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
  • C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
• • 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
  • 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
• • 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
  • C10N2020/069—Linear chain compounds
• • 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
• • 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
  • 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
• • 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
  • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
• • 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 refrigeration lubricant composition. More specifically, the present invention relates to a refrigeration lubricant composition that is used for a chlorine-free hydrofluorocarbon refrigerant, wherein the composition comprises a polyol ester as the main component and has excellent low-temperature stability, lubricity, stability under coexistence with a chlorine-free hydrofluorocarbon refrigerant, and has excellent compatibility with chlorine-free hydrofluorocarbon refrigerants.
• the present invention also relates to a refrigerant working fluid containing the refrigeration lubricant composition and a refrigerating apparatus including the refrigerant working fluid.
• refrigerants containing chlorofluorocarbon have been used for air conditioning equipment such as room air conditioners and packaged air conditioners, low temperature apparatuses such as refrigerator-freezers for home use, industrial refrigerators, and automotive air conditioners such as hybrid cars and electric cars.
• chlorofluorocarbon refrigerants such as those containing 1,1,1,2-tetrafluoroethane (R-134a), pentafluoroethane (R-125), difluoromethane (R-32), and mixtures thereof has been promoted because of problems such as the depletion of the ozone layer. Consequently, a variety of refrigeration oils containing a polyol ester, which has good compatibility with chlorine-free hydrofluorocarbon refrigerants, as a base stock have been proposed.
• 10-8084 discloses refrigeration oils containing an ester obtained from pentaerythritol and a mixed fatty acid of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid as the main component and discloses that such refrigeration oils have good stability at high temperatures.
• Japanese Laid-Open Patent-Publication No. 5-209181 discloses esters obtained from pentaerythritol, dipentaerythritol, and tripentaerythritol and discloses the viscosity and the compatibility with fluorocarbons of such esters.
• 6-330061 discloses refrigeration oils containing an ester obtained from pentaerythritol and a mixed fatty acid of a linear or branched fatty acid having 6 to 8 carbon atoms and 3,5,5-trimethylhexanoic acid as the main component.
• the publication discloses that such refrigeration oils have an excellent compatibility with refrigerants and have improved electric insulation properties.
• esters obtained from a fatty acid mixture and a polyhydric alcohol wherein the fatty acid mixture includes 3,5,5-trimethylhexanoic acid and a saturated fatty acid other than 3,5,5-trimethylhexanoic acid, wherein the saturated fatty acid has an alkyl group as a side chain and has a total of 9 carbon atoms.
• a part of the refrigeration lubricant In a refrigerating cycle, a part of the refrigeration lubricant generally circulates through the cycle along with a refrigerant, and thus the refrigeration lubricant is exposed to a high temperature region and a low temperature region.
• the above-described hindered esters in particular, the mixed esters of the patent publications noted above satisfy the performance requirements.
• a part of the refrigeration lubricant ejected from the compressor may stagnate in the low temperature region.
• the lubricant stagnates in the low temperature region for a long period of time, then it is crystallized and the amount of the circulating refrigerant in the refrigerating cycle is reduced, which may lead to problems such as poor refrigeration. Therefore, it is critical to the reliability of refrigerating apparatuses to develop a refrigeration lubricant higher stability in which no precipitation occurs over a long period of time even at low temperatures.
• the mixed esters obtained from a combination of a polyhydric alcohol and a specific carboxylic acid as described in the patent publications noted above have not been sufficiently examined for their ability of maintaining low-temperature stability over a long period of time. Thus, it is not possible to prevent crystallization from occurring in the low temperature region, and thus these esters lack long-term stability.
• the inventors of the present invention carefully examined the low-temperature stability of refrigeration lubricant compositions and the compatibility thereof with chlorine-free hydrofluorocarbon refrigerants and performed molecular design by combining a variety of polyhydric alcohols with mixed carboxylic acids containing a variety of carboxylic acids having different structures. As a result, the inventors found that the above-described problems can be solved by an ester obtained by reacting a mixed alcohol containing pentaerythritol and dipentaerythritol in a specific ratio with a mixed carboxylic acid containing a specific amount of isononanoic acid, and thus the present invention was accomplished.
