Classifications

• • 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
• • 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
• • 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
• • 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
  • C10N2020/02—Viscosity; Viscosity index
• • 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
  • C10N2020/09—Characteristics associated with water
  • C10N2020/097—Refrigerants
  • C10N2020/101—Containing Hydrofluorocarbons
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

• the present invention relates to a base oil for refrigeration oil, a refrigeration oil, and a working fluid composition.
• Refrigeration machines such as refrigerators, car air conditioners, room air conditioners, and vending machines are equipped with compressors to circulate refrigerant in the refrigeration cycle.
• the compressors are filled with refrigeration oil to lubricate the sliding parts.
• the refrigeration oil contains base oil as the main component.
• the base oil is selected according to the required characteristics.
• Patent Document 1 discloses a refrigeration oil that contains an ester of dipentaerythritol and a fatty acid, in which the proportion of 2-methylpentanoic acid in the fatty acid is 20 mol % or more.
• the ester is a hexaester and has a relatively large molecular weight, which is effective in maintaining the kinetic viscosity and refrigerant dissolution viscosity of the base oil (refrigeration oil) high at high temperatures (e.g., 100°C), but the kinetic viscosity and refrigerant dissolution viscosity at low temperatures (e.g., -20°C) become unnecessarily high.
• one aspect of the present invention aims to provide a refrigeration oil base oil, a refrigeration oil, and a working fluid composition that can maintain the kinetic viscosity on the high temperature side while keeping the refrigerant dissolution viscosity on the low temperature side low.
• a mixed base oil in which at least one selected from a diester of neopentyl glycol and a tetraester of pentaerythritol and a specific fatty acid is mixed with a hexaester can maintain the kinetic viscosity on the high temperature side while keeping the refrigerant dissolution viscosity on the low temperature side low.
• a base oil for refrigeration oils comprising at least one ester selected from the group consisting of a hexaester of dipentaerythritol and a fatty acid, a diester of neopentyl glycol and a fatty acid, and a tetraester of pentaerythritol and a fatty acid containing a fatty acid having 4 to 6 carbon atoms.
• a base oil for refrigeration oils comprising at least one ester selected from the group consisting of a hexaester of dipentaerythritol and a fatty acid, a diester of neopentyl glycol and a fatty acid, and a tetraester of pentaerythritol and a fatty acid containing a fatty acid having 4 to 6 carbon atoms.
• a refrigeration oil base oil a refrigeration oil
• a working fluid composition that can maintain a kinetic viscosity on the high temperature side while keeping the refrigerant dissolution viscosity on the low temperature side low.
• One embodiment of the present invention is a base oil for refrigeration oils, which contains at least one ester (hereinafter also referred to as “ester (B)”) selected from the group consisting of a hexaester of dipentaerythritol and a fatty acid (hereinafter also referred to as “ester (A)”), a diester of neopentyl glycol and a fatty acid (hereinafter also referred to as “ester (B-1)”), and a tetraester of pentaerythritol and a fatty acid containing a fatty acid having 4 to 6 carbon atoms (hereinafter also referred to as “ester (B-2)").
• ester selected from the group consisting of a hexaester of dipentaerythritol and a fatty acid (hereinafter also referred to as “ester (A)”), a diester of neopentyl glycol and a fatty acid
• the fatty acid constituting the ester (A) is preferably a saturated fatty acid, more preferably a saturated fatty acid having 4 to 9, 5 to 9, 6 to 9, 7 to 9, or 8 to 9 carbon atoms.
• the fatty acid may be linear or branched.
• the fatty acid preferably includes a fatty acid having a branch at the ⁇ -position and/or the ⁇ -position.
• the fatty acid more preferably includes at least one selected from the group consisting of 2-methylpropanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, neopentanoic acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-methylheptanoic acid, 2-ethylhexanoic acid, and 3,5,5-trimethylhexanoic acid, and from the viewpoint of easier maintenance of a high kinetic viscosity at 100°C, it is even more preferable to include at least one selected from the group consisting of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid.
• the fatty acid may be a mixed fatty acid of branched fatty acids.
• the mixed fatty acid include a mixed fatty acid of 2-methylpropanoic acid and 2-ethylhexanoic acid or 3,5,5-trimethylhexanoic acid, a mixed fatty acid of 2-methylbutanoic acid and 2-ethylhexanoic acid or 3,5,5-trimethylhexanoic acid, a mixed fatty acid of 2-methylpentanoic acid and 2-ethylhexanoic acid or 3,5,5-trimethylhexanoic acid, and a mixed fatty acid of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid.
