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WO2004041977A1 - Huile lubrifiante - Google Patents

Huile lubrifiante Download PDF

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Publication number
WO2004041977A1
WO2004041977A1 PCT/JP2003/014032 JP0314032W WO2004041977A1 WO 2004041977 A1 WO2004041977 A1 WO 2004041977A1 JP 0314032 W JP0314032 W JP 0314032W WO 2004041977 A1 WO2004041977 A1 WO 2004041977A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
lubricating oil
molecular weight
average molecular
boron
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2003/014032
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English (en)
Japanese (ja)
Inventor
Naozumi Arimoto
Tetsuo Okawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
Original Assignee
Nippon Oil Corp
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Filing date
Publication date
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Application filed by Nippon Oil Corp filed Critical Nippon Oil Corp
Priority to AU2003280701A priority Critical patent/AU2003280701A1/en
Priority to US10/533,710 priority patent/US20060105921A1/en
Priority to EP03770108A priority patent/EP1559772B1/fr
Publication of WO2004041977A1 publication Critical patent/WO2004041977A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
    • 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
    • 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
    • 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
    • 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
    • C10M2209/086—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 polycarboxylic, e.g. maleic acid
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
    • C10M2215/28—Amides; Imides
    • 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
    • C10N2020/02—Viscosity; Viscosity index
    • 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
    • C10N2030/02—Pour-point; Viscosity index
    • 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
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/045—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for continuous variable transmission [CVT]
    • 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
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • the present invention relates to a lubricating oil composition, and more particularly, to a low-viscosity lubricating oil composition having excellent anti-wear properties, and particularly capable of maintaining anti-wear properties for a long period of time.
  • Conventional transmission oils for automobiles include those that can maintain various performances such as transmission characteristics for a long period of time, such as synthetic oil and / or mineral oil-based lubricating base oils, antiwear agents, extreme pressure agents, metal detergents, and none.
  • a compound in which an ash dispersant, a friction modifier and the like have been optimized and blended has been disclosed (see, for example, JP-A-3-39399, JP-A-7-268375, and JP-A-2000-63869).
  • the viscosity index improver is generally selected from those having an average molecular weight of 1,000 to 1,000, 000, and a lubricating oil containing a low molecular weight viscosity index improver.
  • Examples thereof include, for example, 1 to 15% by weight of a monoolefin polymer or copolymer having a number average molecular weight of 1,000 to 10,000, and a saturated aliphatic monovalent having an average molecular weight of 5,000 to 50,000. 1 to 5 mass of an ester copolymer of alcohol and methallylic acid. / 0 and an ethylene / ⁇ -olefin copolymer having a number average molecular weight of 26,000 to 40,000 (see Japanese Patent Application Laid-Open No. 61-9497).
  • the present invention has been made in view of such circumstances, and it is an object of the present invention to provide a lubricating oil composition having low viscosity and sufficient anti-wear properties even after initial and long-term use.
  • An object of the present invention is to provide a low-viscosity lubricating oil composition suitable for an engine or a continuously variable transmission.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a low-viscosity lubricating oil obtained by optimizing and blending a specific nitrogen-containing compound and a viscosity index improver with a specific molecular weight into a lubricating base oil.
  • the inventors have found that the composition can solve the above problems, and have completed the present invention. That is, the present invention provides (A) a lubricating base oil comprising a mineral oil, a synthetic oil or a mixture thereof, and (B) a nitrogen-containing compound having at least one alkyl group or alkenyl group having a number average molecular weight of 900 or more.
  • the index improver is compounded so that the viscosity index of the composition is at least 160 and the kinematic viscosity at 40 ° C of the composition is 20 to 30 mm 2 / s.
  • Lubricating oil composition is a viscosity having a weight average molecular weight of 40,000 or less.
  • the component (B) is preferably a nitrogen-containing compound having two alkyl groups or alkenyl groups having a number average molecular weight of 1200 or more and Z or a derivative thereof.
