including all isomers), hexadecyl group (including all isomers), heptadecyl group (including all isomers), octade (Including all isomers) group, (including all isomers) nonadecyl group (including all isomers) eicosyl group. The alkyl group may be linear or branched, but is preferably a branched alkyl group from the viewpoint of stability, viscosity characteristics, etc., and particularly from the viewpoint of availability, propylene, Branched alkyl groups derived from olefin oligomers such as butene and isobutylene are more preferred.

  The number of alkyl groups in alkylbenzene (A) is 1 to 4, but from the viewpoint of stability and availability, alkylbenzene having one or two alkyl groups, that is, monoalkylbenzene, dialkylbenzene, or These mixtures are most preferably used.

  The alkylbenzene (A) is not only a single structure alkylbenzene but also 1 to 4 alkyl groups having 1 to 19 carbon atoms, and the total carbon number of the alkyl groups is 9 to 19 As long as the alkylbenzene satisfies the above, it may be a mixture of alkylbenzenes having different structures.

  Specific examples of the alkyl group having 1 to 40 carbon atoms that the alkylbenzene (B) has include a methyl group, an ethyl group, a propyl group (including all isomers), and a butyl group (all isomers). ), Pentyl group (including all isomers), hexyl group (including all isomers), heptyl group (including all isomers), octyl group (including all isomers), nonyl group (including all isomers) All isomers included, decyl group (including all isomers), undecyl group (including all isomers), dodecyl group (including all isomers), tridecyl group (including all isomers) ), Tetradecyl group (including all isomers), pentadecyl group (including all isomers), hexadecyl group (including all isomers), heptadecyl group (including all isomers), o Tadecyl group (including all isomers), nonadecyl group (including all isomers), icosyl group (including all isomers), heicosyl group (including all isomers), docosyl group (all isomers) ), Tricosyl group (including all isomers), tetracosyl group (including all isomers), pentacosyl group (including all isomers), hexacosyl group (including all isomers), heptacosyl Groups (including all isomers), octacosyl groups (including all isomers), nonacosyl groups (including all isomers), triacontyl groups (including all isomers), hentriacontyl groups (all Isomers), dotriacontyl group (including all isomers), tritriacontyl group (including all isomers), tetratriacontyl group (including all isomers) All isomers), pentatriacontyl group (including all isomers), hexatriacontyl group (including all isomers), heptatriacontyl group (including all isomers) , Octatriacontyl group (including all isomers), nonatriacontyl group (including all isomers), tetracontyl group (including all isomers) and the like. The alkyl group may be linear or branched, but is preferably a branched alkyl group from the viewpoint of stability, viscosity characteristics, etc., and particularly from the viewpoint of availability, propylene, Branched alkyl groups derived from olefin oligomers such as butene and isobutylene are more preferred.

  The number of alkyl groups in the alkylbenzene (B) is 1 to 4, but from the viewpoint of stability and availability, alkylbenzene having one or two alkyl groups, that is, monoalkylbenzene, dialkylbenzene, or These mixtures are most preferably used.

  Moreover, as alkylbenzene (B), not only the alkylbenzene of a single structure but 1 to 4 alkyl groups having 1 to 40 carbon atoms and the total number of carbon atoms in the alkyl groups is 20 to 40 As long as the alkylbenzene satisfies the above, it may be a mixture of alkylbenzenes having different structures.

The viscosity of the alkylbenzene contained in the working fluid composition for a refrigerator of the present invention is not particularly limited, but the kinematic viscosity at 40 ° C. is preferably 3 to 100 mm ² / s, more preferably 4 to 80 mm ² / s, and further Preferably it is 5-70 mm < ² > / s.

  The method for producing the alkylbenzene used in the present invention is arbitrary and is not limited at all, but can be generally produced by the synthesis method shown below.

  Specific examples of the aromatic compound used as a raw material include benzene, toluene, xylene, ethylbenzene, methylethylbenzene, diethylbenzene, and mixtures thereof. As the alkylating agent, specifically, for example, a lower monoolefin such as ethylene, propylene, butene, and isobutylene, preferably a linear or branched olefin having 6 to 40 carbon atoms obtained by polymerization of propylene; A linear or branched olefin having 6 to 40 carbon atoms obtained by thermal decomposition of wax, heavy oil, petroleum fraction, polyethylene, polypropylene, etc .; n-paraffin is separated from petroleum fractions such as kerosene, light oil, etc. C6-C40 linear olefin obtained by olefinating with a catalyst; and a mixture thereof can be used.

  In addition, as alkylation catalysts in the alkylation, Friedel-Crafts type catalysts such as aluminum chloride and zinc chloride; acidic catalysts such as sulfuric acid, phosphoric acid, silicotungstic acid, hydrofluoric acid, activated clay; A catalyst is used.

［上記一般式（１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一でも異なっていても良く、それぞれ水素原子又は炭素数１〜４０の炭化水素基を示し、かつＲ^１、Ｒ^２、Ｒ^３及びＲ^４の合計炭素数が１〜４０である。］ As the alkylnaphthalene, a compound represented by the general formula (1) is preferably used.

[In the above general formula (1), R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms, and R ¹ , R ² , R ³ and R ⁴ have 1 to 40 total carbon atoms. ]

R ¹ , R ² , R ³ and R ⁴ in the general formula (1) may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms. Yes. Examples of the hydrocarbon group herein include an alkyl group, an alkenyl group, an aryl group, an alkaryl group, and an aralkyl group.

Specific examples of preferred hydrocarbon groups represented by R ¹ , R ² , R ³ and R ^{4 in the} general formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, A linear or branched butyl group, a linear or branched pentyl group, a linear or branched hexyl group, a linear or branched heptyl group, a linear or branched octyl group, etc. An alkyl group having 1 to 8 carbon atoms; an ethenyl group (vinyl group), a 1-propenyl group, a 2-propenyl group (allyl group), a 1-methylethenyl group (isopropenyl group), a linear or branched butenyl group, An alkenyl group having 2 to 8 carbon atoms such as a linear or branched pentenyl group, a linear or branched hexenyl group, a linear or branched heptenyl group, a linear or branched octenyl group; Phenyl group, tolyl group, xylyl Aryl group or alkaryl group having 6 to 8 carbon atoms such as ethylphenyl group or vinylphenyl group; aralkyl having 7 to 8 carbon atoms such as benzyl group, 1-phenylethyl group or 2-phenylethyl group (phenethyl group) Group; and the like. Furthermore, among these, a C1-C8 alkyl group and a C2-C8 alkenyl group are especially preferable, Most preferably, it is a branched thing among these.

The total carbon number of R ¹ , R ² , R ³ and R ^{4 in} the general formula (1) is 1 to 40, preferably 1 to 10, more preferably 1 to 8. Within this range, R ¹ , R ² , R ³ and R ⁴ may be the same or different. That is, as the alkylnaphthalene of the formula (1), R ¹ , R ² , R ³ and R ⁴ may be all hydrocarbon groups, or at least one of R ¹ , R ² , R ³ and R ^4. One may be a hydrocarbon group and the other may be a hydrogen atom. Among these, from the viewpoint of compatibility with the refrigerant, ¹ to 3 of R ¹ , R ² , R ³ and R ⁴ are hydrocarbon groups and the others are hydrogen atoms, and the total number of carbon atoms is 3 to 8 Are preferred.

When ^{two of} R ¹ , R ² , R ³ and R ⁴ are hydrocarbon groups, the combination is arbitrary, and the same condensed ring (benzene ring) such that R ¹ and R ² are hydrocarbon groups Two hydrocarbon groups may be bonded to each other, and one hydrocarbon group is bonded to each of different condensed rings (benzene rings) such that R ¹ and R ³ are hydrocarbon groups. It may be what you have.

  Specific examples of preferable alkylnaphthalene represented by the general formula (1) include (n-propyl) naphthalene, isopropylnaphthalene, (n-butyl) naphthalene, isobutylnaphthalene, (sec-butyl) naphthalene, (Tert-butyl) naphthalene, (sec-pentyl) naphthalene, (1-ethylpropyl) naphthalene, (tert-pentyl) naphthalene, (1-methylpentyl) naphthalene, (1-ethylbutyl) naphthalene, (1,1-dimethyl) Butyl) naphthalene, (1-ethyl-1-methylpropyl) naphthalene, (1-methylhexyl) naphthalene, (1-ethylpentyl) naphthalene, (1-propylbutyl) naphthalene, (1,1-dimethylpentyl) naphthalene, (1-ethyl-1-methylbutane ) Naphthalene, (1,1-diethylpropyl) naphthalene, (1-methylheptyl) naphthalene, (1-ethylhexyl) naphthalene, (1-propylpentyl) naphthalene, (1,1-dimethylhexyl) naphthalene, (1- Ethyl-1-methylpentyl) naphthalene, (1-methyl-1-propylbutyl) naphthalene, (1,1-diethylbutyl) naphthalene, ethylmethylnaphthalene, diethylnaphthalene, methyl (n-propyl) naphthalene, methylisopropylnaphthalene, Di (n-propyl) naphthalene, diisopropylnaphthalene, (n-butyl) methylnaphthalene, isobutylmethylnaphthalene, (sec-butyl) methylnaphthalene, (tert-butyl) methylnaphthalene, di (n-butyl) naphthalene, diisobutyl Lunaphthalene, di (sec-butyl) naphthalene, di (tert-butyl) naphthalene, trimethylnaphthalene, triethylnaphthalene, ethyldimethylnaphthalene, diethylmethylnaphthalene, dimethyl (n-propyl) naphthalene, dimethylisopropylnaphthalene, methyldi (n-propyl) ) Naphthalene, methyldiisopropylnaphthalene, (n-butyl) dimethylnaphthalene, isobutyldimethylnaphthalene, (sec-butyl) dimethylnaphthalene, (tert-butyl) dimethylnaphthalene, phenylnaphthalene, tolylnaphthalene, xylylnaphthalene, (ethylphenyl) naphthalene , (Vinylphenyl) naphthalene, benzylnaphthalene, phenethylnaphthalene, (1-phenylethyl) naphthalene and the like.

