WO2011033953A1 - Lubricant composition - Google Patents
Lubricant composition Download PDFInfo
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- WO2011033953A1 WO2011033953A1 PCT/JP2010/065136 JP2010065136W WO2011033953A1 WO 2011033953 A1 WO2011033953 A1 WO 2011033953A1 JP 2010065136 W JP2010065136 W JP 2010065136W WO 2011033953 A1 WO2011033953 A1 WO 2011033953A1
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- WIPO (PCT)
- Prior art keywords
- mass
- lubricating oil
- terms
- oil composition
- alkaline earth
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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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/42—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids
- C10M105/46—Complex esters, i.e. compounds containing at least three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compound: monohydroxy compounds, polyhydroxy compounds, monocarboxylic acids, polycarboxylic acids and hydroxy carboxylic acids derived from the combination of monohydroxy compounds, dihydroxy compounds and dicarboxylic acids only and having no free hydroxy or carboxyl groups
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
- C10M105/54—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen containing carbon, hydrogen, halogen and oxygen
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/76—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing silicon
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- 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
- C10M141/12—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 compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
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- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/027—Neutral salts thereof
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- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
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- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- C10M2215/223—Five-membered rings containing nitrogen and carbon only
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- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C10M2223/045—Metal containing thio derivatives
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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/54—Fuel economy
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
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- C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
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Definitions
- the present invention relates to a lubricating oil composition, and more particularly to a lubricating oil composition that contains zinc dithiophosphate but exhibits a low coefficient of friction when used as a lubricating oil for low friction sliding materials.
- the performance required for engine oil includes appropriate viscosity characteristics, oxidation stability, clean dispersibility, antiwear, antifogging, etc., and these performances can be improved by combining various base oils and additives. Is planned.
- zinc dithiophosphate (ZnDTP) is often used as an engine oil additive because it is excellent as an antiwear additive.
- the sliding material as a material for a part having a severe frictional wear environment (for example, a sliding part of an engine), there is a material having a hard film such as a TiN film or a CrN film that contributes to an improvement in wear resistance.
- a material having a hard film such as a TiN film or a CrN film that contributes to an improvement in wear resistance.
- the friction coefficient can be lowered by using a diamond-like carbon (DLC) film in the air and in the absence of a lubricating oil, and a material having a DLC film (hereinafter referred to as a DLC material) has a low friction sliding property.
- a DLC material a material having a DLC film
- Patent Document 1 discloses a lubricating oil composition used for a low friction sliding member containing an ether-based ashless friction reducing agent.
- Patent Documents 2 and 3 include a fatty acid ester-based ashless friction modifier and an aliphatic amine-based ashless friction adjustment on the sliding surface between the DLC member and the iron base member and the sliding surface between the DLC member and the aluminum alloy member.
- Patent Document 4 discloses a technique using a low friction agent composition containing an oxygen-containing organic compound or an aliphatic amine compound in a low friction sliding mechanism having a DLC coating sliding member.
- Lubricating oil compositions for low-friction sliding materials have been developed in this way, but even when these technologies are applied, the friction coefficient can be increased by adding ZnDTP to further improve wear resistance. Tended to be larger. Therefore, for the purpose of obtaining a lubricating oil having various performance and good balance, a lubricating oil composition containing ZnDTP but having a low friction coefficient when used as a lubricating oil for a low friction sliding material. Things are sought.
- JP 2006-36850 A Japanese Patent Laid-Open No. 2003-238882 Japanese Patent Application Laid-Open No. 2004-155891 JP 2005-98495 A
- the present invention has been made in view of the above circumstances, and contains a lubricating oil composition that exhibits a low coefficient of friction when used as a lubricating oil for low friction sliding materials while containing ZnDTP as an antiwear agent.
- An object of the present invention is to provide a lubricating oil composition for a low friction sliding material that has both wear and low friction properties.
- the present invention has been completed based on such findings. That is, the present invention 1.
- Boron-free succinic acid having (A) alkaline earth metal salicylate and / or alkaline earth metal sulfonate detergent, (B) alkenyl group or alkyl group having a number average molecular weight of 500 to 4000 Formulated with imide-based ashless dispersant, (C) zinc dialkyldithiophosphate and (D) polysulfide compound, sulfurized oil, sulfurized olefin, thiophosphate, thiophosphite, and amine salts of these esters
- the blending amount of the composition based on the total amount of the composition is such that (A) component is 0.05 to 0.25% by mass in terms of alkaline earth metal concentration, and (B) component is nitrogen concentration 0.03 to 0.50 mass% in terms of conversion, component (
- Sulfur compounds are represented by the general formula (I) R 1 -S n -R 2 (I) (Wherein n represents an integer selected from 1 to 4, and R 1 and R 2 each independently represents an alkyl group or an aralkyl group)
- the lubricating oil composition according to 1 above which is a compound represented by: 5.
- the lubricating oil composition as described in 1 above, wherein the low friction sliding material is a material having a diamond-like carbon (DLC) film.
- DLC diamond-like carbon
- a lubricating oil composition having a low friction coefficient when used as a lubricating oil for a low friction sliding material while containing ZnDTP as an antiwear agent.
- the lubricating oil composition of the present invention comprises (A) an alkaline earth metal salicylate and / or alkaline earth metal sulfonate detergent as essential additives in the lubricating base oil, and (B) a number average molecular weight of 500 to 4000.
- the lubricating base oil used by this invention can select suitably from well-known mineral base oil and synthetic base oil used conventionally.
- the mineral oil for example, a distillate obtained by atmospheric distillation of paraffinic crude oil, intermediate crude oil or naphthenic crude oil, or vacuum distillation residual oil, or The refined oil obtained by refine
- examples of the synthetic oil include poly ( ⁇ -olefin) which is an ⁇ -olefin oligomer having 8 to 14 carbon atoms, polybutene, polyol ester, and alkylbenzene.
- the base oil one kind of the above mineral oil may be used, or two or more kinds may be used in combination.
- the said synthetic oil may be used 1 type and may be used in combination of 2 or more type. Further, one or more mineral oils and one or more synthetic oils may be used in combination.
- the base oil those having a kinematic viscosity at 100 ° C. of usually 2 to 50 mm 2 / s, preferably 3 to 30 mm 2 / s, particularly preferably 3 to 15 mm 2 / s are advantageous.
- the kinematic viscosity at 100 ° C. is 2 mm 2 / s or more, the evaporation loss is small, and when it is 50 mm 2 / s or less, the power loss due to the viscous resistance is suppressed, and the fuel efficiency improvement effect is exhibited well.
- the base oil preferably has a viscosity index of 60 or more, more preferably 70 or more, and particularly preferably 80 or more. When the viscosity index is 60 or more, the viscosity change due to the temperature of the base oil is small, and stable lubricating performance is exhibited.
