WO2015025977A1 - 緩衝器用潤滑油組成物 - Google Patents
緩衝器用潤滑油組成物 Download PDFInfo
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- WO2015025977A1 WO2015025977A1 PCT/JP2014/072187 JP2014072187W WO2015025977A1 WO 2015025977 A1 WO2015025977 A1 WO 2015025977A1 JP 2014072187 W JP2014072187 W JP 2014072187W WO 2015025977 A1 WO2015025977 A1 WO 2015025977A1
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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
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- 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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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/08—Amides
- C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
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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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- 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
- C10M2223/043—Ammonium or amine salts thereof
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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
- C10M2223/045—Metal containing thio derivatives
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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
- C10M2223/049—Phosphite
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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
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
- C10M2223/065—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds containing sulfur
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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
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/02—Unspecified siloxanes; Silicones
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
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- 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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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/36—Seal compatibility, e.g. with rubber
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
Definitions
- the present invention relates to a lubricating oil composition for a shock absorber, and more particularly to a lubricating oil composition for a shock absorber used for a shock absorber for a four-wheeled vehicle.
- a vehicle body such as a four-wheeled vehicle has a shock absorber (hereinafter sometimes referred to as a “shock absorber”) to alleviate vibrations caused by road surface unevenness and vibrations generated during sudden acceleration and braking.
- a built-in suspension is used.
- the structure of the shock absorber is basically a cylindrical structure utilizing the flow resistance of oil, and specifically, a hydraulic piston having a small hole is used.
- a bush serving as a bearing is provided at a sliding portion between the cylinder and the piston rod, and a sealing property is secured by an oil seal.
- the bush is made of bronze and the oil seal is made of rubber.
- Patent Document 1 a lubricating oil composition for a shock absorber in which a phosphate ester is blended as an extreme pressure agent and a secondary amine is blended is known.
- a lubricating oil composition cannot sufficiently reduce the friction with respect to a bronze bush and a rubber oil seal.
- Patent Document 2 also discloses that a tertiary amine is blended in a lubricating oil composition for a continuously variable transmission, together with an extreme pressure agent composed of a phosphate ester and a metal compound such as a metal sulfonate. ing.
- the present invention has been made in view of the above problems, and reduces the coefficient of friction with respect to a bronze bush and a rubber oil seal without generating precipitates over a long period of time even when an extreme pressure agent is added. It is an object of the present invention to provide a lubricating oil composition for a shock absorber that can be used.
- the present inventors have found that the friction coefficient against rubber and bronze can be reduced by adding a predetermined zinc dithiophosphate to a lubricating oil composition for shock absorbers in addition to a predetermined tertiary amine. .
- the occurrence of precipitation due to extreme pressure agents was determined by the reaction with zinc dithiophosphate, and a phosphate ester amine salt that does not react with zinc dithiophosphate for a long period of time was formulated as an extreme pressure agent.
- the inventors have found that the friction coefficient against rubber and bronze can be reduced without generating precipitates, and have completed the present invention described below.
- A a base oil composed of mineral oil and / or synthetic oil
- B a tertiary amine represented by the following general formula (I)
- C a zinc dithiophosphate represented by the following general formula (II)
- D a lubricating oil composition for a shock absorber, comprising a phosphate ester amine salt.
- R 1 and R 2 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms
- R 3 is an aliphatic hydrocarbon group having 12 to 24 carbon atoms.
- R 4 to R 7 are each independently a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, and a linear, branched or cyclic group having 1 to 24 carbon atoms. It is selected from cyclic alkenyl groups.
- R 1 and R 2 are each independently a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms, and a linear or branched group having 1 to 5 carbon atoms.
- R 3 is a linear, branched or cyclic alkyl group having 12 to 24 carbon atoms, and a linear, branched or cyclic group having 12 to 24 carbon atoms.
- the lubricating oil composition for a shock absorber according to the above (1) which is selected from alkenyl groups.
- (3) The lubricating oil composition for a shock absorber according to the above (1) or (2), wherein, in the general formula (I), R 3 is a linear, branched or cyclic alkyl group having 16 to 20 carbon atoms.
- (4) The lubricating oil composition for a shock absorber according to the above (3), wherein R 3 is a stearyl group in the general formula (I).
- R 4 to R 7 are each independently a linear, branched or cyclic alkyl group having 10 to 20 carbon atoms, and a linear or branched group having 10 to 20 carbon atoms.
- R 11 represents a hydrogen atom, a linear, branched or cyclic alkyl group having 8 to 24 carbon atoms, and a linear, branched or cyclic alkenyl group having 8 to 24 carbon atoms.
- R 12 is selected from a linear, branched or cyclic alkyl group having 8 to 24 carbon atoms, and a linear, branched or cyclic alkenyl group having 8 to 24 carbon atoms.
- R 11 and R 12 are each independently an alkyl group having 16 to 20 carbon atoms or an alkenyl group having 16 to 20 carbon atoms. object.
- (11) The lubricating oil composition for a shock absorber according to any one of the above (1) to (10), wherein in the general formula (I), R 1 and R 2 each have 1 or 2 carbon atoms.
- the lubricating oil composition for shock absorbers which can reduce the friction coefficient with respect to the bronze bush and rubber
- the lubricating oil composition for a shock absorber of the present invention comprises (A) a base oil, (B) a tertiary amine, (C) a zinc dithiophosphate compound, and (D) a phosphate ester amine salt.
- A a base oil
- B a tertiary amine
- C a zinc dithiophosphate compound
- D a phosphate ester amine salt
- Mineral oil and / or synthetic oil is used as the base oil in the lubricating oil composition for shock absorbers of the present invention.
- Mineral oils include paraffin-based mineral oils, intermediate-based mineral oils and naphthenic-based mineral oils obtained by ordinary refining methods such as solvent refining and hydrogenation refining, or waxes produced by the Fischer-Tropsch process (gas (Turi Liquid Wax) and mineral oil-based waxes.
- synthetic oils include hydrocarbon synthetic oils and ether synthetic oils.
- hydrocarbon-based synthetic oil examples include polybutene, polyisobutylene, 1-octene oligomer, 1-decene oligomer, ⁇ -olefin oligomer such as ethylene-propylene copolymer, or a hydride thereof, alkylbenzene, alkylnaphthalene, and the like.
- ether synthetic oils include polyoxyalkylene glycol and polyphenyl ether.
- one or more mineral oils and one or more synthetic oils may be used in combination.