  The alkylnaphthalene is not limited to a compound having a single structure, but may be a mixture of compounds having different structures as long as the general formula (1) is satisfied.

  The production method of the alkylnaphthalene used in the present invention is arbitrary, and can be produced by various known methods. Examples of this include, for example, halogenated hydrocarbons having 1 to 10 carbon atoms, olefins having 2 to 10 carbon atoms, or styrenes having 8 to 10 carbon atoms, sulfuric acid, phosphoric acid, silicotungstic acid, and hydrofluoric acid. And a method of adding to naphthalene in the presence of an acid catalyst such as Friedel Crafts catalyst which is a solid acid substance such as mineral acid such as acid clay, acid clay and activated clay and metal halide such as aluminum chloride and zinc chloride.

The viscosity of the alkylnaphthalene contained in the working fluid composition for a refrigerator of the present invention is not particularly limited, but the kinematic viscosity at 40 ° C. is preferably ² to 500 mm ² / s, more preferably 2.3 to 300 mm ² /. s, more preferably 3 to 200 mm ² / s.

［上記一般式（２）中、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は同一でも異なっていても良く、それぞれ水素原子又は炭素数１〜４０の炭化水素基を示し、かつＲ^５、Ｒ^６、Ｒ^７及びＲ^８の合計炭素数が１〜４０である。］ Moreover, as alkylbiphenyl, the compound represented by General formula (2) is used preferably.

[In the above general formula (2), R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms, and R ⁵ , R ^6, the total number of carbon atoms of ^{R 7} and ^{R 8} are 1-40. ]

R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (2) may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms. Yes. Examples of the hydrocarbon group herein include an alkyl group, an alkenyl group, an aryl group, an alkaryl group, and an aralkyl group.

Specific examples of preferred hydrocarbon groups represented by R ⁵ , R ⁶ , R ⁷ and R ^{8 in the} general formula (2) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, A linear or branched butyl group, a linear or branched pentyl group, a linear or branched hexyl group, a linear or branched heptyl group, a linear or branched octyl group, etc. An alkyl group having 1 to 8 carbon atoms; an ethenyl group (vinyl group), a 1-propenyl group, a 2-propenyl group (allyl group), a 1-methylethenyl group (isopropenyl group), a linear or branched butenyl group, An alkenyl group having 2 to 8 carbon atoms such as a linear or branched pentenyl group, a linear or branched hexenyl group, a linear or branched heptenyl group, a linear or branched octenyl group; Phenyl group, tolyl group, xylyl Aryl group or alkaryl group having 6 to 8 carbon atoms such as ethylphenyl group or vinylphenyl group; aralkyl having 7 to 8 carbon atoms such as benzyl group, 1-phenylethyl group or 2-phenylethyl group (phenethyl group) Group; and the like. Furthermore, among these, a C1-C8 alkyl group and a C2-C8 alkenyl group are especially preferable, Most preferably, it is a branched thing among these.

Formula ^{(2) R 5, R 6} , the total number of carbon atoms of ^{R 7} and ^{R 8} in is from 1 to 10, preferably 1-8. Within this range, R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different. That is, as the alkylbiphenyl of the formula (2), R ⁵ , R ⁶ , R ⁷ and R ⁸ may be all hydrocarbon groups, or at least one of R ⁵ , R ⁶ , R ⁷ and R ^8. One may be a hydrocarbon group and the other may be a hydrogen atom. Among these, from the viewpoint of compatibility with the refrigerant, 1 to ³ of R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrocarbon groups and the others are hydrogen atoms, and the total number of carbon atoms is 3 to 8 Are preferred.

When two of R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrocarbon groups, the combination is arbitrary, and two groups in the same benzene ring such that R ⁵ and R ⁶ are hydrocarbon groups are used. A hydrocarbon group may be bonded, or one hydrocarbon group may be bonded to different benzene rings such that R ⁵ and R ⁷ are hydrocarbon groups.

  Specific examples of preferable alkylbiphenyl represented by the general formula (2) include (n-propyl) biphenyl, isopropylbiphenyl, (n-butyl) biphenyl, isobutylbiphenyl, (sec-butyl) biphenyl, (Tert-butyl) biphenyl, (sec-pentyl) biphenyl, (1-ethylpropyl) biphenyl, (tert-pentyl) biphenyl, (1-methylpentyl) biphenyl, (1-ethylbutyl) biphenyl, (1,1-dimethyl) Butyl) biphenyl, (1-ethyl-1-methylpropyl) biphenyl, (1-methylhexyl) biphenyl, (1-ethylpentyl) biphenyl, (1-propylbutyl) biphenyl, (1,1-dimethylpentyl) biphenyl, (1-ethyl-1-methylbutane Ru) biphenyl, (1,1-diethylpropyl) biphenyl, (1-methylheptyl) biphenyl, (1-ethylhexyl) biphenyl, (1-propylpentyl) biphenyl, (1,1-dimethylhexyl) biphenyl, (1- Ethyl-1-methylpentyl) biphenyl, (1-methyl-1-propylbutyl) biphenyl, (1,1-diethylbutyl) biphenyl, ethylmethylbiphenyl, diethylbiphenyl, methyl (n-propyl) biphenyl, methylisopropylbiphenyl, Di (n-propyl) biphenyl, diisopropylbiphenyl, (n-butyl) methylbiphenyl, isobutylmethylbiphenyl, (sec-butyl) methylbiphenyl, (tert-butyl) methylbiphenyl, di (n-butyl) biphenyl, diisobutene Rubiphenyl, di (sec-butyl) biphenyl, di (tert-butyl) biphenyl, trimethylbiphenyl, triethylbiphenyl, ethyldimethylbiphenyl, diethylmethylbiphenyl, dimethyl (n-propyl) biphenyl, dimethylisopropylbiphenyl, methyldi (n-propyl) ) Biphenyl, methyldiisopropylbiphenyl, (n-butyl) dimethylbiphenyl, isobutyldimethylbiphenyl, (sec-butyl) dimethylbiphenyl, (tert-butyl) dimethylbiphenyl, phenylbiphenyl, tolylbiphenyl, xylylbiphenyl, (ethylphenyl) biphenyl , (Vinylphenyl) biphenyl, benzylbiphenyl, phenethylbiphenyl, (1-phenylethyl) biphenyl, and the like.

  The alkylbiphenyl is not limited to a compound having a single structure, but may be a mixture of compounds having different structures as long as the general formula (2) is satisfied.

  The production method of the alkylbiphenyl used in the present invention is arbitrary, and can be produced by various known methods. Examples of this include, for example, halogenated hydrocarbons having 1 to 10 carbon atoms, olefins having 2 to 10 carbon atoms, or styrenes having 8 to 10 carbon atoms, sulfuric acid, phosphoric acid, silicotungstic acid, and hydrofluoric acid. And a method of adding to biphenyl in the presence of an acid catalyst such as a Friedel Crafts catalyst which is a solid acid substance such as mineral acid such as acid clay, activated clay, and aluminum halide, and metal halide such as zinc chloride.

The viscosity of the alkylbiphenyl contained in the working fluid composition for a refrigerator of the present invention is not particularly limited, but the kinematic viscosity at 40 ° C. is preferably ² to 500 mm ² / s, more preferably 2.5 to 300 mm ² /. s, more preferably 3 to 200 mm ² / s.

［上記一般式（３）中、Ｒ^９は炭素数１〜４０のアルキレン基又はアルケニレン基を示し、Ｒ^１０、Ｒ^１１、Ｒ^１２及びＲ^１３は同一でも異なっていても良く、それぞれ水素原子又は炭素数１〜４０のアルキル基を示す。］ Further, as diphenylalkane, a compound represented by the following general formula (3) is preferably used.

[In the general formula (3), R ⁹ represents an alkylene group or alkenylene group having 1 to 40 carbon atoms, and R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different, and each represents a hydrogen atom or An alkyl group having 1 to 40 carbon atoms is shown. ]

R ⁹ in the general formula (3) represents an alkylene group having 1 to 40 carbon atoms or an alkenylene group.

