WO2006129889A1 - Hydraulic fluid composition for buffer - Google Patents

Hydraulic fluid composition for buffer Download PDF

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Publication number
WO2006129889A1
WO2006129889A1 PCT/JP2006/311680 JP2006311680W WO2006129889A1 WO 2006129889 A1 WO2006129889 A1 WO 2006129889A1 JP 2006311680 W JP2006311680 W JP 2006311680W WO 2006129889 A1 WO2006129889 A1 WO 2006129889A1
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Prior art keywords
group
carbon atoms
hydraulic fluid
fluid composition
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PCT/JP2006/311680
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French (fr)
Japanese (ja)
Inventor
Shinichi Shirahama
Toru Aoki
Naozumi Arimoto
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Nippon Oil Corporation
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Filing date
Publication date
Priority claimed from JP2005164736A external-priority patent/JP4815153B2/en
Priority claimed from JP2005164735A external-priority patent/JP4987251B2/en
Application filed by Nippon Oil Corporation filed Critical Nippon Oil Corporation
Publication of WO2006129889A1 publication Critical patent/WO2006129889A1/en

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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
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/16—Amides; Imides
    • 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
    • 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
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M149/14—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds a condensation reaction being involved
    • C10M149/22—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/44—Boron free or low content boron compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids

Definitions

  • the present invention relates to a hydraulic fluid composition for a shock absorber, and more specifically, hydraulic operation for a shock absorber for maintaining high friction between a seal material and a piston port in the shock absorber, and improving vehicle wobbling and riding comfort. It relates to an oil composition.
  • shock absorbers There are various types of shock absorbers, but they basically consist of a valved piston and cylinder (also called an outer cylinder or tube).
  • the piston is fixed to the rod, and the piston slides on the inner surface of the cylinder, and the rod slides on the seal of the rod guide.
  • the shock absorber acts as a buffer by the resistance of the hydraulic oil that passes through the valve with the hydraulic oil and, if necessary, gas.
  • hydraulic fluid for shock absorbers has been used to reduce the seal friction coefficient of hydraulic fluid in order to prevent stick-slip between the shock absorber seal and the rod and to ensure the durability of the seal.
  • additives such as phosphate esters and aliphatic amine compounds that reduce friction are generally added to hydraulic oil (see, for example, Patent Documents 1 to 5). ).
  • shock absorbers for automobiles, etc. are always in a vibrating state, and repeat a slight amplitude even on a paved road with little displacement.
  • the hydraulic damping is very small. It becomes easy to repeat the minute amplitude due to the minimal displacement of the road surface.
  • the vehicle body (sprung load) fluctuated and it was found that the driver and passengers feel uncomfortable. Development of compositions has become necessary.
  • Nitrile rubber or fluorine-based rubber is used as the seal for the shock absorber mouth and mouth guide, and a sliding material called a piston band is attached to the piston. It is important to adjust the friction characteristics of the hydraulic oil according to each material.
  • Patent Document 1 Japanese Patent Laid-Open No. 5-2 5 5 6 8 3
  • Patent Document 2 Japanese Patent Laid-Open No. 7-2 2 4 2 9 3
  • Patent Document 3 Japanese Patent Laid-Open No. 7-2 5 8 6 7 8
  • Patent Document 4 Japanese Patent Laid-Open No. 6-1 2 8 5 8 1
  • Patent Document 5 Japanese Patent Laid-Open No. 2 00 0-1 9 2 0 6 7
  • Patent Document 6 Japanese Patent Application Laid-Open No. 2 00 2-1 9 4 3 7 6
  • a hydraulic oil composition is provided.
  • a hydraulic fluid composition for a shock absorber that can maintain friction at a high level, particularly when using a bitrile-based seal material, and can achieve both stick-slip suppression. Is.
  • the inventors of the present invention are able to maintain a high level of friction when a composition having a specific structure is used, particularly when a tritolic sealant is used.
  • the present invention has found that the damping force at the neutral position of the shock absorber can be increased, the fluctuation of the vehicle body (sprung load) at a small amplitude can be suppressed, and the uncomfortable feeling of the driver and the occupant can be reduced. It came to complete.
  • the present invention provides a lubricating base oil having [I] (A) a phosphoric acid ester having 3 to 10 carbon atoms, a phosphorous acid ester or a salt thereof, and (B) carbon A saturated or unsaturated fatty acid of number 6 to 30 and / or an ester of the fatty acid, or [ ⁇ ] (C1) imino group Z amino group ratio is 15 or less, and the number average molecular weight is A succinic acid (anhydride) monopolyamine reaction product and / or a derivative thereof having an alkyl group or an alkenyl group of 1500 or less,
  • a hydraulic fluid composition for a shock absorber comprising at least one selected from those having an imino group / amino group ratio of less than 3.
  • the present invention provides a lubricant base oil comprising: (A) a phosphoric acid ester having a hydrocarbon group having 3 to 10 carbon atoms, a phosphite ester or a salt thereof; and (B) a carbon number 6 to 3 A hydraulic fluid composition for a shock absorber comprising 0 saturated or unsaturated fatty acid and Z or an ester of the fatty acid, and (C) an ashless dispersant.
  • the present invention also provides a lubricating base oil comprising: (A) a phosphoric acid ester having 3 to 10 carbon atoms, a phosphite or a salt thereof, and (C 1) an imino group Za.
  • Succinic acid (anhydride) having an alkyl group or an alkenyl group having a mino group ratio of 15 or less and a number average molecular weight of 1500 or less, a polyamine reaction product and / or a derivative thereof, C 1 a) Contains at least one selected from those having an imino group amino group ratio of 3 to 15 and essentially free of boron and (C lb) imino group amino group ratio of less than 3.
  • a hydraulic fluid composition for shock absorbers is provided.
  • the present invention provides a lubricating base oil comprising: (A) a phosphoric acid ester having a hydrocarbon group having 3 to 10 carbon atoms, a phosphite ester or a salt thereof; and (B) a carbon number 6 to 3 0 saturated or unsaturated fatty acid and / or ester of the fatty acid, and (C 1) an alkyl group or alkenyl group having an imino group / amino group ratio of 15 or less and a number average molecular weight of 1500 or less.
  • the hydraulic fluid composition for a shock absorber is characterized by containing at least one selected from those having an amino group ratio of less than 3.
  • the present invention also provides the hydraulic fluid composition for a shock absorber according to the above, wherein the component (A) is a hydrogen phosphate having a hydrocarbon group having 3 to 10 carbon atoms. is there.
  • the present invention resides in the hydraulic fluid composition for a shock absorber described above, wherein the component (B) is an unsaturated fatty acid having 12 to 18 carbon atoms and a unsaturated fatty acid ester. .
  • the present invention also resides in a method for increasing the friction between the seal material of the shock absorber and the piston opening using the hydraulic fluid composition for shock absorbers described above.
  • the present invention is a method for achieving both high friction between the sealant material of the shock absorber and the piston rod and suppression of stick-slip using the hydraulic fluid composition for shock absorbers described above.
  • the present invention is the method described above, wherein the sealing material is a nitrile sealing material.
  • the sealing material is a nitrile sealing material.
  • the lubricating base oil in the hydraulic fluid composition for shock absorbers of the present invention is not particularly limited, and mineral base oils and synthetic base oils used for ordinary lubricating oils can be used.
  • mineral oil base oils can be obtained by removing the solvent oil fraction obtained by depressurizing and distilling atmospheric residual oil obtained by atmospheric distillation of crude oil, solvent extraction, hydrogen Base oil produced by isomerization of one or more treatments such as hydrocracking, solvent dewaxing, hydrorefining, etc., or wax isomerized mineral oil, GTLWAX (gastric liquid wax) Etc. can be illustrated.
  • synthetic base oils include polybutene or a hydride thereof; poly- ⁇ -olefins such as 1-octene oligomer, 1-decenoligoma, or a hydride thereof; ditridecyl glutarate, Diesters such as di-2-ethylhexyl adipate, diisodecyl adipate, ditridecinorea dipate, di-2-ethylhexyl sebacate, etc .; neopentyl glycol ester, trimethylolpropane power pre-relate, g Polyol esters such as dimethylolpropane sulfonate, pentaerythritol 1-ethenorehexanoate, pentaerythritol pelargonate; aromatic synthetic oils such as alkylnaphthalene, alkylbenzene and aromatic ester; mixtures thereof Etc. can be illustrated.
  • the mineral base oil, the synthetic base oil, or an arbitrary mixture of two or more selected from these can be used.
  • examples thereof include one or more mineral base oils, one or more synthetic base oils, and a mixed oil of one or more mineral base oils and one or more synthetic base oils.
  • the kinematic viscosity of the lubricating base oil used in the present invention is not particularly limited.
  • the lower limit of the kinematic viscosity at 40 ° C is preferably 3 mm 2 / s, more preferably 6 mm 2 Z s, while the upper limit is Preferably it is 60 mm 2 / s, more preferably 40 mm 2 Z s, more preferably 20 mm 2 Z s, and more preferably 10 0 in that a composition with a lower friction can be obtained. It is desirable that it is not more than mm 2 Z s, particularly preferably not more than 9 mm 2 / s.
  • the viscosity index of the lubricating base oil used in the present invention is not particularly limited and is arbitrary.
  • the damping performance which is a basic performance required for the shock absorber, depends on the viscosity of the hydraulic fluid and depends on the temperature. From the viewpoint of minimizing the change in damping force, the viscosity index is preferably 80 or more, more preferably 95 or more.
  • the hydraulic fluid composition for a shock absorber according to the present invention comprises: (A) a phosphate ester having a hydrocarbon group having 3 to 10 carbon atoms, a phosphite ester, or a salt thereof; B) A saturated or unsaturated fatty acid having 6 to 30 carbon atoms and / or an ester of the fatty acid.
  • (A) phosphate ester, phosphite ester or salt thereof having a hydrocarbon group having 3 to 10 carbon atoms include a phosphate ester represented by the general formula (1). Phosphites represented by the general formula (2), salts thereof and mixtures thereof.
  • RR 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 3 to 10 carbon atoms, preferably 4 to 8 carbon atoms, and R 1 , R 2 and R 3 At least one of them is a hydrocarbon group having 3 to 10 carbon atoms.
  • R 4 , R 5 and R 6 are each independently a hydrogen atom or Is a hydrocarbon group having 3 to 10 carbon atoms, preferably 4 to 8 carbon atoms, and at least one of R 4 , R 5 and R 6 is a hydrocarbon group having 3 to 10 carbon atoms.
  • the hydrocarbon group may have one or more heteroatoms selected from a nitrogen atom, a sulfur atom, and an oxygen atom.
  • R 6 is an acidic phosphite diester having a hydrogen atom or an acidic phosphite monoester having R 5 and R 6 is a hydrogen atom, respectively
  • the mutants may be represented by the following general formulas (3) and (4), but they represent the same compound.
  • R 5 H
  • Specific examples of the hydrocarbon group having 3 to 10 carbon atoms as described above include propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like.
  • Alkyl groups (these alkyl groups may be linear or branched); probenole group, butenol group, pentul group, hexenino group, heptenyl group, octenol group, nonenyl group, decenyl group, etc.
  • the alkenyl group may be linear or branched, and the position of the double bond is arbitrary.
  • Aryl groups such as phenyl, naphthyl, etc .: each alkylaryl group having 7 to 10 carbon atoms such as tolyl, xylyl, ethenylphenyl, propylphenyl, butylphenyl, etc. In a chain May be branched, and the substitution position is arbitrary. ); Each arylalkyl group having 7 to 10 carbon atoms such as benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, etc. (The alkyl group may be linear or branched, and the substitution position is also arbitrary.) ); Etc.
  • the component (A) in the hydraulic fluid composition for a shock absorber of the present invention is particularly preferably a hydrogen phosphate having a hydrocarbon group having 3 to 10 carbon atoms represented by the following general formula (5).
  • the content of the component (A) in the hydraulic fluid composition for shock absorbers of the present invention is not particularly limited, but the friction between the sealing material such as a 2-tri-seal material and the mouth is further increased to prevent wear.
  • the amount in terms of phosphorus element is preferably 0.05 to 0.2 mass 0 /. More preferably, it is 0.01 to 0.1% by mass, and particularly preferably 0.01 5 to 0.06% by mass.
  • the component (B) in the hydraulic fluid composition for a shock absorber according to the present invention is a saturated or unsaturated fatty acid having 6 to 30 carbon atoms and / or an ester of the fatty acid.
  • the fatty acid may be a linear fatty acid or a branched fatty acid, may be a saturated fatty acid or an unsaturated fatty acid, and may be a monobasic acid or a polybasic acid.
  • Specific examples of the fatty acid include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, and hexadecane.
  • saturated or unsaturated monobasic fatty acids having 12 to 18 carbon atoms such as lauric acid, stearic acid, and oleic acid are particularly preferable.
  • fatty acids having 6 to 30 carbon atoms preferably 12 to 18 carbon atoms (which may be linear or branched) and 1 to 30 carbon atoms are preferable.
  • an ester of a monohydric alcohol having 1 to 18 carbon atoms or a polyhydric alcohol and an ester of a monobasic fatty acid and a polyhydric alcohol or an ester of a dibasic fatty acid and a monohydric alcohol is preferred. It is preferably an ester of a monobasic fatty acid and a polyhydric alcohol.
  • Examples of monohydric alcohols include saturated or unsaturated aliphatic alcohols having 1 to 30 carbon atoms, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol monole, Examples include otatanol, nonanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, oleiranoreconole
  • polyhydric alcohol examples include divalent to hexavalent polyhydric alcoholols (including multimers). Specific examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycolate, glycerin, diglycerin, so / levitane, trimethylolethane, And polyhydric alcohols such as trimethylololepropane, pentaerythritol> ⁇ re, and dipentaerythritol.
  • preferable compounds as esters of monobasic fatty acids and polyhydric alcohols include glycerin monooleate, glycerin dilate, and glycerin tritate.
  • Saturated or unsaturated monobasic fatty acids having 12 to 18 carbon atoms such as oleate, solebitantanate, sonorebitane diolate, sonorebitane trioleate, etc. Can be exemplified.
  • esters of dibasic fatty acids and monohydric alcohols include n-dodecyl succinic acid monomethyl ester, n-dodecyl succinic acid dimethinole ester, and n-tetradecino succinic acid.
  • Monomethylestenole, n-tetradecino] Dimethylolestenole succinate n—Hexadecyl succinic acid monomethyl ester, n—Hexadecyl succinic acid dimethyl ester, n—Octadecinosuccinic acid monomethyl ester, n— Examples thereof include esters of saturated or unsaturated dibasic acids having 12 to 18 carbon atoms and monohydric alcohols having 1 to 18 carbon atoms, such as dimethyl deca succinate.
  • the content of the component (B) in the hydraulic fluid composition for shock absorbers of the present invention does not reduce the friction between the seal material such as a 2-tril seal material and the piston mouth, and does not reduce the stickiness. in that can be expected to improve the flop characteristics, the total amount of the composition, preferably 0.0 0 1-2 mass 0/0, more preferably 0.0 1 to 1 by weight 0/0, the preferred especially 0.02 to 0.1% by mass.
  • the hydraulic fluid composition for a shock absorber according to the present invention preferably further contains (C) an ashless dispersant.
  • any ashless dispersant used in lubricating oils can be used.
  • a nitrogen-containing compound having at least one linear or branched alkyl group having 40 to 400 carbon atoms or an alkyl group in the molecule or a derivative thereof can be used.
  • the alkyl group or alkenyl group has 40 to 40, preferably 60 to 35, carbon atoms. If the alkyl group or alkenyl group has less than 40 carbon atoms, the solubility of the compound in the lubricating base oil will be reduced, whereas if the alkyl group or alkenyl group has more than 400 carbon atoms, lubrication will not occur.
  • the alkyl group or alkenyl group may be linear or branched, but specific examples include specific ligomers such as propylene, 1-butene, isobutylene, and ethylene. And branched alkyl groups and branched alkenyl groups derived from propylene ligomers.
  • Specific examples of the component (c) include the following compounds. One or two or more compounds selected from these can be used.
  • (C3) a polyamine having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof
  • Examples of the (C 1) succinic acid (anhydride) monopolyamine reaction product include alkyl or alkenyl succinic acid imide having a monoimide structure, and alkyl or alkenyl succinic acid having a biimide structure. And reaction products having imids or other structures, and mixtures thereof.
  • poly (iso) butenyl succinic acid imide usually poly (iso) butene, chlorinated poly (iso) butene or a mixture of these with maleic anhydride at 100 ° C. to 200 ° C. Poly obtained by reaction
  • Examples of the (C 2) benzylamine include, for example, polyolefins such as propylene ligomer, polybutene, and ethylene 1-olefin copolymer, which are reacted with phenol to form alkylphenol, and then formaldehyde.
  • Examples thereof include benzylamine obtained by reacting polyamines such as dimethylamine, triethylenetetramine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine with Mannich reaction.
  • benzylamine a derivative obtained by acylating the benzylamine obtained as described above with an oxygen-containing organic compound such as carboxylic acid, or an acid or boric acid, phosphoric acid, sulfuric acid, or the like.
  • an oxygen-containing organic compound such as carboxylic acid, or an acid or boric acid, phosphoric acid, sulfuric acid, or the like.
