WO2005012469A1 - 冷凍機油組成物 - Google Patents
冷凍機油組成物 Download PDFInfo
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- WO2005012469A1 WO2005012469A1 PCT/JP2004/010840 JP2004010840W WO2005012469A1 WO 2005012469 A1 WO2005012469 A1 WO 2005012469A1 JP 2004010840 W JP2004010840 W JP 2004010840W WO 2005012469 A1 WO2005012469 A1 WO 2005012469A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/008—Lubricant compositions compatible with refrigerants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
- C10M2207/2825—Esters of (cyclo)aliphatic oolycarboxylic acids used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
Definitions
- the present invention relates to a refrigerating machine oil composition used for a compressor of a refrigerating air conditioner.
- Patent Document 1 Japanese Patent Publication No. Hei 3-505602
- Patent Document 2 JP-A-3-128992
- Patent Document 3 JP-A-3-200895
- the present invention has been made in view of the above-mentioned problems of the related art, and has excellent lubricating properties in refrigeration and air-conditioning equipment using various refrigerants such as HFC, and has been used for a long time. It is an object of the present invention to provide a refrigerating machine oil composition capable of operating stably over a long period of time.
- the present invention provides a refrigerating machine oil composition containing a predetermined base oil, a phosphorus-based extreme pressure agent, and an ester-based additive.
- a phosphorus-based extreme pressure agent and an oil agent are used in combination.
- both the wear resistance and the frictional characteristics of the refrigerator oil composition are sufficiently enhanced, it is possible to stably operate the refrigerator air conditioner for a long period of time even when used with an HFC refrigerant or the like.
- the effect of improving the wear resistance and friction characteristics of the refrigerating machine oil composition of the present invention can contribute to the improvement of the energy efficiency of the refrigerating and air-conditioning equipment, thereby saving energy and further reducing the manufacturing cost of the refrigerating and air-conditioning equipment. It is very useful from the viewpoint of reduction.
- reduction of wear and friction caused by refrigeration oil has not been sufficiently studied, and there is a concern that the use of wear-resistance improvers and oil-based agents may have adverse effects. It was common practice to improve wear resistance and friction characteristics by improving the hardware side such as.
- the sliding load inside the compressor is sufficiently reduced due to its excellent abrasion resistance and friction characteristics. It is possible to improve the energy efficiency of refrigeration and air conditioning equipment without making improvements on the side. Further, the effect of improving the abrasion resistance and friction characteristics according to the present invention makes it possible to use a low-grade, low-grade sliding member, that is, an inexpensive sliding member as a sliding member of a compressor. Cost reduction can be realized. On the other hand, by combining the refrigerating machine oil composition of the present invention with a compressor or the like having improved wear resistance, energy efficiency can be dramatically improved.
- the effect of improving the wear resistance and friction characteristics of the refrigerating machine oil composition of the present invention can be obtained for the first time by using a phosphorus-based extreme pressure agent and an oil agent in combination. Or, it is dramatic compared to the case where one of the oil agents is used alone.
- the effect of improving abrasion resistance and friction characteristics becomes insufficient, or the thermal and oxidation stability of the refrigerating machine oil increases. Prevention of precipitation in a refrigerant atmosphere and at a low temperature may be impaired.
- an extreme pressure agent such as a phosphorus compound is used alone, the friction characteristics may be reduced.
- these characteristics can be maintained at a high level.
- phosphorous extreme pressure agent includes phosphorus esters such as phosphate esters, acidic phosphate esters, amine salts of acidic phosphate esters, chlorinated phosphate esters, and phosphite esters. system Additives, as well as phosphorothionates (thiophosphates) are included.
- the phosphorus-based extreme pressure agent preferably contains phosphorothionate.
- the phosphorothionate and the oily agent in combination, it is possible to achieve both abrasion resistance and friction characteristics of the refrigerating machine oil composition at a high level in a well-balanced manner.
- the phosphorus-based extreme pressure agent preferably contains both phosphorothioate and a phosphorus-based extreme pressure agent other than the phosphorothionate.
- the above-mentioned effect of the present invention is obtained. Effect can be obtained at a higher level, and in particular, the wear resistance can be further improved.
- the refrigerator oil composition of the present invention preferably further contains an epoxy compound.
- the oil agent preferably contains an ester oil agent.
- the oil agent may contain at least one selected from an ester of a monobasic acid and a monohydric alcohol and an ester of a linear dibasic acid and a monohydric alcohol. More preferably, it contains at least one selected from esters of preferred monobasic acids having 12 or more carbon atoms and monohydric alcohols and esters of linear dibasic acids and monohydric alcohols.
- the oily agent contains an ester oily agent, and the content of the ester oily agent is 0.0110% by mass based on the total amount of the composition. Is preferred.
- the base oil is at least one selected from an ester of a polyhydric alcohol and a monohydric fatty acid and an ester of an aliphatic cyclic dibasic acid and a monohydric alcohol.
- the oil agent comprises at least one selected from esters of monobasic acids and monohydric alcohols and esters of linear dibasic acids and monohydric alcohols.
- the combination of the power and the ester base oil and the ester oil agent can further improve the abrasion resistance and the abrasion characteristics, and the precipitation prevention under a refrigerant atmosphere and at a low temperature.
- the refrigerating machine oil composition of the present invention excellent lubricity can be obtained in a refrigeration / air-conditioning device using various refrigerants such as HFC, and the refrigeration / air-conditioning device can be stably operated for a long period of time. It becomes possible.
- the base oil used in the present invention may be either a mineral oil or a synthetic oil, or may be a mixed base oil of a mineral oil and a synthetic oil.
- the mineral oil for example, a lubricating oil fraction obtained by atmospheric distillation and vacuum distillation of a paraffin-based crude oil, an intermediate-based crude oil or a naphthenic-based crude oil is subjected to solvent removal, solvent extraction, Paraffinic mineral oil or naphthenic mineral oil obtained by appropriately combining one or two or more refining means of hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment No.
- highly refined mineral oil (hereinafter, referred to as "highly refined mineral oil”) because of its superior thermal stability.
- highly refined mineral oil a distillate obtained by distilling a paraffin-based crude oil, an intermediate-base crude oil or a naphthenic-based crude oil under normal pressure, or distilling a residual oil obtained by distillation under reduced pressure under reduced pressure is usually used.
- Refined oil obtained by refining according to the method deep-dewaxed oil obtained by further deep-dewaxing after refining; hydrogenated oil obtained by hydrogenation treatment, and the like.
- the purification method in the above-mentioned purification step is not particularly limited, and a conventionally known method may be used.
- Power that can be performed for example, (a) hydrogenation treatment, (b) dewaxing treatment (solvent dewaxing or hydrogenation dewaxing), (c) solvent extraction treatment, (d) alkali washing or sulfuric acid washing treatment, (e ) A method of performing any of the clay treatments alone or by combining two or more in an appropriate order. It is also effective to repeat any one of the processes (a) to (e) in a plurality of stages.
- a method of hydrotreating a distillate or a method of performing an alkali washing or a sulfuric acid washing treatment after the hydrogenation;
- a method of hydrotreating the distillate Dewaxing method;
- Hydrogenation treatment after distillate is subjected to solvent extraction;
- Distillation oil is subjected to two-stage or three-stage hydrogenation treatment, followed by alkali washing Or a method of performing a sulfuric acid washing treatment;
- V a method of performing the above treatment (i)-(iv), and then performing a dewaxing treatment again to obtain a deeply dewaxed oil.
- naphthenic mineral oils and mineral oils obtained by deep dewaxing are preferred in view of low-temperature fluidity and no wax precipitation at low temperatures. is there.
- This deep dewaxing treatment is usually performed by a solvent dewaxing method under severe conditions, such as a catalytic dewaxing method using a zeolite catalyst.
- the non-aromatic unsaturated component (unsaturation degree) of the highly refined mineral oil is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, and particularly preferably. 0.1% by mass or less. If the non-aromatic unsaturated content exceeds 10% by mass, sludge will be generated and become chewy, and as a result, expansion mechanisms such as cabilli which constitute the refrigerant circulation system will tend to be clogged.
- synthetic oils used in the present invention include hydrocarbon oils such as olefin polymers, naphthalene conjugates, and alkylbenzenes; esters, polyoxyalkylene glycolones, polybutyl ethers, ketones, and polyphenyl ethers. And oxygen-containing synthetic oils such as silicone, polysiloxane, and perfluoroether.
- Examples of the olefin polymer include those obtained by polymerizing an olefin having 2 to 12 carbon atoms, and those obtained by subjecting a compound obtained by the polymerization to a hydrogenation treatment.
- Examples of the olefin polymer include polybutene, polyisobutene and 5 carbon atoms.
- — 12 oligomers of polyolefins (polyolefins), ethylene-propylene copolymers and their hydrogenated ones are preferably used.
- the method for producing the olefin polymer is not particularly limited, and can be produced by various known methods.
- poly- ⁇ -olefins are produced by using ⁇ -olefins produced from ethylene as raw materials and subjecting them to known polymerization methods such as the Ziegler catalyst method, radical polymerization method, aluminum chloride method, and boron fluoride method. You.
- the naphthalene compound is not particularly limited as long as it has a naphthalene skeleton. From the viewpoint of excellent compatibility with a refrigerant, the naphthalene compound has 114 alkyl groups having 11 to 10 carbon atoms, and has an alkyl group. Are preferably those having 1 to 10 alkyl groups having 1 to 8 carbon atoms, and those having 3 to 8 total carbon atoms in the alkyl group. Les ,.
- alkyl group having 11 to 10 carbon atoms in the naphthalene compound include a methyl group, an ethyl group, an ⁇ -propyl group, an isopropyl group, a linear or branched butyl group, and a straight-chain or branched butyl group.
- Linear or branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched Examples include a branched nonyl group, a linear or branched desinole group, and the like.
- naphthalene compound When a naphthalene compound is used, a compound having a single structure may be used alone, or two or more compounds having different structures may be used in combination.
- the method for producing the naphthalene compound is not particularly limited, and can be produced by various known methods. Examples of this include halogenated hydrocarbons having 11 to 10 carbon atoms, olefins having 2 to 10 carbon atoms or styrenes having 8 to 10 carbon atoms, such as sulfuric acid, phosphoric acid, keitandastenoic acid, and hydrofluoric acid.
