WO1997010319A1 - Composition d'huile lubrifiante - Google Patents

Composition d'huile lubrifiante Download PDF

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Publication number
WO1997010319A1
WO1997010319A1 PCT/JP1996/002389 JP9602389W WO9710319A1 WO 1997010319 A1 WO1997010319 A1 WO 1997010319A1 JP 9602389 W JP9602389 W JP 9602389W WO 9710319 A1 WO9710319 A1 WO 9710319A1
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WO
WIPO (PCT)
Prior art keywords
carbon atoms
group
acid
lubricating oil
compound
Prior art date
Application number
PCT/JP1996/002389
Other languages
English (en)
Japanese (ja)
Inventor
Toshiya Hagihara
Masahiro Fukuda
Hiroyasu Togashi
Shoji Nakagawa
Original Assignee
Kao Corporation
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Filing date
Publication date
Application filed by Kao Corporation filed Critical Kao Corporation
Publication of WO1997010319A1 publication Critical patent/WO1997010319A1/fr

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    • 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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/18—Ethers, e.g. epoxides
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/48—Esters of carbonic acid
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    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
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    • C10N2040/36—Release agents or mold release agents
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    • 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
    • C10N2040/38—Conveyors or chain belts
    • 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
    • C10N2040/40—Generators or electric motors in oil or gas winning field
    • 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
    • C10N2040/42—Flashing oils or marking oils
    • 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
    • C10N2040/44—Super vacuum or supercritical use
    • 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
    • C10N2040/50—Medical uses

Definitions

  • the present invention relates to a lubricating oil composition containing a phosphorus compound having a specific structure and having excellent lubricity. Further, the present invention relates to a composition for a working fluid of a refrigerator using the lubricating oil composition. Furthermore, the present invention relates to a method for industrially and inexpensively producing a reaction mixture containing a phosphorus compound having a specific structure.
  • ethers such as polyalkylene glycol and esters such as aliphatic diester / hindered ester have been developed, and engine oils, hydraulic oils and grease groups have been developed. Used for oil, gear oil, rolling oil, precision machine oil, etc.
  • the refrigerant is chlorofluorocarbon (CFC) or chlorofluorocarbon (HFC).
  • CFC is replaced by hydrofluorocarbon (HFC)
  • refrigeration oil uses polyalkylene glycol di-hindered ester and carbonic acid ester, which are compatible with the fluorocarbon at the mouth. Due to the pollution of soil and lakes due to leaks, esters with good biodegradability have been used in hydraulic oil, grease, chain saw oil, two-stroke engine oil, etc.
  • oxygen-containing compounds such as the above-mentioned esters, polyalkylene glycols, carbonates, and the like have higher polarities than hydrocarbon compounds such as mineral oils, and therefore have excellent adsorption properties to metal surfaces. For this reason, there has been a problem that the adsorption of oiliness improvers, antiwear agents, extreme pressure agents and the like to metal surfaces is inhibited, and the effect of these additives is reduced.
  • an object of the present invention is to provide a lubricating oil composition which is excellent in lubricity even when a highly polar base oil is used, does not corrode metal due to additives, a composition for a working fluid of a refrigerator, and a polar oil. It is to provide a lubricant additive. It is a further object of the present invention to provide a method for producing a component having a low acid value, which contains a phosphorus compound having a specific structure.
  • the present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that a lubricating base oil is added with a phosphorus compound having a group in which a hydroxyl group is bonded to each adjacent carbon atom.
  • the present inventors have found that in the production of a phosphorus compound having such a specific structure, by limiting the amount of glycidol to be added, it is possible to reduce the amount of the compound to which glycidol is added in a multimolar amount. Furthermore, they have found that the acid value of the reaction mixture can be reduced by adding an alkylene oxide. The present invention has been completed based on such knowledge.
  • the gist of the present invention is:
  • a lubricating oil composition containing a phosphorus compound having a group in which a hydroxyl group is bonded to each adjacent carbon atom;
  • R 1 and R 2 may be the same or different and represent a linear or branched alkylene group having 2 to 4 carbon atoms.
  • P and q represent 0 to 30.
  • R 3 and R 4 may be the same or different, and represent a hydrogen atom, a linear alkyl group having 1 to 30 carbon atoms, A branched alkyl group having 3 to 30 carbon atoms, a linear alkenyl group having 2 to 30 carbon atoms, a branched alkenyl group having 3 to 30 carbon atoms, and an aryl group having 6 to 30 carbon atoms Represents an aralkyl group having 7 to 30 carbon atoms, a halogenated alkyl group having 1 to 30 carbon atoms, or a halogenated aryl group having 6 to 30 carbon atoms.
  • R 3 is not a hydrogen atom
  • R 4 is not a hydrogen atom
  • R 5 is a straight ⁇ alkyl group having 1 to 3 0 carbon atoms, minute ⁇ alkyl group having from 3 3 0 carbon atoms, straight chain Aruke radicals having the number of 2-3 0 carbon number 3-3 0 carbon
  • a branched alkenyl group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms? Represents an aralkyl group having 1 to 30 carbon atoms, a halogenated alkyl group having 1 to 30 carbon atoms, or a halogenated aryl group having 6 to 30 carbon atoms.
  • R 1 and R 2 may be the same or different and represent a linear or branched alkylene group having 2 to 4 carbon atoms.
  • P and q represent 0 to 30.
  • R 3 and R 4 may be the same or different, and include a hydrogen atom, a linear alkyl group having 1 to 30 carbon atoms, a branched alkyl group having 3 to 30 carbon atoms, and 2 to 2 carbon atoms.
  • a linear alkenyl group having 30 carbon atoms, a branched alkenyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, and 1 to 3 carbon atoms Represents a halogenated alkyl group having 0 or a halogenated aryl group having 6 to 30 carbon atoms, provided that when p is 0, R 3 is not a hydrogen atom, and when q is 0, R 4 is a hydrogen atom. such have.
  • R 5 represents a straight-chain alkyl group, min ⁇ alkyl group having from 3 3 0 carbon atoms having 1 to 3 0 carbon atoms, Choku ⁇ Aruke radicals having prime 2-3 0, branched alkenyl group having the number of 3-3 0 carbon atoms, 6 carbon atoms
  • a glycidol is added to the compound represented by any of the formulas (1) to (9) to obtain a phosphorus compound represented by any of the general formulas (1) to (9), and then a reaction mixture containing the phosphorus compound is obtained.
  • the lubricating oil composition according to (3) wherein the lubricating oil composition according to the above (3) uses a reaction mixture having an acid value of 3 O mg KO HZg or less, which is obtained by performing an addition reaction of an alkylene oxide to the product.
  • the aforementioned lubricating base oil is a base oil containing an oxygen-containing compound as a main component
  • oxygen-containing compound is at least one compound selected from the group consisting of an ester compound, a cyclic ketal or cyclic acetal compound, a polyether compound, a polyalkylene glycol compound, and a carbonate compound.
  • a lubricating oil composition wherein the oxygen-containing compound is at least one compound selected from the group consisting of an ester compound, a cyclic ketal or cyclic acetal compound, a polyether compound, a polyalkylene glycol compound, and a carbonate compound.
  • ester compound is at least one compound selected from the group consisting of the following (a) to (d):
  • component-1 a divalent to hexavalent saturated aliphatic polyhydric alcohol having 2 to 10 carbon atoms
  • component-1 a divalent to hexavalent saturated aliphatic polyhydric alcohol having 2 to 10 carbon atoms
  • component 2 a linear or branched saturated aliphatic monocarboxylic acid having 2 to 9 carbon atoms, rubonic acid or a derivative thereof.
  • component 14 (d) a C2 to C10 divalent to hexavalent saturated aliphatic polyhydric alcohol (component-1) and a C1 to C10 linear or branched saturated aliphatic monohydric alcohol (component-1) ) And a divalent to hexavalent polyvalent force having 2 to 10 carbon atoms, rubonic acid or a derivative thereof (component 14).
  • a cyclic ketal or a cyclic acetal compound is a compound represented by the general formula (10)
  • R 6 represents a hydrogen atom or a straight chain having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms
  • R 7 represents a carbon atom.
  • straight chain having 1-1 2 shows a branched alkyl group with carbon number 3-1 2, or having a carbon number of 3-1 bicyclic or
  • R e and R 7 are - become cord carbon number 2 1 3 shows an alkylene group.
  • the total number of carbon atoms of R e and R 7 is from 1 to 1 3.
  • the polyether compound is represented by the following one-branch formula (16).
  • R 8 to R 13 may be the same or different and each represents a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms. However, the total carbon number of R 8 to R 13 is 8 to 40)
  • R 14 represents a linear or branched alkylene group having 2 to 4 carbon atoms.
  • R 15 represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, or a carbon atom having 2 to 4 carbon atoms.
  • A represents a hydrogen atom, a w-valent alcohol residue having 1 to 15 carbon atoms, or a w-valent phenol residue having 6 to 15 carbon atoms.
  • V is a number from 1 to 50, w is a number from 1 to 6. However, V R 14 ⁇ , w R 15 and w 0— (R 140 ) V—R 15 may be the same or different. )
  • R 16 and R ′ 11 may be the same or different and each have an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, or
  • R 20 O represents a group represented by R 19 .
  • R 19 is an alkyl group having 1 to 18 carbon atoms, an aryl group, or an aralkyl group, and R 2 ° is a carbon atom.
  • the alkylene group, arylene group, or aralkylene group represented by the formulas 2 to 18, and z represents an integer of 1 to 100.
  • z R 2 . 0 may be the same or different.
  • R17 is an alkylene group, arylene group, or aralkylene group having 2 to 18 carbon atoms
  • X is an integer of 1 to 100
  • y is 0 to 10
  • X R 170 may be the same or different, and y
  • composition for a working fluid of a refrigerator comprising the lubricating oil composition according to any one of (1) to (13) and hydrofluorocarbon;
  • the phosphorus compound represented by any of the general formulas (31) to (38) is added to the phosphorus compound in a molar ratio of 0.1 to 1 with respect to the phosphorus compound.
  • alkylene oxide was added to the reaction mixture containing the phosphorus compound.
  • any one of the general formulas (1) to (9) is characterized in that an addition reaction of an alkylene oxide is performed to reduce the acid value of the reaction mixture.
  • the phosphorus compound used in the present invention is a phosphorus compound having a group in which a hydroxyl group is bonded to an adjacent carbon atom, and preferably, the phosphorus compound has 2 to 4 hydroxyl groups. Things. Specific examples of the group to which the hydroxyxyl group is bonded include 2,3-dihydroxylpyryl group, 2,3—dihydroxybutyl group, 2,3,4—trihydroxybutyl group, and 2,3-dihiboxy group. Examples include a droxyoctyl group and a 3,4-dihydroxybutyl group.
  • Suitable examples of such a phosphorus compound include compounds represented by any of the following general formulas (1) to (9), but are not limited to these in the present invention. .
  • R 1 and R 2 may be the same or different and represent a linear or branched alkylene group having 2 to 4 carbon atoms.
  • P and q represent 0 to 30).
  • R 3 and R 4 may be the same or different, and include a hydrogen atom, a linear alkyl group having 1 to 30 carbon atoms, a branched alkyl group having 3 to 30 carbon atoms, and a carbon number.
  • R 5 is branched chain alkyl group having a straight-chain alkyl group, 3 carbon 3 0 having 1 to 3 0 carbon atoms, Linear alkene having 2 to 30 carbon atoms Nyl group, branched alkenyl group having 3 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms, aralkyl group having 7 to 30 carbon atoms, halogen having 1 to 30 carbon atoms Represents a halogenated alkyl group or a halogenated aryl group having 6 to 30 carbon atoms.
