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    • 专利摘要:
    The present invention is excellent in lubricity, especially 1,1,1,2-tetrafluoro which can improve the lubricity between aluminum material and steel material, prevent burning and sticking and wear, and do not cause environmental pollution It is related with the refrigerator oil composition suitable as lubricating oil of the refrigerator using hydrogen containing flon refrigerant | coolants, such as ethane. The composition consists of a combination of one or more base oils selected from the group consisting of mineral oils and synthetic oils, and one or more polyoxyethylene-based nonionic surfactants. As said nonionic surfactant, Preferably, the added mole number of an oxyethylene group is 1-40, or the hydrophile-lipophile balance (HLB) is 2-30. Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, polyoxyethylene aryl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan aliphatic esters, polyoxyethylene sorbitol fatty acid esters, and the like. .
    公开号:KR20000022202A
    申请号:KR1019980710621
    申请日:1997-06-18
    公开日:2000-04-25
    发明作者:마사토 가네코
    申请人:도미나가 가즈토；이데미쓰 고산 가부시키가이샤；
    IPC主号:
    专利说明:

    Freezer oil composition
    Generally, a compression type refrigerator is composed of a compressor, a condenser, an expansion valve, and an evaporator, and has a structure in which a mixed liquid of a refrigerant and a lubricating oil circulates in a closed system. In such a compact refrigerator, conventional dichlorodifluoromethane (R12), chlorodifluoromethane (R22), and the like are often used, and various mineral oils and synthetic oils have been used as lubricating oils.
    However, since chlorofluorocarbons, such as R12, may cause environmental pollution such as destroying the ozone layer present in the stratosphere, the use of these chlorofluorocarbons has become increasingly strict in the world. Accordingly, attention has been paid to hydrogen-containing flon compounds such as hydrofluorocarbons and hydrochlorofluorocarbons as novel refrigerants. Such hydrogen-containing flon compounds, in particular, hydrofluorocarbons represented by R134a, have no fear of destroying the ozone layer, and can replace R12 and the like without changing the structure of the conventional refrigerators as refrigerants for compressed refrigerators. desirable.
    These novel replacement flon based refrigerants differ in properties from conventional flon based refrigerants, and as the refrigeration oil used in combination therewith, for example, polyalkylene glycols, polyesters, polyol esters, polycarbonates, poly Based on vinyl ether and the like, a composition in which various additives such as an antioxidant, an extreme pressure additive, an antifoaming agent, and a hydrolysis inhibitor has been found to be useful.
    However, these refrigeration oils are inferior in lubrication performance in the refrigerant atmosphere, and in particular, increase the wear between the aluminum material and the steel material of the refrigerator such as automobile air conditioner or electric refrigeration degree, and thus have a large practical problem. Such friction part of aluminum material and steel material is used for reciprocating compressor (particularly in inclined plate type, piston and piston shoe, inclined plate and shoe part, etc., and in rotary type compressor, in ben and housing part, etc. to be.
    On the other hand, various wear resistance enhancers are known, but it is a fact that there are no known means that can effectively prevent the wear of aluminum and steel materials under a special condition called a flon atmosphere without compromising stability.
    Summary of the Invention
    SUMMARY OF THE INVENTION The present invention has been made in view of the above, and has a hydrogen-containing flan refrigerant such as R134a which has excellent lubrication performance, in particular, improves the lubricity of aluminum and steel materials, prevents seizure and wear, and does not cause environmental pollution. An object of the present invention is to provide a refrigerator oil composition suitable as a lubricant of a used refrigerator.
    The present inventors have endeavored to complete the present invention by discovering that the combination of a base oil consisting of mineral oil and synthetic oil, and a polyoxyethylene-based nonionic surfactant can effectively achieve the object of the present invention. .
    That is, the gist of the present invention is as follows:
    (1) A refrigerator oil composition comprising a base oil selected from the group consisting of mineral oil and synthetic oil, and at least one polyoxyethylene-based nonionic surfactant.
    (2) The refrigerator oil composition as described in (1) whose addition mole number of the oxyethylene group of a polyoxyethylene type nonionic surfactant is 1-40.
    (3) The refrigerator oil composition according to (1) or (2), wherein the hydrophile-lipophile balance (HLB) of the polyoxyethylene nonionic surfactant is 2 to 30.
    (4) In the above (1) to (3), the polyoxyethylene nonionic surfactant is selected from (A) polyoxyethylene alkyl ether, (B) polyoxyethylene alkenyl ether, (C) polyoxyethylene aryl ether, A refrigerator oil composition selected from the group consisting of (D) polyoxyethylene fatty acid esters, (E) polyoxyethylene sorbitan fatty acid esters, and (F) polyoxyethylene sorbitol fatty acid esters.
    (5) The refrigerator oil composition according to the above (1) to (4), wherein the blending amount of the polyoxyethylene nonionic surfactant is 0.01 to 30% by weight based on the total amount of the composition.
    TECHNICAL FIELD The present invention relates to a refrigerator oil composition, and specifically, has excellent lubricating performance, in particular, the lubricity between the aluminum material and the steel material is improved, burned and pressed (hereinafter referred to as baking) and worn out. It is related with the refrigerator oil composition which can be prevented and is preferable as lubricating oil of the refrigerator using hydrogen containing flon refrigerants, such as 1,1,1,2- tetrafluoroethane (R134a) which does not cause environmental pollution.
    Hereinafter, the best mode for implementing this invention is demonstrated.
    First, in the refrigerating oil composition of the present invention, mineral oil and / or synthetic oil are used as the base oil. Such mineral oils and synthetic oils are generally preferred as long as they are used as base oils for refrigerator oils, and are not particularly limited, but have a kinematic viscosity of 1 to 100 mm 2 / sec, preferably 2 to 60 mm at 100 ° C. It is suitably in the range of 2 / sec, more preferably 3 to 40 mm 2 / sec. Moreover, there is no restriction | limiting in particular in the pour point which is an index of low temperature fluidity of this base oil, It is preferable that it is -10 degrees C or less.
    Although such mineral oil and synthetic oil are various, it is preferable to select suitably according to a use etc. Examples of mineral oils include paraffinic mineral oils, naphthalene mineral oils, intermediate mechanical mineral oils, and the like, while synthetic oils include oxygen-containing organic compounds and hydrocarbon synthetic oils.
    In the synthetic oil, as the oxygen-containing organic compound, synthetic oil containing an ether group, a ketone group, an ester group, a carbonate group, a hydroxyl group and the like in the molecule, and at the same time as these groups, heteroatoms (S, P, F, Cl, Si, N) And synthetic oils), and specifically, (1) polyalkylene glycol, (2) polyvinyl ether, (3) polyester, (4) polyol ester, (5) carbonate derivative, (6) Polyether ketones, and (7) fluorinated oils.
    In the said oxygen containing organic compound, it demonstrates later.
    Examples of the hydrocarbon synthetic oils include olefin polymers such as poly-α-olefins, alkylbenzenes, alkylnaphthalenes, and the like.