  • the lubricating oil composition of the present invention may further comprise, as the component (B), a nitrogen-modifying compound, which is a nitrogen-containing compound having at least one alkyl group or alkenyl group having a number average molecular weight of 900 or more. It is preferable that the boron content be 0.02% by mass or more based on the total amount of the substance and essential.
  • a nitrogen-modifying compound which is a nitrogen-containing compound having at least one alkyl group or alkenyl group having a number average molecular weight of 900 or more. It is preferable that the boron content be 0.02% by mass or more based on the total amount of the substance and essential.
  • the boron-modified compound is preferably a boron-modified compound of a nitrogen-containing compound having at least one alkyl group or alkylene group having a number average molecular weight of 1200 or more.
  • the boron-modified compound is preferably a boron-modified compound of a nitrogen-containing compound having two alkyl groups or alkoxyl groups having a number average molecular weight of 1200 or more. Further, the boron-modified compound is preferably a boron-modified compound of a nitrogen-containing compound having two alkyl groups or two alkenyl groups having a number average molecular weight of 170 or more.
  • the mass ratio (B / N ratio) of boron and nitrogen in the boron-modified compound is preferably 0.01 to 3.
  • the component (B) is preferably a boron-modified succinimide of a bis-type succinimide having a poly (iso) butenyl group having a number average molecular weight of 20 ° 0 or more.
  • the component (B) is a bis-type succinimide having a poly (iso) butenyl group having a number average molecular weight of 900 to less than 200, and a number average molecular weight of 200 or more.
  • the lubricating oil composition of the present invention is preferably used for an automatic transmission or a continuously variable transmission.
  • the present invention also relates to a method for maintaining wear resistance of an automatic transmission or a continuously variable transmission, wherein the method uses the lubricating oil composition.
  • the component (A) in the present invention is a lubricating base oil composed of mineral oil, synthetic oil, or a mixture thereof, and is not particularly limited, and is usually used as a base oil of a lubricating oil composition. If used, mineral oil and synthetic oil can be used.
  • mineral base oils lubricating oil fractions obtained by atmospheric and vacuum distillation of crude oil are subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining. And paraffinic and naphthenic mineral oil-based lubricating base oils and normal paraffins, which are appropriately combined with refining treatments such as sulfuric acid washing and clay treatment.
  • Examples of synthetic base oils include poly- ⁇ -olefin (polybutene, 1-octene oligomer, 1-decene oligomer, ethylene-propylene oligomer, etc.) and hydrides, isobutene oligomers and the like.
  • isoparaffins alkylbenzenes, alkylnaphthalenes, diesters (ditridecyl glutarate, di-2-ethylhexyl adipate, disodecyl adipate, ditridecyl adipate, di-21-ethylhexyl sebacate, etc.), polyols Esters (trimethylolpropane caprylate, trimethylolpropaneperalgonate, pentaerythritol tonole 2-ethylhexanoate, pentaerythritol peralgonate, etc.), polyoxyalkylene glycolonole, dianolequinolesiphenylenole Athenole, polypheninoleatenole and the like.
  • the lubricating base oil of the present invention may be a mixture of two or more mineral base oils or a mixture of two or more kinds of synthetic base oils, and may be a mixture of a mineral base oil and a synthetic base oil. It does not matter.
  • the mixing ratio of two or more base oils in the above mixture can be arbitrarily selected.
  • the kinematic viscosity of these lubricating base oils in the present invention is not particularly limited, the lower limit of the kinematic viscosity at 100 ° C. is l mm 2 Zs, preferably 2 mm 2 / s.
  • the upper limit of the kinematic viscosity at 100 ° C. is desirably 5 mm 2 Zs, preferably 4 mm 2 / s, and particularly preferably 3.5 mm 2 / s.
  • the viscosity index of these lubricating base oils in the present invention is not particularly limited, but the viscosity index is desirably 80 or more, preferably 90 or more, and particularly preferably 110 or more. By setting the viscosity index to 80 or more, it is possible to obtain a composition having excellent anti-wear properties after long-term use.
  • the component (B) of the present invention is a nitrogen-containing compound having at least one alkyl group or alkenyl group having a number average molecular weight of 900 or more and Z or a derivative thereof, and one or two selected arbitrarily from these. More than one kind can be blended.
