WO2015076103A1 - 潤滑剤組成物及びそれを含有する潤滑油組成物 - Google Patents
潤滑剤組成物及びそれを含有する潤滑油組成物 Download PDFInfo
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- WO2015076103A1 WO2015076103A1 PCT/JP2014/079329 JP2014079329W WO2015076103A1 WO 2015076103 A1 WO2015076103 A1 WO 2015076103A1 JP 2014079329 W JP2014079329 W JP 2014079329W WO 2015076103 A1 WO2015076103 A1 WO 2015076103A1
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/0246—Polyamines containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
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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
- 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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- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
- C10M2219/066—Thiocarbamic type compounds
- C10M2219/068—Thiocarbamate metal salts
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- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/12—Groups 6 or 16
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- 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
- C10N2040/25—Internal-combustion engines
Definitions
- the present invention relates to an additive for lubricating oil that exhibits a good friction reducing effect under a large contact surface pressure, and a lubricating oil composition in which the additive is blended with a base oil.
- Lubricating oil is used in all equipment and machinery that have friction parts. This is because the lubricating oil plays an important role in minimizing friction, wear, seizure, etc., and extending the life of the equipment and machinery.
- the performance required of lubricating oil varies, and in particular, reducing friction under severe conditions where a large contact surface pressure is applied is very important in the lubrication industry. It is considered difficult.
- Examples include on-disk friction and wear tests, ball-on-plate reciprocating wear tests, and line contact includes block-on-ring friction testers and two-cylinder tests.
- Surface contact includes ring-on-disk friction and wear tests and block-on. Examples include plate friction and wear tests. Among them, the point contact test is the most severe test because it requires a larger contact surface pressure than the line contact and surface contact.
- organic molybdenum compounds are well known as those having a high friction reducing effect among existing friction reducing agents (Patent Documents 1 to 4).
- the organomolybdenum compound is said to form a molybdenum disulfide film on the sliding surface where metals contact each other, such as the boundary lubrication region, that is, a portion where a certain amount of temperature and load is applied, and exhibits a friction reducing effect.
- the effect is recognized in all lubricating oils including engine oil.
- the organomolybdenum compound does not exhibit a friction reducing effect under any conditions. Under severe conditions where a large contact surface pressure such as point contact is applied, the effect is weakened, and it may be difficult to reduce friction. Therefore, there has been a strong demand in the market for the development of a lubricating oil additive that effectively exhibits a friction reducing effect under any conditions.
- JP-A-9-151387 Japanese Patent Laid-Open No. 7-53983 JP 2008-189561 A Japanese Patent Laid-Open No. 10-17586
- the problem to be solved by the present invention is to provide a lubricating oil additive composition that exhibits a high friction reducing effect even under severe conditions where a large contact surface pressure is applied, and a lubricating oil composition blended with the lubricating oil composition. There is to do.
- the present inventors diligently studied, and by using molybdenum dithiocarbamate and an acrylic polymer in combination, they have found an additive for lubricating oil that exhibits a high friction reducing effect even under severe conditions where a large contact surface pressure is applied. It came to. That is, the present invention is represented by a molybdenum dithiocarbamate (A) represented by the following general formula (1), a unit (a) represented by the following general formula (2), and the following general formula (3).
- Unit (b) as an essential constituent unit the weight average molecular weight is 5,000 to 150,000, and the constituent ratio of the unit (a) to the unit (b) is (a) / (B)
- a lubricant composition comprising a copolymer (B) in which 50/50 to 90/10.
- R 1 to R 4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and X 1 to X 4 each independently represents a sulfur atom or an oxygen atom.
- R 5 represents an alkyl group having 4 to 18 carbon atoms.
- R 6 represents an alkylene group having 2 to 4 carbon atoms.
- the lubricating oil additive composition of the present invention and a lubricating oil composition blended with the lubricating oil composition show a high friction reducing effect even under severe conditions where a large contact surface pressure is applied.
- the copolymer (B) used in the present invention is combined with the molybdenum dithiocarbamate (A) used in the present invention, the friction reducing effect of the molybdenum dithiocarbamate (A) in the lubricating oil is further strengthened.
- the lubricant composition of the present invention comprises a molybdenum dithiocarbamate (A) represented by the following general formula (1), a unit (a) represented by the following general formula (2), and the following general formula (3 )
- R 1 to R 4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and X 1 to X 4 each independently represents a sulfur atom or an oxygen atom.
- R 5 represents an alkyl group having 4 to 18 carbon atoms.
- R 6 represents an alkylene group having 2 to 4 carbon atoms.
- the organic molybdenum compound used in the present invention is molybdenum dithiocarbamate (A) represented by the following general formula (1).
- R 1 to R 4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and X 1 to X 4 each independently represents a sulfur atom or an oxygen atom.
- R 1 to R 4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms.
- groups include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, branched pentyl, Secondary pentyl group, tertiary pentyl group, n-hexyl group, branched hexyl group, secondary hexyl group, tertiary hexyl group, n-heptyl group, branched heptyl group, secondary heptyl group, primary Tertiary heptyl group, n-octyl group, 2-ethylhexyl group, branched octyl group, secondary octyl group, tertiary octyl group, n-non
- a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group are preferable, and a saturated aliphatic hydrocarbon group is more preferable because the effects of the present invention are easily obtained.
- the saturated aliphatic hydrocarbon group having 3 to 15 carbon atoms is more preferable, and the saturated aliphatic hydrocarbon group having 8 to 13 carbon atoms is more preferable because the effects of the present invention are easily obtained and the production is easy.
