WO2015182173A1 - 冷凍機油組成物およびそれを用いた冷凍機用作動流体組成物 - Google Patents
冷凍機油組成物およびそれを用いた冷凍機用作動流体組成物 Download PDFInfo
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- WO2015182173A1 WO2015182173A1 PCT/JP2015/053425 JP2015053425W WO2015182173A1 WO 2015182173 A1 WO2015182173 A1 WO 2015182173A1 JP 2015053425 W JP2015053425 W JP 2015053425W WO 2015182173 A1 WO2015182173 A1 WO 2015182173A1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/008—Lubricant compositions compatible with refrigerants
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M105/38—Esters of polyhydroxy compounds
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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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/72—Esters of polycarboxylic acids
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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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/74—Esters of polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/24—Only one single fluoro component present
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/042—Epoxides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
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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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/071—Branched chain compounds
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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
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/09—Characteristics associated with water
- C10N2020/097—Refrigerants
- C10N2020/101—Containing Hydrofluorocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/70—Soluble oils
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
Definitions
- the present invention relates to a refrigerator oil composition and a working fluid composition for a refrigerator using the same.
- HFC hydrofluorocarbon
- GWP global warming potential
- refrigerant candidates include refrigerants containing hydrofluoroolefins such as 1,3,3,3-tetrafluoropropene (HFO-1234ze) and 2,3,3,3-tetrafluoropropene (HFO-1234yf). (JP 2012-12239 A).
- the hydrofluoroolefin refrigerant having an unsaturated bond generates an acid by oxidative decomposition, and the generated acid may impair the stability of the refrigerating machine oil composition.
- the hydrofluoroolefin refrigerant is very compatible with the refrigerating machine oil composition, the melt viscosity of the refrigerant is remarkably reduced, and the lubricity indicated by friction or wear may be insufficient. Therefore, the refrigerating machine oil composition used together with the hydrofluoroolefin refrigerant is required to have excellent lubricity.
- additives such as extreme pressure agents and antiwear agents are usually added.
- the responsiveness of such additives (hereinafter referred to as addition) It is also required to have excellent agent responsiveness.
- WO 2013/125528 pamphlet includes tetraester of pentaerythritol and one kind selected from fatty acids having 5 to 18 carbon atoms, and hexaester of one kind selected from dipentaerythritol and fatty acids having 5 to 18 carbon atoms.
- a refrigerating machine oil composition having a kinematic viscosity at 40 ° C. of 3 to 500 mm 2 / sec is disclosed.
- the fatty acid used for the ester additive in International Publication No. 2013/125528 more preferably has 6 to 9 carbon atoms, specifically, tetraester of a fatty acid having 8 carbon atoms and pentaerythritol, 6 carbon atoms. Only the hexaesters of these fatty acids and dipentaerythritol are disclosed.
- An object of the present invention is to provide a refrigerating machine oil composition having excellent performance such as lubricity, additive responsiveness, refrigerant compatibility and the like, and a working fluid composition for a refrigerating machine using the same.
- a refrigerating machine oil composition comprising the following ester additive (a) and the following ester base oil (b), wherein the content of the ester additive (a) is that of the refrigerating machine oil composition.
- a refrigerating machine oil composition in the range of 5 to 45 mass% based on the total amount.
- the working fluid composition for refrigerators which consists of the refrigerant
- the refrigerant containing the hydrofluoroolefin is 1,3,3,3-tetrafluoropropene (HFO-1234ze) or 1,3,3,3-tetrafluoropropene (HFO-1234ze) and difluoromethane (HFC- 32)
- HFO-1234ze 1,3,3,3-tetrafluoropropene
- HFC- 32 difluoromethane
- a refrigerating machine oil composition having excellent performance such as lubricity, additive responsiveness, refrigerant compatibility and the like, and a working fluid composition for a refrigerating machine using the same.
- the refrigerating machine oil composition of the present invention is a refrigerating machine oil composition containing an ester additive (a) and an ester base oil (b), wherein the content of the ester additive (a) is the refrigerating machine oil composition.
- a refrigerating machine oil composition in the range of 5 to 45% by mass based on the total amount of the product.
- the ester additive (a) constituting the refrigerating machine oil composition of the present invention is an ester of isotridecanoic acid and pentaerythritol.
- the isotridecanoic acid indicates a mixture of branched isomers of tridecanoic acid.
- the ester additive (a) is a complete ester in which all the hydroxyl groups of pentaerythritol constituting the ester additive (a) are esterified, but a part of the hydroxyl groups are not esterified and remain as hydroxyl groups.
- a partial ester may be contained as an impurity.
- the ester additive (a) preferably has a kinematic viscosity at 40 ° C. in the range of 80 to 250 mm 2 / sec, from the viewpoint of oil film retention and energy saving of the refrigerating machine oil composition, and 80 to 140 mm 2 / sec. More preferably, it is in the range of 90 to 135 mm 2 / sec.
- the kinematic viscosity can be measured using a Canon-Fenske viscometer according to the method of JIS K2283: 2000.
- the number of terminal methyl groups per molecule of isotridecanoic acid in isotridecanoic acid constituting the ester additive (a) is from the viewpoint of low-temperature fluidity, oxidation stability, low evaporation, etc. of the refrigerating machine oil composition of the present invention. It is preferably in the range of 2.0 to 5.0 on average, more preferably in the range of 2.6 to 3.4 on average, and even more preferably in the range of 2.7 to 3.2 on average. .
- the number of terminal methyl groups per molecule of isotridecanoic acid in isotridecanoic acid constituting the ester additive (a) is obtained as an average value by the following formula 1 using the result of 1 H-NMR measurement of the isotridecanoic acid. It is done.
- the measurement method of 1 H-NMR is as described in the Example column.
- Number of terminal methyl groups per molecule of isotridecanoic acid (sum of integral values of peaks attributable to hydrogen of methyl group / sum of integral values of peaks attributable to hydrogen of hydrocarbon group) ⁇ 25/3 (Formula 1)
- the peak attributed to hydrogen of the methyl group is a peak appearing in the range from 0.5 ppm to the chemical shift (ppm) in the minimum value of the peak appearing in the range of 0.9 to 1.1 ppm. .
- the degree of branching of the hydrocarbon group is known.
- low evaporation means an effect of suppressing the evaporation loss (evaporation) of the lubricating oil in a high temperature range. Since refrigeration oil compositions are used at high temperatures in refrigerant compressors, use of refrigeration oil compositions with poor low evaporation properties causes evaporation, resulting in oil shortage and oil shortage in the lubrication area. It can also be a cause. For this reason, the refrigerating machine oil composition is required to have low evaporation.
- Isotridecanoic acid constituting the ester of the present invention can be produced, for example, by the following methods (i) to (iv).
- ii) A method in which a mixture of tridecanal and tridecanol obtained by hydroformylating a mixture of branched isomers of dodecene is oxidized by a known method such as oxygen oxidation, and the resulting tridecanoic acid is separated by distillation
- (iii) branching of dodecene A method of hydrogenating a mixture of tridecanal and tridecanol obtained by hydroformylating a mixture of isomers to convert the tridecanal in the mixture to tridecanol,
- Examples of the method for hydroformylating a mixture of branched isomers of dodecene described in the above methods (i) to (iii) include a cobalt catalyst or a rhodium catalyst and dodecene in the presence of a mixed gas of hydrogen and carbon monoxide. Examples include a method of reacting a mixture of branched isomers. Examples of the method for oxidizing tridecanol described in the method (iii) include, for example, “Oil Chemical”, published by Japan Oils and Fats Chemical Society, 1970, Vol. 19, No. 20, p 1087-1090, etc. According to the method, a method of oxidizing in the presence of an alkali can be mentioned.
- a hydroformylation method As a method for hydroformylating the mixture of branched isomers of dodecene in the presence of a cobalt catalyst, for example, according to a method described in JP-B-62-1930, Japanese Patent No. 4368454, etc. In the presence of a cobalt catalyst and a mixed gas of hydrogen and carbon monoxide, a hydroformylation method may be mentioned by one step or multiple steps.