Specific examples of such R ⁹ include methylene group; methylmethylene group (ethylidene group), alkylene group having 2 carbon atoms such as ethylene group; ethylmethylene group (propylidene group), dimethylmethylene group (isopropylidene group). Group), an alkylene group having 3 carbon atoms such as methylethylene group (propylene group), trimethylene group; n-propylmethylene group (butylidene group), isopropylmethylene group (isobutylidene group), ethylmethylmethylene group, ethylethylene group, 1 , 1-dimethylethylene group, 1,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, tetramethylene group, etc., alkylene group having 4 carbon atoms; n-butylmethylene group (pentylidene group) , Sec-butylmethylene group, isobutylmethylene group (isopentylidene group) Tert-butylmethylene group, n-propylmethylmethylene group, isopropylmethylmethylene group, diethylmethylene group, n-propylethylene group, isopropylethylene group, 1-ethyl-1-methylethylene group, 1-ethyl-2-methyl Ethylene group, trimethylethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 1,3-dimethyltrimethylene group, 2, 5-alkylene alkylene group such as 2-dimethyltrimethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, pentamethylene group; n-pentylmethylene group (hexylidene group), (1-methylbutyl) methylene group , Isopentylmethylene group (isopentylidene group), (1,2-dimethyl (Propyl) methylene group, n-butylmethylmethylene group, isobutylmethylmethylene group, ethyl-n-propylmethylene group, ethylisopropylmethylene group, butylethylene group, isobutylmethylene group, 1- (n-propyl) -1-methylethylene 1- (n-propyl) -2-methylethylene group, 1-isopropyl-1-methylethylene group, 1-isopropyl-2-methylethylene group, 1,2-diethylethylene group, 1-ethyl-2, 2-dimethylethylene group, tetramethylethylene group, 1-n-propyltrimethylene group, 2-n-propyltrimethylene group, 1-isopropyltrimethylene group, 2-isopropyltrimethylene group, 1-ethyl-3-methyl Trimethylene group, 1-ethyl-2-methyltrimethylene group, 1,1,2-trimethyl Limethylene group, 1,1,3-trimethyltrimethylene group, 1-ethyltetramethylene group, 1,1-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 1,4-dimethyltetramethylene group, 2, Alkylene group having 6 carbon atoms such as 2-dimethyltetramethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group and hexamethylene group (including all isomers of alkylene groups having 6 carbon atoms); n- C7 alkylene groups (including isomers of all C7 alkylene groups) such as hexylmethylene group (heptylidene group) and n-pentylethylene group (heptylene group); n-heptylmethylene group (octylidene group) , N-hexylethylene group (octylene group) and other C8 alkylene groups (all isomers of C8 alkylene groups) An alkenylene group having 2 carbon atoms such as vinylidene group, ethenylene group (vinylene group); alkenylene having 3 carbon atoms such as propenylene group, methyleneethylene group, methylethenylene group, 1-propenylidene group and 2-propenylidene group A group having 4 carbons such as a 3-methylpropenylene group (including all isomers of alkenylene groups having 4 carbons); a 1-methyl-3-methylenetrimethylene group, a 3-ethylpropenylene group, Alkenylene groups having 5 carbon atoms such as 1,3-dimethylpropenylene group, 2,3-dimethylpropenylene group, 3,3-dimethylpropenylene group (including all isomers of alkenylene groups having 5 carbon atoms); 1,1-dimethyl-3-methylenetrimethylene group, 1-ethyl-3-methylenetrimethylene group, 3-ethyl-1-methylpropene Alkenylene groups having 6 carbon atoms such as a len group, 3-ethyl-2-methylpropenylene group, 1,3,3-trimethylpropenylene group, 2,3,3-trimethylpropenylene group (all 6 carbon atoms) Including alkenylene group isomers); 7-carbon alkenylene groups such as heptenylene groups (including all 7-carbon alkenylene group isomers); 8-carbon alkenylene groups such as octenylene groups (all carbon numbers) Including isomers of 8 alkenylene groups).

  Among these, an alkylene group having 1 to 6 carbon atoms and an alkenylene group are preferable, and particularly preferable are a methylene group, a methylmethylene group (ethylidene group), an ethylene group, an ethylmethylene group (propylidene group), a dimethylmethylene group ( Isopropylidene group), methylethylene group (propylene group), trimethylene group, etc., alkylene group having 1 to 3 carbon atoms; vinylidene group, ethenylene group (vinylene group), propenylene group, methyleneethylene group, methylethenylene group, 1- Alkenylene group having 2 to 3 carbon atoms such as propenylidene group and 2-propenylidene group; among alkylene groups having 4 to 6 carbon atoms, 1-methyltrimethylene group, 1-ethyltrimethylene group, 1,1-dimethyltrimethylene group Group, 1,2-dimethyltrimethylene group, 1,3-dimethyltrimethylene 1-ethyl-3-methyltrimethylene group, 1-ethyl-2-methyltrimethylene group, 1,1,2-trimethyltrimethylene group, 1,1,3-trimethyltrimethylene group; Among the 6 alkenylene groups, 3-methylpropenylene group, 1-methyl-3-methylenetrimethylene group, 3-ethylpropenylene group, 1,3-dimethylpropenylene group, 2,3-dimethylpropenylene group, 3,3-dimethylpropenylene group, 1,1-dimethyl-3-methylenetrimethylene group, 1-ethyl-3-methylenetrimethylene group, 3-ethyl-1-methylpropenylene group, 3-ethyl-2- And methyl propenylene group, 1,3,3-trimethylpropenylene group, 2,3,3-trimethylpropenylene group; and the like.

Moreover, R < ¹⁰ >, R <^11> , R < ¹² > and R < ¹³ > in General formula (3) may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 40 carbon atoms. Specific examples of the alkyl group having 1 to 40 carbon atoms include a methyl group, an ethyl group, a propyl group (including all isomers), a butyl group (including all isomers), and a pentyl group. (Including all isomers), hexyl group (including all isomers), heptyl group (including all isomers), octyl group (including all isomers), nonyl group (including all isomers) ), Decyl group (including all isomers), undecyl group (including all isomers), dodecyl group (including all isomers), tridecyl group (including all isomers), tetradecyl group (including all isomers) All isomers), pentadecyl group (including all isomers), hexadecyl group (including all isomers), heptadecyl group (including all isomers), octadecyl group (all isomers) ), Nonadecyl group (including all isomers), icosyl group (including all isomers), heicosyl group (including all isomers), docosyl group (including all isomers), tricosyl group (Including all isomers), tetracosyl group (including all isomers), pentacosyl group (including all isomers), hexacosyl group (including all isomers), heptacosyl group (including all isomers) ), Octacosyl group (including all isomers), nonacosyl group (including all isomers), triacontyl group (including all isomers), hentriacontyl group (including all isomers), dotriacontyl Groups (including all isomers), tritriacontyl groups (including all isomers), tetratriacontyl groups (including all isomers), Tatriacontyl group (including all isomers), Hexatriacontyl group (including all isomers), Heptatriacontyl group (including all isomers), Octatriacontyl group (including all isomers) ), Nonatoriacontyl group (including all isomers), tetracontyl group (including all isomers), and the like.

Moreover, the general formula (3) the total number of carbon atoms of ^{R 10,} R ^{11, R 12} and ^{R 13} in is 1 to 40, preferably 1 to 6.

