WO2004003118A1 - Additif pour huile de graissage, composition d'huile de graissage le renfermant et procede de fabrication dudit additif - Google Patents

Additif pour huile de graissage, composition d'huile de graissage le renfermant et procede de fabrication dudit additif Download PDF

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Publication number
WO2004003118A1
WO2004003118A1 PCT/JP2003/008337 JP0308337W WO2004003118A1 WO 2004003118 A1 WO2004003118 A1 WO 2004003118A1 JP 0308337 W JP0308337 W JP 0308337W WO 2004003118 A1 WO2004003118 A1 WO 2004003118A1
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WIPO (PCT)
Prior art keywords
lubricating oil
group
mass
general formula
additive
Prior art date
Application number
PCT/JP2003/008337
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English (en)
Japanese (ja)
Inventor
Kazuhiro Yagishita
Original Assignee
Nippon Oil Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Oil Corporation filed Critical Nippon Oil Corporation
Priority to AU2003244023A priority Critical patent/AU2003244023A1/en
Priority to JP2004517339A priority patent/JP4532268B2/ja
Priority to CN038173549A priority patent/CN1671828B/zh
Priority to EP03736321A priority patent/EP1516911A4/fr
Publication of WO2004003118A1 publication Critical patent/WO2004003118A1/fr
Priority to US11/020,087 priority patent/US7732385B2/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M169/045—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution and non-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
    • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
    • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
    • C10M137/04—Phosphate esters
    • C10M137/06—Metal salts
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    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/10—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
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    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C—CHEMISTRY; METALLURGY
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    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/123—Reaction products obtained by phosphorus or phosphorus-containing compounds, e.g. P x S x with organic compounds
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    • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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    • C10M167/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound, a non-macromolecular compound and a compound of unknown or incompletely defined constitution, each of these compounds being essential
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    • C10M169/04—Mixtures of base-materials and additives
    • C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
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    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
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    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/0406—Ethers; Acetals; Ortho-esters; Ortho-carbonates used as base material
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/16—Naphthenic acids
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    • C10M2207/26—Overbased carboxylic acid salts
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    • C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
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    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the present invention relates to a lubricating oil additive, and more particularly, to a lubricating oil additive obtained by dissolving a metal salt of a phosphorus compound that is insoluble or has low solubility in a lubricating base oil, and a lubricating oil composition comprising the same.
  • a lubricating oil additive obtained by dissolving a metal salt of a phosphorus compound that is insoluble or has low solubility in a lubricating base oil, and a lubricating oil composition comprising the same.
  • the present inventors have developed a monothiophosphate-based compound in which sulfur in the molecule is reduced in place of a sulfur-containing antiwear agent and antioxidant such as zinc dialkyldithiophosphate to enhance long drain performance of lubricating oil.
  • a low-sulfur lubricating oil composition containing a metal salt or a metal salt of a phosphoric acid ester-based compound or a metal salt of a phosphonate ester that does not contain sulfur in the molecule maintains the anti-wear property while maintaining the base. It has been found that it has excellent long drain performance such as valency maintenance and oxidation stability, and exhibits high-temperature detergency, low friction, and the like.
  • a patent application has already been filed for this invention (Japanese Patent Application No. 200-02-015351, Japanese Patent Application No. 2000-246946).
  • An object of the present invention is to provide a technique for liquefying a metal salt of a phosphorus compound having low solubility in lubricating oil and dissolving it in the lubricating oil efficiently in a short time in view of the above circumstances.
  • a lubricating oil composition containing a metal salt of a specific phosphorus compound exhibiting extremely excellent performance such as tang drainage can be industrially efficiently produced. That is. '
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that solubility in a lubricating oil can be improved by previously dissolving or reacting the phosphorus compound in an amine compound, thereby completing the present invention. Reached.
  • the present invention provides (A) a metal salt of a phosphorus compound represented by the general formula (1), a metal salt of a phosphorus compound represented by the general formula (2), and a metal salt of the general formula (3). And (B) an amine compound which is dissolved or reacted with at least one compound selected from the group consisting of metal salts of phosphorus compounds.
  • X 1 , 2 and 3 each independently represent an oxygen atom or a sulfur atom, and at least one of them is an oxygen atom, and R 11 R 12 and R 13 individually represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of these is a hydrogen atom.
  • X 4, X 5, X 6 and X 7 are each independently an oxygen atom or a sulfur atom, and at least three of these is an oxygen atom, R 14, R 15 and R 16 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of them is a hydrogen atom.
  • X 8 , X 9 and X 1 Q each independently represent an oxygen atom or a sulfur atom, and at least two of them are oxygen atoms
  • R 17 , R 18 and ⁇ R 19 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of them is a hydrogen atom, and a is 0 or 1.