• a mixed carboxylic acid is constituted by considering the length of a main chain (regardless of whether a linear carboxylic acid or a branched carboxylic acid) and the length of the longest side chain of branched carboxylic acids; and the carboxylic acids in the mixed carboxylic acid and the alcohols in the mixed alcohol satisfy a certain quantitative relation.
• the refrigeration lubricant composition of the present invention comprises a mixed ester obtained from a mixed alcohol and a mixed carboxylic acid as a main component; and the mixed alcohol includes 65 to 99.95 mol % of pentaerythritol and 0.05 to 35 mol % of dipentaerythritol, the mixed carboxylic acid includes 25 to 55 mol % of monocarboxylic acid having 5 to 8 carbon atoms and 45 to 75 mol % of isononanoic acid, and the composition has a hydroxyl value of 5.0 mgKOH/g or less and an acid value of 0.05 mgKOH/g or less.
• the mixed ester is obtained by a reaction of the mixed alcohol and the mixed carboxylic acid, wherein the mixed carboxylic acid and the mixed alcohol comprise carboxylic acids and alcohols, respectively, which satisfy the following relation: 1.09 ⁇ ⁇ ⁇ ⁇ ( A ⁇ B ) - ( C ⁇ D ) ⁇ E ⁇ 1.33 ( 1 )
• a kinematic viscosity of the composition at 40° C. is 30 to 150 mm 2 /s.
• the isononanoic acid contains 88.50 to 99.95 mol % of 3,5,5-trimethylhexanoic acid.
• the composition is used for a chlorine-free hydrofluorocarbon refrigerant.
• the refrigerant working fluid of the present invention comprises the refrigeration lubricant composition and a chlorine-free hydrofluorocarbon refrigerant.
• the refrigerant compression type refrigerating apparatus of the present invention comprises a compressor, a condenser, an expansion mechanism, an evaporator, and the above mentioned working fluid.
• the refrigeration lubricant composition of the present invention does not cause precipitation of crystals over a long period of time in the low temperature region, and thus it has excellent low-temperature stability. Moreover, it also has good lubricity, stability under coexistence with a chlorine-free hydrofluorocarbon refrigerant (evaluated by sealed tube test), and compatibility with chlorine-free hydrofluorocarbon refrigerants, which are required for refrigeration lubricant compositions. Therefore, the refrigeration lubricant composition of the present invention is useful for a lubricant for refrigerating machines that employ a chlorine-free hydrofluorocarbon refrigerant or as a refrigerant working fluid in which it is mixed with a chlorine-free hydrofluorocarbon refrigerant.
• an ester obtained by reacting a mixed alcohol containing pentaerythritol and dipentaerythritol in a specific ratio with a mixed carboxylic acid containing a specific amount of isononanoic acid and, if necessary, containing a carboxylic acid other than isononanoic acid has excellent low-temperature stability.
• a mixed ester contained in the composition of the present invention a refrigeration lubricant composition containing the mixed ester, a refrigerant working fluid containing the composition, and a refrigerant compression type refrigerating apparatus employing the refrigerant working fluid will be described;
• the mixed ester contained in the refrigeration lubricant composition of the present invention is obtained by reacting a mixed alcohol and mixed carboxylic acids, wherein the mixed alcohol comprises 65 to 99.95 mol % of pentaerythritol and 0.05 to 35 mol % of dipentaerythritol, and wherein the mixed carboxylic acid comprises 25 to 55 mol % of monocarboxylic acid having 5 to 8 carbon atoms and 45 to 75 mol % of isononanoic acid.
• reaction between the mixed alcohol and the mixed carboxylic acid that are employed satisfy the following relation: 1.09 ⁇ ⁇ ⁇ ⁇ ( A ⁇ B ) - ( C ⁇ D ) ⁇ E ⁇ 1.33 ( 1 )
• the inventors of the present invention found the following: when a mixed ester contains branched esters that are derived from carboxylic acids having a side chain or side chains with different carbon numbers, the carboxylic acid having the longest side chain contributes to the low temperature stability of the mixed ester more effectively than carboxylic acids having a shorter branched chain does.