  • a linear or branched alkyl group a linear or branched alkenyl group, an aryl group, an aralkyl group, a halogenated alkyl group, and a halogenated aryl
  • the carbon number of the group is 30 or less from the viewpoint that as the carbon number increases, the polarity decreases and the abrasion prevention effect deteriorates. It is preferably 24 or less, more preferably 18 or less, particularly preferably 4 or more and 12 or less.
  • the number of carbon atoms is preferably 18 or less, more preferably 12 or less from the viewpoint of compatibility with hydrofluorocarbon.
  • linear alkyl group having 1 to 30 carbon atoms 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, Dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, tetracosyl, octacosyl, triacontyl and the like.
  • Examples of the branched alkyl group having 3 to 30 carbon atoms include isopropyl, 1-methylpropyl, 2-methylpropyl, t-butyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, cyclopentyl, 2-methylpentyl, 2-ethylbutyl, 2,3-dimethylbutyl, cyclohexyl, 2-methylhexyl, 3-methylhexyl, 2 —Ethylpentyl group , 2-methylheptyl, 2-ethylhexyl, 3,5-dimethylhexyl, 3,5,5-trimethylhexyl, 2,4,6—trimethylheptyl, 2 , 4, 6, 8 —tetramethylnonyl, 2 — (3, —methylbutyl) 1 7 —methyloctyl, 2 —pentylnonyl, 2 —hexyldecyl, 2 —heptyl
  • linear alkenyl group having 2 to 30 carbon atoms examples include a propenyl group, a 2-decenyl group, a 9-decenyl group, a 9-decenyl group, a 10-decenyl group, a 2-dodecenyl group and a 3-dodecenyl group.
  • Examples of the branched alkenyl group having 3 to 30 carbon atoms include an isopropenyl group, a 3-methyl-2-nonenyl group, a 2,4-dimethyl-12-decenyl group, and a 2-methyl-9-butadecenyl group. And the like.
  • aryl group having 6 to 30 carbon atoms examples include phenyl, 4-methylphenyl, 4-ethylphenyl, 2,4-dimethylphenyl, 4-t-butylphenyl, naphthyl, and 2-methylnaphthyl.
  • Examples of the aralkyl group having 7 to 30 carbon atoms include a benzyl group, a 4-methylbenzyl group, a phenethyl group, a sec-phenethyl group, a 3,5-dimethylbenzyl group, a 4-ethylbenzyl group, a 3-phenylpropyl group, 4-isopropylpyrubenzyl group, 4-monobutylbenzyl group, 4-t-butylbenzyl group, 1,1-dimethyl-3-phenylphenyl group, 5-phenylpentyl group, naphthylmethyl group, naphthylethyl group, etc. No.
  • halogen atom of the halogenated alkyl group having 1 to 30 carbon atoms examples include a fluorine, chlorine, bromine, and iodine atom, with chlorine being preferred.
  • Specific examples of the halogenated alkyl group include: 8-cycloethyl group, 2,3-dichloropropyl group and the like.
  • Examples of the halogen atom of the halogenated aryl group having 6 to 30 carbon atoms include a fluorine, chlorine, bromine, and iodine atom, and chlorine is preferred.
  • Specific examples of the halogenated aryl group include a monochlorophenyl group, a dichlorophenyl group, a monomethylphenylphenyl group, a dichloro-4-methylphenyl group, and the like.
  • R 1 and R 2 each represent a linear or branched alkylene group having 2 to 4 carbon atoms.
  • Examples of the linear or branched alkylene group having 2 to 4 carbon atoms include an ethylene group and a propylene group. Group, trimethylene group, butylene group, isobutylene group, tetramethylene group and the like.
  • the molecular weight increases and the number of 0 to 30 is preferred from the viewpoint that solubility in the base oil decreases and that the phosphorus concentration decreases and the effect of addition decreases. It is more preferably 0 to 20 and particularly preferably 0 to 10.
  • this phosphorus compound is When used in a composition for a working fluid, 0 to 20 is preferable, 0 to 10 is more preferable, and 0 to 10 is particularly preferable from the viewpoint that as the number of P and q increases, electric insulation becomes inferior. ⁇ 5.
  • p and q may be the same or different.
  • the above phosphorus compounds may be used alone, or two or more phosphorus compounds may be used.
  • the phosphorous compounds represented by any of the general formulas (1) to (9) are commercially available phosphoric acid diesters, phosphoric acid monoesters, phosphorous acid monoesters, phosphorous acid diesters, and phosphorous diesters. Reaction of glycidol with carboxylic acid, monoester of phosphoric acid, etc., or a halogenated compound such as oxychloric acid or phosphorous trichloride with an alcoholic or phenolic compound; It can be obtained by reacting glycerin.
  • the general formulas (8) and (9) are preferably carried out by the latter reaction from the viewpoint of yield.
  • the former reaction with glycidol is carried out without a solvent or in a polar solvent such as tetrahydrofuran or ethanol, or without a catalyst or a phase transfer catalyst such as tetraammonium bromide bromide.
  • Glycidol can be added dropwise to the raw material phosphorus compound at a temperature of 10 to 100 ° C., preferably 25 to 100 ° C., more preferably 40 to 70 ° C. .
  • the latter reaction can be carried out without a solvent or in an inert solvent such as hexane or toluene, while dropwise adding an alcoholic compound or a phenolic compound, and then glycerin to the phosphorus halide compound.
  • the generated hydrogen chloride can be driven out of the system together with an inert gas such as nitrogen, or trapped by a basic substance such as amine.
  • the reaction temperature one 4 0 ⁇ 1 5 0 'C, preferred properly one 2 0 ⁇ 1 2 0 e C, Shi further preferred Or — at 5 to 70 ° C.
  • a basic substance such as amine
  • the reaction can be carried out at a reaction temperature of 140 to 60, preferably -5 to 10.
  • both may be purified as required by washing, adsorption, distillation, column chromatography, thin-layer chromatography, or the like.
  • the contaminated material may be used as a “phosphorus compound”. That is, the reaction mixture containing the desired phosphorus compound, unreacted raw materials, by-products, etc., obtained during the production of the phosphorus compound, can be used as it is or at low cost such as washing, adsorption, distillation, etc. It can be used as a “lin compound” after purification.
  • the phosphoric acid compound preferably has a low acid value.
  • the acid value of the phosphorus compound is measured by the method of JIS K 0700, it is preferably 5 O mg KOHZg or less, more preferably 3 O mg KOHZg or less, and 15 mg KOHZ. g or less, more preferably 1 O mg KOH / g or less, particularly preferably 5 mg K 0 HZg or less, and particularly preferably 2 mg KO HZ g or less.
  • the content is preferably 5 mg KOHZg or less, more preferably 2 mgKOH / g or less, and particularly preferably 1 mgKOHZg or less.
  • Such a reaction mixture having a low acid value used as a phosphorus compound can be obtained, for example, by the following method.
  • R 1 and R 2 may be the same or different and represent a linear or branched alkylene group having 2 to 4 carbon atoms.
  • P and q represent 0 to 30).
  • R 3 and R 4 may be the same or different, and include a hydrogen atom, a linear alkyl group having 1 to 30 carbon atoms, a branched chain alkyl group having 3 to 30 carbon atoms, and 2 carbon atoms.
  • R 3 is not a hydrogen atom
  • R 5 is a straight-chain alkyl group having 1 to 30 carbon atoms, 3 to 3 carbon atoms
  • a glycidol is added to the compound represented by any of the formulas (1) to (9) to obtain a phosphorus compound represented by any of the general formulas (1) to (9), and then a reaction mixture containing the phosphorus compound is obtained. It is obtained by performing an addition reaction of an alkylene oxide to the product.
  • 13 ⁇ 41-1 to 1 in the general formulas (31) to (38)? 5 ,, and q are the same as in the general formulas (1) to (9).
  • the reaction mixture thus obtained contains a phosphorus compound represented by any of the general formulas (1) to (9), and has an acid value of 30 mg KOH / g or less. .
  • the reaction mixture obtained is acidified.
  • the molar ratio of glycidol to the raw material phosphorus compound represented by (31) to (38) must be changed. It must be 1.6 times or more.
  • a polymol adduct of glycidol which is a component insoluble in the base oil, is formed.
  • the acid value of the obtained reaction mixture is 35 to 60 O. It is considerably higher with mg KO HZg. If the reaction mixture used as the phosphorus compound exhibits such a high acid value, there is a concern that corrosion of metals and hydrolysis of the base oil esters and carbonates may be accelerated.
  • Another possible method is to remove the phosphorus compounds (31) to (38) of the raw material that contribute to the increase in the acid value in the reaction mixture. However, such a phosphorus compound depends on the alkyl chain length.
  • the starting phosphorus compounds (31) to (38) are reacted with glycidol in a molar ratio of 0.1 to 1.0 to obtain a compound represented by the general formulas (1) to (9).
  • the addition reaction of the alkylene oxide is performed, and the acid value of the reaction mixture can be reduced to a predetermined acid value or less. Since such a reaction mixture has a reduced amount of glycidol multimol adduct and a low acid value, it can be incorporated into a lubricating oil composition without further purification. However, from the viewpoint of obtaining a higher quality lubricating oil composition, the reaction mixture may be further purified.
  • the phosphorus compound used as the raw material is preferably (31) in order to increase the yield of this reaction.
  • the production method of the present invention can be divided into two stages. Next, an explanation will be given for each stage.
  • the first step in the reaction is to add glycidol to the raw phosphorus compound.
  • Glycidole reacts most easily with acidic phosphoric acid moieties.
  • a glycidol adduct is formed with respect to this compound.
  • a side reaction such as formation of an adduct of polyglycidol occurs with this compound.
  • 2 mol of glycidol was added to the raw material or the desired phosphorus compound.
  • a molar adduct or a multimolecule adduct in which glycidol is multimoleculated are formed.
  • the second stage of the reaction is a reaction in which an alkylene oxide is added to an unreacted raw material phosphorus compound or the like.
  • the acid value of the reaction mixture is reduced by adding an alkylene oxide to the hydroxyl group of the starting phosphorus compound.
  • the alkylene oxide is added not only to the raw phosphorus compound but also to the desired phosphorus compound, the above-mentioned 2-mol adduct and multi-mol adduct.
  • alkylene oxides react most readily with acidic phosphoric acid moieties, but when a compound having a hydroxyl group is present, the side reaction of forming an alkylene oxide adduct with this compound also occurs. Because it occurs.
  • a desired phosphorus compound, a part of other multimolecule adduct, and the like, and a compound in which an alkylene oxide is added to an unreacted raw material phosphorus compound are generated as by-products.
  • reaction mixture thus obtained has a low acid value, it may be used as it is as a phosphorus compound, or may be used after further purification. Is also good.
  • a multimol adduct of glycidol has poor solubility in a base oil, and causes turbidity of a lubricating oil composition. Therefore, its content is preferably smaller.
  • the production of such a multimol adduct can be suppressed by using a polar solvent during the addition reaction of glycidol.
  • the amount of glycidol to be added is 0.1 to 0, preferably 0.5 to 1.0, more preferably 0.8 to 1.0 in molar ratio of glycidol to the starting phosphorus compound. It is 0. If the above molar ratio is greater than 1.0, the ratio of the formation of a multi-mol adduct of glycidol, which is a by-product, increases, and the lubricating oil composition tends to become turbid. Is preferably 1.0 or less. From the viewpoint of increasing the purity of the desired phosphorus compound as a main product, the above molar ratio is preferably 0.1 or more.
  • the temperature conditions for glycidol addition are 10 to 100.
  • C the preferred properly 2 5 ⁇ 1 0 0 e C, is more preferable properly is 4 0 ⁇ 7 0 ° C.
  • the time spent for supplying glycidol depends on the reaction temperature, but 0.5 to 4 hours is preferred. Further, an aging time of 1 to 3 hours may be provided.
  • Conditions for alkylene oxide addition Examples of the alkylene oxide used include those having 2 to 8 carbon atoms, and specific examples include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. Of these, propylene oxide is most preferred from the viewpoints of reactivity, cost, solubility of the resulting alkylene oxide adduct in base oil, antiwear properties, and the like.