- R 1 to R 4 in the general formula (1) may be the same or different from each other, but the effects of the present invention can be easily obtained due to the synergistic effect with the copolymer (B). It is preferable that it is composed of two or more groups.
- X 1 to X 4 each independently represents a sulfur atom or an oxygen atom.
- X 1 and X 2 is a sulfur atom
- X 1 and X 2 is a sulfur atom
- X 3 and X 4 is an oxygen atom preferable.
- the production method of molybdenum dithiocarbamate (A) represented by the general formula (1) used in the present invention is not particularly problematic as long as it is a known production method.
- it is a patent publication in Japan.
- Examples thereof include the production methods described in JP-A-62-181396, JP-A-7-53983, JP-A-8-217782, JP-A-10-17586, and the like. These technical contents are appropriately incorporated and made a part of this specification.
- the copolymer (B) used in the present invention comprises a unit (a) represented by the following general formula (2) and a unit (b) represented by the following general formula (3) as essential constituent units. Copolymer.
- R 5 represents an alkyl group having 4 to 18 carbon atoms.
- R 6 represents an alkylene group having 2 to 4 carbon atoms.
- R 5 in the general formula (2) represents an alkyl group having 4 to 18 carbon atoms, for example, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n- Nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, etc.
- Primary alkyl group of the chain isobutyl group, branched primary pentyl group, branched primary hexyl group, branched primary heptyl group, branched primary octyl group (eg 2 -Ethylhexyl group), branched primary nonyl group, branched primary decyl group, branched primary undecyl group, branched primary dodecyl group, branched primary tridecyl group, Branched primary tetradecyl group, branched chain Branched primary alkyl groups such as primary pentadecyl groups, branched primary hexadecyl groups, branched primary heptadecyl groups, branched primary octadecyl groups; s-butyl groups, secondary Pentyl group, secondary hexyl group, secondary heptyl group, secondary octyl group, secondary nonyl group, secondary dec
- a copolymer that effectively exhibits the effects of the present invention since it is preferably a primary alkyl group (in this case, it may be linear or branched), A copolymer that effectively exhibits the effects of the present invention can be obtained, and a copolymer having good solubility in a base oil can be obtained. Therefore, a primary alkyl group having 10 to 18 carbon atoms (this In this case, it may be a straight chain or branched chain), and is more preferably a primary alkyl group having 12 to 18 carbon atoms (in this case, it may be a straight chain or branched chain). It is even more preferable that a linear primary alkyl group having 12 to 18 carbon atoms is most preferable.
- R 6 in the general formula (3) represents an alkylene group having 2 to 4 carbon atoms.
- ethylene group propane-1,3-diyl group, propane-1,2-diyl group, propane-2,2- Diyl group, butane-1,4-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,1-diyl group, butane- Examples include 2,2-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group and the like.
- an alkylene group having 2 to 3 carbon atoms is preferable, and an ethylene group is more preferable because a copolymer that effectively exhibits the effects of the present invention can be obtained.
- the copolymer (B) has the unit (a) represented by the general formula (2) and the unit (b) represented by the general formula (3) as essential constituent units, the copolymer (B) One or more units (a) having different R 5 may be contained, and one or more units (b) having different R 6 in the general formula (3) may be contained.
- the unit (a) and the unit (b) are 90 in total.
- the copolymer (B) is preferably contained in an amount of not less than mass%, more preferably a copolymer (B) contained in an amount of not less than 95 mass%. Still more preferably, the copolymer (B) consists essentially of unit (a) and unit (b).
- “being essentially” means that the copolymer (B) mainly contains the unit (a) and the unit (b), and the unit other than the unit (a) and the unit (b) is 1% by mass or less. Including.
- copolymer (B) consists of unit (a) and unit (b).
- the copolymer (B) having the unit (a) and the unit (b) as essential constituent units must have a weight average molecular weight of 5,000 to 150,000.
- a weight average molecular weight of 5,000 to 150,000.
- it is preferably 10,000 to 130,000, 40,000 Is more preferably 130,000, more preferably 40,000 to 110,000, still more preferably 50,000 to 110,000, and most preferably 50,000 to 75,000.
- the weight average molecular weight is less than 5,000, the effect of the present invention may not be exhibited.
- the weight average molecular weight is more than 150,000, it may not be dissolved in the base oil.
- the weight average molecular weight is measured by GPC and is calculated in terms of styrene.
- the method for producing the copolymer (B) used in the present invention is not particularly specified, and any method may be used as long as it is a known method.
- the raw material for forming the unit (a) has 4 carbon atoms. It is preferable to use an alkyl acrylate having an alkyl group of ⁇ 18, and it is preferable to use a hydroxyalkyl acrylate having an alkylene group of 2 to 4 carbon atoms as a raw material for forming the unit (b). That is, examples of the method for producing the copolymer (B) using these as raw materials include bulk polymerization, emulsion polymerization, suspension polymerization, and solution polymerization.
- the lubricant composition of the present invention is used by being added to a base oil such as mineral oil or synthetic oil
- a base oil such as mineral oil or synthetic oil
- bulk polymerization or solution polymerization can be performed by a polymerization method using water as a solvent, such as emulsion polymerization or suspension polymerization.
- solution polymerization is more preferable because the reaction proceeds smoothly.