- the alkylbenzene that works in the present invention is not particularly limited. However, from the viewpoint of excellent compatibility with a refrigerant, the alkylbenzene has 114 alkyl groups having 1 to 40 carbon atoms, and has a total carbon number of the alkyl groups of 1 to 40. Those having 1 to 40 preferably have 1 to 30 alkyl groups having 1 to 30 carbon atoms, and more preferably those having a total of 3 to 30 carbon atoms in the alkyl groups.
- alkyl group having 1 to 40 carbon atoms included in the alkylbenzene include a methyl group, an ethyl group, an ⁇ -propyl group, an isopropyl group, a linear or branched butyl group, and a straight-chain or branched butyl group.
- the above alkyl group may be linear, branched, or displaced, but from the viewpoint of compatibility with the organic material used in the refrigerant circulation system, the linear alkyl group Is preferred.
- branched alkyl groups are preferred in terms of refrigerant compatibility, thermal stability, lubricity, etc.
- branched alkyl groups derived from oligomers of olefins such as propylene, butene, and isobutylene Alkyl groups are more preferred.
- alkylbenzene When alkylbenzene is used, a compound having a single structure may be used alone, or two or more compounds having different structures may be used in combination.
- the method for producing the above-mentioned alkylbenzene is arbitrary, and is not limited at all. However, for example, it can be produced by the following synthesis method.
- aromatic compound as a raw material examples include benzene, toluene, xylene, and benzene. Stylbenzene, methylethylbenzene, getylbenzene and mixtures thereof are used.
- linear or branched C6-40 carbon olefins obtained by polymerization of lower monoolefins (preferably propylene) such as ethylene, propylene, butene, and isobutylene; waxes, heavy oils, petroleum oils Distillate, linear or branched C6-40 carbon obtained by pyrolysis of polyethylene, polypropylene, etc .; n-paraffins are separated from petroleum fractions such as kerosene and gas oil, A straight-chain olefin having 940 carbon atoms obtained by olefin formation, a mixture thereof and the like can be used.
- lower monoolefins preferably propylene
- waxes heavy oils, petroleum oils Distillate
- n-paraffins are separated from petroleum fractions such as kerosene and gas oil
- a Friedel-Crafts type catalyst such as aluminum chloride, zinc chloride, etc., sulfuric acid, phosphoric acid, kytungstic acid, hydrogen fluoride
- a conventionally known alkylation catalyst such as an acid catalyst such as an acid and activated clay can be used.
- ester examples include an aromatic ester, a dibasic acid ester, a polyol ester, a complex ester, a carbonate ester, and a mixture thereof.
- the strong aromatic ester may be an aromatic carboxylic acid having a valency of 116, preferably 114, and more preferably a trivalent, and a fatty acid having a carbon number of 11 to 18, preferably 11 to 12 Esters with aliphatic alcohols.
- Specific examples of the hexavalent aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and mixtures thereof.
- the aliphatic alcohol having 118 carbon atoms may be linear or branched. Specifically, methanol, ethanol, linear or branched aliphatic alcohol may be used.
- Propanol linear or branched butanol, linear or branched pentanol, linear or branched hexanol, linear or branched heptanol, linear or branched Branched octanol, linear or branched nonanol, linear or branched decanol, linear or branched pendanol, linear or branched dodecanol, linear Linear or branched tridecanol, linear or branched tetradecanol, linear or branched pentadecanol, linear or branched hexadecanol, linear or branched Heptadecanol, linear or branched octadecanol and Mixtures of al the like.
- aromatic ester obtained by using the above aromatic compound and an aliphatic alcohol include dibutyl phthalate, di (2-ethylhexyl) phthalate, dinonyl phthalate, and phthalate.
- an aromatic carboxylic acid having a valency of 2 or more when used, it may be a simple ester composed of one kind of aliphatic alcohol, or composed of two or more kinds of aliphatic alcohols. It may be a complex ester.
- dibasic acid ester examples include gnooleic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, and 4-cyclohexene-1,2- A linear or cyclic aliphatic dibasic acid having 5 to 10 carbon atoms, such as dicarboxylic acid, and methanol, ethanol, ethanol, propanol, butanol, pentano, hexanol, heptano, octanol, nonanol, decanol, and decanol , Dodecanol, tridecanol, tetradecanol, pentadecanol and the like, esters with a straight-chain or branched monohydric alcohol having a carbon number of 115, and mixtures thereof are preferably used.
- an ester of a diol or a polyol having 3 to 20 hydroxyl groups and a fatty acid having 620 carbon atoms is preferably used.
- the diolefin include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, and 2-methynole-1,3-propane.
- Diol 1,5_pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethynole_2-methinole 1,3_propanediol, 1,7_heptanediol, 2-methylinole_2_propynole 1,3_propanediole, 2,2_jetinole_1,3_propanediole, 1,8_octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11 —Condecandiol, 1,12-dodecanediol and the like.
- polyol specifically, trimethylolethane, trimethylolpropane, trimethylolbutane, di (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di (pentaerythritol), tri- (pentaerythritol) Pentaerythritol), glycerin, polyglycerin (2 to 20-mer of glycerin), 1,3,5-pentanetrinone, reci'tonore, recvi'tan, reci, toluglycerin condensate, adnitol, arabitol, Polyvalent anoreconore such as xylitol and mannitol, xylose, arabinose, ribose, rhamnose, gnoleose, fructose, galactose, mannose, sonorebose, cellobiose, manoletoo
- neopentyl glycol trimethylolethane, trimethylolpropane, trimethylolbutane, di (trimethylolpropane), tri (trimethylolpropane), pentaerythritol, di (pentaerythritol), Hindered alcohols such as tri- (pentaerythritol) are preferred.
- the fatty acid used in the polyol ester has no particular restriction on the number of carbon atoms, but usually one having 1 to 24 carbon atoms is used.
- the fatty acids having 1 to 24 carbon atoms those having 3 or more carbon atoms are preferred from the viewpoint of lubricity, those having 4 or more carbon atoms are more preferred, and those having 5 or more carbon atoms are even more preferred 10 The above are particularly preferred.
- those having 18 or less carbon atoms are preferred, those having 12 or less carbon atoms are more preferred, and those having 9 or less carbon atoms are more preferred.
- the fatty acid to be used may be either a linear fatty acid or a branched fatty acid, but from the viewpoint of lubricity, it is preferred from the viewpoint of hydrolysis stability that linear fatty acids are preferred. Branched fatty acids are preferred. Further, the fatty acid may be a saturated fatty acid or an unsaturated fatty acid.
- fatty acid examples include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, pendecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, and hexadecane Acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, oleic acid, etc., and these fatty acids are linear fatty acids and branched fatty acids.
- any of them may be a fatty acid (neo acid) in which the ⁇ carbon atom is a quaternary carbon atom.
- valeric acid ⁇ -pentanoic acid
- caproic acid ⁇ -hexanoic acid
- enanthic acid ⁇ -heptanoic acid
- caprylic acid ⁇ -octanoic acid
- pelargonic acid ⁇ -nonanoic acid
- Acid payingc acid ⁇ -decanoic acid
- oleic acid cis-9-octadecenoic acid
- isopentanoic acid (3-methylbutanoic acid)
- 2-methylhexanoic acid 2-ethylpentanoic acid
- 2-ethylhexanoic acid 2-ethylhexanoic acid
- 3,5,5_trimethylhexanoic acid are preferably used.
- the polyol ester which can be used in the present invention may be a partial ester in which some of the hydroxyl groups of the polyol remain without being esterified as long as the polyol ester has two or more ester groups. It may be a perfect ester in which all of the hydroxyl groups are esterified, or a mixture of a partial ester and a perfect ester, and is preferably a perfect ester.
- the complex ester is an ester of a fatty acid and a dibasic acid with a monohydric alcohol and a polyol.
- a fatty acid the dibasic acid, the monohydric alcohol and the polyol
- the above-mentioned dibasic acid ester and The fatty acids, dibasic acids, monohydric alcohols and polyols exemplified in the description of the polyol ester can be used.
- Is a compound having a carbonic acid ester bond represented by The number of the carbonate bond represented by the above formula (1) may be one or two or more per molecule.
- the alcohol constituting the carbonate ester use is made of the monohydric alcohols and polyols exemplified in the description of the dibasic acid ester and the polyol ester, and those obtained by adding polyglycol to polyglycol or polyol. be able to. Also
- a compound obtained from carbonic acid and a fatty acid and / or a dibasic acid may be used.
- a compound having a single structure may be used alone, or two or more compounds having different structures may be used in combination.
- esters dibasic acid esters, polyol esters and carbonate esters are preferred because of their excellent compatibility with refrigerants.
- Alicyclic dicarboxylic acid esters such as oral hexene 1,2-dicarboxylic acid are more preferred in view of compatibility with a refrigerant and stability of heat and hydrolysis.
- dibasic acid ester preferably used in the present invention include at least one monohydric alcohol selected from the group consisting of butanol, pentanol, hexanol, heptanol, octanol and nonanol;
- dibasic acid esters obtained from at least one dibasic acid selected from the group consisting of 2-cyclohexanedicarboxylic acid and 4-cyclohexene-1,2-dicarboxylic acid, and mixtures thereof.
- the monohydric alcohol constituting the dibasic acid ester is divalent. Les, preferably more than species.
- a dibasic acid ester composed of two or more monohydric alcohols refers to a mixture of two or more esters of a dibasic acid and one alcohol, and a mixed alcohol of two or more dibasic acids and two or more alcohols. It is intended to include the ester of the above.
- neopentyl dalycol trimethylolethane, trimethylolpropane, trimethylolbutane, di (trimethylolpropane), tri- (trimethylol) are more excellent in hydrolytic stability.
- Esters of hindered alcohols such as propane), pentaerythritol, di (pentaerythritol), and tri (pentaerythritol) are more preferred.
- Esters of erythritol are more preferred, and esters of pentaerythritol are most preferred because they are particularly excellent in compatibility with a refrigerant and hydrolytic stability.