  • component (B) specifically, for example,
  • (B-1) a succinimide having at least one alkyl group or alkenyl group having a number average molecular weight of 900 or more or a derivative thereof
  • (B-2) Benzylamine having at least one alkyl or alkenyl group having a number average molecular weight of 900 or more or a derivative thereof
  • (B-3) a polyamine having at least one alkyl group or alkenyl group having a number average molecular weight of 900 or more or a derivative thereof
  • examples of the above-mentioned (B-1) succinimide include compounds represented by the following formula (1) or (2).
  • R 1 represents an alkyl group or an alkenyl group having a number average molecular weight of 900 or more, and a represents an integer of 1 to 5, preferably 2 to 4.
  • R 2 and R 3 each independently represent an alkyl group or an alkenyl group having a number average molecular weight of 900 or more, and b represents an integer of 0 to 4, preferably 1 to 3.
  • the imidized succinic acid is a so-called mono-type succinimide as shown in the formula (1) in which succinic anhydride is added to one end of a polyamine when imidization is performed.
  • the component (B-1) any of them can be used. It is preferable to use a bis-type, that is, a succinimide having two alkyl groups or alkenyl groups having a number average molecular weight of 900 or more, because the anti-wear property is easily maintained.
  • examples of the above (B-2) benzylamine include compounds represented by the following formula (3).
  • R 4 represents an alkyl group or an alkenyl group having a number average molecular weight of 900 or more, and c represents an integer of 1 to 5, preferably 2 to 4.
  • the method for producing this benzylamine is not limited at all.
  • a polyolefin such as a propylene oligomer, a polybutene, or an ethylene-a-olefin copolymer is reacted with a phenol to form an alkylphenol, which is then subjected to formaldehyde.
  • polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine by reacting with a Mannich reaction.
  • examples of the polyamine (B-3) include compounds represented by the following formula (4).
  • R 5 represents an alkyl group or an alkenyl group having a number average molecular weight of 900 or more, and d is 1 to 5, preferably 2 to 5. Indicates an integer of 4.
  • the method for producing the polyamine is not limited at all.
  • a polyolefin such as propylene oligomer, polybutene, and ethylene- ⁇ -olefin copolymer
  • ammonia ethylenediamine, diethylenetriamine, trie
  • a polyamine such as tylenetetramine, tetraethylenepentamine or pentaethylenehexamine.
  • the nitrogen-containing compound as described above may have 2 to 30 carbon atoms.
  • a boron compound such as boric acid, a borate or a borate ester is allowed to act on the above-mentioned nitrogen-containing compound to remove residual amino and / or imino groups.
  • a so-called boron-modified compound in which part or all of the compound has been neutralized or amidified a sulfur-modified compound obtained by reacting a sulfur-containing compound with the above-described nitrogen-containing compound; and an acid-modified nitrogen-containing compound as described above. , Boron-modified, and sulfur-modified conjugates.
  • the alkyl group or alkenyl group having a number average molecular weight of 900 or more in the component (II) of the present invention may be linear or branched, but preferred examples thereof include propylene, 1 Olefin oligomers such as butene and isobutylene, and branched alkyl and branched alkenyl groups derived from ethylene and propylene co-oligomers, preferably poly (iso) butenyl groups, and their number average molecular weight Is preferably 1 2 It is at least 0, more preferably at least 1,700, still more preferably at least 2,000, particularly preferably at least 2,300.
  • the upper limit of the number average molecular weight is not particularly limited, but is preferably 500 or less, more preferably 350 or less, and particularly preferably 300 or less.
  • the number average molecular weight of the alkyl group or alkenyl group is preferably 900 or more, it is easy to maintain the wear resistance after long-term use, and by setting the number average molecular weight to 500 or less, the composition has excellent low-temperature fluidity. You can get things.
  • the nitrogen content of the nitrogen-containing compound of component (B) is arbitrary, but from the viewpoints of wear resistance, oxidation stability and friction characteristics, the nitrogen content is usually 0.01 to 10% by mass. , Preferably 0 .: to 10% by mass.