- the hydroformylation conditions include, for example, a reaction pressure of 5 to 35 MPa, preferably 10 to 30 MPa, a reaction temperature of 120 to 200 ° C., preferably 140 to 170 ° C., and a mixed gas ratio of hydrogen and carbon monoxide.
- (Hydrogen / carbon monoxide: molar ratio) is 0.8 to 2.0, preferably 1.0 to 1.6.
- the cobalt catalyst include cobalt carbonyl complexes such as octacarbonyl dicobalt, organic acid cobalt such as cobalt acetate, cobalt hydroxide, and cobalt oxide.
- the method for hydroformylating the mixture of branched isomers of dodecene in the presence of a rhodium catalyst is in accordance with a known method, for example, the method described in JP-A-63-225328, Japanese Patent No. 3847466, etc.
- a hydroformylation method may be mentioned by one step or multiple steps.
- the reaction pressure is 0.5 to 20 MPa, preferably 0.5 to 10 MPa
- the reaction temperature is 50 to 170 ° C., preferably 90 to 150 ° C.
- hydrogen and carbon monoxide The mixed gas ratio (hydrogen / carbon monoxide: molar ratio) is 0.8 to 2.0, preferably 1.0 to 1.6.
- rhodium catalysts include rhodium carbonyl complexes such as carbonylhydridotris (triphenylphosphine) rhodium and (acetylacetonato) dicarbonylrhodium, rhodium acetate and other organic acid rhodium, rhodium nitrate and other inorganic acid rhodium, rhodium oxide and the like. Is mentioned.
- rhodium carbonyl complexes such as carbonylhydridotris (triphenylphosphine) rhodium and (acetylacetonato) dicarbonylrhodium, rhodium acetate and other organic acid rhodium, rhodium nitrate and other inorganic acid rhodium, rhodium oxide and the like.
- sulfuric acid, phosphoric acid, and the like can be used according to a known method, for example, the method described in JP-B 61-4377, WO 96/10006 pamphlet and the like.
- Examples include a method of reacting a mixture of branched isomers of dodecene in the presence of a catalyst such as hydrogen fluoride and boron trifluoride, carbon monoxide, and water.
- a catalyst such as hydrogen fluoride and boron trifluoride
- carbon monoxide and water.
- reaction conditions for example, the partial pressure of carbon monoxide is 0.1 to 10 MPa, preferably 0.2 to 5 MPa, and the reaction temperature is ⁇ 40 to 80 ° C., preferably ⁇ 20 to 60 ° C.
- Examples of the mixture of branched isomers of dodecene include butene trimer, isobutene trimer, propylene tetramer, mixtures thereof and the like, and the low-temperature flow of the refrigerating machine oil composition of the present invention From the viewpoints of properties, oxidation stability, low evaporation, etc., it is preferable to use a butene trimer or a mixture of branched isomers of dodecene containing a butene trimer as a main component.
- butene refers to a mixture of 1-butene, 2-butene and isobutene, and the content of isobutene in the mixture is the low-temperature fluidity, oxidation stability, low evaporation of the refrigerating machine oil composition of the present invention. From the viewpoint of properties and the like, it is preferably less than 30% by mass, and more preferably less than 10% by mass.
- the butene trimer preferably has an initial boiling point in the range of 185 to 195 ° C and a dry point in the range of 195 to 215 ° C.
- esters of isotridecanoic acid and pentaerythritol which are derived from a mixture of branched isomers via the hydroformylation process, tend to deviate from the range of 80-140 mm 2 / sec at 40 ° C.
- the mixture of branched isomers of dodecene is obtained by a known method, for example, by oligomerizing butene, isobutene or propylene in the presence of a homogeneous catalyst or a heterogeneous catalyst, and then distilling and purifying an olefin fraction having 12 carbon atoms. It can be manufactured by acquiring.
- homogeneous catalysts include solubilized nickel complexes, and specific examples of solubilized nickel complexes include nickel carboxylates, alkylaluminum halides and alkylene glycols described in JP-B 61-26888.
- the catalyst include.
- the heterogeneous catalyst include a fixed bed catalyst containing nickel described in Japanese Patent No. 2726138, a solid phosphoric acid catalyst described in Japanese Patent Laid-Open No. 3-275145, and the like.
- the number of terminal methyl groups per molecule of isotridecanoic acid is affected by the number of terminal methyl groups per molecule in the mixture of branched isomers of dodecene used as a raw material.
- the catalyst can be adjusted according to the type of catalyst, reaction rate, distillation conditions, etc. in each production method.
- Examples of the method for producing isotridecanoic acid constituting the ester of the present invention include the above-mentioned methods (i) to (iii) from the viewpoints of low-temperature fluidity, oxidation stability, low evaporation and the like of the refrigerating machine oil composition of the present invention.
- the catalyst used for hydroformylation in these processes can also be used advantageously with cobalt and rhodium catalysts.
- the ester additive (a) can be produced by reacting the isotridecanoic acid and pentaerythritol at 120 to 300 ° C. for 5 to 40 hours, for example.
- a catalyst may be used, and examples of the catalyst include mineral acids, organic acids, Lewis acids, organic metals, solid acids and the like.
- the mineral acid include hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, nitric acid and the like.
- the organic acid include p-toluenesulfonic acid, benzenesulfonic acid, butanesulfonic acid, propanesulfonic acid, ethanesulfonic acid, methanesulfonic acid and the like.
- Specific examples of the Lewis acid include boron trifluoride, aluminum chloride, tin tetrachloride, titanium tetrachloride and the like.
- Specific examples of the organic metal include tetrapropoxy titanium, tetrabutoxy titanium, tetrakis (2-ethylhexyloxy) titanium, and the like.
- Specific examples of the solid acid include a cation exchange resin.
- the amount of isotridecanoic acid used is preferably 1.1 to 1.4 times mol of the hydroxyl group of pentaerythritol used.
- a solvent may be used.
- the solvent include hydrocarbon solvents such as benzene, toluene, xylene, hexane, heptane, isohexane, isooctane, isononane, decane, and the like.
- ester additive (a) and the isotridecanoic acid the reaction product obtained in each step is, if necessary, a method usually used in organic synthetic chemistry (washing with water and / or alkaline aqueous solution, activated carbon , Treatment with an adsorbent, etc., various chromatography, distillation, etc.).
- the ester additive (a) exhibits excellent performance such as lubricity and additive responsiveness when added to the ester base oil (b).
- the ester base oil (b) constituting the refrigerating machine oil composition of the present invention contains an ester composed of two or more aliphatic monocarboxylic acids selected from aliphatic monocarboxylic acids having 4 to 9 carbon atoms and pentaerythritol. , An ester of a polyhydric alcohol.
- examples of the polyhydric alcohol include pentaerythritol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2- Examples include dimethylpropanoate, trimethylolethane, trimethylolpropane, dipentaerythritol, and ditrimethylolpropane.
- the content of the ester base oil (b) is preferably in the range of 55 to 93% by mass based on the total amount of the refrigerating machine oil composition of the present invention.
- the ester base oil (b) may be an ester composed of two or more aliphatic monocarboxylic acids selected from aliphatic monocarboxylic acids having 4 to 9 carbon atoms and pentaerythritol.
- An ester containing an ester of a monohydric alcohol may be used.
- Other polyhydric alcohol esters are used in combination to prepare a refrigerating machine oil composition with an optimal viscosity and optimal two-layer separation temperature (refrigerant compatibility) from the viewpoint of oil film retention and energy saving. Is done.
- the content of the other polyhydric alcohol ester is preferably 25% by mass or less based on the total amount of the refrigerator oil composition.
- Examples of other polyhydric alcohol esters include esters of one or more aliphatic monocarboxylic acids selected from aliphatic monocarboxylic acids having 4 to 13 carbon atoms and neopentyl glycol, and esters having 4 to 9 carbon atoms. Examples thereof include esters of two or more aliphatic monocarboxylic acids selected from aliphatic monocarboxylic acids and dipentaerythritol.
- Examples of the aliphatic monocarboxylic acid having 4 to 9 carbon atoms in the ester base oil (b) include linear aliphatic monocarboxylic acids such as butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, and nonanoic acid.