- raw materials for forming the unit (a) include n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, isononyl acrylate, n-decyl acrylate, n-undecyl acrylate, n-dodecyl acrylate, n-tridecyl acrylate, n-tetradecyl acrylate, n-penta Examples include decyl acrylate, n-hexadecyl acrylate, n-heptadecyl acrylate, and n-octadecyl
- n-octyl acrylate 2-ethylhexyl acrylate, n-nonyl acrylate, isononyl acrylate, n-decyl acrylate, n-undecyl acrylate, n-dodecyl acrylate, n-tridecyl acrylate, n-tetradecyl acrylate, n-penta Preferred are decyl acrylate, n-hexadecyl acrylate, n-heptadecyl acrylate, and n-octadecyl acrylate.
- Examples of the raw material for forming the unit (b) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate and the like.
- 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 3-hydroxypropyl acrylate are preferable, and 2-hydroxyethyl acrylate is more preferable because a copolymer that effectively exhibits the effects of the present invention can be obtained. preferable.
- a raw material monomer that forms unit (a) and a raw material monomer that forms unit (b) are reacted in a solvent so that the total monomer content is 5 to 80% by mass.
- the temperature is raised to about 50 to 120 ° C., and an initiator of 0.1 to 10 mol% is added all at once or divided with respect to the total amount of monomers, and stirred for 1 to 20 hours.
- the reaction may be performed so that the weight average molecular weight is 5,000 to 150,000.
- the monomer and catalyst may be charged all at once, the temperature may be raised to 50 to 120 ° C., and the mixture may be stirred for 1 to 20 hours to cause a weight average molecular weight of 5,000 to 150,000.
- solvents examples include alcohols such as methanol, ethanol, propanol and butanol; hydrocarbons such as benzene, toluene, xylene and hexane; esters such as ethyl acetate, butyl acetate and isobutyl acetate; acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone; ethers such as methoxybutanol, ethoxybutanol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monobutyl ether, dioxane; paraffin type Mineral oil, naphthenic mineral oil or these are hydrorefined, solvent removed, solvent extracted, solvent dewaxed, hydrogenated Mineral oil such as refined mineral oil such as wax, catalytic de
- Examples of the initiator that can be used include 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis- (N, N-dimethyleneisobutylamidine) dihydrochloride, 1,1′-azobis (cyclohexyl-1-carbonitrile) and other azo initiators, hydrogen peroxide and benzoyl peroxide, t-butyl hydroperoxide, cumene hydroper Organic peroxides such as oxide, methyl ethyl ketone peroxide, perbenzoic acid, persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate, redox initiators such as hydrogen peroxide-Fe 3+ , and other existing radical initiation Agents and the like.
- 2,2′-azobis (2-methylpropionitrile) 2,2′-azobis (2-amidinopropane) dihydrochloride
- the copolymer (B) used in the lubricant composition of the present invention exhibits the effects of the present invention when the weight average molecular weight is 5,000 to 150,000, but the reaction temperature, polymerization time, initiator amount By controlling the above, it is possible to adjust the molecular weight of the polymer and produce a polymer having the target molecular weight.
- a polymer with a high molecular weight can be produced relatively easily by adjusting the reaction temperature, polymerization time, initiator amount, etc., but a polymer with a low molecular weight is polymerized using a solvent with a high chain transfer constant.
- Examples of the solvent having a high chain transfer constant include ethanol, propanol, isopropanol, butanol, isobutanol, toluene, ethylbenzene, isopropylbenzene, methyl ethyl ketone, chloroform, carbon tetrachloride and the like.
- chain transfer agent examples include mercaptoethanol, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, 2-mercaptoethanesulfonic acid, butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecane Thiol compounds such as thiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 3-mercaptopropionate; secondary alcohols such as isopropyl alcohol, and the like.
- copolymer (B) More detailed methods for producing the copolymer (B) are described in Japanese Patent Publication Nos. 2012-41407 and 2013-124266.
- the copolymer (B) used in the present invention can be produced by the methods described in these publications. These technical contents are appropriately incorporated and made a part of this specification.
- the copolymer (B) copolymerizes other monomers in addition to the raw material monomer that forms the unit (a) and the raw material monomer that forms the unit (b), as long as the effects of the present invention are not impaired. be able to.
- the method for polymerizing other monomers is not particularly specified, and the unit (a) is formed even if the other monomers are copolymerized after polymerization of the raw material monomer forming the unit (a) and the raw material monomer forming the unit (b).
- Other monomers may be copolymerized together with the raw material monomer to be formed and the raw material monomer to form the unit (b).
- the other monomer may be any monomer as long as it has a double bond.
- aromatic monomers such as styrene, vinyltoluene, 2,4-dimethylstyrene, 4-ethylstyrene, 2-vinylnaphthalene, etc.
- Vinyl monomers aliphatic vinyl monomers such as vinyl acetate, vinyl proionate, vinyl octoate, methyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether; vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, dichlorostyrene, etc.
- Halogen-based vinyl monomers alkyl acrylates other than the raw materials forming the unit (a) such as methyl acrylate, ethyl acrylate, propyl acrylate; allylamine, aminoethyl acrylate, aminopropyl acrylate, aminobutyl Examples thereof include amino group-containing monomers such as acrylate, methylaminoethyl acrylate, 2-diphenylamine acrylamide, dimethylaminomethyl acrylate, dimethylaminomethyl acrylamide, N, N-dimethylaminostyrene, 4-vinylstyrene, and N-vinylpyrrolidone.
- the content of these other monomers in the obtained copolymer is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less.
- content of these other monomers in a copolymer (B) exceeds 10 mass%, the effect of this invention may be inhibited.