  • the (C 3) polyamine include chlorination of polyolefins such as propylene oligomers, polybutenes, and ethylene- ⁇ -olefin copolymers, and then ammonia, ethylenediamine, diethylenetriamine.
  • polyamines obtained by reacting polyamines such as triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
  • a polyamine derivative a derivative obtained by acylating the polyamine obtained as described above with an oxygen-containing organic compound such as carboxylic acid, or an acid such as boric acid, phosphoric acid, sulfuric acid, or the like
  • an oxygen-containing organic compound such as carboxylic acid, or an acid such as boric acid, phosphoric acid, sulfuric acid, or the like
  • the number average molecular weight of the alkyl group or alkenyl group in the (C) ashless dispersant is usually 700 to 500, but it is possible to maintain a higher seal friction such as a two-trill sealant. In this respect, it is preferably from 90 to 1500, more preferably 1400 or less, further preferably 1300 or less, and particularly preferably 1220 or less.
  • the component (C) of the present invention is not particularly limited in its imino group amino group ratio.
  • the compound containing no imino group such as ethylenediamine mono (alkenyl) succinic acid imide. It can be infinite for compounds that do not contain an amino group such as diethylenetriaminebis (alkenyl) succinic acid imide, but in terms of production cost, it may be 0.1 to 50. preferable.
  • the imino group amino group ratio is preferably 15 or less from the viewpoint of obtaining a composition having a higher flexion, and preferably 1 or more from the viewpoint of stability and production cost. It is.
  • a succinic acid (anhydrous) having a (C 1) imino group noamino group ratio of 15 or less and a number average molecular weight of 1500 or less and having an alkyl group or alkenyl group (polyhydrate) It is particularly preferred to use the reaction products and cocoons or their derivatives.
  • the (C 1) component when the (C 1 a) imino group amino group ratio is 3 to 15, the one that does not essentially contain boron is more suitable for a 2-tolyl-type sealing material, etc. This is preferable because the friction between the sealant and the piston head can be easily maintained at a high level. Also, the ratio of the imino group and the Z amino group of the component (C 1 a) makes the composition of higher friction. It is preferably 3.5 to 12, more preferably 4 to 9, and particularly preferably 4.5 to 6 in that it can be obtained.
  • the component (CI) may contain or not contain boron when the (C 1 b) imino group noamino group ratio is less than 3, but preferably contains boron. .
  • the imino group noamino group ratio is less than 3, it is easy to maintain a high friction between the sealant such as a 2-tril seal and the biston rod, and the imino group Z amino It exhibits a special behavior for boron-containing materials with a base ratio of 3 or more.
  • the imino group amino group ratio of the component (C 1 b) is 0 to less than 3, it is preferably 1 or more, more preferably 1 to 2.5, and particularly preferably 1. 5 to 2.5.
  • the mass ratio of boron content Z nitrogen content (B "N ratio) is not particularly limited, but the sealant and piston port In view of maintaining high friction between the heads and stability when used in combination with component (A), preferably 0.1 to 1, more preferably 0.5 to 1, particularly preferably 0. 7 to 0.9.
  • the imino group represents a group represented by 1 NH—
  • the amino group represents a group represented by 1 NH 2
  • the imino group amino ratio is the amino group in the component (C).
  • the imino group and the amino group and the ratio thereof can be obtained by the following method.
  • Peaks are obtained at (a) chemical shift 6 6 ppm 7 2 ppm and (b) chemical shift 7 4 ppm 7 9 ppm.
  • the peak of (a) is obtained by the reaction of imino group (1NH-) in component (C) with trifluorosuccinic anhydride as shown in the following formula (I).
  • the peak of (b) is obtained by reacting the amino group (one NH 2 ) in component (C) with trifluoroacetic anhydride as shown in the following formula (iii): Peak of group represented by (i) It is estimated that
  • component (C) 0.5 g of component (C) is dissolved in 20 ml of hexane, 1.0 g of trifluoroacetic anhydride is added thereto, and the mixture is reacted at 20 ° C. for 20 minutes while stirring. Thereafter, 10 ml of methanol and 0.5 ml of concentrated hydrochloric acid were added to the reaction product, and stirring was continued at 20 ° C for 20 minutes. Unreacted trifluoroacetic anhydride and the reaction by-product trifluoroacetic acid were added to methanol. Remove into layers. Next, the oil layer is taken out, and hexane is distilled off by distillation to obtain a reaction product of the component (C) and trifluoroacetic acid. Using 100 mg of the reaction product thus obtained as a sample, it is analyzed by i 9 F 1 NMR at a resonance frequency of 5 64.4 MHz.
  • the imino group / amino group ratio in the component (C) defined in the present invention is specified by the peak area of (a) // the ratio of the peak area of (b) obtained by this method.
  • Value that is, the ratio of the nitrogen atom constituting the imino group (one NH-) in the component (C) to the nitrogen atom constituting the amino group (one NH 2 ) in the component (C) .
  • another measurement method using the same theory may be used.
  • the content of the component (C) is usually 0.01 to 5% by mass on the basis of the total amount of the composition, and the content of the component (C) as the nitrogen content is Preferably, 0.001% by mass or more, more preferably 0.002% by mass or more.
  • the content is not less than 0.05% by mass, an effect corresponding to the content cannot be obtained, and the low-temperature characteristics tend to deteriorate, so that it is preferably 0.2% by mass or less, more preferably Is not more than 0.05% by mass, particularly preferably not more than 0.01% by mass.
  • the content of boron is usually 0.001 to 0. 2% by mass, preferably from 0.02 to 0.05% by mass, more preferably from 0.01% by mass or less, particularly preferably from the viewpoint of stability in the presence of component (A).
  • the content is 0 to 8% by mass or less.
  • the hydraulic fluid composition for a shock absorber according to the present invention contains the component (A) and the component (B), or further contains the component (C), so that the piston rod and the sealing material in the fine amplitude region are contained.
  • the friction coefficient can be maintained at a high level and the stick-lip characteristics can be improved, the damping force at the neutral position of the shock absorber is increased, and the fine amplitude This reduces the wobbling of the vehicle body (sprung load) and reduces the discomfort of the driver and passengers.
  • the hydraulic fluid composition for a shock absorber according to the present invention includes an alkyl group having a (C 1) imino group amino group ratio of 15 or less and a number average molecular weight of 1500 or less.
  • a succinic acid having a alkenyl group, a polyamine reaction product and / or a derivative thereof, (C 1 a) imino group / amino group ratio of 3 to 15 and essentially free of boron And (C lb) imino group and at least one selected from those having a Z amino group ratio of less than 3.
  • the number average molecular weight of the alkyl group or alkenyl group in the component (C 1) is 1550 or less, preferably 1400 or less, more preferably 1300 or less, particularly preferably 1 It is desirable to set it to 200 or less.
  • the number average molecular weight is
  • the number average molecular weight is preferably 1500 or more in terms of oil solubility, more preferably 3100 or more, and a higher-friction composition can be obtained. More preferably, it is desirable to set it at 700 or more, particularly preferably 900 or more.
  • the content of the component (C 1) is the composition On the basis of the total amount, it is usually from 0 to 1 to 5% by mass, and the content of the (C 1) component as nitrogen is preferably 0.001% by mass or more, more preferably 0.0 0 2 It is preferably at least 0.2% by mass, particularly preferably at least 0.05% by mass, and since an effect corresponding to the content cannot be obtained and the low-temperature characteristics tend to deteriorate, it is preferably at least 0.2. % By mass or less, more preferably 0.05% by mass or less, particularly preferably 0.01% by mass or less.
  • the content of boron is usually from 0.001 to 0.2% by mass, preferably from 0.002 to 0%, based on the total amount of the composition. 0.5% by mass, and as described later, when the component (A) is used in combination, it is more preferably 0.01% by mass or less, particularly preferably 0.00% by mass or less in terms of stability. Is desirable.
  • the hydraulic fluid composition for a shock absorber according to the present invention contains the above component (C 1) in the base oil, so that it is between the piston mouth and the seal material in the fine amplitude region, particularly a nitrile seal.
  • the friction can be maintained at a high level when the material is used, the damping force at the neutral position of the shock absorber is increased, the fluctuation of the vehicle body (sprung load) at a small amplitude is suppressed, and the driver and It has the effect of reducing passenger discomfort.
  • the component (A) is used in combination, so that the piston rod and the seal material in the fine amplitude region, particularly nitrile, are used. The friction can be further increased when the seal material is used.
  • the component (A) is preferably a hydrogen phosphite represented by the general formula (5).
  • the content when component (A) is contained further increases the friction between a sealing material such as a nitrile sealing material and the mouth, and is expected to have an effect of preventing wear.
  • a sealing material such as a nitrile sealing material
  • the total amount of the composition it is preferably 0.005 to 0.2 mass%, more preferably 0.01 to 0.1 mass%, particularly preferably 0.0, in terms of phosphorus element. 1 5 to 0.06 mass%. Even if it exceeds 0.2% by mass, it is difficult to obtain an effect commensurate with the content, and the oxidation stability tends to deteriorate.
  • the hydraulic fluid composition for shock absorbers according to the present invention is further improved in performance as required.
  • any additive generally used in lubricating oils can be included.
  • additives include (A) component and friction modifiers other than component (B), viscosity index improvers, antiwear agents, antioxidants, fluidity improvers, metal deactivators.
  • various additives such as metal detergents, corrosion inhibitors, antifungal agents, demulsifiers, and coloring agents can be mentioned.
  • any compound usually used as a friction modifier for lubricating oil can be used.
  • molybdenum dithiocarbamate molybdenum dithiophosphine Having at least one straight chain alkyl group or straight chain alkenyl group having 6 to 30 carbon atoms, particularly a straight chain alkyl group or straight chain alkenyl group having 6 to 30 carbon atoms.
  • Ashless friction modifiers such as fatty acid amides, aliphatic amines, aliphatic alcohols, aliphatic ethers, etc., and usually in the range of 0.001 to 5% by mass based on the total amount of the composition. Is possible.
  • any compound usually used as a viscosity index improver for lubricating oils can be used.
  • the weight of one or more monomers selected from various methacrylic acid esters can be used.
  • a so-called non-dispersed viscosity index improver such as a polymer or copolymer or a hydrogenated product thereof, or a so-called dispersed viscosity index improver obtained by copolymerizing various methacrylate esters containing a nitrogen compound.
  • Dispersed or dispersed ethylene- ⁇ -olefin copolymers examples include propylene, 1-butene, 1_pentene, etc.
  • ⁇ -olefin examples include propylene, 1-butene, 1_pentene, etc.
  • hydrides thereof polyisobutylene or examples thereof include hydrogenated products thereof, hydrogenated products of styrene-gen copolymers, styrene-mono-anhydride maleate copolymers, and polyalkylstyrenes.
  • the number average molecular weight of the viscosity index improver is, for example, usually 5,000 to 1,000,000, preferably 100,000 to 900,000 in the case of dispersed and non-dispersed polymethacrylates.
  • 0 polyisobutylene or a hydride thereof
  • 800 to 500,000, preferably 1,000 to 4,000 is an ethylene-one ⁇ -olefin copolymer or its hydrogen.
  • 800 to 500,000, preferably 3,00 to 200,000 is preferably used.
  • the content of the viscosity index improver is usually from 0.0 to 20% by mass based on the total amount of the composition.
  • any compound usually used as an antiwear agent for lubricating oils can be used, and examples thereof include phosphorus and / or sulfur-containing antiwear agents, such as thiophosphates, Phosphate esters, phosphate esters, hydrogen phosphates having a hydrocarbon group with 11 to 30 carbon atoms, derivatives thereof, metal salts thereof, amine salts thereof, and disulfides, sulfides Examples include sulfur-containing compounds such as olefins, sulfurized fats and oils, dithiocarbamate, and zinc dithiocarbamate.
  • These antiwear agents can be contained in the composition of the present invention usually in the range of 0.01 to 5% by mass based on the total amount of the composition.
  • any compound usually used as an antioxidant for lubricating oils can be used.
  • phenolic antioxidants such as phenyl- ⁇ -naphthylamine, alkylphenyl ct-naphthylamine, and dialkyldiphenylamine.
  • These antioxidants can be contained in the composition of the present invention usually in the range of 0.01 to 5% by mass based on the total amount of the composition.
  • any compound usually used as a fluidity improver for lubricating oils can be used, and examples thereof include polymetatalate fluidity improvers.
  • Metal deactivators include imidazoline, pyrimidine derivatives, alkyl thiadiazoles, mercaptobenzothiazoles, benzotriazol or derivatives thereof, 1, 3, 4-thiadiazole polysulfide, 1, 3, 4-thiadiazolyl 1-2 , 5—bisdialkyldithiocarbamate, 2— (alkyldithio) benzimidazole, and i3— (o-carboxybenzylthio) propiononitrile.
  • antifoaming agent examples include silicone, fluorosilicol, and fluoroalkyl ether.
  • metal detergents include alkali metal or alkaline earth metal sulfonates, buinates, salicylates, and phosphonates.
  • corrosion inhibitor examples include benzotriazole series, tritriazole series, thiadiazole series,. And imidazole series compounds.
  • antifungal agent examples include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.
  • demulsifier examples include polyalkylene dallic-based nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alcohol naphthyl ether.
  • polyalkylene dallic-based nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alcohol naphthyl ether.
  • the content is based on the total amount of the composition, and a fluidity improver, metal detergent, corrosion inhibitor, antifungal agent, It is usually selected in the range of 0.05 to 5% by mass for demulsifiers, 0.05 to 1% by mass for metal deactivators, and 0.05 to 1% by mass for antifoaming agents. .
  • the hydraulic fluid composition for a shock absorber according to the present invention maintains a high level of friction between piston rods and seal materials, particularly when a two-trile seal material is used as the seal material. It is possible to increase the damping force at the neutral position of the shock absorber, to suppress the fluctuation of the vehicle body (sprung load) at a small amplitude, and to reduce driver and passenger discomfort.
  • Lubricating oil compositions according to the present invention having the compositions shown in Table 1 (Examples 1 to 2), comparative lubricating oil compositions (Comparative Examples 1 to 3), and reference lubricating oil compositions (Reference Example 1) Were prepared respectively. These compositions were subjected to the following friction test, and the results are shown in Table 1.
  • the compositions according to the present invention (Examples 1 and 2) have a high coefficient of friction between the nitrile sealant and the steel, and have excellent sticky lip characteristics. ing.
  • the component (A) and the component (B) are not used together (Comparative Examples 1 to 3), it can be seen that either the friction coefficient or the stick-lip property is inferior.
  • the composition of Reference Example 1 containing the component (A) and the component (C) can maintain a high coefficient of friction, but is inferior in the stick-rip characteristics.
  • Example 2 The same composition as in Example 2 was evaluated in the same manner except that 0.05% by mass of succinic acid monoester having an alkyl having 12 to 18 carbon atoms was used instead of the component (B) in Example 1. As a result, a similar effect was confirmed.
  • Lubricating oil composition according to the present invention having the composition shown in Table 1 (Examples 3 to 6), comparative lubricating oil composition (Comparative Examples 4 to 6), and friction coefficient (friction) Lubricating oil compositions serving as evaluation criteria were prepared. Friction tests were conducted on these compositions, and the rate of decrease in the friction coefficient with respect to the reference oil was evaluated. The results are shown in Table 2. The smaller the rate of decrease in the coefficient of friction with respect to the reference oil, the higher the seal friction. It means that it is easy to hold.
  • compositions (Examples 3 to 6) containing the component (C 1) satisfying the requirements of the present invention have a small friction reduction rate with respect to the reference oil. Further, when the component (A) is used in combination (Example 6), the friction coefficient can be further increased. On the other hand, when a compound similar to the component (C 1) that does not satisfy the requirements of the present invention is used (Comparative Examples 4 to 6), the rate of decrease in the coefficient of friction with respect to the reference oil increases, and the seal friction It can be seen that it is difficult to maintain a high level.
  • Alkyl group / alkenyl group Polyvinyl group having a number average molecular weight of 1000 and a diluent.
  • Imino group / amino group ratio 5.5: 1, nitrogen content: 2.3 mass%, boron content 0% child
  • B alkyl group / alkenyl group: polyvinyl group having a number average molecular weight of 1000, including diluent.
  • Imino group / amino group ratio 7.0: 1, nitrogen content: 1.9 mass 96, boron content 0 mass%
  • C alkyl group / alkenyl group: polyvinyl group having a number average molecular weight of 1000, including diluent.
  • Imino group / amino group ratio 2.0: 1, nitrogen content: 1.9 mass%, boron content 1.6 mass%
  • Alkyl group / alkenyl group Polyvinyl group having a number average molecular weight of 1000, including a diluent.
  • Imino group / amino group ratio 4.2: 1, nitrogen content: 2.3 mass%, boron content 1.9 mass%
  • alkyl group Z alkenyl group a polybutenyl group having a number average molecular weight of 2200 and a diluent.
  • Imino group / amino group ratio 7.6: 1, nitrogen content: 1.2% by mass, boron content 0% by mass
  • alkyl group alkenyl group polybutenyl group having a number average molecular weight of 1500-2000, including diluent.