- butyric acid, pentanoic acid, heptanoic acid, isobutyric acid, 2-methylbutyric acid, 2-ethylhexanoic acid, or 3,5,5-trimethylhexanoic acid is preferable from the viewpoint of availability.
- Examples of the aliphatic monocarboxylic acid having 4 to 13 carbon atoms in the ester base oil (b) include those exemplified as the aliphatic monocarboxylic acid having 4 to 9 carbon atoms, isotridecanoic acid, and the like. Among them, those exemplified as preferable for the aliphatic monocarboxylic acid having 4 to 9 carbon atoms or isotridecanoic acid are preferable from the viewpoint of availability.
- ester b-PE an ester composed of two or more aliphatic monocarboxylic acids selected from the aliphatic monocarboxylic acids having 4 to 9 carbon atoms and pentaerythritol
- ester b-PE pentaerythritol
- isobutyric acid and 3 5,5-trimethylhexanoic acid and pentaerythritol ester
- isobutyric acid 2-ethylhexanoic acid and pentaerythritol ester
- pentane Acid heptanoic acid, 3,5,5-trimethylhexanoic acid and pentaerythritol ester
- an ester of isobutyric acid 3,5,5-trimethylhexanoic acid and pentaerythritol
- an ester of pentanoic acid 3,5,5-trimethylhexanoic acid and pentaerythritol
- pentanoic acid and heptanoic acid 3,5,5 Esters of 5-trimethylhexanoic acid and pentaerythritol
- esters in which the constituent carboxylic acids are the same but differ only in composition ratio A mixture of two or more of these is preferred.
- esters of one or more aliphatic monocarboxylic acids selected from the aliphatic monocarboxylic acids having 4 to 13 carbon atoms and neopentyl glycol include isobutyric acid and 3 , 5,5-trimethylhexanoic acid and neopentyl glycol ester, isobutyric acid, 2-ethylhexanoic acid and neopentyl glycol ester, 2-ethylhexanoic acid and neopentyl glycol ester, 3,5,5 -Ester of trimethylhexanoic acid and neopentyl glycol, ester of isotridecanoic acid and neopentyl glycol, etc.
- ester of 2-ethylhexanoic acid and neopentyl glycol, or Esters are preferred.
- esters of two or more aliphatic monocarboxylic acids selected from the aliphatic monocarboxylic acids having 4 to 9 carbon atoms and dipentaerythritol include isobutyric acid and 3, Esters of 5,5-trimethylhexanoic acid and dipentaerythritol, esters of isobutyric acid, 2-ethylhexanoic acid and dipentaerythritol, esters of pentanoic acid, 3,5,5-trimethylhexanoic acid and dipentaerythritol , Esters of pentanoic acid, heptanoic acid, 3,5,5-trimethylhexanoic acid and dipentaerythritol, esters of 2-methylbutyric acid, 3,5,5-trimethylhexanoic acid and dipentaerythritol, 2-methylbutyric acid Ester of 2-ethylhe
- esters of isobutyric acid, 3,5,5-trimethylhexanoic acid and dipentaerythritol, pentanoic acid and 3 Esters of 5,5-trimethylhexanoic acid and dipentaerythritol, esters of pentanoic acid and heptanoic acid and 3,5,5-trimethylhexanoic acid and dipentaerythritol, or 2-ethylhexanoic acid and 3,5,5 -Esters of trimethylhexanoic acid and dipentaerythritol are preferred.
- the ester base oil (b) is an ester preferred in the ester b-PE, a mixture of an ester preferred in the ester b-PE and an ester preferred in the b-NPG, or the ester b-PE.
- Preferred is a mixture of the ester preferred in the above and the ester preferred in the b-DPE, the ester preferred in the ester b-PE, or the ester preferred in the ester b-PE and the b-NPG.
- a mixture with the above ester is more preferred.
- the ester base oil (b) is a complete ester in which all the hydroxyl groups of the polyhydric alcohol are esterified, but a partial ester that remains as a hydroxyl group without being partially esterified is contained as an impurity. May be.
- ester base oil (b) is ester b-PE
- the aliphatic monocarboxylic acid having 4 to 9 carbon atoms and pentaerythritol are reacted at 120 to 300 ° C. for 5 to 40 hours, for example. Can be manufactured. It is preferable to carry out the reaction while removing water produced by the reaction from the reaction mixture.
- the amount of the aliphatic monocarboxylic acid having 4 to 9 carbon atoms is preferably 1.1 to 1.4 times the mole of the hydroxyl group of pentaerythritol to be used.
- a catalyst or a solvent may be used. Specific examples include the catalyst and the solvent exemplified in the method for producing the ester additive (a).
- ester base oil (b) is, for example, a mixture of an ester b-PE and an ester b-NPG, or a mixture of an ester b-PE and an ester b-DPE, except that the corresponding raw material is changed
- ester b-PE and ester b-NPG or ester b-DPE may be produced independently, and then mixed to form ester base oil (b).
- ester b-PE and the carboxylic acid constituting the ester b-NPG or the ester b-DPE are all in common, the ester b-PE and the ester b-NPG or the ester b-DPE
- the raw materials used in the production of the above may be combined into one and produced in a lump according to the above reaction method to obtain the ester base oil (b).
- the refrigerating machine oil composition of the present invention is a refrigerating machine oil composition containing the ester additive (a) and the ester base oil (b), wherein the content of the ester additive (a) is the refrigerating machine oil.
- a refrigerating machine oil composition in the range of 5 to 45% by mass based on the total amount of the composition.
- the proportion of the ester additive (a) is less than 5% by mass, the refrigerating machine oil composition of the present invention has poor lubricity and additive responsiveness, while when it exceeds 45% by mass, the refrigerating machine oil of the present invention.
- the refrigerant compatibility of the composition becomes poor.
- the refrigerant is a mixed refrigerant of hydrofluoroolefin and hydrofluorocarbon, the range of 5 to 30% by mass is preferable from the viewpoint of refrigerant compatibility.
- the refrigerator oil composition of the present invention may contain a lubricating oil base oil other than the ester base oil (b) and a lubricating oil additive other than the ester additive (a), if necessary.
- the total amount of the ester additive (a) and the ester base oil (b) in the refrigerator oil composition is preferably in the range of 70 to 99% by mass based on the total amount of the refrigerator oil composition, and 95 to 99. More preferably, it is in the range of mass%.
- Examples of the lubricating base oil other than the ester base oil (b) include mineral oil and synthetic base oil.
- the mineral oil include paraffinic crude oil, intermediate crude oil, and naphthenic crude oil. Further, refined oils obtained by purifying these by distillation or the like can also be used.
- Synthetic base oils include, for example, poly- ⁇ -olefins (polybutene, polypropylene, ⁇ -olefin oligomers having 8 to 14 carbon atoms, etc.), aliphatic esters other than the ester base oil (b) (fatty acid monoesters, aliphatics).
- aliphatic esters other than the ester base oil (b) include esters of 1,2-cyclohexanedicarboxylic acid and 2-ethylhexanol, and esters of sebacic acid and 2-ethylhexanol.
- the content of the lubricating base oil other than the ester base oil (b) is within a range that does not impair the refrigerant compatibility, lubricity, additive responsiveness, etc. in the presence of the refrigerant. However, it is preferably 30% by mass or less, more preferably 20% by mass or less, and most preferably 10% by mass or less based on the total amount of the refrigerator oil composition.
- lubricating oil additives other than the ester additive (a)
- examples of lubricating oil additives include, for example, antioxidants, wear reducing agents (antiwear agents, anti-seizure agents, extreme pressure agents, etc.), Examples include friction modifiers, oiliness agents, acid scavengers, metal deactivators, rust inhibitors, and antifoaming agents.
- the content of these lubricating oil additives is preferably 0.001 to 5% by mass based on the total amount of the refrigerating machine oil composition.
- antioxidants examples include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 4,4′-methylenebis (2,6-diphenol). -Tert-butylphenol) and the like, and amine-based antioxidants such as phenyl- ⁇ -naphthylamine and N, N′-di-phenyl-p-phenylenediamine.