- the unit (a) and the unit (b) have an acrylic group, but if this group is a methacrylic group, the effect of the present invention cannot be obtained.
- a copolymer prepared using alkyl methacrylate or hydroxyalkylene methacrylate is not available. Even if the polymer is used in combination with molybdenum dithiocarbamate (A), the effect of reducing friction cannot be obtained.
- the lubricant composition of the present invention is a lubricant composition containing these, and the effects of the present invention are exhibited only when both are used in combination.
- the proportion of molybdenum dithiocarbamate (A) and copolymer (B) used is that the molybdenum content of molybdenum dithiocarbamate (A) is 0.005 to 0.5 parts by mass with respect to 1 part by mass of copolymer (B).
- the molybdenum content of molybdenum dithiocarbamate (A) is 1 part by weight of copolymer (B).
- the amount is more preferably 0.008 to 0.3 parts by mass, still more preferably 0.01 to 0.2 parts by mass, and most preferably 0.03 to 0.15 parts by mass. If the molybdenum content of the molybdenum dithiocarbamate (A) is less than 0.005 parts by mass, the friction reduction effect may not be obtained. If the molybdenum content is more than 0.5 parts by mass, the friction reduction effect corresponding to the addition amount is observed. It may not be possible.
- a dilute oil may be added in addition to the molybdenum dithiocarbamate (A) and the copolymer (B) to dilute the active ingredient.
- the dilution rate is not particularly limited and may be appropriately determined depending on the purpose of use and use conditions.
- the diluent oil is preferably 10 to 90% by mass with respect to the total amount of the molybdenum dithiocarbamate (A), the copolymer (B) and the diluent oil.
- the diluent oil is less than 10% by mass, the viscosity of the lubricant composition may become high and handling may be difficult.
- the active ingredient is used when the lubricant composition is used as an additive. In some cases, the amount of additives used is increased due to the small amount.
- the dilutable oil that can be used is not particularly limited, and is appropriately selected from mineral base oils, chemically synthesized base oils, animal and plant base oils, and mixed base oils thereof according to the purpose and conditions of use.
- the mineral base oil for example, a distillate obtained by atmospheric distillation of paraffin-based crude oil, naphthene-based crude oil, or intermediate-base crude oil, or by distilling atmospheric residue oil under reduced pressure or Examples include refined oils obtained by refining them according to conventional methods, specifically solvent refined oils, hydrogenated refined oils, dewaxed oils, and clay-treated oils.
- Examples of chemically synthesized base oils include poly- ⁇ -olefin, polyisobutylene (polybutene), monoester, diester, polyol ester, silicate ester, polyalkylene glycol, polyphenyl ether, silicone, fluorinated compound, alkylbenzene, and GTL. Base oils and the like. Among these, poly- ⁇ -sodium olefins, polyisobutylene (polybutene), diesters and polyol esters can be used for general purposes. Examples of poly- ⁇ -olefins include 1-hexene.
- 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene and the like polymerized or oligomerized, or hydrogenated thereof.
- diester include glutaric acid, Adipic acid, azelaic acid, Examples include dibasic acids such as basic acid and dodecanedioic acid, and diesters of alcohols such as 2-ethylhexanol, octanol, decanol, dodecanol and tridecanol.
- polyol esters examples include neopentyl glycol, trimethylolethane, Examples include esters of polyols such as methylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol with fatty acids such as caproic acid, caprylic acid, lauric acid, capric acid, myristic acid, palmitic acid, stearic acid and oleic acid. It is done.
- animal and plant base oils include castor oil, olive oil, cacao butter, sesame oil, rice bran oil, safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, sunflower oil, cottonseed oil and palm.
- vegetable oils such as oil, beef tallow, pork fat, milk fat, fish oil and whale oil.
- One of these various diluent oils listed above may be used, or two or more may be used in appropriate combination.
- the lubricating oil composition of the present invention is obtained by adding the lubricant composition of the present invention to a base oil.
- the addition amount of the lubricant composition of the present invention to the base oil is not particularly limited, but in order to exert a better friction reducing effect, the content of molybdenum dithiocarbamate (A) is determined by adding the base oil and the additive.
- the molybdenum content is preferably 50 to 5,000 ppm by mass, more preferably 80 to 3,000 ppm by mass, and more preferably 100 to 2,000 ppm by mass with respect to the lubricating oil composition included. Even more preferred is 300-1500 ppm by mass. If the amount is less than 50 ppm by mass, the friction reducing effect may not be seen.
- the content of the copolymer (B) in the lubricating oil composition is determined based on the use ratio of the molybdenum dithiocarbamate (A) and the copolymer (B) in the above-described lubricant composition of the present invention and the lubricating oil composition described above. It is preferable to calculate from the content of a preferable organic molybdenum compound in and to add an amount corresponding to this. If the content of the copolymer (B) is too small, the combined use effect with the molybdenum dithiocarbamate (A) may not be obtained, and if it is too large, the effect corresponding to the addition amount may not be obtained.
- the base oil of the usable lubricating oil composition is not particularly limited, and is appropriately selected from a mineral base oil, a chemically synthesized base oil, an animal and vegetable base oil, and a mixed base oil thereof according to the purpose and conditions of use.
- a mineral base oil for example, a distillate obtained by atmospheric distillation of paraffin-based crude oil, naphthene-based crude oil, or intermediate-base crude oil, or by distilling atmospheric residue oil under reduced pressure or Examples include refined oils obtained by refining them according to conventional methods, specifically solvent refined oils, hydrogenated refined oils, dewaxed oils, and clay-treated oils.