  • the amount of the alkylene oxide to be added may be an amount capable of reducing the reaction mixture to a predetermined acid value.
  • the reaction temperature at the time of addition of the alkylene oxide is from 10 to 100 ° C, preferably from 25 to 100 ° C, and more preferably from 40 to 60 ° C.
  • the time required for the addition is preferably 0.5 to 4 hours, more preferably 0.5 to 2 hours. In addition, a aging time of 1 to 12 hours is acceptable.
  • a polar solvent as a solvent in the addition reaction of glycidol, since the formation of a polymol adduct of glycidol can be suppressed, and a desired phosphorus compound can be obtained with high yield. Since a polymol adduct of glycidol has poor compatibility with hydrofluorocarbon, the use of a polar solvent as a solvent in the addition reaction of glycidol is particularly effective for a composition for a working fluid of a refrigerator. It is effective when using the phosphorus compound of the present invention.
  • a polar solvent may be used in the first step and Z or the second step of the reaction of the present invention.
  • the polar solvent used include ethers such as getyl ether and dibutyl ether; cyclic ethers such as tetrahydrofuran and dioxane; Methanol, ethanol, isopropanol, t — Alkylene oxides with 2 to 8 carbon atoms were added to lower alcohols such as butanol, and lower alcohols with 1 to 6 carbon atoms and lower diols with 2 to 6 carbon atoms.
  • examples include polyalkylene glycols which may or may not be alkyl-capsulated or acyl-capped at the end.
  • the polyalkylene glycol is preferably 40 and has a viscosity of 100 mm 2 s or less, more preferably 70 mm 2 s or less, more preferably Is 50 mm 2 Z s or less, and more preferably 30 mm 2 Z s or less.
  • borylene glycol glycol examples include, for example, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethyl glycol dimethyl ether, triethylene glycol monoethyl ether, and diethylene glycol getyl ether. And ethylene glycol dibutyl ether, butanol, ethylene oxide adduct of butanol, propylene oxide adduct of butanol, and butylene oxide adduct of butanol. Most preferably, it is a propylene oxide additive of a lower alcohol such as bushanol.
  • polar solvent it is preferable to use a large amount of the polar solvent to suppress local heat generation as described below.However, from the viewpoint of cost and performance, it is preferable to use a large amount of the polar solvent with respect to 100 parts by weight of the raw material phosphorus compound. 0 to 400 parts by weight, more preferably 50 to 200 parts by weight, is preferably used.
  • a polar solvent in the present invention, local heat generated when glycidol reacts can be suppressed, and polyglycidol is produced by polymerization of glycidol, and the desired phosphorylated product is produced. Addition of glycidol or polyglycidol to the hydroxyl group of the compound Side reactions can be effectively suppressed. In other words, the by-product of poorly soluble base oil and poorly compatible with the fluoridated carbon at the mouth opening of the multimol adduct of glycidyl is reduced.
  • examples of embodiments of the production method of the present invention include:
  • Glycidol is added to the phosphorus compound represented by any of formulas (31) to (38) to contain the phosphorus compound represented by any of formulas (1) to (9)
  • the phosphorus compound represented by any of the general formulas (31) to (38) is added to the phosphorus compound in a molar ratio of 0.1 to 1.0 with respect to the phosphorus compound.
  • Glycidol is reacted to obtain a phosphorus compound represented by any of the general formulas (1) to (9), and then an alkylene oxide is added to the reaction mixture containing the phosphorus compound to obtain an alkylene oxide.
  • the obtained phosphorus compound-containing component is treated as a reaction mixture containing the phosphorus compound represented by any of the general formulas (1) to (9).
  • the acid value of the reaction mixture is more preferably 30 mg KOHZg or less.
  • R z is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aralkyl Represents a hydroxyl group.
  • the first stage of the reaction is a reaction in which glycidol is added to the raw phosphorus compound (31). From the properties of glycidol shown above, in addition to the main product (1), it is a 2-mol adduct of glycidol (41) and a polymolar adduct of glycidol (51) Are formed.
  • the second stage of the reaction is a reaction in which an alkylene oxide is mainly added to the unreacted starting compound, the phosphorus compound (31).
  • the raw material phosphorus compound (31) is added with the alkylene oxide to become (61).
  • the phosphorus compound (1) which is the main product, is partially (62), (41) is partially (63), and (51) is partially (64). Change o
  • R y O, (0 CH 2 CHCH 2 ) n (0 CH 2 CH-) 0 H (n is an integer of 3 or more, m is an integer of 1 or more)
  • reaction mixture contains (41), (51), (61) to (64), etc. in addition to (1).
  • the lubricating oil additive for polar oil of the present invention contains the above phosphorus compound as an active ingredient.
  • the phosphorus compound may be used alone or in combination of two or more.
  • an antioxidant, a detergent / dispersant, an oiliness improver, an extreme pressure agent, a viscosity index improver, a corrosion inhibitor, a corrosion inhibitor, , Money It can be used in combination with a lubricating oil additive such as a genus deactivator.
  • the lubricating oil additive for polar oils of the present invention when used for polar oils as described below, is particularly excellent in lubricity because of its superior adsorption to metal surfaces as compared to base oils.
  • Base oils used in the present invention include mineral oils such as polybutene, polyolefin, hydrocarbon synthetic oils such as alkylbenzene, aliphatic diesters and neopentylpolyolesters, polyalkylene glycols, polyphenyl ethers, and the like. Examples include carbonate, phosphoric acid ester, silicate ester, silicone oil, and verfluoroboryl ether. Specific examples are “New Edition, Physical Chemistry of Lubrication” (Koshobo) and “ Oil Basics and Applications ”(Corona).
  • the lubricating base oil is preferably a base oil containing an oxygen-containing compound as a main component.
  • the oxygen-containing compound is preferably an ester-based, cyclic ketal, or cyclic acetal-based It is preferably at least one compound selected from the group consisting of polyether, polyalkylene glycol, and carbonate.
  • the base oil is preferably an oxygen-containing compound from the viewpoint of compatibility with hydrofluorocarbon.
  • ester type One or more compounds selected from the group consisting of cyclic ketals or cyclic acetal compounds, polyether compounds, polyalkylene glycol compounds, and carbonate compounds are preferred, and esters, cyclic ketones and cyclic acetal compounds are particularly preferred. I like it.
  • ester, cyclic ketal Z cyclic acetal, polyether compound, polyalkylene alcohol, and carbonate used in the composition for a working fluid of a refrigerator according to the present invention will be described below.
  • ester synthetic oil used in the present invention a phosphorus compound which is compatible with hydrofluoric carbon, has a pour point of 0'C or less, and is represented by any of the general formulas (1) to (9), There is no particular limitation as long as the ester is soluble. For example, an ester selected from the following group is preferred.
  • component-1 a straight-chain or branched-chain saturated lipoprotective monovalent alcohol having 1 to 10 carbon atoms (component-1), and a 2 to 10 carbon-containing divalent to hexavalent polycarboxylic acid or Esters obtained from derivatives (component-1 4).
  • the alcohol of component 1 has a valency of 2 to 6, preferably 2 to 4.
  • the valence is preferably 2 or more from the viewpoint of having an appropriate viscosity, and is preferably 6 or less from the viewpoint of avoiding unnecessary viscosity and compatibility with the hydrofluorocarbon.
  • the number of carbon atoms is 2-10, preferably 2-6.
  • the number of carbon atoms is preferably 2 or more from the viewpoint of having an appropriate viscosity, and is preferably 10 or less from the viewpoint of avoiding unnecessary viscosity and compatibility with the hydrofluorocarbon. Further, it is preferable not to include unsaturated bonds from the viewpoint of heat resistance.
  • the alcohol of the component-1 include hindered compounds such as neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol.
  • Alcohol and ethylene glycol, ethylene glycol, propylene glycol, dipropylene glycol, 1,3-brobandiol, 4-butanediol, 6-hexanediol, glycerin, diglycerin, Polyhydric alcohols such as triglycerin, sorbitol and mannitol are available.
  • hindered alcohol is particularly superior in terms of heat resistance.
  • the carbon number of the carboxylic acid of component 1 is from 2 to 9, preferably from 5 to 9
  • the number of carbon atoms is preferably 2 or more from the viewpoint of suppressing the corrosiveness to the metal, and is preferably 9 or less from the viewpoint of compatibility with the fluorocarbon at the opening.
  • Branched saturated fatty acids are more preferable than linear saturated fatty acids from the viewpoint of compatibility with the fluorcarbon at the mouth and hydrolysis resistance.
  • straight-chain saturated fatty acids are preferred over branched-chain saturated fatty acids.
  • a suitable material is selected according to the mode of use as the composition for the working fluid of the refrigerator. From the viewpoint of heat resistance, it is more preferable not to include unsaturated bonds.
  • carboxylic acid of the component-2 examples include: phenolic acid, itvaleric acid, 2-methylbutyric acid, cabronic acid, enanthic acid, 2-ethylethylconic acid, and 2-methylhexane Acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, 3,5,5-trimethylhexanoic acid and the like.
  • carboxylic acid derivative of Component 12 include methyl esters, ethyl esters, and acid anhydrides of these carboxylic acids.
  • the alcohol of component 13 has 1 to 10 carbon atoms, preferably 5 to 9 carbon atoms. It is preferably 10 or less from the viewpoint of compatibility with the fluorocarbon at the mouth. Branched saturated alcohols are more preferable than straight chain saturated alcohols from the viewpoint of compatibility with the fluorene carbonate at the mouth and resistance to hydrolysis. From the viewpoint of lubricity, a straight-chain saturated alcohol is more preferable than a branched-chain saturated alcohol. In the present invention, a suitable one is selected according to the mode of use as the composition for the working fluid of the refrigerator. In addition, from the viewpoint of heat conductivity, it is more preferable not to include unsaturated bonds.
  • the alcohol of the component 13 include methanol, ethanol, brono, 'nor, isopronor, busu nor, t-bu no, penu 2, 2-methylbutanol, 2, 2-dimethylpropanol, hexanol, 2-methylpentanol, 2-ethylbutanol, 2, 3-dimethylbutanol, heptanol Knol, 2—Methylhexanol, 3—Methylhexanol, 5—Methylhexanol, Octanol, 2—Ethylhexanol, Nonanol, 3,5,5—Tri Examples include methylhexanol, decyl alcohol, and 2,4,6—trimethylhexanol. Among them, hexanol, 3-methylhexanol, heptanol, 2-ethylhexanol, octanol, 3,5,5—trimethylhexanol,
  • the valency of the carboxylic acid of the component 14 is 2 to 6, preferably 2 to 4, and more preferably 2 to 3.
  • the valence is preferably 2 or more from the viewpoint of having an appropriate viscosity, and is preferably 6 or less from the viewpoint of avoiding unnecessary undulation and compatibility with the hydrofluorocarbon.
  • the carbon number is 2 to 10, preferably 4 to 9. 10 or less is preferred from the viewpoint of compatibility with the high-mouth fluorocarbon o
  • carboxylic acid of the component 14 include saturated lipoprotective dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid, and 1,2,3-propane tricarboxylic acid. Acids, methyltricarboxylic acids, saturated fatty acid tricarboxylic acids such as rubonic acid, and fluoric acid, Aromatic polyvalent carboxylic acids such as phthalic acid, trimellitic acid and pyromellitic acid, and the like can be mentioned.
  • carboxylic acid derivative of the component 14 include methyl esters, ethyl esters, and acid anhydrides of these carboxylic acids. Among these, glutaric acid and adipic acid are preferred from the viewpoint of industrial availability.
  • the number of carbon atoms of the carboxylic acid of Component 1 is 2 to 10, preferably 4 to 6. From the viewpoint of compatibility with hydrofluorocarbon, 10 or less is preferable. From the viewpoint of heat resistance, it is more preferable not to include unsaturated bonds.