• the fatty acid may be a straight-chain fatty acid, or a mixed fatty acid of a straight-chain fatty acid and a branched fatty acid.
• straight-chain fatty acids include n-butanoic acid, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, and n-nonanoic acid.
• Examples of mixed fatty acids of straight-chain fatty acids and branched fatty acids include a mixed fatty acid of n-pentanoic acid and 2-methylbutanoic acid, a mixed fatty acid of n-pentanoic acid and 3,5,5-trimethylhexanoic acid, a mixed fatty acid of n-heptanoic acid and 3,5,5-trimethylhexanoic acid, and a mixed fatty acid of n-pentanoic acid, n-heptanoic acid, and 3,5,5-trimethylhexanoic acid.
• the fatty acid constituting the ester (B-1) is preferably a saturated fatty acid, more preferably a saturated fatty acid having 4 to 9, 5 to 9, 6 to 9, 7 to 9, or 8 to 9 carbon atoms.
• the fatty acid may be linear or branched.
• the fatty acid is preferably branched, more preferably selected from 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid, and even more preferably 3,5,5-trimethylhexanoic acid.
• the fatty acid constituting the ester (B-2) includes a fatty acid having 4 to 6 carbon atoms (hereinafter also referred to as "C4-C6 acid").
• the C4-C6 acid is preferably a saturated fatty acid, more preferably a saturated fatty acid having 4 to 5 or 4 carbon atoms.
• the C4-C6 acid may be linear or branched.
• the C4-C6 acid may be at least one selected from the group consisting of linear or branched butanoic acid, linear or branched pentanoic acid, and linear or branched hexanoic acid, preferably at least one selected from the group consisting of branched butanoic acid, branched pentanoic acid, and branched hexanoic acid, more preferably at least one selected from the group consisting of 2-methylpropanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, neopentanoic acid, and 2-methylpentanoic acid, at least one selected from the group consisting of 2-methylpropanoic acid and 2-methylbutanoic acid, and even more preferably 2-methylpropanoic acid.
• the fatty acid constituting the ester (B-2) may further contain other fatty acids in addition to the C4-C6 acids.
• the other fatty acids are preferably fatty acids having 7 to 9 carbon atoms (hereinafter also referred to as "C7-C9 acids").
• the C7-C9 acids are preferably saturated fatty acids, more preferably saturated fatty acids having 8 to 9 carbon atoms.
• the C7-C9 acids may be linear or branched.
• the C7-C9 acids are preferably branched, more preferably selected from 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid, and even more preferably 3,5,5-trimethylhexanoic acid.
• the fatty acid constituting the ester (B-2) may be a mixed fatty acid of a linear fatty acid and a branched fatty acid.
• An example of such a mixed fatty acid is a mixed fatty acid of one or more selected from n-pentanoic acid and n-heptanoic acid and 3,5,5-trimethylhexanoic acid.
• the molar ratio of C4-C6 acids to C7-C9 acids (C4-C6 acids/C7-C9 acids) in the fatty acids constituting the ester (B-2) may be 10/90 or more, 20/80 or more, or 30/70 or more, and may be 90/10 or less, 80/20 or less, 70/30 or less, 60/40 or less, or 50/50 or less.
• Ester (A) may contain an ester having 40 or more or 50 or more carbon atoms, and from the viewpoint of easily maintaining a high kinetic viscosity at 100°C, preferably contains an ester having 54 or more or 60 or more and 64 or less carbon atoms.
• the number of carbon atoms in ester (A) is 34 to 64.
• Ester (B) may contain an ester having 38 or less or 35 or less carbon atoms, and preferably contains an ester having 31 or less or 25 or less carbon atoms, or 18 or more or 20 or more carbon atoms, from the viewpoint of increasing the amount of refrigerant dissolved at low temperatures and easily decreasing the refrigerant dissolving viscosity at low temperatures.
• the number of carbon atoms in ester (B-1) is 13 to 23.
• the number of carbon atoms in ester (B-2) is 21 to 41.
• the difference between the maximum carbon number (maximum carbon number) of the esters and the minimum carbon number (minimum carbon number) of the esters in the mixture of esters (A) and (B) is preferably 28 or more, 35 or more, 37 or more, or 41 or more, and is preferably 46 or less or 44 or less.