- Examples of chemically synthesized base oils include poly- ⁇ -olefin, polyisobutylene (polybutene), monoester, diester, polyol ester, silicate ester, polyalkylene glycol, polyphenyl ether, silicone, fluorinated compound, alkylbenzene, and GTL. Base oils, and the like.
- poly- ⁇ -olefin, polyisobutylene (polybutene), diester, polyol ester and the like can be used for general purposes.
- Examples of poly- ⁇ -olefin include 1-hexene.
- the diester include glutaric acid, Adipic acid, azelaic acid, ce
- dibasic acids such as succinic acid and dodecanedioic acid
- diesters of alcohols such as 2-ethylhexanol, octanol, decanol, dodecanol and tridecanol.
- polyol esters examples include neopentyl glycol, trimethylol ethane, Examples include esters of polyols such as methylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol with fatty acids such as caproic acid, caprylic acid, lauric acid, capric acid, myristic acid, palmitic acid, stearic acid and oleic acid. It is done.
- animal and plant base oils include castor oil, olive oil, cacao butter, sesame oil, rice bran oil, safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, palm oil, palm kernel oil, sunflower oil, cottonseed oil and palm.
- vegetable oils such as oil, beef tallow, pork fat, milk fat, fish oil and whale oil.
- it is preferable that it is a mineral base oil and a chemically synthesized base oil, and it is more preferable that it is a mineral base oil.
- the lubricating oil composition of the present invention is obtained by adding the lubricating composition of the present invention to a base oil.
- the effect of the present invention is that molybdenum dithiocarbamate (A) and a copolymer (B) are used in combination. It is obtained by. Therefore, a lubricant composition containing molybdenum dithiocarbamate (A) and copolymer (B) may be added to the base oil at the same time, and an additive containing molybdenum dithiocarbamate (A) in the base oil; You may add the additive containing a copolymer (B) separately.
- the lubricating oil composition of the present invention can be appropriately used with known lubricating oil additives depending on the purpose of use.
- lubricating oil additives include ash dispersants, antiwear agents, antioxidants, viscosity index improvers, pour point depressants, rust inhibitors, corrosion inhibitors, metal deactivators, and antifoaming agents. These additives may be used alone or in combination of two or more compounds, and the total amount of additives used is preferably 0.01 to 40% by mass based on the lubricating oil composition.
- metal detergents include sulfonates such as calcium, magnesium, and barium, phenates, salicylates, phosphates, and overbased salts thereof. Of these, overbased salts are preferred, and among the overbased salts, those having a TBN (total basic number) of 10 to 500 mgKOH / g are more preferred.
- a preferable blending amount of these metallic detergents is 0.5 to 10% by mass, more preferably 1 to 8% by mass with respect to the base oil.
- any ashless dispersant used in lubricating oils can be used without particular limitation. For example, a linear or branched alkyl group having 40 to 400 carbon atoms or an alkenyl group can be used.
- a nitrogen-containing compound having at least one in the molecule, or a derivative thereof include succinimide, succinic amide, succinic ester, succinic ester-amide, benzylamine, polyamine, polysuccinimide, and Mannich base, and derivatives thereof include boron compounds.
- examples thereof include boron compounds such as acids and borates, phosphorus compounds such as thiophosphoric acid and thiophosphate, organic acids and hydroxypolyoxyalkylene carbonate. When the carbon number of the alkyl group or alkenyl group is less than 40, the solubility of the compound in the lubricating base oil may be reduced.
- the lubricating oil composition The low temperature fluidity of the product may deteriorate.
- a preferable blending amount of these ashless dispersants is 0.5 to 10% by mass, more preferably 1 to 8% by mass with respect to the base oil.
- antiwear agent examples include sulfurized fats and oils, olefin polysulfides, sulfurized olefins, dibenzyl sulfide, ethyl-3-[[bis (1-methylethoxy) phosphinothioyl] thio] propionate, tris-[(2, or 4) -Isoalkylphenol] thiophosphate, 3- (di-isobutoxy-thiophosphorylsulfanyl) -2-methyl-propionic acid, triphenylphosphorothionate, ⁇ -dithiophosphorylated propionic acid, methylenebis (dibutyldithiocarbamate) ), O, O-diisopropyl-dithiophosphorylethyl propionate, 2,5-bis (n-nonyldithio) -1,3,4-thiadiazole, 2,5-bis (1,1,3,3- Tetramethylbutanethio) 1,3,4-
- R 7 to R 10 each independently represents a primary alkyl group, secondary alkyl group, or aryl group having 1 to 20 carbon atoms.
- R 7 to R 10 each independently represents a hydrocarbon group having 1 to 20 carbon atoms.
- examples of such groups include a methyl group, an ethyl group, a propyl group, a butyl group, and pentyl.
- antioxidants examples include 2,6-di-tert-butylphenol (hereinafter, tert-butyl is abbreviated as t-butyl), 2,6-di-tert-butyl-4-methylphenol, 2, 6-di-t-butyl-4-ethylphenol, 2,4-dimethyl-6-t-butylphenol, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-bis ( 2,6-di-tert-butylphenol), 4,4′-bis (2-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2 '-Methylenebis (4-ethyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 4,4'-isopropylidenebis (2,6-di-t-) Tilphenol), 2,2'-methylenebis (4-methyl-6-
- viscosity index improver examples include poly (C1-18) alkyl methacrylate, (C1-18) alkyl acrylate / (C1-18) alkyl methacrylate copolymer, and dimethylaminoethyl methacrylate / (C1-18) alkyl methacrylate.