    In the refrigerating oil composition of the present invention, one kind of the mineral oil may be used or two or more kinds thereof may be used as the base oil, one kind of the synthetic oil may be used or two or more kinds may be used and the mineral oil 1 may be used. Although at least one species and at least one synthetic oil may be used in combination, an oxygen-containing organic compound is particularly preferred because of its good compatibility with flan refrigerants such as R-134a and excellent lubricating performance.
    In the refrigerator oil composition of the present invention, at least one polyoxyethylene-based nonionic surfactant is blended with the base oil.
    The added mole number of the oxyethylene group of the polyoxyethylene nonionic surfactant of this invention becomes like this. Preferably it is 1-40, More preferably, it is 1-20. If the number of added moles is too large, it becomes a solid at room temperature, inferior in solubility in base oil, high hygroscopicity, and lower insulation, which is not preferable. The HLB value of the polyoxyethylene nonionic surfactant of the present invention is preferably 2 to 30, more preferably 3 to 15. If the HLB value is too low, the lubricity may be lowered. If the HLB value is too high, it becomes a solid at room temperature, the solubility in the base oil is inferior, the hygroscopicity is high, and the insulation is also not preferable.
    As a polyoxyethylene type nonionic surfactant, (A) polyoxyethylene alkyl ether, (B) polyoxyethylene alkenyl ether, (C) polyoxyethylene aryl ether, (D) polyoxyethylene fatty acid ester, (E) Polyoxyethylene sorbitan fatty acid ester, (F) polyoxyethylene sorbitol fatty acid ester, etc. are mentioned. Hereinafter, (A)-(F) is demonstrated.
    (A) polyoxyethylene alkyl ether
    The alkyl moiety in the polyoxyethylene alkyl ester is preferably a straight alkyl group having 11 to 25 carbon atoms, for example, an undecyl group (C 11 H 23 ), a lauryl group (C 12 H 25 ), and a tridecyl group (C 13 H 27 ), myristyl group (C 14 H 29 ), pentadecyl group (C 15 H 31 ), cetyl group (C 16 H 33 ), heptadecyl group (C 17 H 35 ), stearyl group (C 18 H 37 ), a biphenyl group (C 22 H 45 ), and the like. Among them, polyoxyethylene lauryl ether, polyoxyethylene tridecylethyl, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene behenyl ether are particularly preferable.
    (B) polyoxyethylene alkenyl ether
    The alkenyl moiety in the polyoxyethylene alkenylethyl is preferably a straight alkenyl group having 11 to 25 carbon atoms, for example, undecenyl group (C 11 H 21 ), dodecenyl group (C 12 H 23 ), tri Desenyl group (C 13 H 25 ), tetradecenyl group (C 14 H 27 ), pentadecenyl group (C 15 H 29 ), hexadecenyl group (C 16 H 31 ), heptadecenyl group (C 17 H 33 ), an oleyl group (C 18 H 35 ), and the like. The position of the double bond in the alkenyl moiety is not limited. Among the polyoxyethylene alkenyl ethers, specifically, polyoxyethylene oleyl ethers are suitable.
    (C) polyoxyethylene aryl ether
    Polyoxyethylene alkylaryl ether is a nonionic surfactant which has a structure where the aryl group couple | bonds with polyoxyethylene through O- (oxygen). It is preferable that carbon number of the alkylaryl group which comprises polyoxyethylene alkylaryl ether is 12-20, for example, n-hexylphenyl group, n-heptylphenyl group, n-octylphenyl group, n-nonylphenyl group, n-decylphenyl group , n-undecylphenyl group, n-dodecylphenyl group, n-tridecylphenyl group, tetradecylphenyl group, etc. are mentioned. Among them, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, and polyoxyethylene dodecylphenyl ether are particularly preferable.
    (D) polyoxyethylene fatty acid ester
    As a fatty acid which consists of a polyoxyethylene fatty acid ester raw material, a C10-C20 linear or unsaturated fatty acid is preferable, and in this case, the position of the double bond of unsaturated fatty acid is not limited. Moreover, as ester which comprises polyoxyethylene fatty acid ester, monoester, diester, etc. are preferable. Examples of such fatty acids include capric acid (C 9 H 19 COOH), undecanoic acid (C 10 H 21 COOH), lauric acid (C 11 H 23 COOH), tridecyl acid (C 12 H 25 COOH), US Listic acid (C 13 H 27 COOH), pentadecyl acid (C 14 H 29 COOH), palmitic acid (C 15 H 31 COOH), margaric acid (C 16 H 33 COOH), stearic acid (C 17 H 35 COOH), nonadexylic acid (C 18 H 37 COOH), arachic acid (C 19 H 39 COOH), caproleinic acid (C 9 H 17 COOH), undecylenic acid (C 10 H 19 COOH), lean acid ( C 11 H 21 COOH), tridecenoic acid (C 12 H 23 COOH), myristic acid (C 13 H 25 COOH), pentadecenoic acid (C 14 H 27 COOH), palmitreic acid (C 15 H 29 COOH) And oleic acid (C 17 H 33 COOH) and eicosane acid (C 19 H 37 COOH). Among these, specifically, polyoxyethylene monolaurate, polyoxyethylene monostearate, and polyoxyethylene monooleate are preferable.
    (E) polyoxyethylene sorbitan fatty acid ester
    Since polyoxyethylene sorbitan which is a raw material of the polyoxyethylene sorbitan fatty acid ester has three OHs, there are several fatty acid esters in the polyoxyethylene sorbitan fatty acid ester, but any of them is preferable. Carbon number and kind of preferable fatty acid are the same as said (D). Among them, specifically, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate And polyoxyethylene sorbitan trioleate are preferred.
    (F) polyoxyethylene sorbitol fatty acid ester
    Since polyoxyethylene sorbitol, which is a raw material of the polyoxyethylene sorbitol fatty acid ester, has five OH groups, there are several fatty acid esters in the polyoxyethylene sorbitol fatty acid ester, but any of them is preferable. Preferably, carbon number and species of fatty acid are the same as said (D). Among these, specifically, polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, and polyoxyethylene sorbitol tetraoleate are preferable.
    In the refrigerator oil composition of the present invention, the polyoxyethylene-based nonionic surfactant may be used alone or in combination of two or more thereof. In addition, the amount is preferably in the range of 0.01 to 30% by weight based on the total weight of the composition. If the blending amount is less than 0.01% by weight, the effect of improving lubricity is not sufficiently exhibited. If the blending amount is greater than 30% by weight, the effect is expected to be improved compared to the amount thereof, but the solubility in the base oil may decrease. In view of defects such as improvement in lubricity and solubility, a particularly preferable compounding amount is in the range of 0.01 to 15% by weight, particularly preferably in the range of 0.05 to 10% by weight.
    The refrigerator oil composition of the present invention includes, as necessary, various known additives, for example, extreme pressure additives such as phosphate ester and phosphite ester; Phenyl- and amine-based antioxidants; Stabilizers such as epoxy compounds such as phenyl glycidyl ether, cyclohexene oxide, and epoxidized soybean oil; Copper inactivating agents such as benzotriazole and benzotriazole derivatives; Antifoaming agents, such as silicone oil and silicone fluoride oil, can be mix | blended suitably.