- alkaline earth metal salicylate and alkaline earth metal sulfonate used as the detergent for the component (A) conventionally known compounds such as compounds having an alkyl group can be used.
- alkaline earth metal include calcium and magnesium, and calcium is particularly preferable.
- these detergents any of neutral salts, basic salts and overbased salts can be used, and one kind may be used alone, or two or more kinds may be used in combination. .
- the total base number of the detergent can be arbitrarily selected according to the required performance of the lubricating oil composition.
- the perchloric acid method is 0 to 500 mgKOH / g, preferably 50 to 400 mgKOH / g.
- the blending amount of the detergent based on the total amount of the composition is 0.05 to 0.25% by mass in terms of alkaline earth metal concentration, preferably 0.06 to 0.25% by mass, more preferably 0.8%. It is 1 to 0.22% by mass. If the alkaline earth metal concentration exceeds 0.25% by mass, it is difficult to reduce the friction coefficient.
- alkaline earth metal-containing detergent compounds other than the component (A) are also known, and examples thereof include alkaline earth metal phenate detergents.
- alkaline earth metal phenate detergents when an alkaline earth metal phenate detergent is blended, it is difficult to reduce the friction coefficient. Therefore, in the present invention, it is necessary to limit its use.
- the content based on the total amount of the composition is 0.1% by mass or less, preferably 0.05% by mass or less, particularly preferably not contained at all, in terms of alkaline earth metal concentration.
- a boron-free succinimide compound having an alkenyl group or alkyl group having a number average molecular weight of 500 to 4000 (hereinafter, the succinimide compound is referred to as “the present invention”).
- the number average molecular weight of the alkenyl group or alkyl group is 500 or more, a good cleansing effect is exhibited, and when it is 4000 or less, the low temperature fluidity is good.
- the succinimide compound of the present invention include the following general formula (II) or general formula (III):
- R 3 to R 5 each independently represents an alkenyl group or an alkyl group having a number average molecular weight of 500 to 4000, and m represents an integer of 1 to 5.
- m is an integer of 1 to 5, the cleanliness is improved, and an integer of 2 to 4 is more preferable.
- R 3 to R 5 in the general formulas (II) and (III) are, for example, polybutene obtained by polymerizing a high purity isobutene or a mixture of 1-butene and isobutene with a boron fluoride catalyst or an aluminum chloride catalyst, etc.
- the method for producing the succinimide compound of the present invention is not particularly limited.
- butenyl succinic acid obtained by reacting polybutene or a chlorinated polybutene with maleic anhydride at about 100 to 200 ° C. is converted into diethylenetriamine, triethylene or triethylene. It can be obtained by reacting with polyamines such as ethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.
- the polybutene or the like that is a precursor of an alkenyl group or an alkyl group is usually removed by an appropriate method such as an adsorption method or sufficient washing with water by removing a trace amount of fluorine and chlorine remaining due to a catalyst in the production process. It is advantageous to use after removing to 50 mass ppm or less, preferably 10 mass ppm or less, particularly preferably 1 mass ppm or less.
- a succinimide compound containing no boron is used.
- This boron-free means that the succinimide compound treated with the boron compound is excluded from the component (B). That is, as an ashless dispersant, a boron compound such as boric acid, borate, and boric acid ester is allowed to act on a polybutenyl succinimide compound so that a part or all of the remaining amino groups and / or imino groups can be added.
- Boron-containing polybutenyl succinimide compounds are known, but when such boron-containing polybutenyl succinimide is blended, friction is reduced when used as a lubricant for low friction sliding materials. Becomes difficult.
- one kind of the succinimide compound of the present invention may be blended, or two or more kinds may be blended in combination.
- the blending amount of the succinimide compound of the present invention based on the total amount of the composition is 0.03 to 0.50 mass%, preferably 0.05 to 0.30 mass% in terms of nitrogen concentration. When the nitrogen concentration is within the above range, favorable effects can be obtained in terms of the balance of cleanliness, demulsibility and economic efficiency.
- the content based on the total amount of the composition is 0.04% by mass or less, preferably 0.02% by mass in terms of nitrogen concentration, and it is particularly preferable that no content is contained at all.
- Examples of the (C) component zinc dialkyldithiophosphate include, for example, the general formula (IV)
- R 6 to R 9 each independently represents an alkyl group, preferably an alkyl group having 1 to 24 carbon atoms.
- the alkyl group having 1 to 24 carbon atoms may be linear, branched or cyclic, and specifically includes various propyl groups and butyl groups including isomers including methyl and ethyl groups.
- zinc dialkyldithiophosphate represented by the general formula (IV) include, for example, zinc diisopropyldithiophosphate, zinc diisobutyldithiophosphate, zinc di-sec-butyldithiophosphate, zinc di-sec-pentyldithiophosphate, di- zinc n-hexyldithiophosphate, zinc di-sec-hexyldithiophosphate, zinc di-octyldithiophosphate, zinc di-2-ethylhexyldithiophosphate, zinc di-n-decyldithiophosphate, zinc di-n-dodecyldithiophosphate, Examples include zinc diisotridecyl dithiophosphate. Among these, zinc dialkyldithiophosphate having a secondary alkyl group is preferable from the viewpoint of the effect of improving wear resistance.
- the zinc dialkyldithiophosphate may be blended in one kind or in combination of two or more kinds.
- the blending amount of zinc dialkyldithiophosphate based on the total amount of the composition is 0.01 to 0.12% by mass, preferably 0.03 to 0.10% by mass in terms of phosphorus concentration.
- the sulfur compound of the component (D) is a compound selected from polysulfide compounds, sulfurized fats and oils, sulfurized olefins, thiophosphate esters, thiophosphite esters, and amine salts of these esters.
- polysulfide compounds are preferred, and in particular, the general formula (I) R 1 -S n -R 2 (I) The compound shown by these is preferable.
- n represents an integer selected from 1 to 4, and n is particularly preferably 2 or 3.
- R 1 and R 2 each independently represents an alkyl group or an aralkyl group.
- R 1 and R 2 are preferably a group having 4 to 24 carbon atoms, and more preferably a group having 8 to 18 carbon atoms.
- the sulfur compounds may be used alone or in combination of two or more.
- the compounding amount of the sulfur-based compound based on the total amount of the composition is 0.02 to 2.0% by mass, preferably 0.02 to 1.0% by mass in terms of sulfur concentration. Even when the amount is less than 0.02% by mass or more than 2.0% by mass, it is difficult to reduce the friction coefficient.
- the lubricating oil composition of the present invention may be blended with conventionally known additives as long as the effects of the present invention are not impaired, for example, friction reducers, viscosity index improvers, pour point depressants, antioxidants, An antirust agent etc. are mentioned.
- friction reducers examples include ashless friction reducing agents such as fatty acid esters, aliphatic amines, and higher alcohols.
- viscosity index improver include so-called non-dispersion type viscosity index improvers such as various methacrylate esters or copolymers and hydrogenated products thereof, and various nitrogen compounds.