  • an alkyl or alkenyl succinimide having the number average molecular weight as described above can be more preferably used because the anti-wear property is easily maintained.
  • the number-average molecular weight particularly the number-average molecular weight of 200 or more alkyl- or boron-modified compound of alkielsuccinimide is excellent in wear prevention properties at the initial stage and after long-term use, It is particularly preferable to include the boron-modified compound as an essential component.
  • the mass ratio (B / N ratio) of boron and nitrogen in the boron-modified compound of the nitrogen-containing compound is not particularly limited, and is usually 0.01 to 3, but is preferably 0.05 or more. , More preferably 0.1 or more, further preferably 0.2 or more, and preferably 1 or less, more preferably 0.8 or less, and still more preferably 0.6 or less. .
  • a boron-modified compound having a BZN ratio within the above range, it is possible to obtain a composition having excellent anti-wear properties even after initial use and after long-term use.
  • the nitrogen-containing compound and its boron-modified carboxylic acid compound are used in combination, for example, a bis-type succinic acid having a poly (iso) butyr group having a number average molecular weight of 900 to less than 2000 is preferred.
  • a bis-type succinic acid having a poly (iso) butyr group having a number average molecular weight of 900 to less than 2000 is preferred.
  • the imide is used in combination with a boron-modified compound of a bis-type poly (iso) butercosuccinimide having a number-average molecular weight of 2000 or more, synergistically improve the anti-wear properties during initial and long-term use. Can be. Even in such a case, it is preferable that the mass ratio of boron caused by the boron-modified compound to the total nitrogen caused by the component (B) is also in the above range.
  • the lower limit of the content of the component (B) is the total amount of the lubricating oil composition.
  • the amount of nitrogen is 0.01% by mass, preferably 0.02% by mass.
  • the upper limit of the content is 0.2% by mass as the amount of nitrogen based on the total amount of the lubricating oil composition. It is preferably 0.18% by mass. If the content of the component (B) is less than 0.01% by mass in terms of nitrogen based on the total amount of the lubricating oil composition, it is difficult to maintain the wear prevention after long-term use due to the component (B).
  • the content exceeds 2% by mass, the low-temperature fluidity of the lubricating oil composition deteriorates, which is not preferable.
  • the component (B) is a nitrogen-containing compound having two alkyl groups or alkenyl groups having a number average molecular weight of 1200 or more
  • the upper limit of the content can be set to 0.07% by mass or less.
  • sufficient anti-wear properties can be exhibited even if the content is 0.04% by mass or less.
  • the lower limit of the content is preferably 0.002% by mass or more, more preferably 0.1% by mass or more, as the amount of boron. It is at least 004 mass%, particularly preferably at least 0.008 mass%.
  • the upper limit of the content is preferably 0.05 mass in terms of boron. / 0 or less, more preferably 0.02% by mass or less, particularly preferably 0.015% by mass or less.
  • the component (C) in the present invention is a viscosity index improver having a weight average molecular weight of 40,000 or less, specifically, a non-dispersion type viscosity index improver having a weight average molecular weight of 40,000 or less and / or a dispersion type. And viscosity index improvers.
  • non-dispersion type viscosity index improver specifically, one or two or more monomers (C—) selected from the compounds represented by the following formulas (5), (6) and (7) Examples thereof include the copolymer (1) and hydrides thereof.
  • dispersion-type viscosity index improver specifically, a copolymer of two or more monomers selected from the compounds represented by the general formulas (8) and (9) or a hydride thereof is used. With an oxygen-containing group introduced into the compound of the general formula (5)
  • R 6 represents hydrogen or a methyl group
  • R 7 represents an alkyl group having 1 to 18 carbon atoms.
  • R 8 represents a hydrogen or a methyl group
  • 1 9 represents a number 1 to 1 2 hydrocarbon group having a carbon.
  • hydrocarbon group having 1 to 12 carbon atoms for R 9 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group.