  • Imino group / amino group ratio 24: 1, nitrogen content: 1.5 mass "1 ⁇ 2, boron content 0.5 mass%

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Abstract

A hydraulic fluid composition for buffers which keeps the friction between the sealing material and the piston rod in a buffer high to thereby mitigate vehicle body falter and improve comfortableness in riding. The hydraulic fluid composition for buffers comprises a lube base oil and, incorporated therein, either [I] (A) a phosphoric ester or phosphorous ester having a C3-30 hydrocarbon group or a salt of any of the esters and (B) a C6-30 (un)saturated fatty acid and/or an ester of the fatty acid or [II] (C1) a succinic acid (anhydride)/polyamine reaction product having an imino group/amino group proportion of 15 or lower and a number-average molecular weight of 1,500 or lower and having an alkyl or alkenyl group and/or a derivative of the reaction product, the ingredient (C1) comprising at least one member selected among (C1a) ones having an imino group/amino group proportion of from 3 to 15 and containing essentially no boron and (C1b) ones having an imino group/amino group proportion less than 3.

Description

明 細 書 緩衝器用油圧作動油組成物  Description Hydraulic fluid composition for shock absorbers
[技術分野] [Technical field]
本発明は、 緩衝器用油圧作動油組成物に関し、 詳しくは緩衝器におけるシール 材と ビス トン口ッ ド間の摩擦を高く維持し、 車体のふらつきや乗り心地を改善す るための緩衝器用油圧作動油組成物に関する。  TECHNICAL FIELD The present invention relates to a hydraulic fluid composition for a shock absorber, and more specifically, hydraulic operation for a shock absorber for maintaining high friction between a seal material and a piston port in the shock absorber, and improving vehicle wobbling and riding comfort. It relates to an oil composition.
[背景技術] [Background]
緩衝器にはさまざまな形式があるが、 基本的に弁のついたビス トンとシリ ンダ ― (外筒若しくはチューブともいう） からなる。 ピス トンはロッ ドに固定されて おり、 ピス トンはシリ ンダー内面を摺動し、 ロッ ドはロッ ドガイ ド部のシールを 摺動する。 緩衝器は作動油と必要によりガスを封入し弁を通過する作動油の抵抗 によ り緩衝作用を行う。  There are various types of shock absorbers, but they basically consist of a valved piston and cylinder (also called an outer cylinder or tube). The piston is fixed to the rod, and the piston slides on the inner surface of the cylinder, and the rod slides on the seal of the rod guide. The shock absorber acts as a buffer by the resistance of the hydraulic oil that passes through the valve with the hydraulic oil and, if necessary, gas.
従来、 緩衝器用油圧作動油は、 緩衝器のシールとロ ッ ド間のスティ ックスリ ツ プ防止とシールの耐久性を確保するために、 作動油のシール摩擦係数を下げるこ とが行われてきた。 このフ リ クショ ンを低減するため、 一般に作動油には摩擦を 低減する リ ン酸エステル類や脂肪族ァミ ン化合物等の添加剤が配合されている (例えば、 特許文献 1〜 5参照。）。 また、 近年、 自動車の振動を緩和して、 乗り 心地や操縦安定性を改善する研究が進められた結果、 ビス トンロ ッ ド Zシール間 の摩擦力を高め、 同時にピス トンロ ッ ド/ブッシュ、 ピス トンバン ド シリ ンダ —の摩擦力を低減させる機能を持つ、 特定のアミン化合物等を含む新しい緩衝器 用油圧作動油組成物が提案されている （例えば、 特許文献 6参照。）。  Conventionally, hydraulic fluid for shock absorbers has been used to reduce the seal friction coefficient of hydraulic fluid in order to prevent stick-slip between the shock absorber seal and the rod and to ensure the durability of the seal. . In order to reduce this friction, additives such as phosphate esters and aliphatic amine compounds that reduce friction are generally added to hydraulic oil (see, for example, Patent Documents 1 to 5). ). Also, in recent years, as a result of research on reducing the vibration of automobiles and improving ride comfort and driving stability, the frictional force between the piston rod Z seals has been increased, and at the same time, piston rod / bush, piston A new hydraulic fluid composition for shock absorbers containing a specific amine compound and the like having a function of reducing the frictional force of the tomb band cylinder has been proposed (for example, see Patent Document 6).
しかしながら、 自動車用等の緩衝器は常に振動状態にあり、 変位の少ない舗装 道路においても微振幅を繰り返し、 そのよ うな状態における緩衝器のニュー トラ ル位置では、 油圧減衰は非常に小さいため、 舗装路面の極小変位による微振幅を 繰り返しやすくなる。 その結果、 車体 （ばね上荷重） がふらつく と ともに、 運転 者と乗員に不快感を与えることが判明し、 従来にない新規な緩衝器用油圧作動油 組成物の開発が必要となってきた。 However, shock absorbers for automobiles, etc. are always in a vibrating state, and repeat a slight amplitude even on a paved road with little displacement. At the neutral position of the shock absorber in such a state, the hydraulic damping is very small. It becomes easy to repeat the minute amplitude due to the minimal displacement of the road surface. As a result, the vehicle body (sprung load) fluctuated and it was found that the driver and passengers feel uncomfortable. Development of compositions has become necessary.
なお、 緩衝器の口 ッ ドと口ッ ドガイ ド部のシール材には二 ト リルゴムゃフッ素 系ゴム等が使用され、 ピス トンには、 ピス トンバン ドと呼ばれる摺動材が装着さ れる。 各材料に合せて作動油の摩擦特性を調整することが重要である。  Nitrile rubber or fluorine-based rubber is used as the seal for the shock absorber mouth and mouth guide, and a sliding material called a piston band is attached to the piston. It is important to adjust the friction characteristics of the hydraulic oil according to each material.
特許文献 1 ： 特開平 5 — 2 5 5 6 8 3号公報  Patent Document 1: Japanese Patent Laid-Open No. 5-2 5 5 6 8 3
特許文献 2 ： 特開平 7 - 2 2 4 2 9 3号公報  Patent Document 2: Japanese Patent Laid-Open No. 7-2 2 4 2 9 3
特許文献 3 ： 特開平 7— 2 5 8 6 7 8号公報  Patent Document 3: Japanese Patent Laid-Open No. 7-2 5 8 6 7 8
特許文献 4 ： 特開平 6 - 1 2 8 5 8 1号公報  Patent Document 4: Japanese Patent Laid-Open No. 6-1 2 8 5 8 1
特許文献 5 ： 特開 2 0 0 0 ― 1 9 2 0 6 7号公報  Patent Document 5: Japanese Patent Laid-Open No. 2 00 0-1 9 2 0 6 7
特許文献 6 ： 特開 2 0 0 2 ― 1 9 4 3 7 6号公報  Patent Document 6: Japanese Patent Application Laid-Open No. 2 00 2-1 9 4 3 7 6
[発明の開示] [Disclosure of the Invention]
本発明は、 以上のよ うな事情に鑑み、 路面の極小変位による微振幅を抑制し、 車体 （ばね上荷重） めふらつきを抑制するとともに、 運転者と乗員の不快感を軽 滅できる緩衝器用油圧作動油組成物を提供するものである。 特に二 ト リル系のシ 一ル材を使用した場合にフリクショ ンを高いレベルで維持でき、 さらにはスティ ックス リ ップ抑制との両立を図ることができる緩衝器用油圧作動油組成物を提供 するものである。  In view of the circumstances as described above, the present invention suppresses a slight amplitude due to a minimal displacement of the road surface, suppresses vehicle body (sprung load) stagger, and reduces the driver's and passenger's discomfort. A hydraulic oil composition is provided. Provided is a hydraulic fluid composition for a shock absorber that can maintain friction at a high level, particularly when using a bitrile-based seal material, and can achieve both stick-slip suppression. Is.
本発明者らは、 上記課題を解決するために鋭意検討した結果、 特定の構成から なる組成物が、 特に二 ト リル系のシール材を使用した場合にフリ クショ ンを高い レベルで維持することができ、 緩衝器のニュー トラル位置での減衰力を高め、 微 振幅時の車体 （ばね上荷重） のふらつきを抑制すると ともに、 運転者と乗員の不 快感を軽減しうることを見出し、 本発明を完成するに至った。  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention are able to maintain a high level of friction when a composition having a specific structure is used, particularly when a tritolic sealant is used. The present invention has found that the damping force at the neutral position of the shock absorber can be increased, the fluctuation of the vehicle body (sprung load) at a small amplitude can be suppressed, and the uncomfortable feeling of the driver and the occupant can be reduced. It came to complete.
すなわち、 本発明は、 潤滑油基油に、 [ I ] ( A ) 炭素数 3〜 1 0の炭化水素基 を有するリ ン酸エステル、 亜リ ン酸エステル又はこれらの塩、 及び （B ) 炭素数 6〜 3 0の飽和若しく は不飽和脂肪酸及び/又は該脂肪酸のエステル、 又は、 [ Π ] ( C 1 ) イ ミ ノ基 Zアミ ノ基比率が 1 5以下であり、 数平均分子量が 1 5 0 0以下のアルキル基若しくはアルケニル基を有するコハク酸 （無水物） 一ポリア ミン反応生成物及び/又はその誘導体であって、  That is, the present invention provides a lubricating base oil having [I] (A) a phosphoric acid ester having 3 to 10 carbon atoms, a phosphorous acid ester or a salt thereof, and (B) carbon A saturated or unsaturated fatty acid of number 6 to 30 and / or an ester of the fatty acid, or [Π] (C1) imino group Z amino group ratio is 15 or less, and the number average molecular weight is A succinic acid (anhydride) monopolyamine reaction product and / or a derivative thereof having an alkyl group or an alkenyl group of 1500 or less,
( C 1 a ) ィ ミ ノ基 Zァミ ノ基比率が 3〜 1 5かつホウ素を本質的に含有しない もの及び (C 1 a) imino group Z-amino group ratio of 3 to 15 and essentially free of boron Things and
(C 1 b )イミノ基/ァミノ基比率が 3未満のものから選ばれる少なく とも 1種、 を含有することを特徴とする緩衝器用油圧作動油組成物にある。  (C 1 b) A hydraulic fluid composition for a shock absorber, comprising at least one selected from those having an imino group / amino group ratio of less than 3.
また、 本発明は、 潤滑油基油に、 （A) 炭素数 3〜 1 0の炭化水素基を有するリ ン酸エステル、 亜リン酸エステル又はこれらの塩、 及び （B) 炭素数 6 ~ 3 0の 飽和若しくは不飽和脂肪酸及び Z又は該脂肪酸のエステル、 並びに （C) 無灰分 散剤を含有することを特徴とする緩衝器用油圧作動油組成物にある。  Further, the present invention provides a lubricant base oil comprising: (A) a phosphoric acid ester having a hydrocarbon group having 3 to 10 carbon atoms, a phosphite ester or a salt thereof; and (B) a carbon number 6 to 3 A hydraulic fluid composition for a shock absorber comprising 0 saturated or unsaturated fatty acid and Z or an ester of the fatty acid, and (C) an ashless dispersant.
また、 本発明は、 潤滑油基油に、 （A) 炭素数 3〜 1 0の炭化水素基を有するリ ン酸エステル、 亜リン酸エステル又はこれらの塩、 並びに （C 1 ) イミノ基 Zァ ミノ基比率が 1 5以下であり、 数平均分子量が 1 5 0 0以下のアルキル基若しく はアルケニル基を有するコハク酸 （無水物） —ポリアミン反応生成物及び/又は その誘導体であって、 （C 1 a )イミノ基 アミノ基比率が 3〜 1 5かつホウ素を 本質的に含有しないもの及ぴ （C l b ) イミノ基 アミノ基比率が 3未満のもの から選ばれる少なく とも 1種、 を含有することを特徴とする緩衝器用油圧作動油 組成物にある。  The present invention also provides a lubricating base oil comprising: (A) a phosphoric acid ester having 3 to 10 carbon atoms, a phosphite or a salt thereof, and (C 1) an imino group Za. Succinic acid (anhydride) having an alkyl group or an alkenyl group having a mino group ratio of 15 or less and a number average molecular weight of 1500 or less, a polyamine reaction product and / or a derivative thereof, C 1 a) Contains at least one selected from those having an imino group amino group ratio of 3 to 15 and essentially free of boron and (C lb) imino group amino group ratio of less than 3. A hydraulic fluid composition for shock absorbers is provided.
また、 本発明は、 潤滑油基油に、 （A) 炭素数 3〜 1 0の炭化水素基を有するリ ン酸エステル、 亜リン酸エステル又はこれらの塩、 及び （B) 炭素数 6〜 3 0の 飽和若しくは不飽和脂肪酸及び/又は該脂肪酸のエステル、並びに、 （C 1 )イミ ノ基/ァミノ基比率が 1 5以下であり、 数平均分子量が 1 5 0 0以下のアルキル 基若しくはアルケニル基を有するコハク酸 （無水物） 一ポリアミン反応生成物及 び Z又はその誘導体であって、 （C 1 a )イミノ基/アミノ基比率が 3〜 1 5かつ ホウ素を本質的に含有しないもの及び （C l b ) イミノ基 アミノ基比率が 3未 満のものから選ばれる少なく とも 1種、 を含有することを特徴とする緩衝器用油 圧作動油組成物にある。  Further, the present invention provides a lubricating base oil comprising: (A) a phosphoric acid ester having a hydrocarbon group having 3 to 10 carbon atoms, a phosphite ester or a salt thereof; and (B) a carbon number 6 to 3 0 saturated or unsaturated fatty acid and / or ester of the fatty acid, and (C 1) an alkyl group or alkenyl group having an imino group / amino group ratio of 15 or less and a number average molecular weight of 1500 or less. Succinic acid (anhydride) monopolyamine reaction product and Z or a derivative thereof, wherein (C 1 a) has an imino group / amino group ratio of 3 to 15 and is essentially free of boron and ( C lb) Imino group The hydraulic fluid composition for a shock absorber is characterized by containing at least one selected from those having an amino group ratio of less than 3.
また、 本発明は、 前記 （A) 成分が、 炭素数 3〜 1 0の炭化水素基を有するハ ィ ドロゲンホスフアイ トであることを特徴とする前記記載の緩衝器用油圧作動油 組成物にある。  The present invention also provides the hydraulic fluid composition for a shock absorber according to the above, wherein the component (A) is a hydrogen phosphate having a hydrocarbon group having 3 to 10 carbon atoms. is there.
また、 本発明は、 前記 （B) 成分が、 炭素数 1 2〜 1 8の不飽和脂肪酸及びノ 又は不飽和脂肪酸エステルであることを特徴とする前記記載の緩衝器用油圧作動 油組成物にある。 また、 本発明は、 前記記載の緩衝器用油圧作動油組成物を用いて緩衝器のシ一 ル材とビス トン口ッ ド間の高摩擦化方法にある。 Further, the present invention resides in the hydraulic fluid composition for a shock absorber described above, wherein the component (B) is an unsaturated fatty acid having 12 to 18 carbon atoms and a unsaturated fatty acid ester. . The present invention also resides in a method for increasing the friction between the seal material of the shock absorber and the piston opening using the hydraulic fluid composition for shock absorbers described above.
また、 本発明は、 前記記載の緩衝器用油圧作動油組成物を用いて緩衝器のシー ル材とピス トンロ ッ ド間の高摩擦化及びスティ ックスリ ップ抑制を両立する方法 しある  Further, the present invention is a method for achieving both high friction between the sealant material of the shock absorber and the piston rod and suppression of stick-slip using the hydraulic fluid composition for shock absorbers described above.
さらに、 本発明は、 前記シール材がニ ト リル系シール材であることを特徴とす る前記記載の方法にある。 以下、 本発明について詳述する。  Furthermore, the present invention is the method described above, wherein the sealing material is a nitrile sealing material. Hereinafter, the present invention will be described in detail.
本発明の緩衝器用油圧作動油組成物における潤滑油基油と しては、 特に制限は なく、 通常の潤滑油に使用される鉱油系基油、 合成系基油が使用できる。  The lubricating base oil in the hydraulic fluid composition for shock absorbers of the present invention is not particularly limited, and mineral base oils and synthetic base oils used for ordinary lubricating oils can be used.
鉱油系基油と しては、 具体的には、 原油を常圧蒸留して得られる常圧残油を減 圧蒸留して得られた潤滑油留分を、 溶剤脱れき、 溶剤抽出、 水素化分解、 溶剤脱 ろう、 水素化精製等の処理を 1つ以上行って精製したもの、 あるいはワックス異 性化鉱油、 G T L W A X (ガス ト ウ リキッ ドワックス） を異性化する手法で製 造される基油等が例示できる。  Specifically, mineral oil base oils can be obtained by removing the solvent oil fraction obtained by depressurizing and distilling atmospheric residual oil obtained by atmospheric distillation of crude oil, solvent extraction, hydrogen Base oil produced by isomerization of one or more treatments such as hydrocracking, solvent dewaxing, hydrorefining, etc., or wax isomerized mineral oil, GTLWAX (gastric liquid wax) Etc. can be illustrated.