- Examples thereof include a so-called dispersed viscosity index improver obtained by copolymerizing a methacrylic acid ester. Further, non-dispersed or dispersed ethylene- ⁇ -olefin copolymers (for example, propylene, 1-butene, 1-pentene etc.) and hydrides thereof, polyisobutylene and hydrogenated products thereof, styrene- Examples thereof include diene hydrogenated copolymers, styrene-maleic anhydride copolymers, and polyalkylstyrenes. The molecular weight of these viscosity index improvers needs to be selected in consideration of shear stability.
- the number average molecular weight of the viscosity index improver is, for example, 5000 to 1000000, preferably 100000 to 800000 for dispersed and non-dispersed polymethacrylates, 800 to 5000 for polyisobutylene or a hydride thereof, ethylene-
- the ⁇ -olefin copolymer and its hydride are 800 to 300,000, preferably 10,000 to 200,000.
- Such a viscosity index improver can be contained alone or in any combination of two or more kinds, but the content is usually about 0.1 to 40.0% by mass based on the total amount of the lubricating oil composition. is there.
- the pour point depressant include polymethacrylate.
- antioxidants include phenolic antioxidants and amine antioxidants.
- phenolic antioxidants include 4,4′-methylenebis (2,6-di-t-butylphenol); 4,4′-bis (2,6-di-t-butylphenol); 4,4′- Bis (2-methyl-6-tert-butylphenol); 2,2′-methylenebis (4-ethyl-6-tert-butylphenol); 2,2′-methylenebis (4-methyl-6-tert-butylphenol); 4 4,4′-butylidenebis (3-methyl-6-tert-butylphenol); 4,4′-isopropylidenebis (2,6-di-tert-butylphenol); 2,2′-methylenebis (4-methyl-6- Nonylphenol); 2,2′-isobutylidenebis (4,6-dimethylphenol); 2,2′-methylenebis (4-methyl-6-cyclohexylphenol); 2,6-di-t-butyl- 2,6-di-t-butan
- amine antioxidants include monooctyl diphenylamine; monoalkyl diphenylamines such as monononyl diphenylamine; 4,4′-dibutyldiphenylamine; 4,4′-dipentyldiphenylamine; 4,4′-dihexyldiphenylamine; 4,4′-diheptyldiphenylamine; 4,4′-dioctyldiphenylamine; dialkyldiphenylamines such as 4,4′-dinonyldiphenylamine; tetrabutyldiphenylamine; tetrahexyldiphenylamine; tetraoctyldiphenylamine; polyalkyldiphenylamine such as tetranonyldiphenylamine And naphthylamine type, specifically ⁇ -naphthylamine; phenyl- ⁇ -naphthylamine; and butylphenyl
- dialkyldiphenylamine type and naphthylamine type are preferable.
- the rust inhibitor include alkyl benzene sulfonate, dinonyl naphthalene sulfonate, alkenyl succinate, polyhydric alcohol ester and the like.
- the lubricating oil composition of the present invention is applied to a sliding surface having a low-friction sliding material and can impart excellent low-friction characteristics, and particularly when applied to an internal combustion engine, provides a fuel-saving effect. can do.
- a sliding surface having the low friction sliding material one having a DLC material as a low friction sliding material on one side is particularly preferable.
- the mating material is not particularly limited, and examples thereof include a sliding surface between the DLC material and the iron-based material or a sliding surface between the DLC material and the aluminum alloy material.
- the DLC material has a DLC film on the surface, and the DLC material constituting the film is amorphous mainly composed of carbon element, and the bonding form between carbons is a diamond structure (SP 3 bond). ) And graphite bonds (SP 2 bonds).
- aC amorphous carbon
- aC hydrogen amorphous carbon
- some metal elements such as titanium (Ti) and molybdenum (Mo).
- examples of the iron base material include carburized steel SCM420 and SCr420 (JIS).
- the aluminum alloy material a hypoeutectic aluminum alloy or a hypereutectic aluminum alloy containing 4 to 20% by mass of silicon and 1.0 to 5.0% by mass of copper is preferably used.
- AC2A, AC8A, ADC12, ADC14 (JIS), etc. can be mentioned.
- the surface roughness of each of the DLC material and the iron base material, or the DLC material and the aluminum alloy material is preferably an arithmetic average roughness Ra of 0.1 ⁇ m or less from the viewpoint of sliding stability. is there.
- the DLC material preferably has a surface hardness of Hv 1000 to 3500 in micro Vickers hardness (98 mN load) and a thickness of 0.3 to 2.0 ⁇ m.
- the iron-based material preferably has a surface hardness of HRC45-60 in terms of Rockwell hardness (C scale). This case is effective because the durability of the film can be maintained even under sliding conditions under a high surface pressure of about 700 MPa as in a cam follower member.
- the aluminum alloy material preferably has a surface hardness of Brinell hardness HB 80 to 130.
- the surface hardness and thickness of the DLC material are within the above ranges, abrasion and peeling are suppressed. Further, when the surface hardness of the iron-based material is HRC45 or more, it is possible to suppress buckling and peeling under high surface pressure. On the other hand, if the surface hardness of the aluminum alloy material is within the above range, the wear of the aluminum alloy is suppressed.
- the sliding part to which the lubricating oil composition of the present invention is applied is not particularly limited as long as two metal surfaces are in contact with each other and at least one of them has a low friction sliding material.
- the sliding part of an engine can be mentioned preferably. In this case, it is effective because a low friction characteristic which is extremely excellent as compared with the conventional case is obtained and a fuel saving effect is exhibited.
- the DLC member a disk-shaped shim or lifter crown surface coated with DLC on a steel material substrate is exemplified
- the iron base member low alloy chilled cast iron, carburized steel or tempered carbon steel, and The cam lobe using the material which concerns on these arbitrary combinations is mentioned.
- Example 1 to 6 and Comparative Examples 1 to 5 A lubricating oil composition having the composition shown in Table 1 was prepared, and the friction characteristic test shown below was conducted to obtain the friction coefficient. The results are shown in Table 2.
- SCM420 cylinder ⁇ 15 mm ⁇ 22 mm
- Lubricating base oil hydrocracked mineral oil (100 ° C. kinematic viscosity 4.47 mm 2 / s)
- Ca phenate Ca phenate (Ca content: 9.25% by mass)
- DLC DLC containing 20% hydrogen
- DLC W 20% hydrogen (tungsten added)
- Comparative Examples 1 and 2 have a high coefficient of friction because Ca phenate and boron-containing succinimide are blended as a metallic detergent and an ashless dispersant, respectively. Since the comparative example 3 does not contain a sulfur compound, the friction coefficient is high. In Comparative Examples 4 and 5, the amount of phosphorus or calcium is excessive, and thus the friction coefficient is high.
