US20150038384A1 - Lubricating oil composition for shock absorber - Google Patents

Lubricating oil composition for shock absorber Download PDF

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Publication number
US20150038384A1
US20150038384A1 US14/384,112 US201314384112A US2015038384A1 US 20150038384 A1 US20150038384 A1 US 20150038384A1 US 201314384112 A US201314384112 A US 201314384112A US 2015038384 A1 US2015038384 A1 US 2015038384A1
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Prior art keywords
shock absorber
lubricating oil
composition
oil composition
mass
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US14/384,112
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Shuichi Sakanoue
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Assigned to IDEMITSU KOSAN CO., LTD. reassignment IDEMITSU KOSAN CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SAKANOUE, SHUICHI
Publication of US20150038384A1 publication Critical patent/US20150038384A1/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00Lubricating 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
    • C10M141/10Lubricating 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68Esters
    • C10M129/76Esters containing free hydroxy or carboxyl groups
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04Mixtures of base-materials and additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/283Esters of polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/287Partial esters
    • C10M2207/289Partial esters containing free hydroxy groups
    • C10M2207/2895Partial esters containing free hydroxy groups used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/045Metal containing thio derivatives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/08Hydraulic fluids, e.g. brake-fluids

Definitions

  • the present invention relates to a lubricating oil composition for a shock absorber. More specifically, the present invention relates to a lubricating oil composition for a shock absorber mainly used at a sliding part between a guide bush and a piston rod in a shock-absorber of a four-wheeled vehicle.
  • Lubricating oil for shock absorbers in automobiles is employed mainly for damping vibration in order to attain optimum attenuation force and maintain driving stability.
  • shock absorbers are disposed in an automobile between the body and the tires and attenuate vibration of the car body caused by bumps of a road, jolting generated at quick acceleration or heavy braking, and other motions.
  • lubricating oils for shock absorbers in automobiles have exhibited enhanced vibration damping effect through reducing the friction at a sliding interface between an oil seal and a piston rod, a piston rod and a guide bush, a piston band and a cylinder, etc. in a shock absorber (see, for example, Patent Documents 1 and 2).
  • Patent Document 3 discloses a lubricating oil composition containing a base oil and at least one species selected from among an alkenyl succinimide, an acidic phosphite diester, and a perbasic sulfonate, phenate, or salicylate of an alkaline earth metal, for the purposes of enhancing frictional force at the interface between an oil seal and a piston rod, reducing the friction coefficient between the piston rod and the guide bush, and suppressing foaming.
  • a lubricating oil composition containing a base oil and at least one species selected from among an alkenyl succinimide, an acidic phosphite diester, and a perbasic sulfonate, phenate, or salicylate of an alkaline earth metal, for the purposes of enhancing frictional force at the interface between an oil seal and a piston rod, reducing the friction coefficient between the piston rod and the guide bush, and suppressing foaming.
  • a shock absorber is arranged not in a direction orthogonal to the road but is slanted from the orthogonal direction, since the slant arrangement provides more excellent riding comfort.
  • a shock absorber oil shock absorber fluid: SAF
  • SAF shock absorber fluid
  • the piston rod/guide bush friction has been reduced by use of a phosphorus-containing additive or a fatty acid.
  • phosphorus-containing additives generally have poor thermal stability, and fatty acids generally have poor wear resistance.
  • Patent Document 1 Japanese Patent Application Laid-Open (kokai) No. Hei 5-255683
  • Patent Document 2 Japanese Patent Application Laid-Open (kokai) No. 2000-192067
  • Patent Document 3 Japanese Patent Application Laid-Open (kokai) No. 2009-298886
  • an object of the present invention is to provide a lubricating oil composition for a shock absorber that can improve lubricity between bronze and chromium, which are materials generally used in a guide bush and a piston rod; specifically, the composition lowers the friction coefficient therebetween and reduces wear area of bronze, to thereby reduce the friction coefficient between a piston rod and a guide bush and, furthermore, to prevent wearing of the guide bush.
  • the present inventor has conducted extensive studies to develop a lubricating oil composition for solving the aforementioned problems, and has found that the object can be attained by adding a specific amount of a specific polyhydric alcohol partial ester to a specific base oil.
  • the present invention has been accomplished on the basis of this finding.
  • the present invention provides the following.
  • a lubricating oil composition for a shock absorber comprising:
  • a lubricating oil composition for a shock absorber that can improve lubricity between bronze and chromium, which are materials generally used in a guide bush and a piston rod; specifically, the composition lowers the friction coefficient therebetween and reduces wear area of bronze, to thereby reduce the friction coefficient between a piston rod and a guide bush and, furthermore, to prevent wearing of the guide bush.
  • the lubricating oil composition for a shock absorber of the present invention can provide automobile users with excellent riding comfort through reduction in friction coefficient.
  • the lubricating oil composition of the present invention prevents friction in a shock absorber, to thereby enhance durability of the shock absorber, whereby the shock absorber can exhibit excellent riding comfort and high durability.