合成系基油と しては、 具体的には、 ポリブテン又はその水素化物 ； 1—ォクテ ンオリ ゴマー、 1 ーデセンォリ ゴマ一等のポリ _ α—ォレフィン又はその水素化 物 ； ジト リデシルグルタレー ト、 ジ一 2 _ェチルへキシルアジペー ト、 ジイソデ シルアジペート、 ジト リデシノレアジペー ト、 ジ— 2—ェチルへキシルセバケー ト 等のジエステル ； ネオペンチルグリ コールエステル、 ト リ メチロールプロパン力 プリ レ一 ト、 ト リ メチロールプロパンぺヲルゴネ一 ト、 ペンタエリ スリ トール一 2—ェチノレへキサノエ一 ト、 ペンタエリスリ トールペラルゴネート等のポリオ一 ルエステル ； アルキルナフタレン、 アルキルベンゼン及び芳香族エステル等の芳 香族系合成油 ； これらの混合物等が例示できる。  Specific examples of synthetic base oils include polybutene or a hydride thereof; poly-α-olefins such as 1-octene oligomer, 1-decenoligoma, or a hydride thereof; ditridecyl glutarate, Diesters such as di-2-ethylhexyl adipate, diisodecyl adipate, ditridecinorea dipate, di-2-ethylhexyl sebacate, etc .; neopentyl glycol ester, trimethylolpropane power pre-relate, g Polyol esters such as dimethylolpropane sulfonate, pentaerythritol 1-ethenorehexanoate, pentaerythritol pelargonate; aromatic synthetic oils such as alkylnaphthalene, alkylbenzene and aromatic ester; mixtures thereof Etc. can be illustrated.
本発明における潤滑油基油と しては、 上記鉱油系基油、 上記合成系基油又はこ れらの中から選ばれる 2種以上の任意混合物等が使用できる。 例えば、 1種以上 の鉱油系基油、 1種以上の合成系基油、 1種以上の鉱油系基油と 1種以上の合成 系基油との混合油等を挙げることができる。  As the lubricating base oil in the present invention, the mineral base oil, the synthetic base oil, or an arbitrary mixture of two or more selected from these can be used. Examples thereof include one or more mineral base oils, one or more synthetic base oils, and a mixed oil of one or more mineral base oils and one or more synthetic base oils.
本発明において用いる潤滑油基油の動粘度は特に制限はないが、 一般の緩衝器 に要求される減衰力に適合させる観点から、 4 0 °Cにおける動粘度の下限値は、 好ましくは 3 mm2/ s、 より好ましくは 6 mm2Z sであり、 一方、 その上限値 は、 好ましくは 6 0 mm2/ s、 より好ましくは 4 0 mm2Z s、 さらに好ましく は 2 0 mm2Z sであり、 より低摩擦の組成物を得ることができる点で、 さらに 好ましくは 1 0 mm2 Z s以下、特に好ましくは 9 mm2/ s以下であることが望 ましい。 The kinematic viscosity of the lubricating base oil used in the present invention is not particularly limited. From the viewpoint of adapting to the damping force required for the above, the lower limit of the kinematic viscosity at 40 ° C is preferably 3 mm 2 / s, more preferably 6 mm 2 Z s, while the upper limit is Preferably it is 60 mm 2 / s, more preferably 40 mm 2 Z s, more preferably 20 mm 2 Z s, and more preferably 10 0 in that a composition with a lower friction can be obtained. It is desirable that it is not more than mm 2 Z s, particularly preferably not more than 9 mm 2 / s.
まだ、 本発明において使用する潤滑油基油の粘度指数も特に限定されず任意で あるが、 緩衝器に要求される基本的性能である減衰作用が油圧作動油の粘度に依 存し、 温度による減衰力の変化をできるだけ小さくするという観点から、 粘度指 数は 8 0以上が好ましく、より好ましくは 9 5以上のものを用いるのが望ましレ、。 本発明の緩衝器用油圧作動油組成物は、 前記潤滑油基油に、 （A) 炭素数 3〜 1 0の炭化水素基を有するリン酸エステル、 亜リン酸エステル又はこれらの塩、 及 び （B) 炭素数 6〜 3 0の飽和若しくは不飽和脂肪酸及び/又は該脂肪酸のエス テルを含有するものである。  The viscosity index of the lubricating base oil used in the present invention is not particularly limited and is arbitrary. However, the damping performance, which is a basic performance required for the shock absorber, depends on the viscosity of the hydraulic fluid and depends on the temperature. From the viewpoint of minimizing the change in damping force, the viscosity index is preferably 80 or more, more preferably 95 or more. The hydraulic fluid composition for a shock absorber according to the present invention comprises: (A) a phosphate ester having a hydrocarbon group having 3 to 10 carbon atoms, a phosphite ester, or a salt thereof; B) A saturated or unsaturated fatty acid having 6 to 30 carbon atoms and / or an ester of the fatty acid.
前記 （A) 炭素数 3〜 1 0の炭化水素基を有するリン酸エステル、 亜リン酸ェ ステル又はこれらの塩としては、 具体的には、 一般式 （ 1 ) で表されるリン酸ェ ステル類、 一般式 （2 ) で表される亜リン酸エステル類、 これらの塩及ぴこれら の混合物等を示す。  Specific examples of the (A) phosphate ester, phosphite ester or salt thereof having a hydrocarbon group having 3 to 10 carbon atoms include a phosphate ester represented by the general formula (1). Phosphites represented by the general formula (2), salts thereof and mixtures thereof.
Figure imgf000006_0001
上記 （ 1 ) 式中、 R R 2及び R3は、 それぞれ個別に、 水素原子若しくは炭 素数 3〜 1 0、 好ましくは炭素数 4〜 8の炭化水素基であり、 R 1、 R 2及び R 3 のうち少なく とも 1つが炭素数 3〜 1 0の炭化水素基である。
Figure imgf000006_0001
In the above formula (1), RR 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 3 to 10 carbon atoms, preferably 4 to 8 carbon atoms, and R 1 , R 2 and R 3 At least one of them is a hydrocarbon group having 3 to 10 carbon atoms.
また上記 （2 ) 式中、 R4、 R5及び R6は、 それぞれ個別に、 水素原子若しく は炭素数 3〜 1 0、 好ましくは炭素数 4〜 8の炭化水素基であり、 R 4、 R 5及び R 6のうち少なく ども 1つが炭素数 3〜 1 0の炭化水素基である。 In the above formula (2), R 4 , R 5 and R 6 are each independently a hydrogen atom or Is a hydrocarbon group having 3 to 10 carbon atoms, preferably 4 to 8 carbon atoms, and at least one of R 4 , R 5 and R 6 is a hydrocarbon group having 3 to 10 carbon atoms.
ここで、 上記炭化水素基は、 窒素原子、 硫黄原子、 酸素原子から選ばれる 1種 又は 2種以上のへテロ原子を有していても良い。 なお、 上記 （ 2 ) 式において、 R 6が水素原子である酸性亜リ ン酸ジエステル や、 R 5及び R 6が水素原子である酸性亜リ ン酸モノエステルである場合、 それぞ れ、 互変異性体である下記一般式 （ 3 )、 ( 4 ) の形で表されることもあるが、 こ れらは同じ化合物を示すものである。 Here, the hydrocarbon group may have one or more heteroatoms selected from a nitrogen atom, a sulfur atom, and an oxygen atom. In the above formula (2), when R 6 is an acidic phosphite diester having a hydrogen atom or an acidic phosphite monoester having R 5 and R 6 is a hydrogen atom, respectively, The mutants may be represented by the following general formulas (3) and (4), but they represent the same compound.
R50 、H
Figure imgf000007_0001
上記のよ うな炭素数 3〜 1 0の炭化水素基と しては、具体的には、プロピル基、 ブチル基、 ペンチル基、 へキシル基、 ヘプチル基、 ォクチル基、 ノニル基、 デシ ル基等のアルキル基 （これらアルキル基は直鎖状でも分枝状でもよい。） ； プロべ 二ノレ基、 ブテニノレ基、 ペンテュル基、 へキセニノレ基、 ヘプテニル基、 ォクテ二ノレ 基、 ノネニル基、 デセニル基等のアルケニル基 （これらアルケニル基は直鎖状で も分枝状でもよく 、 二重結合の位置は任意である。） ； シクロペンチル基、 シクロ へキシル基、 シク口へプチル基等の炭素数 5〜 7のシクロアルキノレ基 ； メチノレシ ク ロペンチノレ基、 ジメチノレシク ロペンチノレ基、 メチノレエチノレシク ロペンチノレ基、 ジェチルシクロペンチル基、 メチルシクロへキシル基、 ジメチルシクロへキシル 基、 メチ /レエチノレシクロへキシル基、 ジェチルシクロへキシル基、 メチルシクロ ヘプチル基、 ジメチルシクロへプチル基、 メチルェチルシクロへプチル基等の炭 素数 6〜 1 0のァノレキルシク ロアルキル基 ； フエニル基、 ナフチル基等のァリー ル基 ： ト リル基、 キシリル基、 ェチルフエ二ル基、 プロ ピルフエニル基、 ブチル フヱニル基等の炭素数 7〜 1 0の各アルキルァリ一ル基 （アルキル基は直鎖状で も分枝状でも良く、 また置換位置も任意である。） ； ベンジル基、 フエニルェチル 基、 フエニルプロピル基、 フエニルブチル基等の炭素数 7〜 1 0の各ァリールァ ルキル基 （アルキル基は直鎖状でも分枝状でも良く 、 また置換位置も任意であ る） ； 等が挙げられる。 R 5 0, H
Figure imgf000007_0001
Specific examples of the hydrocarbon group having 3 to 10 carbon atoms as described above include propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like. Alkyl groups (these alkyl groups may be linear or branched); probenole group, butenol group, pentul group, hexenino group, heptenyl group, octenol group, nonenyl group, decenyl group, etc. (The alkenyl group may be linear or branched, and the position of the double bond is arbitrary.); Cyclopentyl group, cyclohexyl group, cyclopentyl heptyl group, etc. 7 cycloalkynole group: methinores chloropentinole group, dimethino cycleno chineno group, methino ethino benzo pentenore group, jetyl cyclopentyl group, methylcyclo Xylyl group, dimethylcyclohexyl group, methyl / retinorecyclohexyl group, jetylcyclohexyl group, methylcycloheptyl group, dimethylcycloheptyl group, methylethylcycloheptyl group, etc. Aryl groups such as phenyl, naphthyl, etc .: each alkylaryl group having 7 to 10 carbon atoms such as tolyl, xylyl, ethenylphenyl, propylphenyl, butylphenyl, etc. In a chain May be branched, and the substitution position is arbitrary. ); Each arylalkyl group having 7 to 10 carbon atoms such as benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, etc. (The alkyl group may be linear or branched, and the substitution position is also arbitrary.) ); Etc.
本発明の緩衝器用油圧作動油組成物における （A) 成分と しては、 特に下記一 般式 （ 5) で示される炭素数 3〜 1 0の炭化水素基を有するハイ ドロゲンホスフ アイ トが好ましい。  The component (A) in the hydraulic fluid composition for a shock absorber of the present invention is particularly preferably a hydrogen phosphate having a hydrocarbon group having 3 to 10 carbon atoms represented by the following general formula (5).
Figure imgf000008_0001
本発明の緩衝器用油圧作動油組成における （A) 成分の含有量は、 特に制限は ないが、二 ト リルシ一ル材などのシール材と口ッ ド間のフリ クショ ンをより高め、 摩耗防止効果も期待できる点で、 組成物全量基準で、 リ ン元素換算量で、 好まし くは 0. 0 0 5〜 0. 2質量0 /。、 より好ましくは 0. 0 1〜 0. 1質量％、 特に 好ましくは 0. 0 1 5〜 0. 0 6質量％である。 （A) 成分の含有量が少なすぎる と摩耗防止効果が小さく、 また、 0. 2質量％を超えても含有量に見合うだけの 効果を得にく く、 腐食や劣化の原因となる傾向にある。 本発明の緩衝器用油圧作動油組成物における （B) 成分は、 炭素数 6〜 3 0の 飽和又は不飽和脂肪酸及び 又は該脂肪酸のエステルである。
Figure imgf000008_0001
The content of the component (A) in the hydraulic fluid composition for shock absorbers of the present invention is not particularly limited, but the friction between the sealing material such as a 2-tri-seal material and the mouth is further increased to prevent wear. From the point of view of the effect, based on the total amount of the composition, the amount in terms of phosphorus element is preferably 0.05 to 0.2 mass 0 /. More preferably, it is 0.01 to 0.1% by mass, and particularly preferably 0.01 5 to 0.06% by mass. (A) If the content of the component is too small, the effect of preventing wear is small, and even if it exceeds 0.2% by mass, it is difficult to obtain an effect commensurate with the content, which tends to cause corrosion and deterioration. is there. The component (B) in the hydraulic fluid composition for a shock absorber according to the present invention is a saturated or unsaturated fatty acid having 6 to 30 carbon atoms and / or an ester of the fatty acid.
脂肪酸と しては直鎖脂肪酸でも分枝脂肪酸でもよく 、 また飽和脂肪酸でも不飽 和脂肪酸.でもよく 、また、一塩基酸でも多塩基酸でもよい。 この脂肪酸と しては、 具体的には、 へキサン酸、 ヘプタン酸、 オクタン酸、 ノナン酸、 デカン酸、 ゥン デカン酸、 ドデカン酸、 ト リデカン酸、 テ トラデカン酸、 ペンタデカン酸、 へキ サデカン酸、 ヘプタデカン酸、 ォクタデカン酸等の炭素数 6〜 3 0、 好ましくは 炭素数 1 2〜 1 8の飽和脂肪酸 （これらは直鎖状でも分枝状でもよい。） ； ドデセ ン酸、 ト リデセン酸、 テ トラデセン酸、 ペンタデセン酸、 へキサデセン酸、 ヘプ タデセン酸、 ォクタデセン酸等の炭素数 6〜 3 0、 好ましく は炭素数 1 2〜 1 8 の不飽和脂肪酸 （これらは直鎖状でも分枝状でもよく、 また二重結合の位置も任 意である。） ； ドデシルコハク酸、 ト リデシルコハク酸、 テ トラデシルコハク酸、 ペンタデシルコハク酸、 へキサデシルコハク酸、 ヘプタデシノレコハク酸、 ォクタ デシルコハク酸等の炭素数 6 〜 3 0、 好ましく は炭素数 1 2 〜 1 8の飽和二塩基 脂肪酸 （これらは直鎖状でも分枝状でもよい。） ； ドデセエルコハク酸、 ト リデセ ニノレコノヽク酸、 テ トラテセニノレコハク酸、 ペンタデセニノレコノヽク酸、 へキサテセ エルコハク酸、 ヘプタデセニルコハク酸、 ォクタデセニルコハク酸等の炭素数 6 〜 3 0、 好ましく は炭素数 1 2 〜 1 8の不飽和二塩基脂肪酸 （これらは直鎖状で も分枝状でもよく、 また二重結合の位置も任意である。） 等が挙げられる。 これら の中でも、 ラウ リ ン酸、 ステアリ ン酸、 ォレイン酸等の炭素数 1 2 〜 1 8の飽和 又は不飽和一塩基脂肪酸が特に好ましい。 The fatty acid may be a linear fatty acid or a branched fatty acid, may be a saturated fatty acid or an unsaturated fatty acid, and may be a monobasic acid or a polybasic acid. Specific examples of the fatty acid include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, and hexadecane. Saturated fatty acids having 6 to 30 carbon atoms, preferably 12 to 18 carbon atoms, such as acids, heptadecanoic acid, and octadecanoic acid (these may be linear or branched); dodecenoic acid, tridecenoic acid Unsaturated fatty acids having 6 to 30 carbon atoms, preferably 12 to 18 carbon atoms, such as tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid and octadecenoic acid (these are linear or branched) But also the position of the double bond I mean. ); Carbon number of dodecyl succinic acid, tridecyl succinic acid, tetradecyl succinic acid, pentadecyl succinic acid, hexadecyl succinic acid, heptadecino succinic acid, octadecyl succinic acid, etc., preferably carbon number 12- 1 8 saturated dibasic fatty acids (these may be linear or branched); dodecere succinic acid, tridecenino succinic acid, tetrathesino succinic acid, pentadecenino succinic acid, hexatece Unsaturated dibasic fatty acids having 6 to 30 carbon atoms, preferably 12 to 18 carbon atoms, such as eruccinic acid, heptadecenyl succinic acid, and octadecenyl succinic acid. It may be branched, and the position of the double bond is also arbitrary.) Of these, saturated or unsaturated monobasic fatty acids having 12 to 18 carbon atoms such as lauric acid, stearic acid, and oleic acid are particularly preferable.
脂肪酸エステルと しては、 上記した炭素数 6 〜 3 0、 好ましくは炭素数 1 2 〜 1 8の脂肪酸 （これらは直鎖状でも分枝状でも良い） と炭素数 1 〜 3 0、 好まし くは炭素数 1 〜 1 8の 1価アルコール又は多価アルコールとのエステル等が挙げ られ、 一塩基脂肪酸と多価アルコールとのエステルあるいは、 二塩基脂肪酸と 1 価アルコールとのエステルが好ましく、 特に一塩基脂肪酸と多価アルコールとの エステルであることが好ましい。  As the fatty acid ester, fatty acids having 6 to 30 carbon atoms, preferably 12 to 18 carbon atoms (which may be linear or branched) and 1 to 30 carbon atoms are preferable. Or an ester of a monohydric alcohol having 1 to 18 carbon atoms or a polyhydric alcohol, and an ester of a monobasic fatty acid and a polyhydric alcohol or an ester of a dibasic fatty acid and a monohydric alcohol is preferred. It is preferably an ester of a monobasic fatty acid and a polyhydric alcohol.
