WO2004111162A1 - Composition lubrifiante pour moteur a combustion interne - Google Patents

Composition lubrifiante pour moteur a combustion interne Download PDF

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Publication number
WO2004111162A1
WO2004111162A1 PCT/JP2004/007337 JP2004007337W WO2004111162A1 WO 2004111162 A1 WO2004111162 A1 WO 2004111162A1 JP 2004007337 W JP2004007337 W JP 2004007337W WO 2004111162 A1 WO2004111162 A1 WO 2004111162A1
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Prior art keywords
internal combustion
mass
group
combustion engine
lubricating oil
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PCT/JP2004/007337
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English (en)
Japanese (ja)
Inventor
Kazuhiro Yagishita
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Eneos Corp
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Nippon Oil Corp
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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
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
    • C10M2223/061—Metal salts
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines

Definitions

  • the present invention relates to a lubricating oil composition for an internal combustion engine, and more particularly, to a low phosphorus, low sulfur type lubricating oil composition for an internal combustion engine having excellent wear resistance.
  • Lubricating oil is used in internal combustion engines and automatic transmissions to facilitate their operation.
  • lubricating oil (engine oil) for internal combustion engines is used to improve the performance, output, and operating conditions of internal combustion engines. Due to the severeness of the oil, high performance is required, and from the viewpoint of recent environmental problems, improvement of long drainability to extend the oil renewal interval is required. Therefore, in order to satisfy such required performance, various additives such as antiwear agents, metal detergents, ashless dispersants, and antioxidants are blended in conventional engine oils to improve their performance.
  • ZDTP zinc dialkyldithiophosphate
  • an anti-wear and anti-oxidant has been used as an almost essential additive.
  • DPFs Diesel Particulate Filters
  • ILSACGF-4 calls for lowering the phosphorus content to 0.08% by mass or less for compatibility with exhaust gas catalysts, and further reducing phosphorus (for example, studies are ongoing.
  • ILSACGF-5 standard (draft): Phosphorus content 0.05% by mass or less).
  • Patent Document 1 JP-A-62-153691
  • Patent Document 2 Japanese Patent Application Publication No. Hei 11-50910
  • Patent Document 3 Japanese Patent Application Laid-Open No. 6-4-1568
  • Patent Document 4 JP-A-63-304095
  • Patent Document 5 JP-A-63-3-4096
  • Patent Document 6 JP-A-52-704
  • Patent Document 7 Japanese Patent Application Laid-Open No. 62-243692
  • Patent Document 8 JP-T-62-5011917
  • Patent Document 9 JP-T-62-5011572
  • Patent Document 10 Japanese Patent Application Laid-Open No. 2000-1 63862
  • Patent Document 11 Japanese Patent Application Laid-Open No. H8-488989
  • Patent Document 1 Japanese Patent Application Laid-Open No. H8-2 53782
  • Patent Document 14 JP-A-2000-256690
  • the wear-preventing performance is maintained by blending a sulfur-containing compound instead of zinc dithiophosphate. It increases the sulfur content of the composition, which has an adverse effect on exhaust gas aftertreatment equipment, ie, purification of exhaust gas from oxidation catalysts, three-way catalysts, NOx absorption reduction catalysts, etc.
  • the problem of catalyst poisoning due to sulfur such as catalysts, DPFs, or a system combining the above exhaust gas purifying catalyst and DPF, especially an exhaust gas treatment system combining an oxidation catalyst and DPF or a NOx storage reduction catalyst and DPF.
  • the problem of clogging of DPF has not been solved yet, and the oxidation stability, base number maintenance performance, cleanability, etc. of the lubricating oil will be significantly deteriorated.
  • the present invention has been made in view of the above circumstances, and provides a lubricating oil composition for an internal combustion engine having extremely excellent wear resistance even when zinc dithiophosphate is reduced. It is intended to provide an engine lubricating oil.
  • the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, by using a specific phosphorus compound and a specific zinc dithiophosphate together, they are more synergistically resistant than when each is used alone.
  • the present inventors have found that it is possible to improve the wear properties and to achieve low phosphorus and low sulfur in lubricating oil for internal combustion engines, and have completed the present invention.
  • the present invention provides a lubricating base oil comprising at least one compound selected from the group consisting of (A) a phosphorus compound represented by the general formula (1) and a salt thereof, and (B) a secondary monoalkyl group.
  • a lubricating oil composition for an internal combustion engine characterized in that the lubricating oil composition contains zinc dithiophosphate.
  • 2 Oyobi 1 3 are each independently hydrogen or carbon atoms from 1 to 3 0 of hydrocarbon group ( Nitrogen and may contain Z or oxygen).
  • the lubricating base oil contains at least one kind selected from the above-mentioned component (A) and zinc zinc dithiophosphate, and the sulfur content of the composition is 0.1% based on the total amount of the composition.
  • the present invention will be described in detail.
  • the lubricating base oil in the lubricating oil composition of the present invention is not particularly limited, and a mineral base oil and / or a synthetic base oil used for ordinary lubricating oils can be used.