    As the refrigerant that can be used in the refrigerator to which the refrigerator oil composition of the present invention is applied, hydrogen-containing flon compounds such as hydrofluorocarbon and hydrochlorofluorocarbon are preferable, and for example, 1,1,1,2-tetrafluoro Roethane (R134a); Chlorodifluoromethane (R22); A mixture of chlorodifluoromethane and 1-chloro-1,1,2,2,2-pentafluoroethane (R502); 1,1-difluoroethane (R152a); Pentafluoroethane (R125); 1,1,1-trifluoroethane (R143a); Difluoromethane (R32); Trifluoromethane (R23); 1,3-dichloro-1,1,2,2,3-pentafluoropropane (R225cb); 3,3-dichloro-1,1,1,2,2-pentafluoropropane (R225ca); 1,1-dichloro-1-fluoroethane (R141b); 1,1-dichloro-2,2,2-trifluoroethane (R123); 1-chloro-1,1-difluoroethane (R142b); Although 2-chloro-1,1,2-tetrafluoroethane (R124) etc. are mentioned, Among these, the hydrofluorocarbon starting with R134a is especially preferable.
    Moreover, fluorine compounds, such as tetrafluoromethane (R14), hexafluoroethane (R116), and octafluoropropane (R218), can also be used, Especially ammonia or a carbon gas; Hydrocarbon compounds such as propane, cyclopropane, butane, isobutane, pentane; Ether compounds such as dimethyl ether and methyl ethyl ether; Monofluorodimethyl ester, difluorodimethyl ether, trifluorodimethyl ether, tetrafluorodimethyl ether, pentafluorodimethyl ether, hexafluorodimethyl ether, heptafluoro n-propylmethyl ether, heptafluoroisopropyl Fluorinated ether compounds such as methyl ether, pentafluoroethyl methyl ether and trifluoromethoxy-1,1,2,2-tetrafluoroethane can also be used as the refrigerant.
    Hereinafter, the synthesis oil of an oxygen containing organic compound type is demonstrated in said base oil. Examples of the polyalkylene glycol of the above (1) include a compound of formula (I):
    R 1 -[(OR 2 ) m -OR 3 ] n
    Where
    R 1 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms or a fatty acid hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding sites;
    R 2 is an alkylene group having 2 to 4 carbon atoms;
    R 3 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acyl group having 2 to 10 carbon atoms;
    n is an integer from 1 to 6;
    m is a number whose average value of mxn becomes 6-80.
    In formula (I), the alkyl group in R 1 , R 3 is linear, branched or cyclic. Specific examples of such alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, and cyclopentyl groups. And a cyclohexyl group may be mentioned. When the number of carbon atoms in the alkyl group exceeds 10, compatibility of the flon refrigerant may decrease, and phase separation may occur. Preferably, the alkyl group has 1 to 6 carbon atoms.
    In addition, the alkyl group part of the acyl group in R <1> , R <3> is linear, branched, or cyclic. Specific examples of the alkyl group moiety in such an acyl group include various groups having 1 to 9 carbon atoms listed as specific examples of the alkyl group. When the carbon number of the alkyl group in the acyl group is greater than 10, the compatibility of the flon refrigerant decreases, and phase separation may occur. Preferably, the acyl group has 2 to 6 carbon atoms.
    When any group of R 1 and R 3 is an alkyl group or an acyl group, R 1 and R 3 may be the same or different from each other.
    In addition, when n is two or more, some R <3> in 1 molecule may be same or different.
    When R 1 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 binding sites, such aliphatic hydrocarbon group may be linear or cyclic. Examples of the aliphatic hydrocarbon group having two bonding sites include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a cyclopentylene group, and a cyclohexylene. And the like can be mentioned. As the aliphatic hydrocarbon group having 3 to 6 binding sites, for example, trimethylolpropane, glycerin, pentaerythritol and sorbitol; 1,2,3-trihydroxycyclohexane; The residue remove | excluding the hydroxy group from polyhydric alcohols, such as 1,3, 5- trihydroxy cyclohexane, is mentioned.
    When the carbon number of such an aliphatic hydrocarbon group exceeds 10, compatibility with a flon refrigerant may fall, and phase separation may occur. Preferred carbon number is 2-6.
    In said general formula (I), R <2> is a C2-C4 alkylene group and an oxyethylene group, an oxypropylene group, an oxybutylene group is mentioned as an oxyalkylene group of a repeating unit. Although the oxyalkylene groups in one molecule may be the same and may contain two or more oxyalkylene groups, it is preferable to contain at least an oxypropylene unit in one molecule, in particular 50 mol% or more in the oxyalkylene unit Preference is given to containing oxypropylene units. In addition, when two or more oxyalkylene groups are contained, it may be a random copolymer or a block copolymer.
    N in the formula (I) is an integer of 1 to 6, and can be determined according to the number of binding sites of R 1 . For example, when R 1 is an alkyl group or an acyl group, n is 1, and when R 1 is an aliphatic hydrocarbon group having 2, 3, 4, 5 and 6 binding sites, n is 2, 3, 4, 5 and 6 becomes. In addition, m is a number whose average value of m * n becomes 6-80, and when the average value of m * n is out of the said range, the objective of this invention will not fully be achieved.
    The polyalkylene glycol of the general formula (I) contains a polyalkylene glycol having a hydroxy group at the terminal, even if it contains a content such that the content of the hydroxy group is 50 mol% or less relative to the total terminal group. It can be used preferably. When content of such a hydroxyl group exceeds 50 mol%, hygroscopicity may increase and a viscosity index may fall.
    As the polyalkylene glycol of the formula (I), polyoxypropylene glycol dimethyl ether, polyoxyethylene polyoxypropylene glycol dimethyl ether, polyoxypropylene glycol monobutyl ether, polyoxypropylene glycol diacetate, and the like are preferable in view of economic efficiency and effectiveness. .
    In addition, for the polyalkylene glycol of the formula (I), any of the substances disclosed in detail in Japanese Patent Application Laid-open No. 90-305893 can be used.
    As polyvinyl ether of said (2), the polyvinyl ether type compound (1) which has a structural unit of following General formula (II) is mentioned, for example:
    Where
    R 4 to R 6 are each a hydrogen atom or a hydrocarbon group of 1 to 8 carbon atoms, which may be the same or different from each other;
    R 7 is a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent ether bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms;
    R 8 is a hydrocarbon group of 1 to 20 carbon atoms;
    a represents a number having an average value of 0 to 10;
    R 4 to R 8 may be the same or different for each structural unit,
    In addition, R 7 O is in the case of plurality, the plurality of R 7 O may be the same or different.
    It is also possible to use polyvinyl ether compounds (2) consisting of a block or a random copolymer having the structural unit of formula (II) and the structural unit of formula (III):
    Where
    R 9 to R 12 are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different;
    In addition, R 9 to R 12 may be the same or different for each structural unit.