- Polymer ethylene / (C1-18) alkyl methacrylate copolymer, polyisobutylene, polyalkylstyrene, ethylene / propylene copolymer, styrene / maleic ester copolymer, styrene / isoprene hydrogenated copolymer, olefin copolymer (OCP) and a star polymer.
- a dispersion-type or multifunctional viscosity index improver imparted with dispersion performance may be used.
- the weight average molecular weight is about 10,000 to 1,500,000, preferably about 20,000 to 500,000.
- a preferred blending amount of these viscosity index improvers is 0.1 to 20% by mass, more preferably 0.3 to 15% by mass with respect to the base oil.
- pour point depressant examples include polyalkyl methacrylate, polyalkyl acrylate, polyalkyl styrene, ethylene-vinyl acetate copolymer and polyvinyl acetate, and the weight average molecular weight is 1,000 to 100,000, preferably It is about 5,000 to 50,000.
- a preferable blending amount of these pour point depressants is 0.005 to 3% by mass, more preferably 0.01 to 2% by mass with respect to the base oil.
- rust preventive examples include sodium nitrite, oxidized paraffin wax calcium salt, oxidized paraffin wax magnesium salt, beef tallow fatty acid alkali metal salt, beef tallow fatty acid alkaline earth metal salt, alkenyl succinic acid, alkenyl succinic acid half ester (alkenyl group).
- alkenyl succinic acid alkenyl succinic acid half ester (alkenyl group).
- sorbitan monoester nonylphenol ethoxylate, and lanolin fatty acid calcium salt.
- a preferable blending amount of these rust preventives is 0.01 to 3% by mass, more preferably 0.02 to 2% by mass with respect to the base oil.
- corrosion inhibitor and metal deactivator examples include 2-hydroxy-N- (1H-1,2, which is a triazole, tolyltriazole, benzotriazole, benzimidazole, benzothiazole, benzothiadiazole or a derivative of these compounds.
- antifoaming agents examples include polydimethyl silicone, dimethyl silicone oil, trifluoropropyl methyl silicone, colloidal silica, polyalkyl acrylate, polyalkyl methacrylate, alcohol ethoxy / propoxylate, fatty acid ethoxy / propoxylate, and sorbitan partial fatty acid ester. Is mentioned.
- a preferable blending amount of these antifoaming agents is 0.001 to 0.1% by mass, more preferably 0.001 to 0.01% by mass with respect to the base oil.
- the lubricating oil composition of the present invention includes vehicle lubricating oil (for example, gasoline engine oil, diesel engine oil, etc. for automobiles and motorcycles), industrial lubricating oil (for example, gear oil, turbine oil, oil film bearing oil, refrigerator). Lubricating oil, vacuum pump oil, compression lubricating oil, multipurpose lubricating oil, etc.).
- vehicle lubricating oil for example, gasoline engine oil, diesel engine oil, etc. for automobiles and motorcycles
- industrial lubricating oil for example, gear oil, turbine oil, oil film bearing oil, refrigerator.
- Lubricating oil, vacuum pump oil, compression lubricating oil, multipurpose lubricating oil, etc. is preferably used for vehicle lubricating oil because the effects of the present invention are easily obtained.
- Organic Molybdenum Compound I Molybdenum Dithiocarbamate (A) -1)
- the monomer raw material used when manufacturing the copolymer used by a present Example and a comparative example is as follows.
- Copolymers (B) -1 to (b) -8 are copolymers (B) that can be used in the lubricant composition of the present invention.
- Copolymers (B ′)-1 to (B ′) ) -4 is a copolymer (B ′) used in the comparative example.
- the GPC of the copolymers (B) -1 to (B) -8 and (B ′)-1 to (B) -4 ′ was measured under the following conditions.
- GPC apparatus Semicro HPLC 7400 (manufactured by GL Sciences) Column: 4 columns of GPCKF-401HQ, GPCKF-402.5, GPCLF-404, and GPCLF-404 are connected in series. (All are made by Showa Denko KK) Detector: GL-7454 (manufactured by GL Sciences) Flow rate: 0.3 ml / min Sample concentration: 0.2% by mass (THF solution) Sample volume: 5 ⁇ l Column temperature: 40 ° C Standard sample: Polystyrene
- the mixture was reacted for 5 hours to obtain a copolymer (B) -1.
- the constituent ratio of the unit (a) represented by the general formula (2) of the copolymer (B) -1 and the unit (b) represented by the general formula (3) is 60/40 (molar ratio).
- the weight average molecular weight in terms of styrene was 61,000.
- Copolymers (B) -2 to (B) -8 and (B ′)-1 to (B) -4 ′ Using the monomer materials described above according to Table 1, copolymer (B) -1 Copolymers (B) -2 to (B) -8 and (B ′)-1 to (B) -4 ′ were synthesized in the same manner as described above. In addition, when manufacturing each copolymer, the quantity of the initiator, the kind of solvent, etc. were adjusted suitably, and the copolymer of the composition and molecular weight which are shown in Table 1 was obtained.
- Test condition load 1.96N Maximum contact pressure 0.5 GPa Sliding speed 10mm / second amplitude 10mm Test distance 600 reciprocating test temperature 80 °C Test material: Ball ⁇ 12.7mm (1/2 inch) SUJ2 Test material plate: SUJ2
- a lubricating oil composition containing molybdenum dithiocarbamate (A) -1 or (A) -2 represented by general formula (1) and any of copolymers (B) -1 to (B) -8 was found to exhibit a high friction reducing effect under severe conditions where a large contact surface pressure is applied.