- the wear reducing agent examples include phosphorous extreme pressure agents such as phosphoric acid esters, thiophosphoric acid esters, acidic phosphoric acid esters, phosphorous acid esters, and amine salts of acidic phosphoric acid esters.
- phosphorous extreme pressure agents such as phosphoric acid esters, thiophosphoric acid esters, acidic phosphoric acid esters, phosphorous acid esters, and amine salts of acidic phosphoric acid esters.
- tricresyl phosphate is preferably used as the phosphate ester.
- amine salt of acidic phosphate ester what is marketed by product names, such as Lubdyne 3000 (made by SC Organic Chemical Co., Ltd.) and IRGALUBE349 (made by Ciba Specialty Chemicals Co., Ltd.), is used preferably, for example.
- Examples of the acid scavenger include epoxy acid scavengers such as glycidyl ether and glycidyl ester.
- Examples of the glycidyl ether include 2-ethylhexyl glycidyl ether.
- Examples of the glycidyl ester include neodecanoic acid glycidyl ester.
- metal deactivator examples include benzotriazole, 2,5-dialkylmercapto-1,3,4-thiadiazole, and among them, benzotriazole is preferable.
- antifoaming agent examples include dimethylsiloxane.
- the refrigerating machine oil composition of the present invention has excellent performance such as lubricity, additive responsiveness, refrigerant compatibility, etc. required for the refrigerating machine oil composition and the working fluid composition for the refrigerating machine, and low temperature fluidity, sealing. Sufficient performance such as material compatibility.
- the lubricity refers to both lubricity in the presence of a refrigerant and lubricity in the absence of a refrigerant.
- the refrigerating machine oil composition of this invention contains the said ester additive (a), it can maintain high refrigerant
- Lubricity includes, for example, friction reduction, wear reduction (wear resistance), extreme pressure, etc. With reference to ASTM D4172, ASTM D2783, etc., by a friction wear tester such as a shell-type four-ball friction tester Can be evaluated. Lubricating oil with high lubricity is preferable in terms of energy saving, long life of equipment, etc. by reducing frictional resistance between machine elements and wear loss of sliding members. When lubricating oil is used as refrigerating machine oil, not only lubricity in the absence of refrigerant but also lubricity in the presence of refrigerant is required.
- the lubricity in the presence of refrigerant is: sealed pressure type block-on-ring friction and wear tester (made by FALEX) according to ASTM D2714, sealed pressure type pin and bee block type friction wear according to ASTM D2670. It can be evaluated by a friction and wear tester such as a tester (manufactured by FALEX).
- the additive responsiveness is also expressed by “Additive Response” or the like. This means the addition effect when additives such as antioxidants and wear reducing agents are added to the refrigerating machine oil composition.
- the additive effect of the additive may vary depending on the refrigerating machine oil composition, and it can be said that the additive responsiveness is better as the additive effect, that is, the improvement in physical properties is larger.
- Refrigerant compatibility refers to the compatibility between the refrigerant and the refrigerating machine oil composition. If the refrigerant compatibility is poor, the refrigerant and the refrigerating machine oil composition undergo phase separation, and the refrigerating machine oil composition discharged from the refrigerant compressor is There is a possibility that problems such as poor lubrication in the refrigerant compressor due to stagnation in the refrigerant circulation cycle may occur.
- Refrigerant compatibility is generally expressed using the two-layer separation temperature.
- the two-layer separation temperature can be measured according to the method of JIS K2211: 2009. It can be said that the lower the two-layer separation temperature, the better the refrigerant compatibility on the low temperature side.
- the refrigerant compatibility of the refrigerating machine oil composition is too high, there are places where the refrigerant melts greatly in the refrigerant compressor where the change in temperature and pressure is large. In such places, the working fluid composition for the refrigerating machine causes the refrigerant viscosity to decrease. If the refrigerant viscosity decreases, it will be difficult to retain the oil film necessary for lubrication, and problems with poor lubricity such as seizure and increased wear may occur, so the refrigerant oil composition has a high refrigerant viscosity. Is also required.
- Refrigerant dissolution viscosity can be determined by, for example, sealing a refrigerant and a refrigerating machine oil composition in a pressure vessel, stabilizing the pressure in the gas phase and the temperature in the vessel in a predetermined state, and then measuring the viscosity in the liquid phase by an inline viscometer. Etc. can be measured.
- Sealing material compatibility refers to the compatibility between the refrigerator oil composition and the sealing material.
- the sealing material include O-rings made of acrylonitrile-butadiene rubber, ethylene-propylene-diene rubber, hydrogenated acrylonitrile-butadiene rubber, silicone rubber, fluorine rubber and the like.
- a refrigerant compressor of a refrigerator has a refrigerator oil composition and a refrigerant sealed with a sealing material. However, if the refrigerating machine oil composition has poor sealing material compatibility, the sealing material swells or shrinks, causing problems such as refrigerant leakage and oil leakage.
- Low temperature fluidity refers to viscosity characteristics in a low temperature range, and is represented by a pour point, a freezing point, a channel point, and the like.
- the pour point of the refrigerator oil composition of the present invention is preferably ⁇ 40 ° C. or lower.
- a refrigerating machine oil composition having a low pour point is preferable in that it does not deteriorate in fluidity even in a low temperature environment such as in winter or in a cold region, and does not cause malfunction of equipment using the refrigerating machine oil composition.
- the pour point means a pour point measured according to the method of JIS K2269.
- the kinematic viscosity at 40 ° C. of the refrigerating machine oil composition of the present invention is preferably 20 to 100 mm 2 / sec from the viewpoint of oil film retention and energy saving.
- the viscosity index of the refrigerating machine oil composition of the present invention is not particularly limited, but is preferably 80 or more from the viewpoint of oil film retention and energy saving.
- the viscosity index represents viscosity-temperature characteristics, and it can be said that the higher the viscosity index, the better the viscosity-temperature characteristics.
- the kinematic viscosity and the viscosity index can be measured using a Canon-Fenske viscometer according to the method of JIS K2283: 2000.
- the working fluid composition for a refrigerator of the present invention comprises the refrigerant oil composition of the present invention and a refrigerant containing a hydrofluoroolefin.
- the refrigerator oil composition of the present invention is usually present in the form of a working fluid composition for a refrigerator mixed with a refrigerant in a refrigerant circulation cycle such as a refrigerator.
- the mixing ratio of the refrigerating machine oil composition and the refrigerant in this fluid composition is not particularly limited, but is preferably 1 to 1000 parts by mass of the refrigerating machine oil composition of the present invention with respect to 100 parts by mass of the refrigerant. More preferred is part by mass.
- the refrigerating machine oil composition of the present invention and the refrigerant containing hydrofluoroolefin are preferably compatible with each other at 0 ° C. without being separated into two layers.
- the global warming potential (GWP) of the refrigerant containing hydrofluoroolefin is preferably 500 or less, and more preferably 300 or less.
- Examples of the refrigerant containing hydrofluoroolefin include hydrofluoroolefin or a mixed refrigerant of hydrofluoroolefin and another refrigerant.
- hydrofluoroolefin examples include 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,2,3. , 3,3-pentafluoropropene (HFO-1225ye), 1,1,2-trifluoroethylene (HFO-1123), and the like.
- 1,3,3,3-tetrafluoropropene (HFO-1234ze) is preferable from the viewpoint of chemical stability.
- refrigerants include difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1-difluoroethane. (HFC-152a), hydrofluorocarbon refrigerants such as monofluoroethane (HFC-161), hydrocarbon refrigerants such as propane (R290), butane (R600), isobutane (R600a), carbon dioxide refrigerant (R744), ammonia refrigerant ( R717) and the like.
- difluoromethane (HFC-32), 1,1-difluoroethane (HFC-152a), propane (R290), and carbon dioxide (R744) are preferable.