    In Formula II, R 4 to R 6 each represent a hydrogen atom or a hydrocarbon having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Here, specifically, a hydrocarbon group is an alkyl group, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups; Cycloalkyl groups such as cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, and various dimethylcyclohexyl groups; Aryl groups, such as a phenyl group, various methylphenyl groups, various ethylphenyl groups, and various dimethylphenyl groups; Aryl alkyl groups, such as a benzyl group, various phenyl ethyl groups, and various methyl benzyl groups, are mentioned. Moreover, as these R <4> -R <6> , a hydrogen atom is especially preferable.
    On the other hand, R 7 in formula (II) represents a divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 2 to 10 carbon atoms or a divalent ether bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, wherein the divalent hydrocarbon having 1 to 10 carbon atoms Specific examples of the group include methylene group, ethylene group, phenylethylene group, 1.2-propylene group, 2-phenyl-1,2-propylene group, 1,3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, Divalent aliphatic groups such as various heptylene groups, various octylene groups, various nonylene groups, and various decylene groups; Alicyclic groups having two bonding sites in alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, and propylcyclohexane; Divalent aromatic hydrocarbon groups such as various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, various naphthylene groups and the like; Alkyl aromatic groups each having a monovalent bonding site in the alkyl group portion and the aromatic portion of an alkyl aromatic hydrocarbon such as toluene, xylene, ethylbenzene and the like; The alkyl aromatic group which has a coupling site in the alkyl group part of polyalkyl aromatic hydrocarbons, such as xylene and diethylbenzene, etc. are mentioned. Of these, aliphatic groups having 2 to 4 carbon atoms are particularly preferable.
    Moreover, as a specific example of a C2-C20 divalent ether bond oxygen containing hydrocarbon group, a methoxymethylene group, a methoxyethylene group, a methoxymethylethylene group, 1, 1-bis methoxymethylethylene group, 1,2- Bismethoxymethylethylene group, ethoxymethylethylene group, (2-methoxyethoxy) methylethylene group, (1-methyl-2-methoxy) methylethylene group, etc. are mentioned suitably. In addition, in formula (II), a represents the repeating number of R <7> O, and the average value is the number of the range of 0-10, Preferably it is 0-5. When R 7 O is plural, the plural R 7 O may be the same or different.
    In addition, in the formula (II), R 8 represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of such hydrocarbon groups include methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, Alkyl groups such as various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups; Cycloalkyl groups such as cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, and various dimethylcyclohexyl groups; Aryl groups such as a phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups and various naphthyl groups; A benzyl group, various phenyl ethyl groups, various methyl benzyl groups, various phenyl propyl groups, aryl alkyl groups of various phenyl butyl groups, etc. are mentioned.
    The polyvinyl ether compound (1) of Formula II preferably has a carbon / oxygen molar ratio in the range of 4.2 to 7.0. If this ratio is less than 4.2, hygroscopicity may become high, and when it exceeds 7.0, compatibility with a flon may fall.
    In formula (III), R 9 to R 12 each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other. Here, as the hydrocarbon group having 1 to 20 carbon atoms, it may be the same as exemplified in the description of R 8 in the general formula (II). In addition, R 9 to R 12 may be the same or different for each structural unit.
    The polyvinyl ether compound (2) composed of a block or a random copolymer having a structural unit of formula (II) and a structural unit of formula (III) also preferably has a carbon / oxygen molar ratio in the range of 4.2 to 7.0. If the molar ratio is less than 4.2, the hygroscopicity can be increased, and if it is less than 7.0, the compatibility of the flon can be lowered.
    In addition, in the present invention, a mixture of the polyvinyl ether compound (1) and the polyvinyl ether compound (2) can also be used.
    The polyvinyl ether compounds (1) and (2) which can be used in the present invention are each polymerized with a vinyl ether monomer, and a hydrocarbon monomer having a corresponding olefinic double bond, and a copolymerization of a corresponding vinyl ether monomer. It can manufacture by.
    As the polyvinyl ether compound used in the present invention, a compound having the following terminal structure, i.e., one terminal thereof has the structure of Formula IV or Formula V, and the other terminal has the structure of Formula VI or Formula VII It is preferred that the compound, and one terminal thereof, have the structure of formula IV or formula V, and the remaining terminals of formula VIII:

    Where
    R 13 to R 15 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different from each other;
    R 18 to R 21 each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and may be the same or different from each other;
    R 16 is a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent ether bonded oxygen containing hydrocarbon group having 2 to 20 carbon atoms;
    R 17 is a hydrocarbon group having 1 to 20 carbon atoms;
    b represents a number whose average value is from 0 to 10;
    When R 16 O is plural, a plurality of R 16 O may be the same or different;
    R 22 to R 24 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms and may be the same or different from each other;
    R 27 to R 30 each represent a hydrocarbon or a hydrocarbon group having 1 to 20 carbon atoms and may be the same or different from each other;
    R 25 is a divalent hydrocarbon group of 1 to 10 carbon atoms;
    R 26 is a hydrocarbon group of 1 to 20 carbon atoms;
    c is a number with an average value of 0 to 10;
    When R 25 O is plural, a plurality of R 25 O may be the same or different;
    R 31 to R 33 are each a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different from each other.
    (1) one terminal has a structure of Formula IV or Formula V, and the other end has a structure of Formula VI or Formula VII, and in Formula II, R 4 to R 6 together are a hydrogen atom;
    a is a number from 0 to 4;
    R 7 is a divalent hydrocarbon group having 2 to 4 carbon atoms and R 8 is a hydrocarbon group having 1 to 20 carbon atoms.
    (2) having only the structural unit of formula (II), one terminal of which is of formula (IV), the other terminal of which has the structure of formula (VI), in formula (II), R 4 to R 6 together are a hydrogen atom, and a is 0 to 4 And R 7 is a divalent hydrocarbon group having 2 to 4 carbon atoms and R 8 is a hydrocarbon group having 1 to 20 carbon atoms.
    (3) one end is of formula (IV) or of formula (V), and the other end has a structure of formula (VIII), in formula (II) R 4 to R 6 together are a hydrogen atom, a is a number from 0 to 4, R 7 is A compound having 2 to 4 carbon atoms, and R 8 is a hydrocarbon group having 1 to 20 carbon atoms.
    (4) having only the structural unit of formula (II), one terminal of which is of formula (IV), the other terminal of which has the structure of formula (VII), in formula (II), R 4 to R 6 together are a hydrogen atom, a of 0 to 4 And R 7 is a divalent hydrocarbon group having 2 to 4 carbon atoms and R 8 is a hydrocarbon group having 1 to 20 carbon atoms.
    In addition, in the present invention, a polyvinyl ether compound having a structure of Formula II, wherein one terminal is Formula IV and the other terminal is Formula IX, may be used:
    Where
    R 34 to R 36 are each a hydrogen atom or a hydrocarbon group of 1 to 8 carbon atoms, and may also be the same or different from each other;
    R 37 and R 39 are each a divalent hydrocarbon group having 2 to 10 carbon atoms, and may also be the same or different from each other;
    R 38 and R 40 are each a hydrocarbon having 1 to 10 carbon atoms, and may also be the same or different from each other;
    d and e each have a mean value of 0 to 10 and may also be the same or different from each other;
    In addition, when a plurality of R 37 O, a plurality of R 37 O may be the same as or different from each other;
    When a plurality of R 39 O, a plurality of R 39 O may also be the same or different from each other.