- the kinematic viscosity of the base oil is not particularly limited. However, when the lubricating oil composition for a shock absorber according to the present invention is used, for example, as an automobile shock absorber oil, the kinematic viscosity at 40 ° C. is preferably 2 to 20 mm 2 / s, and 5 to 14 mm. 2 / s is more preferable. In addition, when using 2 or more types of mineral oil and / or synthetic oil, the said numerical value means dynamic viscosity of the base oil formed by mixing them.
- the content of the base oil (A) in the total amount of the lubricating oil composition for shock absorbers is preferably 80 to 99% by mass, and more preferably 90 to 98% by mass.
- the tertiary amine used in the lubricating oil composition for shock absorbers of the present invention is represented by the following general formula (I).
- R 1 and R 2 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms
- R 3 is an aliphatic hydrocarbon group having 12 to 24 carbon atoms.
- R 1 and R 2 are each independently a linear, branched or cyclic alkyl group having 1 to 5 carbon atoms, or a linear, branched or cyclic group having 1 to 5 carbon atoms, or A cyclic alkenyl group is preferred.
- R 1 and R 2 may be different from each other or the same, but are preferably the same.
- R 3 is preferably a linear, branched or cyclic alkyl group having 12 to 24 carbon atoms, or a linear, branched or cyclic alkenyl group having 12 to 24 carbon atoms.
- R 1 and R 2 are more preferably alkyl groups from the viewpoint of improving stability and the like and further reducing the friction coefficient.
- R 1 and R 2 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a vinyl group, a propenyl group, a butenyl group, and a pentenyl group, which are linear or branched. Any of an annular shape may be used. Among these, a methyl group or an ethyl group is preferable, and a methyl group is most preferable.
- R 3 preferably has 16 to 20 carbon atoms, more preferably 18 carbon atoms.
- the tertiary amine (B) is preferably a tertiary amine having R 3 of 16 to 20 as a main component, and more preferably a tertiary amine having 18 carbon atoms.
- a main component means containing 50 mass% or more with respect to (B) tertiary amine whole quantity, 80 mass% or more is preferable, and 90 mass% or more is more preferable.
- R 3 is preferably an alkyl group. Further, R 3 should be linear. Examples of the alkyl group of R 3 include dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, These may be linear, branched or cyclic.
- alkenyl group examples include dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group, henicosenyl group, dococenyl group, tricocenyl group and tetracocenyl group. May be linear, branched or cyclic, and the position of the double bond is arbitrary.
- an octadecyl group such as a hexadecyl group and a stearyl group
- an octadecenyl group such as an oleyl group, an icosyl group, and the like
- a stearyl group is most preferable.
- Preferred specific compounds of tertiary amines include dimethyl monostearylamine, diethylstearylamine and the like.
- the tertiary amine is preferably contained in an amount of 0.01 to 3% by mass based on the total amount of the lubricating oil composition for the shock absorber. By setting it within the above range, the friction coefficient against bronze can be reduced with an appropriate amount of tertiary amine. From such a viewpoint, the tertiary amine is more preferably contained in an amount of 0.1 to 1.5% by mass with respect to the total amount of the lubricating oil composition for a shock absorber.
- the zinc dithiophosphate used in the present invention is represented by the following general formula (II).
- R 4 to R 7 are each independently a linear, branched or cyclic alkyl group having 1 to 24 carbon atoms, or a linear or branched group having 1 to 24 carbon atoms, A cyclic alkenyl group, which may be the same or different from each other, the same ones are preferred from the viewpoint of ease of production;
- gum of a lubricating oil composition can be favorably reduced by using said zinc dithiophosphate with tertiary amine.
- R 4 to R 7 preferably have 10 to 20 carbon atoms, more preferably 12 to 18 carbon atoms. By making the number of carbon atoms of zinc dithiophosphate in these ranges, the coefficient of friction against rubber can be reduced more effectively.
- R 4 to R 7 are preferably linear, and R 4 to R 7 are preferably alkyl groups.
- alkyl group in R 4 to R 7 examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Examples include tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, and tetracosyl group, which are linear, branched, or cyclic.
- alkenyl groups include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl Group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group, henicocenyl group, dococenyl group, tricocenyl group, tetracocenyl group, these may be any of linear, branched or cyclic, double The position of the bond is also arbitrary.
- dodecyl groups such as lauryl group, octadecyl groups such as tetradecyl group, hexadecyl group and stearyl group, and octadecenyl groups such as icosyl group and oleyl group are preferable, but lauryl group is most preferable.
- (C) Zinc dithiophosphate is preferably contained in an amount of 0.01 to 3% by mass based on the total amount of the lubricating oil composition for the shock absorber. By setting it within the above range, the friction with respect to bronze and rubber can be reduced with an appropriate amount of zinc (C) zinc dithiophosphate. From such a viewpoint, it is more preferable that (C) zinc dithiophosphate is contained in an amount of 0.1 to 1.5% by mass based on the total amount of the lubricating oil composition for shock absorbers.
- the phosphate ester amine salt includes an acidic phosphate amine salt obtained by reacting an acidic phosphate ester with an amine, and / or an acidic sublimation obtained by reacting an acidic phosphite ester with an amine.
- acidic phosphoric acid ester amine salt is preferable.
- the (D) phosphate ester amine salt has a function as a so-called extreme pressure agent, and can improve abrasion resistance while preventing seizure. Moreover, even if (D) phosphate ester amine salt is stored for a long time, it does not react with, for example, (C) zinc dithiophosphate to cause precipitation.
- R 11 represents a hydrogen atom, an alkyl group having 8 to 24 carbon atoms, or an alkenyl group having 8 to 24 carbon atoms, and among them, an alkyl group or an alkenyl group is preferable.
- R 12 represents an alkyl group having 8 to 24 carbon atoms or an alkenyl group having 8 to 24 carbon atoms.
- the alkyl group and alkenyl group for R 11 and R 12 may be linear, branched or cyclic, but is preferably linear.
- the alkyl group and alkenyl group of R 11 and R 12 preferably have 12 to 24 carbon atoms, more preferably 16 to 20 carbon atoms, still more preferably one or both of R 11 and R 12 are carbon atoms.
- Equation 18 the acidic phosphoric acid ester constituting the amine salt preferably has R 11 and R 12 having 16 to 20 carbon atoms as the main component, and those having 18 carbon atoms as the main component. It is more preferable.
- R 11 and R (D) an alkyl group, and having 16 to 20 carbon atoms in the alkenyl group in the total amount of R 11 and R 12 in the acidic phosphoric acid ester constituting the amine salt (or 18)
- the ratio of 12 means 50% by mass or more, and the content is preferably 80% by mass or more, more preferably 90% by mass or more.