  • a mineral base oil specifically, lubricating oil fractions obtained by depressurizing distillation of atmospheric residual oil obtained by atmospheric distillation of crude oil are subjected to solvent removal, solvent extraction, and hydrocracking. , Purified by one or more treatments such as solvent dewaxing, hydrorefining, etc.
  • examples include mineralized mineral oils, lubricating base oils produced by a method of isomerizing GTL WAX (gas to liquid wax) produced by the Fischer-Tropsch process, and the like.
  • the percentage of mineral base oil is not particularly limited, but is preferably 5 or less, more preferably 3 or less, and further preferably 2 or less. Moreover,% C A may be 0, but it is preferable that in view of the solubility of additives is 0. 4 or more, and more preferably 1 or more.
  • the above-mentioned% ⁇ 8 indicates the percentage of the number of aromatic carbons to the total number of carbons obtained by the method specified in ASTM D3238_85.
  • the sulfur content in the mineral base oil is not particularly limited, but is preferably 0.05% by mass or less, more preferably 0.01% by mass or less, and 0.005% by mass or less. It is particularly preferred that the content be 1% by mass or less.
  • the synthetic base oil examples include polybutene or a hydride thereof; 1-octene oligomer, poly- ⁇ -olefin such as 1-decene oligomer or a hydride thereof; ditridecyl glutarate, and di-2-ethyl.
  • Diesters such as hexyl adipate, diisodecyl adipate, ditridecyl adipate, and di-2-hexyl hexyl sebacate; trimethylolpropane caprylate, trimethylol propane perperanolegonate, and pentaerythritol 1-2-ethyl Polyester esters such as hexanoate and pentaerythritol pelargonate; copolymers of dicarboxylic acids such as dibutyl maleate and ⁇ -olefins having 2 to 30 carbon atoms, alkylnaphthalene, alkylbenzene, and fragrance Aromatic synthetic oils such as aromatic esters or Mixtures of these can be exemplified.
  • a mineral base oil a synthetic base oil, or an arbitrary mixture of two or more kinds of lubricating oils selected from these can be used.
  • examples thereof include one or more mineral base oils, one or more synthetic base oils, and a mixed oil of one or more mineral base oils and one or more synthetic base oils.
  • the kinematic viscosity of the lubricating base oil is not particularly limited, but its kinematic viscosity at 100 ° C is preferably 20 mm 2 / s or less, more preferably 10 mm 2 / s or less. is there. On the other hand, the kinematic viscosity is preferably 1 mm 2 / s or more, more preferably Znim 2 / s or more.
  • the kinematic viscosity of the lubricating base oil at 100 ° C exceeds 20 mm 2 / s, the low-temperature viscosity characteristics deteriorate, while if the kinematic viscosity is less than 1 mm 2 / s, the lubricating point Insufficient lubrication due to insufficient formation of an oil film at the same time, and evaporation loss of the lubricating base oil increases, which is not preferable.
  • the evaporation loss of the lubricating base oil is preferably 20% by mass or less, more preferably 16% by mass or less, particularly preferably 10% by mass or less, in terms of NOACK evaporation amount. preferable.
  • NOACK evaporation amount of the lubricating base oil exceeds 20% by mass, not only the lubricating oil evaporation loss is large, but also the sulfur compounds, phosphorus compounds, or metals in the composition are discharged together with the lubricating base oil in the exhaust gas. It is not preferable because it may accumulate in the purification device and not only increases the oil consumption but also adversely affects the exhaust gas purification performance.
  • the NO ACK evaporation amount is a measurement of the evaporation amount of the lubricating oil measured according to ASTM D5800.
  • the viscosity index of the lubricating base oil is not particularly limited, but is preferably 80 or more, more preferably 100 or more, and most preferably 100 or more so as to obtain excellent viscosity characteristics from low to high temperatures. Is 1 20 or more.
  • the upper limit of the viscosity index is not particularly limited.Normal paraffin, slack wax, GTL wax, or the like, or about 135 to 180 such as isoparaffinic mineral oil obtained by isomerizing these, or complex ester base oil Approximately 150 to 250 oils such as and HV I-PAO base oils can also be used. If the viscosity index of the lubricating base oil is less than 80, the low-temperature viscosity characteristics deteriorate, which is not preferable.
  • the component (A) in the lubricating oil composition of the present invention is at least one compound selected from the group consisting of phosphorus compounds represented by the following general formula (1) and salts thereof. (1)
  • the number 1 or more hydrocarbon group having a carbon preferably a hydrocarbon group having 1 to 30 carbon atoms, R 2 ⁇ Pi 1 3 are each independently hydrogen or a C 1 -C Represents up to 30 hydrocarbon groups. These hydrocarbon groups may contain nitrogen or Z or oxygen.
  • hydrocarbon group examples include an alkyl group, a cycloalkyl group, an alkyl group, an alkyl-substituted cycloalkyl group, an aryl group, an alkyl-substituted aryl group, and an arylalkyl group.
  • Phenyl, naphthyl, and other aryl groups tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, and other C7-C10 alkylaryl groups. May be substituted or substituted at any position.
  • Alkyl groups (these alkyl groups may be linear or branched).