  • the lubricating oil composition for a shock absorber of the present invention comprises;
  • component (A) a base oil composed of a mineral oil and/or a synthetic oil (hereinafter may be referred to simply as “component (A)”), and;
  • component (B) a polyhydric alcohol partial ester having a C10 to C20 fatty acid residue (hereinafter may be referred to simply as “component (B)”), in an amount of 0.05 mass % to 10 mass % with respect to the total amount of the composition.
  • the base oil (A) of the lubricating oil composition of the present invention is a mineral oil and/or a synthetic oil. No particular limitation is imposed on the type of the mineral oil and synthetic oil.
  • the mineral oil include paraffin-based mineral oil, intermediate mineral oil, and naphthene-based mineral oil, which are produced through a routine refining method such as solvent refining or hydrogenation refining.
  • Examples of the synthetic oil include polybutene, polyolefins [e.g., ⁇ -olefin (co)polymers], esters (e.g., polyol-esters, dibasic acid esters, and phosphoric acid esters), and ethers (e.g., polyphenyl ether), alkylbenzenes, and alkylnaphthalenes.
  • polyolefins e.g., ⁇ -olefin (co)polymers
  • esters e.g., polyol-esters, dibasic acid esters, and phosphoric acid esters
  • ethers e.g., polyphenyl ether
  • alkylbenzenes e.g., polyphenylnaphthalenes.
  • the mineral oil may be used, as the base oil, singly or in combination of two or more species.
  • the synthetic oil may be used, as the base oil, singly or in combination of two or more species.
  • one or more mineral oils may be combined with one or more synthetic oils.
  • mineral oils particularly paraffin-based mineral oils; ⁇ -olefin polymers, such as 1-decene oligomers; and mixtures thereof are preferably employed.
  • the lubricating oil composition of the present invention is mainly employed as an automobile shock absorber oil.
  • the viscosity of the base oil is preferably within the range of 2 to 20 mm 2 /s, more preferably 3 to 15 mm 2 /s, and still more preferably 4 to 10 mm 2 /s in terms of kinematic viscosity at 40° C.
  • the viscosity index of the base oil is preferably 95 or higher, more preferably 100 or higher, still more preferably 105 or higher.
  • properties of the base oils including viscosity index mean those of the base oil mixture.
  • the base oil preferably has a flash point of 150° C. or higher, more preferably 155° C. or higher.
  • the flash point of the base oil is 150° C. or higher, foaming is suppressed in use of the oil composition, which may enhance riding comfort.
  • the flash point is generally measured through JIS K2265 (COC method).
  • the component (A) content of the lubricating oil composition of the present invention is preferably 50 mass % to 99.9 mass %, with respect to the total amount of the composition, more preferably 70 mass % to 99.8 mass %, still more preferably 80 mass % to 99.7 mass %.
  • Component (B) is a polyhydric alcohol partial ester having a C10 to C20 fatty acid residue.
  • fatty acid residue refers to a residue formed through removal of a carboxyl group from a fatty acid.
  • the residue may be branched or linear-chain, or may be an unsaturated aliphatic hydrocarbon residue or a saturated aliphatic hydrocarbon residue.
  • Specific examples of the fatty acid residue include decyl, lauryl, palmityl, stearyl, and oleyl.
  • polyhydric alcohol examples include dihydric alcohols, such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; trihydric alcohols, such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 1,3,5-pentanetriol, 1,2,4-butanetriol, 1,2,6-hexanetriol; tetrahydric alcohols, such as pentaerythritol, 1,2,3,4-butanetetrol, and sorbitan; and polyhydric alcohols, such as adonitol, arabitol, xylytol, sorbitol, and mannitol.
  • dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol
  • trihydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 1,
  • the number of hydroxyl groups is preferably 3 or more, more preferably 4.
  • the polyhydric alcohol preferably has 1 to 3 ester substituted sites, more preferably 2 to 3 ester substituted sites.
  • the polyhydric alcohol partial ester preferably has 2 or more hydroxyl groups.
  • Examples of preferred polyhydric alcohol partial esters include pentaerythritol dioleate, pentaerythritol dilaurylate, and pentaerythritol distearylate.
  • pentaerythritol dioleate and pentaerythritol dilaurylate are particularly preferred.
  • the component (B) content of the lubricating oil composition of the present invention is 0.05 mass % to 10 mass %, with respect to the total amount of the composition, preferably 0.2 mass % to 4 mass %, more preferably 0.3 mass % to 3 mass %.
  • the lubricating oil composition of the present invention preferably contains (C) a phosphorus-containing compound (hereinafter may be referred to simply as “component (C)”).
  • component (C) a phosphorus-containing compound
  • the phosphorus-containing compound exerts synergistically with polyhydric alcohol partial ester (B), to thereby provide considerably enhanced wear resistance.
  • Examples of the phosphorus-containing compound (C) include phospho-ester compounds such as a phosphate ester, an acidic phosphate monoester amine salt, and an acidic phosphite diester, and zinc dithiophosphate (ZnDTP).
  • phospho-ester compounds such as a phosphate ester, an acidic phosphate monoester amine salt, and an acidic phosphite diester, and zinc dithiophosphate (ZnDTP).
  • the lubricating oil composition of the present invention preferably contains, as a phosphorus-containing compound among them, ZnDTP having a C7 to C12 alkyl group.