- At least one fatty acid selected from the group consisting of 2, 2-ethylpentanoic acid, 2-ethylhexanoic acid and 3,5,5_trimethylhexanoic acid, neopentinoleglycorone, trimethylolethane, trimethylolpropane
- at least one alcohol selected from the group consisting of trimethylolbutane and pentaerythritol, diesters, triesters, tetraesters, and mixtures thereof obtained.
- a polyol ester of two or more fatty acids includes a mixture of two or more esters of a polyol and one fatty acid, and an ester of a polyol and two or more mixed fatty acids. It is.
- X 1 is a hydrogen atom, an alkyl group, a cycloalkyl group or the following general formula (3): [0062] Y 2 _ ( ⁇ A 3 )-(3)
- Y 2 represents a hydrogen atom, an alkyl group or a cycloalkyl group
- a 3 represents an alkylene group having 24 carbon atoms
- e represents an integer of 150
- a 1 and A 2 each represent an alkylene group having 24 carbon atoms, which may be the same or different, Y 1 represents a hydrogen atom, an alkyl group or a cycloalkyl group, and B represents A represents a residue of a compound having 3 to 20 hydroxyl groups, a represents an integer of 1 to 20, b represents an integer of 0 to 19 and a + b represents 3 to 20, c represents an integer of 0 to 50, d represents an integer of 1 to 50].
- X 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group or a group represented by the above formula (3).
- the number of carbon atoms in the alkyl group referred to herein is not particularly limited, but is usually 124, preferably 118, and more preferably 112.
- the alkyl group may be straight-chain or branched.
- alkyl group having 1 to 24 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec_butyl group, and a tert_butyl group.
- cycloalkyl group examples include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
- examples of the alkylene group having 2 to 4 carbon atoms represented by A 3 include an ethylene group, a propylene group, a trimethylene group, a butylene group, a tetramethylene group, and a 1-methylene group.
- examples thereof include a rutrimethylene group, a 2-methyltrimethylene group, a 1,1-dimethylethylene group, and a 1,2-dimethylethylene group.
- Y 2 in the above formula (2) represents a hydrogen atom, an alkyl group or a cycloalkylalkyl group.
- the number of carbon atoms of the alkyl group is not particularly limited, but is usually 124, preferably 118, more preferably 112.
- the alkyl group may be linear or branched.
- the alkyl group of 1 one 24 carbon atoms include alkyl groups shown examples in the description of the X 1.
- cycloalkyl group examples include a cyclopentyl group, a cyclohexynole group, and a cycloheptyl group.
- a hydrogen atom or an alkyl group having 11 to 12 carbon atoms is preferable, and a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, —Butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentynole group, n-hexynole group, iso-hexynole group, n_ Heptinole group, iso-heptinole group,
- n-octinole iso-octinole, n-noninole, iso-noninole, n_tesinole, iso-desinole, n-indecyl, iso-indecyl, n-dodecyl or iso-dodecyl It is more preferable to be one of them.
- E represents an integer of 1 to 50.
- the group represented by X 1 is preferably a hydrogen atom, an alkyl group having 11 to 12 carbon atoms, or a hydrogen atom, preferably a group represented by the above general formula (3).
- Specific examples of the compound having B as a residue and having 320 hydroxyl groups include the aforementioned polyols.
- a 1 and A 2 may be the same or different and each represent an alkylene group having 2 to 4 carbon atoms.
- the alkylene group include an ethylene group, a propylene group, a trimethylene group, a butylene group, a tetramethylene group, a 1-methyltrimethylene group, a 2_methyltrimethylene group, a 1,1-dimethylethylene group, and a 1-dimethylethylene group. , 2-dimethylethylene group and the like.
- Y 1 represents a hydrogen atom, an alkyl group or a cycloalkyl group.
- the number of carbon atoms in the alkyl group referred to herein is not particularly limited, but is usually 124, preferably 118, and more preferably 112.
- the alkyl group may be linear or branched.
- the alkyl group having a carbon number of 1 one 24, and specific examples thereof include Al kill groups exemplified in the description of X 1.
- cycloalkyl group examples include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
- the group represented by Y 1 is preferably a hydrogen atom or a hydrogen atom, preferably an alkyl group having 11 to 12 carbon atoms, a methyl group, an ethyl group, an n-propyl group, an iso- Propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentynole, neo-pentynole, n-hexynole, iso-hexynole , N-Heptinole group, iso-Heptinole group, n-octynole group, iso-octynole group, n-noninole group, iso-noninole group, n-decyl group, iso_decyl group, n-indecyl group, iso_ More preferably, it is any one of
- c, d and e indicate the degree of polymerization of the polyoxyalkylene chain, and the polyoxyalkylene chains in the molecule may be the same or different. Good. Further, when the carbonate represented by the above formula (2) has a plurality of different polyoxyalkylene chains, the copolymerization of the oxyalkylene group is not restricted by random copolymerization even if it is random copolymerized. May be. [0077]
- the method for producing the carbonate ester used in the present invention is arbitrary. For example, a polyalkylene glycol polyol ether is produced by adding an alkylene oxide to a polyol compound.
- alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
- alkali metal alkoxides such as sodium methoxide and sodium ethoxide
- alkalis such as sodium metal. It is obtained by reacting with C.
- a polyalkylene glycol polyol ether may be supplied with a source of carbonic acid such as polyester carbonate or phosgene by an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an alkali metal alcohol such as sodium methoxide or sodium ethoxide. It is obtained by reacting at 150 ° C in the presence of an alkali such as side or sodium metal. Thereafter, free hydroxyl groups are etherified as required.
- the product obtained from the above-mentioned raw materials may be purified to remove by-products and unreacted products, but a small amount of by-products and unreacted products are excellent in the lubricating oil of the present invention. As long as performance is not impaired, there is no problem even if present.
- a compound having a single structure may be used alone, or two or more compounds having different structures may be used in combination.
- the molecular weight of the carbonate ester used in the present invention is not particularly limited, but the number average molecular weight is preferably from 200 to 4,000 to improve the hermeticity of the compressor. More preferably, there is.
- the kinematic viscosity of the carbonate ester used in the present invention is 100 ° C., preferably 2-150 mm 2 / s, more preferably 4-100 mm 2 / s.
- the polyoxyalkylene glycol used in the lubricating oil of the present invention includes, for example, the following general formula (4):
- R 1 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a residue of a compound having 2 to 8 acryl groups or 2 to 8 hydroxyl groups
- R 2 represents 2 carbon atoms.
- R 3 represents a hydrogen atom, an alkyl group having 110 carbon atoms or an acyl group having 210 carbon atoms
- f represents an integer of 180
- g represents an integer of 18 Represents
- the alkyl group represented by R 3 is linear, branched, or cyclic. Any of these may be used. Specific examples of the alkyl group include a methynole group, an ethyl group, an n-propyl group, an isopropyl group, a linear or branched butyl group, a linear or branched acetyl group, and a linear Or a branched hexyl group, a straight-chain or branched heptyl group, a straight-chain or branched octyl group, a straight-chain or branched nonyl group, a straight-chain or branched , A cyclopentyl group, a cyclohexyl group, and the like. When the carbon number of the alkyl group exceeds 10, the compatibility with the refrigerant is reduced, and phase separation tends to occur. Preferred alkyl groups have 116 carbon atoms.
- the alkyl group portion of the acyl group represented by R 3 may be linear, branched, or cyclic. Specific examples of the alkyl group portion of the acyl group include those having 119 carbon atoms among the alkyl groups exemplified as the specific examples of the above alkyl group. If the number of carbon atoms in this acyl group exceeds 10, the compatibility with the refrigerant may be reduced, and phase separation may occur.
- a preferred acyl group has 2 to 6 carbon atoms.
- both bases represented by R 3 are alkyl groups, or when both bases are acyl groups,
- the groups represented by R 3 may be the same or different. If g is 2 or more, The groups represented by R 3 may be the same or different.
- the compound may be a chain or a cyclic compound, .
- Specific examples of the compound having two hydroxyl groups include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, and 2-methynole-1,3_ Propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-1,2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methylpropane 2_propynole 1,3_propanediol, 2,2_jetinole_1,3_propanediol, 1,8_octanediol, 1,9-nonanediol, 1,10-decaned
- Examples of the compound having 38 hydroxyl groups include trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), and tri- (trimethylolonepropane).
- R 3 is an alkyl group (preferably an alkyl group having 14 to 14 carbon atoms), and particularly preferably a methyl group from the viewpoint of refrigerant compatibility. Further, from the viewpoint of thermal stability, it is preferable that both R 1 and R 3 are an alkyl group, preferably an alkyl group having 14 to 14 carbon atoms. It is preferable that From the viewpoint of ease of production and cost, one of R 1 and R 3 may be an alkyl group (more preferably, an alkyl group having 14 to 14 carbon atoms), and the other may be a hydrogen atom. More preferably, one is a methyl group and the other is a hydrogen atom.
- R 2 in the general formula (4) represents an alkylene group with carbon number 2 4, as such an alkylene group include an ethylene group, a propylene group, butylene group and the like .
- Examples of the oxyalkylene group of the repeating unit represented by OR 2 include an oxyethylene group, an oxypropylene group, and an oxybutylene group.
- the oxyalkylene groups in the same molecule may be the same, or may contain two or more oxyalkylene groups.
- polyoxyalkylene glycols represented by the general formula (4) from the viewpoints of refrigerant compatibility and viscosity-temperature characteristics, a copolymer containing an oxyethylene group (EO) and an oxypropylene group (PO) is preferred.
- the ratio of oxyethylene groups to the total of oxyethylene groups and oxypropylene groups (EOZ (P ⁇ + EO)) is determined from the viewpoint of baking load, viscosity-temperature characteristics. It is preferably in the range of 0.1-0.8, and more preferably in the range of 0.3-0.6.
- the value of £ ⁇ / (? 0 + £ ⁇ ) is preferably in the range of 0-0.5, preferably in the range of 0-0.2. Something is more preferred 0 (i.e. Most preferably, it is an oxide homopolymer).
- f is an integer of 180
- g is an integer of 118.
- g is 1 when R 7 is an alkyl group or an acyl group.
- R 7 is a residue of a compound having 2 to 8 hydroxyl groups
- g is the number of hydroxyl groups of the compound.