  • the hydrocarbon group is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms. And more preferably an alkyl group having 1 to 18 carbon atoms.
  • Examples of the phosphorus compound represented by the general formula (1) include: a hydrocarbon group having 1 or more carbon atoms, a phosphonic acid having both R 2 and R 3 being hydrogen; and a hydrocarbon having 1 or more carbon atoms.
  • a group, R 2 in ⁇ Pi 1 3 on one hydrocarbon group having 1 to 3 0 carbon atoms, phosphonate monoester other person is hydrogen, but Ri 1 or more hydrocarbon groups der carbon atoms
  • R Examples include phosphonic acid diesters in which 2 and R 3 are both hydrocarbon groups having 1 to 30 carbon atoms, and mixtures thereof.
  • these phosphorus compounds include mono-n-butylphosphonic acid, mono-isobutinolephosphonic acid, mono-n-pentynolephosphonic acid, mono-n-hexynolephosphonic acid, and mono-1,3-dimethylbutylphosphonic acid , Mono 4-methyl-1-pentyl phosphonic acid, Mono n-heptyl phosphonic acid, Mono n-octyl phosphonic acid, Mono 2-ethylhexyl phosphonic acid, Monoisodecyl / lephosphonic acid, Mono n-dodecyl phosphonic acid, Monodiisotridecyl phosphonic acid Alkyl or alkynolephosphonic acid such as acid, monooleylphosphonic acid, monostearylphosphonic acid, monon-octadecylphosphonic acid, etc .; n-butynolephosphonic acid mono-n-butynole ester, isoptinole
  • a phosphorus compound wherein R i is a hydrocarbon group having 1 or more carbon atoms and at least one of R 2 and R 3 is hydrogen
  • Metal bases such as metal oxides, metal hydroxides, metal carbonates, and metal chlorides, ammonia, amines having only a hydrocarbon group having 1 to 30 carbon atoms or a hydroxyl group-containing hydrocarbon group in the molecule Salts obtained by reacting a nitrogen compound such as a compound to neutralize a part or all of the remaining acidic hydrogen can be given.
  • Examples of the metal in the metal base include alkali metals such as lithium, sodium, potassium and cesium, alkaline earth metals such as calcium, magnesium, and palladium, zinc, copper, iron, lead, and nickel. And heavy metals such as silver, manganese and molybdenum. Of these, alkaline earth metals such as calcium and magnesium and zinc are preferred, and zinc is particularly preferred.
  • the structure of the metal salt of the phosphorus compound varies depending on the valence of the metal and the number of OH groups of the phosphorus compound. Therefore, the structure is not limited at all.
  • lead lmo 1 and phosphonic acid monoester (one OH group) 2 mo 1 are reacted, it is thought that a compound having the structure represented by the following formula is obtained as the main component, but there are also polymerized molecules. it seems to do.
  • nitrogen compound examples include ammonia, monoamine, diamine, and polyamine. More specifically, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, noelamine, decylamine, pendecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, pentadecylamine, hexadecamine Decylamine, octadecylamine, dimethylamine, getylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didecylamine, didodecylamine, ditridecylamine Ditetradecy
  • Alkenylamines methanolamine, ethanolamine, propanolamine, butanolamine, pentanolamine, hexanolamine, heptanolamine, octanol / reamine, nonanolamine, methanolethanolanolamine, methanolpropanolamine, methanolbutanol C1-C30 alkanol groups such as amide, ethanolpropanolamine, ethanolbutanolamine and propanolbutanolamine (these alkanol groups may be linear or branched)
  • aliphatic amines having an alkyl or alkenyl group having 10 to 20 carbon atoms such as decylamine, dodecylamine, tridecylamine, heptadecylamine, octadecylamine, oleylamine, and stearylamine (these are directly It may be chain or branched.) Is a preferred example.
  • these components (A) can be arbitrarily compounded.
  • the wear resistance when used in combination with the component (B), the wear resistance can be synergistically improved, and further lower phosphorus and lower ash can be achieved.
  • the content of the component (A) in the lubricating oil composition for an internal combustion engine of the present invention is particularly limited.
  • the lower limit is usually based on the total amount of the composition, in terms of phosphorus element,
  • the upper limit is not particularly limited. Although it may also be provided, it is usually 0.2% by mass, preferably 0.1% by mass, more preferably 0.08% by mass, particularly preferably 0% by mass in terms of phosphorus element, based on the total amount of the composition. .05% by mass.
  • the component (B) in the present invention is zinc dithiophosphate having a secondary alkyl group.
  • R 4 , R 5 , R 6 and R 7 each independently represent a secondary alkyl group having 3 to 24 carbon atoms.
  • the secondary alkyl group refers to a group represented by the following general formula (3).
  • 18 and 19 each independently have 1 to 22 carbon atoms, preferably 1 to 8 carbon atoms, and the total carbon number of R 8 and R 9 is 2 to 23 A linear or branched alkyl group, preferably 2-9.
  • R 8 and R 19 are each independently a linear or branched methyl group, ethyl group, propyl group, butyl group, benzyl group, hexyl group, heptyl group, and octyl group.