  • ZnDTP includes compounds represented by the following formula (I)
  • R 1 and R 2 represents a C7 to C12 linear-chain, branched, or cyclic alkyl group.
  • alkyl group R 1 or R 2 in formula (I) include heptyl, isoheptyl, cyclohexylmethyl, octyl, 2-ethylhexyl, isooctyl, cyclooctyl, nonyl, isononyl, 3,5,5-trimethylhexyl, cyclooctylmethyl, decyl, 3,7-dimethyloctyl, 2-propylheptyl, isodecyl, undecyl, dodecyl, 2-butyloctyl, and isododecyl.
  • C7 to C10 alkyl groups are more preferred.
  • R 1 and R 2 may be identical to or different from each other. However, they are preferably the same group, from the viewpoint of easiness of production.
  • the phosphate ester compound examples include an acidic phosphoric acid monoester amine salt formed from an acidic phosphoric acid monoester having a C1 to C8 alkyl or alkenyl group; e.g., monomethyl hydrogenphosphate or monoethyl hydrogenphosphate, and an amine compound having a C8 to C20 alkyl or alkenyl group.
  • the lubricating oil composition of the present invention preferably has a component (C) content; i.e., a phosphorus-containing compound content, of 0.3 to 2 mass %, with respect to the total amount of the composition, more preferably 0.5 to 1.5 mass %.
  • the shock absorber oil of the present invention may appropriately contain, as an optional additive, at least one species selected from among an ashless detergent-dispersant, a metallic detergent, a lubrication improver, an antioxidant, a rust preventive, a metal deactivator, a viscosity index improver, a pour point depressant, and a defoaming agent.
  • an ashless detergent-dispersant e.g., a metallic detergent, a lubrication improver, an antioxidant, a rust preventive, a metal deactivator, a viscosity index improver, a pour point depressant, and a defoaming agent.
  • the amounts of these components are preferably 0.1 to 20 mass %, with respect to the total amount of the composition, more preferably 0.3 to 10 mass %, still more preferably 0.3 to 5 mass %.
  • Examples of the ashless detergent-dispersant include divalent carboxamides, such as a succinimide, a boron-containing succinimide, a benzylamine, a boron-containing benzylamine, and succinic acid.
  • Examples of the metallic detergent include a neutral metal sulfonate, a neutral metal phenate, a neutral metal salicylate, a neutral metal phosphonate, a basic sulfonate, a basic phenate, a basic salicylate, a perbasic sulfonate, a perbasic salicylate, and a perbasic phosphonate.
  • Examples of the type of the lubrication improver include an extreme pressure agent, an antiwear agent, and an oiliness agent
  • examples of the material of the lubrication improver include organometallic compounds, such as zinc dithiocarbamate (ZnDTC), oxysulfidomolybdenum organophosphorodithioate (MoDTP), and oxysulfidomolybdenum dithiocarbamate (MoDTC).
  • sulfur-containing extreme pressure agent examples include sulfurized oils, sulfurized fatty acids, sulfurized esters, sulfurized olefins, dihydrocarbyl polysulfide, thiadiazole compounds, alkylthiocarbamoyl compounds, triazine compounds, thioterpene compounds, and dialkylthio dipropionate compounds.
  • oiliness agent examples include aliphatic saturated and unsaturated monocarboxylic acids, such as stearic acid and oleic acid; polymerized fatty acids, such as dimer acid and hydrogenated dimer acid; hydroxy fatty acids, such as ricinoleic acid and 12-hydroxystearic acid; aliphatic saturated and unsaturated monoalcohols, such as lauryl alcohol and oleyl alcohol; aliphatic saturated and unsaturated monoamines, such as stearylamine and oleylamine; and aliphatic saturated and unsaturated monocarboxamides, such as lauriamide and oleamide.
  • monocarboxylic acids such as stearic acid and oleic acid
  • polymerized fatty acids such as dimer acid and hydrogenated dimer acid
  • hydroxy fatty acids such as ricinoleic acid and 12-hydroxystearic acid
  • aliphatic saturated and unsaturated monoalcohols such as lauryl alcohol and oleyl alcohol
  • antioxidants examples include polycyclic phenol-based antioxidants, such as 4,4′-methylenebis(2,6-di-tert-butylphenol) and 2,2′-methylenebis(4-ethyl-6-tert-butylphenol); amine-based antioxidants, such as monoalkyldiphenylamine compounds; e.g., monooctyldiphenylamine and monononyldiphenylamine, dialkyldiphenylamine compounds; e.g., 4,4′-dibutyldiphenylamine, 4,4′-dipentyldiphenylamine, 4,4′-dihexyldiphenylamine, 4,4′-diheptyldiphenylamine, 4,4′-dioctyldiphenylamine, and 4,4′-dinonyldiphenylamine, polyalkyldiphenylamine compounds; e.g., tetrabutyldiphenylamine, te
  • Examples of the rust preventive include metal sulfonates and succinate esters.
  • Examples of the metal deactivator include benzotriazole and thiadiazole.
  • viscosity index improver examples include polymethacrylates, dispersed polymethacrylates, olefin copolymers (e.g., ethylene-propylene copolymer), dispersed olefin copolymers, and styrene copolymers such as (e.g., styrene-diene hydrogenated copolymer).