- the lubricating oil composition of the present invention is applied to a sliding surface made of a low-friction sliding material such as a DLC material and can impart excellent low-friction characteristics, particularly when applied to an internal combustion engine. A fuel efficiency effect can be imparted.
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Abstract
Description
例えば、特許文献1にはエーテル系無灰摩擦低減剤を含む、低摩擦摺動部材に用いられる潤滑油組成物が開示されている。特許文献2、3には、DLC部材と鉄基部材との摺動面やDLC部材とアルミニウム合金部材との摺動面に、脂肪酸エステル系無灰摩擦調整剤や脂肪族アミン系無灰摩擦調整剤を含有する潤滑油組成物を用いる技術が開示されている。特許文献4には、DLCコーティング摺動部材を有する低摩擦摺動機構において、含酸素有機化合物や脂肪族アミン系化合物を含有する低摩擦剤組成物を用いる技術が開示されている。
このように低摩擦摺動材料用の潤滑油組成物が開発されているが、これらの技術を応用した場合であっても、耐摩耗性等の更なる向上を求めてZnDTPを配合すると摩擦係数が大きくなるという傾向があった。したがって、種々の性能に優れ、バランスの良い潤滑油を得ることを目的にすると、ZnDTPを含有しながらも、低摩擦摺動材料用の潤滑油として用いた際に低い摩擦係数を示す潤滑油組成物が求められている。 However, the DLC material may have a small friction reducing effect in the presence of lubricating oil, and in this case, it is difficult to obtain a fuel saving effect. For this reason, a lubricating oil composition for a low friction sliding material such as a DLC material has been developed so far.
For example, Patent Document 1 discloses a lubricating oil composition used for a low friction sliding member containing an ether-based ashless friction reducing agent. Patent Documents 2 and 3 include a fatty acid ester-based ashless friction modifier and an aliphatic amine-based ashless friction adjustment on the sliding surface between the DLC member and the iron base member and the sliding surface between the DLC member and the aluminum alloy member. A technique using a lubricating oil composition containing an agent is disclosed. Patent Document 4 discloses a technique using a low friction agent composition containing an oxygen-containing organic compound or an aliphatic amine compound in a low friction sliding mechanism having a DLC coating sliding member.
Lubricating oil compositions for low-friction sliding materials have been developed in this way, but even when these technologies are applied, the friction coefficient can be increased by adding ZnDTP to further improve wear resistance. Tended to be larger. Therefore, for the purpose of obtaining a lubricating oil having various performance and good balance, a lubricating oil composition containing ZnDTP but having a low friction coefficient when used as a lubricating oil for a low friction sliding material. Things are sought.
すなわち本発明は、
1.潤滑油基油に、(A)アルカリ土類金属サリシレート系および/またはアルカリ土類金属スルフォネート系清浄剤、(B)数平均分子量500~4000のアルケニル基またはアルキル基を有する、ホウ素未含有コハク酸イミド系無灰分散剤、(C)ジアルキルジチオリン酸亜鉛および(D)ポリスルフィド化合物、硫化油脂、硫化オレフィン、チオリン酸エステル、チオ亜リン酸エステル及びこれらのエステルのアミン塩から選ばれる硫黄系化合物を配合してなる潤滑油組成物であって、組成物全量基準の配合量が、(A)成分がアルカリ土類金属濃度換算で、0.05~0.25質量%、(B)成分が窒素濃度換算で、0.03~0.50質量%、(C)成分がリン濃度換算で0.01~0.12質量%、(D)成分が硫黄濃度換算で0.02~2.0質量%であって、アルカリ土類金属フェネート系清浄剤がアルカリ土類金属濃度換算で0.10質量%以下、ホウ素含有コハク酸イミドが窒素濃度換算で、0.04質量%以下である、低摩擦摺動材料に用いられる潤滑油組成物、
2.ジアルキルジチオリン酸亜鉛の配合量が、リン濃度換算で0.03~0.10質量%である上記1に記載の潤滑油組成物、
3.数平均分子量500~4000のアルケニル基またはアルキル基を有する、ホウ素未含有コハク酸イミド系無灰分散剤の配合量が、窒素濃度換算で0.05~0.30質量%である上記1に記載の潤滑油組成物、
4.硫黄系化合物が、一般式(I)
R1-Sn-R2 (I)
(式中、nは1~4から選ばれる整数を表し、R1及びR2は、それぞれ独立にアルキル基またはアラルキル基を表す)
で示される化合物である上記1に記載の潤滑油組成物、
5.一般式(I)中のnが2または3である上記4に記載の潤滑油組成物および
6.低摩擦摺動材料がダイヤモンドライクカーボン(DLC)皮膜を有する材料である上記1に記載の潤滑油組成物を提供するものである。 As a result of intensive studies, the present inventors have found that the above problem can be solved by blending a specific amount of a specific additive. The present invention has been completed based on such findings.
That is, the present invention
1. Boron-free succinic acid having (A) alkaline earth metal salicylate and / or alkaline earth metal sulfonate detergent, (B) alkenyl group or alkyl group having a number average molecular weight of 500 to 4000 Formulated with imide-based ashless dispersant, (C) zinc dialkyldithiophosphate and (D) polysulfide compound, sulfurized oil, sulfurized olefin, thiophosphate, thiophosphite, and amine salts of these esters The blending amount of the composition based on the total amount of the composition is such that (A) component is 0.05 to 0.25% by mass in terms of alkaline earth metal concentration, and (B) component is nitrogen concentration 0.03 to 0.50 mass% in terms of conversion, component (C) is 0.01 to 0.12 mass% in terms of phosphorus concentration, and component (D) is 0 in terms of sulfur concentration 02 to 2.0 mass%, alkaline earth metal phenate detergent is 0.10 mass% or less in terms of alkaline earth metal concentration, and boron-containing succinimide is 0.04 mass% in terms of nitrogen concentration A lubricating oil composition used for a low friction sliding material,
2. 2. The lubricating oil composition according to 1 above, wherein the amount of zinc dialkyldithiophosphate is 0.03 to 0.10% by mass in terms of phosphorus concentration,
3. 2. The blending amount of a boron-free succinimide ashless dispersant having an alkenyl group or an alkyl group having a number average molecular weight of 500 to 4000 is 0.05 to 0.30% by mass in terms of nitrogen concentration. Lubricating oil composition,
4). Sulfur compounds are represented by the general formula (I)
R 1 -S n -R 2 (I)
(Wherein n represents an integer selected from 1 to 4, and R 1 and R 2 each independently represents an alkyl group or an aralkyl group)
The lubricating oil composition according to 1 above, which is a compound represented by:
5. 5. The lubricating oil composition according to 4 above, wherein n in the general formula (I) is 2 or 3, and The lubricating oil composition as described in 1 above, wherein the low friction sliding material is a material having a diamond-like carbon (DLC) film.