  • Nonyl group nonyl group, decyl group, resin Examples thereof include a sil group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, and a hexadecyl group.
  • the method for producing the zinc secondary alkyldithiophosphate is not particularly limited, and any conventional method can be employed.
  • an alcohol or phenol having a secondary monoalkyl group corresponding to R 4 , R 5 , R 6 and R 7 is reacted with diphosphorus pentasulfide to produce dithiophosphoric acid, which is neutralized with zinc oxide or the like. It can be synthesized by letting it go. Thereby, zinc dithiophosphate having a secondary alkyl group can be obtained.
  • zinc secondary (sec) alkyldithiophosphate are zinc mono- or di-sec-butyldithiophosphate, zinc mono- or di-sec-pentyldithiophosphate, mono- or di-4-methyl-2-pentyldithiophosphate.
  • the content of the component (B) in the lubricating oil composition for an internal combustion engine of the present invention is not particularly limited, but its lower limit is usually 0.001 based on the total amount of the composition and in terms of phosphorus element.
  • the mass is 0 » preferably 0.01 mass%, more preferably 0.02 mass%, and the upper limit is not particularly limited, and a high concentration lubricating oil additive composition may be used.
  • a force based on the total amount of the composition which can provide, in terms of phosphorus amount is usually 0.1 mass 0/0, preferably from 0.08% by mass, more preferably 0.05 mass%, particularly preferably 0.035 % By mass.
  • the content of the component (B) By setting the content of the component (B) to be equal to or more than the above lower limit, excellent extreme pressure properties and antiwear properties can be obtained.
  • the amount when the amount is less than the above upper limit, it is possible to realize a low phosphorous content of the lubricating oil. It is possible to obtain an extremely low lubricating oil composition for a low phosphorus type internal combustion engine.
  • the content ratio of the component (A) to the component (B) in the present invention is not particularly limited, but is preferably 10:90 to 90:10 in terms of the mass ratio in terms of the amount of phosphorus element.
  • the ratio is more preferably 20:80 to 80:20, even more preferably 30:70 to 70:30, and particularly preferably 35:65 to 65:35.
  • the wear resistance can be synergistically improved.
  • the total content of the component (A) and the component (B) in the present invention is not particularly limited, but the lower limit is usually 0.001 in terms of phosphorus element based on the total amount of the composition.
  • the mass 0/0 preferably 0.0 1% by weight, more preferably from 0.02% by mass
  • the upper limit is not particularly limited, a high concentration of the lubricating oil additive composition
  • it is usually 0.2% by mass, preferably 0.1% by mass, more preferably 0.08% by mass, and further preferably, in terms of phosphorus element, based on the total amount of the composition.
  • 0.06 mass% particularly preferably 0.05 mass%.
  • the content of the component (A) to the component (B) at or above the lower limit, excellent extreme pressure properties and wear resistance can be obtained. Further, when the amount is not more than the above upper limit, the phosphorus content of the lubricating oil can be reduced. In particular, since a synergistic effect of the component (A) and the component (B) can be expected, further reduction of the phosphorus can be realized. In particular, by setting the total content of the components (A) and (B) to 0.08% by mass or less, and even 0.05% by mass or less, a low-phosphorous type that has extremely little effect on exhaust gas purification devices and the like. The lubricating oil composition for an internal combustion engine can be obtained.
  • the lubricating oil composition of the present invention preferably contains (C) a chain terminator.
  • Chain terminators are generally distinguished from peroxide decomposers such as sulfur-containing organometallic compounds or organosulfur compounds (eg, zinc dithiophosphate, molybdenum dithiophosphate, olefin sulfide, sulfide, etc.).
  • the function of stopping the chain of oxidative deterioration such as capturing and stabilizing the radicals generated during the oxidative deterioration process of the lubricating oil, either becoming stable radicals themselves or further capturing and stabilizing the radicals.
  • the chain terminator include a phenol-based antioxidant, an amine-based antioxidant, and the like, but are not limited to compounds having the same action mechanism.
  • phenolic antioxidants examples include 4,4,1-methylenebis (2,6-di-tert-butylphenol) and 4,4′-bis (2,6-ditert-butyl-butenophenol) , 4,4'-bis (2-methynole-6-tert-butynolepheno), 2,2'-methylenebis (4-ethyl-6-tert-ptinolephenone), 2,2'-methylenebis (4— Methynoreh 6-tert-butyl phenol), 4, 4,1-butylidenebis (3-methyl-6-tert-butylphenol), 4,4'-isopropylidenebis (2,6-di-tert-butylphenol), 2,2, -methylenebis (4-methyl-6-noyl) Phenol), 2,2,1-isobutylidenebis (4,6-dimethylphenol), 2,2, -methylenebis (4-methynole 6-hexylhexylphenol), 2,6-
  • amine-based antioxidants examples include phenyl-naphthylamine, alkylphenyla-naphthylamine, dialkyldiphenylamine, and phenothiazine. These may be used as a mixture of two or more.
  • an antioxidant composed of a phenolic antioxidant and a Z or amine antioxidant is particularly preferable.