  • olefin copolymers e.g., ethylene-propylene copolymer
  • dispersed olefin copolymers e.g., ethylene-propylene copolymer
  • styrene copolymers such as (e.g., styrene-diene hydrogenated copolymer).
  • pour point depressant examples include polymethacrylates having a mass average molecular weight of about 50,000 to about 150,000.
  • the defoaming agent is preferably a silicone polymer-based defoaming agent.
  • silicone polymer-based defoaming agent Through incorporation of the silicone polymer-based defoaming agent, defoaming performance can be effectively attained, whereby riding comfort can be improved.
  • silicone polymer-based defoaming agent examples include organopolysiloxanes. Among them, fluorine-containing organopolysiloxanes such as trifluoropropylmethylsilicone oil are particularly preferred.
  • the lubricating oil composition of the present invention may be applied to any of a multi-cylinder shock absorber and a single-cylinder shock absorber, and shock absorbers of a four-wheeled vehicle or a two-wheeled vehicle.
  • the composition of the present invention is particularly suitably used in four-wheeled vehicles.
  • the lubricating oil composition of the present invention lowers friction coefficient at the interface between bronze and chromium and reduces wear area of bronze.
  • the composition of the present invention is suitably used as a lubricant for a shock absorber which has a guide bush at least including a bronze surface, and a piston rod at least including a sliding part which comes into contact with the guide bush and which is made of chromium (e.g., chromium plating).
  • Tester Bowden-type reciprocating kinetic friction tester
  • Tester Bowden-type reciprocating kinetic friction tester
  • An oil composition sample was supplied to a plate, in an amount corresponding to several drops.
  • the wear area of the phosphor bronze ball was measured.
  • Lubricating oil compositions shock absorber oils containing the components given in Table 1 were prepared. Each composition was subjected to the friction coefficient measurement and the wear test. Table 1 shows the results.
  • Base oil secondary hydro-reformed mineral oil (paraffin-base) having a kinematic viscosity of 7.83 mm 2 /s measured at 40° C.
  • Pentaerythritol dioleate UNISTER H481D, product of NOF Corporation
  • Pentaerythritol monooleate EKISUPARU PE-MO
  • Pentaerythritol tetraoleate UNISTER H481R, product of NOF Corporation
  • Methyl acid phosphate amine salt VANLUBE 672, product of Vandarbilt
  • Zn-DTP(pri) OLOA 5286, C8 to C10 mixed alkyl groups, product of Ethyl Corporation
  • oil compositions of the Examples each containing (A) a base oil composed of a mineral oil and/or a synthetic oil and a specific amount of (B) a polyhydric alcohol partial ester having a C10 to C20 fatty acid residue, friction coefficient and wear area were found to be reduced. Particularly in the case of the oil composition of Example 2, containing component (B) and component (C), wear area was considerably reduced.
  • Comparative Example 1 employing a complete ester of a polyhydric alcohol, friction coefficient and wear area were at high levels.
  • Comparative Example 2 employing stearic acid, friction coefficient was low, but wear area was large.
  • Comparative Example 3 employing ZnDTP instead of component (B), friction coefficient and wear area were at high levels.
  • Comparative Example 4 employing a phosphate amine salt, friction coefficient was higher than that obtained in the Examples.
  • the lubricating oil composition of the present invention can be used for automobile shock absorbers.
  • the composition is applicable to both four-wheeled vehicles and two-wheeled vehicles.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

To provide a lubricating oil composition for a shock absorber for preventing wearing a piston rod and a guide bush in a shock absorber, which composition lowers the friction coefficient at the interface between bronze and chromium and reduces wear area of bronze.
The lubricating oil composition for a shock absorber contains (A) a base oil composed of a mineral oil and/or a synthetic oil, and (B) a polyhydric alcohol partial ester having a C10 to C20 fatty acid residue, in an amount of 0.05 mass % to 10 mass %, with respect to the total amount of the composition.

Description

    TECHNICAL FIELD
  • The present invention relates to a lubricating oil composition for a shock absorber. More specifically, the present invention relates to a lubricating oil composition for a shock absorber mainly used at a sliding part between a guide bush and a piston rod in a shock-absorber of a four-wheeled vehicle.
  • BACKGROUND ART
  • Lubricating oil for shock absorbers in automobiles is employed mainly for damping vibration in order to attain optimum attenuation force and maintain driving stability. Generally, shock absorbers are disposed in an automobile between the body and the tires and attenuate vibration of the car body caused by bumps of a road, jolting generated at quick acceleration or heavy braking, and other motions.
  • Hitherto, lubricating oils for shock absorbers in automobiles have exhibited enhanced vibration damping effect through reducing the friction at a sliding interface between an oil seal and a piston rod, a piston rod and a guide bush, a piston band and a cylinder, etc. in a shock absorber (see, for example, Patent Documents 1 and 2).
  • Patent Document 3 discloses a lubricating oil composition containing a base oil and at least one species selected from among an alkenyl succinimide, an acidic phosphite diester, and a perbasic sulfonate, phenate, or salicylate of an alkaline earth metal, for the purposes of enhancing frictional force at the interface between an oil seal and a piston rod, reducing the friction coefficient between the piston rod and the guide bush, and suppressing foaming.