- a mixed refrigerant of hydrofluoroolefin and other refrigerants specifically, a mixed refrigerant of 1,3,3,3-tetrafluoropropene (HFO-1234ze) and difluoromethane (HFC-32), A refrigerant mixture of 3,3,3-tetrafluoropropene (HFO-1234ze), 2,3,3,3-tetrafluoropropene (HFO-1234yf) and difluoromethane (HFC-32), 3-tetrafluoropropene (HFO-1234ze), a mixed refrigerant of difluoromethane (HFC-32) and 1,1-difluoroethane (HFC-152a), 1,3,3,3-tetrafluoropropene (HFO-1234ze) And propane (R290) mixed refrigerant or 1,3,3,3-tetrafluoropropene (HFO-12) Preferably mixed refrigerant 4Ze) and carbon dioxide (R74
- the refrigerator oil composition and the working fluid composition for refrigerators of the present invention include room air conditioners, packaged air conditioners, car air conditioners, dehumidifiers, refrigerators, freezers, refrigerator refrigerators, vending machines, showcases, chemical plant refrigerators, etc. Is preferably used.
- the resulting butene trimer was treated with a mixed gas of hydrogen and carbon monoxide (hydrogen / carbon monoxide) using hydride tetracarbonylcobalt generated by treating cobalt hydroxide with a mixed gas of hydrogen and carbon monoxide.
- Isotridecanoic acid A was obtained by 165-175 ° C. and reduced pressure 5 Torr).
- the number of terminal methyl groups contained in one molecule of isotridecanoic acid A was 2.9.
- reaction product was stirred at 216 to 230 ° C. for 3 hours under a reduced pressure of 0.4 kPa to distill off unreacted carboxylic acid in the reaction product.
- the reaction product was washed at 80 ° C. for 1 hour with 1025 mL of an aqueous alkaline solution containing sodium hydroxide twice as much as the acid value of the reaction product.
- the reaction product was then washed 3 times with 1000 mL of water at 90 ° C. for 1 hour. Subsequently, the reaction product was dried by stirring at 100 ° C. for 2 hours under reduced pressure of 0.6 kPa while performing nitrogen bubbling.
- Refrigerating machine oil compositions 1 to 45 having the compositions shown in Tables 2 to 9 were prepared using the ester additives (a) of Production Examples 3 to 5 and the ester base oils (b) of Production Examples 6 to 14. did.
- Examples 37 to 53 refrigeration oil compositions having the compositions shown in Tables 10 to 12 using the refrigeration oil compositions 1, 3, 8, 28, 32, 34 and 35 and the lubricating oil additives shown below were used. 46-62 were prepared.
- Antioxidant 2,6-di-tert-butyl-4-methylphenol acid scavenger-1: glycidyl neodecanoate acid scavenger-2: 2-ethylhexyl glycidyl ether extreme pressure agent-1: tricresyl phosphate Pressure agent-2: Lubdyne 3000 (manufactured by SC Organic Chemical Company) The following evaluation tests were carried out for each refrigerator oil composition.
- Test Example 2 Measurement of pour point The pour point of the refrigerating machine oil compositions 1 to 45 was measured according to the method of JIS K2269: 1987 using an automatic pour point measuring device RPC-01CML (manufactured by Rouai Co., Ltd.). The results are shown below.
- TCP / BZT additive oil 19.78 g of refrigerating machine oil composition 1, 0.2 g of tricresyl phosphate (TCP, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.02 g of benzotriazole (BZT, manufactured by Aldrich) And dissolved at 50 ° C. to prepare TCP / BZT-added oil 1.
- TCP tricresyl phosphate
- BZT benzotriazole
- the wear scar diameters of three fixed balls were measured.
- the wear scar diameter was the average value of all three fixed spheres in the vertical and horizontal directions.
- the results are shown in Tables 2-9.
- the smaller the wear scar diameter the better the lubricity (wear resistance) of the refrigeration oil composition.
- the wear scar diameter of the refrigeration oil composition and the wear scar diameter of the corresponding TCP / BZT added oil The larger the difference, the more refrigeration oil composition with high additive responsiveness.
- Test Example 4 Measurement of two-layer separation temperature with HFO-1234ze (evaluation of refrigerant compatibility) 0.6 g of any of the refrigerating machine oil compositions 1 to 62 and 2.4 g of HFO-1234ze (manufactured by Honeywell) are sealed in a pressure-resistant glass tube, and the mixture is heated from 30 ° C. according to the method of JIS K2211: 2009. The mixture was cooled at a rate of 0.5 ° C. per minute, and the temperature at which the mixture separated into two layers or became cloudy was defined as the two-layer separation temperature. The results are shown in Tables 2-12.
- Test Example 5 Measurement of two-layer separation temperature of mixed refrigerant of HFO-1234ze and HFC-32 (confirmation of refrigerant compatibility) 0.6 g of any of the refrigerating machine oil compositions 1 to 45 and 2.4 g of the following mixed refrigerant were sealed in a pressure-resistant glass tube, and the two-layer separation temperature was measured in the same manner as in Test Example 4. The results are shown below.
- the friction and wear test was conducted under the following conditions while introducing HFO-1234ze (manufactured by Honeywell) or the mixed refrigerant shown in Test Example 5 as a refrigerant so that the absolute pressure in the pressure vessel became 600 kPa. did.
- the wear marks on the block test pieces after the frictional wear test were observed, and those that showed seizure were regarded as “seizure”. For those that did not show seizure, the wear scar width of the block specimen was measured. The results are shown in Tables 2-9.
- Test materials Ring (FALEX Type S-10), Block (FALEEX Type H-60) Test start temperature: 60 ° C Test time: 1 hour Sliding speed: 0.5 m / s Load: 600N Absolute pressure of refrigerant atmosphere: 600kPa
- the wear scar diameters of the refrigerating machine oil compositions 1 to 36 are 0.47 mm to 0.53 mm, respectively, and the refrigerating machine oil compositions 1 to 36 are excellent in lubricity in the absence of a refrigerant.
- the wear scar diameter of the additive oil to which TCP and BZT are added is 0.37 mm or less, indicating that the refrigerating machine oil compositions 1 to 36 are excellent in additive responsiveness.
- the refrigerating machine oil compositions 37 and 40 to 45 which are not the present invention show 0.45 mm or more in the wear scar diameter of the additive oil to which TCP and BZT are added, indicating that the additive responsiveness is not excellent. Further, seizure occurred in the additive oil of the refrigerator oil composition 39.
- the two-layer separation temperatures of the refrigerating machine oil compositions 1 to 36 and 46 to 62 with HFO-1234ze are all ⁇ 13 ° C. or less and have excellent refrigerant compatibility. I understand.
- the two-layer separation temperature of the refrigerating machine oil composition 38 that is not the present invention is 3 ° C., and it is understood that the refrigerant oil composition does not have sufficient refrigerant compatibility with HFO-1234ze.
- the wear scar width of the refrigerating machine working fluid composition comprising the refrigerating machine oil compositions 1 to 36 and HFO-1234ze was 0.80 mm or less.
- the wear scar width of the working fluid composition for a refrigerator composed of the refrigerator oil compositions 1 to 36, the mixed refrigerant of HFO-1234ze, and HFC-32 was 0.65 mm or less. It can be seen that the working fluid composition for a refrigerator of the present invention is excellent in lubricity even in the presence of any one of HFO-1234ze and a mixed refrigerant of HFO-1234ze and HFC-32.
- the refrigerator oil compositions 37 and 40 to 45 which are not of the present invention are seized in the presence of any refrigerant and are not excellent in lubricity.
- the wear scar width of the refrigerating machine working fluid composition comprising the refrigerating machine oil compositions 46 to 62 containing the lubricating oil additive and HFO-1234ze was 0.73 mm or less.
- the wear scar width of the refrigerating machine working fluid composition comprising the refrigerating machine oil compositions 52 and 56 containing the lubricating oil additive, and the mixed refrigerant of HFO-1234ze and HFC-32, respectively, They were 0.54 mm and 0.49 mm. It can be seen that the refrigerating machine oil composition of the present invention has excellent lubricity in the presence of not only HFO-1234ze but also a mixed refrigerant of HFO-1234ze and HFC-32.