- Examples of the alkyl group in R 11 and R 12 include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, Examples include a heicosyl group, a docosyl group, a tricosyl group, and a tetracosyl group, which may be linear, branched, or cyclic.
- the alkenyl group includes octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icocenyl, heicosenyl, dococenyl Group, tricocenyl group and tetracocenyl group may be mentioned. These may be linear, branched or cyclic, and the position of the double bond is also arbitrary.
- a linear alkyl group or an alkenyl group is preferable, but an octadecenyl group such as an oleyl group is most preferable.
- an octadecenyl group such as an oleyl group is most preferable.
- acidic phosphoric acid ester dioleyl acid phosphate is mentioned.
- R 21 represents a hydrogen atom, an alkyl group having 8 to 24 carbon atoms, or an alkenyl group having 8 to 24 carbon atoms, and among these, an alkyl group or an alkenyl group is preferable.
- R 22 represents an alkyl group having 8 to 24 carbon atoms or an alkenyl group having 8 to 24 carbon atoms.
- the alkyl group and alkenyl group of R 21 and R 22 may be linear, branched or cyclic, but is preferably linear.
- the alkyl group and alkenyl group of R 21 and R 22 preferably have 12 to 24 carbon atoms, more preferably 16 to 20 carbon atoms, and particularly preferably one or both of R 21 and R 22 are carbon atoms.
- Equation 18 the acidic phosphite constituting the amine salt preferably has R 21 and R 22 having 16 to 20 carbon atoms as the main component, and those having 18 carbon atoms as the main component. More preferably.
- R 21 and (D) an alkyl group, and having 16 to 20 carbon atoms in the alkenyl group in the total amount of R 21 and R 22 in the acid phosphite constituting the amine salt (or 18) It means that the ratio of R 22 is 50% by mass or more, and the content ratio is preferably 80% by mass or more, and more preferably 90% by mass or more.
- Examples of the alkyl group in R 21 and R 22 include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, Examples include a heicosyl group, a docosyl group, a tricosyl group, and a tetracosyl group, which may be linear, branched, or cyclic.
- the alkenyl group includes octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icocenyl, heicosenyl, dococenyl Group, tricocenyl group and tetracocenyl group may be mentioned. These may be linear, branched or cyclic, and the position of the double bond is also arbitrary.
- the amine for forming the phosphate ester amine salt may be any of primary amines, secondary amines and tertiary amines, but primary amines are preferred.
- the amine is represented by the general formula NR 3 , preferably 1 to 3 of R are aliphatic hydrocarbon groups and the rest are hydrogen atoms.
- the aliphatic hydrocarbon group is preferably an alkyl group or an unsaturated hydrocarbon group having 1 to 2 unsaturated bonds, and the alkyl group and the unsaturated hydrocarbon group are linear or branched, respectively. Any of cyclic structures may be used, but linear structures are preferred.
- the phosphoric acid ester amine salt is liquid at room temperature (25 ° C.) in terms of solubility in base oil and prevention of precipitation at low temperature.
- the aliphatic hydrocarbon group has 6 to 6 carbon atoms. Those having 20 carbon atoms are preferred, and those having 12 to 20 carbon atoms are more preferred.
- Examples of the amine include dilaurylamine, dimyristylamine, distearylamine, dioleylamine, trilaurylamine, trimyristylamine, tristearylamine, trioleylamine, and beef tallow amine. These alkylamines may be used alone or in combination of two or more.
- the content of the (D) phosphate ester amine salt is preferably 0.1 to 3% by mass, and preferably 0.2 to 1% by mass, based on the total amount of the lubricating oil composition for shock absorbers.
- the component (D) is preferably a phosphate ester amine salt and then mixed with other components to prepare a shock absorber lubricating oil composition. However, each of the phosphate ester and the amine is separately added to the composition. May be reacted in the composition to form an amine salt.
- the total amount of acidic phosphate ester and acidic phosphite ester that do not form an amine salt is preferably less than 0.05% by mass.
- the content is more preferably less than 01% by mass, and more preferably not contained in the lubricating oil composition for shock absorbers.
- Acid phosphates and acid phosphites that do not form amine salts react with the above (C) zinc dithiophosphate to generate precipitates when stored for a long period of time, but the amount is suppressed to less than about 0.05% by mass. And precipitation is less likely to occur.
- the lubricating oil composition for shock absorbers of the present invention is selected from (E) other optional ashless dispersants, friction modifiers, antioxidants, viscosity index improvers, and antifoaming agents. At least one kind may be appropriately contained as long as the object of the present invention is not impaired. Further, if desired, other additives conventionally used in the lubricating oil composition for shock absorbers, such as metal detergents, rust inhibitors, metal deactivators, pour point depressants and the like may be contained.
- the content ratio of the (E) optional additive component in the total amount of the lubricating oil composition for shock absorbers is usually preferably 10% by mass or less, and more preferably 3 to 8% by mass.
- Examples of the ashless dispersant include succinimides, boron-containing succinimides, benzylamines, boron-containing benzylamines, succinic esters, monovalent or divalent typified by fatty acids or succinic acid.
- Examples include amides of carboxylic acids, and among these, fatty acid amides are preferable.
- the partial ester compound obtained by reaction with a fatty acid and aliphatic polyhydric alcohol is mentioned.
- the fatty acid is preferably a fatty acid having a linear or branched hydrocarbon group having 6 to 30 carbon atoms, and the hydrocarbon group preferably has 8 to 24 carbon atoms, particularly preferably 10 to 10 carbon atoms. 20.
- fatty acids include saturated fatty acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid, myristoleic acid, palmitoleic acid, oleic acid, and Examples include unsaturated fatty acids such as linolenic acid, preferably oleic acid.
- the aliphatic polyhydric alcohol is a divalent to hexavalent alcohol, and examples thereof include ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and the like, with sorbitan being preferred.
- partial ester compounds may be used individually by 1 type, and may be used in combination of 2 types.
- aliphatic saturated monoamines and unsaturated monoamines having about 10 to 20 carbon atoms such as stearylamine and oleylamine can be suitably used as friction modifiers.