  • Generally, a shock absorber is arranged not in a direction orthogonal to the road but is slanted from the orthogonal direction, since the slant arrangement provides more excellent riding comfort. Thus, during expansion and contraction of a shock absorber, large lateral force attributed to a generated bending moment is applied to the shock absorber. In order to facilitate expansion and contraction of the shock absorber under application of lateral force, a shock absorber oil (shock absorber fluid: SAF) is required to reduce friction of a bearing (guide bush). Particularly when the guide bush of a shock absorber has worn, oil leakage occurs, thereby failing to gain appropriate attenuation power, which is problematic.
  • As described above, the piston rod/guide bush friction has been reduced by use of a phosphorus-containing additive or a fatty acid. However, phosphorus-containing additives generally have poor thermal stability, and fatty acids generally have poor wear resistance.
  • PRIOR ART DOCUMENTS Patent Documents
  • Patent Document 1: Japanese Patent Application Laid-Open (kokai) No. Hei 5-255683
  • Patent Document 2: Japanese Patent Application Laid-Open (kokai) No. 2000-192067
  • Patent Document 3: Japanese Patent Application Laid-Open (kokai) No. 2009-298886
  • SUMMARY OF THE INVENTION Problems to be Solved by the Invention
  • Under such circumstances, an object of the present invention is to provide a lubricating oil composition for a shock absorber that can improve lubricity between bronze and chromium, which are materials generally used in a guide bush and a piston rod; specifically, the composition lowers the friction coefficient therebetween and reduces wear area of bronze, to thereby reduce the friction coefficient between a piston rod and a guide bush and, furthermore, to prevent wearing of the guide bush.
  • Means for Solving the Problems
  • The present inventor has conducted extensive studies to develop a lubricating oil composition for solving the aforementioned problems, and has found that the object can be attained by adding a specific amount of a specific polyhydric alcohol partial ester to a specific base oil. The present invention has been accomplished on the basis of this finding.
  • Accordingly, the present invention provides the following.
  • [1] A lubricating oil composition for a shock absorber, comprising:
  • (A) a base oil composed of a mineral oil and/or a synthetic oil, and;
  • (B) a polyhydric alcohol partial ester having a C10 to C20 fatty acid residue, in an amount of 0.05 mass % to 10 mass %, with respect to the total amount of the composition.
  • [2] A lubricating oil composition for a shock absorber as described in [1] above, wherein the component (B) is a tetrahydric alcohol partial ester.
  • [3] A lubricating oil composition for a shock absorber as described in [1] or [2] above, wherein the component (B) is pentaerythritol dioleate and/or pentaerythritol dilaurylate.
  • [4] A lubricating oil composition for a shock absorber as described in any of [1] to [3] above, which further comprises (C) a phosphorus-containing compound.
  • Effects of the Invention
  • According to the present invention, there can be provided a lubricating oil composition for a shock absorber that can improve lubricity between bronze and chromium, which are materials generally used in a guide bush and a piston rod; specifically, the composition lowers the friction coefficient therebetween and reduces wear area of bronze, to thereby reduce the friction coefficient between a piston rod and a guide bush and, furthermore, to prevent wearing of the guide bush. Particularly, the lubricating oil composition for a shock absorber of the present invention can provide automobile users with excellent riding comfort through reduction in friction coefficient. Furthermore, the lubricating oil composition of the present invention prevents friction in a shock absorber, to thereby enhance durability of the shock absorber, whereby the shock absorber can exhibit excellent riding comfort and high durability.
  • Modes for Carrying Out the Invention
  • The lubricating oil composition for a shock absorber of the present invention comprises;
  • (A) a base oil composed of a mineral oil and/or a synthetic oil (hereinafter may be referred to simply as “component (A)”), and;
  • (B) a polyhydric alcohol partial ester having a C10 to C20 fatty acid residue (hereinafter may be referred to simply as “component (B)”), in an amount of 0.05 mass % to 10 mass % with respect to the total amount of the composition.
  • <(A) Base Oil>
  • The base oil (A) of the lubricating oil composition of the present invention is a mineral oil and/or a synthetic oil. No particular limitation is imposed on the type of the mineral oil and synthetic oil. Examples of the mineral oil include paraffin-based mineral oil, intermediate mineral oil, and naphthene-based mineral oil, which are produced through a routine refining method such as solvent refining or hydrogenation refining.
  • Examples of the synthetic oil include polybutene, polyolefins [e.g., α-olefin (co)polymers], esters (e.g., polyol-esters, dibasic acid esters, and phosphoric acid esters), and ethers (e.g., polyphenyl ether), alkylbenzenes, and alkylnaphthalenes.
  • In the present invention, the mineral oil may be used, as the base oil, singly or in combination of two or more species. Also, the synthetic oil may be used, as the base oil, singly or in combination of two or more species. Furthermore, one or more mineral oils may be combined with one or more synthetic oils.
  • Among these oils, mineral oils, particularly paraffin-based mineral oils; α-olefin polymers, such as 1-decene oligomers; and mixtures thereof are preferably employed.