- the product of f and g (f Xg) is not particularly limited, the average value of fx g should be 6-80 in order to satisfy the above-mentioned required performance as a lubricating oil for refrigerators in a well-balanced manner. It is preferable that
- Polyoxypropylene glycol monobutyl ether represented by the following general formula (8):
- a polyoxypropylene glycol monomethyl ether represented by the following general formula (9): [0098] CH 0- (C H O) _ (C H O) — H (9)
- the polyoxypropylene glycol diacetate represented by is preferable in terms of economy and the like.
- polyoxyalkylene glycol is represented by the general formula (12):
- R 4 to R 7 may be the same or different and each may be a hydrogen atom, a monovalent hydrocarbon group having 1 or 10 carbon atoms, or the following general formula (13):
- R 8 and R 9 may be the same or different and each represent a hydrogen atom, a C 1-10 monovalent hydrocarbon group or a C 2-20 alkoxyalkyl group
- R 1Q represents an alkylene group having 2 to 5 carbon atoms, a substituted alkylene group having a total of 25 carbon atoms having an alkyl group as a substituent or a substituted alkylene group having a total carbon number of 4 to 10 having an alkoxyalkyl group as a substituent.
- R represents an integer of 020, and R 13 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms.) Wherein at least one of R 8 to R 11 is a group represented by the general formula (13).]
- a polyoxyalkylene glycol derivative having at least one structural unit represented by the formula: I can do it.
- each of R 4 to R 7 represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a group represented by the above general formula (13).
- the monovalent hydrocarbon group of 1 to 10 include a linear or branched alkyl group having 1 to 10 carbon atoms and a linear or branched alkenyl group having 2 to 10 carbon atoms.
- monovalent hydrocarbon groups having 6 or less carbon atoms, particularly alkyl groups having 3 or less carbon atoms, specifically, methyl group, ethyl group, n-propyl group, and isopropyl group Is preferred.
- R 8 and R 9 each represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms. Among them, an alkyl group having 3 or less carbon atoms or an alkoxyalkyl group having 6 or less carbon atoms is preferable. Specific examples of the alkyl group having 3 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
- alkoxyalkyl group having 2 to 6 carbon atoms examples include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, sec.
- R 1Q represents an alkylene group having 25 carbon atoms, a substituted alkylene group having a total of 25 carbon atoms having an alkyl group as a substituent, or a total having 25 alkylene groups or an alkoxyalkyl group having a substituent.
- Specific examples of the alkylene group having 2 to 4 carbon atoms include an ethylene group, a propylene group, and a butylene group.
- Examples of the substituted ethylene group having a total carbon number of 6 or less include 1- (methoxymethyl) ethylene group, 2- (methoxymethyl) ethylene group, 1- (methoxyethyl) ethylene group and 2- (methoxyethyl) ethylene group.
- R 11 represents a monovalent hydrocarbon group having 110 to 10 carbon atoms, and the hydrocarbon group is, specifically, a straight-chain hydrocarbon having 11 to 10 carbon atoms.
- a monovalent hydrocarbon group having 6 or less carbon atoms is preferable, and an alkyl group having 3 or less carbon atoms is particularly preferable, and specifically, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferable.
- R 4 to R 7 is a group represented by the general formula (13).
- one of R 4 and R 6 is a group represented by the above general formula (13), and the other one of R 4 or R 6 and R 5 and R 7 are each a hydrogen atom or a carbon atom. It is preferably a monovalent hydrocarbon group of the number 1-10.
- the polyoxyalkylene glycol having the structural unit represented by the general formula (12), which is preferably used in the present invention, is a homopolymer composed of only the structural unit represented by the general formula (12);
- — R lb may be the same or different and each represents a hydrogen atom or an alkyl group having 13 to 13 carbon atoms.
- a preferred example of the homopolymer has 11 to 200 structural units A represented by the general formula (12), and has a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms and a terminal group having 1 to 10 carbon atoms, respectively. Those comprising an alkoxy group or an aryloxy group can be exemplified.
- preferable examples of the copolymer include two or more types of structural units A and B represented by the general formula (12), each having 1,200 units, or a structural unit A represented by the general formula (12).
- the structural unit A and the structural unit B are alternately copolymerized, random copolymerized, a block copolymer, or the structural unit B is grafted to the main chain of the structural unit A. Any polymerization type of the bonded graft copolymer may be used.
- polybutyl ether used in the present invention, for example, the following general formula (15):
- R 1S — represents a hydrogen atom or a hydrocarbon group having 118 carbon atoms, which may be the same or different
- R 19 represents a divalent hydrocarbon group having 11 to 10 carbon atoms.
- R 2 ° is a carbon group having 1 to 20 carbon atoms.
- R lb — may be the same or different for each structural unit, and is represented by the general formula (15). that when the structural unit has a R 19 ⁇ of multiple, multiple R 19 ⁇ may be the same or different
- — R 24 represents a hydrogen atom or a hydrocarbon group having 120 carbon atoms, which may be the same or different, and R 21 — R 24 may be the same or different for each structural unit. Good
- a polybutyl ether-based compound consisting of a block copolymer or a random copolymer having a structural unit represented by the following formula (1) can also be used.
- R 16 to R 18 each represent a hydrogen atom or a hydrocarbon group having 118 carbon atoms (preferably a hydrocarbon group having 114 carbon atoms), and they are the same or different. You can do it.
- the strong hydrocarbon group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, various pentyl groups, Alkyl groups such as various hexyl groups, various heptyl groups, various octyl groups; cycloalkyl groups such as cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various dimethylcyclohexyl groups; Phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups and other aryl groups; benzyl group, various phenylethyl groups, various methylbenzyl groups and other arylalkyl groups, and the like.
- R 19 in the above general formula (15) is a divalent hydrocarbon group having 110 (preferably 210) carbon atoms or a divalent ether-bonded oxygen-containing carbon group having 220 carbon atoms. Represents a hydrogen group.
- Specific examples of the divalent hydrocarbon group having 1 to 10 carbon atoms include a methylene group, an ethylene group, and a fluorocarbon group.
- Nylethylene group 1,2_propylene group, 2_phenylenol 1,2_propylene group, 1,3_propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octaylene groups, Divalent aliphatic hydrocarbon groups such as various nonylene groups and various decylene groups; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, and propylcyclohexane An alicyclic hydrocarbon group having two binding sites; a divalent aromatic carbon such as various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, various naphthylene groups, etc.
- Hydrogen group An alkyl group having an alkyl group portion and an aromatic portion each having a monovalent bonding site in an alkyl aromatic hydrocarbon such as toluene, xylene, and ethylbenzene.
- Aromatic hydrocarbon group xylene, alkyl aromatic hydrocarbon group having a binding site in an alkyl group moiety of polyalkyl aromatic hydrocarbons such as Jefferies chill benzene, and the like. Of these, an aliphatic chain hydrocarbon group having 2 to 4 carbon atoms is particularly preferred.
- divalent ether-linked oxygen-containing hydrocarbon group having 2 to 20 carbon atoms include a methoxymethylene group, a methoxyethylene group, a methoxymethylethylene group, a 1,1_bismethoxymethylethylene group, Preferable examples include a 1,2-bismethoxymethylethylene group, an ethoxymethylethylene group, a (2-methoxyethoxy) methylethylene group, and a (1-methyl-2-methoxy) methylethylene group.
- s represents the number of repetitions of R 19 °, and the average value thereof is a number in the range of 0 to 10, preferably 0 to 5.
- the general formula (15) in the R 2 ° is 1 one 20 carbon atoms, preferably represents a hydrocarbon group of 1 one 10, as the force Cal hydrocarbon group, specifically, methyl Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, see-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups Groups, various noninole groups, various decyl groups and other alkyl groups; cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various procyclocyclohexinole groups, various dimethylcyclohexyl groups Cycloalkyl groups such as phenyl group, various methyl phenol groups, various ethyl pheny
- R 22 — R 26 may be the same or different for each structural unit.
- the carbon / oxygen molar ratio is 4.2-7.0. It is preferably in the range. If the molar ratio is less than 4.2, the hygroscopicity becomes excessively high, and if it exceeds 7.0, the compatibility with the refrigerant tends to decrease.
- R 21 to R 24 may be the same or different and each represent a hydrogen atom or a hydrocarbon group having 120 carbon atoms.
- examples of the hydrocarbon group having 120 carbon atoms include the hydrocarbon groups exemplified in the description of R 2 ° in the general formula (15). Note that R 21 to R 24 may be the same or different for each structural unit.
- the polybutyl ether useful in the present invention is a block copolymer or a random copolymer having a structural unit represented by the general formula (15) and a structural unit represented by the general formula (16).
- the molar ratio of carbon / oxygen is preferably in the range of 4.2-7.0. If the molar ratio is less than 4.2, the hygroscopicity tends to be excessively high, and if it exceeds 7.0, the compatibility with the refrigerant tends to decrease.
- a homopolymer composed of only the structural unit represented by the general formula (15), the homopolymer composed of the structural unit represented by the general formula (15) and the homopolymer represented by the general formula (16) A mixture of a block copolymer or a random copolymer comprising the constituent units to be used can also be used.
- These homopolymers and copolymers can be produced by polymerization of the corresponding vinyl ether monomers and copolymerization of the corresponding hydrocarbon monomers having a olefinic double bond with the corresponding butyl ether monomers. .
- one of the terminal structures has the following general formula (17) or (18):
- R — represents a hydrogen atom or a hydrocarbon group having 118 carbon atoms, which may be the same or different, and R 28 represents a divalent hydrocarbon group having 11 to 10 carbon atoms or Represents a divalent ether-linked oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, R 29 represents a hydrocarbon group having 120 carbon atoms, and t represents a number having an average value of 0 to 10;
- the terminal structure represented by the general formula (17) has a plurality of R 28 s , the plurality of R 280 may be the same or different.
- R 3U R 31 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 120 carbon atoms.
- R 34 -R 36 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 118 carbon atoms, and R 37 represents a divalent carbon atom having 11 to 10 carbon atoms.
- R 37 represents a divalent carbon atom having 11 to 10 carbon atoms.
- R 38 represents a hydrocarbon group having 1 to 20 carbon atoms
- t represents a number having an average value of 0 to 10.