• the inventors conducted molecular design of esters and found that when the above-noted formula was satisfied, a mixed ester having excellent low-temperature stability over a longer period of time could be obtained.
• “Number of carbon atoms in main chain of a carboxylic acid in the mixed carboxylic acid” defined in item A of the above-noted relation refers to the number of carbon atoms of the longest chain of the carboxylic acid and excluding carbon atoms in side chains.
• the number of carbon atoms in the main chain of the carboxylic acid is 8.
• the number of carbon atoms in the main chain of the carboxylic acid is 6, which is obtained by subtracting 2 (i.e., the number of carbon atoms in the branched ethyl group) from the total number of carbon atoms 8 in the carboxylic acid (i.e., 2-ethylhexanoic acid).
• Molar fraction of carboxylic acid of item A defined in item B of the above-noted relation refers to a value of the molar amount of the carboxylic acid having the number of carbon atoms in main chain defined in item A when the total molar amount of the mixed carboxylic acid is 1.
• “Number of carbon atoms in the longest side chain of carboxylic acids in the mixed carboxylic acid” defined in item C of the above-noted relation refers to the number of carbon atoms in the longest side chain of carboxylic acids having the longest side chain in the branched carboxylic acids that are contained in the mixed carboxylic acid.
• the number of carbon atoms in the longest side chain is 2, which is the number of carbon atoms from the ethyl group of 2-ethylhexanoic acid.
• Molar fraction of carboxylic acid having the longest branched chain defined in item D of the above-noted relation refers to a value of the molar amount of the carboxylic acid having the longest side chain when the total molar amount of the mixed carboxylic acid is 1.
• Average number of hydroxyl groups of each alcohol in the mixed alcohol refers to the sum of values, each of which is obtained by multiplying the number of hydroxyl groups of each alcohol contained in a mixed alcohol by the molar fraction of each alcohol, wherein molar fraction is a value of the molar amount of that alcohol when the total molar amount of the mixed alcohol is 1.
• the mixed alcohol that serves as a raw material of the above-described mixed ester is made of pentaerythritol and dipentaerythritol, as described above.
• the pentaerythritol content in the mixed alcohol is 65 to 99.95 mol %, preferably 70 to 99.95 mol %, and more preferably 75 to 99.95 mol %.
• the dipentaerythritol content in the mixed alcohol is 0.05 to 35 mol %, preferably 0.05 to 30 mol %, and more preferably 0.05 to 25 mol %.
• the pentaerythritol content in the mixed alcohol is 65 mol % or more,.
• the resultant ester has high levels of viscosity, low-temperature fluidity, and compatibility with chlorine-free hydrofluorocarbon refrigerants, and when it is 99.95 mol % or less, then the resultant ester has long-term low-temperature stability.
• the dipentaerythritol content in the mixed alcohol is 0.05 mol % or more, then the resultant ester has long-term low-temperature stability, and when it is 35 mol % or less, then the resultant ester has suppressed deterioration in compatibility with chlorine-free hydrofluorocarbon refrigerants and suppressed increase in viscosity.
• the mixed carboxylic acid that serves as a raw material of the above-described mixed ester is made of a monocarboxylic acid having 5 to 8 carbon atoms and an isononanoic acid.
• the monocarboxylic acid having 5 to 8 carbon atoms is contained in the mixed carboxylic acid in a ratio of 25 to 55 mol %, preferably 30 to 55 mol %, more preferably 33 to 55 mol %, and even more preferably 35 to 50 mol %.
• the isononanoic acid is contained in the mixed carboxylic acid in a ratio of 45 to 75 mol %, preferably 45 to 70 mol %, more preferably 45 to 67 mol %, and even more preferably 50 to 65 mol %.