  • decyl, pendecyl, dodecyl, and other alkyl groups (these alkyl groups may be straight-chain or branched); butenyl, pentyl, hexenyl, heptenyl, otathenyl, nonenyl, Alkenyl groups such as decenyl group, pendecenyl group and dodecenyl group (these alkenyl groups may be linear or branched, and the position of the double bond is arbitrary); cyclopentyl group, cyclohexyl group, cyclohexyl group C5-C7 cycloalkyl group such as butyl group; methylcyclopentyl group, dimethylcyclopentyl group, pentyl group of methyl ethynoleic mouth, ethynole Pennole group, Methylhexyl group, Methylhexyl group, Methylethylhe
  • Aryl groups trialkyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl and other alkylaryl groups having 7 to 12 carbon atoms (these alkyl groups are linear Or the position of substitution on the aryl group is arbitrary); C 7 carbon atoms such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, and phenylhexyl groups; To 12 phenylalkyl groups (the alkyl groups may be linear or branched); and the like.
  • 0 1 ⁇ Pi 13 2 are each independently a hydrogen atom, residue of ⁇ Le Kill alcohol having a carbon number of 1 to 1 8 (_ ⁇ _R: R is alkyl having 1 to 1 8 carbon atoms Group) or a residue of a monoalkylamine having 1 to 18 carbon atoms (one NHR: R is an alkyl group having 1 to 18 carbon atoms).
  • R 10 represents a hydrogen atom or a methyl group
  • R 11 represents an alkylene group having 1 to 18 carbon atoms
  • £ 1 represents 1 to 2 nitrogen atoms and an oxygen atom. It shows 0 to 2 amide residues or heterocyclic residues.
  • E is an integer of 0 or 1.
  • alkylene group having 8 to 8 carbon atoms examples include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an otathylene group, a nonylene group, a decylene group, a decylene group, Dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octa And decylene groups (these alkylene groups may be linear or branched).
  • Specific examples of the group represented by E 1 include a dimethylamino group, a dimethylamino group, a dipropylamino group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group, an acetylamino group, a benzoylamino group, a morpholino group, a pyrrolyl group, Examples thereof include a pyrrino group, a pyridyl group, a methylpyridyl group, a pyrrolidinyl group, a piperidinyl group, a quinonyl group, a pyrrolidonyl group, a pyrrolidno group, an imidazolino group, and a virazino group.
  • R 12 represents a hydrogen atom or a methyl group
  • E 2 represents an amine residue or a heterocyclic residue containing 1 to 2 nitrogen atoms and 0 to 2 oxygen atoms. I have.
  • group representing E 2 examples include a dimethylamino group, a dimethylamino group, a dibutylamino group, a dibutylamino group, an anilino group, a toluidino group, a xylidino group, an acetylamino group, a benzoylamino group, a morpholino group, a pyrrolyl group, and a pyrrolino group.
  • pyridyl group methylpyridyl group, pyrrolidinyl group, piperidinyl group, quinonyl group, pyrrolidonyl group, pyrrolidno group, imidazolino group, virazino group and the like.
  • Preferred as the monomer of the (C-1) component are, specifically, alkyl acrylates having 1 to 18 carbon atoms, alkyl methacrylates having 1 to 18 carbon atoms, and olefins having 2 to 20 carbon atoms. , Styrene, methstyrene, maleic anhydride ester, maleic anhydride amide, and mixtures thereof.
  • Preferred as the monomer of the component (C-12) are, specifically, dimethylaminomethyl methacrylate, dimethylaminomethyl methacrylate, dimethylaminomethyl methacrylate, dimethylaminomethyl methacrylate, 2-methyl_ Examples thereof include 5-vinylpyridine, morpholinomethyl methacrylate, morpholinoethyl methacrylate, vinylvinylpyrrolidone, and mixtures thereof.
  • the molar ratio between the (C-11) component and the (C-12) component is arbitrary, but in general, 80: 20 to 95: It is about 5.
  • the reaction method of the copolymerization is also optional, but usually, the component (C-11) and the component (C-2) are subjected to radical solution polymerization in the presence of a polymerization initiator such as benzoyl peroxide. A copolymer can be easily obtained.