  • the content of the component (c) is usually preferably 5.0 % by mass / 0 or less, more preferably 3.0% by mass, based on the total amount of the lubricating oil composition. /. Less than And more preferably 2.5% by mass or less. If the content is more than 5.0% by mass, it is not preferable because sufficient base number maintenance property corresponding to the compounding amount cannot be obtained. On the other hand, its content is preferably at least 0.1% by mass, more preferably at least 1% by mass, based on the total amount of the lubricating oil composition in order to further enhance the base number retention.
  • the lubricating oil composition of the present invention preferably contains (D) an ashless dispersant and Z or (E) a metal-based detergent.
  • any ashless dispersant used in lubricating oils can be used.
  • a linear or branched alkyl or alkenyl group having 40 to 400 carbon atoms can be used.
  • the carbon number of this alkyl group or alkenyl group is 40 to 400, preferably 60 to 350.
  • the alkyl group or alkenyl group may be linear or branched, but is preferably a group selected from oligomers of olefins such as propylene, 1-butene and isobutylene, and co-oligomers of ethylene and propylene. Derived branched alkyl groups and branched alkenyl groups are exemplified.
  • component (D) include, for example, the following compounds. One or more compounds selected from these can be used.
  • (D-1) succinic imid having at least one alkyl or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof
  • (D-2) Benzylamine having at least one alkyl or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof
  • (D-3) a polyamine having at least one alkyl or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof
  • R 2 ° represents an alkyl group or an alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350, and h represents an integer of 1 to 5, preferably 2 to 4. Is shown.
  • R 2 1 ⁇ Pi R 2 2 are each independently C 4 0-4 0 0, preferably an 6 0-3 5 0 alkyl or alkenyl group, is Poributeyuru group Is preferred.
  • i represents an integer of 0 to 4, preferably 1 to 3.
  • succinic acid imid is a so-called mono-type succinic acid imid represented by the formula (4) in which succinic anhydride is added to one end of a polyamine, and a compound in which succinic anhydride is added to both ends of a polyamine.
  • Power containing so-called bis-type succinic acid imid represented by (5) The composition of the present invention may contain any of them or a mixture thereof.
  • the method for producing these succinic acid imides is not particularly limited.
  • a compound having an alkyl group or an alkyl group having 40 to 400 carbon atoms is mixed with maleic anhydride at 100 to 200 ° C.
  • a polyamine include dimethylene triamine, triethylene tetramine, tetraethylene pentamine, and pentaethylene hexamine.
  • R 23 represents an alkyl group or an alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms, and j represents an integer of 1 to 5, preferably 2 to 4.
  • the method for producing this benzylamine is not particularly limited.
  • a polyolefin such as a propylene oligomer, a polybutene, and an ethylene-olefin copolymer is reacted with a phenol to form an alkylphenol, which is then added to formaldehyde.
  • a polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine by reacting by Mannich reaction.
  • examples of the polyamine (D-3) include compounds represented by the following general formula (7).
  • R 24 represents an alkyl group or an alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms, and k represents an integer of 1 to 5, preferably 2 to 4.
  • the method for producing this polyamine is not limited at all.
  • polyolefin such as propylene oligomer, polybutene, and ethylene monoolefin copolymer
  • ammonia ethylenediamine, diethylenetol, etc. It can be obtained by reacting a polyamine such as liamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
  • a polyamine such as liamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
  • the derivatives of the nitrogen-containing compound mentioned as an example of the component (D) specifically, for example, the above-mentioned nitrogen-containing compound may be a monocarboxylic acid having 1 to 30 carbon atoms (such as a fatty acid).
  • Polycarboxylic acids having 2 to 30 carbon atoms such as acids, trimellitic acid and pyromellitic acid or anhydrides or ester compounds thereof; alkylene oxides having 2 to 6 carbon atoms; hydroxy (poly) oxyalkylene carbonate Etc.
  • the boric acid-modified compound of alkenyl succinic acid imid has excellent heat resistance and antioxidant properties, and is effective in the lubid
  • the component (D) When the component (D) is contained in the lubricating oil composition of the present invention, its content is usually 0.01 to 20% by mass, preferably 0.1 to 1% by mass, based on the total amount of the lubricating oil composition. 0% by mass. When the content of the component (D) is less than 0.01% by mass, the effect on high-temperature cleanability is small. On the other hand, when the content exceeds 20% by mass, the low-temperature fluidity of the lubricating oil composition is significantly reduced. It is not preferable because it worsens.
  • metal-based detergent known metal-based detergents used for lubricating oils can be used.
  • T as an alkali metal or earth metal sulfonate is used to sulfonate an alkyl aromatic compound having a molecular weight of 100 to 150, preferably 200 to 700.
  • Specific examples of the alkyl aromatic sulfonic acid include so-called petroleum Examples include sulfonic acid and synthetic sulfonic acid.
  • Petroleum sulfonic acid is generally a sulfonated alkyl aromatic compound in the lubricating oil fraction of mineral oil. So-called mahoganic acid, which is a by-product of white oil production. Are used.