1価アルコールと しては、 炭素数 1 〜 3 0の飽和又は不飽和脂肪族アルコール が挙げられ、 具体的には、 メタノール、 エタノール、 プロパノール、 ブタノール、 ペンタノ一ル、 へキサノール、 ヘプタノ一ノレ、 オタタノ一ル、 ノナノ一ル、 デカ ノール、 ドデカノ一ル、 テ トラデカノール、 へキサデ力ノール、 ォクタデカノー ル、 ォレイルァノレコーノレ等を例示  Examples of monohydric alcohols include saturated or unsaturated aliphatic alcohols having 1 to 30 carbon atoms, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol monole, Examples include otatanol, nonanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, oleiranoreconole
することができる。 can do.
また多価アルコールと しては、 2 〜 6価の多価ァノレコール （多量体も含む） 等 が挙げられる。 具体的には、 エチレングリ コール、 ジエチレングリ コール、 ト リ エチレングリ コール、 プロピレングリ コール、 ジプロピレングリ コール、 ト リプ ロピレングリ コ一ノレ、 グリセリ ン、 ジグリセリ ン、 ソ /レビタン、 ト リ メチローノレ ェタン、 ト リ メチローノレプロパン、 ペンタエリスリ ト一 >^レ、 ジペンタエリスリ ト —ル等の多価アルコール等が挙げられる。  Examples of the polyhydric alcohol include divalent to hexavalent polyhydric alcoholols (including multimers). Specific examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycolate, glycerin, diglycerin, so / levitane, trimethylolethane, And polyhydric alcohols such as trimethylololepropane, pentaerythritol> ^ re, and dipentaerythritol.
一塩基脂肪酸と多価アルコールとのエステルと して好ましい化合物と しては、 具体的には、 グリセリ ンモノォレート、 グリセリ ンジォレー ト、 グリセリ ント リ ォレー ト、 ソ ^レビタンモノォレー ト、 ソノレビタンジォレー ト、 ソノレビタン ト リ オ レー ト等の炭素数 1 2〜 1 8の飽和又は不飽和一塩基脂肪酸と 3価以上のアルコ 一ノレとのエステルが例示できる。 Specific examples of preferable compounds as esters of monobasic fatty acids and polyhydric alcohols include glycerin monooleate, glycerin dilate, and glycerin tritate. Saturated or unsaturated monobasic fatty acids having 12 to 18 carbon atoms such as oleate, solebitantanate, sonorebitane diolate, sonorebitane trioleate, etc. Can be exemplified.
二塩基脂肪酸と 1価アルコールとのエステルと して好ましい化合物と しては、 具体的には、 n— ドデシルコハク酸モノメチルエステル、 n— ドデシルコハク酸 ジメチノレエステル、 n —テ トラデシノレコハク酸モノメチルエステノレ、 n—テ トラ デシノ] コハク酸ジメチノレエステノレ、 n —へキサデシルコハク酸モノメチルエステ ル、 n —へキサデシルコハク酸ジメチルエステル、 n —ォクタデシノレコハク酸モ ノメチルエステル、 n—ォクタデシルコハク酸ジメチルエステル等、 炭素数 1 2 〜 1 8の飽和又は不飽和二塩基酸と炭素数 1〜1 8の 1価アルコールとのエステ ルが例示できる。  Specific examples of preferable compounds as esters of dibasic fatty acids and monohydric alcohols include n-dodecyl succinic acid monomethyl ester, n-dodecyl succinic acid dimethinole ester, and n-tetradecino succinic acid. Monomethylestenole, n-tetradecino] Dimethylolestenole succinate, n—Hexadecyl succinic acid monomethyl ester, n—Hexadecyl succinic acid dimethyl ester, n—Octadecinosuccinic acid monomethyl ester, n— Examples thereof include esters of saturated or unsaturated dibasic acids having 12 to 18 carbon atoms and monohydric alcohols having 1 to 18 carbon atoms, such as dimethyl deca succinate.
本発明の緩衝器用油圧作動油組成物における （B ) 成分の含有量は、 二 ト リル シール材などのシール材とピス トン口ッ ド間のフリ クショ ンを低下させることな く、 スティ ックスリ ップ特性を改善することが期待できる点で、 組成物全量基準 で、 好ましく は 0 . 0 0 1〜 2質量0 /0、 より好ましくは 0 . 0 1〜 1質量0 /0、 特 に好ましくは 0 . 0 2〜0 . 1質量％である。 本発明の緩衝器用油圧作動油組成物には、 前記 （A ) 成分および （B ) 成分に 加え、 さらに （C ) 無灰分散剤を含有させることが好ましい。 The content of the component (B) in the hydraulic fluid composition for shock absorbers of the present invention does not reduce the friction between the seal material such as a 2-tril seal material and the piston mouth, and does not reduce the stickiness. in that can be expected to improve the flop characteristics, the total amount of the composition, preferably 0.0 0 1-2 mass 0/0, more preferably 0.0 1 to 1 by weight 0/0, the preferred especially 0.02 to 0.1% by mass. In addition to the components (A) and (B), the hydraulic fluid composition for a shock absorber according to the present invention preferably further contains (C) an ashless dispersant.
無灰分散剤と しては、 潤滑油に用いられる任意の無灰分散剤を用いることがで きる。 例えば、 炭素数 4 0〜4 0 0の直鎖若しくは分枝状のアルキル基又はアル ケ-ル基を分子中に少なく とも 1個有する含窒素化合物又はその誘導体が挙げら れる。 このアルキル基又はアルケニル基の炭素数は 4 0〜 4 0 0、 好ましくは 6 0〜3 5 0である。 アルキル基又はアルケニル基の炭素数が 4 0未満の場合は化 合物の潤滑油基油に対する溶解性が低下し、 一方、 アルキル基又はアルケニル基 の炭素数が 4 0 0を越える場合は、 潤滑油組成物の低温流動性が悪化するため、 それぞれ好ましくない。 このアルキル基又はアルケニル基は、 直鎖状でも分枝状 でもよいが、 好ましいものと しては、 具体的には、 プロ ピレン、 1 ーブテン、 ィ ソブチレン等の才レフィ ンの才リ ゴマーやエチレンとプロ ピレンのコ才リ ゴマー から誘導される分枝状アルキル基や分枝状アルケニル基等が挙げられる。 ( c ) 成分の具体例と しては、 例えば、 下記の化合物が挙げられる。 これらの 中から選ばれる 1種又は 2種以上の化合物を用いることができる。 As the ashless dispersant, any ashless dispersant used in lubricating oils can be used. For example, a nitrogen-containing compound having at least one linear or branched alkyl group having 40 to 400 carbon atoms or an alkyl group in the molecule or a derivative thereof can be used. The alkyl group or alkenyl group has 40 to 40, preferably 60 to 35, carbon atoms. If the alkyl group or alkenyl group has less than 40 carbon atoms, the solubility of the compound in the lubricating base oil will be reduced, whereas if the alkyl group or alkenyl group has more than 400 carbon atoms, lubrication will not occur. Since the low-temperature fluidity | liquidity of an oil composition deteriorates, it is unpreferable respectively. The alkyl group or alkenyl group may be linear or branched, but specific examples include specific ligomers such as propylene, 1-butene, isobutylene, and ethylene. And branched alkyl groups and branched alkenyl groups derived from propylene ligomers. Specific examples of the component (c) include the following compounds. One or two or more compounds selected from these can be used.
( C 1 ) 炭素数 4 0〜 4 0 0のアルキル基又はアルケニル基を分子中に少なく と も 1個有するコハク酸 （無水物） 一ポリアミン反応生成物、 あるいはその誘導体 (C1) Succinic acid (anhydride) monopolyamine reaction product or derivative thereof having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule
( C 2 ) 炭素数 4 0〜4 0 0のアルキル基又はアルケニル基を分子中に少なく と も 1個有するベンジルァミ ン、 あるいはその誘導体 (C2) Benzylamine having at least one alkyl or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof
( C 3 ) 炭素数 4 0〜4 0 0のアルキル基又はアルケニル基を分子中に少なく と も 1個有するポリアミン、 あるいはその誘導体  (C3) a polyamine having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof
上記 （C 1 ) コハク酸 （無水物） 一ポリアミン反応生成物と しては、 例えば、 モノイ ミ ド構造を有するアルキル又はアルケニルコハク酸イ ミ ド、 ビスイ ミ ド構 造を有するアルキル又はアルケニルコハク酸ィ ミ ド、 あるいはその他の構造を有 する反応生成物及びこれらの混合物が挙げられる。 ポリ （イソ） ブテニルコハク 酸イ ミ ドの場合、 通常、 ポリ （イ ソ） ブテン、 塩素化ポリ （イソ） ブテン又はこ れらの混合物を無水マレイ ン酸と 1 0 0〜 2 0 0 °Cで反応させて得られるポリ Examples of the (C 1) succinic acid (anhydride) monopolyamine reaction product include alkyl or alkenyl succinic acid imide having a monoimide structure, and alkyl or alkenyl succinic acid having a biimide structure. And reaction products having imids or other structures, and mixtures thereof. In the case of poly (iso) butenyl succinic acid imide, usually poly (iso) butene, chlorinated poly (iso) butene or a mixture of these with maleic anhydride at 100 ° C. to 200 ° C. Poly obtained by reaction
(イ ソ） ブテュルコハク酸 （無水物） と、 エチレンジァミ ン、 ジエチレント リア ミ ン、 ト リエチレンテ トラ ミ ン、 テ トラエチレンペンタ ミ ン、 ペンタエチレンへ キサミ ン、 へキサエチレンヘプタ ミン等のポリアミンと反応させることによ り得 ることができる。 また、 アルキル又はアルケニルコハク酸 （無水物） 一ポリアミ ン反応生成物の誘導体と しては、 該反応生成物に、 カルボン酸等の含酸素有機化 合物等でァシル化した誘導体、 あるいはホウ酸、 リ ン酸、 硫酸等の酸又はそれら の塩を作用させて得られた誘導体等が挙げられる。 (Iso) Reacts butyrsuccinic acid (anhydride) with polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexaamine, hexaethyleneheptamine, etc. Can be obtained. In addition, as a derivative of an alkyl or alkenyl succinic acid (anhydride) monopolyamine reaction product, a derivative obtained by acylating the reaction product with an oxygen-containing organic compound such as carboxylic acid, or boric acid And derivatives obtained by the action of acids such as phosphoric acid and sulfuric acid or salts thereof.
上記 （C 2 ) ベンジルァミ ンと しては、 例えば、 プロ ピレンォリ ゴマ一、 ポリ ブテン、 及びェチレン一 α—ォレフィン共重合体等のポリオレフインをフエノー ルと反応させてアルキルフエノールと した後、 これにホルムアルデヒ ドとジェチ レン ト リ アミ ン、 ト リエチレンテ トラ ミ ン、 テ トラエチレンペンタ ミ ン、 及びべ ンタエチレンへキサミン等のポリアミ ンをマンニッヒ反応により反応させること により得られるベンジルァミンを挙げることができる。 また、 ベンジルァミ ンの 誘導体と しては、 上記のように得られたベンジルァミンに、 カルボン酸等の含酸 素有機化合物等でァシル化した誘導体、 あるいはホウ酸、 リ ン酸、 硫酸等の酸又 はそれらの塩を作用させて得られた誘導体等が挙げられる。 上記 （C 3 ) ポリアミンと しては、 例えば、 プロ ピレンオリ ゴマー、 ポリブテ ン、及びエチレン一 α—ォレフィン共重合体等のポリォレフィンを塩素化した後、 これにアンモニアやエチレンジァミ ン、 ジエチレン ト リ アミ ン、 ト リエチレンテ トラミ ン、 テ トラエチレンペンタ ミ ン、 及びペンタエチレンへキサミ ン等のポリ アミンを反応させることにより得られるポリアミンを挙げることができる。また、 ポリアミンの誘導体と しては、 上記のように得られたポリアミ ンに、 カルボン酸 等の含酸素有機化合物等でァシル化した誘導体、 あるいはホウ酸、 リ ン酸、 硫酸 等の酸又はそれらの塩を作用させて得られた誘導体等が挙げられる。 Examples of the (C 2) benzylamine include, for example, polyolefins such as propylene ligomer, polybutene, and ethylene 1-olefin copolymer, which are reacted with phenol to form alkylphenol, and then formaldehyde. Examples thereof include benzylamine obtained by reacting polyamines such as dimethylamine, triethylenetetramine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine with Mannich reaction. In addition, as a derivative of benzylamine, a derivative obtained by acylating the benzylamine obtained as described above with an oxygen-containing organic compound such as carboxylic acid, or an acid or boric acid, phosphoric acid, sulfuric acid, or the like. Includes derivatives obtained by the action of salts thereof. Examples of the (C 3) polyamine include chlorination of polyolefins such as propylene oligomers, polybutenes, and ethylene-α-olefin copolymers, and then ammonia, ethylenediamine, diethylenetriamine. And polyamines obtained by reacting polyamines such as triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. In addition, as a polyamine derivative, a derivative obtained by acylating the polyamine obtained as described above with an oxygen-containing organic compound such as carboxylic acid, or an acid such as boric acid, phosphoric acid, sulfuric acid, or the like Derivatives obtained by reacting a salt of
本発明における （C ) 無灰分散剤におけるアルキル基又はアルケニル基の数平 均分子量は、 通常 7 0 0〜 5 0 0 0であるが、 二 ト リルシール材等のシールフリ クシヨ ンをよ り高く維持できる点で、 好ましくは 9 0 0〜 1 5 0 0であり、 より 好ましくは 1 4 0 0以下、 さらに好ましくは 1 3 0 0以下、 特に好ましくは 1 2 0 0以下とすることが望ましい。  In the present invention, the number average molecular weight of the alkyl group or alkenyl group in the (C) ashless dispersant is usually 700 to 500, but it is possible to maintain a higher seal friction such as a two-trill sealant. In this respect, it is preferably from 90 to 1500, more preferably 1400 or less, further preferably 1300 or less, and particularly preferably 1220 or less.
また、 本発明の （C ) 成分は、 そのィ ミノ基 アミノ基比率に特に限定はなく、 例えば、 エチレンジァミンモノ （ァルケニル） コハク酸イ ミ ドのようなィ ミノ基 を含まない化合物では 0 となり、 ジエチレント リアミ ンビス （ァルケニル） コハ ク酸イ ミ ドのよ うなアミ ノ基を含まない化合物では無限大となり うるが、 製造コ ス トの点で、 0 . 1〜 5 0 とすることが好ましい。 また、 よ り高フ リ クショ ンの 組成物を得ることができる点で、 イ ミノ基 アミノ基比率が 1 5以下とすること が好ましく、 安定性、 製造コス トの点で、 好ましくは 1以上である。  In addition, the component (C) of the present invention is not particularly limited in its imino group amino group ratio. For example, in the compound containing no imino group such as ethylenediamine mono (alkenyl) succinic acid imide. It can be infinite for compounds that do not contain an amino group such as diethylenetriaminebis (alkenyl) succinic acid imide, but in terms of production cost, it may be 0.1 to 50. preferable. In addition, the imino group amino group ratio is preferably 15 or less from the viewpoint of obtaining a composition having a higher flexion, and preferably 1 or more from the viewpoint of stability and production cost. It is.
本発明においては、 （C 1 ) ィ ミ ノ基ノアミノ基比率が 1 5以下であり、 数平均 分子量が 1 5 0 0以下のアルキル基若しくはアルケニル基を有するコハク酸 （無 水物） —ポリ アミ ン反応生成物及び Ζ又はその誘導体を用いることが特に好まし レ、。  In the present invention, a succinic acid (anhydrous) having a (C 1) imino group noamino group ratio of 15 or less and a number average molecular weight of 1500 or less and having an alkyl group or alkenyl group (polyhydrate) It is particularly preferred to use the reaction products and cocoons or their derivatives.