- the terminal structure represented by the general formula (19) has a plurality of R 37 ⁇ , the plurality of R 37 ⁇ ⁇ Techyore,]
- R 39 R 4 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 120 carbon atoms.
- — R 4b is the same or different and each represents a hydrogen atom or a hydrocarbon group having 118 carbon atoms.
- one end is represented by the general formula (17) or (18), the other has the structure represented by the general formula (19) or (20), R in the general formula (15) 16 R 18 is a hydrogen atom, s is a number from 0 to 4, R 19 is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R 2 ° is a 1 to 20 carbon atom. Being a hydrocarbon group;
- R 16 — R 18 in the general formula (15) are all hydrogen atoms, s is a number from 0 to 4, and R 19 is a divalent hydrocarbon group having 2 to 4 carbon atoms.
- R 2 ° is a hydrocarbon group having 120 carbon atoms; (3) One of the terminals has a structure represented by the general formula (17) or (18), and the other has a structure represented by the general formula (19), and R 16 — R 18 in the general formula (15) is All are hydrogen atoms, s is a number from 0 to 4, R 19 is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R 2 ° is a hydrocarbon group having 1 to 20 carbon atoms. some stuff;
- R 16 — R 18 in the general formula (15) are all hydrogen atoms, s is a number from 0 to 4, and R 19 is a divalent hydrocarbon group having 224 carbon atoms. And R 2 ° is a hydrocarbon group having 120 carbon atoms.
- the present invention has a structural unit represented by the above general formula (15), and one of its terminals is represented by the general formula (17), and the other is represented by the following general formula (22):
- R 4S — R 4S may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 18 carbon atoms, and R 49 and R 51 may be the same or different.
- the terminal structure represented by the above general formula (22) has a plurality of R 49 ⁇ or R 51 ⁇
- a plurality of R 49 ⁇ ⁇ or R 51 ⁇ ⁇ may be the same or different
- a polybutyl ether compound having a structure represented by the following formula can also be used.
- R 53 represents a hydrocarbon group having 118 carbon atoms.
- R 54 represents a hydrocarbon group having 118 carbon atoms
- R 55 represents an alkyl group having 13 to 13 carbon atoms
- R 56 represents a hydrocarbon group having 18 to 18 carbon atoms.
- R 57 represents a hydrocarbon group having 118 carbon atoms.
- a polybutyl ether-based compound consisting of a homopolymer or a copolymer of an alkylbutyl ether having a structure represented by the following formula can also be used.
- only one kind selected from the group consisting of the above-mentioned mineral oils and synthetic oils may be used alone, or two or more kinds may be used in combination.
- HFC-based refrigerants polyoxyalkylene glycols, esters, and polyvinyl ethers are used for open-type compressors such as car air conditioners, and alkylbenzenes, esters, and polybutylenes are used for closed-type compressors such as refrigerators and air conditioners.
- Ether is preferably used.
- Examples of the phosphorus-based extreme pressure agent contained in the refrigerator oil composition of the present invention include phosphorothioate ( At least one selected from the group consisting of phosphoric acid esters, phosphoric acid esters, acidic phosphoric acid esters, amine salts of acidic phosphoric acid esters, chlorinated phosphoric acid esters and phosphites.
- the phosphorus additives other than phosphorothionate are esters of phosphoric acid or phosphorous acid with alkynol, polyether alcohols or derivatives thereof.
- the phosphorothionate according to the present invention has the following general formula (27):
- R 58 R 6 ° may be the same or different and each represents a hydrocarbon group having 124 carbon atoms.
- Examples of the hydrocarbon group having a carbon number of 1 one 24 represented by R 58 R 6 ° specifically, an alkyl group, a cycloalkyl group, an alkenyl group, an alkylcycloalkyl group, Ariru group, Al Kiruariru group, Arylalkyl groups and the like.
- alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a pendecyl group, a dodecyl group, and a tridecinole group , Tetradecyl group, pentadecinole group, hexadecinole group, heptadecyl group, octadecinole group, and other alkyl groups (these alkyl groups may be linear or branched).
- Examples of the cycloalkyl group include cycloalkyl groups having 5 to 7 carbon atoms such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
- Examples of the alkylcycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a getylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylethylcyclohexyl group.
- Jetilsik Alkylcycloalkyl groups having 6 to 11 carbon atoms such as methylhexyl group, methylcycloheptyl group, dimethylcycloheptyl group, heptyl group of methylethyl group, heptyl group of methylethyl group, etc. (substitution of alkyl group with cycloalkyl group) Position is also arbitrary)
- alkenyl group examples include a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an otatyl group, a nonenolone group, a decenyl group, a pendecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, and a pentadecenyl group.
- alkenyl groups such as hexadecenyl group, heptadecenyl group and octadecenyl group (these alkenyl groups may be linear or branched and the position of the double bond is arbitrary).
- Examples of the aryl group include aryl groups such as a phenyl group and a naphthyl group.
- Examples of the alkylaryl group include a tolyl group, a xylyl group, an ethyl phenyl group, a propyl phenyl group, a butyl phenyl group, a pentyl phenyl group, a hexyl phenyl group, a heptyl phenyl group, an octyl phenyl group, C 7 -C 18 alkylaryl group such as nonylphenyl group, decylphenyl group, undecylphenyl group, dodecylphenyl group (the alkyl group may be linear or branched, and the substitution position on aryl group Are also arbitrary).
- arylalkyl group examples include an arylalkyl group having 7 to 12 carbon atoms such as a benzyl group, a phenylethyl group, a phenylpropynole group, a phenylbutyl group, a phenylpentyl group, and a phenylhexyl group.
- the alkyl group may be straight-chain or branched).
- the R 58 - a hydrocarbon group having a carbon number of 1 one 24 represented by R 6 ° is an alkyl group, Ariru group, an alkyl ⁇ aryl group is it is preferable instrument number 4 one 18 alkyl carbon atoms, More preferably, it is a C 7-24 anolequinolylene group or a phenyl group.
- phosphorothionate represented by the general formula (27) include tributyl phosphorotionate, tripentyl phosphorotionate, trihexyl phosphorotionate, and triheptyl phosphorotionate.
- Thionate trioctylphosphorothionate, trinonylphosphorothionate, tridecylphosphorothionate, tridecylphosphorothionate, tridodecylphosphorothionate, tritridecylphosphoro Thionate, tritetradecylphosphorothionate, tripentadecylphosphorothionate, trihexadecylphosphorothionate, triheptadecylphosphorothionate, trioctadecylphosphorothionate, trioleylphosphoro Thionate, triphenylphosphorothionate, tricresylphosphorothionate, trixylenylphosphorothionate, cresyldiphenylphosphorothionate, xylenyldiphenylphosphorothionate, tris (n-propylphenylinolate) Phosphorothionate, tris (isopropylphenyl) phospho
- the content of the phosphorothionate is not particularly limited. However, the content is usually 0.01% based on the total amount of the refrigerator oil composition (based on the total amount of the base oil and all the additives blended). It is 10% by mass, preferably 0.01% to 5% by mass, more preferably 0.01% to 3% by mass.
- phosphate esters include tributinolephosphate, tripentinolephosphate, trihexynolephosphate, triheptinolephosphate, trioctylphosphate, Trinonyl phosphate, tridecyl phosphate, tridindecyl phosphate, tridodecyl phosphate, tritridecyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl Phosphate, Triphenyl phosphate, Tricresyl phosphate, Trixylenyl phosphate, Tarezyl diphenyl phosphate, Xylenyl diphenyl phosphate Eto and the like;
- Examples of the acidic phosphoric acid ester include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, and monounyl acid phosphate.
- Decyl acid phosphate monododecyl acid phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl Acidho Phosphate, dibutyl acid phosphate, dipentyl acid phosphate, dihexyl oleic acid phosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinoyl acid phosphate, didecyl acid phosphate, didecyl acid phosphate, didodecyl acid Decyl acid phosphate, ditetradecyl acid phosphate, dipentadecyl acid phosphate, dihexadecyl acid phosphate, diheptadecyl acid phosphate,
- Examples of the amine salt of the acidic phosphoric acid ester include the acidic phosphoric acid ester methylamine, ethynoleamine, propylamine, butynoleamine, pentylamine, hexylamine, heptinoleamine, octylamine, dimethylamine, getylamine, dipropylamine, dibutynoleamine, dipentylamine.
- Salts with amines such as min, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, trippropinoleamine, tributinoleamine, tripentylamine, trihexinoleamine, triheptylamine, trioctylamine and the like;
- chlorinated phosphoric acid ester examples include tris'dichloropropyl phosphate, tris'chloroethylene phosphate, tris'chlorophenyl phosphate, polyoxyalkylene'bis [di (chloroanolequinole)] phosphate and the like;
- Examples of the phosphite include dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptinole phosphite, dioctinole phosphite, dinoninole phosphite, didecyl phosphite, and diphenyl phosphite.
- Decyl phosphite didodecyl phosphite, dioleyl phosphite, diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl Examples include phosphite, tridecyl phosphite, tridecyl phosphite, tridodecyl phosphite, trioleyl phosphite, triphenyl phosphite, and trithalinole phosphite. Also, a mixture of these can be used.
- the blending amount is not particularly limited, but is usually based on the total amount of the refrigerator oil composition (base oil and total blending).
- the phosphorus-based extreme pressure agent may be blended in such an amount that the content thereof is 0.01-5.0% by mass, more preferably 0.02-3.0% by mass (based on the total amount of additives). desirable.
- the refrigerating machine oil composition of the present invention has a high thermal stability due to the ability to use one of the above-mentioned extreme pressure agents alone or in combination of two or more. From the viewpoint of superiority, it is preferable to use phosphorothionate.
- oil agent examples include an ester oil agent, a monohydric alcohol oil agent, a carboxylic acid oil agent, and an ether oil agent.
- the ester oil agent may be a natural product (usually contained in natural fats and oils derived from animals and plants) or a synthetic product.
- a synthetic ester is preferable from the viewpoint of the stability of the obtained refrigerator oil composition and the uniformity of the ester component.
- a synthetic ester as an ester oily agent is obtained by reacting an alcohol with a carboxylic acid.
- the alcohol may be a monohydric alcohol or a polyhydric alcohol.