  • the synthetic sulfonic acid include an alkylbenzene having a linear or branched alkyl group, which is obtained as a by-product from an alkylbenzene production plant used as a raw material of a detergent or obtained by alkylating polyolefin to benzene. Is used as a raw material, and a sulfonated product thereof or a sulfonated product of dinonylnaphthalene is used.
  • the sulfonating agent used for sulfonating these alkyl aromatic compounds is not particularly limited, but fuming sulfuric acid or sulfuric acid is usually used.
  • alkali metal or alkaline earth metal phenate more specifically, an alkyl phthalate having at least one linear or branched alkyl group having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms.
  • Phenol an alkylphenol sulfide obtained by reacting this alkylphenol with elemental sulfur, or an alkali metal salt or an alkali metal salt of a Mannich reaction product of an alkylphenol obtained by reacting this alkylphenol with formaldehyde.
  • Earth metal salts particularly magnesium salts and potassium salts, are preferably used.
  • the alkali metal or alkaline earth metal salicylate includes at least one straight-chain or branched alkyl group having 1 to 30 carbon atoms, preferably 10 to 26 carbon atoms.
  • Alkali or alkaline earth metal salts of alkylsalicylic acid e.g., phenol or talesol, etc., which are obtained by alkoxylation of olefins having 10 to 26 carbon atoms
  • Alkali metal or alkaline earth metal sulfonate, alkali metal or alkaline earth metal phenate, and alkali metal or alkaline earth metal salicylate include anolequinole aromatic sulfonic acid, alkyl phenol, alkyl phenol sulfide, alkyl Mannich reaction product of phenol, alkyl salicylic acid, etc. is directly reacted with metal bases such as oxides or hydroxides of alkali metals or alkaline earth metals, or once alkalis such as sodium salts and potassium salts.
  • neutral salts obtained by substituting an alkaline earth metal salt with a metal salt
  • these neutral salts normal salts
  • excess alkali metal or alkaline earth metal salts Al-li metal or Al-earth metal base (Al-li metal or Al-earth metal
  • Al-li metal or Al-earth metal The hydroxide or oxide) or basic salts obtained by heating in the presence of water
  • An overbased compound obtained by reacting a neutral salt (normal salt) with a base such as an alkali metal or alkaline earth metal hydroxide in the presence of carbon dioxide and boric acid or borate. Salts (ultrabasic salts) are also included.
  • Metal-based detergents are usually commercially available diluted with a light lubricating base oil or the like, and are available. Generally, the metal content is 1.0 to 20 mass%. %, preferably 2.0 to 1 to use of 6 mass 0/0 it is desirable.
  • the total base number of the component (E) is preferably from 0 to 50 OmgKOH / g, more preferably from 20 to 45 OmgKOHZg.
  • the component (E) alkali metal or alkaline earth metal sulfonate, phenate, salicylate, etc. can be used alone or in combination of two or more kinds. Is preferably used as an essential component.
  • the total base number means the total base number measured by the perchloric acid method according to JIS K2501, “Petroleum products and lubricating oil-neutralization value test method”, paragraph 7.
  • the component (E) of the present invention is not particularly limited in its metal ratio, and it is usually 20 or less, preferably 1-15.
  • a metal-based detergent in that the antiwear property can be enhanced. Therefore, by appropriately selecting the type and metal ratio of these metal-based detergents and using them alone or in combination, it is possible to obtain desired base number maintenance properties and antiwear properties.
  • the metal ratio is represented by the valence of the metal element in the metal-based detergent X the content of the metal element (mo 1%) / the content of the soap group (mo 1%).
  • the soap group means a sulfonic acid group, a salicylic acid group and the like.
  • the compounding amount of the component (E) is not particularly limited, but usually, the upper limit is preferably 1% by mass in terms of a metal element, more preferably 0.5, based on the total amount of the composition. % By mass, more preferably 0.2% by mass, and can be appropriately selected according to the requirement of the sulfated ash content of the composition.
  • the lower limit is usually 0.01% by mass, Preferably it is 0.02% by mass, particularly preferably 0.05% by mass.
  • any additive generally used in lubricating oils can be added according to the purpose.
  • additives include, for example, anti-wear agents other than component (A) and component (B), friction modifiers, viscosity index improvers, corrosion inhibitors, antioxidants, demulsifiers, metal deactivators And additives such as an antifoaming agent and a coloring agent.
  • Examples of the antiwear agent other than the component (A) and the component (B) include zinc dithiophosphate other than the component (B) (eg, zinc dithiophosphate having a primary alkyl group or aryl group), and zinc dithiophosphate other than the component (B).
  • zinc dithiophosphate other than the component (B) eg, zinc dithiophosphate having a primary alkyl group or aryl group
  • zinc dithiophosphate other than the component (B) examples include zinc dithiophosphate other than the component (B) (eg, zinc dithiophosphate having a primary alkyl group or aryl group), and zinc dithiophosphate other than the component (B).
  • a sulfur-containing compound that is, these anti-wear agents are used.
  • the content of the sulfur-containing compound used should be limited, for example, 0.1% by mass or less, preferably 0.05% by mass or less in terms of sulfur element. It is particularly preferred not to do so.