    In addition, in this invention, it consists of a structural unit of the following general formula (X) or the following general formula (XI), and also has a weight average molecular weight of 300-3000 (preferably 300-2000), and one terminal is a following general formula (XII) or (XIII) Polyvinyl ether based compounds consisting of homopolymers or copolymers of alkyl vinyl ethers having the structure can also be used:
    -CH = CHOR 43
    Where
    R 41 is a hydrocarbon having 1 to 8 carbon atoms;
    R 42 is an alkyl group having 1 to 3 carbon atoms;
    R 43 is a hydrocarbon group having 1 to 8 carbon atoms.
    As the polyvinyl ether, any compound described in detail in the specifications of Japanese Patent Application Laid-Open No. 94-128578, Japanese Patent Application Laid-Open No. 94-234814, and Japanese Patent Application Laid-open No. 94-234815 can be used. Can be.
    Examples of the polyester of (3) include aliphatic polyester derivatives having a structural unit represented by the following formula (XIV) and having a molecular weight of 300 to 2000:
    Where
    R 44 is an alkylene group having 1 to 10 carbon atoms;
    R 45 is an alkylene group having 2 to 10 carbon atoms or an oxaalkylene group having 4 to 20 carbon atoms.
    R 44 in the formula (XIV) represents an alkylene group having 1 to 10 carbon atoms, specifically, methylene group, ethylene group, propylene group, ethylmethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, n-butylethylene group, isobutylethylene group, 1-ethyl-2-methylethylene group, 1-ethyl-1-methylethylene group, trimethylene group, tetramethylene group, pentamethylene group, etc. may be mentioned, but preferably Is an alkylene group having 6 or less carbon atoms. In addition, R 45 represents an alkylene group having 2 to 10 carbon atoms or an oxaalkylene group having 4 to 20 carbon atoms. The alkylene group is specifically the same as the specific example of R 44 (except the methylene group), preferably an alkylene group having 2 to 6 carbon atoms, and the oxaalkylene group is specifically 3-oxa-1,5 -Pentylene group, 3,6-dioxa-1,8-octylene group, 3,6-9-trioxa-1,11-undecylene group, 3-oxa-1,4-dimethyl-1,5-pentyl Len, 3,6-dioxa-1,4,7-trimethyl-1,8-octylene group, 3,6,9-trioxa-1,4,7,10-tetramethyl-1,11-undecylene Group, 3-oxa-1,4-diethyl-1,5-pentylene group, 3,6-dioxa-1,4-7-triethyl-1.8-octylene group, 3,6,9-trioxa- 1,4,7,10-tetraethyl-1,11-undecylene group, 3-oxa-1,1,4,4-tetramethyl-1,5-pentylene group, 3,6-dioxa-1, 1,4,4,7,7-hexamethyl-1,8-octylene group, 3,6,9-trioxa-1,1,4,4,7,7,10,10-octamethyl-1, 1,1-undecylene group, 3-oxa-1,2,4,5-tetramethyl-1,5-pentylene group, 3,6-dioxa-1,2,4,5,7,8-hexa Methyl-1,8-octylene group, 3,6,9-trioxa-1,2,4,5,7,8,10,11-octamethyl-1,1,1-undecylene group, 3- Sa-1-methyl-1,5, -pentylene group, 3-oxa-1-ethyl-1,5-pentylene group, 3-oxa-1,2-dimethyl-1,5-pentylene group, 3-oxa- 1-methyl-4-ethyl-1,5-pentylene group, 4-oxa-2,2,5,6,6-tetramethyl-1,7-heptylene group, 4,8-dioxa-2,2, 6,6,10,10-hexamethyl- 1,11-undecylene group etc. are mentioned. In addition, R 44 and R 45 may be the same or different for each structural unit.
    In addition, the aliphatic polyester derivative of formula (XIV) preferably has a molecular weight (measured by GPC) of 300 to 2000. If the molecular weight is less than 300, the kinematic viscosity is too small, and if it is larger than 2000, since it is in the form of wax, neither is preferable as a refrigerator oil.
    In such polyesters, any of those described in detail in WO 91/07479 can be used.
    Examples of the polyol ester of (4) include carbonate esters of polyhydric hydroxy compounds containing two or more hydroxy groups, but for example, those of the general formula (XV) can be used:
    R 46 [OCOR 47 ] f
    Where
    R 46 is a hydrocarbon group;
    R 47 is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms;
    f is an integer from 2 to 6;
    The plurality of -OCOR 47 may be the same or different.
    In the general formula (XV), R 46 is a hydrocarbon group, and either linear or branched chain is possible, preferably an alkyl group having 2 to 10 carbon atoms.
    R 47 is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, preferably an alkyl group having 2 to 16 carbon atoms.
    The polyol ester of formula (XV) may be obtained by reacting a polyhydric alcohol of formula (XVI) with a reactive derivative such as a carbonate or ester or acid halide of formula (XVII):
    R 46 (OH) f
    R 47 COOH
    Where
    R 46 , R 47 and f are as described above.
    Examples of the polyhydric alcohol of the formula (XVI) include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, trimethylol ethane, trimethylol propane, glycerin, pentaerythritol, dipentaerythritol, sorbitol and the like. . In addition, in the carbonate of the formula (XVII), for example, propionic acid, butyric acid, pivalic acid, valeric acid, capronic acid, heptanoic acid, 3-methylhexanoic acid, 2-ethylhexanoic acid, caprylic acid, decanoic acid, lauric acid, Myristylic acid, palmitic acid, etc. are mentioned.
    As the carbonate derivative of the above (5), for example, a polycarbonate of the formula (XVIII):
    Where
    R 48 and R 50 are each a hydrocarbon group having 30 or less carbon atoms or a hydrocarbon group having an ether bond of 2 to 30 carbon atoms, which may be the same or different from each other;
    R 49 is an alkylene group having 2 to 24 carbon atoms;
    g is an integer from 1 to 100;
    h is an integer from 1 to 10.
    In the above formula (XVIII), R 48 and R 50 are each a hydrocarbon group having 30 or less carbon atoms or a hydrocarbon group having 2 to 30 carbon atoms, and specific examples of the hydrocarbon group having 30 or less carbon atoms include methyl group, ethyl group, and n-. Propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetra Aliphatic hydrocarbon groups such as decyl group, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, various nonadecyl groups, and various ecosyl groups; Alicyclic hydrocarbon groups such as cyclohexyl group, 1-cyclohexenyl group, methylcyclohexyl group, dimethylcyclohexyl group, decahydronaphthyl group and tricyclodecanyl group; Aromatic hydrocarbon groups such as phenyl group, various triyl groups, various xylyl groups, mesityl groups and various naphthyl groups; And aromatic aliphatic hydrocarbon groups such as benzyl group, methylbenzyl group, phenylethyl group, 1-methyl-1-phenylethyl group, styryl group, and cinnamic group.