  • the phosphorus compounds represented by the formulas (1) to (3) may have one (OR ′) n — group between X—R bonds, R ′ is an alkylene group having 1 to 4 carbon atoms, and n is Shows an integer of 1 to 10.
  • the metal in the component (A) is preferably at least one metal selected from lithium, magnesium, calcium and zinc.
  • the component (B) is preferably at least one amine compound selected from an amine-based antioxidant, an aliphatic amine, an ashless dispersant and a derivative thereof.
  • One of the lubricating oil additives of the present invention is a lubricating oil additive obtained by dissolving the component (A) in an amine antioxidant.
  • one of the lubricating oil additives of the present invention is a lubricating oil additive obtained by reacting the component (A) or the lubricating oil additive with an aliphatic amine.
  • One of the lubricating oil additives of the present invention is a lubricating oil additive obtained by reacting the component (A) or the lubricating oil additive with an ashless dispersant and / or a derivative thereof.
  • the lubricating oil additive preferably has a reaction ratio of the aliphatic amine, the ashless dispersant or the derivative thereof to the component (A) of 0.15 or more by mass ratio.
  • the ashless dispersant and / or a derivative thereof have a total base number of 5 mg KOH / g or more by a hydrochloric acid method.
  • the derivative of the ashless dispersant is a boron compound derivative of the ashless dispersant.
  • the present invention further provides a lubricant base oil, an antioxidant, an ashless dispersant, a metal detergent, a friction modifier, an antiwear agent, a corrosion inhibitor, an antioxidant, a demulsifier, a metal, At least one selected from deactivators, defoamers, coloring agents, and viscosity index improvers And a lubricating oil additive.
  • the present invention resides in a lubricating oil composition
  • a lubricating oil composition comprising the lubricating oil additive and a lubricating base oil.
  • the present invention provides (A) a metal salt of a phosphorus compound represented by the general formula (1), a metal salt of a phosphorus compound represented by the general formula (2), and a phosphorus compound represented by the general formula (3).
  • a method for producing a lubricating oil additive comprising: dissolving or reacting at least one compound selected from the group consisting of metal salts of compounds with an amine compound (B).
  • the present invention resides in a method for producing a lubricating oil composition, which comprises blending the lubricating oil additive into a lubricating oil.
  • a method for producing a lubricating oil composition which comprises blending the lubricating oil additive into a lubricating oil.
  • the component (A) includes a phosphorus compound represented by the general formula (1), a phosphorus compound represented by the general formula (2), or a phosphorus compound represented by the general formula (3).
  • Salts obtained by reacting a metal base such as an oxide, a metal hydroxide, a metal carbonate, or a metal chloride to neutralize a part or all of the remaining acidic hydrogen can be given.
  • X 1 , X 2 and X 3 each independently represent an oxygen atom or a sulfur atom, and at least one of them is an oxygen atom.
  • R 11 R 12 and R 13 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of them is a hydrogen atom.
  • X 4 , X 5 , X 6 and X 7 each independently represent an oxygen atom or a sulfur atom, and at least three of them are oxygen atoms.
  • R 14 , R 15 and R 16 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of them is a hydrogen atom.
  • X 8 , X 9 and X 1 Q each independently represent an oxygen atom or a sulfur atom, and at least two of them are oxygen atoms
  • R 17 , R 18 and R 19 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 ° carbon atoms, and at least one of these is a hydrogen atom, and a is 0 or 1.
  • the phosphorus compounds represented by the above general formulas (1) to (3) may or may not have one (OR ′) n — group between the X—R bonds, and R ′ has 1 to 1 carbon atoms. 4, preferably 1 or 2 alkylene groups, and n represents an integer of 1 to 10, preferably 1 to 4. It is more preferable that there is no ( ⁇ R ′) n — group between the X—R bonds in view of higher abrasion prevention performance or extreme pressure performance.
  • Specific examples of the metal in the above metal base include lithium metal, lithium, sodium, potassium, cesium and other alkaline metals, calcium, magnesium, barium and other alkaline earth metals, zinc, copper, iron, lead, nickel, and the like. Examples include heavy metals such as silver, manganese, and molybdenum. Of these, alkali metals such as lithium and sodium, alkaline earth metals such as magnesium and calcium, and zinc are preferred, and zinc is most preferred.
  • the structure of the metal salt of the phosphorus compound varies depending on the valency of the metal and the number of OH groups or SH groups of the phosphorus compound, and thus the structure is not limited at all.
  • 1 mol of zinc oxide When 1 and phosphoric acid diester (one OH group) 2 mo 1 are reacted, it is thought that a compound having a structure represented by the following formula is obtained as a main component. However, if there is a polymerized molecule, Conceivable.
  • hydrocarbon group having 1 to 30 carbon atoms represented by ⁇ 11 to! ⁇ 19 include an alkyl group, a cycloalkyl group, an alkenyl group, an alkyl-substituted cycloalkyl group, an aryl group, and an alkyl group.