  • component (C) examples include non-dispersible and dispersed polymethacrylates, non-dispersed and dispersed ethylene-monoolefin copolymers and hydrides thereof, polyisobutylene and hydrides thereof, and styrene-digen hydrogen. Copolymerized copolymer, styrene-maleic anhydride copolymer, polyalkylstyrene and the like.
  • the molecular weight of the component (C) is 40,000 or less, preferably 35,000 or less in terms of weight average molecular weight. If the weight average molecular weight exceeds 40,000, it is not preferable because the abrasion resistance after long-term use is poor.
  • the weight average molecular weight of the component (C) is not particularly limited and may be 900 or more, but is preferably 10,000 or more, and more preferably 20,000 or more.
  • a viscosity index improver having a weight average molecular weight of less than 10,000 of the component for example, polyisobutylene having a weight average molecular weight of 900 to less than 10,000 has a small effect of improving the viscosity index and needs to be blended in a large amount for a long time. Since it is difficult to maintain the anti-wear property after use, the weight average molecular weight of the component (C) is preferably 10,000 or more.
  • the component (C) in the present invention is particularly preferable because a non-dispersible polymethacrylate having a weight average molecular weight of 10,000 to 40,000 easily maintains abrasion resistance after long-term use.
  • the content of the component (C) in the lubricating oil composition of the present invention is desirably set so that the viscosity index of the composition is 160 or more, preferably 165 or more.
  • kinematic viscosity of at 40 ° C of the composition it is necessary to contain the amount of component (C) such that 20 to 30 mm 2 / s, as preferably, as a 22 ⁇ 28 mm 2 / s Is desirably contained.
  • the content is 1% by mass or more, preferably 5% by mass or more, particularly preferably 6% by mass or more, and 20% by mass or less. Below, preferably 15% by mass or less, particularly preferably 12% by mass or less.
  • the viscosity index of the composition is less than 160, the abrasion resistance after long-term use deteriorates, which is not preferable. If the kinematic viscosity at 40 ° C is less than the above range, the initial and long-term If the kinematic viscosity at 40 ° C. exceeds the above range, the anti-wear property after use deteriorates, and it is difficult to obtain fuel economy due to reduced stirring resistance.
  • the component (A) is used as a base oil, the component (B) is blended in a specific amount, and the component (C) is added to the composition at a viscosity index of at least 160 and at a temperature of 40 ° C of the composition.
  • Such additives include antiwear agents or extreme pressure agents, metal detergents, friction modifiers, deterrent agents, corrosion inhibitors, pour point depressants, rubber swelling agents, antifoaming agents, coloring agents, etc. Can be mentioned. These compounds can be used alone or in combination of several kinds.
  • antiwear agent or extreme pressure agent that can be used in combination with the lubricating oil composition of the present invention include antiwear agents or extreme pressure agents for lubricating oils such as sulfur additives, phosphorus additives, sulfur and phosphorus additives.
  • any compound commonly used as an agent for example, sulfur compounds such as disulphides, sulfides, sulfuric oils and fats, monophosphates, diesters, and triesters , Phosphite monoesters, phosphite diesters, phosphite triesters, phosphorus compounds such as salts of these esters with amines or alkanolamines, zinc dithiophosphate, thiophosphoric acid Sulfur and phosphorus compounds such as esters can be used.
  • the content of these wear inhibitors or extreme pressure agents is not particularly limited, but is usually 0.01 to 5.0% by mass based on the total amount of the lubricating oil composition.
  • any compound that is commonly used as a metal-based detergent for lubricating oils can be used.
  • alkali metal or alkaline earth metal can be used.
  • Sulfonates, phenates, salicylates, naphthenates and the like can be used alone or in combination of two or more in the composition of the present invention.
  • sodium potassium is exemplified as the alkali metal
  • calcium, magnesium, etc. are exemplified as the alkaline earth metal.
  • calcium or Gnesium sulfonates, phenates and salicylates are preferably used.