ここで、鉱油としては、例えばパラフィン基系原油、中間基系原油あるいはナフテン基系原油を常圧蒸留するか、又は常圧蒸留の残渣油を減圧蒸留して得られる留出油、あるいはこれを常法に従って精製することによって得られる精製油、例えば溶剤精製油、水添精製油、脱ろう処理油、白土処理油などを挙げることができる。
一方、合成油としては、例えば炭素数8~14のα-オレフィンオリゴマーであるポリ(α-オレフィン)、ポリブテン、ポリオールエステル、アルキルベンゼンなどを挙げることができる。
本発明においては、基油として、上記鉱油を一種用いてもよく、二種以上を組み合わせて用いてもよい。また、上記合成油を一種用いてもよく、二種以上を組み合わせて用いてもよい。さらには、鉱油一種以上と合成油一種以上とを組み合わせて用いてもよい。 There is no restriction | limiting in particular in the lubricating base oil used by this invention, It can select suitably from well-known mineral base oil and synthetic base oil used conventionally.
Here, as the mineral oil, for example, a distillate obtained by atmospheric distillation of paraffinic crude oil, intermediate crude oil or naphthenic crude oil, or vacuum distillation residual oil, or The refined oil obtained by refine | purifying in accordance with a conventional method, for example, solvent refined oil, hydrogenated refined oil, dewaxing process oil, clay-treated oil, etc. can be mentioned.
On the other hand, examples of the synthetic oil include poly (α-olefin) which is an α-olefin oligomer having 8 to 14 carbon atoms, polybutene, polyol ester, and alkylbenzene.
In the present invention, as the base oil, one kind of the above mineral oil may be used, or two or more kinds may be used in combination. Moreover, the said synthetic oil may be used 1 type and may be used in combination of 2 or more type. Further, one or more mineral oils and one or more synthetic oils may be used in combination.
また、この基油は、粘度指数が60以上、さらには70以上、特に80以上のものが好ましい。粘度指数が60以上であると、基油の温度による粘度変化が小さく、安定した潤滑性能を発揮する。 As the base oil, those having a kinematic viscosity at 100 ° C. of usually 2 to 50 mm 2 / s, preferably 3 to 30 mm 2 / s, particularly preferably 3 to 15 mm 2 / s are advantageous. When the kinematic viscosity at 100 ° C. is 2 mm 2 / s or more, the evaporation loss is small, and when it is 50 mm 2 / s or less, the power loss due to the viscous resistance is suppressed, and the fuel efficiency improvement effect is exhibited well.
The base oil preferably has a viscosity index of 60 or more, more preferably 70 or more, and particularly preferably 80 or more. When the viscosity index is 60 or more, the viscosity change due to the temperature of the base oil is small, and stable lubricating performance is exhibited.
また、これらの清浄剤としては、中性塩、塩基性塩、過塩基性塩のいずれも使用することができ、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。 As the alkaline earth metal salicylate and alkaline earth metal sulfonate used as the detergent for the component (A), conventionally known compounds such as compounds having an alkyl group can be used. Examples of the alkaline earth metal include calcium and magnesium, and calcium is particularly preferable.
Further, as these detergents, any of neutral salts, basic salts and overbased salts can be used, and one kind may be used alone, or two or more kinds may be used in combination. .
本発明のコハク酸イミド化合物としては、例えば、以下の一般式(II)または一般式(III) In the present invention, as the ashless dispersant of the component (B), a boron-free succinimide compound having an alkenyl group or alkyl group having a number average molecular weight of 500 to 4000 (hereinafter, the succinimide compound is referred to as “the present invention”). A succinimide compound ”). When the number average molecular weight of the alkenyl group or alkyl group is 500 or more, a good cleansing effect is exhibited, and when it is 4000 or less, the low temperature fluidity is good.
Examples of the succinimide compound of the present invention include the following general formula (II) or general formula (III):
一般式(IV)において、R6~R9は、それぞれ独立にアルキル基を示し、好ましくは炭素数1~24のアルキル基が用いられる。 The compound represented by these is mentioned.
In the general formula (IV), R 6 to R 9 each independently represents an alkyl group, preferably an alkyl group having 1 to 24 carbon atoms.
R1-Sn-R2 (I)
で示される化合物が好ましい。(I)式中、nは1~4から選ばれる整数を表し、特にnが2または3が好ましい。R1及びR2は、それぞれ独立にアルキル基またはアラルキル基を表す。R1およびR2は、好ましくは炭素数4~24の基であり、より好ましくは炭素数8~18の基である。 The sulfur compound of the component (D) is a compound selected from polysulfide compounds, sulfurized fats and oils, sulfurized olefins, thiophosphate esters, thiophosphite esters, and amine salts of these esters. Of these, polysulfide compounds are preferred, and in particular, the general formula (I)
R 1 -S n -R 2 (I)
The compound shown by these is preferable. In the formula (I), n represents an integer selected from 1 to 4, and n is particularly preferably 2 or 3. R 1 and R 2 each independently represents an alkyl group or an aralkyl group. R 1 and R 2 are preferably a group having 4 to 24 carbon atoms, and more preferably a group having 8 to 18 carbon atoms.
摩擦低減剤としては、脂肪酸エステル系、脂肪族アミン系、高級アルコール系などの無灰摩擦低減剤が挙げられる。粘度指数向上剤としては、具体的には、各種メタクリル酸エステル又はこれらの任意の組合せに係る共重合体やその水添物等のいわゆる非分散型粘度指数向上剤、及び更に窒素化合物を含む各種メタクリル酸エステルを共重合させたいわゆる分散型粘度指数向上剤等が例示できる。また、非分散型又は分散型エチレン-α-オレフィン共重合体(α-オレフィンとしては、例えばプロピレン、1-ブテン、1-ペンテン等)及びその水素化物、ポリイソブチレン及びその水添物、スチレン-ジエン水素化共重合体、スチレン-無水マレイン酸エステル共重合体、並びにポリアルキルスチレン等も例示できる。これら粘度指数向上剤の分子量は、せん断安定性を考慮して選定することが必要である。具体的には、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では5000~1000000、好ましくは100000~800000がよく、ポリイソブチレン又はその水素化物では800~5000、エチレン-α-オレフィン共重合体及びその水素化物では800~300000、好ましくは10000~200000がよい。また、かかる粘度指数向上剤は、単独で又は複数種を任意に組合せて含有させることができるが、通常その含有量は、潤滑油組成物全量に基づき0.1~40.0質量%程度である。流動点降下剤としては、例えばポリメタクリレートなどが挙げられる。 The lubricating oil composition of the present invention may be blended with conventionally known additives as long as the effects of the present invention are not impaired, for example, friction reducers, viscosity index improvers, pour point depressants, antioxidants, An antirust agent etc. are mentioned.