- the two-layer separation temperatures of the mixed refrigerant of HFO-1234ze and HFC-32 in the refrigerator oil compositions 1 to 3, 5 to 6, 8 to 14, and 17 to 36 were all 0 ° C. It was the following. It can be seen that the refrigerating machine oil composition of the present invention has excellent refrigerant compatibility not only with HFO-1234ze but also with a mixed refrigerant of HFO-1234ze and HFC-32. On the other hand, the two-layer separation temperature of the refrigerating machine oil composition 38 not according to the present invention was 20 ° C. or higher, and the refrigerant compatibility with the mixed refrigerant of HFO-1234ze and HFC-32 was poor.
- the refrigerant melt viscosity of the refrigerator oil composition 2 is 9.2 cP
- the refrigerant melt viscosity of the refrigerator oil composition 3 is 9.9 cP
- the refrigerant melt viscosity of the refrigerator oil composition 7 is 9
- the refrigerant viscosity of the refrigerator oil composition 14 was 9.0 cP. It turns out that the refrigerating machine oil composition of this invention has the outstanding refrigerant
- the refrigerant viscosity of the refrigerating machine oil compositions 37, 39, and 41 that are not the present invention are 7.8 cP, 7.2 cP, and 6.3 cP, respectively, compared with the refrigerating machine oil composition of the present invention. It can be seen that the refrigerant does not have sufficient melt viscosity.
- a refrigerating machine oil composition and a working fluid composition for a refrigerating machine having excellent performance such as lubricity, additive responsiveness, refrigerant compatibility, and the like can be provided.
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Abstract
Description
[1]下記のエステル添加剤(a)と、下記のエステル基油(b)とを含有する冷凍機油組成物であって、前記エステル添加剤(a)の含有量が前記冷凍機油組成物の全量基準で5~45質量%の範囲にある冷凍機油組成物。
エステル添加剤(a);イソトリデカン酸とペンタエリスリトールとのエステル
エステル基油(b);炭素数4~9の脂肪族モノカルボン酸から選ばれる2種以上の脂肪族モノカルボン酸とペンタエリスリトールとからなるエステルを含む、多価アルコールのエステル
[2][1]に記載の冷凍機油組成物と、ハイドロフルオロオレフィンを含む冷媒とからなる冷凍機用作動流体組成物。
[3]前記ハイドロフルオロオレフィンを含む冷媒が1,3,3,3-テトラフルオロプロペン(HFO-1234ze)または1,3,3,3-テトラフルオロプロペン(HFO-1234ze)とジフルオロメタン(HFC-32)との混合冷媒である[2]に記載の冷凍機用作動流体組成物。
本発明の冷凍機油組成物を構成するエステル添加剤(a)は、イソトリデカン酸とペンタエリスリトールとのエステルである。ここで、前記イソトリデカン酸は、トリデカン酸の分岐異性体の混合物を示す。前記エステル添加剤(a)は、エステル添加剤(a)を構成するペンタエリスリトールの水酸基が全てエステル化された完全エステルであるが、水酸基の一部がエステル化されずに水酸基のまま残っている部分エステルが不純物として含まれていても良い。
イソトリデカン酸1分子当たりの末端メチル基の数=(メチル基の水素に帰属されるピークの積分値の総和/炭化水素基の水素に帰属されるピークの積分値の総和)×25/3 ・・・(式1)
ここで、メチル基の水素に帰属されるピークは、0.5ppmから、0.9~1.1ppmの範囲に現れるピークの最小値におけるケミカルシフト(ppm)までの範囲に現れるピークのことである。式1により求められる末端メチル基の数より、炭化水素基の分岐度合いが分かる。
(i)ドデセンの分岐異性体の混合物をヒドロホルミル化して得られたトリデカナールとトリデカノールの混合物から、トリデカナールを蒸留で分離して、その留分を酸素酸化等の公知の方法で酸化する方法
(ii)ドデセンの分岐異性体の混合物をヒドロホルミル化して得られたトリデカナールとトリデカノールの混合物を酸素酸化等の公知の方法で酸化し、生成したトリデカン酸を蒸留で分離する方法
(iii)ドデセンの分岐異性体の混合物をヒドロホルミル化して得られたトリデカナールとトリデカノールの混合物を水添して、混合物中のトリデカナールをトリデカノールに変換してから、得られたトリデカノールを酸化する方法
(iv)ドデセンの分岐異性体の混合物をコッホ反応する方法
本発明の冷凍機油組成物を構成するエステル基油(b)は、炭素数4~9の脂肪族モノカルボン酸から選ばれる2種以上の脂肪族モノカルボン酸とペンタエリスリトールとからなるエステルを含む、多価アルコールのエステルである。ここで、多価アルコールとしては、ペンタエリスリトール、ネオペンチルグリコール、2-ブチル-2-エチル-1,3-プロパンジオール、3-ヒドロキシ-2,2-ジメチルプロピル-3-ヒドロキシ-2,2-ジメチルプロパノエート、トリメチロールエタン、トリメチロールプロパン、ジペンタエリスリトール、ジトリメチロールプロパン等が挙げられる。
本発明の冷凍機油組成物は、前記エステル添加剤(a)と前記エステル基油(b)とを含有する冷凍機油組成物であって、前記エステル添加剤(a)の含有量が前記冷凍機油組成物の全量基準で5~45質量%の範囲にある冷凍機油組成物である。前記エステル添加剤(a)の割合が5質量%未満になると、本発明の冷凍機油組成物の潤滑性および添加剤応答性が不良となり、一方、45質量%より大きくなると、本発明の冷凍機油組成物の冷媒相溶性が不良となる。特に冷媒がハイドロフルオロオレフィンとハイドロフルオロカーボンとの混合冷媒の場合は、冷媒相溶性の観点から、5~30質量%の範囲が好ましい。
本発明の冷凍機用作動流体組成物は、本発明の冷凍機油組成物とハイドロフルオロオレフィンを含む冷媒とからなる。本発明の冷凍機油組成物は通常、冷凍機等の冷媒循環サイクルにおいて、冷媒と混合された冷凍機用作動流体組成物の形で存在している。この流体組成物における冷凍機油組成物と冷媒との混合割合は特に制限されないが、冷媒100質量部に対して、本発明の冷凍機油組成物1~1000質量部であるのが好ましく、2~800質量部であるのがより好ましい。
[1H-NMR]
<測定機器>
日本電子社製JNM-ECA500(500MHz)
<測定条件>
標準物;テトラメチルシラン(TMS)
溶媒;CDCl3
試料濃度;40質量%
積算回数;64回
化学シフトのリファレンス;TMS=0ppm