• the average carbon number of the ester (A) may be 40 or more or 50 or more, preferably 54 or more or 60 or more, and may be 64 or less.
• the average carbon number of the ester (B) may be 38 or less or 35 or less, preferably 31 or less or 25 or less, and preferably 18 or more or 20 or more.
• the average carbon number of the mixture of the ester (A) and the ester (B) contained in the base oil is preferably 35 or more, 38 or more, or 40 or more, and preferably 58 or less, 55 or less, 52 or less, 48 or less, or 45 or less.
• the value obtained by dividing the difference between the maximum and minimum carbon numbers in a mixture of ester (A) and ester (B) by the average carbon number is preferably 0.70 or more, 0.80 or more, 0.85 or more, or 0.90 or more, and preferably 1.50 or less, 1.20 or less, 1.00 or less, or 0.97 or less.
• this value indicates the degree of dispersion of the molecular weight of the ester, and even with the same average carbon number, the value is 0 for a single molecule, and increases as the maximum and minimum values of the molecular weight of the ester increase, but it is preferable that the value is within the above range in terms of the balance between the refrigerant compatibility, flash point, 100°C kinetic viscosity, and the effect of reducing the refrigerant dissolution viscosity.
• the ratio (Mw/Mn) of the number average molecular weight (Mn) to the weight average molecular weight (Mw) in the mixture of ester (A) and ester (B) may be 1.01 or more, 1.05 or more, or 1.10 or more, and may be 1.5 or less, 1.4 or less, or 1.3 or less.
• Mw and Mn refer to values obtained by GPC analysis (converted into polystyrene (standard sample) values).
• a solution is prepared using tetrahydrofuran as a solvent, diluted to a sample concentration of 1 mass%, and a GPC device (for example, Waters ACQUITY APC UV RI system) is used to perform analysis with a solvent flow rate of 0.7 ml/min and a temperature of 40°C, using a column with an analyzable molecular weight of 100 to 10,000, and a refractive index detector.
• a GPC device for example, Waters ACQUITY APC UV RI system
• a column retention time and the molecular weight is obtained using a polystyrene standard with a clear molecular weight, and a calibration curve is separately prepared, and the molecular weight is determined from the obtained retention time.
• the content of ester (A) and ester (B) (and further ester (B-1) and ester (B-2)) in the base oil is appropriately adjusted according to the desired kinematic viscosity of the base oil, etc.
• the content of ester (A) in the base oil may be 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, or 50 mass% or more based on the total amount of the base oil, and may be 90 mass% or less, 80 mass% or less, 70 mass% or less, 60 mass% or less, or 50 mass% or less.
• the content of ester (B) in the base oil may be 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more based on the total amount of the base oil, and may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less.
• the content of ester (B-1) in the base oil may be 1 mass% or more, 3 mass% or more, 5 mass% or more, 10 mass% or more, or 20 mass% or more, based on the total amount of the base oil, and may be 50 mass% or less, 45 mass% or less, 40 mass% or less, 35 mass% or less, or 30 mass% or less.
• the content of ester (B-2) in the base oil may be 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, or 50% by mass or more, and may be 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, or 70% by mass or less, based on the total amount of the base oil.
• the ester (B) may contain either the ester (B-1) or the ester (B-2), or may contain both the ester (B-1) and the ester (B-2).
• the ester (B) preferably contains both the ester (B-1) and the ester (B-2).
• the base oil preferably contains the ester (A), the ester (B-1), and the ester (B-2).
• the content of ester (B-1) may be 1 mass% or more, 3 mass% or more, 5 mass% or more, 7 mass% or more, or 9 mass% or more based on the total amount of the base oil, and may be 50 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, or 15 mass% or less.
• ester (B-2) may be 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, or 50 mass% or more based on the total amount of the base oil, and may be 90 mass% or less, 80 mass% or less, 70 mass% or less, 60 mass% or less, or 50 mass% or less.
• the proportion of dipentaerythritol in the total amount of alcohol constituting the ester (A) and the ester (B) in the base oil may be 5 mol% or more, 10 mol% or more, 15 mol% or more, or 20 mol% or more, and may be 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, or 30 mol% or less.
• the proportion of neopentyl glycol in the total amount of alcohol constituting the ester (A) and ester (B) in the base oil may be 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, or 20 mol% or less, or may be 0 mol%, 5 mol% or more, or 10 mol% or more.