Specific examples of the diphenylalkane represented by the general formula (3) include diphenylmethane, phenyltolylmethane, phenylxylylmethane, ditolylmethane, tolylxylylmethane, dixylylmethane, (ethylphenyl) phenylmethane, and (ethylphenyl). ) Tolylmethane, (ethylmethylphenyl) phenylmethane, (ethylphenyl) xylylmethane, (ethylmethylphenyl) tolylmethane, (ethylmethylphenyl) xylylmethane, (diethylphenyl) phenylmethane, bis (ethylphenyl) methane, (diethylphenyl) tolylmethane , (Ethylmethylphenyl) (ethylphenyl) methane, phenyl (n-propylphenyl) methane, phenyl (isopropylphenyl) methane, (n-propylphenyl) tolyl Tan, (isopropylphenyl) tolylmethane, (methyl-n-propylphenyl) phenylmethane, (methylisopropylphenyl) phenylmethane, (methyl-n-propylphenyl) tolylmethane, (methylisopropylphenyl) tolylmethane, (n-propylphenyl) Xylylmethane, (isopropylphenyl) xylylmethane, (ethyl-n-propylphenyl) phenylmethane, (ethylisopropylphenyl) phenylmethane, (ethylphenyl) (n-propylphenyl) methane, (ethylphenyl) (isopropylphenyl) methane, ( n-butylphenyl) phenylmethane, (isobutylphenyl) phenylmethane, (sec-butylphenyl) phenylmethane, (tert-butylphenyl) phenylmethane, n-butylmethylphenyl) phenylmethane, (isobutylmethylphenyl) phenylmethane, (sec-butylmethylphenyl) phenylmethane, (tert-butylmethylphenyl) phenylmethane, (n-butylphenyl) tolylmethane, (isobutylphenyl) tolylmethane Diphenylalkanes having a methylene group such as (sec-butylphenyl) tolylmethane, (tert-butylphenyl) tolylmethane;
1,1-diphenylethane, 1-phenyl-1-tolylethane, 1-phenyl-1-xylylethane, 1,1-ditolylethane, 1-tolyl-1-xylylethane, 1,1-dixylethane, 1- (ethylphenyl)- 1-phenylethane, 1- (ethylphenyl) -1-tolylethane, 1- (ethylmethylphenyl) -1-phenylethane, 1- (ethylphenyl) -1-xylylethane, 1- (ethylmethylphenyl) -1- Tolylethane, 1- (diethylphenyl) -1-phenylethane, 1,1-bis (ethylphenyl) ethane, 1-phenyl-1- (n-propylphenyl) ethane, 1-phenyl-1- (isopropylphenyl) ethane 1- (n-propylphenyl) -1-tolylethane, 1- (isopropylphenyl) -1 Tolylethane, 1- (methyl-n-propylphenyl) -1-phenylethane, 1- (methylisopropylphenyl) -1-phenylethane, 1- (n-butylphenyl) -1-phenylethane, 1- (isobutylphenyl) ) Diphenylalkane having a methylmethylene group (ethylidene group) such as 1-phenylethane, 1- (sec-butylphenyl) -1-phenylethane, 1- (tert-butylphenyl) -1-phenylethane;
1,2-diphenylethane, 1-phenyl-2-tolylethane, 1-phenyl-2-xylylethane, 1,2-ditolylethane, 1-tolyl-2-xylylethane, 1,2-dixylethane, 1- (ethylphenyl)- 2-phenylethane, 1- (ethylphenyl) -2-tolylethane, 1- (ethylmethylphenyl) -2-phenylethane, 1- (ethylphenyl) -2-xylylethane, 1- (ethylmethylphenyl) -2- Tolylethane, 1- (diethylphenyl) -2-phenylethane, 1,2-bis (ethylphenyl) ethane, 1-phenyl-2- (n-propylphenyl) ethane, 1-phenyl-2- (isopropylphenyl) ethane , 1- (n-propylphenyl) -2-tolylethane, 1- (isopropylphenyl) -2 Tolylethane, 1- (methyl-n-propylphenyl) -2-phenylethane, 1- (methylisopropylphenyl) -2-phenylethane, 1- (n-butylphenyl) -2-phenylethane, 1- (isobutylphenyl) ) Diphenylalkane having an ethylene group such as 2-phenylethane, 1- (sec-butylphenyl) -2-phenylethane, 1- (tert-butylphenyl) -2-phenylethane;
1,1-diphenylpropane, 1-phenyl-1-tolylpropane, 1-phenyl-1-xylylpropane, 1,1-ditolylpropane, 1-tolyl-1-xylylpropane, 1- (ethylphenyl) -1-phenylpropane, 1- (ethylphenyl) -1-tolylpropane, 1- (ethylmethylphenyl) -1-phenylpropane, 1-phenyl-1- (n-propylphenyl) propane, 1-phenyl-1 -Diphenylalkane having an ethylmethylene group (propylidene group) such as-(isopropylphenyl) propane;
1,2-diphenylpropane, 1-phenyl-2-tolylpropane, 1-phenyl-2-xylylpropane, 1,2-ditolylpropane, 1-tolyl-2-xylylpropane, 1- (ethylphenyl) 2-phenylpropane, 1- (ethylphenyl) -2-tolylpropane, 1- (ethylmethylphenyl) -2-phenylpropane, 1-phenyl-2- (n-propylphenyl) propane, 1-phenyl-2 -(Isopropylphenyl) propane, 2-phenyl-1-tolylpropane, 2-phenyl-1-xylylpropane, 2-tolyl-1-xylylpropane, 2- (ethylphenyl) -1-phenylpropane, 2- (Ethylphenyl) -1-tolylpropane, 2- (ethylmethylphenyl) -1-phenylpropane, 2-phenyl-1 (N- propyl) propane, 2-phenyl-1-diphenylalkane having methyl groups such as (isopropylphenyl) propane (propylene group);
1,3-diphenylpropane, 1-phenyl-3-tolylpropane, 1-phenyl-3-xylylpropane, 1,3-ditolylpropane, 1-tolyl-3-xylylpropane, 1- (ethylphenyl) -3-phenylpropane, 1- (ethylphenyl) -3-tolylpropane, 1- (ethylmethylphenyl) -3-phenylpropane, 1-phenyl-3- (n-propylphenyl) propane, 1-phenyl-3 -Diphenylalkane having a trimethylene group such as (isopropylphenyl) propane;
2,2-diphenylpropane, 2-phenyl-2-tolylpropane, 2-phenyl-2-xylylpropane, 2,2-ditolylpropane, 2-tolyl-2-xylylpropane, 2- (ethylphenyl) -2-phenylpropane, 2- (ethylphenyl) -2-tolylpropane, 2- (ethylmethylphenyl) -2-phenylpropane, 2-phenyl-2- (n-propylphenyl) propane, 2-phenyl-2 -Diphenylalkane having a dimethylmethylene group (isopropylidene group) such as-(isopropylphenyl) propane;
1,3-diphenylbutane, 1-phenyl-3-tolylbutane, 1-phenyl-3-xylylbutane, 1- (ethylphenyl) -3-phenylbutane, 1,3-ditolylbutane, 3-phenyl-1-tolylbutane, Diphenylalkanes having a 1-methyltrimethylene group such as 3-phenyl-1-xylylbutane and 3- (ethylphenyl) -1-phenylbutane;
Diphenylalkanes having a tetramethylene group such as 1,4-diphenylbutane, 1-phenyl-4-tolylbutane, 1-phenyl-4-xylylbutane, 1- (ethylphenyl) -3-phenylbutane, 1,4-ditolylbutane ;
1,2-dimethylethylene groups such as 2,3-diphenylbutane, 2-phenyl-3-tolylbutane, 2-phenyl-3-xylylbutane, 2- (ethylphenyl) -3-phenylbutane and 2,3-ditolylbutane Diphenylalkane having
Diphenylalkanes having a 1-ethyltrimethylene group such as 1,3-diphenylpentane, 1-phenyl-3-tolylpentane, 3-phenyl-1-tolylpentane;
Diphenylalkanes having a 1-methyltetramethylene group such as 1,4-diphenylpentane, 1-phenyl-4-tolylpentane, 4-phenyl-1-tolylpentane;
Diphenylalkanes having a pentamethylene group such as 1,5-diphenylpentane, 1-phenyl-5-tolylpentane;
Diphenylalkanes having a 1-ethyl-2-methylethylene group such as 2,3-diphenylpentane, 2-phenyl-3-tolylpentane, 3-phenyl-2-tolylpentane;
Diphenylalkanes having a 1,3-dimethyltrimethylene group such as 2,4-diphenylpentane and 2-phenyl-4-tolylpentane;
Diphenylalkanes having a 1,2-dimethyltrimethylene group such as 2-methyl-1,3-diphenylbutane, 2-methyl-1-phenyl-3-tolylbutane, 2-methyl-3-phenyl-1-tolylbutane;