    As the hydrocarbon group having an ether bond having 2 to 30 carbon atoms, for example, a glycol ether group represented by the following general formula (XIX), specifically, an ethylene glycol monomethyl ether group, an ethylene glycol monobutyl ether group, diethylene glycol mono-n-butyl Ether groups, triethylene glycol monoethyl ether groups, propylene glycol monomethyl ether groups, propylene glycol monobutyl ether groups, dipropylene glycol monoethyl ether groups, tripropylene glycol mono-n-butyl ether groups, and the like.
    -(R 51 -O) i -R 52
    Where
    R 51 is an alkylene group having 2 or 3 carbon atoms (ethylene group, propylene group, trimethylene group);
    R 52 is an aliphatic, cycloaliphatic or aromatic hydrocarbon group having up to 28 carbon atoms (the same as the groups mentioned for the specific examples of R 48 and R 50 );
    i is an integer from 1 to 20.
    Among them, n-butyl group, isobutyl group, isoamyl group, cyclohexyl group, isoheptyl group, 3-methylhexyl group, 1,3-dimethylbutyl group, hexyl group, octyl group, 2-ethylhexyl group, etc. An alkyl group; Ethylene glycol monomethylethyl group, ethylene glycol monobutyl ether group, diethylene glycol monomethyl ether group, triethylene glycol monomethyl ether group, propylene glycol monomethyl ether group, propylene glycol monobutyl ether group, dipropylene glycol monoethyl ether group And alkylene glycol monoalkyl ether groups such as tripropylene glycol monon-butyl ether group and the like are preferable.
    In Formula XVIII, R 49 is an alkylene group having 2 to 24 carbon atoms, and specific examples thereof include an ethylene group, a propylene group, a butylene group, an amylene group, a methyl amylene group, an ethyl amylene group, a hexylene group, and a methyl group. Hexylene group, ethyl hexylene group, octamethylene group, nonamethylene group, decamethylene group, dodecamethylene group, tetradecamethylene group, etc. are mentioned. When there are a plurality of R 49 O's, the plurality of R 49 's may be the same or different.
    The polycarbonate of the formula (XVIII) is preferably a molecular weight (weight average molecular weight) of 300 to 3000, preferably 400 to 1500. If the molecular weight is less than 300, the kinematic viscosity is not small, so it is unsuitable as lubricating oil. On the contrary, if the molecular weight is larger than 3000, it becomes waxy and difficult to use as lubricating oil.
    Although such a polycarbonate can be manufactured by various methods, carbonate ester forming derivatives, such as carbon diester or phosgene, and aliphatic dihydric alcohol are manufactured as a raw material normally.
    The preparation of polycarbonates using these may be in accordance with the conventional method for preparing polycarbonates, and generally in accordance with the transesterification method or the phosgene method.
    As the polycarbonate, any compound disclosed in detail in Japanese Patent Laid-Open No. 91-217459 can be used.
    In addition, glycol ether carbonates of the general formula (XX) may be used as the carbonate derivative:
    R 53 -O- (R 55 O) j -CO- (OR 56 ) k -OR 54
    Where
    R 53 and R 54 are each an aliphatic, alicyclic, aromatic or aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other;
    R 55 and R 56 are each an ethylene group or an isopropylene group, which may be the same or different from each other;
    j and k are each a number from 1 to 100.
    In the above formula (XX), specific examples of the aliphatic hydrocarbon group in R 53 and R 54 include methyl group, ethyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, Various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, Various nonadecyl groups, various eicosyl groups, etc. are mentioned. Specific examples of the alicyclic hydrocarbon group include alicyclic hydrocarbon groups such as cyclohexyl group, 1-cyclohexenyl group, methylcyclohexyl group, dimethylcyclohexyl group, decahydronaphthyl group and tricyclodecanyl group; A phenyl group, various trilyl groups, various xylyl groups, mesityl group, various naphthyl groups, etc. are mentioned. Specific examples of the aromatic alicyclic hydrocarbon group include benzyl group, methylbenzyl group, phenylethyl group, 1-methyl-1-phenylethyl group, styryl group, cinnamil group and the like.
    The glycol ether carbonates of formula (XX) can be prepared, for example, by transesterification of polyalkylene glycol monoalkylethers in the presence of excess of carbonate esters of alcohols of relatively low boiling point.
    In the glycol ether carbonate, any of those described in detail in JP-A-91-149295 can be used.
    In addition, as the carbonate derivative, carbonate esters of the general formula XXI can be used:
    Where
    R 57 and R 58 are each an alkyl group having 1 to 15 carbon atoms or a divalent alcohol residue having 2 to 12 carbon atoms, and may be the same or different from each other;
    R 59 is an alkylene group having 2 to 12 carbon atoms;
    p is an integer of 0-30.
    In formula (XXI), R 57 and R 58 are each an alkyl group having 1 to 15 carbon atoms, preferably 2 to 9 carbon atoms or a divalent alcohol residue having 2 to 12 carbon atoms, preferably 2 to 9 carbon atoms;
    R 59 is an alkylene group having 2 to 12 carbon atoms, preferably 2 to 9 carbon atoms;
    p is an integer of 0-30, Preferably it is 1-30.
    Use of a carbonate ester that does not satisfy the above conditions is not preferable because various performances such as compatibility with a flon refrigerant are inferior. Specific examples of the alkyl group having 1 to 15 carbon atoms for R 57 and R 58 include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group and n-jade Tyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, isopropyl group, isobutyl group, t- Butyl group, isopentyl group, isohexyl group, isoheptyl group, isooctyl group, isononyl group, isodecyl group, isoundecyl group, isodecyl group, isotridecyl group, isotetradoyl group, isopentadecyl group Can be mentioned.
    As the divalent alcohol residue having 2 to 12 carbon atoms, specifically, ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 8-methyl-1,3-propane Diol, 1,5-pentanediol, neopentylglycol, 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-undecandiol, And residues such as 1,12-dodecanediol.
    Examples of the alkylene group having 2 to 12 carbon atoms for R 59 include ethylene group, trimethylene, propylene group, tetramethylene group, butylene group, 2-methyltrimethylene group, pentamethylene group, and 2,2-dimethyltri. Methylene group, hexamethylene group, 2-ethyl-2-methyltrimethylene group, heptamethylene group, 2-methyl-2-propyltrimethylene group, 2,2-diethyltrimethylene group, octamethylene group, nonamethylene group And those having a straight chain or branched chain structure, such as a decamethylene group, an undecamethylene group, and a dodecamethylene group.
    Although the molecular weight of the said carbonate ester is not specifically limited, From a viewpoint of further improving the sealing property of a compressor, etc., it is preferable that the number average molecular weight is 200-3000, It is used preferably that the number average molecular weight is 300-2000. do.
    As the carbonate ester, those described in detail in Japanese Patent Application Laid-Open No. 92-63893 can be used.