• the proportion of pentaerythritol in the total amount of alcohol constituting the ester (A) and the ester (B) in the base oil may be 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, or 30 mol% or less, or it may be 0 mol%, or it may be 5 mol% or more, 10 mol% or more, 15 mol% or more, or 20 mol% or more.
• the proportion of C7-C9 acids in the total amount of fatty acids constituting the esters (A) and (B) in the base oil may be 40 mol% or more, 50 mol% or more, 60 mol% or more, or 70 mol% or more, or may be 100 mol%, or may be 90 mol% or less, 85 mol% or less, or 80 mol% or less.
• the proportion of fatty acids with 8 to 9 carbon atoms (C8-C9 acids) in the total amount of fatty acids constituting the esters (A) and esters (B) in the base oil may be within the above range.
• the proportion of fatty acids having 9 carbon atoms (C9 acids) in the total amount of fatty acids constituting the esters (A) and (B) in the base oil may be 10 mol% or more, 30 mol% or more, 40 mol% or more, or 50 mol% or more, and may be 90 mol% or less, 85 mol% or less, 80 mol% or less, 75 mol% or less, or 70 mol% or less.
• the proportion of fatty acids having 8 carbon atoms (C8 acids) in the total amount of fatty acids constituting the esters (A) and (B) in the base oil may be 80 mol% or less, 85 mol% or less, 50 mol% or less, 30 mol% or less, 20 mol% or less, 16 mol% or less, or 14 mol% or less, and may be 5 mol% or more, 7 mol% or more, 9 mol% or more, or 10 mol% or more.
• the proportion of C4-C6 acids in the fatty acids constituting the esters (A) and (B) in the base oil may be 50 mol% or less, 35 mol% or less, 30 mol% or less, or 26 mol% or less, or 5 mol% or more, 10 mol% or more, 15 mol% or more, or 20 mol% or more.
• the proportion of fatty acids with 4 carbon atoms (C4 acids), the proportion of fatty acids with 5 carbon atoms (C5 acids), or the sum of C4 acids and C5 acids in the total amount of fatty acids constituting the esters (A) and (B) in the base oil may each be within the above range.
• the ratio of C4-C6 acids to C7-C9 acids (molar ratio of C4-C6 acids/C7-C9 acids) in the fatty acids constituting the esters (A) and (B) in the base oil may be 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, or 0.4 or less, or may be 0, 0.1 or more, 0.15 or more, or 0.2 or more.
• the ratio of C4 acids to C8-C9 acids (molar ratio of C4 acids/C8-C9 fatty acids) in the fatty acids constituting the esters (A) and (B) in the base oil may be 0.9 or less, 0.8 or less, 0.7 or less, 0.6 or less, 0.5 or less, or 0.4 or less, or may be 0, 0.1 or more, 0.15 or more, or 0.2 or more.
• the ratio of C5 acids to C8-C9 acids (molar ratio of C5 acids/C8-C9 fatty acids) in the fatty acids constituting the esters (A) and (B) in the base oil, or the ratio of the sum of C4 acids and C5 acids to C8-C9 acids (molar ratio of C4 acids and C5 acids/C8-C9 fatty acids) may be in the above range.
• the average carbon number of the fatty acids constituting the ester (A) and the ester (B) in the base oil may be 5 or more, 6 or more, 6.5 or more, 7 or more, or 7.5 or more, and may be 9.0 or less, 8.4 or less, 8.2 or less, or 8.0 or less.
• the kinetic viscosity of the ester (A) at 40°C may be 40 mm 2 /s or more, 100 mm 2 /s or more, 150 mm 2 /s or more, or 200 mm 2 /s or more, and may be 500 mm 2 /s or less, 400 mm 2 /s or less, 300 mm 2 /s or less, or 250 mm 2 /s or less.
• the kinetic viscosity of the ester (B) at 40°C may be 3 mm 2 /s or more, 5 mm 2 /s or more, 10 mm 2 /s or more, or 20 mm 2 /s or more, and may be 100 mm 2 /s or less, 90 mm 2 /s or less, 80 mm 2 /s or less, or 70 mm 2 /s or less.
• the kinetic viscosity of the ester (B-1) at 40° C. may be 3 mm 2 /s or more, 5 mm 2 /s or more, or 10 mm 2 /s or more, and may be 50 mm 2 /s or less, 30 mm 2 /s or less, 20 mm 2 /s or less, or 15 mm 2 /s or less.