  • the total base number and content of these metallic detergents can be arbitrarily selected according to the required lubricating oil performance, but the total base number is usually 0 to 500 mg KOH by the perchloric acid method. The content is 0.01 to 10% by mass.
  • any compound that is usually used as a friction modifier for lubricating oils can be used, and an alkyl group or alkenyl having 6 to 30 carbon atoms can be used.
  • examples thereof include amine compounds, fatty acid esters, fatty acid amides, and fatty acid metal salts having at least one group, particularly a straight-chain alkyl group or a straight-chain alkenyl group having 6 to 30 carbon atoms, in the molecule.
  • Examples of the amine compound include linear or branched, preferably linear, aliphatic monoamines having 6 to 30 carbon atoms, linear or branched, preferably linear, aliphatic polyamines, or these. Examples thereof include alkylene oxide adducts of aliphatic amines.
  • Examples of the fatty acid ester include esters of a linear or branched, preferably linear, fatty acid having 7 to 31 carbon atoms with an aliphatic monohydric alcohol or an aliphatic polyhydric alcohol.
  • Examples of the fatty acid amide include an amide of a linear or branched, preferably linear, fatty acid having 7 to 31 carbon atoms and an aliphatic monoamine or an aliphatic polyamine.
  • fatty acid metal salts examples include alkali earth metal salts (such as magnesium salts and calcium salts) and zinc salts of linear or branched, preferably linear, fatty acids having 7 to 31 carbon atoms. .
  • alkali earth metal salts such as magnesium salts and calcium salts
  • one or more compounds arbitrarily selected from these friction modifiers can be contained in an arbitrary amount. It is desirably 0.01 to 5.0% by mass, preferably 0.03 to 3.0% by mass on the basis.
  • any compounds generally used in lubricating oils such as phenolic compounds and amine compounds can be used.
  • alkyl phenols such as 2-6-di-tert-butyl-4-methylphenol, and bisphenols such as methylene-1,4,4-bisphenol (2,6-di-tert-butyl-4-methylphenol)
  • Naphthylamines such as phenyl ⁇ -naphthylamine
  • dialkyldiphenylamines zinc dialkyldithiophosphates such as zinc di-diethylhexyldithiophosphate
  • One or more compounds arbitrarily selected from these can be contained in any amount, but usually the content is 0.01 to 0.1% based on the total amount of the lubricating oil composition. 5.0 mass. / 0 is desirable.
  • any compound that is usually used as a corrosion inhibitor for lubricating oils can be used.
  • examples thereof include benzotriazole-based and tritritriazole-based compounds.
  • One or two or more compounds arbitrarily selected from these can be contained in an arbitrary amount, but usually, the content is 0.01 to 0.1% based on the total amount of the lubricating oil composition. Desirably, the mass is 3.0 / 0 .
  • any compound that is usually used as an antifoaming agent for lubricating oils can be used. Is mentioned. One or more compounds arbitrarily selected from these can be contained in an arbitrary amount. Usually, the content is 0.001 to 1 based on the total amount of the lubricating oil composition. It is desirably 0.05% by mass.
  • the lubricating oil composition of the present invention has excellent anti-wear properties even after initial and long-term use and can reduce agitation resistance caused by lubricating oil. Therefore, the lubricating oil composition for automobiles, for example, for internal combustion engines and transmissions, By using it for an automatic transmission or a continuously variable transmission, it will be possible to contribute to improving the fuel efficiency of automobiles.
  • Various lubricating base oils and additives shown in Table 1 or Table 2 were blended to form a lubricating oil thread (Examples 1 to 5 in Table 1) according to the present invention and a lubricating oil composition for comparison (Table 1). Comparative Examples 1 to 3) in Table 2 Prepared. The amount of each additive is based on the total amount of the composition.
  • the anti-wear properties at the initial stage and after long-term use were evaluated by the abrasion test shown in the following (1).
  • the new oil was used for the initial evaluation of wear resistance, and the deteriorated oil that had been deteriorated in advance by the ultrasonic shear test shown in (2) was used for the wear resistance evaluation of oil used for a long period.
  • the results of the performance evaluation are also shown in Tables 1 and 2.