なお、 （C 1 ) 成分において、 （C 1 a ) ィ ミノ基 アミ ノ基比率が 3〜 1 5の 場合には、 ホウ素を本質的に含有しないものの方が、 二 ト リル系シール材等のシ 一ル材とピス トン口 ッ ド間のフリ クショ ンを高く維持しやすくなるため好ましい また、 （C 1 a ) 成分のィ ミノ基 Zアミノ基比率は、 より高フリ クショ ンの組成物 を得ることができる点で、 好ましくは 3 . 5〜 1 2、 さらに好ましくは 4〜 9、 特に好ましく は 4 . 5〜6である。 また （C I ) 成分は、 （C 1 b ) イ ミノ基ノアミノ基比率が 3未満の場合には、 ホウ素を含有していても、 含有していなくても良いが、 ホウ素を含有するものが 好ましい。 ホウ素を含有するものであっても、 イミノ基ノアミノ基比率が 3未満 であれば二 ト リルシール等のシール材とビス トンロ ッ ド間のフ リ クショ ンを高く 維持しやすくなり、 イミノ基 Zアミノ基比率が 3以上のホウ素含有物に対し、 特 異的な挙動を示す。 （C 1 b )成分のィミノ基 アミノ基比率は 0〜 3未満である が、 ^定性、 造コス トの点で、 好ましくは 1以上、 より好ましくは 1〜 2. 5、 特に好ましくは 1. 5〜 2. 5である。 （C 1 b ) 成分としてホウ素を含有するも のを使用する場合、 そのホウ素含有量 Z窒素含有量の質量比 （B "N比） は、 特 に制限はないが、 シール材とピス トン口ッ ド間のフリクションを高く維持しゃす い点及ぴ （A) 成分と併用した場合の安定性の点で、 好ましくは 0. 1〜 1、 よ り好ましくは 0. 5〜 1、 特に好ましくは 0. 7〜0. 9である。 In addition, in the (C 1) component, when the (C 1 a) imino group amino group ratio is 3 to 15, the one that does not essentially contain boron is more suitable for a 2-tolyl-type sealing material, etc. This is preferable because the friction between the sealant and the piston head can be easily maintained at a high level. Also, the ratio of the imino group and the Z amino group of the component (C 1 a) makes the composition of higher friction. It is preferably 3.5 to 12, more preferably 4 to 9, and particularly preferably 4.5 to 6 in that it can be obtained. The component (CI) may contain or not contain boron when the (C 1 b) imino group noamino group ratio is less than 3, but preferably contains boron. . Even if it contains boron, if the imino group noamino group ratio is less than 3, it is easy to maintain a high friction between the sealant such as a 2-tril seal and the biston rod, and the imino group Z amino It exhibits a special behavior for boron-containing materials with a base ratio of 3 or more. Although the imino group amino group ratio of the component (C 1 b) is 0 to less than 3, it is preferably 1 or more, more preferably 1 to 2.5, and particularly preferably 1. 5 to 2.5. (C 1 b) When using boron as a component, the mass ratio of boron content Z nitrogen content (B "N ratio) is not particularly limited, but the sealant and piston port In view of maintaining high friction between the heads and stability when used in combination with component (A), preferably 0.1 to 1, more preferably 0.5 to 1, particularly preferably 0. 7 to 0.9.
なお、 ここでいぅィミノ基とは、 一 NH—で表される基を示し、 ァミノ基とは 一 NH2で表される基を示し、 イミノ基 アミノ比率は （C) 成分中のアミノ基Here, the imino group represents a group represented by 1 NH—, the amino group represents a group represented by 1 NH 2 , and the imino group amino ratio is the amino group in the component (C).
(一 NH2) を構成する窒素原子に対する （C) 成分中のイミノ基 （_NH_) を構成する窒素原子との比率を表している。 例えば、 エチレンジァミ ンモノ （ァ ルケニル） コハク酸イミ ドのよ うなイミノ基を含まない化合物では 0となり、 ジ エチレントリアミンビス （ァルケ-ル） コハク酸イミ ドのようなアミノ基を含ま ない化合物では無限大となり うる。 It represents the ratio of the nitrogen atom composing the imino group (_NH_) in the component (C) to the nitrogen atom composing (one NH 2 ). For example, it is 0 for compounds that do not contain an imino group such as ethylenediamine mono (alkenyl) succinic acid imide, and infinite for compounds that do not contain an amino group such as diethylenetriaminebis (alkenyl) succinic acid imide. It can be.
ィミノ基とアミノ基及びその比率は、 具体的には、 以下の方法により求めるこ とができる。  Specifically, the imino group and the amino group and the ratio thereof can be obtained by the following method.
(C) 成分のような、 イミノ基及びノ又はアミノ基を有する化合物を無水トリ フルォロ酢酸と反応させて得られた反応物は、 i9F _ NMRに供した際に、 トリ フルォロ酢酸を標準物質としてそのピーク位置を _ 7 6. 8 p p mとした場合に、(C) The reaction product obtained by reacting a compound having an imino group and a no- or amino group, such as component (C), with trifluoroacetic anhydride is standardized with trifluoroacetic acid when subjected to i 9 F_NMR. If the peak position of the substance is _ 7 6.8 ppm,
( a ) 化学シフ トー 6 6 p p m 7 2 p p mの位置と （ b ) 化学シフ トー 7 4 p p m 7 9 p p mの位置にそれぞれピークが得られる。 この （ a ) のピーク は、 以下の （ I ) 式のように （C) 成分中のイミノ基 （一 NH— ) と無水トリフ ルォロ齚酸が反応して得られる、 （ァ） で表される基のピークを示すと推定され、 また （b ) のピークは、 以下の （Π) 式のように （C) 成分中のアミノ基 （一 N H2) と無水トリフルォロ酢酸が反応して得られる、 （ィ） で表される基のピーク を示すと推定される。 Peaks are obtained at (a) chemical shift 6 6 ppm 7 2 ppm and (b) chemical shift 7 4 ppm 7 9 ppm. The peak of (a) is obtained by the reaction of imino group (1NH-) in component (C) with trifluorosuccinic anhydride as shown in the following formula (I). The peak of (b) is obtained by reacting the amino group (one NH 2 ) in component (C) with trifluoroacetic anhydride as shown in the following formula (iii): Peak of group represented by (i) It is estimated that
Figure imgf000014_0001
なお、 （C) 成分を無水トリフルォロ酢酸と反応させる手順、 i9F_NMRによ る測定手順は以下のとおりである。
Figure imgf000014_0001
The procedure for reacting the component (C) with trifluoroacetic anhydride and the measurement procedure by i 9 F_NMR are as follows.
まず、 （C) 成分 0. 5 gをへキサン 20m lに溶解させた後、 これに無水トリ フルォロ酢酸 1.0 gを添加し、系を撹拌しながら 20°Cで 2 0分間反応させる。 その後、 反応生成物にメタノール 1 0 m 1 と濃塩酸 0. 5m l を加え、 20 °Cで 2 0分間攪拌を続け、 未反応の無水トリフルォロ酢酸及び反応副成物である トリ フルォロ酢酸をメタノール層に除去する。 次いで油層を取り出し、 へキサンを蒸 留により留去し、 （C) 成分と トリフルォロ酢酸との反応生成物を得る。 こうして 得られる反応生成物 1 00 m gを試料として、 共鳴周波数 5 6 4. 4 MH zの i9 F一 NMRで分析する。 First, 0.5 g of component (C) is dissolved in 20 ml of hexane, 1.0 g of trifluoroacetic anhydride is added thereto, and the mixture is reacted at 20 ° C. for 20 minutes while stirring. Thereafter, 10 ml of methanol and 0.5 ml of concentrated hydrochloric acid were added to the reaction product, and stirring was continued at 20 ° C for 20 minutes. Unreacted trifluoroacetic anhydride and the reaction by-product trifluoroacetic acid were added to methanol. Remove into layers. Next, the oil layer is taken out, and hexane is distilled off by distillation to obtain a reaction product of the component (C) and trifluoroacetic acid. Using 100 mg of the reaction product thus obtained as a sample, it is analyzed by i 9 F 1 NMR at a resonance frequency of 5 64.4 MHz.
すなわち、 本発明で規定する （C) 成分中のイミノ基/アミノ基比率は、 この 方法により得られた、 上記 （ a ) のピーク面積 //上記 （b) のピーク面積の比率 によって特定される値、 すなわち、 （C) 成分中のアミノ基 （一 NH2) を構成す る窒素原子に対する （C) 成分中のイミノ基 （一 NH—） を構成する窒素原子と の比率を意味している。 ただし、 同様の結果が得られるのであれば、 同様の理論 等を用いた別の測定方法を用いても良い。 That is, the imino group / amino group ratio in the component (C) defined in the present invention is specified by the peak area of (a) // the ratio of the peak area of (b) obtained by this method. Value, that is, the ratio of the nitrogen atom constituting the imino group (one NH-) in the component (C) to the nitrogen atom constituting the amino group (one NH 2 ) in the component (C) . However, if a similar result can be obtained, another measurement method using the same theory may be used.
本発明の緩衝器用油圧作動油組成物において、 （C)成分の含有量は、組成物全 量基準で、通常 0.0 1〜 5質量％であり、 （C)成分の窒素量としての含有量は、 好ましくは、 0. 00 1質量％以上、 より好ましくは 0. 00 2質量％以上、 特 に好ましくは 0. 0 0 5質量％以上であり、 また含有量に見合うだけの効果が得 られず、 また低温特性が悪化する傾向にあることから、 好ましくは 0. 2質量％ 以下、 より好ましくは 0. 0 5質量％以下、 特に好ましくは 0. 0 1質量％以下 である。 また、 ホウ素を含む （C) 成分、 例えば、 ホウ素を含む （C 1— 2 ) 成 分を含有させる場合の含有量は、 組成物全量基準で、 ホウ素量として通常 0. 0 0 1〜 0. 2質量％、 好ましくは 0. 0 0 2〜 0. 0 5質量％であり、 （A) 成分 共存下での安定性の点でより好ましくは 0.0 1質量％以下、特に好ましくは 0.In the hydraulic fluid composition for a shock absorber of the present invention, the content of the component (C) is usually 0.01 to 5% by mass on the basis of the total amount of the composition, and the content of the component (C) as the nitrogen content is Preferably, 0.001% by mass or more, more preferably 0.002% by mass or more. Preferably, the content is not less than 0.05% by mass, an effect corresponding to the content cannot be obtained, and the low-temperature characteristics tend to deteriorate, so that it is preferably 0.2% by mass or less, more preferably Is not more than 0.05% by mass, particularly preferably not more than 0.01% by mass. In addition, when the (C) component containing boron, for example, the (C 1-2) component containing boron is included, the content of boron is usually 0.001 to 0. 2% by mass, preferably from 0.02 to 0.05% by mass, more preferably from 0.01% by mass or less, particularly preferably from the viewpoint of stability in the presence of component (A).
0 0 8質量％以下とすることが望ましい。 It is desirable that the content is 0 to 8% by mass or less.
本発明の緩衝器用油圧作動油組成物は、 上記 （A) 成分及び （B) 成分を含有 させ、 あるいはさらに （C) 成分を含有させることで微振幅領域におけるピス ト ンロ ッ ドとシール材間、 特に二トリル系のシール材を使用した場合に摩擦係数を 高いレベルで維持するとともに、スティ ックス リ ップ特性を改善することができ、 緩衝器のニュートラル位置での減衰力を高め、 微振幅時の車体 （ばね上荷重） の ふらつきを抑制するとともに運転者と乗員の不快感を軽減しうる効果を有する。 また、 本発明の緩衝器用油圧作動油組成物は、 前記潤滑油基油に、 （C 1 ) イミ ノ基 アミノ基比率が 1 5以下であり、 数平均分子量が 1 5 0 0以下のアルキル 基若しくはアルケニル基を有するコハク酸 （無水物） 一ポリアミン反応生成物及 び 又はその誘導体であって、 （C 1 a )ィミノ基/ァミノ基比率が 3〜 1 5かつ ホウ素を本質的に含有しないもの及び （C l b ) イミノ基 Zアミノ基比率が 3未 満のものから選ばれる少なく とも 1種を含有するものでもある。  The hydraulic fluid composition for a shock absorber according to the present invention contains the component (A) and the component (B), or further contains the component (C), so that the piston rod and the sealing material in the fine amplitude region are contained. Especially when using nitrile sealant, the friction coefficient can be maintained at a high level and the stick-lip characteristics can be improved, the damping force at the neutral position of the shock absorber is increased, and the fine amplitude This reduces the wobbling of the vehicle body (sprung load) and reduces the discomfort of the driver and passengers. Further, the hydraulic fluid composition for a shock absorber according to the present invention includes an alkyl group having a (C 1) imino group amino group ratio of 15 or less and a number average molecular weight of 1500 or less. Or a succinic acid (anhydride) having a alkenyl group, a polyamine reaction product and / or a derivative thereof, (C 1 a) imino group / amino group ratio of 3 to 15 and essentially free of boron And (C lb) imino group and at least one selected from those having a Z amino group ratio of less than 3.
本発明における （C 1 ) 成分におけるアルキル基又はアルケニル基の数平均分 子量は 1 5 0 0以下であり、 好ましくは 1 4 0 0以下、 より好ましくは 1 3 0 0 以下、 特に好ましくは 1 2 0 0以下とすることが望ましい。 当該数平均分子量が In the present invention, the number average molecular weight of the alkyl group or alkenyl group in the component (C 1) is 1550 or less, preferably 1400 or less, more preferably 1300 or less, particularly preferably 1 It is desirable to set it to 200 or less. The number average molecular weight is
1 5 0 0を超える場合には、 二トリルシール材等のシールフリクションを高く維 持しにくい。 また、 当該数平均分子量は、 油溶性の点で 1 5 0以上であることが 好ましく、 より好ましくは 3 0 0以上であり、 より高フ リ クショ ンの組成物を得 ることができる点でさらに好ましくは 7 0 0以上、 特に好ましくは 9 0 0以上と することが望ましい。 If it exceeds 1500, seal friction such as nitrile sealant is high and difficult to maintain. In addition, the number average molecular weight is preferably 1500 or more in terms of oil solubility, more preferably 3100 or more, and a higher-friction composition can be obtained. More preferably, it is desirable to set it at 700 or more, particularly preferably 900 or more.
本発明の緩衝器用油圧作動油組成物において、 （C 1 )成分の含有量は、組成物 全量基準で、 通常 0. 0 1〜5質量％であり、 （C 1 ) 成分の窒素量としての含有 量は、 好ましくは、 0. 0 0 1質量％以上、 より好ましくは 0. 0 0 2質量％以 上、 特に好ましくは 0. 0 0 5質量％以上であり、 また含有量に見合うだけの効 果が得られず、 また低温特性が悪化する傾向にあることから、 好ましくは 0. 2 質量％以下、 より好ましくは 0. 0 5質量％以下、特に好ましくは 0. 0 1質量％ 以下である。 In the hydraulic fluid composition for a shock absorber of the present invention, the content of the component (C 1) is the composition On the basis of the total amount, it is usually from 0 to 1 to 5% by mass, and the content of the (C 1) component as nitrogen is preferably 0.001% by mass or more, more preferably 0.0 0 2 It is preferably at least 0.2% by mass, particularly preferably at least 0.05% by mass, and since an effect corresponding to the content cannot be obtained and the low-temperature characteristics tend to deteriorate, it is preferably at least 0.2. % By mass or less, more preferably 0.05% by mass or less, particularly preferably 0.01% by mass or less.
ま 、 ホウ素を含む （C l b ) 成分を含有させる場合の含有量は、 組成物全量 基準で、 ホウ素量として通常 0. 0 0 1〜0. 2質量％、 好ましくは 0. 0 0 2 〜 0. 0 5質量％であり、 後記するように （A) 成分を併用する場合には、 安定 性の点でより好ましくは 0. 0 1質量％以下、 特に好ましくは 0. 0 0 8質量％ 以下とすることが望ましい。  In addition, when the component containing boron (C lb) is contained, the content of boron is usually from 0.001 to 0.2% by mass, preferably from 0.002 to 0%, based on the total amount of the composition. 0.5% by mass, and as described later, when the component (A) is used in combination, it is more preferably 0.01% by mass or less, particularly preferably 0.00% by mass or less in terms of stability. Is desirable.
本発明の緩衝器用油圧作動油組成物は、 基油に、 上記 （C 1 ) 成分を含有させ ることで微振幅領域におけるピス トン口ッ ドとシール材間、 特に二トリル系のシ 一ル材を使用した場合にフリクションを高いレベルで維持することができ、 緩衝 器のニュートラル位置での減衰力を高め、 微振幅時の車体 （ばね上荷重） のふら つきを抑制するとともに、 運転者と乗員の不快感を軽減しうる効果を有するもの である。  The hydraulic fluid composition for a shock absorber according to the present invention contains the above component (C 1) in the base oil, so that it is between the piston mouth and the seal material in the fine amplitude region, particularly a nitrile seal. The friction can be maintained at a high level when the material is used, the damping force at the neutral position of the shock absorber is increased, the fluctuation of the vehicle body (sprung load) at a small amplitude is suppressed, and the driver and It has the effect of reducing passenger discomfort.
本発明の緩衝器用油圧作動油組成物においては、 （C 1 )成分に加え、 さらに前 記 （A) 成分を併用することにより、 微振幅領域におけるピス トンロッ ドとシー ル材間、 特に二トリル系のシ一ル材を使用した場合にフリクシヨンをさらに高め ることができる。 特に、 （A) 成分としては、 前記一般式 （5) で示されるハイ ド ロゲンホスファイ トが好ましい。  In the hydraulic fluid composition for a shock absorber according to the present invention, in addition to the component (C 1), the component (A) is used in combination, so that the piston rod and the seal material in the fine amplitude region, particularly nitrile, are used. The friction can be further increased when the seal material is used. In particular, the component (A) is preferably a hydrogen phosphite represented by the general formula (5).