  • carboxylic acid of Component-1-5 include the linear or branched saturated aliphatic dicarboxylic acids in the carboxylic acids mentioned in Component-1-4.
  • carboxylic acid derivative of Component-5 examples include the methyl ester, ethyl ester, and acid anhydride of the dicarbonic acid.
  • esters described in the above (a) to (d) used in the present invention Taking into account the balance of required properties such as compatibility with hydrofluorocarbon, thermal stability, lubricity, and electrical insulation in the esters described in the above (a) to (d) used in the present invention.
  • the ester compound described in (a) is preferred.
  • a divalent to hexavalent hindered alcohol having 2 to 10 carbon atoms is used as the polyhydric alcohol, and a saturated aliphatic monocarbohydrate having 5 to 9 carbon atoms is used as the monocarboxylic acid. Hindered esters using acid are particularly preferred.
  • neopentyl glycol trimethylolethane, trimethylolprono, ozone, pentaerythritol, ditrimethylolpropane, dipentaerythritol and the like are preferable.
  • Monocarboxylic acids include phosphoric acid, isophorenoic acid, 2-methylbutyric acid, caproic acid, enanthic acid, 2-ethylpentanoic acid, 2_methylhexanoic acid, and caprilic acid. Acids, 2-ethylhexanoic acid, belargonic acid, 3,5,5-trimethylhexanoic acid and the like are preferred.
  • Specific examples of the preferred ester described in (a) include 3,5,5-trimethylhexanoate of neopentyl glycol, 2-ethylhexanoate of neopentyl glycol, and trimethylolpropane.
  • the ester used in the present invention can be obtained by a known esterification reaction or transesterification reaction usually performed from each of the above-mentioned components. That is, with respect to the above-mentioned ester (a), the alcohol of the component 11 And at least one of the alcohol of component 13 and the carboxylic acid of component -4 or at least one of the carboxylic acid or the derivative thereof.
  • ester of (c) from one or more of the derivatives, one or more of the alcohol of the component-11, one or more of the carboxylic acid of the component-12 or a derivative thereof and the carboxylic acid of the component-15 or the derivative thereof And at least one of the alcohols of component-1 and at least one of the alcohols of component-3, and at least one of the carboxylic acids of component-4 or derivatives thereof. From the above, it can be obtained by a commonly known esterification reaction or ester exchange reaction.
  • the acid value of the ester obtained as described above, which is used in the present invention, is not particularly limited, but a viewpoint of suppressing corrosion of a metal material, reduction of abrasion resistance, reduction of thermal stability, and reduction of electrical insulation.
  • To 1 mg KOH / g or less more preferably 0.2 mg KOHZg or less, even more preferably 0.1 mg KOHZg or less, and particularly preferably 0.05 mg KOHZg or less.
  • the hydroxyl value of the ester used in the present invention is not particularly limited, but is preferably 0.1 to 50 mg KOHZg, more preferably 0.1 to 30 mg KOHZg, and particularly preferably 0.1 to 2 Omg KOHZg. Preferred. 0.1 mg KOHZg or more is preferable from the viewpoint of shochu abrasion, and 5 O mg KOHZg or less is preferable from the viewpoint of hygroscopicity.
  • the iodine value (ImgZ100g) of the ester used in the present invention is not particularly limited, but is preferably 10 or less, more preferably 5 or less from the viewpoint of thermal oxidation stability of the obtained lubricating oil composition. , 3 or less are more preferred, and 1 or less is particularly preferred.
  • the ester used in the present invention has a low Two phases ⁇ degree in temperature is desirably low, 1 is preferably from o ° c, more preferably 0 hands less, further preferred properly one 1 0 'C or less, particularly preferred properly one 3 0 e C or less And most preferably less than 150 ° C. Further, it is desirable that the two-phase separation temperature at a high temperature is high, preferably 30 ° C or higher, more preferably 40 ° C or higher, still more preferably 50 ° C or higher, and 60 ° C. or as particularly preferred, 8 0 e C or higher is most preferred arbitrariness.
  • the kinematic viscosity at 1 0 0 e C esters used in the present invention is not particularly limited constant, from the viewpoint of compatibility with Hyde port Furuorokabon 1 0 0 mm 2 Z s or less laid preferred, usually 1 to 1 0 0 mm 2 Z s is laid preferred, 1 ⁇ 3 0 mm 2 Z s is laid more preferred, 2 ⁇ 2 0 mm 2 / s is arbitrarily favored especially.
  • the cyclic ketal used in the present invention The cyclic acetal compound-based synthetic oil is compatible with the fluorocarbon at the mouth, has a pour point of 0 ° C or less, and is represented by the general formulas (1) to (9).
  • the cyclic ketal Z cyclic acetal compound is not particularly limited as long as it is a cyclic ketal Z cyclic acetal compound that dissolves the cyclic compound.
  • Preferred examples of the cyclic ketal Z cyclic acetal compound include compounds described in WO966Z06939 In particular, at least one kind of polyhydric alcohol having an even number of valences of 4 or more and 8 or less is represented by the general formula (10)
  • R 8 represents a hydrogen atom or a straight chain having 1 to 12 carbon atoms, a branch having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms
  • R 7 represents a straight chain having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms.
  • R e and R 7 are linked to each other to represent an alkylene group having 2 to 13 carbon atoms.
  • the total carbon number of R e and R 7 is from 1 to 13.
  • a cyclic ketal or a cyclic acetal obtained from at least one kind of ketone or acetal which is a reactive compound of the formula or a reactive derivative thereof.
  • the valence of the polyhydric alcohol used as a raw material of the cyclic ketal or cyclic acetal used in the present invention is preferably tetravalent, hexavalent, or octavalent, and more preferably tetravalent or hexavalent. If the valency of the polyhydric alcohol is greater than 8, the resulting cyclic ketal or cyclic acetal may have too high a viscosity and poor compatibility with the hydrofluorocarbon. If the valency of the polyhydric alcohol is smaller than 4, the molecular weight is too low, and the boiling point and the flash point are undesirably low.
  • the polyvalent alcohol used as a starting material for the cyclic ketal or the cyclic acetal preferably has 4 to 25 carbon atoms, more preferably 4 to 15 carbon atoms, and particularly preferably 4 to 10 carbon atoms. If the carbon number of the polyhydric alcohol is greater than 25, the resulting cyclic ketal or cyclic acetal has poor compatibility with the hydrofluorocarbon, which is not preferred. Also, polyvalent Al If the carbon number of the coal is less than 4, the molecular weight becomes too low, and the boiling point and the flash point become unfavorably low.
  • erythritol diglycerin, arabinose, ribose, sorbitol, mannitol, galactitol, digitol, talitol, aritol, 4,7-dioxadecane-1 , 2,9,10-Tetraol, 5-methyl-4,7-dioxadecane-1,2,9,10-Tetraol, 4,7,10-Trioxatridecane-1, 2,12,13-Tetraol, 1,6-dimethoxyhexane-2,3,4.5-Tetraol, 3,4-diethoxyhexane-1,2,5,6-Polyvalent such as tetraol Alcohol, pentaerythritol, ditrimethylolethane, ditrimethylolprohan, dipentyl erythritol, tripentyl erythritol, 2,9-ethyl -2,9 -Dihydroxy
  • a raw material of the cyclic ketal or cyclic acetal used in the present invention is a saturated aliphatic alcohol. Unsaturated bonds are not preferred because the resulting lubricating oil composition has poor thermal stability.
  • the polyhydric alcohol used as a raw material of the cyclic ketal or the cyclic acetal used in the present invention is most preferably one having no ether bond in the molecule from the viewpoint of having good electric insulation. Even if it has an ether bond, only one is preferred. Having two or more is not preferred because of poor electrical insulation.
  • Specific examples of polyhydric alcohols having no ether bond in the molecule include erythritol, sorbitol, mannitol, galactitol, iditol, evening litor, aritol, and pentaerythritol, and ether bonds.
  • Specific examples of the polyhydric alcohol having one are diglycerin, ditrimethylolpronon, ditrimethyi monolethane, and the like.
  • the melting point of the obtained cyclic ketal or cyclic acetal increases, and the melting point of the obtained lubricating oil composition increases. It is not preferred for fluids.
  • the carbonyl compound serving as a raw material of the cyclic ketal or cyclic acetal used in the present invention is a ketone or aldehyde represented by the general formula (10).
  • the ketone or aldehyde represented by the general formula (10) has 2 to 14 carbon atoms, preferably 2 to 11 carbon atoms, and more preferably 2 to 6 carbon atoms.
  • the cyclic ketal or cyclic ⁇ Not preferred, as the compatibility of the cetal with the hydrofluorocarbon is poor.
  • R 6 represents a hydrogen atom or a straight chain having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms, preferably a hydrogen atom or a carbon atom.
  • R 7 represents a straight chain having 1 to 12 carbon atoms, a branched chain having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms, preferably a straight chain having 1 to 8 carbon atoms.
  • 5 to 5 alkyl groups are examples of the alkyl groups.
  • R e and R 7 are carbon number 2-1 3 together, it favored properly 0 1 4 carbon, further preferred properly may form an alkylene group having 5 4 carbon.
  • the total number of carbon atoms in R beta and R 7 is 1 to 1 3, preferably from 1 to 1 0, more preferably 1 to 5.
  • R 6 and R 7 may be the same or different.
  • compatibility with high Dorofuruoroka one Bonn cyclic ketal or cyclic Asetaru obtained is not properly preferred to become worse.
  • the resulting cyclic ketal or cyclic acetal will have poor compatibility with hydrofluorocarbon.
  • the alkyl groups of R 6 and R 7 preferably have a branched or cyclic structure rather than a straight-chain structure, because of the compatibility of the resulting ring-bound keel or cyclic acetal with the fluorocarbon of the mouth opening. R 6 and R 7 together form an alkylene group It is preferable not to form
  • keto ting to the ⁇ Se tons R s and R 7 is an alkyl group, Mechiruechiruke tons, Mechirupuro Piruke tons, Mechirui Sopu port Piruke tons, Mechirubuchiruke tons, Mechirui Sopuchiruke DOO , Methyl-tert-butylketone, methylamylketone, ethylbutylketone, dipropylketone, methylhexylketone, ethylpentylketone, 4-methyl-3-heptanone, 2 -Methyl-3-heptanone, methylcyclohexylketone, ethylhexylketone, dibutylketone, methyloctylketone, methylnonylketone, dipentylketone, dihexylketone, 6,10-dimethyl -2_ ⁇
  • ketones which form an alkylene group by R 6 and R 7 being linked to each other include cyclopentyne, cyclohexanone, 3-methylcyclobenzene, and 3-methylcyclohexane.
  • R e is a hydrogen atom
  • the ketone represented by the general formula (10) used in the present invention is a high-temperature decarboxylation dimerization reaction of a fatty acid, a catalytic oxidation reaction of an olefin ( ⁇ cker method), or an oxidation or dehydrogenation of a secondary alcohol. It is easily obtained by oxidation of cycloalkane. ⁇ In the case of the Kecker method, the ketone obtained can be separated and purified into individual products by precision distillation.
  • the aldehyde represented by the general formula (10) used in the present invention includes, for example, a dehydrogenation reaction of a fatty alcohol, a hydroformylation reaction of an olefin (oxo method), and a fatty acid chloride. It can be easily obtained by Rosemund reduction or direct hydrogenation from fatty acids. In the case of the oxo method, a linear product and a branched product are produced, but they can be separately purified by precision distillation.
  • the reactive derivative of the carbonyl compound used in the present invention includes the above-mentioned ketal, aldehyde and ketal which is easily synthesized from an alcohol having 1 to 6 carbon atoms by an acid catalyst. , There is acetal. Specific examples of lower alcohols having 1 to 6 carbon atoms include methanol, ethanol, propanol, isopronool, busuanol, isobutanol, sec-bubutanol, and ter.