  • Examples include a substituted aryl group and an arylalkyl group.
  • alkyl group examples 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, a nonyl group, a decyl group, a pendecyl group, a dodecyl group, a tridecyl group, and a tetradecyl group.
  • alkyl groups such as a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group (the alkyl groups may be linear or branched).
  • Examples of the above-mentioned cycloalkyl group include a cycloalkyl group having 5 to 7 carbon atoms such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • alkylcycloalkyl group examples include a methylcyclopentyl group, a dimethynolecyclopentyl group, a methylpentyl pentinole group, a ethynolectic pentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylethylcyclohexyl group, Alkylcycloalkyl groups having 6 to 11 carbon atoms, such as acetylcyclohexyl group, methylcycloheptyl group, dimethylcyclyl heptinol group, methinoleethylcyclyl heptyl group, getylcycloheptyl group, etc.
  • the substitution position of is also arbitrary.).
  • alkenyl group examples include, for example, a ptenyl group, a pentenyl group, a hexenyl group, a hepturyl group, an otaturyl group, a nonenyl group, a decenyl group, a pendecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, and a hexadecenyl group.
  • Alkenyl groups such as octadecenyl, heptadecenyl and octadecenyl
  • the alkenyl group may be linear or branched, and the position of the double bond is also arbitrary.).
  • Examples of the aryl group include aryl groups such as a phenyl group and a naphthyl group.
  • Examples of the alkylaryl group include, for example, a tolyl group, an xylyl group, an ethylphenol group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, and a nonylphenyl group.
  • C7-C18 alkylaryl group such as a benzyl group, a decylphenyl group, a decylphenyl group, a dodecylphenyl group (the alkyl group may be linear or branched, and the position of substitution with the aryl group may be Is optional).
  • arylalkyl group examples include arylalkyl groups having 7 to 12 carbon atoms, such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, and phenylhexyl. May be linear or branched).
  • the hydrocarbon group having 0 to 0 carbon atoms represented by ⁇ is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, and more preferably 3 to 18 carbon atoms. It is more preferably an alkyl group having 4 to 10 carbon atoms, and particularly preferably an alkyl group having 4 to 6 carbon atoms because of having high anti-wear performance and extreme pressure properties.
  • Examples of the phosphorus compound represented by the general formula (1) include: phosphorous acid, monothiophosphorous acid, dithiophosphorous acid; the above-mentioned phosphorous acid monoester having one hydrocarbon group having 1 to 30 carbon atoms Phosphite monoester, dithiophosphite monoester; phosphite diester having two hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphite diester, dithiophosphite diester and the like; Mixtures can be mentioned.
  • X ⁇ X 3 in the general formula (1) is preferably 2 or more of them are oxygen atom, more preferably all three oxygen atoms.
  • Examples of the phosphorus compound represented by the general formula (2) include phosphoric acid and monothiophosphoric acid; the above-mentioned phosphoric acid monoester having one hydrocarbon group having 1 to 30 carbon atoms, and monothiophosphoric acid. Monophosphoric acid esters; phosphoric acid diesters having two hydrocarbon groups having 1 to 30 carbon atoms; monothiophosphoric acid diesters; and mixtures thereof.
  • all of X 4 to X 7 in the general formula (2) are preferably oxygen atoms.
  • the phosphorus compound represented by the general formula (3) for example, the above-mentioned phosphonic acid having one hydrocarbon group having 1 to 30 carbon atoms, monothiophosphonic acid; the hydrocarbon group having 1 to 30 carbon atoms And monothiophosphonic acid monoesters having two of these; and mixtures thereof.
  • all of X 8 to X 1 Q in the general formula (3) are preferably oxygen atoms.
  • One or more of these components (A) can be arbitrarily compounded.
  • a known general production method can be used, and there is no particular limitation.
  • a zinc base such as zinc oxide, zinc hydroxide, zinc carbonate, zinc chloride, etc. is added to 2 moles of the phosphorus compound represented by the general formula (2).
  • ⁇ 2 mol preferably 0.5-1 mol, particularly preferably 0.8-0.98 mol, preferably 0.2-2 L, preferably 0.5-1.5 L of organic solvent and water ⁇ 0.5 to 1 L, preferably 0.1 to 0.5 L mixed at 40 to 100 ° C, preferably 60 to 90 ° C for 0.5 to: 10 hours
  • the reaction is preferably carried out by heating for 1 to 6 hours. Then, the aqueous layer is removed, and the organic solvent layer is removed. After filtration, the organic solvent is removed by distillation under reduced pressure or the like.
  • a zinc base such as zinc oxide, zinc hydroxide, zinc carbonate, zinc chloride or the like is used in an amount of 0.2 to 4 mol per 2 mol of the phosphorus compound represented by the general formula (2).