Diphenylalkanes having a 1,1-dimethyltrimethylene group such as 3-methyl-1,3-diphenylbutane, 3-methyl-1-phenyl-3-tolylbutane, 3-methyl-3-phenyl-1-tolylbutane;
Diphenylalkanes having a 2-methyltetramethylene group such as 2-methyl-1,4-diphenylbutane, 2-methyl-1-phenyl-4-tolylbutane, 2-methyl-4-phenyl-1-tolylbutane;
Diphenylalkanes having a 1,1,2-trimethylethylene group such as 2-methyl-2,3-diphenylbutane, 2-methyl-2-phenyl-3-tolylbutane, 2-methyl-3-phenyl-2-tolylbutane;
1,1-diphenylhexane, 1,2-diphenylhexane, 1,3-diphenylhexane, 1,4-diphenylhexane, 1,5-diphenylhexane, 1,6-diphenylhexane, 2,2-diphenylhexane, 2 , 3-diphenylhexane, 2,4-diphenylhexane, 2,5-diphenylhexane, 3,3-diphenylhexane, 3,4-diphenylhexane, 2-methyl-1,1-diphenylpentane, 4-methyl-1 , 1-diphenylpentane, 2-methyl-1,2-diphenylpentane, 4-methyl-1,2-diphenylpentane, 2-methyl-1,3-diphenylpentane, 4-methyl-1,3-diphenylpentane, 2-methyl-1,4-diphenylpentane, 2-methyl-1,5-diphenylpentane, 4-methyl 2,2-diphenylpentane, 2-methyl-2,3-diphenylpentane, 2-methyl-2,4-diphenylpentane, 2-methyl-3,4-diphenylpentane, 2-methyl-2,5-diphenylpentane 2-methyl-3,3-diphenylpentane, 2,3-dimethyl-1,1-diphenylbutane, 2,3-dimethyl-1,2-diphenylbutane, 2,3-dimethyl-1,3-diphenylbutane 2,3-dimethyl-1,4-diphenylbutane, 2,3-dimethyl-2,3-diphenylbutane, 2-benzyl-1-phenylpentane, 2-benzyl-3-methyl-1-phenylbutane, etc. Diphenylalkane having a C6 alkylene group;
1,1-diphenylethene, 1-phenyl-1-tolylethene, 1-phenyl-1-xylylethene, 1,1-ditolylethene, 1-tolyl-1-xylylethene, 1,1-dixylethene, 1- (ethylphenyl)- 1-phenylethene, 1- (ethylphenyl) -1-tolylethene, 1- (ethylmethylphenyl) -1-phenylethene, 1- (ethylphenyl) -1-xylylethene, 1- (ethylmethylphenyl) -1- Tolylethene, 1- (diethylphenyl) -1-phenylethene, 1,1-bis (ethylphenyl) ethene, 1-phenyl-1- (n-propylphenyl) ethene, 1-phenyl-1- (isopropylphenyl) ethene 1- (n-propylphenyl) -1-tolylethene, 1- (isopropylphenyl) -1 Tolylethene, 1- (methyl-n-propylphenyl) -1-phenylethene, 1- (methylisopropylphenyl) -1-phenylethene, 1- (n-butylphenyl) -1-phenylethene, 1- (isobutylphenyl) ) Diphenylalkane having a vinylidene group such as 1-phenylethene, 1- (sec-butylphenyl) -1-phenylethene, 1- (tert-butylphenyl) -1-phenylethene;
1,2-diphenylethene, 1-phenyl-2-tolylethene, 1-phenyl-2-xylylethene, 1,2-ditolylethene, 1-tolyl-2-xylylethene, 1,2-doxysilylethene, 1- (ethylphenyl)- 2-phenylethene, 1- (ethylphenyl) -2-tolylethene, 1- (ethylmethylphenyl) -2-phenylethene, 1- (ethylphenyl) -2-xylylethene, 1- (ethylmethylphenyl) -2- Tolylethene, 1- (diethylphenyl) -2-phenylethene, 1,2-bis (ethylphenyl) ethene, 1-phenyl-2- (n-propylphenyl) ethene, 1-phenyl-2- (isopropylphenyl) ethene 1- (n-propylphenyl) -2-tolylethene, 1- (isopropylphenyl) -2 Tolylethene, 1- (methyl-n-propylphenyl) -2-phenylethene, 1- (methylisopropylphenyl) -2-phenylethene, 1- (n-butylphenyl) -2-phenylethene, 1- (isobutylphenyl) ) Diphenylalkane having an ethenylene group (vinylene group) such as 2-phenylethene, 1- (sec-butylphenyl) -2-phenylethene, 1- (tert-butylphenyl) -2-phenylethene;
1,2-diphenylpropene, 1-phenyl-2-tolylpropene, 1-phenyl-2-xylylpropene, 1,2-ditolylpropene, 1-tolyl-2-xylylpropene, 1- (ethylphenyl) 2-phenylpropene, 1- (ethylphenyl) -2-tolylpropene, 1- (ethylmethylphenyl) -2-phenylpropene, 1-phenyl-2- (n-propylphenyl) propene, 1-phenyl-2 -(Isopropylphenyl) propene, 2-phenyl-1-tolylpropene, 2-phenyl-1-xylylpropene, 2-tolyl-1-xylylpropene, 2- (ethylphenyl) -1-phenylpropene, 2- (Ethylphenyl) -1-tolylpropene, 2- (ethylmethylphenyl) -1-phenylpropene, 2-phenyl-1 (N- propylphenyl) propene, 2-phenyl-1-diphenylalkane having (isopropylphenyl) methylethenylene group propene and the like;
1,3-diphenylpropene, 1-phenyl-3-tolylpropene, 1-phenyl-3-xylylpropene, 1,3-ditolylpropene, 1-tolyl-3-xylylpropene, 1- (ethylphenyl) -3-phenylpropene, 1- (ethylphenyl) -3-tolylpropene, 1- (ethylmethylphenyl) -3-phenylpropene, 1-phenyl-3- (n-propylphenyl) propene, 1-phenyl-3 -(Isopropylphenyl) propene, 3-phenyl-1-tolylpropene, 3-phenyl-1-xylylpropene, 3-tolyl-1-xylylpropene, 3- (ethylphenyl) -1-phenylpropene, 3- (Ethylphenyl) -1-tolylpropene, 3- (ethylmethylphenyl) -1-phenylpropene, 3-phenyl-1 (N- propylphenyl) propene, 3-phenyl-1-diphenylalkane having (isopropylphenyl) propenylene group propene and the like;
2,3-diphenylpropene, 2-phenyl-3-tolylpropene, 2-phenyl-3-xylylpropene, 2,3-ditolylpropene, 2-tolyl-3-xylylpropene, 2- (ethylphenyl) -3-phenylpropene, 2- (ethylphenyl) -3-tolylpropene, 2- (ethylmethylphenyl) -3-phenylpropene, 2-phenyl-3- (n-propylphenyl) propene, 2-phenyl-3 -(Isopropylphenyl) propene, 3-phenyl-2-tolylpropene, 3-phenyl-2-xylylpropene, 3-tolyl-2-xylylpropene, 3- (ethylphenyl) -2-phenylpropene, 3- (Ethylphenyl) -2-tolylpropene, 3- (ethylmethylphenyl) -2-phenylpropene, 3-phenyl-2 (N- propylphenyl) propene, 3-phenyl-2-diphenylalkane having (isopropyl) methylene ethylene propene and the like;
1,3-diphenylbutene, 1-phenyl-3-tolylbutene, 1-phenyl-3-xylylbutene, 1- (ethylphenyl) -3-phenylbutene, 1,3-ditolylbutene, 3-phenyl-1-tolylbutene, 3 A diphenylalkane having a 3-methylpropenylene group such as phenyl-1-xylylbutene, 3- (ethylphenyl) -1-phenylbutene;
Diphenylalkanes having a 3-ethylpropenylene group such as 1,3-diphenylpentene, 1-phenyl-3-tolylpentene, 3-phenyl-1-tolylpentene;
Diphenylalkanes having a 1-methyl-3-methylenepropenylene group such as 2,4-diphenylpentene, 2-phenyl-4-tolylpentene, 4-phenyl-2-tolylpentene;
Diphenylalkanes having a 1,3-dimethylpropenylene group such as 2,4-diphenyl-2-pentene, 2-phenyl-4-tolyl-2-pentene, 4-phenyl-2-tolyl-2-pentene;
Diphenylalkanes having 2,3-dimethylpropenylene groups such as 2-methyl-1,3-diphenylbutene, 2-methyl-1-phenyl-3-tolylbutene, 2-methyl-3-phenyl-1-tolylbutene;
Diphenylalkanes having a 3,3-dimethylpropenylene group such as 3-methyl-1,3-diphenylbutene, 3-methyl-1-phenyl-3-tolylbutene, 3-methyl-3-phenyl-1-tolylbutene;
2,4-diphenylhexene, 2,4-diphenyl-2-hexene, 2-methyl-1,3-diphenylpentene, 4-methyl-2,4-diphenylpentene, 4-methyl-2,4-diphenyl-2 A diphenylalkane having a C 6 alkenylene group such as pentene and 2,3-dimethyl-1,3-diphenylbutene;