- Antioxidants include monocyclic phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4-ethylphenol; 4,4′-methylenebis (2,6-di-tert-butylphenol), polycyclic phenolic antioxidants such as 2,2′-methylenebis (4-ethyl-6-tert-butylphenol); monoalkyls such as monooctyldiphenylamine and monononyldiphenylamine Diphenylamine compounds, 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, 4,4'-dihexyldiphenylamine, 4,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, 4,4'- Dialkyldiphenylamines such as dinonyldiphenylamine Compounds, polyalkyl
- the viscosity index improver examples include polymethacrylates, dispersed polymethacrylates, olefin copolymers (for example, ethylene-propylene copolymers), dispersed olefin copolymers, styrene copolymers (for example, styrene- Diene hydrogenated copolymer and the like), and polymethacrylate is preferred.
- olefin copolymers for example, ethylene-propylene copolymers
- styrene copolymers for example, styrene- Diene hydrogenated copolymer and the like
- polymethacrylate is preferred.
- the antifoaming agent a high molecular silicone antifoaming agent is preferable, and by including this high molecular silicone antifoaming agent, antifoaming properties are effectively exhibited.
- the polymer silicone antifoaming agent include fluorinated organopolysiloxanes such
- the metal detergent neutral metal sulfonate, neutral metal phenate, neutral metal salicylate, neutral metal phosphonate, basic sulfonate, basic phenate, basic salicylate, overbased sulfonate, overbased salicylate And overbased phosphonates.
- the rust inhibitor include metal sulfonates and succinates
- the metal deactivator include benzotriazole and thiadiazole.
- the pour point depressant polymethacrylate having a weight average molecular weight of about 50,000 to 150,000 can be used.
- the lubricating oil composition for shock absorbers of the present invention preferably has a kinematic viscosity at 40 ° C. of 18 mm 2 / s or less, more preferably 2 to 15 mm 2 / s, from the viewpoint of low temperature fluidity.
- the lubricating oil composition of the present invention can reduce the friction coefficient against bronze and rubber by containing (B) tertiary amine and (C) zinc dithiophosphate. Moreover, by including (D) phosphate ester amine salt as an extreme pressure agent, abrasion resistance and seizure resistance can be improved, and it can be made suitable as a lubricating oil composition for a shock absorber. Furthermore, in the present invention, since the extreme pressure agent is (D) a phosphate ester amine salt, for example, it does not react with (C) zinc dithiophosphate to cause precipitation.
- the lubricating oil composition for a shock absorber according to the present invention preferably has a friction coefficient ⁇ against rubber of less than 0.09 at a load of 1 to 3 kgf, and 0.08 at a load of about 5 to 7 kgf. It is preferable to become less than.
- the friction coefficient ⁇ against bronze is preferably less than 0.18 at a load of about 1 kg, preferably less than 0.20 at a load of 2 to 3 kgf, and less than 0.28 at a load of 5 to 7 kgf. It is preferable that In the present invention, when the friction coefficient ⁇ with respect to rubber and bronze falls within the above range, riding comfort performance is improved.
- the friction coefficient ⁇ is measured by the method described later.
- the lubricating oil composition for a shock absorber according to the present invention can be used for both a double-cylinder shock absorber and a single-cylinder shock absorber, and can also be used for either a four-wheel or a two-wheel shock absorber. In particular, it is suitably used for four wheels.
- the lubricating oil composition of the present invention can be suitably used for a shock absorber in which at least the inner surface which is a sliding surface with the piston rod is a bronze bush such as phosphor bronze and the oil seal is made of rubber.
- the oil seal is more suitable for increasing the tightening force and improving the dust resistance.
- the sliding surface of the piston rod with the bush is generally made of chrome by chrome plating or the like.
- the lubricating oil composition for shock absorbers of the present invention can be suitably used for industrial hydraulic fluids, construction machinery hydraulic fluids, and the like.
- Friction coefficient ⁇ against bronze was measured with a Bowden reciprocating friction tester under the following test conditions. In Table 1, it is represented as “bronze ⁇ ”. Temperature: 23 ° C.
- Table 1 Each material in Table 1 is as follows.
- Mineral oil 1 40 ° C. kinematic viscosity: 7.117 mm 2 / s, viscosity index: 109, density (15 ° C.): 0.8200 g / cm 3 paraffinic mineral oil mineral oil 2: 40 ° C. kinematic viscosity: 29.48 mm 2 / s , Viscosity index: 131, density (15 ° C.): 0.8399 g / cm 3 paraffinic mineral oil Viscosity of base oils of Examples and Comparative Examples obtained by mixing base oil 1 and base oil 2 Is as described in the table.
- Tertiary amine 1 Dimethyl monostearyl amine
- Tertiary amine 2 Diethyl monostearyl amine zinc dithiophosphate 1: Zinc dilauryl dithiophosphate zinc dithiophosphate in which all of R 4 to R 7 are lauryl groups in general formula (II)
- 2 Zinc dioleyl dithiophosphate zinc dithiophosphate in which all of R 4 to R 7 are oleyl groups in the general formula (II) 3: R 4 to R 7 in the general formula (II) are n-hexyl groups, It is a mixture of isopropyl group and n-butyl group.
- Extreme pressure agent 1 An amine salt (acid phosphate ester amine salt) of dioleyl acid phosphate in which R 11 and R 12 are both oleyl groups in the formula (III). In addition, beef tallow amine was used as the amine.
- Extreme pressure agent 2 Dilauryl hydrogen phosphite (phosphite)
- Extreme pressure agent 3 Dioleyl acid phosphate (acidic phosphate ester)
- Extreme pressure agent 4 ethyl-3-[[bis (1-methylethoxy) phosphinothioyl] thio] propionate (dithiophosphate)
- Extreme pressure agent 5 tricresyl phosphate (TCP)
- Antioxidant 2,6-di-tert-butyl-p-cresol (DBPC)
- Ashless dispersant Fatty acid amide (isostearic acid-tetraethylenepentamine reaction product)
- Friction modifier 1 Sorbitan monooleate
- Friction modifier 2 Monooleylamine friction modifier 3: Glycerin partial ester metal deactivator: Thiadiazole series (2,5-bis (1,1,3,3-tetramethylbuta Dithio) 1,3,4-thiadiazole)
- the lubricant composition for the shock absorber contains (B) a tertiary amine and (C) zinc dithiophosphate, so that the friction coefficient of rubber and bronze over a wide load range. Can be sufficiently reduced. Moreover, since the extreme pressure agent which consists of (D) phosphate ester amine salt was mix
- the lubricating oil composition for shock absorbers of the present invention can be used for various types of shock absorbers, for example, can be suitably used for both a double cylinder type shock absorber and a single cylinder type shock absorber. Although it can be used for other shock absorbers, it is particularly preferably used for four wheels.