  • Mol preferably 1-2 mol, particularly preferably 1.6-1.96 mol, can be obtained using the method as described above.
  • the organic solvent used herein is not particularly limited, but may be a generally known organic solvent such as alcohol, hexane, benzene, toluene, xylene, decalin, other compounds having an aromatic ring, or a lubricating oil. Base oil and the like can be exemplified.
  • the neutralization ratio of the phosphorus compound with the metal salt is preferably 50% or more, more preferably 80% or more, and particularly preferably 90% or more.
  • Compounds obtained by such a method include, for example, zinc di (2-ethylhexyl) phosphate, zinc di (2-ethylhexyl) monothiophosphate, calcium di (2-ethylhexyl) phosphate, dibutyl phosphate
  • zinc, zinc 1,3-dimethylbutyl phosphate, etc. it is a white solid, and as it is, lubricating base oil, additives other than component (B), and lubricating oil not containing component (B) It has low solubility in the composition, and even if it is dissolved in the above-mentioned organic solvent, it may precipitate when the organic solvent is distilled off.
  • the component (A) obtained in a solid state as described above is previously mixed or dissolved in an organic solvent prior to mixing with the component (B). Further, in the above Production Examples, the component (A) obtained without distilling off the organic solvent can be used for mixing with the component (B).
  • the components (B) or the components (B) may be mixed in advance with the above-mentioned raw materials and reacted.
  • the component (B) in the present invention is an amine compound, and includes various amine compounds.
  • Preferred examples of the component (B) include amine antioxidants, aliphatic amines, ashless dispersants, and / or derivatives thereof.
  • amine antioxidant examples include various aromatic amine compounds, such as alkyldiphenylamine, alkylnaphthylamine, phenyl ⁇ -naphthylamine, and alkylphenyl-amine.
  • Amine-based antioxidants generally known for lubricating oil applications such as ⁇ -naphthylamine are preferred. These are preferably liquid at room temperature, and can be preferably used because the solubility of the component (II) is extremely high.
  • the alkyl group is an alkyl group having 1 to 30, preferably 3 to 20, and particularly preferably 4 to 10 carbon atoms, and the number of substitution is 1 to 4, preferably:! ⁇ 2.
  • ashless dispersant examples include ( ⁇ -2) succinic acid imide, ( ⁇ -3) benzylamine, ( ⁇ -4) polyamine, or Mannich reaction product of alkyl or alkenylphenol, formaldehyde and polyamine, and the like. It is preferably at least one compound selected from compound derivatives.
  • the total base number in the hydrochloric acid method is preferably 5 mgKOH / g or more from the viewpoint of the solubility of the component ( ⁇ ) or the reactivity with the component ( ⁇ ), It is more preferably at least 1 OmgKOHZg, particularly preferably at least 20 mgKOH / g.
  • the total salt value in the hydrochloric acid method means a value measured by a method specified in 6. Potentiometric titration method (base number) of JIS K 2501.
  • examples of the above ( ⁇ -2) succinic acid imide include compounds represented by the following general formula (4) or (5).
  • R 21 represents an alkyl group or an alkenyl group having 12 to 400 carbon atoms, preferably 60 to 200, particularly preferably 70 to 150, and a represents 1 to 5, preferably 2 Indicates an integer from 4 to 4.
  • R 22 and R 23 each independently represent an alkyl group or an alkenyl group having 12 to 400 carbon atoms, preferably 60 to 200, particularly preferably 70 to 150, and a polybutenyl group Is particularly preferred.
  • b represents an integer of 0 to 4, preferably 1 to 3.
  • succinic acid imid is a so-called monotype succinic acid imid represented by general formula (4) in which succinic anhydride is added to one end of a polyamine by imidation, and an anhydride at both ends of the polyamine.
  • succinic acid imid represented by general formula (5) to which succinic acid is added, but any of these (B_2) components and a mixture thereof can be used.
  • the method for producing the succinic acid imide is not particularly limited.
  • chlorinated polybutene or polyisobutene (these usually have a vinylidene structure at the end of 5 to 10 Omo 1%), or polybutene from which chlorine or fluorine has been sufficiently removed is mixed with maleic anhydride and 100 to 200
  • a method of reacting polybutenyl succinic acid obtained by reacting at ° C with a polyamine for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.
  • a polyamine for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.
  • the polybutenyl succinic acid may be reacted twice as much as the amount of the polyamine (molar ratio).
  • the polyamine may be reacted in the same amount (molar ratio).
  • polybutulbissuccinimide is preferable because it can impart oxidation stability, sludge dispersibility and the like to the lubricating oil composition.
  • examples of the benzylamine (B-3) include a compound represented by the following general formula (6).