- the carboxylic acid may be a monobasic acid or a polybasic acid.
- the monohydric alcohol constituting the ester oily agent one having usually 124, preferably 111, and more preferably 118 carbon atoms is used, and as such an alcohol, a straight-chain alcohol is used. However, it may be branched or saturated or unsaturated.
- alcohol having 124 carbon atoms include, for example, methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, and linear Linear or branched hexanol, linear or branched octanol, linear or branched octanol, linear or branched nonanol, linear or branched decanol, linear or branched Linear or branched dodecanol, linear or branched tridecanol, linear or branched tetradecanol, linear or branched pentadecanol, linear or branched Branched hexadecanol, linear or branched heptadecanol, linear or branched octadecanol, linear or branched nonadenicol, linear or branched Cosanol, Examples thereof include linear or branched henicosanol, linear or branche
- the polyhydric alcohol constituting the ester oily agent one having usually 2 to 10 valences, preferably 26 valences is used.
- Specific examples of the polyhydric alcohol of 210 include, for example, ethylene glycol, diethylene glycol, polyethylene glycol (3-15 mer of ethylene glycol), propylene glycol, dipropylene glycol, polypropylene glycol (propylene glycol).
- Polyhydric alcohols include sugars such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, and mixtures thereof.
- ethylene glycol, diethylene glycol, polyethylene glycolone (a 310-mer of ethylene glycolone), propylene glycolone, dipropylene glycol, and polypropylene glycol (a 310-mer of propylene glycol) 1, 3_propanediole, 2-methinole-1,2_propanediole, 2-methinole-1,3_propanediol, neopentyldaricol, glycerin, diglycerin, triglycerin, Trimethylolalkanes (trimethylolethane, trimethylolpropane, trimethylolbutane, etc.) and their dimers, pentaerythritol, dipentaerythritol, 1,2,4_butanetriene, 1,3,5_pentanetriene -Nore, 1, 2, 6-Hexantori, Nore, 1, 2 Preferred are 3,4-
- Still more preferred are ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan, and mixtures thereof.
- neopentyldaricol, trimethylolethane, trimethylolpropane, pentaerythritol, and mixtures thereof are preferable because higher oxidation stability can be obtained.
- the alcohol constituting the ester oily agent that may be used in the present invention may be a monohydric alcohol or a polyhydric alcohol, but when used in combination with a phosphorus-based extreme pressure agent.
- Monohydric alcohols are preferred from the viewpoints of higher abrasion resistance and friction characteristics, and prevention of precipitation in a refrigerant atmosphere and at low temperatures.
- a fatty acid having 2 to 24 carbon atoms is usually used as the monobasic acid, and the fatty acid is linear or branched. However, it may be saturated or unsaturated.
- the polybasic acid examples include a dibasic acid and trimellitic acid, and are preferably a dibasic acid from the viewpoint of preventing precipitation under a refrigerant atmosphere and at a low temperature.
- the dibasic acid may be either a chain dibasic acid or a cyclic dibasic acid. In the case of a linear dibasic acid, it may be either linear or branched, and may be saturated or unsaturated.
- a chain dibasic acid a chain dibasic acid having 2 to 16 carbon atoms is preferred. Specific examples include ethanenic acid, propane diacid, linear or branched butane diacid, and linear dibasic acid.
- Linear or branched pentanedioic acid linear or branched hexanedioic acid, linear or branched heptanedioic acid, linear or branched octanedioic acid, linear or branched Nonanninic acid, linear or branched decandioic acid, linear or branched pendecanedioic acid, linear or branched dodecandioic acid, linear or branched tridecandioic acid, linear Linear or branched tetradecandioic acid, linear or branched heptadecandioic acid, linear or branched hexadecandioic acid, linear or branched hexenedioic acid, linear or branched Heptennic acid, linear or branched otatenedioic acid, linear or branched nonennic acid, linear Is a branched decenedioic acid, a linear or branche
- Examples include tradecenedioic acid, linear or branched heptadecenedioic acid, linear or branched hexadecenedioic acid, and mixtures thereof.
- Examples of the cyclic dibasic acid include 1,2-cyclohexanedicarboxylic acid, 4-cyclohexene-1,1,2-dicarboxylic acid, and aromatic dicarboxylic acid. Among these, a chain dibasic acid is preferred from the viewpoint of stability.
- the acid constituting the ester oil agent may be a monobasic acid or a polybasic acid. Base acids are preferred.
- the combination of an alcohol and an acid in the ester oily agent is arbitrary and not particularly limited, and examples thereof include esters obtained by the following combination (i)-(vii).
- Each of the above (ii) one (vii) ester may be a complete ester obtained by esterifying all of the hydroxyl group of a polyhydric alcohol or the carboxyl group of a polybasic acid.
- the ester may be a partial ester remaining as a carboxy group, but it is preferable that the ester be a complete ester from the viewpoint of less influence on the anti-precipitation property under a cooling atmosphere and at a low temperature. From the viewpoint of the effect of improving the characteristics, a partial ester is preferable.
- esters of (i) (i) esters of monohydric alcohols and monobasic acids,
- Ester of monohydric alcohol and polybasic acid is preferred. Ester of (i) is more preferred. These esters have a very high effect of improving wear resistance and friction characteristics, and have little effect on the anti-precipitation property and thermal oxidation stability under a cooling atmosphere and at low temperatures.
- the carbon number of the monobasic acid is such that the wear resistance and friction characteristics when used in combination with a phosphorus-based extreme pressure agent are further improved, and the thermal and oxidation stability is improved. From the viewpoint, it is preferably 10 or more, more preferably 12 or more, and still more preferably 14 or more. Also one The carbon number of the basic acid is preferably 28 or less, more preferably 26 or less, and still more preferably 24 or less, from the viewpoint of preventing precipitation under a refrigerant atmosphere and at a low temperature. Examples of such esters include methyl stearate, butyl stearate, methyl palmitate, isopropyl palmitate, and the like.
- the monobasic acid and monohydric alcohol constituting the ester (i) may be either straight-chain or branched, respectively. It is preferably a tell.
- the dibasic acid is preferably chain-like.
- esters include diisodecyl adipate, diisononyl adipate, diisobutyl adipate and the like.
- the refrigerator oil composition of the present invention may contain an ester as a base oil in some cases, and the ester as the base oil is at least one selected from polyol esters and diesters of aliphatic cyclic dibasic acids.
- the ester oil agent is at least one selected from an ester of a monohydric alcohol and a monobasic acid and an ester of a linear dibasic acid and a monohydric alcohol.
- Examples of the monohydric alcohol oily agent include the monohydric alcohols exemplified in the description of the ester oily agent.
- the total carbon number of the monohydric alcoholic agent is preferably 6 or more, more preferably 8 or more, and most preferably 10 or more, from the viewpoint of improvement in friction and wear characteristics. If the total number of carbon atoms is too large, precipitation may easily occur in a refrigerant atmosphere. Therefore, the total number of carbon atoms is preferably 20 or less, more preferably 18 or less, and most preferably 16 or less.
- the carboxylic acid oil agent may be a monobasic acid or a polybasic acid.
- Such carboxylic acids include, for example, the monobasic acids and polybasic acids exemplified in the description of the ester oil agent. Of these, monobasic acids are preferred from the viewpoint of improving the friction characteristics and wear characteristics.
- the total carbon number of the carboxylic acid oil agent is preferably 6 or more, more preferably 8 or more, and most preferably 10 or more, from the viewpoint of improving the friction characteristics and wear characteristics. Also, if the total carbon number of the carboxylic acid oil agent is too large, precipitation may easily occur in a refrigerant atmosphere, so the total carbon number is preferably 20 or less, more preferably 18 or less, and more preferably 16 or less. Is most preferred.
- ether oil agent examples include etherified products of a tri- to hexa-valent aliphatic polyhydric alcohol, di- or tri-molecular condensates of a tri- to hexa-valent aliphatic poly- alcohol, and the like.
- the etherified product of a 3-hexavalent aliphatic polyhydric alcohol is, for example, represented by the following general formula (28)
- R 61 and R 85 may be the same or different and each is a hydrogen atom or a linear or branched alkyl group having 118 carbon atoms, an aryl group, an aralkyl group, _ (R a ⁇ )
- R a is an alkylene group having 2 to 6 carbon atoms
- R b is an alkyl group having 1 to 20 carbon atoms
- n is an integer of 1 to 10) Indicates an ether residue.
- 3- to 6-valent aliphatic polyhydric alcohol include glycerin and trimethylolprono. Erythritole, pentaerythritole, arabitonere, sonorebitore, mannitoore, and the like.
- R 61 to R 85 in the above general formulas (28) to (33) represent a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, Various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various decyl groups, various dodecyl groups, various tridecinole groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups Group, phenyl group, benzyl group and the like.
- the etherified product also includes a partially etherified product in which a part of R 61 to R 85 is a hydrogen atom.
- Examples of the bimolecular condensate or trimolecular condensate etherified product of a 3- to 6-valent aliphatic polyhydric alcohol include the same or different compounds represented by the above general formulas (28) to (33).
- Condensates of For example, a bimolecular condensate and an etherified trimolecular condensate of an alcohol represented by the general formula (28) are represented by the general formulas (34) and (35), respectively.
- the bimolecular condensate of the alcohol represented by the general formula (30) and the etherified product of the trimolecular condensate are represented by the general formulas (36) and (37), respectively.
- R 61 - represent the same definition as R 74 - R 63 and R 71 - R 63 and R 7 1 in the formula (31) - R 61 in R 74 are each formula (28) in. ]
- bimolecular condensate and trimolecular condensate of the 3- to 6-valent aliphatic polyhydric alcohol include diglycerin, ditrimethylolpropane, dipentaerythritol, disonorebitone, triglycerin, tritriglycerol, Methylol propane, tripentaerythritol, trisorbitol and the like.
- ether oily agents represented by the general formulas (28) to (37) include trihexyl ether of glycerin, dimethyloctyl triether of glycerin, and di (methyloxyisopropylene) of glycerin.
- diphenyloctyl triether of glycerin, di (methyloxyisopropylene) dodecyl triether of trimethylolpropane, tetrahexyl ether of pentaerythritol, hexapropinolate ether of sonolebitone, Glycerin dimethinoregiooctynole to tetraether, triglycerin tetra (methyloxyisopropylene) decylpentaene, to dipentaerythritole, hexapropynoleatenore, and tripentaerythritole to pentamethyloctyl.