Among the diphenylalkanes represented by the general formula (3), R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ have 1 to 6 carbon atoms in total, and R ¹⁰ , R ¹¹ , R ¹² and R ^13. Are groups selected from a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, and a sec-butyl group, and at least two of them are preferably hydrogen atoms. Most preferably, R is an alkylene group having 1 to 3 carbon atoms or an alkenylene group, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ^{13 have} a total carbon number of 1 to 6, and R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are groups selected from a hydrogen atom, a methyl group, an ethyl group, an isopropyl group and a sec-butyl group, and at least two of them are hydrogen atoms. Or R ⁹ is an alkylene group or alkenylene group having 4 to 6 carbon atoms, and R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are all hydrogen atoms.

As the most preferable diphenylalkane represented by the general formula (3), specifically, for example, diphenylmethane, phenyltolylmethane, phenylxylylmethane, ditolylmethane, (ethylphenyl) phenylmethane, (ethylphenyl) tolylmethane, (Ethylmethylphenyl) phenylmethane, (diethylphenyl) phenylmethane, bis (ethylphenyl) methane, phenyl (isopropylphenyl) methane, (isopropylphenyl) tolylmethane, (methylisopropylphenyl) phenylmethane, (ethylisopropylphenyl) phenylmethane , (Ethylphenyl) (isopropylphenyl) methane, (sec-butylphenyl) phenylmethane, (sec-butylmethylphenyl) phenylmethane, (sec-butyl) Diphenylalkane having a methylene group such as phenyl) Torirumetan;
1,1-diphenylethane, 1-phenyl-1-tolylethane, 1-phenyl-1-xylylethane, 1,1-ditolylethane, 1- (ethylphenyl) -1-phenylethane, 1- (ethylphenyl) -1- Tolylethane, 1- (ethylmethylphenyl) -1-phenylethane, 1- (diethylphenyl) -1-phenylethane, 1,1-bis (ethylphenyl) ethane, 1-phenyl-1- (isopropylphenyl) ethane, Diphenylalkanes having a methylmethylene group (ethylidene group) such as 1- (isopropylphenyl) -1-tolylethane, 1- (methylisopropylphenyl) -1-phenylethane, 1- (sec-butylphenyl) -1-phenylethane ;
1,2-diphenylethane, 1-phenyl-2-tolylethane, 1-phenyl-2-xylylethane, 1,2-ditolylethane, 1- (ethylphenyl) -2-phenylethane, 1- (ethylphenyl) -2- Tolylethane, 1- (ethylmethylphenyl) -2-phenylethane, 1- (diethylphenyl) -2-phenylethane, 1,2-bis (ethylphenyl) ethane, 1-phenyl-2- (isopropylphenyl) ethane, Diphenylalkanes having an ethylene group such as 1- (isopropylphenyl) -2-tolylethane, 1- (methylisopropylphenyl) -2-phenylethane, 1- (sec-butylphenyl) -2-phenylethane;
1,1-diphenylpropane, 1-phenyl-1-tolylpropane, 1-phenyl-1-xylylpropane, 1,1-ditolylpropane, 1- (ethylphenyl) -1-phenylpropane, 1- (ethyl Diphenylalkanes having an ethylmethylene group (propylidene group) such as phenyl) -1-tolylpropane, 1- (ethylmethylphenyl) -1-phenylpropane, 1-phenyl-1- (isopropylphenyl) propane;
2,2-diphenylpropane, 2-phenyl-2-tolylpropane, 2-phenyl-2-xylylpropane, 2,2-ditolylpropane, 2- (ethylphenyl) -2-phenylpropane, 2- (ethyl Diphenylalkanes having a dimethylmethylene group (isopropylidene group) such as phenyl) -2-tolylpropane, 2- (ethylmethylphenyl) -2-phenylpropane, 2-phenyl-2- (isopropylphenyl) propane;
Diphenylalkanes having a C4 alkenylene group such as 1,3-diphenylbutane;
Diphenylalkane having an alkylene group of 5 carbon atoms such as 1,3-diphenylpentane, 2,4-diphenylpentane, 2-methyl-1,3-diphenylbutane, 3-methyl-1,3-diphenylbutane;
An alkylene group having 6 carbon atoms such as 2,4-diphenylhexane, 2-methyl-1,3-diphenylpentane, 2-methyl-2,4-diphenylpentane, and 2,3-dimethyl-1,3-diphenylbutane; Diphenylalkane possessed;
1,1-diphenylethene, 1-phenyl-1-tolylethene, 1-phenyl-1-xylylethene, 1,1-ditolylethene, 1- (ethylphenyl) -1-phenylethene, 1- (ethylphenyl) -1- Tolylethene, 1- (ethylmethylphenyl) -1-phenylethene, 1- (diethylphenyl) -1-phenylethene, 1,1-bis (ethylphenyl) ethene, 1-phenyl-1- (isopropylphenyl) ethene, Diphenylalkanes having vinylidene groups such as 1- (isopropylphenyl) -1-tolylethene, 1- (methylisopropylphenyl) -1-phenylethene, 1- (sec-butylphenyl) -1-phenylethene;
1,2-diphenylethene, 1-phenyl-2-tolylethene, 1-phenyl-2-xylylethene, 1,2-ditolylethene, 1- (ethylphenyl) -2-phenylethene, 1- (ethylphenyl) -2- Tolylethene, 1- (ethylmethylphenyl) -2-phenylethene, 1- (diethylphenyl) -2-phenylethene, 1,2-bis (ethylphenyl) ethene, 1-phenyl-2- (isopropylphenyl) ethene, Diphenylalkane having an ethenylene group (vinylene group) such as 1- (isopropylphenyl) -2-tolylethene, 1- (methylisopropylphenyl) -2-phenylethene, 1- (sec-butylphenyl) -2-phenylethene;
1,2-diphenylpropene, 1-phenyl-2-tolylpropene, 1-phenyl-2-xylylpropene, 1,2-ditolylpropene, 1- (ethylphenyl) -2-phenylpropene, 1- (ethyl Phenyl) -2-tolylpropene, 1- (ethylmethylphenyl) -2-phenylpropene, 1-phenyl-2- (isopropylphenyl) propene, 2-phenyl-1-tolylpropene, 2-phenyl-1-xylyl Propene, 2- (ethylphenyl) -1-phenylpropene, 2- (ethylphenyl) -1-tolylpropene, 2- (ethylmethylphenyl) -1-phenylpropene, 2-phenyl-1- (isopropylphenyl) propene A diphenylalkane having a methylethenylene group such as
1,3-diphenylpropene, 1-phenyl-3-tolylpropene, 1-phenyl-3-xylylpropene, 1,3-ditolylpropene, 1- (ethylphenyl) -3-phenylpropene, 1- (ethyl Phenyl) -3-tolylpropene, 1- (ethylmethylphenyl) -3-phenylpropene, 1-phenyl-3- (isopropylphenyl) propene, 3-phenyl-1-tolylpropene, 3-phenyl-1-xylyl Propene, 3- (ethylphenyl) -1-phenylpropene, 3- (ethylphenyl) -1-tolylpropene, 3- (ethylmethylphenyl) -1-phenylpropene, 3-phenyl-1- (isopropylphenyl) propene A diphenylalkane having a propenylene group such as
2,3-diphenylpropene, 2-phenyl-3-tolylpropene, 2-phenyl-3-xylylpropene, 2,3-ditolylpropene, 2- (ethylphenyl) -3-phenylpropene, 2- (ethyl Phenyl) -3-tolylpropene, 2- (ethylmethylphenyl) -3-phenylpropene, 2-phenyl-3- (isopropylphenyl) propene, 3-phenyl-2-tolylpropene, 3-phenyl-2-xylyl Propene, 3- (ethylphenyl) -2-phenylpropene, 3- (ethylphenyl) -2-tolylpropene, 3- (ethylmethylphenyl) -2-phenylpropene, 3-phenyl-2- (isopropylphenyl) propene Diphenylalkanes having a methyleneethylene group such as
A diphenylalkane having a C4 alkenylene group such as 1,3-diphenylbutene;
5 carbon atoms such as 1,3-diphenylpentene, 2,4-diphenylpentene, 2,4-diphenyl-2-pentene, 2-methyl-1,3-diphenylbutene, 3-methyl-1,3-diphenylbutene A diphenylalkane having an alkenylene group;
2,4-diphenylhexene, 2,4-diphenyl-2-hexene, 2-methyl-1,3-diphenylpentene, 4-methyl-2,4-diphenylpentene, 4-methyl-2,4-diphenyl-2 A diphenylalkane having an alkenylene group having 6 carbon atoms such as pentene and 2,3-dimethyl-1,3-diphenylbutene;

  The production method of diphenylalkane used in the present invention is arbitrary, and can be produced by various known methods. Some examples are shown below.

  Diphenylalkane can be obtained by adding styrenes such as styrene, α-, β-methylstyrene, ethylstyrene and the like to alkylbenzene in the presence of an acid catalyst. Examples of the acid catalyst include mineral acids such as sulfuric acid and phosphoric acid, solid acidic substances such as acidic clay and activated clay, and Friedel-Crafts catalyst which is a metal halide.

  Diphenylalkane is also produced by a polymerization reaction of the above styrenes in the presence of a suitable acid catalyst. At this time, a single styrene compound may be used, or two or more styrene compounds may be copolymerized. Examples of the acid catalyst include mineral acids such as sulfuric acid and phosphoric acid, solid acidic substances such as acidic clay and activated clay, and Friedel-Crafts catalyst which is a metal halide. Usually, the diphenylalkane obtained by this method is a compound in which two benzene rings are bonded by an alkenylene group. However, in the present invention, it may be used as it is, and the hydrotreatment of the alkenylene group in the presence of a suitable catalyst. And a compound in which an alkenylene group is converted to an alkylene group may be used.

  Regarding the alkylation of aromatic compounds, the Friedel-Crafts reaction of chloride is well known, but the diphenylalkane according to the present invention can also be produced by this method. For example, the diphenylalkane according to the present invention can be obtained by reacting an alkylbenzene whose side chain alkyl group is chlorinated with benzene or an alkylbenzene in the presence of a suitable Friedel-Crafts catalyst such as a metal halide. In addition, there is a method of coupling a dihalogenated alkane and benzene or alkylbenzene in the presence of a suitable Friedel-Crafts catalyst such as a metal halide.

Moreover, diphenylalkane may be manufactured by said method etc. using the alkylbenzene which has an alkyl group corresponding to the alkyl group represented by R < ¹⁰ > -R < ¹³ > in General formula (3), or said method It can also be produced by adding the alkyl group to the diphenylalkane produced by the above method by various methods.

  The diphenylalkane is not limited to a compound having a single structure, but may be a mixture of compounds having different structures as long as the general formula (3) is satisfied.

The viscosity of the diphenylalkane contained in the working fluid composition for a refrigerator of the present invention is not particularly limited, but the kinematic viscosity at 40 ° C. is preferably ² to 500 mm ² / s, more preferably 2.3 to 300 mm ² /. s, more preferably 3 to 200 mm ² / s.

  In the working fluid composition for a refrigerator of the present invention, the content of the aromatic compound according to the present invention is not particularly limited, but depends on various performances such as lubricity, refrigerant compatibility, thermal / chemical stability, and electrical insulation. From the point of excellence, it is preferable to contain 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and more preferably 90% by mass or more, based on the total amount of refrigerating machine oil. Is most preferred. The “refrigeration oil” as used in the present invention refers to a component obtained by removing a tetrafluoropropene refrigerant and / or a trifluoroiodomethane refrigerant and other refrigerants from the working fluid composition for a refrigerator (for example, according to the present invention). A composition containing an aromatic compound and other base oils and additives included as necessary. The “total amount of refrigeration oil” means the total amount of components excluding tetrafluoropropene refrigerant and / or trifluoroiodomethane refrigerant and other refrigerants from the working fluid composition for refrigerators (hereinafter the same) .)

  The working fluid composition for a refrigerator of the present invention may further contain a base oil and various additives other than the aromatic compound according to the present invention. In the following description, the contents of the base oil and additives other than the aromatic compound according to the present invention are shown based on the total amount of the refrigerating machine oil described above.

  Base oils other than aromatic compounds according to the present invention include mineral oils, hydrocarbon oils such as olefin polymers, and ester base oils (monoesters, polyol esters containing linear fatty acids and / or branched fatty acids as constituent fatty acids). Etc.), synthetic oils containing oxygen such as polyglycol, polyvinyl ether, ketone, polyphenyl ether, silicone, polysiloxane, perfluoroether may be used in combination. Among the above, as the synthetic oil containing oxygen, polyol ester, polyglycol, and polyvinyl ether are preferably used.