  • R 24 represents an alkyl group or an alkenyl group having 12 to 400 carbon atoms, preferably 60 to 200 carbon atoms, and particularly preferably 70 to 150 carbon atoms. Represents an integer of 2 to 4.
  • This benzylamine is obtained, for example, by reacting a polyolefin (for example, propylene oligomer, polybutene, ethylene monoolefin copolymer, etc.) with phenol to form an alkylphenol, and then adding formaldehyde and a polyamine (for example, diethylenetriamine). , Triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.) by the Mannich reaction.
  • a polyolefin for example, propylene oligomer, polybutene, ethylene monoolefin copolymer, etc.
  • formaldehyde and a polyamine for example, diethylenetriamine
  • examples of the polyamine (B-4) include a compound represented by the following general formula (7).
  • R 25 represents an alkyl group or an alkenyl group having 12 to 400 carbon atoms, preferably 60 to 200, particularly preferably 70 to 150, and d represents:! It preferably represents an integer of 2 to 4.
  • polyolefins are obtained by chlorinating polyolefins (eg, propylene oligomer, polybutene, ethylene- ⁇ -olefin copolymer), and then adding ammonia-polyamines (eg, ethylenediamine, diethylenetriamine, triethylenetetramine). , Tetraethylenepentamine, pentaethylenehexamine, etc.).
  • polyolefins eg, propylene oligomer, polybutene, ethylene- ⁇ -olefin copolymer
  • ammonia-polyamines eg, ethylenediamine, diethylenetriamine, triethylenetetramine.
  • Tetraethylenepentamine pentaethylenehexamine, etc.
  • the derivative of the ashless dispersant specifically, for example, a boron compound, an oxygen-containing organic compound, a sulfur compound, or the like, or a nitrogen compound represented by the above ( ⁇ -2) to ( ⁇ _4), or two kinds thereof are used.
  • the remaining amino group and ⁇ or imino remaining after being acted on in combination Examples include various modified compounds in which some or all of the groups are neutralized or amidated.
  • Examples of the boron compound include boric acid, borates, and borate esters.
  • Specific examples of boric acid include orthoboric acid, metaboric acid and tetraboric acid.
  • Examples of the borate include alkali metal salts, alkaline earth metal salts, and ammonium salts of boric acid.
  • borate ester examples include esters of boric acid and preferably an aliphatic alcohol having 1 to 6 carbon atoms, and more specifically, for example, monomethyl borate, dimethyl borate, trimethyl borate, Monoethyl borate, getyl borate, triethyl borate, monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate, triptyl borate and the like can be mentioned.
  • the succinic acid imid derivative treated with the boron compound is preferably used because it can impart heat resistance and oxidation stability to the lubricating oil composition.
  • the ratio of the nitrogen equivalent to the boron equivalent (B / N equivalent)
  • the (ratio) is not particularly limited, but is preferably 1 or less, more preferably 0.7 or less, and more preferably 0.5 or less because a complex is easily formed with the component (A). Is particularly preferred.
  • oxygen-containing organic compound examples include, for example, formic acid, acetic acid, glycolic acid, propionic acid, lactic acid, butyric acid, valeric acid, cabronic acid, enanthic acid, and caprylic acid.
  • 1-3 carbon atoms such as acid, pelargonic acid, capric acid, pendecylic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, nonadecanoic acid, eicosanoic acid, etc.
  • R 2 6 is a hydrogen atom, an alkyl group having 1-2 4 carbon atoms, an alkenyl group, an alkoxy group, or one O- (R 2 7 0) arsenide Dorokishi (poly) Okishiaruki groups represented by m H are shown, R 2 7 is an alkylene group having 1 to 4 carbon atoms, m is an integer of 1 to 5.
  • components (B-2) to (B-4) and derivatives of these compounds are considered to react with component (A) to form a complex, and are stably present in lubricating oil additives or lubricating oil compositions. It can be used particularly preferably because it can shorten the production time of the lubricating oil composition.
  • (B-2) succinic acid imide and / or a derivative thereof is preferable, or a boron compound derivative of the components (B-2) to (B-4) is preferable, and in particular, (B-2) succinic acid A imide boron compound derivative is particularly desirable in that the lubricating oil additive or the lubricating oil composition of the present invention can further improve the heat resistance, oxidation stability, extreme pressure property and the like.
  • amine compounds as the component (B) include, for example, methylamine, ethynoleamine, propylamine, butynoleamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decinoleamine, pendecylamine, tridecylamine, tridecylamine, tridecylamine, dodecylamine, tridecylamine, tridecylamine, dodecylamine, tridecylamine, tridecylamine, dodecylamine, tridecylamine, dodecylamine Noleamine, pentadecinoleamine, hexadeci / reamine, heptadecinoleamine, octadecinole Amin, dimethamine, getylamine, dipropionamine, dibutynoleamine, dipenty / reamine, dihexylamine, diheptyl
  • Alkylamines which may be branched); ethenylamine, propenylamine, puturamine, otaturamine, oleylamine, octenylmethylamine, decenylmethylamine, dodecenylmethylamine, octadecenyl It has an alkenyl group having 2 to 30 carbon atoms such as tilamine, otaturdimethylamine, decenyldimethylamine, dodecenyldimethylamine, and otadecenyldimethylamine (these alkenyl groups may be linear or branched).