• Examples of the monocarboxylic acid having 5 to 8 carbon atoms include pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 4-methylpentanoic acid, 2-ethylbutanoic acid, 3-ethylbutanoic acid, heptanoic acid, 2-methylhexanoic acid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2,2-dimethylpentanoic acid, 2-ethylpentanoic acid, 3-ethylpentanoic acid, 2-ethylhexanoic acid, 2-methylheptanoic acid, 3-methylheptanoic acid, 4-methylheptanoic acid, 5-methylheptanoic acid, 6-methylheptanoic acid, 2,2-dimethylhexanoic acid, and 3,5-dimethylhe
• 2-ethylhexanoic acid is preferably used since the obtained lubricant has good lubricity and hydrolytic stability and is difficult to corrode metals.
• the above-noted monocarboxylic acids having 5 to 8 carbon atoms may be used either alone or in combination of two or more thereof.
• isononanoic acid examples include 2,5,5-trimethylhexanoic acid, 3,5,5-trimethylhexanoic acid, 4,5,5-trimethylhexanoic acid, 2,2,4,4-tetramethylpentanoic acid, 2-ethyl-4,4-dimethylpentanoic acid, 6,6-dimethylheptanoic acid, 4-ethyl-2-methylhexanoic acid, 2-methyloctanoic acid, and 2-ethylheptanoic acid.
• 2,5,5-Trimethylhexanoic acid, 3,5,5-trimethylhexanoic acid, 4,5,5-trimethylhexanoic acid, and 6,6-dimethylheptanoic acid are preferable, and 3,5,5-trimethylhexanoic acid is more preferable.
• the above-noted isononanoic acids may be used either alone or in combination of two or more thereof.
• the isononanoic acid contains 3,5,5-trimethylhexanoic acid
• the resultant lubricant composition has excellent compatibility with fluorocarbons and has long-term stability in the low temperature region.
• the isononanoic acid contains 3,5,5-trimethylhexanoic acid in a ratio of 88.50 to 99.95 mol %, more preferably 90.0 to 99.5 mol %, and even more preferably 92.0 to 99.0 mol %.
• the value of the numerator of relation (1) from a carboxylic acid selected from the above-described range, determine the average number of hydroxyl groups of the denominator that satisfies the numerical range of relation (1), and determine the amounts of pentaerythritol and dipentaerythritol within the range of the above-described mixing ratio of pentaerythritol and dipentaerythritol such that the determined average number of hydroxyl groups is achieved.
• the mixed ester used in the present invention is obtained by ordinary esterification reaction or transesterification.
• the ratio of the above-described mixed alcohol and the above-described mixed carboxylic acid is determined as appropriate such that the obtained mixed ester has a hydroxyl value of 5.0 mgKOH/g or less and an acid value of 0.05 mgKOH/g or less.
• the mixed ester used in the present invention is obtained in the following manner.
• a mixed carboxylic acid is mixed with a mixed alcohol such that the mixed carboxylic acid is 1.0 to 1.5 equivalents, preferably 1.05 to 1.3 equivalents, with respect to 1 equivalent of hydroxyl group in the mixed alcohol, and then a catalyst is added thereto, if necessary.
• This mixture is reacted for 3 to 15 hours at 220 to 260° C. under a nitrogen, and at the point when the hydroxyl value becomes 3.0 mgKOH/g or less, excess carboxylic acid is removed under a reduced pressure.
• operations such as adsorption treatment using activated clay, acid clay, and a synthesized adsorbent, and steaming are performed either alone or in combination.
• the refrigeration lubricant composition of the present invention contains the above-described mixed ester as the main component and may contain, for example, an ester other than the mixed ester and an additive, if necessary.
• the specific amount of the “main component” is 50 wt % or more, preferably 70 wt % or more, and more preferably 90 wt % or more based on the entire refrigeration lubricant composition.
• ester other than the above-described mixed ester examples include esters obtained from at least one alcohol and the above-described monocarboxylic acid having 5 to 9 carbon atoms, wherein the alcohol is selected from the group consisting of pentaerythritol, dipentaerythritol, and neopentyl polyol having 2 to 8 hydroxyl groups and having 5 to 15 carbon atoms (e.g., neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, trimethylolethane, triethylolethane, trimethylolpropane, tripentaerythritol, and bispentaerythritol).
• the alcohol is selected from the group consisting of pentaerythritol, dipentaerythritol, and neopentyl polyol having 2 to
• the additive examples include a phenol antioxidant, a metal deactivator such as benzotriazole, thiadiazole, and dithiocarbamate, an acid scavenger such as epoxy compounds and carbonimides, and a phosphorous extreme pressure agent.