本発明の緩衝器用油圧作動油組成物において、 （A)成分を含有させる場合の含 有量は、二トリルシール材などのシール材と口ッ ド間のフリクションをより高め、 摩耗防止効果も期待できる点で、 組成物全量基準で、 リン元素換算量で、 0. 0 0 5〜0. 2質量％が好ましく、 より好ましくは 0. 0 1〜0. 1質量％、 特に 好ましくは 0. 0 1 5〜0. 0 6質量％である。 なお、 0. 2質量％を超えても 含有量に見合うだけの効果を得にく く、 酸化安定性が悪化する傾向にある。 本発明の緩衝器用油圧作動油組成物には、 さらに必要に応じて、 その性能をさ らに向上させるために、 又は、 その他の目的に応じて潤滑油に一般的に使用され ている任意の添加剤を含有させることができる。 このよ うな添加剤と しては、 例 えば、 （A) 成分および （B) 成分以外の摩擦調整剤、 粘度指数向上剤、 摩耗防止 剤、 酸化防止剤、 流動性向上剤、 金属不活性化剤、 消泡剤の他、 金属系清浄剤、 腐食防止剤、 防鲭剤、 抗乳化剤、 及び着色剤等の各種添加剤を挙げることができ る。 In the hydraulic fluid composition for a shock absorber according to the present invention, the content when component (A) is contained further increases the friction between a sealing material such as a nitrile sealing material and the mouth, and is expected to have an effect of preventing wear. From the viewpoint of the total amount of the composition, it is preferably 0.005 to 0.2 mass%, more preferably 0.01 to 0.1 mass%, particularly preferably 0.0, in terms of phosphorus element. 1 5 to 0.06 mass%. Even if it exceeds 0.2% by mass, it is difficult to obtain an effect commensurate with the content, and the oxidation stability tends to deteriorate. The hydraulic fluid composition for shock absorbers according to the present invention is further improved in performance as required. In order to improve further, or depending on other purposes, any additive generally used in lubricating oils can be included. Examples of such additives include (A) component and friction modifiers other than component (B), viscosity index improvers, antiwear agents, antioxidants, fluidity improvers, metal deactivators. In addition to agents and antifoaming agents, various additives such as metal detergents, corrosion inhibitors, antifungal agents, demulsifiers, and coloring agents can be mentioned.
(A) 成分および （B) 成分以外の摩擦調整剤と しては、 潤滑油用の摩擦調整 剤と して通常用いられる任意の化合物が使用可能であり、 例えば、 モリブデンジ チォカーバメー トモリブデンジチォホスフエ一ト等のモリブデン系摩擦調整剤、 炭素数 6〜 3 0のアルキル基又はアルケニル基、 特に炭素数 6〜 3 0の直鎖アル キル基又は直鎖アルケニル基を分子中に少なく とも 1個有する、 脂肪酸アミ ド、 脂肪族ァミン、 脂肪族アルコール、 脂肪族エーテル等の無灰摩擦調整剤等が挙げ られ、 通常、 組成物全量基準で 0. 00 1〜 5質量％の範囲で含有させることが 可能である。  As the friction modifier other than the component (A) and the component (B), any compound usually used as a friction modifier for lubricating oil can be used. For example, molybdenum dithiocarbamate molybdenum dithiophosphine. Having at least one straight chain alkyl group or straight chain alkenyl group having 6 to 30 carbon atoms, particularly a straight chain alkyl group or straight chain alkenyl group having 6 to 30 carbon atoms. Ashless friction modifiers such as fatty acid amides, aliphatic amines, aliphatic alcohols, aliphatic ethers, etc., and usually in the range of 0.001 to 5% by mass based on the total amount of the composition. Is possible.
粘度指数向上剤と しては、 潤滑油の粘度指数向上剤と して通常用いられる任意 の化合物が使用可能であり、 例えば、 各種メタクリル酸エステルから選ばれる 1 種又は 2種以上のモノマーの重合体又は共重合体若しく はその水添物などのいわ ゆる非分散型粘度指数向上剤、 又はさらに窒素化合物を含む各種メタク リル酸ェ ステルを共重合させたいわゆる分散型粘度指数向上剤、 非分散型又は分散型ェチ レン一 α—ォレフイ ン共重合体 （α—ォレフィンと してはプロピレン、 1—ブテ ン、 1 _ペンテン等が例示できる。） 若しくはその水素化物、 ポリイ ソブチレン若 しくはその水添物、 スチレン一ジェン共重合体の水素化物、 スチレン一無水マレ ィン酸エステル共重合体及びポリアルキルスチレン等が挙げられる。  As the viscosity index improver, any compound usually used as a viscosity index improver for lubricating oils can be used. For example, the weight of one or more monomers selected from various methacrylic acid esters can be used. A so-called non-dispersed viscosity index improver such as a polymer or copolymer or a hydrogenated product thereof, or a so-called dispersed viscosity index improver obtained by copolymerizing various methacrylate esters containing a nitrogen compound. Dispersed or dispersed ethylene-α-olefin copolymers (Examples of α-olefin include propylene, 1-butene, 1_pentene, etc.) or hydrides thereof, polyisobutylene or Examples thereof include hydrogenated products thereof, hydrogenated products of styrene-gen copolymers, styrene-mono-anhydride maleate copolymers, and polyalkylstyrenes.
粘度指数向上剤の数平均分子量は、 例えば、 分散型及び非分散型ポリメタク リ レートの場合では、 通常 5, 000〜1 , 00 0, 0 0 0、 好ましくは 1 00, 000〜900, 0 0 0のものが、 ポリイソブチレン又はその水素化物の場合は 通常 800〜 5, 00 0、 好ましくは 1， 00 0〜 4, 00 0のものが、 ェチレ ン'一 α—ォレフィン共重合体又はその水素化物の場合は通常 8 00〜 500, 0 0 0、 好ましく は 3， 0 00〜 2 00 , 000のものが用いられる。 上記粘度指 数向上剤の中から任意に選ばれた 1種類あるいは 2種類以上の化合物を任意の量 で含有させることができる。 粘度指数向上剤の含有量は、 通常、 組成物全量基準 で 0 . ：!〜 2 0質量％である。 The number average molecular weight of the viscosity index improver is, for example, usually 5,000 to 1,000,000, preferably 100,000 to 900,000 in the case of dispersed and non-dispersed polymethacrylates. In the case where 0 is polyisobutylene or a hydride thereof, usually 800 to 500,000, preferably 1,000 to 4,000 is an ethylene-one α-olefin copolymer or its hydrogen. In the case of a compound, one having 800 to 500,000, preferably 3,00 to 200,000 is preferably used. One or two or more compounds arbitrarily selected from the above viscosity index improvers in any amount It can be made to contain. The content of the viscosity index improver is usually from 0.0 to 20% by mass based on the total amount of the composition.
摩耗防止剤としては、 潤滑油の摩耗防止剤として通常用いられる任意の化合物 が使用可能であり、 例えば、 リ ン及び 又は硫黄含有摩耗防止剤等が挙げられ、 例えば、 チォリン酸エステル類、 チォ亜リン酸エステル類、 リン酸エステル類、 炭素数 1 1〜 3 0の炭化水素基を有するハイ ドロゲンホスフアイ ト、 これらの誘 導体、 これら金属塩、 これらのアミン塩、 及びジスルフィ ド類、 硫化ォレフィン 類、 硫化油脂類、 ジチォカーバメート、 ジチォ力ルバミン酸亜鉛等の硫黄含有化 合物等が挙げられる。 これらの摩耗防止剤は、 組成物全量基準で、 通常 0 . 0 0 1〜 5質量％の範囲で本発明の組成物に含有させることが可能である。  As the antiwear agent, any compound usually used as an antiwear agent for lubricating oils can be used, and examples thereof include phosphorus and / or sulfur-containing antiwear agents, such as thiophosphates, Phosphate esters, phosphate esters, hydrogen phosphates having a hydrocarbon group with 11 to 30 carbon atoms, derivatives thereof, metal salts thereof, amine salts thereof, and disulfides, sulfides Examples include sulfur-containing compounds such as olefins, sulfurized fats and oils, dithiocarbamate, and zinc dithiocarbamate. These antiwear agents can be contained in the composition of the present invention usually in the range of 0.01 to 5% by mass based on the total amount of the composition.
酸化防止剤としては、 潤滑油の酸化防止剤として通常用いられる任意の化合物 が使用可能であり、 例えば、 2， 6 —ジー t e r t —ブチルー p —ク レゾ一ル、 4 , 4 ' ーメチレンビス （ 2 , 6—ジ一 t e r t —ブチノレフエノール）、 ォクチノレ - 3 - ( 3 , 5—ジー t e r t —ブチル一 4—ヒ ドロキシフエニル） プロビオネ ート、 3—メチル— 5 — t e r t—ブチルー 4—ヒ ドロキシフエニル置換脂肪酸 エステル類等のフエノール系酸化防止剤、 フエニル一 α —ナフチルァミン、 アル キルフエ二ルー ct —ナフチルァミン、 ジアルキルジフエニルァミン等のアミン系 酸化防止剤等が挙げられる。 これらの酸化防止剤は、組成物全量基準で、通常 0 . 0 1〜 5質量％の範囲で本発明の組成物に含有させることが可能である。  As the antioxidant, any compound usually used as an antioxidant for lubricating oils can be used. For example, 2, 6-g tert-butyl-p-cresol, 4, 4'-methylenebis (2, 6-di-tert-butynolephenol), octinore-3-(3,5-di-tert-butyl-1-hydroxyphenyl) Probione, 3-methyl-5-tert-butyl-4-hydroxyphenyl substituted fatty acid ester And phenolic antioxidants such as phenyl-α-naphthylamine, alkylphenyl ct-naphthylamine, and dialkyldiphenylamine. These antioxidants can be contained in the composition of the present invention usually in the range of 0.01 to 5% by mass based on the total amount of the composition.
流動性向上剤としては、 潤滑油の流動性向上剤として通常用いられる任意の化 合物が使用可能であり、 例えば、 ポリメタタリ レート系流動性向上剤等が挙げら れる。  As the fluidity improver, any compound usually used as a fluidity improver for lubricating oils can be used, and examples thereof include polymetatalate fluidity improvers.
金属不活性化剤としては、 イミダゾリン、 ピリ ミジン誘導体、 アルキルチアジ ァゾール、 メルカプトべンゾチアゾール、 ベンゾ ト リアゾ一ル又はその誘導体、 1 , 3， 4ーチアジアゾールポリスルフイ ド、 1 , 3 , 4—チアジアゾリル一 2 , 5 —ビスジアルキルジチォカーバメー ト、 2 — （アルキルジチォ） ベンゾイ ミダ ゾ—ル、 及ぴ i3 — ( o —カルボキシベンジルチオ） プロピオンニ ト リル等が挙げ られる。  Metal deactivators include imidazoline, pyrimidine derivatives, alkyl thiadiazoles, mercaptobenzothiazoles, benzotriazol or derivatives thereof, 1, 3, 4-thiadiazole polysulfide, 1, 3, 4-thiadiazolyl 1-2 , 5—bisdialkyldithiocarbamate, 2— (alkyldithio) benzimidazole, and i3— (o-carboxybenzylthio) propiononitrile.
消泡剤としては、 例えば、 シリ コーン、 フルォロシリ コール、 及ぴフルォロア ルキルエーテル等が挙げられる。 金属系清浄剤と しては、 アルカ リ金属又はアル力リ土類金属のスルホネー ト、 ブイネート、 サリ シレート及びホスホネート等が挙げられる。 Examples of the antifoaming agent include silicone, fluorosilicol, and fluoroalkyl ether. Examples of metal detergents include alkali metal or alkaline earth metal sulfonates, buinates, salicylates, and phosphonates.
腐食防止剤と しては、例えば、ベンゾ ト リァゾ一ル系、 ト リルト リァゾール系、 チアジアゾール系、. 及びィ ミダゾール系化合物等が挙げられる。  Examples of the corrosion inhibitor include benzotriazole series, tritriazole series, thiadiazole series,. And imidazole series compounds.
防鲭剤と しては、例えば、石油スルホネー ト、アルキルベンゼンスルホネート、 ジノニルナフタ レンスルホネー ト、 アルケニルコハク酸エステノレ、 及び多価アル コールエステル等が挙げられる。  Examples of the antifungal agent include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.
抗乳化剤と しては、 例えば、 ポリオキシエチレンアルキルエーテル、 ポリオキ シエチレンアルキルフエニルエーテノレ、 及びポリオキシエチレンァノレキルナフチ ルエーテル等のポリアルキレンダリ コール系非イオン系界面活性剤等が挙げられ る。  Examples of the demulsifier include polyalkylene dallic-based nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alcohol naphthyl ether. The
これらの添加剤を本発明の緩衝器用油圧作動油組成物に含有させる場合には、 その含有量は組成物全量基準で、 流動性向上剤、 金属系清浄剤、 腐食防止剤、 防 鲭剤、 抗乳化剤ではそれぞれ 0 . 0 0 5〜 5質量％、 金属不活性化剤では 0 . 0 0 5〜 1質量％、 消泡剤では 0 . 0 0 0 5 ~ 1質量％の範囲で通常選ばれる。  When these additives are contained in the hydraulic fluid composition for shock absorbers of the present invention, the content is based on the total amount of the composition, and a fluidity improver, metal detergent, corrosion inhibitor, antifungal agent, It is usually selected in the range of 0.05 to 5% by mass for demulsifiers, 0.05 to 1% by mass for metal deactivators, and 0.05 to 1% by mass for antifoaming agents. .
[産業上の利用可能性] [Industrial applicability]
本発明の緩衝器用油圧作動油組成物は、 ピス トンロッ ドとシ一ル材間、 特にシ —ル材と して二 ト リル系シール材を使用した場合にフリ クショ ンを高いレベルで 維持することができ、 緩衝器のニュー トラル位置での減衰力を高め、 微振幅時の 車体 （ばね上荷重） のふらつきを抑制するとともに運転者と乗員の不快感を軽減 することができる。  The hydraulic fluid composition for a shock absorber according to the present invention maintains a high level of friction between piston rods and seal materials, particularly when a two-trile seal material is used as the seal material. It is possible to increase the damping force at the neutral position of the shock absorber, to suppress the fluctuation of the vehicle body (sprung load) at a small amplitude, and to reduce driver and passenger discomfort.
[発明を実施するための最良の形態] [Best Mode for Carrying Out the Invention]
以下、 本発明の内容を実施例及び比較例によってさらに具体的に説明するが、 本発明はこれらに何ら限定されるものではない。  Hereinafter, although the content of the present invention is explained more concretely by an example and a comparative example, the present invention is not limited to these at all.
<実施例 1〜 2、 比較例 1〜 3、 参考例 1 > <Examples 1-2, Comparative Examples 1-3, Reference Example 1>
潤滑油基油に、 表 1 に示す組成の本発明に係る潤滑油組成物 （実施例 1〜 2 )、 比較用の潤滑油組成物 （比較例 1〜 3 ) 及び参考用の潤滑油組成物 （参考例 1 ) をそれぞれ調製した。 これらの組成物に対して、 以下に示す摩擦試験を実施し、 その結果を表 1に示した。 Lubricating oil compositions according to the present invention having the compositions shown in Table 1 (Examples 1 to 2), comparative lubricating oil compositions (Comparative Examples 1 to 3), and reference lubricating oil compositions (Reference Example 1) Were prepared respectively. These compositions were subjected to the following friction test, and the results are shown in Table 1.
(摩擦試験） (Friction test)
バウデン試験機を用い、 厚さ約 2 mmの二 ト リル系シール材を直径 1 0 mmの 穴の開いたホルダ一に敷き、 その上から 1 2インチの鋼球を押し付けた状態 で固 £ (潤滑部は半球状となる） し、 試験油を数滴滴下したク ロムメ ツキ鋼板の 上に設置した。 これに 9. 8 Nの荷重をかけ、 室温、 滑り速度 4 mmZ s、 1 0 mmのス トロークで往復動させ、 滑り始めの摩擦係数 μ i 、 ス トローク中間の摩 擦係数/ z dをそれぞれ測定した。 なお、 μ dが高いほどシール材—鋼材間の摩擦 係数を高く コン トロ一ルしゃすく、 スティ ックスリ ップ特性の指標である ^ i / μ d値が 1. 0 0を超える場合、スティ ックス リ ップが発生しやすい傾向にあり、 小さいほどスティ ックスリ ップが発生しにくレ、。 表 1から明らかな通り、 本発明にかかる組成物 （実施例 1、 2) は、 二 ト リル 系シール材ー鋼材間の摩擦係数を高く コン トロールでき、 スティ ックス リ ップ特 性にも優れている。 一方、 （A) 成分及び （B) 成分を併用しない場合 （比較例 1 〜 3 )では、摩擦係数、スティ ックス リ ップ特性のいずれかが劣ることがわかる。 なお、 （A) 成分と （C) 成分を含有する参考例 1の組成物では、 摩擦係数を高く 維持できるものの、 スティ ックスリ ップ特性に劣ることがわかる。 なお、 実施例 1の （B) 成分に代え、 炭素数 1 2〜 1 8のアルキルを有するコハク酸モノエス テルを 0. 0 5質量％使用した以外は実施例 2 と同じ組成物を同様に評価した結 果、 同様の効果が確認された。  Using a Bowden tester, lay a tritrial sealant with a thickness of about 2 mm on a holder with a hole with a diameter of 10 mm, and press it with a 12 inch steel ball pressed on it. The lubrication part is hemispherical) and was placed on a chromium steel plate with a few drops of test oil. Applying a load of 9.8 N to this, reciprocating with a stroke of room temperature, sliding speed of 4 mmZ s and 10 mm, and measuring the friction coefficient μ i at the beginning of sliding and the friction coefficient / zd between the strokes, respectively. did. Note that the higher the μd, the higher the coefficient of friction between the sealant and the steel, and the control slippery. If the ^ i / μd value, which is an indicator of sticky slip characteristics, exceeds 1.00, the sticky Lips tend to occur easily, and stickiness is less likely to occur as the value is smaller. As is apparent from Table 1, the compositions according to the present invention (Examples 1 and 2) have a high coefficient of friction between the nitrile sealant and the steel, and have excellent sticky lip characteristics. ing. On the other hand, when the component (A) and the component (B) are not used together (Comparative Examples 1 to 3), it can be seen that either the friction coefficient or the stick-lip property is inferior. The composition of Reference Example 1 containing the component (A) and the component (C) can maintain a high coefficient of friction, but is inferior in the stick-rip characteristics. The same composition as in Example 2 was evaluated in the same manner except that 0.05% by mass of succinic acid monoester having an alkyl having 12 to 18 carbon atoms was used instead of the component (B) in Example 1. As a result, a similar effect was confirmed.