  • Alkylene diamine having an alkylene group having 1 to 30 carbon atoms such as methylene diamine, ethylene diamine, propylene diamine, and butylene diamine; diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and the like.
  • Polyamines; monoamines and diamines described above such as pendecyl getylamine, pendecyljetanolamine, dodecyldipropanolamine, oleyljetanolamine, oleylpropylenediamine, stearyltetraethylenepentamine and the like.
  • Preferable examples include aliphatic amines having a group or an alkenyl group (these may be linear or branched).
  • a lubricating oil additive having a further excellent effect of reducing friction between metals. It is particularly preferred to use lubricating oils, since a lubricating oil additive having further excellent extreme pressure properties can be obtained.
  • the component (B) one or a mixture of two or more of the above-mentioned amine compounds can be used.
  • Preferred embodiments of the lubricating oil additive of the present invention include the following.
  • Lubricant additive made by mixing (A) component and amine antioxidant
  • Lubricant additive obtained by reacting component (A) or lubricant additive (1) with aliphatic amine
  • Lubricating oil additive obtained by reacting component (A) with a mixture of amine antioxidant and ashless dispersant and / or its derivative
  • ⁇ Lubricant additive obtained by reacting the component (A) with a mixture of an amine antioxidant and an aliphatic amine
  • the lubricating oil additive of the above (1) is in a state in which the component (A) is dissolved in an amine antioxidant. It is considered that liquefaction was caused by forming a complex with amine, ashless dispersant, and Z or its derivative.
  • the lubricating oil additive of the present invention is preferably the lubricating oil additive of the above (1) to (4), and more preferably the lubricating oil additive of the above (1) or (2).
  • the method for producing the lubricating oil additive of the present invention is not particularly limited as long as the component (A) is dissolved or reacted with the component (B).
  • the component (A) is mixed with the above-mentioned organic solvent in advance.
  • the conditions for mixing and stirring are not particularly limited, but the temperature is preferably 15 to 150 ° C, more preferably 30 to 120 ° C, and particularly preferably 40 to 90 ° C. ° C, and it is preferable to perform the reaction at a temperature equal to or lower than its boiling point from the viewpoint of safety, depending on the type of the organic solvent.
  • the time at that time is preferably 5 minutes to 5 hours, more preferably 20 minutes to 3 hours, and particularly preferably 30 minutes to 1 hour.
  • the distillation of the organic solvent is performed using a method such as vacuum distillation until the organic solvent is distilled off.
  • the lubricating oil additive of the present invention thus obtained usually comprises the component (A) in an amount of 0.5 to 20% by mass, preferably 1 to 20% by mass, in terms of phosphorus element, based on the total amount of the lubricating oil additive. -10% by mass.
  • the mixing ratio of the component (A) and the component (B) is not particularly limited, but the component (B) is added in an amount of 0.1 to 1 part by mass of the component (A). 30 parts by mass, preferably 0.15 parts by mass or more, more preferably 0.2 parts by mass or more, still more preferably 0.3 parts by mass or more, further preferably 0.5 parts by mass or more, particularly preferably 0.8 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less.
  • the lubricating oil additive of the present invention has a long drain performance such as a base number maintenance property and an oxidative stability while maintaining the anti-wear property of the lubricating oil composition, and exhibits high-temperature detergency, low friction property and the like.
  • the lubricating oil additive of the present invention is further added with various lubricating oil additives such as an antioxidant and an ashless At least one selected from powders, metal detergents, friction modifiers, antiwear agents, corrosion inhibitors, antioxidants, demulsifiers, metal deactivators, defoamers, colorants, and viscosity index improvers.
  • various lubricating oil additives such as an antioxidant and an ashless At least one selected from powders, metal detergents, friction modifiers, antiwear agents, corrosion inhibitors, antioxidants, demulsifiers, metal deactivators, defoamers, colorants, and viscosity index improvers.
  • One kind can be blended, and if necessary, a small amount may be mixed with a lubricating base oil for viscosity adjustment.
  • the lubricating oil additive of the present invention can be provided as a package additive in which the various additives described above are arbitrarily mixed according to the required performance of the lubricating oil composition.
  • the lubricating oil composition of the present invention contains the lubricating oil additive of the present invention or a package additive in which various lubricating oil additives are blended, and a lubricating base oil (or other lubricating oil additives as necessary).