• a phenol antioxidant examples include a phenol antioxidant, a metal deactivator such as benzotriazole, thiadiazole, and dithiocarbamate, an acid scavenger such as epoxy compounds and carbonimides, and a phosphorous extreme pressure agent.
• a metal deactivator such as benzotriazole, thiadiazole, and dithiocarbamate
• an acid scavenger such as epoxy compounds and carbonimides
• a phosphorous extreme pressure agent examples include a phenol antioxidant, a metal deactivator such as benzotriazole, thiadiazole, and dithiocarbamate, an acid scavenger such as epoxy compounds and carbonimides, and a phosphorous extreme pressure agent.
• the refrigeration lubricant composition of the present invention has a hydroxyl value of 5.0 mgKOH/g or less, and preferably 3.0 mgKOH/g or less, more preferably 2.0 mgKOH/g or less, and even more preferably 1.0 mgKOH/g or less.
• the hydroxyl value is 5.0 mgKOH/g or less, then the composition has sufficient electric insulation property without deteriorating the volume resistivity of the composition. Therefore, in equipment in which the above-described composition is employed, there is no possibility of an adverse effect such as dissolving a sealing material that is made of an organic material. Also, there is no possibility of an adverse effect on additives that may be contained in the composition.
• the refrigeration lubricant composition of the present invention has an acid value of 0.05 mgKOH/g or less, and preferably it may-have an acid value of 0.03 mgKOH/g or less and more preferably 0.01 mgKOH/g or less. When it has an acid value of 0.05 mgKOH/g or less, then the composition is less likely to corrode metals and has good hydrolytic stability.
• the kinematic viscosity of the refrigeration lubricant composition of the present invention there is no particular limitation regarding the kinematic viscosity of the refrigeration lubricant composition of the present invention.
• the kinematic viscosity at 40° C. is 30 to 150 mm 2 /s.
• the above-described lubricant composition is used for air-conditioning equipment such as room air conditioners and packaged air conditioners; low temperature apparatuses; industrial refrigerators; and compressors in automotive air conditioners such as hybrid cars and electric cars, 55 to 140 mm 2 /s is preferable, and 60 to 130 mm 2 /s is more preferable, in view of the operating efficiency thereof.
• the base stock of the refrigeration lubricant of the present invention has excellent long-term stability even in the low temperature region. Moreover, it has excellent compatibility with fluorocarbons and thermal resistance, and when used for air conditioning equipment and compressors used for automotive air conditioners, it can improve operating efficiency compared with the conventional refrigeration lubricants.
• the base stock of the refrigeration lubricant of the present invention has excellent compatibility with, in particular, chlorine-free hydrofluorocarbons, and thus it is useful for a lubricant for chlorine-free hydrofluorocarbon refrigerant.
• the refrigerant working fluid of the present invention is made of the above-described refrigeration lubricant composition and a chlorine-free hydrofluorocarbon refrigerant.
• a weight ratio of the lubricant composition and the chlorine-free hydrofluorocarbon refrigerant is in the range of 10:90 to 90:10 preferably. If the amounts of the chlorine-free hydrofluorocarbon refrigerant is higher than the above-described range, then the viscosity of the resultant refrigerant working fluid is reduced, which may lead to poor lubrication. If it is lower than the above-described range, then when the obtained working fluid is used for refrigerating apparatuses, refrigerating efficiency may deteriorate.
• chlorine-free hydrofluorocarbon refrigerant examples include 1,1,1,2-tetrafluoroethane (R-134a), pentafluoroethane (R-125), difluoroethane (R-32), trifluoroethane (R-23), 1,1,2,2-tetrafluoroethane (R-134), 1,1,1-trifluoroethane (R-143a), and 1,1-difluoroethane (R-152a).
• These refrigerants may be used either alone or as mixed refrigerants of two or more thereof.
• mixed refrigerants containing at least one of R-134a and R-32 are preferable.