    As a polyether ketone of said (6), the compound of the following general formula (XXII) is mentioned:
    Where
    Q is an alcohol residue of 1 to 8 valent;
    R 60 is an alkylene group having 2 to 4 carbon atoms;
    R 61 is a methyl group or an ethyl group;
    R 62 and R 64 are each a hydrogen atom, an aliphatic, aromatic or aromatic aliphatic hydrocarbon group having 20 or less carbon atoms, which may be the same or different from each other;
    R 63 is an aliphatic, aromatic or aromatic aliphatic hydrocarbon group having 20 or less carbon atoms;
    r and s are numbers from 0 to 30;
    u is a number from 1 to 8;
    v is a number from 0 to 7, and u + v satisfies 1 to 8;
    t is 0 or 1;
    In the general formula (XXII), Q is a 1-8 valent alcohol residue, and the alcohol having Q as a residue is
    As the monohydric alcohol, for example, methyl alcohol, ethyl alcohol, linear or branched propyl alcohol, straight or branched butyl alcohol, straight or branched pentyl alcohol, straight or branched hexyl alcohol, straight or branched chain Heptyl alcohol, straight or branched octyl alcohol, straight or branched nonyl alcohol, straight or branched decyl alcohol, straight or branched undecyl alcohol, straight or branched dodecyl alcohol, straight or branched chain Tridecyl alcohol, straight or branched tetradecyl alcohol, straight or branched pentadecyl alcohol, straight or branched hexadecyl alcohol, straight or branched heptadecyl alcohol, straight or branched octadecyl alcohol, Aliphatic monohydric alcohols such as linear or branched nonadecyl alcohol and linear or branched eicosyl alcohol; Aromatic alcohols such as phenol, methylphenol, nonylphenol, octylphenol and naphthol; Aromatic fatty alcohols such as benzyl alcohol and phenylethyl alcohol; And partial ethyl ether compounds thereof;
    As a dihydric alcohol, For example, linear or branched aliphatic alcohol, such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, tetramethylene glycol; Aromatic alcohols such as catechol, resorcinol, bisphenol A and bisphenyldiol; And partial ethers of these and the like,
    Examples of the trihydric alcohols include linear or branched aliphatic alcohols such as glycerin trimethylol propane, trimethylol ethane, trimethylol butane, 1,3,5-pentanetriol, pyrogallol, methyl pyrogallol, and 5-2. Aromatic alcohols such as tert-butyl pyrogallol; And partial ethers of these and the like,
    Examples of the tetrahydric to octahydric alcohols include aliphatic alcohols such as pentaerythritol, diglycerin, sorbitan, triglycerine, sorbitol, dipentaerythritol, tetraglycerine, pentaglycerin, hexaglycerin and tripentaerythritol, and these. And partial ethers of these compounds.
    In addition, in the general formula (XXII), the alkylene group having 2 to 4 carbon atoms of R 60 is linear or branched, and specific examples thereof include ethylene group, propylene group, ethyl ethylene group, 1,1-dimethylethylene group, 1,2 -Dimethylethylene group etc. are mentioned. As the aliphatic, aromatic or aromatic aliphatic hydrocarbon group having 20 or less carbon atoms of R 62 to R 64 , for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, octyl group, nonyl group, decyl group, Straight chain alkyl groups such as undecyl group, lauryl group, myristyl group, palmityl group, stearyl group, isopropyl group, isobutyl group, isoamide group, 2-ethylhexyl group, isostearyl group, 2-heptyl undecyl group Aryl groups, such as an aryl group, such as a branched chain alkyl group, a phenyl group, and a methylphenyl group, and a benzyl group, etc. are mentioned.
    In the general formula (XXII), r and s are numbers from 0 to 30, and when r and s are greater than 30, the contribution of ether groups in the molecule increases, which is not preferable in view of compatibility, electrical insulation and hygroscopicity of the flon refrigerant. In addition, u is a number from 1 to 8, v is a number from 0 to 7, u + v satisfies a relationship from 1 to 8, these numbers represent average values, and there is no limit to the integer. t is 0 or 1; Also, r x u R 60 may be the same or different, respectively, and s x u R 61 may be the same or different, respectively. When u is 2 or more, u r, s, t, R 62 and R 63 may each be the same or different, and when v is 2 or more, v R 64 may be the same or different, respectively.
    A well-known method can be employ | adopted for the method of manufacturing the polyether ketone of the said general formula (XXII). For example, a method of oxidizing a secondary alkyloxy alcohol with hypochlorite and acetic acid (Japanese Patent Laid-Open No. 92-1267126) or a method of oxidizing using zirconium hydroxide and ketone (Japanese Patent Laid-Open No. 91- 167149) may be used.
    As said fluorinated oil of (7), the fluorinated silicone oil, perfluoro polyether, the reactant of an alkane and a perfluoroalkyl vinyl ether, etc. are mentioned, for example. Examples of reactants of alkanes with perfluoroalkylvinyl ethers include compounds of formula XXV, which can be obtained by reacting perfluoroalkylvinyl ethers of formula XXIII:
    C n H 2n + 2
    CF 2 = CFOC m F 2m + 1
    C n H (2n + 2-w) (CF 2 -CFHOC m F 2m + 1 ) w
    Where
    n is an integer from 6 to 20,
    m is an integer from 1 to 4,
    w is an integer from 1 to 4.
    The alkanes of Formula XXIII may be linear, branched or cyclic, and specific examples thereof include n-octane, n-decane, n-dodecane, cyclooctane, cyclododecane, 2,2,4-trimethylpentane, and the like. The specific examples of the perfluoroalkyl vinyl ether of the general formula (XXIV) include perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoro n-propyl vinyl ether, and perfluoro n-butyl vinyl ether. Etc. can be mentioned.
    Next, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to this example.
    Examples 1-16 and Examples 1 and 2
    The base oils and additives of the types listed in Tables 1a and 1b below were combined in the amounts shown in Tables 1a and 1b based on the total weight of the composition to prepare a freezer oil composition. In this composition, the burn test, the abrasion test and the seal tube test were carried out according to the description indicated below to evaluate the performance. These results are shown in Table 2.
    (1) baking test
    Using a Parex tester, the pin / block material was prepared with A4032 / AISI-C-1137. The pin / block was set and 4 μl of sample oil was applied to the pin. After setting the inside of the tester to the R134a atmosphere, the time (baking time) of baking was measured at room temperature under conditions of a load of 100 Lbs and a rotation speed of 300 rpm.
    (2) abrasion test
    Using a Parex tester, the pin / block material was prepared with A4032 / AISI-C-1137. After setting the pin / block, 200g of sample oil and 200g of R134a were filled into the test container, and then abrasion test was carried out under the conditions of rotation speed 290 rpm, oil temperature 50 ° C, load 400 Lbs, test time 60 minutes, Pin wear was measured.
    (3) sealed tube test
    A catalyst (1.5 mm diameter, 4 cm long iron, copper and aluminum wire) was placed in a glass tube, filled with a mixture of R134a / sample oil / water = 1 g / 4 ml / 0.01 ml and the tube was sealed. . After sealing, the mixture was kept at 175 ° C for 10 days, and then the appearance of oil, appearance of catalyst, increase in total acid value and presence of sludge were examined.
    The total acid value was calculated from the values before and after the test in accordance with JIS K 2501, and the amounts thereof are shown in Table 2 below. In these tables, when the oil appearance is good and the catalyst appearance is good, it is considered that the appearance does not change before and after the test.