  • The lubricating oil composition of the present invention is mainly employed as an automobile shock absorber oil. Thus, the viscosity of the base oil is preferably within the range of 2 to 20 mm2/s, more preferably 3 to 15 mm2/s, and still more preferably 4 to 10 mm2/s in terms of kinematic viscosity at 40° C.
  • No particular limitation is imposed on the viscosity index of the base oil, but it is preferably 95 or higher, more preferably 100 or higher, still more preferably 105 or higher. In the case where a plurality of base oils are used in combination, properties of the base oils including viscosity index mean those of the base oil mixture.
  • The base oil preferably has a flash point of 150° C. or higher, more preferably 155° C. or higher. When the flash point of the base oil is 150° C. or higher, foaming is suppressed in use of the oil composition, which may enhance riding comfort.
  • Therefore, it is not preferred to use a base oil to which an excessive amount of low-viscosity base has been added for the purpose of enhancement of low-temperature flowability.
  • In the present invention, the flash point is generally measured through JIS K2265 (COC method).
  • No particular limitation is imposed on the component (A) content of the lubricating oil composition of the present invention. For example, the component (A) content is preferably 50 mass % to 99.9 mass %, with respect to the total amount of the composition, more preferably 70 mass % to 99.8 mass %, still more preferably 80 mass % to 99.7 mass %.
  • <(B) Polyhydric Alcohol Partial Ester>
  • Component (B) is a polyhydric alcohol partial ester having a C10 to C20 fatty acid residue. As used herein, the term “fatty acid residue” refers to a residue formed through removal of a carboxyl group from a fatty acid.
  • No particular limitation is imposed on the fatty acid residue, and the residue may be branched or linear-chain, or may be an unsaturated aliphatic hydrocarbon residue or a saturated aliphatic hydrocarbon residue. Specific examples of the fatty acid residue include decyl, lauryl, palmityl, stearyl, and oleyl.
  • Examples of the polyhydric alcohol include dihydric alcohols, such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; trihydric alcohols, such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 1,3,5-pentanetriol, 1,2,4-butanetriol, 1,2,6-hexanetriol; tetrahydric alcohols, such as pentaerythritol, 1,2,3,4-butanetetrol, and sorbitan; and polyhydric alcohols, such as adonitol, arabitol, xylytol, sorbitol, and mannitol.
  • No particular limitation is imposed on the valency of the polyhydric alcohol, but the number of hydroxyl groups is preferably 3 or more, more preferably 4.
  • The polyhydric alcohol preferably has 1 to 3 ester substituted sites, more preferably 2 to 3 ester substituted sites.
  • The polyhydric alcohol partial ester preferably has 2 or more hydroxyl groups.
  • Examples of preferred polyhydric alcohol partial esters include pentaerythritol dioleate, pentaerythritol dilaurylate, and pentaerythritol distearylate.
  • Of these, pentaerythritol dioleate and pentaerythritol dilaurylate are particularly preferred.
  • The component (B) content of the lubricating oil composition of the present invention is 0.05 mass % to 10 mass %, with respect to the total amount of the composition, preferably 0.2 mass % to 4 mass %, more preferably 0.3 mass % to 3 mass %.
  • <(C) Phosphorus-Containing Compound>
  • The lubricating oil composition of the present invention preferably contains (C) a phosphorus-containing compound (hereinafter may be referred to simply as “component (C)”). The phosphorus-containing compound exerts synergistically with polyhydric alcohol partial ester (B), to thereby provide considerably enhanced wear resistance.
  • Examples of the phosphorus-containing compound (C) include phospho-ester compounds such as a phosphate ester, an acidic phosphate monoester amine salt, and an acidic phosphite diester, and zinc dithiophosphate (ZnDTP).
  • The lubricating oil composition of the present invention preferably contains, as a phosphorus-containing compound among them, ZnDTP having a C7 to C12 alkyl group. Examples of the ZnDTP includes compounds represented by the following formula (I)
  • Figure US20150038384A1-20150205-C00001
  • (wherein each of R1 and R2 represents a C7 to C12 linear-chain, branched, or cyclic alkyl group).
  • Specific examples of the alkyl group R1 or R2 in formula (I) include heptyl, isoheptyl, cyclohexylmethyl, octyl, 2-ethylhexyl, isooctyl, cyclooctyl, nonyl, isononyl, 3,5,5-trimethylhexyl, cyclooctylmethyl, decyl, 3,7-dimethyloctyl, 2-propylheptyl, isodecyl, undecyl, dodecyl, 2-butyloctyl, and isododecyl. Among them, C7 to C10 alkyl groups are more preferred.
  • R1 and R2 may be identical to or different from each other. However, they are preferably the same group, from the viewpoint of easiness of production.
  • Examples of the phosphate ester compound include an acidic phosphoric acid monoester amine salt formed from an acidic phosphoric acid monoester having a C1 to C8 alkyl or alkenyl group; e.g., monomethyl hydrogenphosphate or monoethyl hydrogenphosphate, and an amine compound having a C8 to C20 alkyl or alkenyl group.
  • The lubricating oil composition of the present invention preferably has a component (C) content; i.e., a phosphorus-containing compound content, of 0.3 to 2 mass %, with respect to the total amount of the composition, more preferably 0.5 to 1.5 mass %.