  • t-butanol, amide alcohol isopropyl alcohol, neopentyl alcohol, 1-methylbutanol, 1,1-dimethylpropanol, 1-ethylpropanol, hexanol, Examples include isohexanol, 2-ethylbutanol, 1-methylamyl alcohol, 1,3-dimethylbutanol, and 1-ethylbutanol.
  • the cyclic ketal and cyclic acetal used in the lubricating oil composition of the present invention can be obtained as follows.
  • An acid catalyst such as paratoluenesulfonic acid, methanesulfonic acid, or sulfuric acid is converted to a polyhydric alcohol by using the polyhydric alcohol and the above ketone, aldehyde, and their reactive derivatives, ketal and acetal, as catalysts.
  • the reaction is carried out using 0.1 mol%, preferably 0.1 to 7.0 mol%, more preferably 0.5 to 5.0 mol%.
  • the reaction is solvent-free or inert, such as xylene, toluene, benzene, octane, isooctane, heptane, hexane, cyclohexane, pentane, rigoline, petroleum ether, etc.
  • solvent-free or inert such as xylene, toluene, benzene, octane, isooctane, heptane, hexane, cyclohexane, pentane, rigoline, petroleum ether, etc.
  • solvent or in a mixed solution of these 20 to 160
  • it is carried out at a temperature of 40 to 130 ° C while removing generated water and low alcohol. In some cases, it is also effective to carry out the reaction under reduced pressure.
  • any of a nitrogen atmosphere and a dry air atmosphere may be used.
  • the reaction time varies depending on various conditions, but usually 5 to 200 hours when using ketone and kettle, and 1 to 30 hours when using aldehyde and acetal.
  • New The obtained cyclic ketal and cyclic cetal can be neutralized, subjected to pretreatments such as lipolysis and washing, and then purified by operations such as clay treatment, crystallization, and distillation.
  • the ratio of ketone to be reacted with polyhydric alcohol or ketal which is a reactive derivative of ketone, or acetal which is aldehyde or a reactive derivative of aldehyde (hereinafter abbreviated as carbonyl compound) is 1 mole of polyhydric alcohol. Is 2 moles of the carbonyl compound A (where A is the valency of the polyhydric alcohol). In order to increase the reaction rate, it is also effective to carry out the reaction using an excess of A / 2 mol carbonyl compound and to remove the excess carbonyl compound after completion of the reaction.
  • the cyclic ketal or cyclic acetal used in the present invention comprises: It can be obtained by reacting one or more polyhydric alcohols with one or more ketones or a ketal or a reactive derivative of a ketone or an aldehyde or an acetal which is a reactive derivative of an aldehyde. Can be.
  • the cyclic ketal or cyclic acetate obtained here can also be used as a mixture.
  • a cyclic ketone obtained from 1 mole of sorbitol and 3 moles of methylethylketone (viscosity 63.1 mm Vs at 40)
  • a cyclic ketone obtained from 1 mole of diglycerin and 2 moles of methylethylketone Ketals (4 O e C viscosity 7.69 raro Vs) can be individually synthesized, and both can be mixed to adjust to the desired viscosity.
  • a specific example is a mixture of 1 mol of cyclic ketal obtained from 1 mol of sorbitol and 3 mol of methylethylketone, and 1 mol of cyclic ketal obtained from 1 mol of diglycerin and 2 mol of methylethylketon.
  • VG22 lubricating oil can be obtained.
  • the above mixture can be obtained by reacting 1 mol of sorbitol, 1 mol of diglycerin and 5 mol of methylethylketone.
  • sorbitol and 2 mol of ketone aldehydes are reacted to form a cyclic ketone used in the present invention.
  • the less unreacted hydroxyl group of the cyclic ketal or cyclic acetal is preferable, it is preferably 10% or less, preferably 5% or less, more preferably 3% or less, particularly preferably 2% or less, most preferably. Is less than 1%. If unreacted hydroxyl groups exceeding 10% remain, the compatibility with hydrofluorocarbon and the electrical insulation are poor, which is not preferable.
  • cyclic ketal or cyclic acetal used in the present invention, those having a structure in which the raw material polyhydric alcohol does not have an ether bond have a high electric insulating property, and thus are preferable. Therefore, as mentioned above, sorbito It is better to use cyclic ketal or cyclic acetal obtained from polyhydric alcohol such as hexahydric alcohol such as erythritol, mannitol, galactitol, iditol, talitol, aritol or erythritol. It is preferable to use a cyclic ketal or a cyclic acetal obtained from an alcohol having one ether bond, such as dimethyl trimethylolpropane.
  • polyhydric alcohol such as hexahydric alcohol such as erythritol, mannitol, galactitol, iditol, talitol, aritol or erythritol
  • the cyclic ketal or cyclic acetate used is preferably a compound containing a 1.3-dioxolane structure and a Z or 1,3-dioxane structure for improving electrical insulation.
  • those containing a 1,3-dioxolane structure are particularly preferable. Therefore, it is preferable to use an alcohol having a hydroxyl group at an adjacent position such as erythritol, diglycerin, sorbitol, mannitol, galactitol, iditol, evening itol, and aritol.
  • Hexahydric alcohols such as sorbitol, mannitol, galactitol, iditol, talitol, aritol, and erythritol can be reacted with ketone or ketal to obtain the formula (11a), the formula (1)
  • the cyclic ketal of 2a) is easily formed, and when reacted with an aldehyde or an acetate, the cyclic acetal of formula (1 lb) or (12b) is easily formed. Therefore, ketones for these alcohols Or the reaction using ketal
  • the cyclic ketals and cyclic acetals used in the present invention among the polyvalent alcohols having even valences, the cyclic ketal or cyclic acetal of hexavalent alcohol represented by the formula (11) or the cyclic acetal represented by the formula (12)
  • the cyclic ketals and cyclic acetates obtained from tetrahydric alcohols such as erythritol, diglycerin, and ditrimethylolpropane shown in (14) show the compatibility with hydrofluorocarbons and It is particularly preferable because various physical properties such as insulation, melting point, and viscosity are balanced.
  • cyclic ketones obtained from pentaerythritol having good symmetry represented by the formula (15a) or (15b) are not preferable because they are both solid at room temperature.
  • compounds represented by the formulas (11) to (14) compounds having a 1,3-dioxolane structure (11a), (1 lb), (12a) and (13) Preferable, among them, especially those having only a 1,3-dioxolane structure (11a), (12a),
  • the melting point of the cyclic ketal or cyclic acetal used in the present invention is 10 It is preferred that the temperature is below 10 ° C, more preferably below 10 ° C, particularly preferably below ⁇ 30 ° C.
  • the cyclic ketal or cyclic acetate having a melting point of more than 10 ° C as in (15a) or (15b) can be used as the other cyclic ketal or cyclic acetate having a low melting point used in the present invention. It can be used by mixing with one or other lubricating oils and limiting the amount added.
  • the cyclic ketal or cyclic acetal used in the present invention preferably has a viscosity at 100 ° C of 1 II 2 / S or more and 100 nun 2 / s or less, more preferably 1 bandage 2 / s. It is not less than 50 mmVs, particularly preferably not less than 1 mm 2 / s and not more than 30 mmVs, most preferably not less than 2 mm 2 / s and not more than 30 mm 2 / s.
  • the cyclic acetal used in the present invention has a low two-phase separation temperature with the hydrofluorocarbon, and is 1 °. C or less, preferable properly is 0 'C or less, the following one 1 0 properly favored et al., Particularly preferred properly is arbitrary and desired this is less than one 3 0 e C is.
  • lay desirable high two-phase separation temperature at high temperature like properly is 3 0 e C or higher, more preferably 4 0 ° C or more, more preferred properly is 5 0 ° C or higher, particularly preferably 6 0 ° C or more, and most preferred municipal district is 8 0 e C or more.
  • polyether type synthetic oils used in the present invention there is compatibility with the high Dorofu Ruorokabon, pour point not more than 0 e C, the re down compound represented by the general formula (1) to (9)
  • preferred polyether compounds include a polyvinyl ether compound disclosed in JP-A-6-128578 and a compound represented by the general formula (1) 6)
  • R 8 to R 13 may be the same or different and each represents a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms. However, the total carbon number of R 8 to R 13 is 8 to 40)
  • sorbitol is the most preferred for its availability and price. No.
  • alkyl group of 1 to 14 carbon atoms represented by R 8 to R 13 which may be linear, branched or cyclic include those exemplified as R 3 , R 4 and R 5
  • alkyl group examples include those having up to 14 carbon atoms.
  • R 8 to R 13 above may be the same alkyl group or different alkyl groups.
  • the ratio of the total number of carbon atoms to the total number of oxygen atoms (CZO) in one molecule is in the range of 2.5 to 7.5. Preferably, it is more preferably in the range of 3.0 to 7.0, particularly preferably in the range of 4.0 to 6.0.
  • the total carbon number of the alkyl group is usually from 8 to 40, preferably from 9 to 39, more preferably from 12 to 36, particularly preferably from 18 to 30.
  • the electrical insulation is poor
  • the total number of carbons exceeds 40, the compatibility with hydrofluorocarbon is poor.
  • the alkyl group structure is preferably a branched or cyclic structure rather than a linear structure, and more preferably a branched structure than a cyclic structure.
  • Alkenyl groups and alkynyl groups having an unsaturated bond are not preferred because of poor thermal stability.
  • polyether compound represented by the general formula (16) examples include 2, 3.4.5—tetramethyl 0—methyl—1,6—di-0— (3,5.5—trimethyl).
  • the ether compound represented by the general formula (16) as described above can be produced by various methods. For example, it can be produced by a reaction between an alcoholate of hexitol, which is a reactive derivative of hexitol, and an alkyl halide.
  • the compound is synthesized by hydrogenating a cyclic ketal z cyclic ester represented by the general formula (11) to obtain a polyhydric ether alcohol, which is further subjected to alkyl capping.
  • the hydrogenation reaction of the cyclic ketal or cyclic acetal represented by the general formula (11) is carried out by using a usual hydrocracking catalyst such as palladium, rhodium, ruthenium, platinum or the like with respect to the cyclic acetal or cyclic ketal for 5 to 500,000. ppm was added, normal pressure ⁇ 2 5 0 k gZ cm 2 hydrogen pressure, temperature 5 0-2 5 0 TeToshi, yo is reacted 1-3 0 h les.
  • a hydrocracking catalyst a catalyst in which 0.1 to 20% of these are supported on carbon, alumina, silica, silica earth, titanium oxide or the like may be used.
  • the hydrocracking catalyst palladium is particularly preferred, and one having a pH of 5 to 8 is particularly preferred. Further, it is preferable that water is removed in advance. This reaction can be carried out in the absence of any solvent, even with decane, octane, isooctane, heptane, hexane, and cyclohexane.
  • An inert solvent such as xane may be used.
  • a hexahydric alcohol aldehyde or ketone represented by the formula (17), which is a raw material of cyclic acetal or cyclic ketal, may be added. Further, a trace amount of an acidic substance such as phosphoric acid may be added.
  • the reaction may be a closed system or a hydrogen circulation system.
  • the human Dorokishiru group portion of a polyhydric ether alcohols obtained in this manner Na Application Benefits um, N a H, N a O CH 3, N a OH, K 0 bases H or the like to act in the Arukora DOO
  • ether capping alkyl capping
  • an alkylating agent such as an alkyl halide, dialkyl sulfate, or alkyl tosylate to obtain a polyether compound represented by the general formula (16).
  • Borieteru compound used in the present invention is preferably 0. 5 ⁇ 3 0 mm 2 Z s viscosity at 1 0 0 ° C, more preferably l ⁇ 3 0 mm 2 / s, more preferred properly 2-3 0 mm 2 / s, particularly preferably 2 to 15 mm 2 Zs. If the viscosity at 100 ° C. exceeds 30 mm 2 / s, the compatibility between this compound and the fluorocarbon at the opening is deteriorated.