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Abstract
Description
ショックアブソーバーは伸縮運動するとき、大きな横力が作用されることがあるが、その際、ブッシュにはフリクションが発生する。フリクションの発生は、乗り心地性能を悪化する要因となるので、ブッシュに対するフリクションの低減が求められている。また、オイルシールの緊迫力を増大させて耐ダスト性が高められた場合、乗り心地性能を良好にするためには、オイルシールに対する摩擦係数の低減も求められている。
また、例えば、特許文献2には、リン酸エステルからなる極圧剤及び金属スルフォネート等の金属化合物とともに、3級アミンが、無段変速機用の潤滑油組成物に配合されることも知られている。しかし、このような潤滑油組成物をそのまま緩衝器用として使用しても、青銅製のブッシュ及びゴム製のオイルシールに対するフリクションが十分に低減できるわけではない。
さらに、従来、ショックアブソーバー用の潤滑油組成物には、摩擦調整剤としてジアルキルジチオリン酸亜鉛を使用することが知られている(特許文献3参照)。しかし、特許文献1、2に記載される潤滑油組成物に、アルキルジチオリン酸亜鉛を単純に配合しても、青銅製のブッシュ及びゴム製のオイルシールに対するフリクション性を必ずしも低減できるわけではない。また、極圧剤を配合した潤滑油組成物では保管中等に沈殿物が生じ、長期安定性に問題が生じる場合もがある。
(1)(A)鉱油及び/又は合成油からなる基油と、(B)下記一般式(I)で示される3級アミンと、(C)下記一般式(II)で示されるジチオリン酸亜鉛と、(D)リン酸エステルアミン塩を含む緩衝器用潤滑油組成物。
(2)一般式(I)においてR1及びR2が、それぞれ独立に、炭素数1~5の直鎖状、分岐状又は環状のアルキル基、及び炭素数1~5の直鎖状、分岐状又は環状のアルケニル基から選択されるとともに、R3が、炭素数12~24の直鎖状、分岐状又は環状のアルキル基、及び炭素数12~24の直鎖状、分岐状又は環状のアルケニル基から選択されるものである上記(1)に記載の緩衝器用潤滑油組成物。
(3)一般式(I)において、R3が炭素数16~20の直鎖状、分岐状又は環状のアルキル基である上記(1)又は(2)に記載の緩衝器用潤滑油組成物。
(4)一般式(I)において、R3がステアリル基である上記(3)に記載の緩衝器用潤滑油組成物。
(5)一般式(II)において、R4~R7は、それぞれ独立に、炭素10~20の直鎖状、分岐状又は環状のアルキル基、及び炭素数10~20の直鎖状、分岐状又は環状のアルケニル基から選ばれるものである上記(1)~(4)のいずれかに記載の緩衝器用潤滑油組成物。
(6)(D)リン酸エステルアミン塩が、以下の一般式(III)で示される酸性リン酸エステルのアミン塩である上記(1)~(5)のいずれかに記載の緩衝器用潤滑油組成物。
(7)一般式(III)において、R11及びR12はそれぞれ独立に炭素数16~20のアルキル基又は炭素数16~20のアルケニル基である上記(6)に記載の緩衝器用潤滑油組成物。
(8)(B)3級アミンが0.01~3質量%含有される上記(1)~(7)のいずれかに記載の緩衝器用潤滑油組成物。
(9)(C)ジチオリン酸亜鉛が、0.01~3質量%含有される上記(1)~(8)のいずれかに記載の緩衝器用潤滑油組成物。
(10)四輪用緩衝器用潤滑油組成物である上記(1)~(9)のいずれかに記載の緩衝器用潤滑油組成物。
(11)一般式(I)において、R1及びR2がそれぞれ炭素数1又は2である上記(1)~(10)のいずれかに記載の緩衝器用潤滑油組成物。
本発明の緩衝器用潤滑油組成物は、(A)基油と、(B)3級アミンと、(C)ジチオリン酸亜鉛化合物と(D)リン酸エステルアミン塩とを含むものである。
以下、各成分について詳細に説明する。
本発明の緩衝器用潤滑油組成物における基油としては、鉱油及び/又は合成油が用いられる。
鉱油としては、溶剤精製、水添精製等の通常の精製法により得られた、パラフィン基系鉱油、中間基系鉱油及びナフテン基系鉱油等、あるいは、フィッシャートロプシュプロセス等により製造されるワックス(ガストゥリキッドワックス)や鉱油系ワックスを異性化することによって製造されるもの等が挙げられる。
合成油としては、炭化水素系合成油、エーテル系合成油等が挙げられる。炭化水素系合成油としては、例えばポリブテン、ポリイソブチレン、1-オクテンオリゴマー、1-デセンオリゴマー、エチレン-プロピレン共重合体等のα-オレフィンオリゴマー又はその水素化物、アルキルベンゼン、アルキルナフタレン等を挙げることができる。エーテル系合成油としては、ポリオキシアルキレングリコール、ポリフェニルエーテル等が挙げられる。
なお、基油としては、上記鉱油及び/又は上記合成油の一種のみを用いても良いが、二種以上を用いても良い。さらには、鉱油一種以上と合成油一種以上とを組み合わせて用いてもよい。
基油としては、これらの中でも添加剤の溶解性の観点から鉱油が好適である。
基油の動粘度は特に制限はないが、本発明の緩衝器用潤滑油組成物を例えば自動車のショックアブソーバー油として用いる場合、40℃の動粘度で2~20mm2/sが好ましく、5~14mm2/sがより好ましい。なお、鉱油及び/又は合成油の二種以上を用いた場合、前記数値は、それらを混合してなる基油の動粘度を意味する。
緩衝器用潤滑油組成物の全量における(A)基油の含有割合は、80~99質量%であることが好ましく、90~98質量%であることがより好ましい。
本発明の緩衝器用潤滑油組成物において使用される3級アミンは、以下の一般式(I)で示されるものである。
一般式(I)においてR1及びR2は、それぞれ独立に炭素数1~5の直鎖状、分岐状、若しくは環状のアルキル基、又は炭素数1~5の直鎖状、分岐状、若しくは環状のアルケニル基であることが好ましい。R1及びR2は、互いに異なってもよいし、同一であっても良いが、同一であることが好ましい。また、R3は、炭素数12~24の直鎖状、分岐状、若しくは環状のアルキル基、又は炭素数12~24の直鎖状、分岐状、若しくは環状のアルケニル基であることが好ましい。
具体的には、R1及びR2は、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ビニル基、プロペニル基、ブテニル基、ペンテニル基が挙げられ、これらは直鎖状、分岐状、環状のいずれでもよい。これらの中ではメチル基又はエチル基が好ましく、メチル基が最も好ましい。
また、(B)3級アミンは、R3が16~20である3級アミンが主成分であることが好ましく、炭素数18である3級アミンが主成分であることがより好ましい。なお、主成分とは、(B)3級アミン全量に対して50質量%以上含むことを意味し、この含有割合は80質量%以上が好ましく、90質量%以上がより好ましい。