  • <Other Optional Components>
  • So long as the object of the present invention is not impaired, the shock absorber oil of the present invention may appropriately contain, as an optional additive, at least one species selected from among an ashless detergent-dispersant, a metallic detergent, a lubrication improver, an antioxidant, a rust preventive, a metal deactivator, a viscosity index improver, a pour point depressant, and a defoaming agent. No particular limitation is imposed on the optional components, and the amounts of these components are preferably 0.1 to 20 mass %, with respect to the total amount of the composition, more preferably 0.3 to 10 mass %, still more preferably 0.3 to 5 mass %.
  • Examples of the ashless detergent-dispersant include divalent carboxamides, such as a succinimide, a boron-containing succinimide, a benzylamine, a boron-containing benzylamine, and succinic acid. Examples of the metallic detergent include a neutral metal sulfonate, a neutral metal phenate, a neutral metal salicylate, a neutral metal phosphonate, a basic sulfonate, a basic phenate, a basic salicylate, a perbasic sulfonate, a perbasic salicylate, and a perbasic phosphonate.
  • Examples of the type of the lubrication improver include an extreme pressure agent, an antiwear agent, and an oiliness agent, and examples of the material of the lubrication improver include organometallic compounds, such as zinc dithiocarbamate (ZnDTC), oxysulfidomolybdenum organophosphorodithioate (MoDTP), and oxysulfidomolybdenum dithiocarbamate (MoDTC).
  • Examples of the sulfur-containing extreme pressure agent include sulfurized oils, sulfurized fatty acids, sulfurized esters, sulfurized olefins, dihydrocarbyl polysulfide, thiadiazole compounds, alkylthiocarbamoyl compounds, triazine compounds, thioterpene compounds, and dialkylthio dipropionate compounds.
  • Examples of the oiliness agent include aliphatic saturated and unsaturated monocarboxylic acids, such as stearic acid and oleic acid; polymerized fatty acids, such as dimer acid and hydrogenated dimer acid; hydroxy fatty acids, such as ricinoleic acid and 12-hydroxystearic acid; aliphatic saturated and unsaturated monoalcohols, such as lauryl alcohol and oleyl alcohol; aliphatic saturated and unsaturated monoamines, such as stearylamine and oleylamine; and aliphatic saturated and unsaturated monocarboxamides, such as lauriamide and oleamide.
  • Examples of the antioxidant include polycyclic phenol-based antioxidants, such as 4,4′-methylenebis(2,6-di-tert-butylphenol) and 2,2′-methylenebis(4-ethyl-6-tert-butylphenol); amine-based antioxidants, such as monoalkyldiphenylamine compounds; e.g., monooctyldiphenylamine and monononyldiphenylamine, dialkyldiphenylamine compounds; e.g., 4,4′-dibutyldiphenylamine, 4,4′-dipentyldiphenylamine, 4,4′-dihexyldiphenylamine, 4,4′-diheptyldiphenylamine, 4,4′-dioctyldiphenylamine, and 4,4′-dinonyldiphenylamine, polyalkyldiphenylamine compounds; e.g., tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, and tetranonyldiphenylamine, and naphthylamine compounds; e.g., α-naphthylamine, phenyl-α-naphthylamine, butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α-naphthylamine, heptylphenyl-α-naphthylamine, octylphenyl-α-naphthylamine, and nonylphenyl-α-naphthylamine; and sulfur-containing antioxidants such as thioterpene compounds; e.g., 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol and a reaction product between phosphorus pentasulfide and pinene, and dialkyl thiodipropionates; e.g., dilauryl thiodipropionate and distearyl thiodipropionate.
  • Examples of the rust preventive include metal sulfonates and succinate esters. Examples of the metal deactivator include benzotriazole and thiadiazole.
  • Examples of the viscosity index improver include polymethacrylates, dispersed polymethacrylates, olefin copolymers (e.g., ethylene-propylene copolymer), dispersed olefin copolymers, and styrene copolymers such as (e.g., styrene-diene hydrogenated copolymer).
  • Examples of the pour point depressant which may be used in the invention include polymethacrylates having a mass average molecular weight of about 50,000 to about 150,000.
  • The defoaming agent is preferably a silicone polymer-based defoaming agent. Through incorporation of the silicone polymer-based defoaming agent, defoaming performance can be effectively attained, whereby riding comfort can be improved.
  • Examples of the silicone polymer-based defoaming agent include organopolysiloxanes. Among them, fluorine-containing organopolysiloxanes such as trifluoropropylmethylsilicone oil are particularly preferred.
  • The lubricating oil composition of the present invention may be applied to any of a multi-cylinder shock absorber and a single-cylinder shock absorber, and shock absorbers of a four-wheeled vehicle or a two-wheeled vehicle. The composition of the present invention is particularly suitably used in four-wheeled vehicles.
  • Particularly, the lubricating oil composition of the present invention lowers friction coefficient at the interface between bronze and chromium and reduces wear area of bronze. Thus, the composition of the present invention is suitably used as a lubricant for a shock absorber which has a guide bush at least including a bronze surface, and a piston rod at least including a sliding part which comes into contact with the guide bush and which is made of chromium (e.g., chromium plating).
  • EXAMPLES
  • The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto.