• the refrigerant compression type refrigerating apparatus of the present invention is provided with a compressor, a condenser, an expansion mechanism, and an evaporator and is configured such that the above-described refrigerant working fluid, which is the refrigerant in the refrigerating apparatus, circulates through these components.
• This refrigerating apparatus may further include a drier.
• Examples of such a refrigerating apparatus include air conditioning equipment such as room air conditioners and packaged air conditioners; low temperature apparatuses; industrial refrigerators; and automotive air conditioners such as hybrid cars and electric cars.
• the mixed alcohol and the mixed carboxylic acid shown in Table 1 were placed in a one-liter four-necked flask provided with a thermometer, a nitrogen inlet tube, a stirrer and a cooling tube such that the ratio of the hydroxyl group in the mixed alcohol and the carboxyl group in the mixed carboxylic acid is 1:1.1 in the equivalent ratio, and then reacted under a nitrogen at 220° C. at an atmospheric pressure while water generated by the reaction was removed by distillation. During the reaction, the hydroxyl value of the reaction mixture was monitored, and the reaction was stopped at the point when the hydroxyl value became lower than 2.0 mgKOH/g.
• ester A this ester is referred to as ester A
• the kinematic viscosity at 40° C. and 100° C. and the viscosity index of the obtained ester A were measured according to the above-described method. Table 1 shows the results.
• Esters i.e., esters B to F
• Esters B to F were obtained in the same manner as in Example 1 except that the mixed alcohols and the mixed carboxylic acids shown in Table 1 were used.
• the kinematic viscosity at 40° C. and 100° C. and the viscosity index of each ester were measured according to the above-described method. Table 1 also shows the results.
• Esters i.e., esters G to K were obtained in the same manner as in Example 1 except that the mixed alcohols and the mixed carboxylic acids shown in Table 1 were used.
• the kinematic viscosity at 40° C. and 100° C. and the viscosity index of each ester were measured according to the above-described method. Table 1 also shows the results.
• TABLE 1 Mixed Kinematic viscosity alcohol *1 Mixed carboxylic acid Value of (mm 2 /s) Viscosity (mol %) (mol %) relation (1) Ester 40° C. 100° C. index Ex.
• ester A was used as a base stock of a lubricant (this base stock is referred to as base stock 1).
• base stock 1 The kinematic viscosity at 40° C. and 100° C., viscosity index, acid value, hydroxyl value, color number, volume resistivity, pour point, two-phase separation temperature, and Falex test pin friction amount of the obtained base stock 1 were measured according to the above-described methods. Furthermore, the long-term low-temperature test and the sealed tube test were performed. Table 2 shows the results.
• esters B to F, H, and K obtained in the above-described examples and comparative examples were employed as shown in Table 2 to prepare base stocks, of a lubricant (i.e., base stocks 2 to 8).
• the base stocks were tested in the same manner as in Example 1. Table 2 also shows the results.
• the base stocks of a lubricant i.e., base stocks 1 to 8 in the examples had excellent stability, so that no precipitate occurred even in the long-term low-temperature test.
• these base stocks 1 to 8 have a low pour point, excellent compatibility with fluorocarbon refrigerants, which is indicated by the two-phase separation temperature, and less susceptibility to deterioration due to thermal oxidation, which is indicated by the results of the sealed tube test, and satisfy the other performance requirements required for base stocks of a refrigeration lubricant. Therefore, it is apparent that these are excellent base oils.
• the refrigeration lubricant composition of the present invention has excellent low-temperature stability. Moreover, it has good compatibility with fluorocarbons, in particular, chlorine-free hydrofluorocarbons, so that it is preferably used as a lubricant for refrigerating machines using a chlorine-free hydrofluorocarbon refrigerant or as a refrigerant working fluid, obtained by mixing this lubricant with a chlorine-free hydrofluorocarbon refrigerant.
• the refrigeration lubricant composition of the present invention and the refrigerant working fluid containing the lubricant and a chlorine-free hydrofluorocarbon refrigerant can be used for air conditioning equipment such as room air conditioners and packaged air conditioners; low temperature apparatuses; industrial refrigerators; and compressors of automotive air conditioners such as hybrid cars and electric cars.

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