[イソトリデカン酸Aの製造]
ブテン(1-ブテン、2-ブテンおよびイソブテンの混合物;ただし、イソブテンの含有量は全体の10質量%未満)を、珪藻土を担体とした固体リン酸触媒を用いて、200℃、5MPaで反応させた後、反応物を蒸留精製することによりブテンの3量体(初留点:192℃、乾点:202℃)を得た。得られたブテンの3量体を、水酸化コバルトを水素と一酸化炭素の混合ガスで処理することにより発生させたヒドリドテトラカルボニルコバルトを触媒とし、水素と一酸化炭素との混合ガス(水素/一酸化炭素の混合比(モル比);1.1/1)の存在下、圧力16MPa、温度150℃の条件でヒドロホルミル化し、触媒を除去した後、酸化し、続いて蒸留精製(留出温度165~175℃、減圧度5Torr)することによりイソトリデカン酸Aを得た。1H-NMR測定の結果、イソトリデカン酸Aの1分子に含まれる末端メチル基の数は2.9であった。
[イソトリデカン酸Bの製造]
プロピレンを、珪藻土を担体とした固体リン酸触媒を用いて、200℃、5MPaで反応させた後、反応物を蒸留精製することによりプロピレンの4量体を得た。得られたプロピレンの4量体を、製造例1と同様の方法で、ヒドロホルミル化、触媒除去、酸化および蒸留精製(留出温度154~169℃、減圧度5Torr)し、イソトリデカン酸Bを得た。1H-NMR測定の結果、イソトリデカン酸Bの1分子に含まれる末端メチル基の数は3.9であった。
[イソトリデカン酸Aとペンタエリスリトールのエステル(エステル添加剤(a)-1)の製造]
ディーンスタークトラップの付いた反応器にペンタエリスリトール458g(3.4モル、広栄パーストープ社製、製品名:ペンタリット-S)およびイソトリデカン酸A3447g(16.1モル)を仕込み混合した。混合物を撹拌しながら80kPaに減圧した後、窒素で常圧まで戻し、この操作を3回行うことで反応器内の空気を窒素に置換した。
次いで、常圧下、窒素バブリングを行いながら混合物を172~232℃で23時間撹拌した。反応後、反応生成物を0.4kPaの減圧下、216~230℃で3時間撹拌することにより、反応生成物中の未反応のカルボン酸を留去した。反応生成物を、該反応生成物の酸価に対して2倍モルの水酸化ナトリウムを含むアルカリ水溶液1025mLで、80℃で1時間洗浄した。次いで、反応生成物を、水1000mLで、90℃で1時間、3回洗浄した。次いで、窒素バブリングを行いながら反応生成物を0.6kPaの減圧下、100℃で2時間撹拌することにより反応生成物を乾燥した。
反応生成物に吸着剤30g(協和化学工業社製、製品名;キョーワード500)および活性炭30g(日本エンバイロケミカルズ社製、製品名;白鷺P)を添加し、窒素バブリングを行いながら反応生成物を0.6kPaの減圧下、100℃で1時間撹拌した後、あらかじめ減圧乾燥しておいた濾過助剤(昭和化学工業社製、製品名;ラヂオライト#500)を用いて、窒素雰囲気下で濾過することにより、エステル添加剤(a)-1を2894g得た。
[イソトリデカン酸Bとペンタエリスリトールのエステル(エステル添加剤(a)-2)の製造]
イソトリデカン酸Aの代わりにイソトリデカン酸Bを用い、ペンタエリスリトールおよびイソトリデカン酸Bの使用量のモル比(ペンタエリスリトール/イソトリデカン酸B)を1/4.8にする以外は、製造例3と同様に操作して、エステル添加剤(a)-2を得た。
[2-エチルヘキサン酸とペンタエリスリトールのエステル(エステル添加剤(a)-3)の製造]
イソトリデカン酸Aの代わりに2-エチルヘキサン酸を用い、ペンタエリスリトールおよび2-エチルヘキサン酸の使用量のモル比(ペンタエリスリトール/2-エチルヘキサン酸)を1/4.8にする以外は、製造例3と同様に操作して、エステル添加剤(a)-3を得た。
エステル添加剤(a)-1、(a)-2、および(a)-3の組成を表1に示す。
[2-エチルヘキサン酸と3,5,5-トリメチルヘキサン酸とのモル比(2-エチルヘキサン酸/3,5,5-トリメチルヘキサン酸比)が51/49であるペンタエリスリトールのエステル(エステル基油(b)-1)の製造]
イソトリデカン酸Aの代わりに2-エチルヘキサン酸と3,5,5-トリメチルヘキサン酸とからなる混合脂肪酸を用い、ペンタエリスリトール、2-エチルヘキサン酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/2-エチルヘキサン酸/3,5,5-トリメチルヘキサン酸)を1/2.74/2.06にする以外は、製造例3と同様に操作して、エステル基油(b)-1を得た。
[2-エチルヘキサン酸と3,5,5-トリメチルヘキサン酸とのモル比(2-エチルヘキサン酸/3,5,5-トリメチルヘキサン酸比)が65/35であるペンタエリスリトールのエステル(エステル基油(b)-2)の製造]
イソトリデカン酸Aの代わりに2-エチルヘキサン酸と3,5,5-トリメチルヘキサン酸とからなる混合脂肪酸を用い、ペンタエリスリトール、2-エチルヘキサン酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/2-エチルヘキサン酸/3,5,5-トリメチルヘキサン酸)を1/3.22/1.58にする以外は、製造例3と同様に操作して、エステル基油(b)-2を得た。
[イソ酪酸と3,5,5-トリメチルヘキサン酸とのモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が37/63であるペンタエリスリトールのエステル(エステル基油(b)-3)の製造]
イソトリデカン酸Aの代わりにイソ酪酸と3,5,5-トリメチルヘキサン酸とからなる混合脂肪酸を用い、ペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸)を1/1.78/3.02にする以外は、製造例3と同様に操作して、エステル基油(b)-3を得た。
[イソ酪酸と3,5,5-トリメチルヘキサン酸とのモル比(イソ酪酸/3,5,5-トリメチルヘキサン酸比)が59/41であるペンタエリスリトールのエステル(エステル基油(b)-4)の製造]
イソトリデカン酸Aの代わりにイソ酪酸と3,5,5-トリメチルヘキサン酸とからなる混合脂肪酸を用い、ペンタエリスリトール、イソ酪酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/イソ酪酸/3,5,5-トリメチルヘキサン酸)を1/2.88/1.92にする以外は、製造例3と同様に操作して、エステル基油(b)-4を得た。
[ペンタン酸と3,5,5-トリメチルヘキサン酸とのモル比(ペンタン酸/3,5,5-トリメチルヘキサン酸比)が27/73であるペンタエリスリトールのエステル(エステル基油(b)-5)の製造]
イソトリデカン酸Aの代わりにペンタン酸と3,5,5-トリメチルヘキサン酸とからなる混合脂肪酸を用い、ペンタエリスリトール、ペンタン酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ペンタン酸/3,5,5-トリメチルヘキサン酸)を1/1.30/3.50にする以外は、製造例3と同様に操作して、エステル基油(b)-5を得た。
[ペンタン酸とヘプタン酸と3,5,5-トリメチルヘキサン酸とのモル比(ペンタン酸/ヘプタン酸/3,5,5-トリメチルヘキサン酸比)が39/24/37であるペンタエリスリトールのエステル(エステル基油(b)-6)の製造]
イソトリデカン酸Aの代わりにペンタン酸とヘプタン酸と3,5,5-トリメチルヘキサン酸とからなる混合脂肪酸を用い、ペンタエリスリトール、ペンタン酸、ヘプタン酸および3,5,5-トリメチルヘキサン酸の使用量のモル比(ペンタエリスリトール/ペンタン酸/ヘプタン酸/3,5,5-トリメチルヘキサン酸)を1/1.82/1.13/1.85にする以外は、製造例3と同様に操作して、エステル基油(b)-6を得た。
[ペンタン酸とヘプタン酸と3,5,5-トリメチルヘキサン酸とのモル比(ペンタン酸/ヘプタン酸/3,5,5-トリメチルヘキサン酸比)が41/20/39であり、ペンタエリスリトールとジペンタエリスリトールのモル比(ペンタエリスリトール/ジペンタエリスリトール比)が67/33である、ペンタエリスリトールのエステルとジペンタエリスリトールのエステルの混合物(エステル基油(b)-7)の製造]