- the lubricating oil composition No. 22 (Comparative Example 9) and lubricating oil composition no. No. 24 (Comparative Example 11) could not be evaluated because the copolymers (B ′)-1 and (B ′)-3 were not dissolved in the engine oil and a precipitate was formed.
- the lubricant composition of the present invention is an additive for lubricating oil that exhibits a high friction reducing effect even under severe conditions where a large contact surface pressure is applied by using molybdenum dithiocarbamate and an acrylic polymer together.
- the present invention is very useful because it can be used as a vehicle lubricant or an industrial lubricant and can be used in various applications in the future.
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Abstract
Description
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であれば特に制限なく用いることができるが、例えば、炭素数40~400の直鎖、若しくは分枝状のアルキル基、又はアルケニル基を分子中に少なくとも1個有する含窒素化合物、又はその誘導体等が挙げられる。具体的には、コハク酸イミド、コハク酸アミド、コハク酸エステル、コハク酸エステル-アミド、ベンジルアミン、ポリアミン、ポリコハク酸イミド及びマンニッヒ塩基等が挙げられ、その誘導体としては、これら含窒素化合物にホウ酸、ホウ酸塩等のホウ素化合物、チオリン酸、チオリン酸塩等のリン化合物、有機酸及びヒドロキシポリオキシアルキレンカーボネート等を作用させたもの等が挙げられる。アルキル基又はアルケニル基の炭素数が40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する場合があり、一方、アルキル基又はアルケニル基の炭素数が400を越える場合は、潤滑油組成物の低温流動性が悪化する場合がある。これらの無灰分散剤の好ましい配合量は、基油に対して0.5~10質量%、より好ましくは1~8質量%である。
以下の有機モリブデン化合物I及びIIは、前述の特開平10-17586号公報に記載の方法で調製した。
有機モリブデン化合物I(モリブデンジチオカルバメート(A)-1)
本実施例及び比較例で使用する共重合体を製造する際に使用したモノマー原料は以下の通りである。
ユニット(a)を形成するモノマー原料
(a)-1:n-ドデシルアクリレート(一般式(2)においてR5=n-ドデシル基となる)
(a)-2:n-オクタデシルアクリレート(一般式(2)においてR5=n-オクタデシル基となる)
(a)-3:n-ブチルアクリレート(一般式(2)においてR5=n-ブチル基となる)
(a)-4:2-エチルヘキシルアクリレート(一般式(2)においてR5=2-エチルヘキシル基となる)
(b)-1:2-ヒドロキシエチルアクリレート(一般式(3)においてR6=エチレン基となる)
(a’)-1:n-ドデシルメタクリレート
(b’)-1:2-ヒドロキシエチルメタクリレート
カラム:GPCKF-401HQ、GPCKF-402.5、GPCLF-404、GPCLF-404の4本のカラムを直列に接続して使用。(いずれも、昭和電工株式会社製)
検出器:GL-7454(GLサイエンス社製)
流量:0.3ml/分
サンプル濃度:0.2質量%(THF溶液)
サンプル量:5μl
カラム温度:40℃
標準サンプル:ポリスチレン
温度計、窒素導入管及び攪拌機を付した容量1000mlの4つ口フラスコに、ユニット(a)を形成するモノマーとして(a)-1を269g(1.12モル)、ユニット(b)を形成するモノマーとして(b)-1を87g(0.75モル)、及び溶媒としてメタノール178g及びジオキサン178gを仕込んだ。フラスコ内を窒素で置換し、開始剤として2,2’-アゾビス(2-メチルプロピオニトリル)を3.3g添加した後、攪拌しながらゆっくり昇温し、85~95℃の温度で還流させながら5時間反応させて共重合体(B)-1を得た。共重合体(B)-1の一般式(2)で表されるユニット(a)と一般式(3)で表されるユニット(b)の構成比は60/40(モル比)であり、GPCで分子量を測定した結果、スチレン換算で重量平均分子量は61,000であった。
前述したモノマー原料を表1に従って使用し、共重合体(B)-1と同様の方法で共重合体(B)-2~(B)-8及び(B’)-1~(B)-4’を合成した。尚、各共重合体を製造する際、開始剤の量や溶媒の種類等を適宜調整し、表1に示す組成及び分子量の共重合体を得ている。
・評価油の調製
大きな接触面圧がかかる厳しい条件での摩擦特性をみる潤滑特性評価を行うため、有機モリブデン化合物I~IV、共重合体(B)-1~(B)-8、(B’)-1~(B)-4’を含有した潤滑剤組成物No.1~No.25を調製し、これらを市販のエンジンオイルに添加し潤滑油組成物No.1~25とした。具体的には、表2及び表3の割合になるよう各潤滑剤組成物No.1~25を市販のエンジンオイルSN GF-5 5W-30(トヨタ自動車株式会社製)に加熱溶解させ、完全に溶解し室温に戻ったサンプルを潤滑油組成物No.1~25としている。表2には本発明の潤滑油組成物No.1~13(実施例1~13)の各成分の配合量を、表3には比較品の潤滑油組成物No.14~25(比較例1~12)の各成分の配合量を示した。また、比較対象として市販のエンジンオイルであるSN GF-5 5W-30(トヨタ自動車株式会社製)のみの評価も同時に行った(比較例13)。