Examples of the friction reducing agent include ashless friction reducing agents such as fatty acid esters, aliphatic amines, and higher alcohols. Specific examples of the viscosity index improver include so-called non-dispersion type viscosity index improvers such as various methacrylate esters or copolymers and hydrogenated products thereof, and various nitrogen compounds. Examples thereof include a so-called dispersed viscosity index improver obtained by copolymerizing a methacrylic acid ester. Further, non-dispersed or dispersed ethylene-α-olefin copolymers (for example, propylene, 1-butene, 1-pentene etc.) and hydrides thereof, polyisobutylene and hydrogenated products thereof, styrene- Examples thereof include diene hydrogenated copolymers, styrene-maleic anhydride copolymers, and polyalkylstyrenes. The molecular weight of these viscosity index improvers needs to be selected in consideration of shear stability. Specifically, the number average molecular weight of the viscosity index improver is, for example, 5000 to 1000000, preferably 100000 to 800000 for dispersed and non-dispersed polymethacrylates, 800 to 5000 for polyisobutylene or a hydride thereof, ethylene- The α-olefin copolymer and its hydride are 800 to 300,000, preferably 10,000 to 200,000. Such a viscosity index improver can be contained alone or in any combination of two or more kinds, but the content is usually about 0.1 to 40.0% by mass based on the total amount of the lubricating oil composition. is there. Examples of the pour point depressant include polymethacrylate.
防錆剤としては、アルキルベンゼンスルフォネート、ジノニルナフタレンスルフォネート、アルケニルコハク酸エステル、多価アルコールエステル等が挙げられる。 Examples of amine antioxidants include monooctyl diphenylamine; monoalkyl diphenylamines such as monononyl diphenylamine; 4,4′-dibutyldiphenylamine; 4,4′-dipentyldiphenylamine; 4,4′-dihexyldiphenylamine; 4,4′-diheptyldiphenylamine; 4,4′-dioctyldiphenylamine; dialkyldiphenylamines such as 4,4′-dinonyldiphenylamine; tetrabutyldiphenylamine; tetrahexyldiphenylamine; tetraoctyldiphenylamine; polyalkyldiphenylamine such as tetranonyldiphenylamine And naphthylamine type, specifically α-naphthylamine; phenyl-α-naphthylamine; and butylphenyl-α-naphthyl Min; pentylphenyl -α- naphthylamine; hexylphenyl -α- naphthylamine; heptylphenyl -α- naphthylamine; octylphenyl -α- naphthylamine; and alkyl-substituted phenyl -α- naphthylamine, such as nonylphenyl -α- naphthylamine. Of these, dialkyldiphenylamine type and naphthylamine type are preferable.
Examples of the rust inhibitor include alkyl benzene sulfonate, dinonyl naphthalene sulfonate, alkenyl succinate, polyhydric alcohol ester and the like.
前記の低摩擦摺動材料を有する摺動面としては、一方の側に低摩擦摺動材料としてDLC材料を有するものが特に好ましい。この場合、相手の材料については特に制限はなく、例えば該DLC材料と鉄基材料との摺動面あるいはDLC材料とアルミニウム合金材料との摺動面などを挙げることができる。
ここで、上記DLC材料は、表面にDLC膜を有し、該膜を構成するDLC材は、炭素元素を主として構成された非晶質であり、炭素同士の結合形態がダイヤモンド構造(SP3結合)とグラファイト結合(SP2結合)の両方から成る。具体的には、炭素元素だけから成るa-C(アモルファスカーボン)、水素を含有するa-C:H(水素アモルファスカーボン)、及びチタン(Ti)やモリブデン(Mo)等の金属元素を一部に含むMeCが挙げられる。 The lubricating oil composition of the present invention is applied to a sliding surface having a low-friction sliding material and can impart excellent low-friction characteristics, and particularly when applied to an internal combustion engine, provides a fuel-saving effect. can do.
As the sliding surface having the low friction sliding material, one having a DLC material as a low friction sliding material on one side is particularly preferable. In this case, the mating material is not particularly limited, and examples thereof include a sliding surface between the DLC material and the iron-based material or a sliding surface between the DLC material and the aluminum alloy material.
Here, the DLC material has a DLC film on the surface, and the DLC material constituting the film is amorphous mainly composed of carbon element, and the bonding form between carbons is a diamond structure (SP 3 bond). ) And graphite bonds (SP 2 bonds). Specifically, aC (amorphous carbon) composed only of carbon elements, aC: H (hydrogen amorphous carbon) containing hydrogen, and some metal elements such as titanium (Ti) and molybdenum (Mo). MeC included in
また、前記DLC材料及び鉄基材料、あるいはDLC材料及びアルミニウム合金材料のそれぞれの表面粗さは、算術平均粗さRaで、0.1μm以下であることが摺動の安定性
の面から好適である。0.1μm以下であると局部的なスカッフィングが形成しにくく、摩擦係数の増大を抑制することができる。更に、上記DLC材料は、表面硬さが、マイクロビッカーズ硬さ(98mN荷重)でHv1000~3500、厚さが0.3~2.0μmであることが好ましい。
一方、前記鉄基材料は、表面硬さがロックウェル硬さ(Cスケール)でHRC45~60であることが好ましい。この場合は、カムフォロワー部材のように700MPa程度の高面圧下の摺動条件においても、膜の耐久性を維持できるので有効である。
また、前記アルミニウム合金材料は、表面硬さがブリネル硬さHB80~130であることが好ましい。
DLC材料の表面硬さ及び厚さが上記範囲にあると摩滅や剥離が抑制される。また、鉄基材料の表面硬さがHRC45以上であると、高面圧下で座屈し剥離するのを抑制することができる。一方、アルミニウム合金材料の表面硬さが上記範囲にあれば、アルミニウム合金の摩耗が抑制される。 On the other hand, examples of the iron base material include carburized steel SCM420 and SCr420 (JIS). As the aluminum alloy material, a hypoeutectic aluminum alloy or a hypereutectic aluminum alloy containing 4 to 20% by mass of silicon and 1.0 to 5.0% by mass of copper is preferably used. Specifically, AC2A, AC8A, ADC12, ADC14 (JIS), etc. can be mentioned.
The surface roughness of each of the DLC material and the iron base material, or the DLC material and the aluminum alloy material is preferably an arithmetic average roughness Ra of 0.1 μm or less from the viewpoint of sliding stability. is there. If it is 0.1 μm or less, local scuffing is difficult to form, and an increase in the friction coefficient can be suppressed. Further, the DLC material preferably has a surface hardness of Hv 1000 to 3500 in micro Vickers hardness (98 mN load) and a thickness of 0.3 to 2.0 μm.
On the other hand, the iron-based material preferably has a surface hardness of HRC45-60 in terms of Rockwell hardness (C scale). This case is effective because the durability of the film can be maintained even under sliding conditions under a high surface pressure of about 700 MPa as in a cam follower member.
The aluminum alloy material preferably has a surface hardness of Brinell hardness HB 80 to 130.