• the kinetic viscosity of the ester (B-2) at 40° C. may be 20 mm 2 /s or more, 30 mm 2 /s or more, 40 mm 2 /s or more, or 50 mm 2 /s or more, and may be 100 mm 2 /s or less, 90 mm 2 /s or less, 80 mm 2 /s or less, or 70 mm 2 /s or less.
• the kinematic viscosity of the base oil at 40°C may be 10 mm 2 /s or more, 20 mm 2 /s or more, 30 mm 2 /s or more, 40 mm 2 /s or more, 50 mm 2 /s or more, 60 mm 2 /s or more, or 70 mm 2 /s or more, and may be 500 mm 2 /s or less, 400 mm 2 /s or less, 300 mm 2 /s or less, 200 mm 2 /s or less, 150 mm 2 /s or less, 100 mm 2 /s or less, 90 mm 2 /s or less, or 80 mm 2 /s or less.
• the kinetic viscosity at 100°C of the ester (A) may be 5 mm2 /s or more, 10 mm2 /s or more, 15 mm2 /s or more, or 20 mm2 /s or more, and may be 50 mm2 /s or less, 40 mm2 /s or less, 30 mm2 /s or less, or 20 mm2 /s or less.
• the kinetic viscosity at 100°C of the ester (B) may be 1 mm2 /s or more, 2 mm2 /s or more, 3 mm2 /s or more, or 5 mm2 /s or more, and may be 20 mm2 /s or less, 15 mm2 /s or less, 10 mm2 /s or less, or 8.5 mm2 /s or less.
• the kinetic viscosity at 100° C. of the ester (B-1) may be 1 mm 2 /s or more, 1.5 mm 2 /s or more, 2 mm 2 /s or more, or 2.5 mm 2 /s or more, and may be 5 mm 2 /s or less, 4 mm 2 /s or less, or 3.5 mm 2 /s or less.
• the kinetic viscosity at 100° C. of the ester (B-2) may be 3 mm 2 /s or more, 5 mm 2 /s or more, 6 mm 2 /s or more, or 8 mm 2 /s or more, and may be 20 mm 2 /s or less, 15 mm 2 /s or less, 10 mm 2 /s or less, or 8.5 mm 2 /s or less.
• the kinematic viscosity of the base oil at 100°C may be 5 mm2 /s or more, 6 mm2 /s or more, 7 mm2 /s or more, 8 mm2 /s or more, 8.5 mm2 /s or more, or 9 mm2 /s or more, and may be 50 mm2 /s or less, 40 mm2 /s or less, 30 mm2 /s or less, 20 mm2 /s or less, 15 mm2 /s or less, 13 mm2 /s or less, 11 mm2 /s or less, or 10.5 mm2 /s or less.
• the kinematic viscosity of the base oil at -20°C may be 5000 mm 2 /s or more, 10000 mm 2 /s or more, 12000 mm 2 /s or more, 14000 mm 2 /s or more, or 20000 mm 2 /s or more, and may be 50000 mm 2 /s or less, 45000 mm 2 /s or less, 40000 mm 2 /s or less, 35000 mm 2 /s or less, or 30000 mm 2 /s or less.
• the viscosity index of ester (A), ester (B), ester (B-1), and ester (B-2) may be 50 or more, 60 or more, 70 or more, or 80 or more, and may be 150 or less, 130 or less, 120 or less, or 100 or less.
• the viscosity index of the base oil may be 70 or more, 80 or more, or 90 or more, and may be 150 or less, 130 or less, or 110 or less.
• the kinetic viscosity and viscosity index refer to the kinetic viscosity and viscosity index measured in accordance with JIS K2283:2000.
• the refrigeration oil base oil described above can maintain the kinetic viscosity on the high temperature side while keeping the refrigerant dissolution viscosity on the low temperature side low.
• the refrigeration oil base oil can also have excellent refrigerant compatibility.
• the refrigeration oil base oil can also keep the kinetic viscosity on the low temperature side low.
• Another embodiment of the present invention is a refrigeration oil containing the above-mentioned base oil for refrigeration oil.
• the above-mentioned base oil for refrigeration oil is included in the refrigeration oil as a base oil constituting the refrigeration oil.