  • the viscosity is preferably 1 to 3 0 011 111 2/5 at 4 0 hand, preferably the further a. 5 to 1 0 0 mm 2 Bruno s.
  • the two-phase separation temperature of the polyether compound used in the present invention at a low temperature with the fluorocarbon at the mouth is low, preferably 10 or less, more preferably 0 or less. It is preferably at most 10 ° C, particularly preferably at most 130 ° C, most preferably at most 150 ° C. It is also desirable that the two-phase separation temperature at high temperature be high, Preferably, more preferably at least 40 ° C, even more preferably at least 50 ° C, particularly preferably at least 60 ° C, most preferably at least 80 ° C
  • the polyalkylene glycol-based synthetic oil used in the present invention has compatibility with hydrofluorocarbon and has a pour point of 0. It is not particularly limited as long as it is C or less and is a polyalkylene glycol that dissolves the phosphorus compound represented by any of the general formulas (1) to (9). For example, those represented by the following general formula (18) are exemplified.
  • R 14 represents a linear or branched alkylene group having 2 to 4 carbon atoms.
  • R 15 represents a hydrogen atom, a hydrocarbon group having 1 to 15 carbon atoms, or an acyl group having 2 to 15 carbon atoms.
  • A represents a hydrogen atom, a w-valent residue having 1 to 15 carbon atoms, or a w-valent phenol residue having 6 to 15 carbon atoms,
  • V represents a number of 1 to 50, w represents a number of 1 to 6, however, V-number of R "0, w pieces of R 15 and w number of 0- (R" 0) V - . be R 15 are not each be the same or different Good.
  • R is, specifically, those shown in R 1 and R 2
  • R 16 is the number of carbon atoms from the viewpoint of compatibility with the Hydro full O b carbon is preferably 1 5 or less, it is inter alia hydrocarbon group or Ashiru group having a carbon number of 2-9 of the carbon number of 1 to 1 0 More preferred.
  • Examples of the acyl group for R 15 include the following.
  • the carbon number of A is preferably 15 or less from the viewpoint of compatibility with hydrofluorocarbon.
  • Examples of the alcohol residue or phenol residue of A include the following.
  • Alcohol residue Polyhydric alcohols mentioned in Ester Component 1-1, monohydric alcohols mentioned in Ester Component 1-3, dodecyl alcohol, tridecyl alcohol, 2,4,6,8-tetramethylnonanol Alcohol residue.
  • Phenol residue 4-methylphenol, 4-ethylphenol, 4-t-butylphenol, 2,4—di-t-butylphenol, 2, 6—di-butylbutylphenol, 2,6 —Di-tert-butyl— 4-Phenol residue of phenol such as methylphenol, 4-nonylphenol, bisphenol A, etc.
  • V is preferably a number of 50 or less from the viewpoint of viscosity and hygroscopicity, and more preferably a number of 1 to 30.
  • w is preferably a number of 6 or less from the viewpoint of viscosity, and more preferably a number of 1 to 3.
  • polyalkylene glycols are, for example, as follows: Can be manufactured. Alkylene oxide is reacted with water or an alcohol in the presence of an alkaline catalyst such as NaOH or K0H to obtain a monoalkyl ether-type polyalkylene glycol-glycol-type polyalkylene glycol. Further, the terminal hydroxyl group is alkylated with an alkyl halide using an alkali metal as a catalyst, and further acylated by reacting with a carboxylic acid or its methyl ester, ethyl ester, or acid anhydride to obtain a dialkyl ether type. Polyalkylene glycol and ester ether type polyalkylene glycol can be obtained.
  • the acid value of the polyalkylene glycol obtained as described above used in the present invention is determined from the viewpoints of suppressing corrosion of metal materials, reduction of wear resistance, reduction of thermal stability, and reduction of electrical insulation.
  • lmg KO HZg or less is preferred, 0.2 mg K 0 HZg or less is more preferred, 0.1 mg K OHZg or less is more preferred, and 0.05 mg KO HZg or less is particularly preferred. .
  • the two-phase separation temperature of the polyalkylene glycol used in the present invention at a low temperature with hydrofluorocarbon is preferably low, preferably 1 O'C or less, more preferably 0 ° C or less. one 1 0 e C or less properly preferred by the et, particularly preferred less properly in one 3 0, most preferred properly is not more than one 5 0 ° C.
  • it is desirable that the two-phase separation temperature at a high temperature is high, preferably 30 or more, more preferably 40 or more, further preferably 50 ° C or more, and particularly preferably. More preferably at least 60 ° C, most preferably at least 80 ° C.
  • the kinematic viscosity at 100 ° C. of the polyalkylene glycol used in the present invention is preferably 100 mm 2 Zs or less from the viewpoint of compatibility with the fluorocarbon at the opening, and usually 1 to 10 mm.
  • 0 mm 2 Z s is preferred Ku
  • 1 ⁇ 3 0 mm 2 Roh s is laid more preferred, particularly preferably 2 ⁇ 3 0 mmVs.
  • the carbonate-based synthetic oil used in the present invention is a phosphorus compound that is compatible with hydrofluorocarbon, has a pour point of 0 ° C. or less, and is represented by any of general formulas (1) to (9). There is no particular limitation as long as the carbonate is soluble. For example, those represented by the following general formula (19) are exemplified.
  • R 16 and R 18 may be the same or different and each have an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, or
  • R 20 O represents a group represented by R 19 .
  • R 1 S is an alkyl group, aryl group, or aralkyl group having 1 to 18 carbon atoms
  • R 2 ° is an alkylene group, arylene group, or aralkylene group having 2 to 18 carbon atoms
  • z is 1 to 10 Represents an integer of 0.
  • Z R 2 . 0 may be the same or different.
  • R 17 represents an alkylene group, arylene group, or aralkylene group having 2 to 18 carbon atoms
  • X represents an integer of 1 to 100
  • y represents an integer of 0 to 100.
  • X R 170 may be the same or different
  • y represents an integer of 0 to 100.
  • R 16 and R 18 are an alkyl group having 1 to 18 carbon atoms, an aryl group, an aralkyl group, or a group represented by — (R 2 ° 0) z —R 19
  • R 19 is a carbon number 1 to 18 alkyl groups, aryl groups, or aralkyl groups.
  • the number of carbon atoms of R 16 , R 18 , and R 19 is preferably 18 or less, more preferably 1 to 10 from the viewpoint of compatibility with the fluorene carbonate at the mouth.
  • alkyl groups, aryl groups and aralkyl groups having up to 18 carbon atoms among the alkyl groups, aryl groups and aralkyl groups mentioned for R 3 , R 5 are exemplified.
  • R 17 and R 2 ° are an alkylene group having 2 to 18 carbon atoms, an arylene group, or an aralkylene group.
  • the number of carbon atoms is preferably 18 or less, more preferably 2 to 10 from the viewpoint of compatibility with hydrofluorocarbon. Specifically, for example, the following are mentioned.
  • alkylene group examples include those listed for R 1 and R 2 and the alcohol residues of the following dihydric alcohols.
  • Examples of the arylene group and aralkylene group include the following divalent phenol or alcohol residues. Catechol, rebrucine, 2—hydroxybenzyl alcohol, 4—methylcatechol, 2—methyllevrunol, 1,4-benzendimethanol, 4-ethyl resorcinol, 1-phenylene 1, 2—ethanediol, 2—phenyl 1,2—pronodiol, 4t-butylcatechol, 4hexylresorcinol, 3,5—d-butylbutylcatechol, 4dodecylresorcinol etc.
  • Z represents an integer of 1 to 100, preferably an integer of 1 to 50, and more preferably an integer of 1 to 30. From the viewpoints of viscosity and hygroscopicity, z is preferably 100 or less.
  • X represents an integer of 1 to 100, preferably an integer of 1 to 50, and more preferably an integer of 1 to 30. From the viewpoints of viscosity and hygroscopicity, X is preferably 100 or less.
  • y represents an integer of 0 to 100, preferably an integer of 1 to 50, and more preferably an integer of 1 to 30. From the viewpoints of viscosity and hygroscopicity, y is preferably 100 or less.
  • These carbonates are generally obtained by a transesterification reaction of one or more monohydric and / or dihydric alcohol phenols with a carbonate ester such as dimethyl carbonate and getyl carbonate.
  • the acid value of the carbonate obtained as described above, which is used in the present invention is 1 mg from the viewpoint of suppressing corrosion of metal material, reduction of wear resistance, reduction of thermal stability, and reduction of electrical insulation.
  • KO HZg or less is preferred, 0.0 S mg KO HZ g or less is more preferred, 0.1 mg KO HZg or less is more preferred, and 0.05 mg KO HZ g or less is particularly preferred.
  • the carbonated hydrofluorocarbon used in the present invention is The two phases ⁇ degree at low temperatures, it undesirable low and this is, 1 o e c less good or properly, more preferred properly is below 0 ° C, is properly favored by et than one 1 0 ° c, Particularly preferred is -30 ° C or less, most preferably -50 ° C or less. It is also desirable that the two-phase separation temperature at a high temperature is high, preferably 30 ° C or higher, more preferably 40 ° C or higher, more preferably 50 ° C or higher, and particularly preferably. Are over 60, most preferably over 80.
  • the kinematic viscosity at 100 e c of the carbonate used in the present invention is not particularly limited, but is preferably 100 mm 2 Zs or less from the viewpoint of compatibility with hydrofluorocarbon, usually 1 to 1 0 mm 2 / s is preferable, 1 to 30 mm 2 Zs is more preferable, and 2 to 30 mm V s is more preferable.
  • 1 0 o ° kinematic viscosity at c is laid preferred is 1 0 0 mm 2 Z s hereinafter in terms of compatibility with the Ha I mud full O b carbon, usually 1 ⁇ 1 0 0 mm 2 / s is preferred, and 1 to 30 mm 2 s is more preferred.
  • ester type, cyclic ketal Z cyclic acetal type, polyether type, polyalkylene glycol type or carbonate type synthetic oil used in the present invention, or a mixed oil thereof is compatible with hydrofluorocarbon.
  • Mineral oils and synthetic oils such as polyolefins, alkylbenzenes, esters and polyalkylene glycols other than those mentioned above, carbonates, phenols, monofluoroboryl ethers, phosphate esters, etc. May be further mixed. Specific examples are described in “Physical Chemistry of Lubrication in New Edition” (Koshobo) and “Basics and Application of Lubricating Oil” (Corona).
  • the lubricating oil composition of the present invention is obtained by converting the above-mentioned phosphorus compound into a lubricating base oil, particularly an oxygen-containing compound, that is, an ester type, a cyclic ketalno, a cyclic acetal type, a polyether type, a polyalkylene glycol type or a carbonaceous compound. It is obtained by blending with a synthetic oil or a base oil containing these oils as a main component.
  • the amount of the phosphorus compound added to the lubricating base oil is not particularly limited as long as the lubricating oil composition of the present invention is at least an amount sufficient to suppress wear while in contact with the metal surface. But preferably, lubricating base oil
  • the phosphorus compound is used in an amount of from 0.003 to 5.0 parts by weight based on 100 parts by weight. is there.
  • the phosphorus compound has the general formula
  • the amount is more preferably from 0.05 to 3.0 parts by weight, particularly preferably from 0.1 to 2.0 parts by weight. From the viewpoint of obtaining the desired wear suppressing effect, the amount is preferably not less than 0.03 parts by weight, and from the viewpoint of reducing the thermal stability of the base oil, it is preferably not more than 5.0 parts by weight. Further, even if the amount exceeds 5.0 parts by weight, the effect of suppressing wear reaches a peak and becomes economically disadvantageous.
  • the lubricating oil composition of the present invention When used in a composition for a working fluid of a refrigerator, the following additives may be appropriately added.
  • An additive for removing water may be added to the lubricating oil composition of the present invention.