- Xaether is preferred.
- an ester oil agent In the refrigerator oil composition of the present invention, one of an ester oil agent, a monohydric alcohol oil agent, a carboxylic acid oil agent and an ether oil agent is used alone as long as it is used in combination with the phosphorus-based extreme pressure agent. You can also use two or more kinds in combination.
- these oil-based agents it is preferable to include an ester oil-based agent as an essential component from the viewpoint of achieving a high level of balance in frictional properties, wear characteristics, precipitation prevention properties, and stability. Ester oil agents not only achieve a high level of wear resistance and friction properties 1 It has better anti-precipitation properties than polyhydric alcohol oils and ether oils, and has better stability than carboxylic acid oils.
- the content of the above oil agent is optional, but from the viewpoint that the combined use of the oil agent and the phosphorus-based extreme pressure agent is excellent in the abrasion resistance and the frictional effect, it is preferably 0.1% based on the total amount of the total composition. It is at least 01% by mass, more preferably at least 0.05% by mass, even more preferably at least 0.1% by mass.
- the content is preferably 10% by mass or less based on the total amount of the composition, since the content is excellent in the anti-precipitation property under a refrigerant atmosphere and at a low temperature, and the heat and oxidation stability of the refrigerator oil composition. , More preferably 7.5% by mass or less, even more preferably 5% by mass or less.
- the ratio between the phosphorus-based extreme pressure agent and the oil agent is preferably 1:10 10: 1, more preferably 1: 5-5: 1, and still more preferably 1: 3 by mass. 1: 1
- By setting the ratio of the phosphorus-based extreme pressure agent to the above-mentioned oily agent within the above range it is possible to further improve the wear resistance and friction characteristics.
- the refrigerating machine oil composition of the present invention contains a predetermined base oil, a phosphorus-based extreme pressure agent and an oily agent as essential components, and benzotriazole and / or a derivative thereof described below,
- the dagger may further contain other additives.
- the refrigerator oil composition of the present invention preferably further contains benzotriazole and / or a derivative thereof.
- benzotriazole and / or a derivative thereof By incorporating benzotriazole and / or a derivative thereof, the effect of improving wear resistance and friction characteristics can be further enhanced.
- Benzotriazole is a compound represented by the following formula (38).
- benzotriazole derivative examples include, for example, an alkylbenzotriazole represented by the following general formula (39) and an (alkyl) aminoalkylbenzozotazole represented by the general formula (40) Liazole and the like.
- R represents a linear or branched alkyl group having 14 to 14 carbon atoms, preferably a methyl group or an ethyl group
- X represents 113, preferably 1 Or indicate the number 2. It is a R 86, for example, a methyl group, Echiru group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, etc. tert- butyl group.
- alkenylbenzotriazole represented by the formula (39) a compound in which R 86 is a methyl group or an ethyl group and X is 1 or 2 is particularly preferred because of its excellent antioxidant properties. Examples thereof include methylbenzotriazole (tolyltriazole), dimethylbenzotriazole, ethylbenzotriazole, ethylmethylbenzotriazole, getylbenzotriazole, and mixtures thereof.
- R 87 represents a linear or branched alkyl group having 14 to 14 carbon atoms, preferably a methyl group or an ethyl group
- R 88 represents a methylene group or an ethylene group
- R 89 and R 9 ° may be the same or different and may be a hydrogen atom or a linear or branched alkyl group having 118 carbon atoms, preferably a linear or branched alkyl group having 11 12 carbon atoms.
- y represents a number of 0-3, preferably 0 or 1.
- R 87 includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl group and the like.
- R 87 is a methyl group
- y is 0 or 1
- R 88 is methylene, because it is particularly excellent in antioxidant properties.
- dialkylaminoalkylbenzotriazoles examples include dimethylaminomethylbenzotriazole, getylaminomethylbenzotriazole, di (linear or branched) propylaminomethylbenzotriazole, and di (linear) Or branched) butylaminomethylbenzotriazole, di (linear or branched) pentylaminomethylbenzotriazole, di (linear or branched) hexylaminomethylbenzotriazole, di (linear or branched) Branched) heptylaminomethylbenzotriazole, di (linear or branched) octylaminomethylbenzotriazole, di (linear or branched) nonylaminomethylbenzotriazole, di (linear or branched) ) Decinoleaminomethylbenzotriazole, di (linear or branched) pentadecylaminomethylbenzotriazole Di (linear or
- the content of benzotriazole and / or a derivative thereof in the refrigerator oil composition of the present invention is arbitrary 0.001% by mass or more, more preferably 0.005% by mass, based on the total amount of the power composition. % By mass or more. If the content is less than 0.001% by mass, the effect of improving the abrasion resistance and frictional properties due to the inclusion of benzotriazole and / or its derivative may be insufficient. Further, the content of benzotriazole and / or a derivative thereof is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, based on the total amount of the composition. If the content exceeds 1.0% by mass, the effect of improving wear resistance and frictional properties that is commensurate with the content may not be obtained, which may be economically disadvantageous.
- phenyldaricidyl ether type epoxy compound include fuel glycidyl ether and alkylphenyldaricidyl ether.
- the alkylphenyldaricidyl ether includes those having 113 alkyl groups having 113 carbon atoms, among which those having one alkyl group having 410 carbon atoms, for example, n Butylphenyldaricidyl ether, i-butylphenyldaricidyl ether, sec-butylphenyldaricidyl ether, tert-butylphenyldaricidyl ether, pentylphenyldaricidyl ether, hexylphenyldaricidyl ether, heptylphenyl Preferred are daricidyl ether, octylphenyldaricidyl ether, nonylphenylglycidylether, decylphenyldar
- alkyl glycidyl ether type epoxy compound examples include decyl glycidyl ether, pendecyl glycidyl ether, dodecyl glycidyl ether, tridecinoleglycidinoleatene, and tetradecinoleglycidinoleatene.
- 2-Ethynolehexynole glycidyl ether 2-Ethynolehexynole glycidyl ether, neopentyl glycol diglycidyl ether, trimethylol pulp triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6_ hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol mono Glycidyl ether, polyalkylene glycol diglycidyl Ether and the like can be exemplified.
- R represents a hydrocarbon group having 118 carbon atoms
- R represents a hydrocarbon group having 11 to 18 carbon atoms, and examples of such a hydrocarbon group include an alkyl group having 11 to 18 carbon atoms and an alkenyl having 2 to 18 carbon atoms.
- an alkyl group having 5 to 15 carbon atoms an alkenyl group having 2 to 15 carbon atoms, a phenyl group, and an alkylphenyl group having an alkyl group having 14 to 14 carbon atoms are preferable.
- glycidyl ester type epoxy compounds preferred are specifically, for example, glycidyl 2,2-dimethyloctanoate, glycidyl benzoate, glycidinyl tert-butyl benzoate, glycidyl atalylate, and glycidyl meta Tallylate and the like can be exemplified.
- aryloxy silane compounds include 1,2-epoxystyrene, alkynole-1,2-epoxystyrene, and the like.
- alkyloxysilane compound specifically, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2 —Epoxy octane, 1, 2-epoxynonane, 1,2-epoxydecane, 1,2-epoxydecane, 1,2-epoxidedodecane, 1,2_epoxytridecane, 1,2-epoxytetradecane, 1 , 2_epoxypentadecane, 1,2-epoxyhexadecane, 1,2_epoxyheptadecane, 1,1,2_epoxyoctadecane, 2_epoxynonadecane, 1,2_epoxyicosane, etc. it can.
- alicyclic epoxy compound the following general formula (42):
- alicyclic epoxy compound examples include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxy.
- epoxidized fatty acid monoester examples include esters of an epoxidized fatty acid having 12 to 20 carbon atoms with an alcohol or phenol or alkylphenol having 118 carbon atoms, and the like. Can be illustrated. Particularly, butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl and butylphenylester of epoxystearic acid are preferably used.
- epoxidized vegetable oil examples include epoxy compounds of vegetable oils such as soybean oil, linseed oil, and cottonseed oil.
- epoxy compounds a phenyldaricidyl ether type epoxy compound, a glycidyl ester type epoxy compound, an alicyclic epoxy compound, Epoxy fatty acid monoesters are preferred. Glycidyl ester type epoxy compounds and alicyclic epoxy compounds are more preferred.
- the blending amount is not particularly limited, but is usually based on the total amount of the refrigerator oil composition (the total amount of the base oil and all the blended additives). It is desirable to incorporate the epoxy conjugate in such an amount that the content becomes 0.1 to 5.0% by mass, more preferably 0.2 to 2.0% by mass on a measurement basis).
- refrigerating machine oil additives such as di-tert-butyl-p-crezo-nore and bisphenolone A may be used, if necessary.
- Phenolic antioxidants such as 1J, phenyl-naphthylamine, N, N-di (2-naphthyl) _p_phenylenediamine amine antioxidants lj, dithiophosphate, etc.
- Pressure agents other than phosphorus-based extreme pressure agents such as chlorinated paraffin and sulfur-based extreme pressure agents, silicone-based antifoaming agents, viscosity index improvers, pour point depressants, and detergent dispersants. It is also possible to mix them alone or in combination of several types.
- the total blending amount 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 the refrigerating machine oil composition (based on the total amount of the base oil and all the blended additives). It is.
- the volume resistivity of the refrigerating machine oil composition of the present invention is not particularly limited, but is preferably 1.0 to 10 9 ⁇ ⁇ o m or more.
- the volume resistivity means a value [ ⁇ 'cm] at 25 ° C measured in accordance with JIS C 2101 “Test method for electrical insulating oil”.
- the water content of the refrigerating machine oil composition of the present invention is not particularly limited, but is preferably 200 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less based on the total amount of the refrigerating machine oil composition. can do.
- a low water content is required from the viewpoint of the thermal stability of the oil and its influence on the electrical insulation.
- the acid value of the refrigerator oil composition of the present invention is not particularly limited, but is preferably 0.1 mgKOH / g or less, more preferably 0.1 mgKOH / g or less, in order to prevent corrosion of metal used in the refrigerator or piping. Preferably, it can be 0.05 mgKOHZg or less.