  • lubricating oil composition and mixed and stirred at 15 ° C to 150 ° C, preferably 40 ° to 120 ° C (particularly preferably 60 ° to 90 ° C). It can be manufactured by the following.
  • the lubricating oil additive of the present invention is added to a lubricating base oil or a lubricating oil composition
  • the preferred lower limit is expressed in terms of phosphorus element based on the total amount of the composition.
  • the value is 0.005% by weight, more preferably 0.01% by weight, particularly preferably 0.02% by weight, while the preferred upper limit is 0.4% by weight, more preferably 0.2 mass. / 0 , particularly preferably 0.1% by mass.
  • the lubricating base oil is not particularly limited, and mineral base oils and synthetic base oils 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. , Refined by one or more treatments such as solvent dewaxing, hydrorefining, etc., or base oils produced by a method of isomerizing wax-catalyzed mineral oil or GTL WAX (gas to liquid wax). Can be illustrated.
  • the total aromatic content of the mineral base oil is not particularly limited, but is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 2% by mass or less. If the total aromatic content of the base oil exceeds 15% by mass, the oxidation stability is poor, which is not preferable.
  • the above-mentioned total aromatic content means a content of aromatic fraction (aromatiicfractione) measured according to ASTM D2549.
  • this aromatic fraction includes, in addition to alkylbenzene and alkylnaphthalene, anthracene, phenanthrene, their alkylated compounds, compounds in which four or more benzene rings are condensed, pyridines, quinolines, phenols, Compounds having heteroaromatics such as naphthols are included.
  • the sulfur content in the mineral oil base oil is not particularly limited, but is preferably 0.01% by mass or less, more preferably 0.005% by mass or less, and 0.001% by mass. It is particularly preferred that: By reducing the sulfur content of the mineral base oil, a lubricating oil composition having more excellent long drain properties can be obtained.
  • the synthetic base oil examples include polybutene or a hydride thereof; poly- a -olefin such as 1-octene oligomer and 1-decene oligomer or a hydride thereof; ditridecinoregolelate, G2-ethyl Diesters such as hexyl adipate, disodecyl adipate, ditridecyl adipate, and di-2-ethylhexyl sebacate; trimethylolpropane caprylate, trimethylol propyl nonoperanolegonate, and pentaerythritol tonole 1-2-ethyl Polyphenols such as hexanoate and pentaerythritol perargonate; triesters of neopentynole glycol; alkyl naphthalenes, alkyl benzenes and fragrances Examples thereof include aromatic synthetic oils such as aromatic esters and mixtures thereof.
  • the mineral base oil, the synthetic base oil, or an arbitrary mixture of two or more 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 the kinematic viscosity at 100 ° C. is preferably 20 m Hi 2 / s or less, more preferably 10 mm 2 / s or less. On the other hand, the kinematic viscosity is preferably at least 1 mm 2 Zs, more preferably at least 2 mm 2 / s.
  • 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 Z s, Insufficient oil film formation leads to poor lubricity and large loss of evaporation of the lubricating base oil, which is not preferred.
  • 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 base oil evaporation loss is large, but also when the lubricating base oil is used as a lubricating oil for internal combustion engines, the sulfur compounds and phosphorus compounds in the composition Alternatively, there is a possibility that the metal component may be deposited on the exhaust gas purification device together with the lubricating base oil, which is not preferable because there is a concern that the exhaust gas purification performance may be adversely affected.
  • the NOACK evaporation here means 250 g of lubricating oil sample according to ASTM D5800. C, is 20 mmH 2 0 that the amount of evaporation was kept 1 hour under reduced pressure of (1 9 6 P a) was measured.
  • the viscosity index of the lubricating base oil is not particularly limited, but the value is preferably 80 or more, more preferably 100 or more, and still more preferably, so as to obtain excellent viscosity characteristics from low to high temperatures. Is 1 20 or more. When the viscosity index is less than 80, the low-temperature viscosity characteristics deteriorate, which is not preferable.
  • any phenol-based antioxidant, metal-based antioxidant, and other compounds generally used in lubricating oils can be used. It is. By adding the antioxidant, it is possible to further enhance the long drain performance of the lubricating oil composition.
  • phenolic antioxidants examples include 4,4, -methylenebis (2,6-di-tert-butynolephenone), 4,4'-bis (2,6-di-tert-butylphenol), 4,4 1,2-bis (2-methyl-1-6-tert-butylphenol), 2,2,1-methylenebis (4-ethynole 6-tert-butynolephene), 2,2, -methylenebis (4-methyl-1-6-tert-butylphenol) ), 4,4'butylidenebis (3-methyl-6-tert-butylphenol), 4,4,1-isopropylidenebis (2,6-di-tert-butylphenol), 2,2,1-methylenebis (4_ Methyl-6-noelphenol, 2,2,1-isobutylidenebis (4,6-dimethylphenol), 2,2, -methylenbis (4-methylenole 6-hexylhexenophenol), 2,6-zy te rt Butinole 4—Methin
  • Examples of the ashless dispersant include the ashless dispersant in the above component (B). This can be preferably used to further improve sludge dispersibility, high temperature cleanability, and oxidation stability.