  • Non-dispersed polymethacrylate (weight average molecular weight 20,000)
  • Non-dispersed polymethacrylate (weight average molecular weight 30,000)
  • Non-dispersed polymethacrylate (weight average molecular weight 50,000)
  • Non-dispersed polymethacrylate (weight average molecular weight 20,000)
  • Non-dispersed polymethacrylate (weight average molecular weight 30,000)
  • Non-dispersed polymethacrylate (weight average molecular weight 50,000)
  • Package additives including antiwear agents, extreme pressure agents, metal detergents, corrosion inhibitors, antioxidants, friction modifiers, rubber swelling agents, defoamers, etc.
  • Example 4 When the compound was used as an essential component (Examples 4 and 5), the composition of Example 1 showed superior results in terms of antiwear properties even after initial and long-term use. Furthermore, when the succinic acid imid used in Example 1 and the boron-modified compound of succinimide used in Example 5 were used together (Example 4), the anti-wear performance was synergistically improved. Met. In contrast, when the content of the component (B) is less than the specified range of the present invention (Comparative Example 1), when the viscosity index of the composition is less than 160 (Comparative Example 2), When the weight-average molecular weight exceeds 40,000 (Comparative Example 3), the anti-wear property of the deteriorated oil is also poor when the fresh oil is used. When the kinematic viscosity at 40 ° C. of the composition was less than 20, the result was that the anti-wear property was even worse than that of the comparative example. Industrial applicability
  • the lubricating oil composition of the present invention has a low viscosity but has excellent anti-wear properties even after initial and long-term use, and can reduce agitation resistance caused by lubricating oil. By using it for transmissions, especially for automatic transmissions or continuously variable transmissions, it is possible to contribute to improving the fuel efficiency of vehicles. Also, lubricating oils for machinery and equipment other than automobiles can reduce the energy consumption of machinery and equipment while maintaining anti-wear properties, such as for wet brakes, hydraulic actuators, It is useful for various applications such as compressors, turbines, gears, refrigerators and bearings.

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

Abstract

Composition d'huile lubrifiante contenant (A) une huile de base d'huile lubrifiante comprenant une huile minérale, une huile synthétique ou leur mélange, (B) un composé contenant de l'azote et possédant au moins un groupe alkyle ou alkenyle et un poids moléculaire moyen en nombre égal ou supérieur à 900 et/ou un des ses dérivés en quantité de 0,01 à 0,20 % massique en teneur d'azote sur la base de la quantité totale de la composition, et (C) un amplificateur d'indice de viscosité possédant un poids moléculaire moyen en poids égal ou inférieur à 40000 et un indice de viscosité égal ou supérieur à 160, ainsi qu'une viscosité cinématique à 40 °C de 20 à 30 mm2/s. Cette composition d'huile lubrifiante présente une viscosité basse et peut présenter d'excellentes caractéristiques anti-usure à la fois à un stade précoce d'utilisation et après une durée prolongée, ce qui permet de la mettre avantageusement en application dans une transmission automatique ou dans une transmission variable en continu.
PCT/JP2003/014032 2002-11-05 2003-10-31 Huile lubrifiante Ceased WO2004041977A1 (fr)

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AU2003280701A AU2003280701A1 (en) 2002-11-05 2003-10-31 Lubricating oil
US10/533,710 US20060105921A1 (en) 2002-11-05 2003-10-31 Lubricating oil
EP03770108A EP1559772B1 (fr) 2002-11-05 2003-10-31 Huile lubrifiante

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JP2002321754A JP4571776B2 (ja) 2002-11-05 2002-11-05 潤滑油組成物

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EP1559772A4 (fr) 2008-09-03
CN100455646C (zh) 2009-01-28
JP2004155873A (ja) 2004-06-03
EP1559772A1 (fr) 2005-08-03
EP1559772B1 (fr) 2013-03-06
CN1711345A (zh) 2005-12-21
AU2003280701A1 (en) 2004-06-07
US20060105921A1 (en) 2006-05-18
JP4571776B2 (ja) 2010-10-27

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