  • friction modifier examples include molybdenum dithiol molybdate, molybdenum dithiophosphate, a molybdenum monoamine complex, a molybdenum-imido succinic acid complex, molybdenum disulfide, and an alkyl or alkenyl group having 6 to 30 carbon atoms.
  • a so-called non-dispersion type viscosity index improver such as a polymer or copolymer of one or more monomers selected from various methacrylates or a hydrogenated product thereof is used.
  • various methacrylic containing nitrogen compounds A so-called dispersion type viscosity index improver obtained by copolymerizing an acid ester, a non-dispersion type or dispersion type ethylene-a-olefin copolymer (Examples of a-olefin include propylene, 1-butene and 1-pentene.) Or hydrides thereof, polyisobutylene or hydrogenated products thereof, hydrides of styrene-one-gen copolymer, styrene-mono-maleic anhydride copolymer, polyalkylstyrene and the like.
  • the molecular weight of these viscosity index improvers must be selected in consideration of shear stability.
  • the number average molecular weight of the viscosity index improver is usually 5, 000 to: 1, 0000, 0000, preferably 1 in the case of, for example, a dispersion type and a non-dispersion type polymethacrylate.
  • the thing of 0,000 to 900,000 is polyisobutylene or a hydride thereof, it is usually 800 to 5,000, preferably 1,000 to 4,0,0.
  • the ethylene is an ethylene-a-olefin copolymer or a hydride thereof, it is usually 800 to 500,000, preferably 3,000 to 200,000. Is used.
  • corrosion inhibitor examples include benzotriazole-based, tolyltriazole-based, thiadiazole-based, and imidazole-based compounds.
  • antioxidants examples include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinate, and polyhydric alcohol ester.
  • demulsifier examples include polyalkylene glycol-based nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene annalequinolephenyl ether, and polyoxyethylene alkynolenaphthyl ether. .
  • metal deactivator examples include, for example, imidazoline, pyrimidine derivative, alkylthiaziazole, mercaptobenzothiazole, benzotriazole or a derivative thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl12 , 5-bisdialkyldithiocarbamate, 2_ (alkyldithio) benzoimidazole, and] 3- (o-potoxybenzylthio) propionnitrile.
  • the antifoaming agent examples include silicone, fluorosilicole, and fluoroalkyl ether.
  • the content is 0.1 to 20% by mass in the viscosity index improver based on the total amount of the lubricating oil composition, a friction modifier, 0.005 to 5% by mass for corrosion inhibitors, antioxidants, and demulsifiers, 0.05 to 1% by mass for metal deactivators, and 0.0005 to 1 for defoamers. Usually selected in the range of mass%.
  • the lubricating oil composition of the present invention can synergistically improve extreme pressure and abrasion resistance by using the component (A) and the component (B) together as described above, It is capable of exhibiting value maintenance performance. Therefore, a low phosphorus lubricating oil composition with a phosphorus content of 0.08% by mass or less, or further reduced to 0.05% by mass or less, as specified in the next ILSACGF-4 gasoline engine oil standard. It is also very useful as a low-phosphorus, low-sulfur lubricating oil composition in which the sulfur content is reduced to 0.3% by mass or less, preferably 0.2% by mass or less, particularly preferably 0.1% by mass or less. It is.
  • the lubricating oil composition of the present invention is excellent in the effect of preventing abrasion, it is preferably used as a lubricating oil for internal combustion engines such as gasoline engines, motorcycle engines, diesel engines, and gas engines for motorcycles, automobiles, power generation and ships.
  • internal combustion engines such as gasoline engines, motorcycle engines, diesel engines, and gas engines for motorcycles, automobiles, power generation and ships.
  • exhaust gas purifying catalysts selected from oxidation catalysts, three-way catalysts, NOX storage reduction catalysts and / or exhaust gas aftertreatment devices such as DPF, especially oxidation catalysts and DPF or NOX storage It is suitable for an internal combustion engine equipped with an exhaust gas aftertreatment device combining a reduction catalyst and DPF.
  • low-sulfur fuels such as gasoline with a sulfur content of 50 mass ppm or less, more preferably 30 mass ppm or less, particularly preferably 10 mass ppm or less, or gas oil or kerosene, or a sulfur content of 1 mass ppm or less
  • fuels LPG, natural gas, hydrogen-free dimethyl ether, alcohol, GTL (gas to liquid) fuel, etc.
  • gasoline engines or gas engines It can be preferably used.
  • lubricating oils of the present invention that require the above-mentioned extreme pressure performance or wear prevention performance, for example, lubricating oils for driving systems such as automatic or manual transmissions, gear oils, darries, wet brake oils It can also be suitably used as a lubricating oil such as a hydraulic oil, a turbine oil, a compressor oil, a bearing oil, and a refrigerating machine oil.
  • the low-sulfur, low-phosphorus engine system of the present invention comprises a lubricating oil composition for an internal combustion engine.
  • a lubricating oil composition containing the above components (A) and (B) in a lubricating base oil, having a sulfur content of 0.3% by mass or less and a phosphorus content of 0.08% by mass or less.