• the refrigeration oil may contain the base oil as a main component.
• the content of the base oil may be 50 mass% or more, 70 mass% or more, 90 mass% or more, or 95 mass% or more based on the total amount of the refrigeration oil.
• the content of ester (A) in the refrigerating machine oil may be 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more based on the total amount of the refrigerating machine oil, and may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less.
• the content of ester (B) in the refrigerating machine oil may be 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more based on the total amount of the refrigerating machine oil, and may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less.
• the content of ester (B-1) in the refrigerating machine oil may be 1 mass% or more, 3 mass% or more, 5 mass% or more, 10 mass% or more, or 20 mass% or more based on the total amount of the refrigerating machine oil, and may be 50 mass% or less, 45 mass% or less, 40 mass% or less, 35 mass% or less, or 30 mass% or less.
• the content of ester (B-2) in the refrigerating machine oil may be 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, or 50% by mass or more, and may be 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, or 70% by mass or less, based on the total amount of the refrigerating machine oil.
• the content of the ester (B-1) may be 1 mass% or more, 3 mass% or more, 5 mass% or more, 7 mass% or more, or 9 mass% or more based on the total amount of the refrigerating machine oil, and may be 50 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, or 15 mass% or less.
• the content of the ester (B-2) may be 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, or 50 mass% or more based on the total amount of the refrigerating machine oil, and may be 90 mass% or less, 80 mass% or less, 70 mass% or less, 60 mass% or less, or 50 mass% or less.
• the base oil constituting the refrigeration oil may contain only the above-mentioned refrigeration oil base oil, or may further contain other base oils in addition to the above-mentioned refrigeration oil base oil.
• the other base oil may be a hydrocarbon oil, and may be a mineral oil or a synthetic hydrocarbon oil.
• mineral oil include paraffinic or naphthenic mineral oils that are made from crude oil or its distillation residue oil and refined by an appropriate combination of normal petroleum refining processes (solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, clay treatment, distillation, etc.).
• Examples of synthetic hydrocarbon oils include poly- ⁇ -olefins or their hydrogenated products, normal paraffins, isoparaffins, alkylbenzenes, alkylnaphthalenes, etc.
• the other base oil may be an oxygen-containing oil other than ester (A) and ester (B).
• oxygen-containing oils include esters other than ester (A) and ester (B), ethers, carbonates, ketones, silicones, polysiloxanes, etc.
• esters include monoesters, polyol esters other than ester (A) and ester (B), aromatic esters, dibasic acid esters, complex esters, and carbonate esters.
• ethers include polyvinyl ethers, polyalkylene glycols, polyphenyl ethers, and perfluoroethers.
• the refrigeration oil may further contain additives.
• additives include anti-wear agents, antioxidants, acid scavengers, oxygen scavengers, metal deactivators, pour point depressants, detergent dispersants, and antifoaming agents.
• the total content of the additives may be 10% by mass or less or 5% by mass or less based on the total amount of the refrigeration oil.
• the kinetic viscosity of the refrigeration oil at 40°C may be 10 mm 2 /s or more, 20 mm 2 /s or more, 30 mm 2 /s or more, 40 mm 2 /s or more, 50 mm 2 /s or more, 60 mm 2 /s or more, 70 mm 2 /s or more, or 75 mm 2 /s or more, and may be 500 mm 2 /s or less, 400 mm 2 /s or less, 300 mm 2 /s or less, 200 mm 2 /s or less, 150 mm 2 /s or less, 100 mm 2 /s or less, 90 mm 2 /s or less, or 87 mm 2 /s or less.
• the kinetic viscosity of the refrigerating oil at 100°C may be 5 mm 2 /s or more, 6 mm 2 /s or more, 7 mm 2 /s or more, 8 mm 2 /s or more, 8.5 mm 2 /s or more, 9 mm 2 /s or more, or 9.5 mm 2 /s or more, and may be 50 mm 2 /s or less, 30 mm 2 /s or less, 20 mm 2 /s or less, 15 mm 2 /s or less, 13 mm 2 /s or less, 12 mm 2 /s or less, or 11 mm 2 /s or less.
• the kinetic viscosity of the refrigerating machine oil at -20°C may be 5,000 mm 2 /s or more, 10,000 mm 2 /s or more, 12,000 mm 2 /s or more, 14,000 mm 2 /s or more, or 20,000 mm 2 /s or more, and may be 50,000 mm 2 /s or less, 45,000 mm 2 /s or less, 40,000 mm 2 /s or less, 35,000 mm 2 /s or less, or 30,000 mm 2 /s or less.