  Moreover, since the working fluid composition for a refrigerator of the present invention contains the aromatic compound according to the present invention, it can be suitably used even in a state where no additive is added, but various additives are blended as necessary. It can also be used in the form.

  In order to further improve the wear resistance and load resistance of the working fluid composition for refrigerators of the present invention, phosphoric acid ester, acidic phosphoric acid ester, thiophosphoric acid ester, amine salt of acidic phosphoric acid ester, chlorinated phosphoric acid At least one phosphorus compound selected from the group consisting of esters and phosphites can be blended. These phosphorus compounds are esters of phosphoric acid or phosphorous acid with alkanols and polyether type alcohols or derivatives thereof.

  Specifically, for example, as phosphate ester, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate, tritridecyl Phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xyl Examples include rhenyl diphenyl phosphate.

  Examples of acidic phosphate esters include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, monododecyl Acid phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl acid phosphate, dibutyl acid phosphate, dipentyl acid , Dihexyl reed Dophosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid phosphate, diundecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate, dipentadecyl acid, dipentadecyl acid Examples include hexadecyl acid phosphate, diheptadecyl acid phosphate, dioctadecyl acid phosphate, dioleyl acid phosphate, and the like.

  Examples of thiophosphates include tributyl phosphorothioate, tripentyl phosphorothionate, trihexyl phosphorothionate, triheptyl phosphorothionate, trioctyl phosphorothionate, trinonyl phosphorothionate, tridecyl phosphorothioate. Phorothionate, triundecyl phosphorothionate, tridodecyl phosphorothionate, tritridecyl phosphorothionate, tritetradecyl phosphorothionate, tripentadecyl phosphorothionate, trihexadecyl phosphorothionate, Triheptadecyl phosphorothioate, trioctadecyl phosphorothionate, trioleyl phosphorothionate, triphenyl phosphorothionate, tricresyl phosphorothionate, trixyl Cycloalkenyl phosphorothionate, cresyldiphenyl phosphorothionate, like carboxymethyl Les sulfonyl diphenyl phosphorothionate.

  Examples of the amine salt of acidic phosphate ester include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, Examples thereof include salts with amines such as dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine.

  Examples of the chlorinated phosphate ester include tris-dichloropropyl phosphate, tris-chloroethyl phosphate, tris-chlorophenyl phosphate, polyoxyalkylene bis [di (chloroalkyl)] phosphate, and the like. As phosphites, dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite, diundecyl phosphite, didodecyl phosphite, dioleyl Phosphite, diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl phosphite Phyto, tridodecyl phosphite, trioleyl phosphite, triphenyl phosphite, tricresyl phosphite and the like can be mentioned. Mixtures of these can also be used.

  When the working fluid composition for a refrigerator of the present invention contains the above phosphorus compound, the content of the phosphorus compound is not particularly limited, but 0 based on the total amount of the refrigerator oil (based on the total amount of the base oil and all the blended additives). It is preferably 0.01 to 5.0% by mass, more preferably 0.02 to 3.0% by mass. In addition, the said phosphorus compound may be used individually by 1 type, and may use 2 or more types together.

  In addition, the working fluid composition for a refrigerator of the present invention includes a phenyl glycidyl ether type epoxy compound, an alkyl glycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, an allyloxirane, in order to further improve the thermal and chemical stability. It can contain at least one epoxy compound selected from a compound, an alkyloxirane compound, an alicyclic epoxy compound, an epoxidized fatty acid monoester, and an epoxidized vegetable oil.

  Specific examples of the phenyl glycidyl ether type epoxy compound include phenyl glycidyl ether and alkylphenyl glycidyl ether. As used herein, the alkylphenyl glycidyl ether includes those having 1 to 3 alkyl groups having 1 to 13 carbon atoms, and those having one alkyl group having 4 to 10 carbon atoms, such as n-butylphenyl glycidyl. Ether, i-butylphenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, pentylphenyl glycidyl ether, hexylphenyl glycidyl ether, heptylphenyl glycidyl ether, octylphenyl glycidyl ether, nonylphenyl glycidyl ether, decylphenyl A glycidyl ether etc. can be illustrated as a preferable thing.

  As the alkyl glycidyl ether type epoxy compound, specifically, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl glycol diglycidyl ether, Examples thereof include trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol monoglycidyl ether, and polyalkylene glycol diglycidyl ether.

  Specific examples of the glycidyl ester type epoxy compound include phenyl glycidyl ester, alkyl glycidyl ester, alkenyl glycidyl ester, etc., and preferable ones are glycidyl-2,2-dimethyloctanoate, glycidyl benzoate, glycidyl acrylate. And glycidyl methacrylate.

  Specific examples of the allyloxirane compound include 1,2-epoxystyrene and alkyl-1,2-epoxystyrene.

  Specific examples of the alkyloxirane compound include 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2- Epoxy nonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2- Examples include epoxyhexadecane, 1,2-epoxyheptadecane, 1,1,2-epoxyoctadecane, 2-epoxynonadecane, 1,2-epoxyicosane and the like.

  Specific examples of the alicyclic epoxy compound include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and bis (3,4 -Epoxycyclohexylmethyl) adipate, exo-2,3-epoxynorbornane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (7-oxabicyclo [4.1.0] hept-3- Yl) -spiro (1,3-dioxane-5,3 ′-[7] oxabicyclo [4.1.0] heptane, 4- (1′-methylepoxyethyl) -1,2-epoxy-2-methyl Examples include cyclohexane and 4-epoxyethyl-1,2-epoxycyclohexane.

  Specific examples of the epoxidized fatty acid monoester include an ester of an epoxidized fatty acid having 12 to 20 carbon atoms with an alcohol or phenol having 1 to 8 carbon atoms or an alkylphenol. In particular, butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl and butylphenyl esters of epoxy stearate are preferably used.

  Specific examples of the epoxidized vegetable oil include epoxy compounds of vegetable oils such as soybean oil, linseed oil and cottonseed oil.

  Among these epoxy compounds, phenyl glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, alicyclic epoxy compounds and epoxidized fatty acid monoesters are preferred. Of these, phenyl glycidyl ether type epoxy compounds and glycidyl ester type epoxy compounds are more preferred, and phenyl glycidyl ether, butylphenyl glycidyl ether, alkyl glycidyl esters or mixtures thereof are particularly preferred.

  When the working fluid composition for a refrigerator of the present invention contains the epoxy compound, the content of the epoxy compound is not particularly limited, but is preferably 0.1 to 5.0% by mass based on the total amount of the refrigerator oil. 0.2 to 2.0% by mass is more preferable. In addition, the said epoxy compound may be used individually by 1 type, and may use 2 or more types together.

  In addition, the working fluid composition for a refrigerator according to the present invention can contain a conventionally known additive for a refrigerator oil, if necessary, in order to further enhance its performance. Examples of such additives include phenolic antioxidants such as di-tert-butyl-p-cresol and bisphenol A, phenyl-α-naphthylamine, N, N-di (2-naphthyl) -p-phenylenediamine, and the like. Amine-based antioxidants, anti-wear agents such as zinc dithiophosphate, extreme pressure agents such as chlorinated paraffin and sulfur compounds, oil-based agents such as fatty acids, antifoaming agents such as silicones, metal inertness such as benzotriazole Agents, viscosity index improvers, pour point depressants, detergent dispersants and the like. These additives may be used individually by 1 type, and may be used in combination of 2 or more type. The content of these additives is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total amount of refrigerating machine oil.

In the working fluid composition for a refrigerator of the present invention, the kinematic viscosity of the refrigerator oil is not particularly limited, but the kinematic viscosity at 40 ° C. is preferably ² to 500 mm ² / s, more preferably 2.3 to 300 mm ² / s. Most preferably, it can be set to 3 to 200 mm ² / s. The kinematic viscosity at 100 ° C. is preferably 1 to 100 mm ² / s, more preferably ² to 50 mm ² / s.

The volume resistivity of the refrigeration oil is not particularly limited, but is preferably 1.0 × 10 ¹² Ω · cm or more, more preferably 1.0 × 10 ¹³ Ω · cm or more, and most preferably 1.0 × 10 ^14. It can be set to Ω · cm or more. In particular, when it is used for a hermetic refrigerator, high electrical insulation tends to be required. In the present invention, the volume resistivity means a value at 25 ° C. measured in accordance with JIS C 2101 “Electrical insulating oil test method”.

  Further, the water content of the refrigerating machine oil is not particularly limited, but can be preferably 100 ppm or less, more preferably 50 ppm or less, and most preferably 30 ppm or less based on the total amount of the refrigerating machine oil. In particular, when it is used for a hermetic type refrigerator, the moisture content is required to be small from the viewpoint of the influence on the thermal / chemical stability and electrical insulation of the refrigerator oil.

  Further, the acid value of the refrigerating machine oil is not particularly limited, but is preferably 0.1 mgKOH / g or less, more preferably 0.05 mgKOH / g or less in order to prevent corrosion to the metal used in the refrigerator or piping. can do. In addition, in this invention, an acid value means the acid value measured based on JISK 2501 "Petroleum products and lubricating oil-neutralization number test method".

  Further, the ash content of the refrigerating machine oil is not particularly limited, but is preferably 100 ppm or less, more preferably 50 ppm or less in order to increase the thermal and chemical stability of the fluoropropene refrigerant refrigerating machine oil of the present invention and suppress the generation of sludge and the like. can do. In the present invention, ash means the value of ash measured in accordance with JISK 2272 “Testing method for ash and sulfated ash of crude oil and petroleum products”.