また、安定性を高め、摩擦係数をより低下させるためには、R3はアルキル基であることが好ましい。さらに、R3は直鎖状であったほうがよい。
R3のアルキル基としては、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、ヘンイコシル基、ドコシル基、トリコシル基、テトラコシル基が挙げられ、これらは直鎖状、分岐状、環状のいずれでもよい。また、アルケニル基としては、ドデセニル基,トリデセニル基,テトラデセニル基,ペンタデセニル基,ヘキサデセニル基,ヘプタデセニル基,オクタデセニル基,ノナデセニル基,イコセニル基,ヘンイコセニル基,ドコセニル基,トリコセニル基,テトラコセニル基を挙げられ、これらは直鎖状、分岐状、環状のいずれでもよく、二重結合の位置も任意である。
これらの中では、ヘキサデシル基、ステアリル基等のオクタデシル基、オレイル基等のオクタデセニル基、又はイコシル基等が好ましいが、ステアリル基が最も好ましい。
また、(B)3級アミンの好ましい具体的な化合物としては,ジメチルモノステアリルアミン、ジエチルステアリルアミン等が挙げられる。
本発明において使用されるジチオリン酸亜鉛は、以下の一般式(II)で示されるものが使用される。
本発明においては、3級アミンとともに、上記のジチオリン酸亜鉛を使用することで、潤滑油組成物の青銅及びゴムに対する摩擦係数を良好に低下させることができる。
一般式(II)において、R4~R7の炭素数は、10~20であることが好ましいが、炭素数12~18であることがより好ましい。ジチオリン酸亜鉛の炭素数をこれら範囲にすることで、特にゴムに対する摩擦係数をより有効に低減できる。
R4~R7は、直鎖状であったほうがよく、またR4~R7は、アルキル基であったほうがよい。
R4~R7におけるアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、ヘンイコシル基、ドコシル基、トリコシル基及びテトラコシル基が挙げられ、これらは直鎖状、分岐状、環状のいずれであってもよい。また、アルケニル基としては、ビニル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基,トリデセニル基,テトラデセニル基,ペンタデセニル基,ヘキサデセニル基,ヘプタデセニル基,オクタデセニル基,ノナデセニル基,イコセニル基,ヘンイコセニル基,ドコセニル基,トリコセニル基,テトラコセニル基が挙げられるが、これらは直鎖状、分岐状、環状のいずれであってもよく、二重結合の位置も任意である。
これらの中ではラウリル基等のドデシル基、テトラデシル基、ヘキサデシル基、ステアリル基等のオクタデシル基、イコシル基、オレイル基等のオクタデセニル基が好ましいが、ラウリル基が最も好ましい。
(D)リン酸エステルアミン塩としては、酸性リン酸エステルとアミンとを反応させて得られる酸性リン酸エステルアミン塩、及び/又は酸性亜リン酸エステルとアミンとを反応させて得られる酸性亜リン酸エステルアミン塩が挙げられるが、本発明では、酸性リン酸エステルアミン塩が好ましい。
本発明において(D)リン酸エステルアミン塩は、いわゆる極圧剤としての機能を有するもので、焼付けを防止しつつ耐摩耗性を良好にすることができる。また、(D)リン酸エステルアミン塩は、長期保管しても、例えば(C)ジチオリン酸亜鉛と反応して沈殿が発生することもない。
R11及びR12のアルキル基及びアルケニル基は、直鎖状、分岐状、環状のいずれであってもよいが、直鎖状であることが好ましい。さらに、R11及びR12のアルキル基及びアルケニル基は、好ましくは炭素数12~24であるが、より好ましくは炭素数16~20であり、さらに好ましくR11及びR12の一方又は両方が炭素数18である。
また、(D)アミン塩を構成する酸性リン酸エステルは、R11及びR12が炭素数16~20であるものが主成分であることが好ましく、炭素数18であるものが主成分であることがより好ましい。なお、主成分であるとは、(D)アミン塩を構成する酸性リン酸エステルにおけるR11及びR12のアルキル基及びアルケニル基総量中における炭素数16~20(又は18)のR11及びR12の割合が、50質量%以上であることを意味し、その含有割合は80質量%以上であることが好ましく、90質量%以上であることがさらに好ましい。
R11及びR12におけるアルキル基としては、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、ヘンイコシル基、ドコシル基、トリコシル基及びテトラコシル基が挙げられ、これらは直鎖状、分岐状、環状のいずれであってもよい。また、アルケニル基としては、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基,トリデセニル基,テトラデセニル基,ペンタデセニル基,ヘキサデセニル基,ヘプタデセニル基,オクタデセニル基,ノナデセニル基,イコセニル基,ヘンイコセニル基,ドコセニル基,トリコセニル基,テトラコセニル基が挙げられるが、これらは直鎖状、分岐状、環状のいずれであってもよく、二重結合の位置も任意である。
これらの中では、直鎖状のアルキル基又はアルケニル基が好ましいが、オレイル基等のオクタデセニル基が最も好ましい。なお、酸性リン酸エステルの具体例としては、ジオレイルアシッドフォスフェートが挙げられる。
R21及びR22のアルキル基及びアルケニル基は、直鎖状、分岐状、環状のいずれであってもよいが、直鎖状であることが好ましい。さらに、R21及びR22のアルキル基及びアルケニル基は、好ましくは炭素数12~24であるが、より好ましくは炭素数16~20であり、特に好ましくR21及びR22の一方又は両方が炭素数18である。
また、(D)アミン塩を構成する酸性亜リン酸エステルは、R21及びR22が炭素数16~20であるものが主成分であることが好ましく、炭素数18であるものが主成分であることがより好ましい。なお、主成分であるとは、(D)アミン塩を構成する酸性亜リン酸エステルにおけるR21及びR22のアルキル基及びアルケニル基総量中における炭素数16~20(又は18)のR21及びR22の割合が、50質量%以上であることを意味し、その含有割合は80質量%以上であることが好ましく、90質量%以上であることがさらに好ましい。