  • the coexistence of water can hydrolyze the ester or carbonate as the base oil, generating carboxylic acid and clogging the cabillary tubes, etc., and generating non-condensable CO 2 and freezing The ability may be reduced.
  • the PET film, etc. which is an insulating material, may be hydrolyzed to form PET oligomers, which may clog the capillary tube.
  • Examples of the additive for removing water include compounds having an epoxy group, and additives such as orthoester, acetal (ketal), and carpoimide.
  • the compound having an epoxy group is one having 4 to 60 carbon atoms, preferably 5 to 25 carbon atoms.
  • butylglycidyl Glycidyl ethers such as 1-ter, 2-ethylhexylglycidyl ether, neopentylglycol diglycidyl ether, and glycidyl esters such as glycidyl adipic acid ester, 2-ethylglycidyl glycidyl ester, and epoxy Monoesters of epoxidized fatty acids such as methylated stearate, vegetable oils such as epoxidized soybean oil, 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, bis (3 Alicyclic epoxy compounds such as 2,4-epoxycyclohexylmethyl) adipate and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.
  • these compounds having an epoxy group may be used alone or in combination of two or more.
  • the amount of the lubricant may be 100 or less based on the lubricating base oil such as ester type, cyclic ketone Z cyclic acetal type, polyether type, polyalkylene glycol type or carbonate type synthetic oil or a mixed oil thereof.
  • the amount is usually from 0.05 to 2.0 parts by weight, preferably from 0.1 to 1.5 parts by weight, more preferably from 0.1 to 1.0 parts by weight, based on parts by weight.
  • Examples of the orthoester used in the present invention include compounds as described in JP-A-6-17073, column 10, lines 27 to 41.
  • the amount of the orthoester added is 100 parts by weight of a lubricating base oil such as an ester, a cyclic ketal, a Z-ring acetal, a polyether, a polyalkylene glycol or a carbonate synthetic oil, or a mixed oil thereof.
  • the amount is usually 0.01 to 100 parts by weight, preferably 0.05 to 30 parts by weight.
  • the acetal or ketal used in the present invention is a compound as described in JP-A-6-17073, columns 11 and 21. Compounds.
  • the amount of acetal or ketal to be added depends on the lubrication of ester, cyclic ketone, cyclic acetate, polyether, borial-kilen glycol or carbonate synthetic oil, or a mixture of these. It is usually from 0.01 to 100 parts by weight, preferably from 0.05 to 30 parts by weight, based on 100 parts by weight of the oil base oil.
  • the calposimid used in the present invention includes those represented by the following general formula (20).
  • R 21 and R 22 represent a hydrocarbon group having 1 to 18 carbon atoms.
  • R 21 and R 22 may be the same or different.
  • the carbon number of R 21 and R 22 is more preferably 1 to 12. Further, specific examples of R 21 and R 22 include those having up to 15 carbon atoms among those exemplified for R 3 , R 4 and R 5 .
  • carposimid examples include 1,3—diisopropylpropyl carimide, 1,3—di-tert-butyl carpoimide, 1,3—dicyclohexyl carpoimide, 1,3— Di- ⁇ -tolyl carpoimide, 1,3-bis- (2,6-diisopropylpropyl) carpoimide, and the like.
  • the amount of carbodiimide added is 100% by weight of lubricating base oil such as ester type, cyclic ketal Z cyclic acetal type, polyether type, polyalkylene glycol type or carbonate type synthetic oil or mixed oil of these.
  • the amount is usually from 0.01 to 10 parts by weight, preferably from 0.05 to 5 parts by weight, per part by weight.
  • the lubricating oil composition of the present invention contains benzotriazole and a Z or bembutriabul derivative as an additive to protect the metal surface in order to prevent metal corrosion by carboxylic acid and the like.
  • a X-nor-based compound having a radical trapping ability for improving thermal stability, or a metal deactivator having a chelating ability may be added.
  • Benzotriazole and benbutriazole derivatives used in the present invention include compounds described in JP-A-5-20971, column 13, lines 9 to 29. Is mentioned. Although not particularly limited, benzotriazole, 5-methyl-11H-benzotriazole and the like are preferred.
  • the amount of the benzotriazole and / or benzotriazole derivative used in the present invention may be an ester, a cyclic ketal Z, a cyclic acetate, a polyether, or a polyalkylene glycol. Or 0.01 to 0.1 part by weight, preferably 0.03 to 0.1 part by weight, based on 100 parts by weight of lubricating base oil such as carbonate-based synthetic oil or a mixed oil thereof. 0.03 parts by weight.
  • Japanese Patent Application Laid-Open No. 6-17073, columns 12 and 3 from the second line to columns 13 and 1 Compounds such as those described on line 8 are mentioned.
  • the amount of the phenol-based compound added is 100 parts by weight of a lubricating base oil such as an ester-based, cyclic ketal / cyclic acetal-based, polyether-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof. Is usually 0.05 to 2.0 parts by weight, Or 0.05 to 0.5 parts by weight.
  • a lubricating base oil such as an ester-based, cyclic ketal / cyclic acetal-based, polyether-based, polyalkylene glycol-based or carbonate-based synthetic oil or a mixed oil thereof.
  • the metal deactivator used in the present invention is preferably one having chelating ability, and is described in JP-A-5-209171, columns 13 and 38 to columns 14 and 8 Examples include compounds as described in the eye. Although not particularly limited, preferably, ⁇ , ⁇ '—disalicylidene 1,2—diaminoethane, ⁇ , ⁇ '—disalicylidene-1,2—diaminobuchi van, acetylaceton, ase Acetic acid ester, alizarin, quinizarin and the like.
  • the amount of the metal deactivator used in the present invention may be selected from lubricating oils such as ester-based, cyclic ketal-cyclic acetal-based, polyether-based, polyalkylene-glycol-based or carbonate-based synthetic oils, and mixed oils thereof.
  • the amount is usually from 0.001 to 2.0 parts by weight, preferably from 0.003 to 0.5 parts by weight, based on 100 parts by weight of the base oil.
  • lubricating oil additives such as antioxidants, extreme pressure agents, oiliness improvers, defoamers, detergent / dispersants, viscosity index improvers, antioxidants, and demulsifiers can be added.
  • antioxidants in addition to the above-mentioned phenolic antioxidants, p, p-dioctylphenylamine, monooctyldiphenylamine, phenothiazine, 3,7-dioctylphenyl Amine-based antioxidants such as notiazine, phenyl-2-naphthylamine, phenyl-2—naphthylamine, alkylphenyl-1-naphthylamine, alkylphenyl-2—naphthylamine, and alkyldisulfate Sulfur-based antioxidants such as eyes, thiodipropionic acid esters and benzothiazole, zinc dialkyldithiophosphate, and diaryldithiolin Zinc acid and the like.
  • the amount added is 100 parts by weight of a lubricating base oil such as an ester type, a cyclic ketal, a cyclic acetal type, a polyether type, a polyalkylene glycol type or a carbonate type synthetic oil or a mixed oil thereof. It is 0.05 to 2.0 parts by weight.
  • a lubricating base oil such as an ester type, a cyclic ketal, a cyclic acetal type, a polyether type, a polyalkylene glycol type or a carbonate type synthetic oil or a mixed oil thereof. It is 0.05 to 2.0 parts by weight.
  • extreme pressure agents and oiliness improvers include, for example, zinc compounds such as zinc dialkyldithiolate and zinc diaryldithiolate, thiodipropionate esters, dialkylsulfides, dibenzylsulfides, and the like.
  • Sulfur compounds such as dialkyl polysulfide, alkyl mercaptan, dibenzothiophene, 2,2'-dithiobis (benzothiazole), chlorine compounds such as chlorinated balafins, molybdenum dicarbamate, molybdenum dithiol Molybdenum compounds such as phosphate and molybdenum disulfide; fluorine compounds such as perfluoroalkylborylene and ethylene trifluoride chloride polymer and graphite fluoride; and fatty acid-modified silicone Such as gay compounds and graphites.
  • the amount added is 100 parts by weight of a lubricating base oil such as an ester, a cyclic ketal / cyclic acetal, a polyether, a polyalkylene glycol or a carbonate synthetic oil, or a mixed oil thereof. And 0.05 to 10 parts by weight.
  • a lubricating base oil such as an ester, a cyclic ketal / cyclic acetal, a polyether, a polyalkylene glycol or a carbonate synthetic oil, or a mixed oil thereof.
  • 0.05 to 10 parts by weight is 100 parts by weight of a lubricating base oil such as an ester, a cyclic ketal / cyclic acetal, a polyether, a polyalkylene glycol or a carbonate synthetic oil, or a mixed oil thereof.
  • Those used as defoaming agents include silicone oils such as dimethylpolysiloxane, and organosilicates such as getyl silicate.
  • the amount of the oil to be added depends on the amount of the lubricating base oil such as ester, cyclic ketal, cyclic acetate, polyether, polyalkylene glycol or carbonate synthetic oil, or a mixture thereof. 0.0005 to 1 part by weight with respect to parts by weight.
  • Those used as detergent dispersants include sulfonate, phenate, salicylate, phosphonate, polybutenylsuccinate imide, polybutenylsuccinate and the like.
  • the amount added is 100 parts by weight of a lubricating base oil such as an ester-based, cyclic ketal, cyclic acetal-based, polyether-based, polyalkylene glycol-based or carbonate-based synthetic oil, or a mixed oil thereof. And 0.05 to 10 parts by weight.
  • a lubricating base oil such as an ester-based, cyclic ketal, cyclic acetal-based, polyether-based, polyalkylene glycol-based or carbonate-based synthetic oil, or a mixed oil thereof.
  • Examples of the anti-emulsifier and the demulsifier include known ones usually used as lubricating oil additives.
  • the amount added is 100 parts by weight of a lubricating base oil such as an ester, cyclic ketal Z cyclic acetal, polyether, polyalkylene glycol or carbonate synthetic oil or a mixture thereof. On the other hand, it is 0.01 to 5 parts by weight.
  • an additive such as an organotin compound or a boron compound for stabilizing a refrigerant refrigerant may be added.
  • Lubricating oils such as esters, cyclic ketals Z cyclic acetates, polyethers, polyalkylene glycols, or carbonated synthetic oils, or a mixture of these oils, etc. Parts are 0.001 to 10 parts by weight.
  • the mixing ratio of the hydrofluorocarbon and the lubricating oil composition in the refrigerator working fluid composition of the present invention is not particularly limited, but the hydrofluorocarbon lubricating oil composition
  • the material is preferably 50 to 1 to 1/20 (weight ratio), and more preferably 10 to 1 Z5 (weight ratio).
  • the ratio of the hydrofluorene carbonate Z lubricating oil composition is preferably higher than 1 Z 20, and the viscosity of the composition for the working fluid of the refrigerator is desirably higher.
  • the ratio of the lubricating oil composition is preferably higher than 50 1.
  • the hydrofluorocarbon used here is not particularly limited as long as it is generally used for refrigerating machine oil.
  • difluoromethane HFC32
  • 1,1-difluoroethane HFC15
  • 2a 1,1.1-Trifluorene
  • HFC43a 1,1,1,2-Tetrafluorene
  • HFC34a 1,1,1,2-Tetrafluorene
  • HFC 13 4 1.1,2,2 -Tetrafluoretane
  • Penhu Fluorohetane HFC 12 5
  • 1, 1, and 2-Tetrahuloretan Gifolometane, Penyu Fluororetan, 1, 1
  • hydrofluorocarbons may be used alone or as a mixture of two or more types of hydrofluorocarbons.
  • a stirrer, a thermometer, a cooling tube, and a dropping funnel were attached to a 2 L four-necked flask.
  • 360 g (1.117 mol) of G2-ethylhexyl phosphate and 700 mL of tetrahydrofuran were placed in the flask.
  • 82.71 g (1.117 mol) of glycidol was added dropwise over 45 minutes while stirring at normal pressure at 60, and then maintained at 60 for 2 hours. Then, aging was performed. After the completion of the reaction, the mixture was cooled and concentrated under reduced pressure at 50 in a rotary evaporator to obtain 45.728 g of a viscous yellow oily substance.