  The working fluid composition for a refrigerator of the present invention contains a tetrafluoropropene refrigerant and / or a trifluoroiodomethane refrigerant, but the refrigerant used in the present invention is a tetrafluoropropene refrigerant or trifluoride. Only one of the iodomethane refrigerant may be used, or a mixed refrigerant of a tetrafluoropropene refrigerant and a trifluoroiodomethane refrigerant may be used. Further, it may be a mixed refrigerant of a tetrafluoropropene refrigerant and / or a trifluoroiodomethane refrigerant and another refrigerant. Examples of the refrigerant other than the tetrafluoropropene refrigerant and the trifluoroiodomethane refrigerant include HFC refrigerants, fluorine-containing ether refrigerants such as bar fluoroethers, and natural refrigerants such as dimethyl ether, ammonia, and hydrocarbons.

  Examples of the HFC refrigerant include hydrofluorocarbons having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms. Specifically, for example, difluoromethane (HFC-32), trifluoromethane (HFC-23), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1, HFC such as 1,1,2-tetrafluoroethane (HFC-134a), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), or two or more thereof And the like. These refrigerants are appropriately selected depending on the application and required performance. For example, HFC-32 alone; HFC-23 alone; HFC-134a alone; HFC-125 alone; HFC-134a / HFC-32 = 60 to 80 mass % / 40-20 mass% mixture; HFC-32 / HFC-125 = 40-70 mass% / 60-30 mass% mixture; HFC-125 / HFC-143a = 40-60 mass% / 60-40 mass % Mixture; HFC-134a / HFC-32 / HFC-125 = 60 wt% / 30 wt% / 10 wt% mixture; HFC-134a / HFC-32 / HFC-125 = 40-70 wt% / 15- 35 mass% / 5 to 40 mass% mixture; HFC-125 / HFC-134a / HFC-143a = 35-55 mass% / 1-15 mass% / 40-60 mass Such as a mixture of preferred examples include. More specifically, a mixture of HFC-134a / HFC-32 = 70/30 mass%; a mixture of HFC-32 / HFC-125 = 60/40 mass%; HFC-32 / HFC-125 = 50/50 mass % Mixture (R410A); HFC-32 / HFC-125 = 45/55 wt% mixture (R410B); HFC-125 / HFC-143a = 50/50 wt% mixture (R507C); HFC-32 / HFC -125 / HFC-134a = 30/10/60 wt% mixture; HFC-32 / HFC-125 / HFC-134a = 23/25/52 wt% mixture (R407C); HFC-32 / HFC-125 / HFC-134a = 25/15/60 mass% mixture (R407E); HFC-125 / HFC-134a / HFC-143a = Mixtures of 4/4/52 wt% (R404A), and the like.

  Specific examples of the fluorine-containing ether-based refrigerant include HFE-134p, HFE-245mc, HFE-236mf, HFE-236me, HFE-338mcf, HFE-365mcf, HFE-245mf, HFE-347mmy, and HFE-. 347mcc, HFE-125, HFE-143m, HFE-134m, HFE-227me and the like.

  As the hydrocarbon refrigerant, a gas refrigerant at 25 ° C. and 1 atm is preferably used. Specifically, it is an alkane, cycloalkane, alkene or a mixture thereof having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include methane, ethylene, ethane, propylene, propane, cyclopropane, butane, isobutane, cyclobutane, methylcyclopropane, or a mixture of two or more thereof. Among these, propane, butane, isobutane or a mixture thereof is preferable.

  When a mixed refrigerant of tetrafluoropropene refrigerant and / or trifluoroiodomethane refrigerant and fluorine-containing ether refrigerant, dimethyl ether, ammonia, hydrofluorocarbon and / or hydrocarbon is used, the mixing ratio is not particularly limited. In the case of a mixed refrigerant of fluoropropene and hydrofluorocarbon and / or hydrocarbon, the total amount of hydrofluorocarbon and hydrocarbon is preferably 1 to 200 parts by mass, and 10 to 100 parts by mass with respect to 100 parts by mass of fluoropropene. More preferably, it is a part.

  The refrigerating machine oil contained in the working fluid composition for a refrigerating machine of the present invention is usually a refrigeration mixed with a refrigerant containing tetrafluoropropene refrigerant and / or trifluoroiodomethane as described above in a refrigerating and air-conditioning apparatus. It exists in the form of a mechanical fluid composition. The mixing ratio of the refrigerating machine oil and the refrigerant in the working fluid composition for a refrigerating machine of the present invention is not particularly limited, but the refrigerating machine oil is preferably 1 to 500 parts by mass, more preferably 2 to 400 parts by mass with respect to 100 parts by mass of the refrigerant. Part.

  The working fluid composition for a refrigerator of the present invention is preferably used for an air conditioner or refrigerator having a reciprocating or rotating hermetic compressor, or a car air conditioner. In addition, the working fluid composition for a refrigerator of the present invention is preferably used for a dehumidifier, a water heater, a freezer, a refrigerator / freezer warehouse, a vending machine, a showcase, a cooling device for a chemical plant, and the like. Furthermore, the refrigerating machine oil and the working fluid composition for a refrigerating machine of the present invention are also preferably used for those having a centrifugal compressor.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

基油７：下記式で表される化合物

基油８：ｎ−ヘプタン酸とペンタエリスリトールとのエステル
基油９：ｎ−ペンタン酸、ｎ−ヘプタン酸、３，５，５−トリメチルヘキサン酸の混合脂肪酸（混合比（モル比）：４５／１０／４５）とペンタエリスリトールとのエステル
基油１０：ナフテン系鉱油
基油１１：ポリプロピレングリコールモノメチルエーテル。 [Examples 1-7, Comparative Examples 1-4]
In Examples 1 to 7 and Comparative Examples 1 to 4, refrigerating machine oils were prepared using base oils 1 to 11 shown below. Various properties of the obtained refrigerator oil are shown in Tables 1 to 3.
(Base oil)
Base oil 1: Branched alkylbenzene A
Base oil 2: Branched alkylbenzene B
Base oil 3: Linear alkylbenzene base oil 4: 2- (1,1′-dimethylpropyl) -naphthalene base oil 5: Alkylnaphthalene (mixture based on dinonylnaphthalene)
Base oil 6: Compound represented by the following formula

Base oil 7: Compound represented by the following formula

Base oil 8: ester base oil of n-heptanoic acid and pentaerythritol 9: mixed fatty acid of n-pentanoic acid, n-heptanoic acid and 3,5,5-trimethylhexanoic acid (mixing ratio (molar ratio): 45 / 10/45) and pentaerythritol ester base oil 10: naphthenic mineral oil base oil 11: polypropylene glycol monomethyl ether.

  Next, the following evaluation tests were carried out for each of the refrigerating machine oils of Examples 1 to 7 and Comparative Examples 1 to 4.

(Evaluation of refrigerant compatibility)
In accordance with JIS-K-2211 “Refrigerating machine oil” “Compatibility test method with refrigerant”, a mixed refrigerant (mixing ratio (mass ratio) of 2,3,3,3-tetrafluoropropene and trifluoroiodomethane. Ratio): 2,3,3,3-tetrafluoropropene / 3 trifluoroiodomethane = 70/30) 2 g of refrigerating machine oil is blended with 18 g, and the refrigerant and refrigerating machine oil are mutually dissolved at 20 ° C. Observed. The obtained results are shown in Tables 1-3. In Tables 1 to 3, “compatible” means that the refrigerant and the refrigerating machine oil are dissolved in each other, and “separation” means that the refrigerant and the refrigerating machine oil are separated into two layers.

(Evaluation of thermal and chemical stability)
In accordance with JIS-K-2211, 1 g of refrigerating machine oil (initial hue L0.5) adjusted to a water content of 10 ppm or less, a mixed refrigerant of 2,3,3,3-tetrafluoropropene and trifluoroiodomethane ( Mixing ratio (mass ratio): 1 g of 2,3,3,3-tetrafluoropropene / 3-fluoroiodomethane = 70/30) and catalyst (iron, copper, and aluminum wires) were sealed in a glass tube. Then, it heated to 150 degreeC and hold | maintained for 1 week. The hue of the refrigerating machine oil and the color change of the catalyst after 1 week were evaluated. Hue was evaluated according to ASTM D156. Further, the color change of the catalyst was visually observed for the appearance, and it was evaluated whether it corresponded to no change, no gloss, or blackening. The obtained results are shown in Tables 1 to 3.

  As is apparent from the results shown in Tables 1 to 3, when the refrigerating machine oils of Examples 1 to 7 are used together with a tetrafluoropropene refrigerant and / or a trifluoroiodomethane refrigerant, refrigerant compatibility and heat / It turns out that it is excellent in chemical stability.

Claims (2)

At least one aromatic compound selected from alkylbenzene, alkylnaphthalene, alkylbiphenyl and diphenylalkane ;
A working fluid composition for a refrigerator comprising a tetrafluoropropene refrigerant and / or a trifluoroiodomethane refrigerant.   The tetrafluoropropene refrigerant contains at least one selected from 1,3,3,3-tetrafluoropropene (HFO-1234ze) and 2,3,3,3-tetrafluoropropene (HFO-1234yf). The working fluid composition for a refrigerator according to claim 1.