R21及びR22におけるアルキル基としては、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、イコシル基、ヘンイコシル基、ドコシル基、トリコシル基及びテトラコシル基が挙げられ、これらは直鎖状、分岐状、環状のいずれであってもよい。また、アルケニル基としては、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基,トリデセニル基,テトラデセニル基,ペンタデセニル基,ヘキサデセニル基,ヘプタデセニル基,オクタデセニル基,ノナデセニル基,イコセニル基,ヘンイコセニル基,ドコセニル基,トリコセニル基,テトラコセニル基が挙げられるが、これらは直鎖状、分岐状、環状のいずれであってもよく、二重結合の位置も任意である。
また、当該アミンを構成する脂肪族炭化水素基の総量のうち、80質量%以上が、アルキル基及び/又は不飽和結合を1個有する不飽和炭化水素基であることが好ましい。
リン酸エステルアミン塩が常温(25℃)で液状であると、基油への溶解性や低温での析出防止の点で好ましく、そのためには、上記脂肪族炭化水素基の炭素数が6~20のものが好ましく、炭素数12~20のものがより好ましい。
当該アミンの例としては、ジラウリルアミン、ジミリスチルアミン、ジステアリルアミン、ジオレイルアミン、トリラウリルアミン、トリミリスチルアミン、トリステアリルアミン、トリオレイルアミン、牛脂アミンなどを挙げることができる。
これらのアルキルアミンは、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
(D)成分は、リン酸エステルアミン塩とした後に、他の成分と混合して緩衝器用潤滑油組成物を調整することが好ましいが、リン酸エステルとアミンを各々個別に組成物に配合して組成物中で反応させてアミン塩を形成してもよい。
アミン塩を形成しない酸性リン酸エステル及び酸性亜リン酸エステルは、長期間保管すると上記(C)ジチオリン酸亜鉛と反応して沈殿を発生させるが、その量を0.05質量%未満程度に抑えると沈殿が発生しにくくなる。
本発明の緩衝器用潤滑油組成物には、(E)任意添加成分として、他の無灰系分散剤、摩擦調整剤、酸化防止剤、粘度指数向上剤、及び消泡剤の中から選ばれる少なくとも1種を、本発明の目的が損なわれない範囲で適宜含有されてよい。また、所望により、従来、緩衝器用潤滑油組成物に慣用されている他の添加剤、例えば金属系清浄剤、錆止め剤、金属不活性化剤、流動点降下剤等が含有されてもよい。
緩衝器用潤滑油組成物の全量における(E)任意添加成分の含有割合は、通常10量%以下であることが好ましく、3~8質量%がより好ましい。
また、ステアリルアミン、オレイルアミン等の炭素数10~20程度の脂肪族飽和モノアミン及び不飽和モノアミンも摩擦調整剤として好適に使用できる。
消泡剤としては、高分子シリコーン系消泡剤が好ましく、この高分子シリコーン系消泡剤を含有させることにより、消泡性が効果的に発揮される。高分子シリコーン系消泡剤としては、例えばオルガノポリシロキサン、トリフルオロプロピルメチルシリコーン油等のフッ素化オルガノポリシロキサン等が挙げられる。
本発明では、ゴム及び青銅に対する摩擦係数μが上記範囲になることにより、乗り心地性能が良好になる。なお、摩擦係数μは後述する方法により測定されたものである。
また、本発明の潤滑油組成物は、少なくともピストンロッドとの摺動面である内面がリン青銅等の青銅製のブッシュであるとともに、オイルシールがゴム製であるショックアブソーバーに好適に使用できる。特に、オイルシールの緊迫力を増大させ耐ダスト性を高めたものにさらに好適である。
なお、ピストンロッドのブッシュとの摺動面は、一般的に、クロムメッキ等によりクロム製とされる。
さらに本発明の緩衝器用潤滑油組成物は、工業用油圧作動油や建機用動作油等にも好適に使用可能である。
なお、本発明における各物性の評価は、以下の方法で行った。
[評価方法]
1.動粘度
JIS K2283に準拠して測定した。
2.ゴムに対する摩擦係数
バウデン式往復動摩擦試験機により,以下の試験条件でゴムに対する摩擦係数μを測定した。なお、表1においては“ゴムμ”と表記した。
温度:23℃(室温)、速度:0.3mm/s、振幅:10mm、テストピース:NBR/クロムメッキ板(50×1000×5mm)
荷重:1kgf、2kgf、3kgf、5kgf、7kgfのそれぞれで行った。
なお、ゴム(NBR)は、ゴムプレートを径15mmの円形に切り出し、径12.7mm球で押し出した。また、プレートにサンプル油を数滴落として、慣らし(速度20mm/s、2分)を行った後、試験を行った。
3.青銅に対する摩擦係数μ
バウデン式往復動摩擦試験機により,以下の試験条件で青銅に対する摩擦係数μを測定した。なお、表1においては“青銅μ”と表記した。
温度:23℃(室温)、速度:0.3mm/s、振幅:10mm、テストピース:リン青銅球(径12.7mmの球)/クロムメッキ板(50×1000×5mm)
荷重:1kgf、2kgf、3kgf、5kgf、7kgfのそれぞれで行った。
なお、プレートにサンプル油を数滴落として、慣らし(速度20mm/s、2分)を行った後、試験を行った。
4.貯蔵試験
調整された緩衝器用潤滑油組成物を密閉容器の中に入れて23℃(室温)環境下で30日間放置した際の外観を観察した。
表1に示すように、実施例1~3、比較例1~5の緩衝器用潤滑油組成物を用意し、それらのゴム、青銅に対する摩擦係数を測定するとともに、貯蔵試験を実施した。
鉱油1:40℃動粘度:7.117mm2/s、粘度指数:109、密度(15℃):0.8200g/cm3のパラフィン系鉱油
鉱油2:40℃動粘度:29.48mm2/s、粘度指数:131、密度(15℃):0.8399g/cm3のパラフィン系鉱油
なお、基油1と基油2とを混合して得た、各実施例、比較例の基油の粘度は、表中に記載したとおりである。
3級アミン1:ジメチルモノステアリルアミン
3級アミン2:ジエチルモノステアリルアミン
ジチオリン酸亜鉛1:一般式(II)において、R4~R7の全てがラウリル基であるジラウリルジチオリン酸亜鉛
ジチオリン酸亜鉛2:一般式(II)において、R4~R7の全てがオレイル基であるジオレイルジチオリン酸亜鉛
ジチオリン酸亜鉛3:一般式(II)において、R4~R7は、n-ヘキシル基、イソプロピル基、n-ブチル基の混合物である。
極圧剤1:式(III)において、R11、R12のいずれもがオレイル基であるジオレイルアシッドフォスフェートのアミン塩(酸性リン酸エステルアミン塩)である。なお、アミンとしては、牛脂アミンを使用した。
極圧剤2:ジラウリルハイドロジェンフォスファイト(亜リン酸エステル)
極圧剤3:ジオレイルアシッドフォスフェート(酸性リン酸エステル)
極圧剤4:エチル-3-[[ビス(1-メチルエトキシ)フォスフィノチオイル]チオ]プロピオネート(ジチオリン酸エステル)
極圧剤5:トリクレジルフォスフェート(TCP)
酸化防止剤:2,6-ジ-tert-ブチル-p-クレゾール(DBPC)
無灰系分散剤:脂肪酸アミド(イソステアリン酸-テトラエチレンペンタミン反応物)