  • the acid value of the obtained substance was 37.5 mg K0HZg, and the hydroxyl value was 244.8 mgKOHZg (theoretical value: 283.01 mgK0H / g). 2 —Ethyl hex
  • the GC purity of luglyceryl phosphate (21b) was 54.8%.
  • the concentration of CH 2 CH 3 was 14.0%, and the concentration of the compound having the structure of (21b) was 81.1%.
  • di-n-butyl phosphate, di-n-dodecyl phosphate, and g-2-ethylhexylhydrogen phosphate were used instead of di-2-ethylhexyl phosphate.
  • ⁇ -dodecyl phosphate were used to obtain phosphorus compounds a, c, d and e, respectively.
  • a stirrer, a thermometer, a cooling pipe, and a dropper outlet were attached to a 50-OmL four-necked flask.
  • 180 g (0.558 mol) of G2-ethylhexyl phosphate were placed in the flask. 50 at normal pressure under nitrogen atmosphere.
  • glycidol 41.34 g (0.558 mole) was added dropwise over 2 hours, and the mixture was kept at 50 "C for 2 hours and aged.
  • the acid value of the reaction mixture was 35.8 mg 1 ⁇ ⁇ 1 ⁇ .
  • a 1 L four-necked flask was equipped with a stirrer, thermometer, cooling tube and dropping funnel.
  • G2 ethylhexyl phosphate 18 Og (0.558 mol) and PAG (Newball LB-65 (manufactured by Sanyo Chemical): propylene oxide adduct of butanol (molecular weight 340)
  • PAG Newball LB-65 (manufactured by Sanyo Chemical): propylene oxide adduct of butanol (molecular weight 340)
  • the phosphorus compounds a to e used in Examples, the phosphorus compounds f to i used in Comparative Examples, and the base oils A to N are shown below.
  • Phosphorus compound a g-n-butylglyceryl phosphate (Formula 21a)
  • Linoleic compound d 2,3-dihydroxypropylphosphonate
  • Linole compound e n—dodecyl diglyceryl phosphate (Formula 2
  • Linoleic compound f G2-ethylhexyl-2-hydroquinoline phosphate (Formula 24)
  • Phosphorus compound g Triglycerol phosphate
  • Viscosity at 100 ° C (hereinafter abbreviated as Vis 100) 8.6
  • Base oil B Esters of pentaerythritol (1.0 mol) and 2-methylhexanoic acid (1.88 mol), 2-ethylhexanoic acid (0.46 mol) and 2-ethylhexanoic acid (1.66 mol)
  • Base oil C Trimethylolpropane (1.0 mol) and 3,5,5 — ester of trimethylhexanoic acid (3.0 mol)
  • Base oil D Ester of pentaerythritol (1.0 mol) and n-heptanoic acid (1.37 mol) and 3,5,5-trimethylhexanoic acid (2.63 mol)
  • Base oil G Poly (oxyethyleneoxypropylene) glycol monobutyl ether (Newball 50HB—100, manufactured by Sanyo Chemical Industries, Ltd.)
  • Base oil H Polyoxypropylene glycol dihexanate
  • Base oil I Carbonate of dimethyl carbonate (1.0 mol) and 3 -methyl-1,5-pentanediol (0.6 mol) and 3 -methylhexanol (0.8 mol)
  • Base oil J Mineral oil (Suniso 4GS, manufactured by Nippon Sun Oil Co., Ltd.)
  • Base oil K Mineral oil (Super oil A, manufactured by Nippon Oil Co., Ltd.)
  • Base oil L ester of trimethylolpropane (10 mol) and oleic acid (3.0 mol)
  • Base oil M trimethylolpropane (1.0 mol) and adipic acid (0.35 mol) caprylic acid, hydrobromic acid, lauric acid (weight ratio 30/30/40) (2 30 mol) ester
  • Base oil N Rapeseed oil (Nichika Yushi Co., Ltd.)
  • the viscosity of the base oil was measured based on JIS K-2 283. Further, the acid value and the hydroxyl value were measured based on JIS 070.
  • Example 1 The viscosity of the base oil was measured based on JIS K-2 283. Further, the acid value and the hydroxyl value were measured based on JIS 070.
  • the product of the present invention has a lower coefficient of friction and better lubricity than the comparative product.
  • the effect is more remarkable in highly polar oxygenated compounds such as esters than in the comparative products.
  • a V block and pins are immersed in a lubricating oil composition containing a predetermined amount of a phosphorus compound, and 1,1,1,1,2—tetrafluoroethane is added to 100 parts by weight. While blowing with Z
  • base oils A to I to which no phosphorus compound is added in the present invention base oils A in which a smaller amount of the phosphorus compound a is added to the base oil A, and base oils A, B, and E in which Compounds f to h, i.e. 21-ethylhexyl 2-, hydroquinine propyl phosphate, triglyceryl phosphate and tri-2-ethylhexyl phosphate were used.
  • Table 3 shows the results.
  • Table 3 shows that the products of the present invention 5 to 25 and 37 to 39 had less wear than the comparative products 6 to 24, and were superior in wear resistance.
  • the product of the present invention was excellent in shochu abrasion characteristics as compared with the case of using a phosphorus compound having only one hydroxy group (comparative products 16, 19, 22).
  • the amount of abrasion was measured using a high pressure abrasion tester (manufactured by Shinko Zoki Co., Ltd.).
  • the working fluid of the refrigerator of the present invention was smaller in abrasion loss and superior in shochu abrasion resistance than the comparative product.
  • the lubricating oil composition shown in Table 5 and 1,1,1,2—tetrafluoroethane were mixed with 10 Z90 to 550 They were mixed at a weight ratio (lubricating oil composition 1, 1, 1, 2, 2-tetrafluoroethane) and the two-phase separation temperature at low temperature was measured.
  • Table 5 shows the results. As can be seen from Table 5, the product of the present invention was excellent in compatibility with the fluorocarbon at the mouth. Table 5
  • a vane pump test according to ASTM D 2882 was conducted to examine the abrasion resistance of the lubricating oil composition. That is, 50 liters of lubricating oil composition Using a Vickers 104 C pump, 1 200 rpm, pressure 14 O kgf / cm 2 , discharge rate 25 LZ min.
  • the product of the present invention is superior in abrasion resistance to the comparative product.
  • a lubricating oil composition that has excellent lubricating properties even when a highly polar base oil is used, does not corrode metals, and is used as a working fluid for refrigerators. It has become possible to provide a composition. Further, according to the production method of the present invention, a phosphorus compound-containing reaction mixture having a low acid value and low cost can be obtained.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)

Abstract

Cette invention concerne une composition d'huile lubrifiante contenant des composés de phosphore qui comportent différents groupes, les groupes hydroxyles étant liés aux atomes de carbone adjacents respectifs. Cette invention concerne également une composition de fluide hydraulique pour réfrigérateurs, laquelle contient des hydrofluorocarbures et une composition d'huile lubrifiante obtenue en mélangeant les composés de phosphore susmentionnés à une huile de base lubrifiante contenant principalement des composés d'oxygène. Ces compositions possèdent d'excellentes qualités lubrifiantes et n'entraînent pas la corrosion des métaux.
PCT/JP1996/002389 1995-09-13 1996-08-26 Composition d'huile lubrifiante WO1997010319A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7/262516 1995-09-13
JP26251695 1995-09-13

Publications (1)

Publication Number Publication Date
WO1997010319A1 true WO1997010319A1 (fr) 1997-03-20

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WO (1) WO1997010319A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000212585A (ja) * 1999-01-27 2000-08-02 Asahi Denka Kogyo Kk リン系潤滑剤
US20170035730A1 (en) * 2014-04-16 2017-02-09 The Scripps Research Institute Pparg modulators for treatment of osteoporosis
WO2018021533A1 (fr) * 2016-07-28 2018-02-01 Ｊｘｔｇエネルギー株式会社 Huile pour machine frigorifique
WO2018181203A1 (fr) * 2017-03-31 2018-10-04 Ｊｘｔｇエネルギー株式会社 Additif destiné à des huiles lubrifiantes, composition d'huile lubrifiante, et mécanisme coulissant
WO2018198645A1 (fr) * 2017-04-28 2018-11-01 Ｊｘｔｇエネルギー株式会社 Additif destiné à un lubrifiant, composition lubrifiante, et mécanisme coulissant
JP2018172510A (ja) * 2017-03-31 2018-11-08 Ｊｘｔｇエネルギー株式会社 潤滑油組成物及びこれを用いた摺動機構
JP2018188519A (ja) * 2017-04-28 2018-11-29 Ｊｘｔｇエネルギー株式会社 潤滑油用添加剤及び潤滑油組成物
JP2018188520A (ja) * 2017-04-28 2018-11-29 Ｊｘｔｇエネルギー株式会社 潤滑油組成物及びこれを用いた摺動機構
JP2018188521A (ja) * 2017-04-28 2018-11-29 Ｊｘｔｇエネルギー株式会社 潤滑油組成物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57164192A (en) * 1973-10-04 1982-10-08 Lubrizol Corp Functional fluid
JPH05171174A (ja) * 1991-04-30 1993-07-09 Tonen Corp 潤滑油組成物
JPH05302093A (ja) * 1992-04-28 1993-11-16 Tonen Corp 潤滑油組成物
JPH06145688A (ja) * 1992-11-10 1994-05-27 Nippon San Sekiyu Kk 冷凍機用潤滑油組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57164192A (en) * 1973-10-04 1982-10-08 Lubrizol Corp Functional fluid
JPH05171174A (ja) * 1991-04-30 1993-07-09 Tonen Corp 潤滑油組成物
JPH05302093A (ja) * 1992-04-28 1993-11-16 Tonen Corp 潤滑油組成物
JPH06145688A (ja) * 1992-11-10 1994-05-27 Nippon San Sekiyu Kk 冷凍機用潤滑油組成物

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000212585A (ja) * 1999-01-27 2000-08-02 Asahi Denka Kogyo Kk リン系潤滑剤
US20170035730A1 (en) * 2014-04-16 2017-02-09 The Scripps Research Institute Pparg modulators for treatment of osteoporosis
US10016394B2 (en) * 2014-04-16 2018-07-10 The Scripps Research Institute PPARG modulators for treatment of osteoporosis
WO2018021533A1 (fr) * 2016-07-28 2018-02-01 Ｊｘｔｇエネルギー株式会社 Huile pour machine frigorifique
CN109072114A (zh) * 2016-07-28 2018-12-21 Jxtg能源株式会社 冷冻机油
JPWO2018021533A1 (ja) * 2016-07-28 2019-05-23 Ｊｘｔｇエネルギー株式会社 冷凍機油
WO2018181203A1 (fr) * 2017-03-31 2018-10-04 Ｊｘｔｇエネルギー株式会社 Additif destiné à des huiles lubrifiantes, composition d'huile lubrifiante, et mécanisme coulissant
JP2018172510A (ja) * 2017-03-31 2018-11-08 Ｊｘｔｇエネルギー株式会社 潤滑油組成物及びこれを用いた摺動機構
WO2018198645A1 (fr) * 2017-04-28 2018-11-01 Ｊｘｔｇエネルギー株式会社 Additif destiné à un lubrifiant, composition lubrifiante, et mécanisme coulissant
JP2018188519A (ja) * 2017-04-28 2018-11-29 Ｊｘｔｇエネルギー株式会社 潤滑油用添加剤及び潤滑油組成物
JP2018188520A (ja) * 2017-04-28 2018-11-29 Ｊｘｔｇエネルギー株式会社 潤滑油組成物及びこれを用いた摺動機構
JP2018188521A (ja) * 2017-04-28 2018-11-29 Ｊｘｔｇエネルギー株式会社 潤滑油組成物

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