- the acid value means a value [mgKOHZg] measured according to JIS K 2501 “Petroleum products and lubricating oils-Neutralization number test method”.
- the ash content of the refrigerator oil composition of the present invention is not particularly limited. However, it is preferable to increase the thermal stability of the refrigerator oil composition of the present invention by hydrolysis and suppress the generation of sludge and the like.
- the ash means a value [ppm] measured according to JIS K 2272 “Test method for ash and sulfated ash of crude oil and petroleum products”.
- Refrigerants used in refrigerators using the refrigerator oil composition of the present invention include HFC refrigerants, fluorinated ether-based refrigerants such as perfluoroethers, non-fluorine-containing ether-based refrigerants such as dimethyl ether, and carbon dioxide, ammonia, and carbon dioxide. Power as a natural refrigerant such as hydrogen These may be used alone or as a mixture of two or more.
- HFC refrigerants include hydrated fluorocarbons having 113, preferably 112 carbon atoms. Specifically, for example, difluoromethane (HFC_32), trifluoromethane (HF C-23), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HF C-134) ), HFCs such as 1,1,1,2-tetrafluroethane (HFC-134a), 1,1,1-trifluorethane (HFC-143a), 1,1-difluoroethane (HFC-152a), or A mixture of two or more of these may be mentioned. These refrigerants are appropriately selected depending on the application and required performance.
- Examples of natural refrigerants include carbon dioxide, ammonia, and hydrocarbons.
- a gaseous refrigerant at 25 ° C. and 1 atm is preferably used as the hydrocarbon refrigerant.
- it is an alkane, cycloalkane, alkene or a mixture thereof having 115, preferably 114 carbon atoms.
- Specific examples include methane, ethylene, ethane, propylene, propane, cyclopropane, butane, isobutane, cyclobutane, methylcyclopropane, and a mixture of two or more thereof.
- propane, butane, isobutane or a mixture thereof is preferred.
- the refrigerating machine oil composition of the present invention usually exists in a refrigerating machine in the form of a refrigerating machine fluid composition mixed with a refrigerant as described above.
- the mixing ratio of the refrigerating machine oil to the refrigerant in the fluid composition is not particularly limited, but the refrigerating machine oil is preferably 11 to 500 parts by weight, more preferably 2 to 400 parts by weight, based on 100 parts by weight of the refrigerant.
- the refrigerating machine oil composition of the present invention sufficiently satisfies all the required properties such as lubricity, refrigerant compatibility, low-temperature fluidity, and stability in a well-balanced manner.
- Refrigerating equipment having a type- ⁇ semi-hermetic or hermetic compressor can be suitably used for heat pumps and the like.
- the refrigerating machine oil composition of the present invention can be used for any type of compressor such as a reciprocating type, a rotary type, and a centrifugal type.
- a refrigerant circulation system in which the refrigerating machine oil composition of the present invention can be suitably used, typically, a refrigerant compressor, a condenser, an expansion mechanism, and an evaporator flow in this order, respectively.
- a refrigerant compressor typically, a motor including a rotor and a stator in a closed container for storing refrigerating machine oil, a rotating shaft fitted to the rotor, and a motor connected via the rotating shaft are connected to the motor.
- a high-pressure container type compressor that houses the compressor part and the high-pressure refrigerant gas discharged from the compressor part stays in the closed container, and consists of a rotor and a stator in a closed container that stores refrigeration oil.
- a motor, a rotating shaft fitted to the rotor, and a compressor unit connected to the motor via the rotating shaft are housed therein, and the high-pressure refrigerant gas discharged from the compressor unit is discharged outside the sealed container. Examples include a low-pressure container type compressor that is directly discharged.
- Examples of the insulating film that is a material of an electric insulation system for a motor include a crystalline plastic film having a glass transition point of 50 ° C or higher, specifically, for example, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, and polyether ether.
- At least one insulating film selected from the group consisting of ketone, polyethylene naphthalate, polyamide imide, and polyimide, or a composite film in which a resin layer with a high glass transition temperature is coated on a film with a low glass transition temperature has tensile strength properties and electrical insulation properties. It is preferably used because it is difficult to cause the deterioration phenomenon.
- an enamel coating having a glass transition temperature of 120 ° C or more for example, a single layer of polyester, polyesterimide, polyamide, polyamideimide, or the like, or a layer having a low glass transition temperature may be used as a lower layer.
- those having an enamel coating in which a composite layer is formed on the upper layer in a high level are preferably used.
- composite-coated enameled wires include polyester imide in the lower layer and polyamide imide in the upper layer (AI / EI), and polyester imide in the lower layer and polyamide imide in the upper layer (AI / PE). .
- a keic acid or an alkali aluminate having a pore diameter of 3.3 angstroms or less and a carbon dioxide absorption capacity at a carbon dioxide gas partial pressure of 250 mmHg at 25 ° C of 1.0% or less.
- a synthetic zeolite composed of a metal complex salt is preferably used. Specifically, for example, trade names XH-9, XH-10, XH-11, XH-600, etc., manufactured by Union Shohe Co., Ltd. may be mentioned.
- Base oil 1 Tetraester of pentaerythritol with an equimolar mixture of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid (kinematic viscosity at 40 ° C: 68.5 mm 2 Zs, pour point: 1 (25 ° C)
- Base oil 2 Diester of 1,2,2-cyclohexanedicarboxylic acid and 2-ethylhexanol (kinematic viscosity at 40 ° C: 15 mm 2 Zs, pour point: ⁇ 40 ° C)
- Base oil 3 random copolymer of burethyl ether and butyl isobutyl ether (molar ratio of vinyl ethyl ether to butyl isobutyl ether: 7Zl, number average molecular weight: 900, kinematic viscosity at 40 ° C: 68. (5 mm 2 / s, kinematic viscosity at 100 ° C: 8 mm 2 / s, pour point: -40 ° C)
- Base oil 4 Naphthenic mineral oil (kinematic viscosity at 40 ° C: 56.6 mm 2 / s, pour point: 30 ° C)
- Base oil 5 Polypropylene glycol monomethyl ether (number average molecular weight: 1000, dynamic at 40 ° C) (Viscosity: 46 mm 2 / s, kinematic viscosity at 100 ° C: 10 mm 2 / s, pour point: 40 ° C).
- A3 Tri (n-octyl) phosphate.
- the sliding part of the FALEX tester (ASTM D2714) was installed in a pressure-resistant container, a coolant was introduced into the container, and the FALEX test was performed under the following conditions.
- Test material steel ring, steel block
- Test start temperature 80 ° C
- Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2
- Example Example Example Example Example Example Example Example Example Example Example Example 110 111 112 113 11 115 116 117 118
- Base oil Base oil Free base oil 4
- Base oil 1 Tetraester of pentaerythritol with an equimolar mixture of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid (kinematic viscosity at 40 ° C: 68.5 mm 2 Zs, pour point: 1 (25 ° C)
- Base oil 2 Diester of 1,2,2-cyclohexanedicarboxylic acid and 2-ethylhexanol (kinematic viscosity at 40 ° C: 15 mm 2 Zs, pour point: ⁇ 40 ° C)
- Base oil 3 random copolymer of burethyl ether and butyl isobutyl ether (molar ratio of vinyl ethyl ether to butyl isobutyl ether: 7Zl, number average molecular weight: 900, kinematic viscosity at 40 ° C: 68. (5 mm 2 / s, kinematic viscosity at 100 ° C: 8 mm 2 / s, pour point: -40 ° C)
- Base oil 4 Naphthenic mineral oil (kinematic viscosity at 40 ° C: 56.6 mm 2 / s, pour point: 1-30 ° C)
- Base oil 5 Polypropylene glycol monomethyl ether (number average molecular weight: 1000, at 40 ° C kinematic viscosity: 46mm 2 / s, 100 ° kinematic viscosity at C: 10mm 2 / s, pour point: a 40 ° C)
- base oil 6 mixture of dipentaerythritol and pentaerythritol (mixing ratio (molar ratio) 1: Complete ester of a mixture of 1), 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid (mixing ratio (molar ratio) 1: 1) (kinematic viscosity at 40 ° C .: 195 mm 2 / s, Pour point: One 30 ° C)
- Base oil 7 Paraffin mineral oil (Kinematic
- A6 Tri (n-octyl) phosphorothionate.
- B2 diisobutyl adipate
- B3 diisodecyl adipate
- Refrigerant blowing rate 10L / h.
- Base oil 3 Base oil 3 Base oil 3 Base oil 3 Base oil 3 Base oil 3 Base oil 3
- Base oil 3 Base oil 3 Base oil 3 Oil Base oil 3
- Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2 Base oil 2
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
Description
Claims
Priority Applications (2)
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JP2005512513A JP5110794B2 (ja) | 2003-08-01 | 2004-07-29 | 冷凍機油組成物 |
US10/565,739 US7959824B2 (en) | 2003-08-01 | 2004-07-29 | Refrigerating machine oil composition |
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JP2003-285409 | 2003-08-01 | ||
JP2003285403 | 2003-08-01 | ||
JP2003-285403 | 2003-08-01 | ||
JP2003285409 | 2003-08-01 |
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WO2005012469A1 true WO2005012469A1 (ja) | 2005-02-10 |
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PCT/JP2004/010840 WO2005012469A1 (ja) | 2003-08-01 | 2004-07-29 | 冷凍機油組成物 |
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US (1) | US7959824B2 (ja) |
JP (2) | JP5110794B2 (ja) |
MY (1) | MY146640A (ja) |
TW (1) | TWI354699B (ja) |
WO (1) | WO2005012469A1 (ja) |
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Also Published As
Publication number | Publication date |
---|---|
JP5110794B2 (ja) | 2012-12-26 |
JP2010209360A (ja) | 2010-09-24 |
US20070032391A1 (en) | 2007-02-08 |
JPWO2005012469A1 (ja) | 2007-09-27 |
TWI354699B (en) | 2011-12-21 |
US7959824B2 (en) | 2011-06-14 |
MY146640A (en) | 2012-09-14 |
TW200506044A (en) | 2005-02-16 |
JP5292362B2 (ja) | 2013-09-18 |
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