    Type of basic oilType of additiveCompounding amount of the additive (wt%) Example 1OneA10.1 Example 2OneA11.0 Example 3OneA110.0 Example 4OneA21.0 Example 5OneA31.0 Example 6OneA41.0 Example 7OneA51.0 Example 82A11.0 Example 93A11.0 Example 104A11.0 Example 115A11.0 Example 126A11.0 Example 137A11.0 Example 148A11.0 Example 15OneA1 / TCP1.0 / 1.0 Example 16OneA1 / TCP10.0 / 1.0
    Type of basic oilType of additiveCompounding amount of the additive (wt%) Comparative Example 1OneB11.0 Comparative Example 2OneTCP3.0 Note: * Type of base oil 1: Polyoxypropylene glycol dimethyl ether Dynamic viscosity 9.3 mm2 / sec (100 ° C), molecular weight 11502: Polyoxyethylene polyoxypropylene glycol dimethyl ether dynamic viscosity 20.5 mm2 / second (100 ° C), molecular weight 15903 : Polyoxypropylene glycol mono butyl ether unirub MB11 (manufactured by Nippon Oil Industries, Ltd.) dynamic viscosity 10.8 mm 2 / sec (100 ° C), molecular weight 10004: polyoxypropylene glycol diacetate dynamic viscosity 10.2 mm 2 / sec (100 ° C), Molecular weight 9805: Polyoxypropylene glycol dimethyl carbonate Dynamic viscosity 9.6 mm 2 / sec (100 ° C.), Molecular weight 8506. Polyvinyl ethyl ether-polyvinyl butyl ether copolymer Dynamic viscosity 7.8 mm 2 / sec (100 ° C.), molecular weight 90087. Hindered ester (Emucalate RL68Se (manufactured by ICI)) Dynamic viscosity 10.2 mm 2 / sec (100 ° C) Alkylbenzene (IM200: manufactured by Samneung Chemical Co., Ltd.) Dynamic Viscosity 4.6 mm 2 / sec (100 ° C.) * Type of Additive A1: Polyoxyethylene Oleyl Ether Emalgen 409P (manufactured by Shipbuilding Co., Ltd.) 9, HLB 12.0A2: polyoxyethylene nonyl phenyl ether malgen 905 (manufactured by Shipbuilding Co., Ltd.) addition mole number 5 of the oxyethylene group, HLB 9.2A3: polyoxyethylene monolaurate emone 1112 (manufactured by Shipbuilding Co., Ltd.) Addition number-of-moles of an oxyethylene group 11, HLB 3.7A4: Polyoxyethylene sorbitan monooleate leodol TW-O-0106 (made by shipper Co., Ltd.) Addition number-of-moles 6, HLB 10.0A5: Polyoxyethylene sorbitol tetra Oleoledol 430 (manufactured by Shipbuilding Co., Ltd.) Addition number of moles of oxyethylene group 30, HLB 10.5B1: Addition number of moles of polyoxypropylene oleyl etheroxypropylene group 9, HLB 7.2 TCP: Tricyl phosphate
    Burn time (seconds)Abrasion amount (mg)Sealed tube test Oil appearanceCatalyst appearanceTotal acid valuePresence of sludge Example 11041.2GoodGood0.1>none Example 22800.3GoodGood0.1>none Example 33500.1>GoodGood0.1>none Example 41501.9GoodGood0.1>none Example 51202.8GoodGood0.2none Example 61302.3GoodGood0.2none Example 71202.6GoodGood0.2none Example 82500.3GoodGood0.1>none Example 91900.9GoodGood0.1>none Example 101103.4GoodGood0.3none Example 111003.9GoodGood0.1none Example 122700.3GoodGood0.1>none Example 131102.7GoodGood0.3none Example 141901.3GoodGood0.1none Example 153600.1>GoodGood0.2none Example 164800.1>GoodGood0.2none Comparative Example 13643GoodGood0.1>none Comparative Example 22095GoodGood1.1none
    The refrigerator oil composition of the present invention has excellent lubricating performance, and in particular, improves the lubricating oil property between the aluminum material and the steel material, prevents seizure and abrasion, and uses a hydrogen-containing flan refrigerant such as R134a that does not cause environmental pollution. It is preferable as a used refrigerator oil composition.
    Therefore, the refrigerator oil composition of the present invention is particularly effective when used in automobile air conditioners, indoor air conditioners, refrigerators, and the like, and its industrial use value is very high.
    权利要求:
    Claims (10)
    [1" claim-type="Currently amended] A refrigeration oil composition comprising at least one base oil selected from the group consisting of mineral oils and synthetic oils, and at least one polyoxyethylene-based nonionic surfactant.
    [2" claim-type="Currently amended] The method of claim 1,
    Refrigerator oil composition whose addition mole number of the oxyethylene group of a polyoxyethylene type nonionic surfactant is 1-40.
    [3" claim-type="Currently amended] The method according to claim 1 or 2,
    A refrigerator oil composition having a hydrophile-lipophile balance (HLB) of 2 to 30 of a polyoxyethylene-based nonionic surfactant.
    [4" claim-type="Currently amended] The method according to claim 1 or 2,
    The polyoxyethylene nonionic surfactant is composed of polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene aryl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester and polyoxyethylene sorbitol fatty acid ester At least one freezer oil composition selected from the group.
    [5" claim-type="Currently amended] The method of claim 3, wherein
    The polyoxyethylene nonionic surfactant is composed of polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene aryl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester and polyoxyethylene sorbitol fatty acid ester At least one freezer oil composition selected from the group.
    [6" claim-type="Currently amended] The method according to claim 1 or 2,
    A refrigerator oil composition, wherein the blending amount of the polyoxyethylene nonionic surfactant is 0.01 to 30% by weight based on the total amount of the composition.
    [7" claim-type="Currently amended] The method of claim 3, wherein
    A refrigerator oil composition, wherein the blending amount of the polyoxyethylene nonionic surfactant is 0.01 to 30% by weight based on the total amount of the composition.
    [8" claim-type="Currently amended] The method of claim 4, wherein
    A refrigerator oil composition, wherein the blending amount of the polyoxyethylene nonionic surfactant is 0.01 to 30% by weight based on the total amount of the composition.
    [9" claim-type="Currently amended] The method of claim 5,
    A refrigerator oil composition, wherein the blending amount of the polyoxyethylene nonionic surfactant is 0.01 to 30% by weight based on the total amount of the composition.
    [10" claim-type="Currently amended] The method according to claim 1 or 2,
    Refrigerator oil composition wherein the kinematic viscosity of the base oil at 100 ° C. is from 1 to 100 mm 2 / sec.
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    同族专利:
    公开号 | 公开日
    KR100496780B1|2005-09-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1996-06-25|Priority to JP96-164321
    1997-06-18|Application filed by 도미나가 가즈토, 이데미쓰 고산 가부시키가이샤
    1997-06-18|Priority to KR10-1998-0710621A
    2000-04-25|Publication of KR20000022202A
    2005-09-09|Application granted
    2005-09-09|Publication of KR100496780B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP96-164321|1996-06-25|
    KR10-1998-0710621A|KR100496780B1|1996-06-25|1997-06-18|Refrigerator oil composition|
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