荷重変動型摩擦・摩耗試験機(HEIDON TYPE:HHS2000,新東科学株式会社製)を用い、表2及び表3の実施例1~13及び比較例1~13についてボールオンプレートの往復摺動での摩擦係数を比較した。試験条件は以下の通りであり、試験終了前の100往復の摩擦係数の平均により摩擦低減効果を比較した。結果は、摩擦係数が小さいほど摩擦低減効果が大きいことを示す。結果を表4及び5に示す。
荷重1.96N
最大接触圧力0.5GPa
摺動速度10mm/秒
振幅10mm
試験距離600往復
試験温度80℃
試験材:ボールφ12.7mm(1/2インチ)SUJ2
試験材プレート:SUJ2
Claims (12)
- 下記の一般式(1)で表されるモリブデンジチオカルバメート(A)と、下記の一般式(2)で表されるユニット(a)及び下記の一般式(3)で表されるユニット(b)を必須の構成ユニットとして含み、重量平均分子量が5,000~150,000であり、該ユニット(a)と該ユニット(b)の構成比がモル比で(a)/(b)=50/50~90/10である共重合体(B)を含有する潤滑剤組成物。
- 前記共重合体(B)がユニット(a)及びユニット(b)を合計で90質量%以上含有する請求項1に記載の潤滑剤組成物。
- 前記共重合体(B)がユニット(a)及びユニット(b)から本質的になる、請求項1に記載の潤滑剤組成物。
- 前記共重合体(B)の重量平均分子量が40,000~110,000である、請求項1~3のいずれか一項に記載の潤滑剤組成物。
- 前記共重合体(B)のユニット(a)とユニット(b)の構成比がモル比で(a)/(b)=60/40~80/20である、請求項1~4のいずれか一項に記載の潤滑剤組成物。
- 前記共重合体(B)のユニット(a)における、一般式(2)のR5が、炭素数12~18の第1級アルキル基であり、かつ、ユニット(b)における一般式(3)のR6がエチレン基である、請求項1~5のいずれか一項に記載の潤滑剤組成物。
- 前記共重合体(B)1質量部に対して、モリブデンジチオカルバメート(A)のモリブデン含量が0.005~0.5質量部である、請求項1~6のいずれか一項に記載の潤滑剤組成物。
- 前記モリブデンジチオカルバメート(A)が、一般式(1)のR1~R4がC8H17とC13H27の組み合わせで、C8H17とC13H27のモル比が1:1であり、X1及びX2が硫黄原子、X3及びX4が酸素原子である化合物、又は、一般式(1)のR1~R4がC8H17で、X1及びX2が硫黄原子、X3及びX4が酸素原子である化合物である、請求項1~7のいずれか一項に記載の潤滑剤組成物。
- 基油に、請求項1~8のいずれか一項に記載の潤滑剤組成物を添加した潤滑油組成物。
- 潤滑油組成物中のモリブデン含量が50~5,000質量ppmである、請求項9に記載の潤滑油組成物。
- 更に、前記潤滑油組成物に対し、金属系清浄剤、無灰分散剤、耐摩耗剤、酸化防止剤、粘度指数向上剤、流動点降下剤、防錆剤、腐食防止剤、金属不活性化剤及び消泡剤から選択される1種又は2種以上を合計で、0.01~40質量%含有する、請求項9又は10に記載の潤滑油組成物。
- 下記の一般式(1)で表されるモリブデンジチオカルバメート(A)と下記の一般式(2)で表されるユニット(a)及び下記の一般式(3)で表されるユニット(b)を必須の構成ユニットとして含み、重量平均分子量が5,000~150,000であり、該ユニット(a)と該ユニット(b)の構成比がモル比で(a)/(b)=50/50~90/10である共重合体(B)を組み合わせることを含む、該モリブデンジチオカルバメート(A)の潤滑油内での摩擦低減効果を増強する方法。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112016011524-4A BR112016011524B1 (pt) | 2013-11-22 | 2014-11-05 | Composição lubrificante, e, composição de óleo lubrificante |
JP2015549061A JP6429244B2 (ja) | 2013-11-22 | 2014-11-05 | 潤滑剤組成物及びそれを含有する潤滑油組成物 |
EP14864922.1A EP3072950B1 (en) | 2013-11-22 | 2014-11-05 | Lubricant agent composition and lubricant oil composition containing same |
KR1020167016249A KR102209010B1 (ko) | 2013-11-22 | 2014-11-05 | 윤활제 조성물 및 그를 함유하는 윤활유 조성물 |
US15/038,225 US10087392B2 (en) | 2013-11-22 | 2014-11-05 | Lubricant composition and lubricant oil composition containing same |
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JP6429244B2 (ja) | 2018-11-28 |
CN105745313B (zh) | 2019-05-28 |
EP3072950B1 (en) | 2018-07-11 |
US20160289589A1 (en) | 2016-10-06 |
BR112016011524A2 (pt) | 2017-08-08 |
EP3072950A1 (en) | 2016-09-28 |
JPWO2015076103A1 (ja) | 2017-03-16 |
HK1226091A1 (zh) | 2017-09-22 |
CN105745313A (zh) | 2016-07-06 |
KR102209010B1 (ko) | 2021-01-27 |
BR112016011524B1 (pt) | 2021-07-13 |
EP3072950A4 (en) | 2017-06-07 |
US10087392B2 (en) | 2018-10-02 |
KR20160088910A (ko) | 2016-07-26 |
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