  • Measurement of friction coefficient and a wear test were carried out through the following procedures.
  • (1) Measurement of bronze-chromium friction coefficient
  • Tester: Bowden-type reciprocating kinetic friction tester
  • Test conditions:
  • Load: 0.5 kgf
  • Stroke: 10 mm
  • Speed: 0.2 mm/s
  • Temperature: 80° C.
  • Friction operation: once
  • Friction members
  • Upper friction member: phosphor bronze ball
  • Lower friction member: chromium-plated sheet
  • (50×1,000×5 mm)
  • In a specific procedure, a ½-inch phosphor bronze was used. An oil composition sample was supplied to a plate, in an amount corresponding to several drops. The ball was conditioned on the plate (8 mm/s, 0.1 kgf for 2 minutes, 0.2 kgf for 2 minutes, 0.3 kgf for 2 minutes, and 0.5 kgf for 2 minutes). Thereafter, the wear test was performed at 0.2 mm/s.
  • (2) Wear test of bronze surface (wear area)
  • Tester: Bowden-type reciprocating kinetic friction tester
  • Test conditions:
  • Load: 0.5 kgf
  • Stroke: 10 mm
  • Speed: 8.0 mm/s
  • Temperature: 80° C.
  • Friction time: 30 minutes
  • Friction members
  • Upper friction member: phosphor bronze ball
  • Lower friction member: chromium-plated sheet
  • (50×1,000×5 mm)
  • In the wear test, a ½-inch phosphor bronze was used.
  • An oil composition sample was supplied to a plate, in an amount corresponding to several drops. The wear area of the phosphor bronze ball was measured.
  • Examples 1 to 6, and Comparative Examples 1 to 4
  • Lubricating oil compositions (shock absorber oils) containing the components given in Table 1 were prepared. Each composition was subjected to the friction coefficient measurement and the wear test. Table 1 shows the results.
  • TABLE 1
    Examples/ Comp. Comp. Comp. Comp.
    Comparative Examples Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 1 Ex. 2 Ex. 3 Ex. 4
    Compo- (A) Base oil 99.50 90.00 99.50 99.90 99.50 95.00 99.50 99.50 99.50 99.50
    nent (B) + α Pentaerythritol dioleate 0.50 0.50 0.10 5.00
    (mass %) Pentaerythritol dilaurylate 0.50
    Pentaerythritol monooleate 0.50
    Pentaerythritol tetraoleate 0.50
    Stearic acid 0.50
    Methyl acid phosphate 0.50
    amine salt
    (C) Zn-DTP (pri) C8-C10 0.50 0.50
    Test results Friction coefficient 0.093 0.105 0.097 0.112 0.115 0.096 0.362 0.084 0.184 0.179
    Wear area (mm2) 0.176 0.124 0.188 0.203 0.241 0.263 0.560 0.550 0.468 0.193
  • The components used in the Examples and Comparative Examples shown in Table 1 are as follows.
  • Base oil: secondary hydro-reformed mineral oil (paraffin-base) having a kinematic viscosity of 7.83 mm2/s measured at 40° C.
  • Pentaerythritol dioleate: UNISTER H481D, product of NOF Corporation
  • Pentaerythritol monooleate: EKISUPARU PE-MO
  • Pentaerythritol tetraoleate: UNISTER H481R, product of NOF Corporation
  • Methyl acid phosphate amine salt: VANLUBE 672, product of Vandarbilt
  • Zn-DTP(pri): OLOA 5286, C8 to C10 mixed alkyl groups, product of Ethyl Corporation
  • According the oil compositions of the Examples, each containing (A) a base oil composed of a mineral oil and/or a synthetic oil and a specific amount of (B) a polyhydric alcohol partial ester having a C10 to C20 fatty acid residue, friction coefficient and wear area were found to be reduced. Particularly in the case of the oil composition of Example 2, containing component (B) and component (C), wear area was considerably reduced.
  • In Comparative Example 1, employing a complete ester of a polyhydric alcohol, friction coefficient and wear area were at high levels. In Comparative Example 2, employing stearic acid, friction coefficient was low, but wear area was large. In Comparative Example 3, employing ZnDTP instead of component (B), friction coefficient and wear area were at high levels. In Comparative Example 4, employing a phosphate amine salt, friction coefficient was higher than that obtained in the Examples.
  • INDUSTRIAL APPLICABILITY
  • The lubricating oil composition of the present invention can be used for automobile shock absorbers. The composition is applicable to both four-wheeled vehicles and two-wheeled vehicles.

Claims (4)

1. A lubricating oil composition for a shock absorber, comprising:
(A) a base oil composed of a mineral oil and/or a synthetic oil, and;
(B) a polyhydric alcohol partial ester having a C10 to C20 fatty acid residue, in an amount of 0.05 mass % to 10 mass %, with respect to the total amount of the composition.
2. A lubricating oil composition for a shock absorber according to claim 1, wherein the component (B) is a tetrahydric alcohol partial ester.
3. A lubricating oil composition for a shock absorber according to claim 1, wherein the component (B) is pentaerythritol dioleate and/or pentaerythritol dilaurylate.
4. A lubricating oil composition for a shock absorber according to claim 1, which further comprises (C) a phosphorus-containing compound.
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