When the surface hardness and thickness of the DLC material are within the above ranges, abrasion and peeling are suppressed. Further, when the surface hardness of the iron-based material is HRC45 or more, it is possible to suppress buckling and peeling under high surface pressure. On the other hand, if the surface hardness of the aluminum alloy material is within the above range, the wear of the aluminum alloy is suppressed.
第1表に示す組成を有する潤滑油組成物を調製し、以下に示す摩擦特性試験を行い、摩擦係数を求めた。その結果を第2表に示す。
<摩擦特性試験>
往復動摩擦試験機(オプティマール社製SRV往復動摩擦試験機)を用いて、以下の方法により摩擦係数を測定した。
テストピースとして、DLCコーティングしたディスク(φ24mm×7.9mm)を用い、その上に試料油(潤滑油組成物)を数滴滴下する。SCM420製のシリンダー(φ15mm×22mm)を上記ディスク上部にセットした状態で、荷重400N、振幅1.5mm、周波数50Hz、温度80℃の条件で摩擦係数を求める。 [Examples 1 to 6 and Comparative Examples 1 to 5]
A lubricating oil composition having the composition shown in Table 1 was prepared, and the friction characteristic test shown below was conducted to obtain the friction coefficient. The results are shown in Table 2.
<Frictional property test>
The friction coefficient was measured by the following method using a reciprocating friction tester (SRV reciprocating friction tester manufactured by Optimar).
As a test piece, a DLC-coated disk (φ24 mm × 7.9 mm) is used, and several drops of sample oil (lubricating oil composition) are dropped on the disk. A friction coefficient is obtained under the conditions of a load of 400 N, an amplitude of 1.5 mm, a frequency of 50 Hz, and a temperature of 80 ° C. with an SCM420 cylinder (φ15 mm × 22 mm) set on the top of the disk.
潤滑油基油:水素化分解鉱油(100℃動粘度4.47mm2/s)
Caスルフォネート(1):Caスルフォネート(Ca含有量15.2質量%)
Caスルフォネート(2):Caスルフォネート(Ca含有量12.0質量%)
Caサリシレート(1):Caサリシレート(Ca含有量7.8質量%)
Caサリシレート(2):Caサリシレート(Ca含有量2.3質量%)
Caフェネート:Caフェネート(Ca含有量9.25質量%)
ホウ素未含有コハク酸イミド(1):前記(III)式で表されるホウ素未含有ポリブテニルコハク酸イミド(窒素含有量2.1質量%、ポリブテニル基数平均分子量1000)
ホウ素未含有コハク酸イミド(2):前記(II)式で表されるホウ素未含有ポリブテニルコハク酸イミド(窒素含有量0.97質量%、ポリブテニル基数平均分子量1300)
ホウ素含有コハク酸イミド:前記(III)式で表されるホウ素含有ポリブテニルコハク酸イミド(窒素含有量1.23質量%、ポリブテニル基数平均分子量1000)
ジアルキルジチオリン酸亜鉛(1):第2級アルキル型ジアルキルジチオリン酸亜鉛(リン含有量8.2質量%)
ジアルキルジチオリン酸亜鉛(2):第1級アルキル型ジアルキルジチオリン酸亜鉛(リン含有量7.4質量%)
硫黄系化合物:ポリサルファイド混合物(R-Sa-R,Rは炭素数12のアルキル基、aは2または3、硫黄含有量22.0質量%)
粘度指数向上剤:ポリメタクリレート(重量平均分子量 Mw=550,000)
流動点降下剤:ポリメタクリレート(重量平均分子量 Mw=69,000)
酸化防止剤(1):ジアルキルジフェニルアミン(窒素含有量4.62質量%)
酸化防止剤(2):4,4’-メチレンビス(2,6-ジ-tert-ブチルフェノール)
防錆剤:N-アルキルベンゾトリアゾール Each component used for the preparation of the lubricating oil composition is as follows.
Lubricating base oil: hydrocracked mineral oil (100 ° C. kinematic viscosity 4.47 mm 2 / s)
Ca sulfonate (1): Ca sulfonate (Ca content 15.2% by mass)
Ca sulfonate (2): Ca sulfonate (Ca content 12.0% by mass)
Ca salicylate (1): Ca salicylate (Ca content 7.8% by mass)
Ca salicylate (2): Ca salicylate (Ca content 2.3 mass%)
Ca phenate: Ca phenate (Ca content: 9.25% by mass)
Boron-free succinimide (1): Boron-free polybutenyl succinimide represented by the formula (III) (nitrogen content 2.1 mass%, polybutenyl group number average molecular weight 1000)
Boron-free succinimide (2): Boron-free polybutenyl succinimide represented by the formula (II) (nitrogen content 0.97% by mass, polybutenyl group number average molecular weight 1300)
Boron-containing succinimide: Boron-containing polybutenyl succinimide represented by the formula (III) (nitrogen content 1.23% by mass, polybutenyl group number average molecular weight 1000)
Zinc dialkyldithiophosphate (1): zinc secondary alkyl type dialkyldithiophosphate (phosphorus content 8.2% by mass)
Zinc dialkyldithiophosphate (2): primary alkyl-type zinc dialkyldithiophosphate (phosphorus content 7.4% by mass)
Sulfur-based compound: polysulfide mixture (R—S a —R, R is an alkyl group having 12 carbon atoms, a is 2 or 3, and sulfur content is 22.0 mass%)
Viscosity index improver: polymethacrylate (weight average molecular weight Mw = 550,000)
Pour point depressant: polymethacrylate (weight average molecular weight Mw = 69,000)
Antioxidant (1): Dialkyldiphenylamine (nitrogen content 4.62% by mass)
Antioxidant (2): 4,4′-methylenebis (2,6-di-tert-butylphenol)
Rust inhibitor: N-alkylbenzotriazole
DLC:水素20%含有DLC
DLC W:水素20%含有(タングステン添加)DLC The following DLC-coated discs were used.