• the viscosity index of the refrigeration oil may be 70 or more, 80 or more, or 90 or more, and may be 150 or less, 130 or less, or 110 or less.
• the refrigeration oil may be present in the refrigerator in the form of a working fluid composition mixed with a refrigerant. That is, another embodiment of the present invention is a working fluid composition containing the above-mentioned refrigeration oil and a refrigerant.
• the content of the refrigeration oil in the working fluid composition may be 1 part by mass or more or 2 parts by mass or more, and may be 500 parts by mass or less or 400 parts by mass or less, per 100 parts by mass of the refrigerant.
• refrigerants include saturated fluorohydrocarbons (also called HFCs), unsaturated fluorohydrocarbons (also called HFOs), hydrocarbons, fluorine-containing ethers, bis(trifluoromethyl)sulfide, trifluoroiodomethane, ammonia, and carbon dioxide.
• HFCs saturated fluorohydrocarbons
• HFOs unsaturated fluorohydrocarbons
• hydrocarbons fluorine-containing ethers
• fluorine-containing ethers also called bis(trifluoromethyl)sulfide, trifluoroiodomethane, ammonia, and carbon dioxide.
• the refrigerant may be one of these refrigerants alone or a mixture of two or more of them.
• the refrigerant preferably contains at least one selected from the group consisting of unsaturated fluorohydrocarbons and hydrocarbons, and more preferably contains at least one selected from the group consisting of unsaturated fluorohydrocarbons.
• unsaturated fluorohydrocarbons include unsaturated fluorohydrocarbons having 2 to 4 carbon atoms, which have one or more carbon-carbon double bonds and which have fluorine and hydrogen.
• the unsaturated fluorohydrocarbons are preferably fluoropropenes, more preferably fluoropropenes having 3 to 5 fluorines.
• unsaturated fluorohydrocarbons include 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,2,3,3-tetrafluoropropene (HFO-1234ye), and 3,3,3-trifluoropropene (HFO-1243zf).
• the unsaturated fluorohydrocarbon is preferably at least one selected from HFO-1225ye, HFO-1234ze, and HFO-1234yf.
• the unsaturated fluorohydrocarbon may be fluoroethylene, preferably fluoroethylene having 1 to 3 fluorine atoms, and more specifically, may be at least one selected from monofluoroethylene (HFO-1141), 1,1-difluoroethylene (HFO-1132a), (E)-1,2-difluoroethylene (HFO-1132(E)), (Z)-1,2-difluoroethylene (HFO-1132(Z)), and 1,1,2 trifluoroethylene (R1123).
• the unsaturated fluorohydrocarbon may be a fluorobutene, preferably a fluorobutene having 1 to 7 fluorine atoms and 4 carbon atoms, and more specifically, for example, at least one selected from (E)-1,1,1,4,4,4-hexafluoro-2-butene (R1336mzz(E)) and (Z)-1,1,1,4,4,4-hexafluoro-2-butene (R1336mzz(Z)).
• the unsaturated fluorohydrocarbon may be an unsaturated fluorohydrocarbon having a chlorine atom and a fluorine atom, and specifically may be, for example, at least one selected from 1-chloro-2,2-difluoroethylene (HCFO-1122), (Z)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(Z)), and (E)-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd(E)).
• HCFO-1122 1-chloro-2,2-difluoroethylene
• Z Z-1-chloro-2,3,3,3-tetrafluoropropene
• E E-1-chloro-2,3,3,3-tetrafluoropropene
• the refrigerant may be a mixed refrigerant containing the above-mentioned unsaturated fluorohydrocarbons having 2 to 4 carbon atoms.
• Specific examples of the mixed refrigerant include R444A, R444B, R445A, R446A, R447A, R447B, R448A, R448B, R449A, R449B, R449C, R450A, R451A, R451B, R452A, R452B, R452C, R454A, R454B, R454C, R455A, R455C, R455D, R456A, R457A, R457B, R457C, R457D, R459A, R459B, R460A, R460B, Examples include refrigerants containing R460C, R463A, R464A, R465A, R468A, R468B, R468C, R
• the GWP of the above-mentioned unsaturated fluorohydrocarbon refrigerants or mixed refrigerants containing unsaturated fluorohydrocarbons may be, for example, 1500 or less, 1000 or less, 500 or less, 300 or less, 150 or less, 100 or less, or 10 or less.