  • the fuel used is a fuel with a sulfur content of 50 mass ppm or less. While having low sulfur and low phosphorus, the anti-wear property is improved, and oxidation catalyst, three-way catalyst, NO x absorption reduction The effect on exhaust gas purifying catalysts selected from catalysts and / or exhaust gas aftertreatment devices such as DPF can be reduced.
  • the lubricating oil composition for an internal combustion engine of the present invention is a lubricating oil composition having excellent extreme pressure properties and antiwear properties. Therefore, the present invention can be applied to the various lubricating oils described above where these performances are required. In addition, high-temperature detergency, oxidation stability, and the like can be further improved by optimizing the type and content of the metal-based detergent and ashless dispersant.
  • low-sulfur, low-phosphorus lubricating oil composition having a sulfur content of 0.3% by mass or less and a phosphorus content of 0.08% by mass or less, Can be set to a desired level (for example, 0.01 to 1.2% by mass, preferably 0.8% by mass or less, more preferably 0.6% by mass or less).
  • Purification equipment for example, exhaust gas catalysts such as three-way catalysts, oxidation catalysts, NOx storage reduction catalysts, etc., and lubricating oils for internal combustion engines, because they do not deteriorate the purification performance of Z or DPF (diesel particulate filter)
  • the present invention provides a low-sulfur, low-phosphorus lubricating oil composition for lubricating an internal combustion engine and using a low-sulfur fuel to improve the performance of an exhaust gas purifying apparatus.
  • Maintain low sulfur, low phosphorus engine It is useful as a stem (for example, low-sulfur gas oil with a sulfur content of 50 mass ppm or less; power-generating engine systems using sulfur-free gasoline, LP gas or natural gas, etc. as fuel, engine systems for automobiles, etc.). is there.
  • a lubricating oil composition of the present invention having the composition shown in Table 1 (Example 1) and a lubricating oil composition for comparison (Comparative Examples 1 to 3) were prepared.
  • the obtained composition was subjected to the following performance evaluation tests (1) and (2), and the obtained results are shown in Table 1.
  • the composition (Example 1) with / 0 was compared with the composition (Comparative Examples 1 and 3) in which the component (B) or the component (A) was not used and the phosphorus content was 0.05% by mass.
  • Excellent anti-wear and extreme pressure properties Especially in the Falex test, it can be seen that the seizure load is synergistically improved.
  • a remarkable seizure load is exhibited as compared with the case of using zinc dithiophosphate having a primary monoalkyl group instead of the component (A) in the composition of Example 1 (Comparative Example 2). It has been confirmed that the base number retention of the composition of Example 1 is superior to that of a conventional composition containing about 0.1% by mass of zinc dithiophosphate in terms of phosphorus element.
  • Additives including viscosity index improver (PMA OCP), defoamer, etc.

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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

L'invention concerne une composition lubrifiante pour moteurs à combustion interne et plus précisément une composition lubrifiante à faible teneur en phosphore et en soufre pour moteurs à combustion interne, présentant d'excellentes caractéristiques de résistance à l'usure et aux pressions extrêmes. Cette composition lubrifiante pour moteurs à combustion interne contient, dans l'huile de base lubrifiante, (A) au moins une substance sélectionnée parmi des phosphonates spécifiques et leurs sels et (B) un dithiophosphate de zinc comportant un groupe alkyle secondaire.
PCT/JP2004/007337 2003-06-11 2004-05-21 Composition lubrifiante pour moteur a combustion interne Ceased WO2004111162A1 (fr)

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GB2444366A (en) * 2006-11-29 2008-06-04 Afton Chemical Corp Lubricant composition comprising phosphorus compounds
CN112166174A (zh) * 2018-05-30 2021-01-01 出光兴产株式会社 驱动系设备用润滑油组合物及其制造方法、驱动系设备的润滑方法、以及驱动系设备
CN113574146A (zh) * 2019-03-29 2021-10-29 出光兴产株式会社 润滑油组合物

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JP5542322B2 (ja) * 2008-11-20 2014-07-09 コスモ石油ルブリカンツ株式会社 農業機械用潤滑油組成物
US8211840B2 (en) * 2008-12-09 2012-07-03 Afton Chemical Corporation Additives and lubricant formulations for improved antiwear properties
US10913916B2 (en) * 2014-11-04 2021-02-09 Shell Oil Company Lubricating composition
SG11202000427RA (en) * 2017-07-17 2020-02-27 Lubrizol Corp Low zinc lubricant composition
JP7089899B2 (ja) * 2018-02-23 2022-06-23 出光興産株式会社 潤滑油組成物、潤滑油組成物の製造方法及び駆動系機器
JP7331919B2 (ja) 2019-03-14 2023-08-23 日油株式会社 潤滑油用添加剤、潤滑油用添加剤組成物およびこれらを含有する潤滑油組成物
CN113574144B (zh) 2019-03-14 2022-12-13 日油株式会社 润滑油用添加剂、润滑油用添加剂组合物及含有该添加剂或添加剂组合物的润滑油组合物

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