イソトリデカン酸Aの代わりにペンタン酸とヘプタン酸と3,5,5-トリメチルヘキサン酸とからなる混合脂肪酸を用い、ペンタエリスリトールの代わりにペンタエリスリトールとジペンタエリスリトールとからなる混合アルコールを用い、ペンタン酸、ヘプタン酸、3,5,5-トリメチルヘキサン酸、ペンタエリスリトールおよびジペンタエリスリトールの使用量のモル比(ペンタエリスリトール/ジペンタエリスリトール/ペンタン酸/ヘプタン酸/3,5,5-トリメチルヘキサン酸)を1/0.50/3.36/1.68/3.36にする以外は、製造例3と同様に操作して、エステル基油(b)-7を得た。
[2-エチルヘキサン酸とネオペンチルグリコールのエステル(エステル基油(b)-8)の製造]
イソトリデカン酸Aの代わりに2-エチルヘキサン酸を、ペンタエリスリトールの代わりにネオペンチルグリコールを用い、ネオペンチルグリコールおよび2-エチルヘキサン酸の使用量のモル比(ネオペンチルグリコール/2-エチルヘキサン酸)を1/2.4にする以外は、製造例3と同様に操作して、エステル基油(b)-8を得た。
[イソトリデカン酸Aとネオペンチルグリコールのエステル(エステル基油(b)-9)の製造]
ペンタエリスリトールの代わりにネオペンチルグリコールを用い、ネオペンチルグリコールおよびイソトリデカン酸Aの使用量のモル比(ネオペンチルグリコール/イソトリデカン酸A)を1/2.4にする以外は、製造例3と同様に操作して、エステル基油(b)-9を得た。
製造例3~5の各エステル添加剤(a)、および製造例6~14の各エステル基油(b)を用いて、表2~9に示す組成を有する冷凍機油組成物1~45を調製した。
[実施例37~53]
実施例37~53においては、冷凍機油組成物1、3、8、28、32、34および35と以下に示す潤滑油添加剤を用いて、表10~12に示す組成を有する冷凍機油組成物46~62を調製した。
酸化防止剤:2,6-ジ-tert-ブチル-4-メチルフェノール
酸捕捉剤-1:ネオデカン酸グリシジルエステル
酸捕捉剤-2:2-エチルヘキシルグリシジルエーテル
極圧剤-1:トリクレジルホスフェート
極圧剤-2:Lubdyne3000(SC有機化学社製)
それぞれの冷凍機油組成物について、以下の評価試験を実施した。
キャノン-フェンスケ粘度計を用い、JIS K2283:2000の方法に準じてエステル添加剤(a)-1~(a)-3および冷凍機油組成物1~62の40℃および100℃における動粘度を測定した。また、同方法に準じて冷凍機油組成物1~62の粘度指数を算出した。結果を表1~12に示す。
自動流動点測定器RPC-01CML(離合社製)を用い、JIS K2269:1987の方法に準じて冷凍機油組成物1~45の流動点を測定した。結果を以下に示す。
1)TCP・BZT添加油の調製
冷凍機油組成物1の19.78gと、トリクレジルホスフェート(TCP、東京化成工業社製)0.2gとベンゾトリアゾール(BZT、アルドリッチ社製)0.02gとを混合し、50℃で溶解させ、TCP・BZT添加油1を調製した。冷凍機油組成物2~45についても、同様の方法で、対応するTCP・BZT添加油2~45を調製した。
冷凍機油組成物1~45およびTCP・BZT添加油1~45のそれぞれについて、シェル式四球摩擦試験機(神鋼造機社製)を用いて摩耗痕径の測定を行なった。荷重230N、回転数600rpm、時間20分、温度40℃、試験材[試験球(SUJ-2)]の条件で試験を行った。試験後の3つの固定球の摩耗痕を観察し、固定球の少なくとも1つに焼付きが見られたものは「焼付き」とした。焼付きが見られなかったものについては、3つの固定球の摩耗痕径を測定した。摩耗痕径は3つの固定球の垂直方向、水平方向全ての平均値とした。結果を表2~9に示す。摩耗痕径の値が小さい程、冷凍機油組成物の潤滑性(耐摩耗性)が優れていることを表し、冷凍機油組成物の摩耗痕径と、対応するTCP・BZT添加油の摩耗痕径との差が大きい程、添加剤応答性の高い冷凍機油組成物であることを表す。
冷凍機油組成物1~62のいずれか0.6gとHFO-1234ze(ハネウェル社製)の2.4gとを耐圧ガラス管に封入し、JIS K2211:2009の方法に準じて、混合物を30℃から毎分0.5℃の速度で冷却し、混合物が二層分離または白濁する温度を二層分離温度とした。結果を表2~12に示す。
冷凍機油組成物1~45のいずれか0.6gと下記混合冷媒の2.4gとを耐圧ガラス管に封入し、試験例4と同様の方法で二層分離温度を測定した。結果を以下に示す。
HFO-1234ze(ハネウェル社製)とHFC-32(ダイキン工業社製)との混合冷媒(HFO-1234zeとHFC-32の質量比[HFO-1234ze/HFC-32]が79/21)
ケンブリッジ・ビスコシティ社製のピストン式粘度計(VISCOpro 2000)を備えた耐圧容器に冷凍機油組成物を入れて、容器内を真空脱気した後、HFO-1234ze(ハネウェル社製)を導入した。冷凍機油組成物2とHFO-1234zeの混合物を撹拌しながら、60℃で絶対圧力が500kPaとなるようにHFO-1234zeを追加または抜き出した。温度、圧力および粘度が安定したところで、冷凍機油組成物2とHFO-1234zeとの混合物の冷媒溶解粘度を測定した。冷凍機油組成物3、7、14、37、39および41も同様の方法で、冷媒溶解粘度を測定した。結果を以下に示す。
ASTM D2714に準じた摩擦摩耗試験により、冷凍機用作動流体組成物の潤滑性を評価した。摺動部が耐圧容器に格納されている密閉加圧型ブロック・オン・リング型摩擦摩耗試験機(FALEX社製)を使用して、該耐圧容器に冷凍機油組成物1~45のいずれかを100ml入れ、該耐圧容器内の絶対圧力が600kPaになるように、冷媒として、HFO-1234ze(ハネウェル社製)または試験例5で示した前記混合冷媒を導入しながら以下の条件で摩擦摩耗試験を実施した。摩擦摩耗試験後のブロック試験片の摩耗痕を観察し、焼付きが見られたものは「焼付き」とした。焼付きが見られなかったものについては、ブロック試験片の摩耗痕幅を測定した。結果を表2~9に示す。
試験材:リング(FALEX Type S-10)、ブロック(FALEX Type H-60)
試験開始温度:60℃
試験時間:1時間
すべり速度:0.5m/s
荷重:600N
冷媒雰囲気の絶対圧力:600kPa
冷凍機油組成物46~62について、冷媒としてHFO-1234ze(ハネウェル社製)を用い、前記試験例7と同様の方法で摩擦摩耗試験を実施した。摩擦摩耗試験後のブロック試験片の摩耗痕を観察し、焼付きが見られたものは「焼付き」とした。焼付きが見られなかったものについては、ブロック試験片の摩耗痕幅を測定した。結果を表10~12に示す。
(試験例9)摩耗痕幅の測定(潤滑油添加剤を含有した冷凍機油組成物のHFO-1234zeとHFC-32の混合冷媒存在下での潤滑性の評価)
冷凍機油組成物52および56について、冷媒として試験例5で示した前記混合冷媒を用い、前記試験例7と同様の方法で摩擦摩耗試験を実施した。摩擦摩耗試験後のブロック試験片の摩耗痕を観察し、焼付きが見られたものは「焼付き」とした。焼付きが見られなかったものについては、ブロック試験片の摩耗痕幅を測定した。結果を以下に示す。
表10~12より、潤滑油添加剤を含有した冷凍機油組成物46~62とHFO-1234zeとからなる冷凍機用作動流体組成物の摩耗痕幅は、いずれも0.73mm以下であった。また、試験例9において、潤滑油添加剤を含有した冷凍機油組成物52および56とHFO-1234zeとHFC-32との混合冷媒とからなる冷凍機用作動流体組成物の摩耗痕幅は、それぞれ0.54mm、0.49mmであった。本発明の冷凍機油組成物はHFO-1234zeだけでなく、HFO-1234zeとHFC-32との混合冷媒のいずれの冷媒存在下においても、潤滑性に優れていることが分かる。
Claims (3)
- 下記のエステル添加剤(a)と、下記のエステル基油(b)とを含有する冷凍機油組成物であって、前記エステル添加剤(a)の含有量が前記冷凍機油組成物の全量基準で5~45質量%の範囲にある冷凍機油組成物。
エステル添加剤(a);イソトリデカン酸とペンタエリスリトールとのエステル
エステル基油(b);炭素数4~9の脂肪族モノカルボン酸から選ばれる2種以上の脂肪族モノカルボン酸とペンタエリスリトールとからなるエステルを含む、多価アルコールのエステル - 請求項1に記載の冷凍機油組成物と、ハイドロフルオロオレフィンを含む冷媒とからなる冷凍機用作動流体組成物。
- 前記ハイドロフルオロオレフィンを含む冷媒が1,3,3,3-テトラフルオロプロペン(HFO-1234ze)または1,3,3,3-テトラフルオロプロペン(HFO-1234ze)とジフルオロメタン(HFC-32)との混合冷媒である請求項2に記載の冷凍機用作動流体組成物。
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