<実施例 3〜 6および比較例 4〜 6 > <Examples 3 to 6 and Comparative Examples 4 to 6>
潤滑油基油に、 表 1 に示す組成の本発明に係る潤滑油組成物 （実施例 3〜 6)、 比較用の潤滑油組成物 （比較例 4〜 6 ) 及び、 摩擦係数 （フリ クション） 評価の 基準となる潤滑油組成物をそれぞれ調製した。 これらの組成物に対して、 摩擦試 験を実施し、 基準油に対する摩擦係数の低下率を評価し、 その結果を表 2に示し た。 基準油に対する摩擦係数の低下率が小さい方がシールフリ クションを高く維 持しやすいことを意味する。 Lubricating oil composition according to the present invention having the composition shown in Table 1 (Examples 3 to 6), comparative lubricating oil composition (Comparative Examples 4 to 6), and friction coefficient (friction) Lubricating oil compositions serving as evaluation criteria were prepared. Friction tests were conducted on these compositions, and the rate of decrease in the friction coefficient with respect to the reference oil was evaluated. The results are shown in Table 2. The smaller the rate of decrease in the coefficient of friction with respect to the reference oil, the higher the seal friction. It means that it is easy to hold.
表 2から明らかな通り、 本発明に要件を満たす （C 1 ) 成分を含有させた組成 物 （実施例 3〜 6 ) は、基準油に対する摩擦低下率が小さいことがわかる。 また、 さらに （A) 成分を併用した場合 （実施例 6 ) には、 さらに摩擦係数を高くする ことができる。 それに対し、 本発明の要件を満たさない、 （C 1 ) 成分と類似の化 合物を使用した場合 （比較例 4〜 6 ) には、 基準油に対する摩擦係数低下率が大 きくなり、 シールフリ クショ ンを高く維持しにくいことがわかる。 As is apparent from Table 2, it can be seen that the compositions (Examples 3 to 6) containing the component (C 1) satisfying the requirements of the present invention have a small friction reduction rate with respect to the reference oil. Further, when the component (A) is used in combination (Example 6), the friction coefficient can be further increased. On the other hand, when a compound similar to the component (C 1) that does not satisfy the requirements of the present invention is used (Comparative Examples 4 to 6), the rate of decrease in the coefficient of friction with respect to the reference oil increases, and the seal friction It can be seen that it is difficult to maintain a high level.
表 1 table 1
Figure imgf000022_0001
Figure imgf000022_0001
1 )水素化精製鉱油（40°C動粘度： 6.1 mmVs)  1) Hydrorefined mineral oil (40 ° C kinematic viscosity: 6.1 mmVs)
2) iso-ブチルハイドロゲンホスファイト  2) Iso-butyl hydrogen phosphite
3)ォレイン酸  3) Oleic acid
4)ォレイン酸グリセライド  4) Glyceride oleate
5)ォレイルァミンエチレンオキサイド付加物  5) Oleylamine ethylene oxide adduct
6)コハク酸イミド系無灰分散剤 (ポリブ亍ニル基の数平均分子量： 1000、ィミノ基/アミノ基比率 =2/1、 窒素含有量： 1.9質量％、ホウ素含有量： 1.6質量％)  6) Succinimide-based ashless dispersant (number average molecular weight of polybenzyl group: 1000, imino group / amino group ratio = 2/1, nitrogen content: 1.9 mass%, boron content: 1.6 mass%)
7)ポリメタクリレート、酸化防止剤、金属不活性化剤、消泡剤等を含む 7) Including polymethacrylate, antioxidant, metal deactivator, antifoaming agent, etc.
表 2 Table 2
Figure imgf000023_0001
Figure imgf000023_0001
1 )水素化精製鉱油（6.1 mm/s @40°C)  1) Hydrorefined mineral oil (6.1 mm / s @ 40 ° C)
2) (A)成分の物性  2) Physical properties of component (A)
A:アルキル基/アルケニル基:数平均分子量 1000のポリブ亍ニル基、希釈剤を含む。ィミノ基/アミノ基比 =5.5: 1、窒素含有量: 2.3質量％、ホウ素含有量 0質童％ B :アルキル基/アルケニル基:数平均分子量 1000のポリブ亍ニル基、希釈剤を含む。ィミノ基/アミノ基比 =7.0: 1、窒素含有量： 1.9質量 96、ホウ素含有量 0質量％ C：アルキル基/アルケニル基：数平均分子量 1000のポリブ亍ニル基、希釈剤を含む。ィミノ基/アミノ基比 = 2.0: 1、窒素含有量： 1.9質量％、ホウ素含有量 1.6質量％ A: Alkyl group / alkenyl group: Polyvinyl group having a number average molecular weight of 1000 and a diluent. Imino group / amino group ratio = 5.5: 1, nitrogen content: 2.3 mass%, boron content 0% child B: alkyl group / alkenyl group: polyvinyl group having a number average molecular weight of 1000, including diluent. Imino group / amino group ratio = 7.0: 1, nitrogen content: 1.9 mass 96, boron content 0 mass% C: alkyl group / alkenyl group: polyvinyl group having a number average molecular weight of 1000, including diluent. Imino group / amino group ratio = 2.0: 1, nitrogen content: 1.9 mass%, boron content 1.6 mass%
3) (A)成分以外の物性 3) Physical properties other than component (A)
D :アルキル基/アルケニル基：数平均分子量 1000のポリブ亍ニル基、希釈剤を含む。ィミノ基/アミノ基比 =4.2 : 1、窒素含有量: 2.3質量％、ホウ素含有量 1.9質量％ D: Alkyl group / alkenyl group: Polyvinyl group having a number average molecular weight of 1000, including a diluent. Imino group / amino group ratio = 4.2: 1, nitrogen content: 2.3 mass%, boron content 1.9 mass%
E:アルキル基 Zアルケニル基:数平均分子量 2200のポリブテニル基、希釈剤を含む。ィミノ基/アミノ基比 =7.6: 1、窒素含有量: 1.2質量％、ホウ素含有量 0質量％E: alkyl group Z alkenyl group: a polybutenyl group having a number average molecular weight of 2200 and a diluent. Imino group / amino group ratio = 7.6: 1, nitrogen content: 1.2% by mass, boron content 0% by mass
F:アルキル基 アルケ二ル基:数平均分子量 1500-2000のポリブテニル基、希釈剤を含む。ィミノ基/アミノ基比 =24: 1、窒素含有量： 1.5質量" ½、ホウ素含有量 0.5質量％F: alkyl group alkenyl group: polybutenyl group having a number average molecular weight of 1500-2000, including diluent. Imino group / amino group ratio = 24: 1, nitrogen content: 1.5 mass "½, boron content 0.5 mass%
4)イソブチルハイドロゲンホスファイト 4) Isobutyl hydrogen phosphite
5)ポリメタクリレート、酸化防止剤、金属不活性化剤、消泡剤等を含む  5) Including polymethacrylate, antioxidant, metal deactivator, defoamer, etc.

Claims

1. 潤滑油基油に、 1. In lubricating base oil,
[ I ] (A)炭素数 3〜 1 0の炭化水素基を有するリ ン酸エステル、 亜リ ン酸エス テル又はこれらの塩、 及び （B) 炭素数 6〜 3 0の飽和若しく は不飽和脂肪酸及 び 又は該脂肪酸のエステル、  [I] (A) Phosphoric ester having a hydrocarbon group having 3 to 10 carbon atoms, phosphorous acid ester or a salt thereof, and (B) Saturated or non-carbon having 6 to 30 carbon atoms. Saturated fatty acids and / or esters of the fatty acids,
又は、 Or
[Π] (C 1 ) イ ミノ基 Zァミノ請基比率が 1 5以下であり、 数平均分子量が 1 50 0以下のアルキル基若しくはアルケニル基を有するコハク酸 （無水物） —ポリア ミ ン反応生成物及ぴノ又はその誘導体であって、  [Π] (C 1) Succinic acid (anhydride) having an alkyl group or alkenyl group having an imino group Z amino group ratio of 15 or less and a number average molecular weight of 1500 or less — Polyamine reaction formation A material or a derivative thereof,
(C 1 a ) ィ ミノ基ノアミノ基比率が 3〜 1 5かつホウ素を本質的に含有しない もの及び  (C 1 a) imino group having a nonamino group ratio of 3 to 15 and essentially free of boron and
囲  Surrounding
(C 1 b ) イ ミノ基 アミノ基比率が 3未満のもの  (C 1 b) Imino group Amino group ratio of less than 3
から選ばれる少なく とも 1種 At least one selected from
を含有することを特徴とする緩衝器用油圧作動油組成物。 A hydraulic fluid composition for shock absorbers.
2. 潤滑油基油に、 2. In lubricating base oil,
( A) 炭素数 3〜 1 0の炭化水素基を有するリ ン酸エステル、 亜リ ン酸エステル 又はこれらの塩、 及び （B) 炭素数 6〜 3 0の飽和若しく は不飽和脂肪酸及び Z 又は該脂肪酸のエステル、  (A) Phosphoric esters, phosphites or salts thereof having a hydrocarbon group having 3 to 10 carbon atoms, and (B) Saturated or unsaturated fatty acids having 6 to 30 carbon atoms and Z Or an ester of the fatty acid,
並びに And
(C) 無灰分散剤  (C) Ashless dispersant
を含有することを特徴とする緩衝器用油圧作動油組成物。 A hydraulic fluid composition for shock absorbers.
3. 潤滑油基油に、 3. In lubricating base oil,
( A) 炭素数 3〜 1 0の炭化水素基を有するリ ン酸エステル、 亜リ ン酸エステル 又はこれらの塩、  (A) Phosphate ester, phosphite ester or salt thereof having a hydrocarbon group having 3 to 10 carbon atoms,
並びに And
(C 1 ) ィ ミノ基 Zァミノ基比率が 1 5以下であり、 数平均分子量が 1 500以 下のアルキル基若しくはアルケニル基を有するコハク酸 （無水物） 一ポリアミン 反応生成物及び 又はその誘導体であって、 (C 1) succinic acid (anhydride) monopolyamine having an alkyl group or an alkenyl group having an imino group Z amino group ratio of 15 or less and a number average molecular weight of 1500 or less A reaction product and / or a derivative thereof,
( C 1 a ) ィ ミノ基/ァミ ノ基比率が 3〜 1 5かつホウ素を本質的に含有しない もの及び  (C1a) imino group / amino group ratio of 3 to 15 and essentially free of boron and
( C 1 b ) イ ミノ基 Zアミノ基比率が 3未満のもの  (C 1 b) Imino group Z amino group ratio less than 3
から選ばれる少なく とも 1種 At least one selected from
を含有することを特徴とする緩衝器用油圧作動油組成物。 A hydraulic fluid composition for shock absorbers.
4 . 潤滑油基油に、 4. In lubricating base oil,
( A ) 炭素数 3〜 1 0の炭化水素基を有するリ ン酸エステル、 亜リ ン酸エステル 又はこれらの塩、 及び （B ) 炭素数 6〜 3 0の飽和若しくは不飽和脂肪酸及び Z 又は該脂肪酸のエステル、  (A) Phosphoric acid ester having 3 to 10 carbon atoms, phosphorous acid ester or a salt thereof, and (B) saturated or unsaturated fatty acid having 6 to 30 carbon atoms and Z or Fatty acid esters,
並びに、 And
( C 1 ) ィ ミノ基ノアミノ基比率が 1 5以下であり、 数平均分子量が 1 5 0 0以 下のアルキル基若しくはアルケニル基を有するコハク酸 （無水物） —ポリアミン 反応生成物及び/又はその誘導体であって、  (C 1) succinic acid (anhydride) having an alkyl group or alkenyl group having an amino group ratio of 15 or less and a number average molecular weight of 15 500 or less —polyamine reaction product and / or its A derivative comprising:
( C 1 a ) イ ミノ基 アミノ基比率が 3〜 1 5かつホウ素を本質的に含有しない もの及び  (C 1 a) Imino group Amino group ratio of 3 to 15 and essentially free of boron and
( C 1 b ) イ ミノ基 アミノ基比率が 3未満のもの  (C 1 b) Imino group Amino group ratio of less than 3
から選ばれる少なく とも 1種 At least one selected from
を含有することを特徴とする緩衝器用油圧作動油組成物。 A hydraulic fluid composition for shock absorbers.
5 . 前記 （A ) 成分が、 炭素数 3〜 1 0の炭化水素基を有するハイ ド ロゲンホスフアイ トであることを特徴とする第 1項〜第 4項のいずれかの項に記 載の緩衝器用油圧作動油組成物。 5. The shock absorber according to any one of items 1 to 4, wherein the component (A) is a hydrogen phosphate having a hydrocarbon group having 3 to 10 carbon atoms. Hydraulic fluid composition.
6 . 前記 （B ) 成分が、 炭素数 1 2〜 1 8の不飽和脂肪酸及び 又は不 飽和脂肪酸エステルであることを特徴とする第 1項〜第 5項のいずれかの項に記 載の緩衝器用油圧作動油組成物。 第 1項〜第 6項のいずれかの項に記載の緩衝器用油圧作動油組成物 を用いて緩衝器のシール材とピス トンロッ ド間の高摩擦化方法。 6. The buffer according to any one of Items 1 to 5, wherein the component (B) is an unsaturated fatty acid having 12 to 18 carbon atoms and / or an unsaturated fatty acid ester. Hydraulic fluid composition for dexterity. The hydraulic fluid composition for a shock absorber according to any one of items 1 to 6 A method to increase the friction between the seal material of the shock absorber and the piston rod.
8 . 第 2項又は第 4項に記載の緩衝器用油圧作動油組成物を用いて緩衝 器のシ一ル材と ビス トン口 ッ ド間の高摩擦化及ぴスティ ックスリ ップ抑制を両立 する方法。 8. Use of the hydraulic fluid composition for shock absorbers described in Item 2 or 4 to achieve both high friction between the seal material of the shock absorber and the screw mouth and suppression of stick-slip. Method.
9 . 前記シール材がニ ト リル系シール材であることを特徴とする第 7項 又は第 8項に記載の方法。 9. The method according to item 7 or 8, wherein the seal material is a nitrile seal material.
PCT/JP2006/311680 2005-06-03 2006-06-05 Hydraulic fluid composition for buffer WO2006129889A1 (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55165996A (en) * 1979-06-14 1980-12-24 Nippon Oil Co Ltd Hydraulic fluid composition for damper
JPH04314794A (en) * 1990-03-31 1992-11-05 Tonen Corp Hydraulic fluid for automobile suspension
JPH06145684A (en) * 1992-10-31 1994-05-27 Tonen Corp Hydraulic actuation oil composition
JPH06179885A (en) * 1992-12-11 1994-06-28 Tonen Corp Hydraulic fluid composition
JPH07224293A (en) * 1994-02-14 1995-08-22 Nippon Oil Co Ltd Hydraulic oil composition for shock absorber
JPH09111277A (en) * 1995-10-19 1997-04-28 Idemitsu Kosan Co Ltd Hydraulic working fluid composition
JP2002194376A (en) * 2000-12-26 2002-07-10 Nippon Mitsubishi Oil Corp Hydraulic working fluid composition for shock absorber
JP2004035624A (en) * 2002-06-28 2004-02-05 Nippon Oil Corp Hydraulic oil composition for shock absorber

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55165996A (en) * 1979-06-14 1980-12-24 Nippon Oil Co Ltd Hydraulic fluid composition for damper
JPH04314794A (en) * 1990-03-31 1992-11-05 Tonen Corp Hydraulic fluid for automobile suspension
JPH06145684A (en) * 1992-10-31 1994-05-27 Tonen Corp Hydraulic actuation oil composition
JPH06179885A (en) * 1992-12-11 1994-06-28 Tonen Corp Hydraulic fluid composition
JPH07224293A (en) * 1994-02-14 1995-08-22 Nippon Oil Co Ltd Hydraulic oil composition for shock absorber
JPH09111277A (en) * 1995-10-19 1997-04-28 Idemitsu Kosan Co Ltd Hydraulic working fluid composition
JP2002194376A (en) * 2000-12-26 2002-07-10 Nippon Mitsubishi Oil Corp Hydraulic working fluid composition for shock absorber
JP2004035624A (en) * 2002-06-28 2004-02-05 Nippon Oil Corp Hydraulic oil composition for shock absorber

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