• the hydrocarbon is preferably a hydrocarbon having 1 to 5 carbon atoms, more preferably a hydrocarbon having 2 to 4 carbon atoms.
• Examples of the hydrocarbon include methane, ethylene, ethane, propylene (R1270), propane (R290), cyclopropane, normal butane, isobutane, cyclobutane, methylcyclopropane, 2-methylbutane, and normal pentane.
• the hydrocarbon is preferably a single refrigerant or a mixed refrigerant of two or more types selected from the group consisting of propane, propylene, normal butane, isobutane, and 2-methylbutane.
• base oils (refrigerating machine oils) were prepared having the compositions (mass % based on the total amount of base oil) shown in Tables 1 and 2.
• the blending ratio of the esters was adjusted so that the kinematic viscosity of each base oil (refrigerating machine oil) at 100°C was approximately the same within the range of 8.5 to 10.5 mm2 /s.
• Ester (A) Hexaester of dipentaerythritol (DiPE) and fatty acid (mixed fatty acid of 50 mol% 2-ethylhexanoic acid (iC8 acid) and 50 mol% 3,5,5-trimethylhexanoic acid (iC9 acid)) (average carbon number: 61, maximum carbon number: 64)
• Ester (B-1) Diester of neopentyl glycol (NPG) and 2-ethylhexanoic acid (iC8 acid) (average carbon number: 21, minimum carbon number: 21, 100° C. kinematic viscosity: 2.0 mm 2 /s, viscosity index: 56) Diester of neopentyl glycol (NPG) and 3,5,5-trimethylhexanoic acid (iC9 acid) (average carbon number: 23, minimum carbon number: 23, 100° C. kinematic viscosity: 3.1 mm 2 /s, viscosity index: 101)
• Ester (B-2) Tetraester of pentaerythritol (PE) and fatty acid (mixed fatty acid of 60 mol % of 2-methylpropanoic acid (iC4 acid) and 40 mol % of 3,5,5-trimethylhexanoic acid (iC9 acid)) (average carbon number: 29, minimum carbon number: 21, 100° C.
• kinematic viscosity 6.3 mm 2 /s
• viscosity index: 78 - Tetraester of pentaerythritol (PE) and fatty acid (mixed fatty acid of 37 mol % of 2-methylpropanoic acid (iC4 acid) and 63 mol % of 3,5,5-trimethylhexanoic acid (iC9 acid)) (average carbon number: 34, minimum carbon number: 21, 100°C kinematic viscosity: 8.2 mm2 /s, viscosity index: 84) Ester (C) Tetraester of pentaerythritol (PE) and fatty acid (mixed fatty acid of 48 mol % of 2-ethylhexanoic acid (iC8 acid) and 52 mol % of 3,5,5-trimethylhexanoic acid (iC9 acid)) (average carbon number: 39, minimum carbon number: 37, 100° C. kinematic viscosity:
• the kinematic viscosity and viscosity index of each of the obtained base oils (refrigeration oils) were measured at -20°C, 40°C, and 100°C in accordance with JIS K2283:2000. In addition, the following measurements were performed using each of the obtained base oils (refrigeration oils). The measurement results are shown in Tables 1 and 2.
• Each refrigerating machine oil was filled into a pressure vessel equipped with a vibration viscometer, a thermometer, and a pressure gauge. After vacuum degassing the pressure vessel, a refrigerant (HFO-1234yf) was filled so that the refrigerant ratio was about 13.6%, and a working fluid composition consisting of a refrigerating machine oil and a refrigerant was prepared (about half the volume of the pressure vessel).
• a refrigerant HFO-1234yf
• the absolute viscosity P (mPa ⁇ s) of the working fluid composition was measured using a vibration viscometer, and the refrigerant dissolution viscosity (mm 2 /s) was calculated from the measurement result of the density (g/cm 3 ) of the working fluid composition.
• Rf Amount of refrigerant charged into the pressure vessel (g)
• Dv refrigerant vapor density (g/cm 3 )
• the refrigerant solution viscosity R-Vis ( mm2 /s) was calculated as P/Dw, obtained by dividing the absolute viscosity P (mPa ⁇ s) by the density Dw (g/ cm3 ) of the working fluid composition.

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