摩擦調整剤1:ソルビタンモノオレエート 摩擦調整剤2:モノオレイルアミン
摩擦調整剤3:グリセリン部分エステル
金属不活性化剤:チアジアゾール系(2,5-ビス(1,1,3,3-テトラメチルブタジチオ)1,3,4-チアジアゾール)
消泡剤:シリコーン系消泡剤(ジメチルポリシロキサン 20℃動粘度=1.25万cSt)
粘度指数向上剤:ポリメタクリレート系(PMA Mw=14万)
一方で、比較例1~3に示すように、(B)3級アミン及び(C)ジチオリン酸亜鉛のいずれか一方又は両方を含まない緩衝器用潤滑油組成物は、広い荷重範囲に亘って、ゴム及び青銅に対する摩擦係数を十分に低下させることができなかった。また、比較例4、5に示すように,ジチオリン酸亜鉛とともに極圧剤としてリン酸エステル又は亜リン酸エステルを使用すると、1ヶ月経過後に沈殿が発生し、長期保管安定性が良好ではなかった。
Claims (11)
- 一般式(I)においてR1及びR2が、それぞれ独立に、炭素数1~5の直鎖状、分岐状又は環状のアルキル基、及び炭素数1~5の直鎖状、分岐状又は環状のアルケニル基から選択されるとともに、R3が、炭素数12~24の直鎖状、分岐状又は環状のアルキル基、及び炭素数12~24の直鎖状、分岐状又は環状のアルケニル基から選択されるものである請求項1に記載の緩衝器用潤滑油組成物。
- 一般式(I)において、R3が炭素数16~20の直鎖状、分岐状、又は環状のアルキル基である請求項2に記載の緩衝器用潤滑油組成物。
- 一般式(I)において、R3がステアリル基である請求項3に記載の緩衝器用潤滑油組成物。
- 一般式(II)において、R4~R7は、それぞれ独立に、炭素数10~20の直鎖状、分岐状又は環状のアルキル基、及び炭素数10~20の直鎖状、分岐状又は環状のアルケニル基から選ばれるものである請求項1~4のいずれかに記載の緩衝器用潤滑油組成物。
- 一般式(III)において、R11及びR12はそれぞれ独立に炭素数16~20のアルキル基又は炭素数16~20のアルケニル基である請求項6に記載の緩衝器用潤滑油組成物。
- (B)3級アミンが0.01~3質量%含有される請求項1~7のいずれかに記載の緩衝器用潤滑油組成物。
- (C)ジチオリン酸亜鉛が、0.01~3質量%含有される請求項1~8のいずれかに記載の緩衝器用潤滑油組成物。
- 四輪用緩衝器用潤滑油組成物である請求項1~9のいずれかに記載の緩衝器用潤滑油組成物。
- 一般式(I)において、R1及びR2がそれぞれ炭素数1又は2である請求項1~10のいずれかに記載の緩衝器用潤滑油組成物。
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- 2014-08-25 US US14/910,845 patent/US20160369200A1/en not_active Abandoned
- 2014-08-25 JP JP2015532932A patent/JP6353840B2/ja active Active
- 2014-08-25 KR KR1020167004385A patent/KR20160042910A/ko not_active Application Discontinuation
- 2014-08-25 EP EP14838669.1A patent/EP3037507B1/en active Active
- 2014-08-25 CN CN201480046145.3A patent/CN105473693B/zh active Active
- 2014-08-25 WO PCT/JP2014/072187 patent/WO2015025977A1/ja active Application Filing
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2017160292A (ja) * | 2016-03-07 | 2017-09-14 | 出光興産株式会社 | 緩衝器用潤滑油組成物、及び緩衝器用潤滑油組成物の製造方法 |
WO2017221446A1 (ja) * | 2016-06-21 | 2017-12-28 | Kyb株式会社 | 作動油 |
WO2020110243A1 (ja) * | 2018-11-28 | 2020-06-04 | コスモ石油ルブリカンツ株式会社 | 潤滑油組成物 |
JPWO2020110243A1 (ja) * | 2018-11-28 | 2021-10-14 | コスモ石油ルブリカンツ株式会社 | 潤滑油組成物 |
JP7245851B2 (ja) | 2018-11-28 | 2023-03-24 | コスモ石油ルブリカンツ株式会社 | 潤滑油組成物 |
JPWO2020218025A1 (ja) * | 2019-04-26 | 2021-05-06 | Kyb株式会社 | 緩衝器用潤滑油組成物、摩擦調整用添加剤、潤滑油添加剤、緩衝器および緩衝器用潤滑油の摩擦調整方法 |
US11932823B2 (en) | 2019-04-26 | 2024-03-19 | Kyb Corporation | Lubricant composition for shock absorbers, additive for friction adjustment, lubricant additive, shock absorber and friction adjustment method for lubricant composition for shock absorbers |
WO2022004870A1 (ja) | 2020-07-02 | 2022-01-06 | 出光興産株式会社 | 潤滑油組成物、緩衝器、及び潤滑油組成物の使用方法 |
Also Published As
Publication number | Publication date |
---|---|
EP3037507A4 (en) | 2017-02-08 |
EP3037507A1 (en) | 2016-06-29 |
EP3037507B1 (en) | 2022-06-29 |
CN105473693B (zh) | 2019-04-02 |
KR20160042910A (ko) | 2016-04-20 |
JPWO2015025977A1 (ja) | 2017-03-02 |
CN105473693A (zh) | 2016-04-06 |
US20160369200A1 (en) | 2016-12-22 |
JP6353840B2 (ja) | 2018-07-04 |
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