DLC: DLC containing 20% hydrogen
DLC W: 20% hydrogen (tungsten added) DLC
Claims (6)
- 潤滑油基油に、(A)アルカリ土類金属サリシレート系および/またはアルカリ土類金属スルフォネート系清浄剤、(B)数平均分子量500~4000のアルケニル基またはアルキル基を有する、ホウ素未含有コハク酸イミド系無灰分散剤、(C)ジアルキルジチオリン酸亜鉛および(D)ポリスルフィド化合物、硫化油脂、硫化オレフィン、チオリン酸エステル、チオ亜リン酸エステル及びこれらのエステルのアミン塩から選ばれる硫黄系化合物を配合してなる潤滑油組成物であって、
組成物全量基準の配合量が、(A)成分がアルカリ土類金属濃度換算で、0.05~0.25質量%、(B)成分が窒素濃度換算で、0.03~0.50質量%、(C)成分がリン濃度換算で0.01~0.12質量%、(D)成分が硫黄濃度換算で0.02~2.0質量%であって、
アルカリ土類金属フェネート系清浄剤がアルカリ土類金属濃度換算で0.10質量%以下、ホウ素含有コハク酸イミドが窒素濃度換算で、0.04質量%以下である、低摩擦摺動材料に用いられる潤滑油組成物。 Boron-free succinic acid having (A) alkaline earth metal salicylate and / or alkaline earth metal sulfonate detergent, (B) alkenyl group or alkyl group having a number average molecular weight of 500 to 4000 Formulated with imide-based ashless dispersant, (C) zinc dialkyldithiophosphate and (D) polysulfide compound, sulfurized oil, sulfurized olefin, thiophosphate, thiophosphite, and amine salts of these esters A lubricating oil composition comprising:
The blending amount based on the total amount of the composition is such that the component (A) is 0.05 to 0.25% by mass in terms of alkaline earth metal concentration, and the component (B) is 0.03 to 0.50 mass in terms of nitrogen concentration. %, (C) component is 0.01-0.12% by mass in terms of phosphorus concentration, (D) component is 0.02-2.0% by mass in terms of sulfur concentration,
The alkaline earth metal phenate detergent is 0.10% by mass or less in terms of alkaline earth metal concentration, and the boron-containing succinimide is 0.04% by mass or less in terms of nitrogen concentration. Lubricating oil composition. - ジアルキルジチオリン酸亜鉛の配合量が、リン濃度換算で0.03~0.10質量%である請求項1に記載の潤滑油組成物。 The lubricating oil composition according to claim 1, wherein the amount of zinc dialkyldithiophosphate is 0.03 to 0.10 mass% in terms of phosphorus concentration.
- 数平均分子量500~4000のアルケニル基またはアルキル基を有する、ホウ素未含有コハク酸イミド系無灰分散剤の配合量が、窒素濃度換算で0.05~0.30質量%である請求項1に記載の潤滑油組成物。 2. The compounding amount of a boron-free succinimide ashless dispersant having an alkenyl group or an alkyl group having a number average molecular weight of 500 to 4000 is 0.05 to 0.30% by mass in terms of nitrogen concentration. Lubricating oil composition.
- 硫黄系化合物が、一般式(I)
R1-Sn-R2 (I)
(式中、nは1~4から選ばれる整数を表し、R1及びR2は、それぞれ独立にアルキル基またはアラルキル基を表す)
で示される化合物である請求項1に記載の潤滑油組成物。 Sulfur compounds are represented by the general formula (I)
R 1 -S n -R 2 (I)
(Wherein n represents an integer selected from 1 to 4, and R 1 and R 2 each independently represents an alkyl group or an aralkyl group)
The lubricating oil composition according to claim 1, which is a compound represented by the formula: - 一般式(I)中のnが2または3である請求項4に記載の潤滑油組成物。 The lubricating oil composition according to claim 4, wherein n in the general formula (I) is 2 or 3.
- 低摩擦摺動材料がダイヤモンドライクカーボン(DLC)皮膜を有する材料である請求項1に記載の潤滑油組成物。 The lubricating oil composition according to claim 1, wherein the low friction sliding material is a material having a diamond-like carbon (DLC) film.
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WO2006009012A1 (en) * | 2004-07-23 | 2006-01-26 | Idemitsu Kosan Co., Ltd. | Lubricant composition |
WO2007123266A1 (en) * | 2006-04-20 | 2007-11-01 | Nippon Oil Corporation | Lubricating oil composition |
WO2008029756A1 (en) * | 2006-09-04 | 2008-03-13 | Idemitsu Kosan Co., Ltd. | Lubricant composition for internal combustion engine |
WO2009104682A1 (en) * | 2008-02-20 | 2009-08-27 | 出光興産株式会社 | Lubricating oil composition for internal combustion engine |
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CA2102892A1 (en) * | 1992-05-15 | 1993-11-16 | Mary F. Salomon | Lubricating compositions and concentrates |
US5744430A (en) * | 1995-04-28 | 1998-04-28 | Nippon Oil Co., Ltd. | Engine oil composition |
JP3555891B2 (en) * | 2002-02-22 | 2004-08-18 | 新日本石油株式会社 | Low friction sliding material and lubricating oil composition used therefor |
EP1609844A4 (en) * | 2003-04-02 | 2008-02-13 | Idemitsu Kosan Co | Conductive lubricant composition |
US20080128184A1 (en) * | 2006-11-30 | 2008-06-05 | Loper John T | Lubricating oil compositions having improved corrosion and seal protection properties |
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2009
- 2009-09-15 JP JP2009213646A patent/JP5463108B2/en not_active Expired - Fee Related
-
2010
- 2010-09-03 WO PCT/JP2010/065136 patent/WO2011033953A1/en active Application Filing
- 2010-09-03 CN CN201080041843.6A patent/CN102597194B/en not_active Expired - Fee Related
- 2010-09-03 US US13/395,668 patent/US20120172266A1/en not_active Abandoned
- 2010-09-03 KR KR1020127006495A patent/KR20120080173A/en not_active Application Discontinuation
- 2010-09-03 EP EP10817066.3A patent/EP2479248A4/en not_active Withdrawn
Patent Citations (4)
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WO2006009012A1 (en) * | 2004-07-23 | 2006-01-26 | Idemitsu Kosan Co., Ltd. | Lubricant composition |
WO2007123266A1 (en) * | 2006-04-20 | 2007-11-01 | Nippon Oil Corporation | Lubricating oil composition |
WO2008029756A1 (en) * | 2006-09-04 | 2008-03-13 | Idemitsu Kosan Co., Ltd. | Lubricant composition for internal combustion engine |
WO2009104682A1 (en) * | 2008-02-20 | 2009-08-27 | 出光興産株式会社 | Lubricating oil composition for internal combustion engine |
Cited By (3)
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CN104169403A (en) * | 2012-03-16 | 2014-11-26 | 出光兴产株式会社 | Lubricating oil composition and sliding mechanism using same |
CN104169402A (en) * | 2012-03-16 | 2014-11-26 | 出光兴产株式会社 | Lubricating oil composition and sliding mechanism using same |
US9803155B2 (en) | 2012-03-16 | 2017-10-31 | Idemitsu Kosan Co., Ltd. | Lubricating oil composition, and sliding mechanism using lubricating oil composition |
Also Published As
Publication number | Publication date |
---|---|
EP2479248A1 (en) | 2012-07-25 |
JP5463108B2 (en) | 2014-04-09 |
CN102597194B (en) | 2014-12-31 |
US20120172266A1 (en) | 2012-07-05 |
EP2479248A4 (en) | 2013-05-15 |
KR20120080173A (en) | 2012-07-16 |
JP2011063654A (en) | 2011-03-31 |
CN102597194A (en) | 2012-07-18 |
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