  • the metal-based detergent examples include alkali metal or alkaline earth metal sulfonates, salicylates, phenates, and phosphonates, and have a neutral, basic, or overbased total base number of 0 to 50 O mg.
  • a known KO HZ g can be used.
  • the alkali metal examples include sodium and potassium, and examples of the alkaline earth metal include calcium and magnesium. Calcium and magnesium are preferred, and calcium is particularly preferred.
  • the metal ratio of these metal-based detergents is usually from 1 to 20% by mass, and is not particularly limited.
  • an alkali metal or alkaline earth metal salicylate having a metal ratio adjusted to 2.3 or less, an alkali metal or alkaline earth metal salicylate having a metal ratio of 1.5 or less, and a metal ratio of 1 to 20 are used. It is preferred to use a mixture of alkali metal or alkaline earth metal sulfonates.
  • 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%), and the metal element is calcium.
  • a soap group means a sulfonic acid group, a salicylic acid group and the like.
  • friction modifier examples include molybdenum dithiol molybdate, molybdenum dithiophosphate, molybdenum disulfide, long-chain aliphatic amine, long-chain fatty acid, long-chain fatty acid ester, long-chain fatty acid amide, and long-chain fatty alcohol. Is mentioned.
  • the anti-wear agents other than the component (A) include phosphoric acid, phosphoric monoester, phosphoric diester, phosphoric triester, phosphorous acid, phosphorous monoester, phosphorous diester, phosphorous triester, And their amine salts, zinc dithiophosphate, zinc dithiophosphate, disulfides, sulfurized olefins, sulfurized fats and oils, etc., which can be used, but those containing no sulfur are particularly preferred.
  • the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.
  • Examples of the protective agent include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinate, and polyvalent Alcohol esters and the like.
  • demulsifier examples include polyalkylene dalicol-based nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether.
  • metal deactivator examples include imidazoline, pyrimidine derivatives, alkylthiadiazole, mercaptobenzothiazole, benzotriazole or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolylol 2 , 5 -bisdialkyldithiocarbamate, 2- (alkyldithio) benzimidazonole, and / 3- (o-potoxybenzinorethio) propionnitrile.
  • thiazoles and thiadiazoles can be used together with the composition of the present invention as an additive having antiwear properties.
  • antifoaming agent examples include silicone, fluorosilicone, and fluoroalkyl ether.
  • 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.
  • ⁇ -olefin is propylene
  • ⁇ -olefin is propylene
  • ⁇ -olefin is propylene
  • ⁇ -olefin is propylene
  • the molecular weight of these viscosity index improvers must be selected in consideration of shear stability. More specifically, the number average molecular weight of the viscosity index improver is usually from 5,000 to 1,000, preferably 100, in the case of dispersible and non-dispersible polymethacrylates. , 000 to 900, 000, when polyisobutylene or a hydride thereof is used, it is usually 800 to 5,000, preferably 1, 000 to 4,000. When the product is an ethylene monoolefin copolymer or a hydride thereof, it is usually from 800 to 500,000, preferably from 3,000 to 200,000. Use Can be
  • a lubricating oil composition having particularly excellent shear stability can be obtained.
  • One or more compounds arbitrarily selected from the above viscosity index improvers can be contained in an arbitrary amount.
  • the content is determined based on the total amount of the lubricating oil composition to prevent oxidation.
  • the sulfur content is reduced to 0.3% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less by reducing or not using the additive containing sulfur.
  • a lubricating oil composition containing substantially no sulfur can be obtained.
  • the lubricating oil additive or lubricating oil composition of the present invention can be preferably used as a lubricating oil additive for internal combustion engines such as gasoline engines, motorcycle engines, diesel engines, and gas engines for motorcycles, automobiles, power generation, and ships.
  • low sulfur fuels such as sulfur
  • the lubricant additive of the present invention can improve the long drain property while maintaining the anti-wear property. Therefore, the lubricant additive for a drive system such as an automatic or manual transmission which requires such performance is used. It can be suitably used as a lubricating oil additive such as lubricating oil, wet brake, hydraulic oil, turbine oil, compressor oil, bearing oil, and refrigeration oil.
  • Lubricating oil additives A to M of the present invention were prepared according to the following formulation.
  • T 50 g of zinc di (2-ethylhexyl) phosphate obtained in the above (1) d), 25 g of dodecyldimethylamine, and 25 g of alkyldiphenylamine (alkyl group: butyl group and octyl group)
  • alkyldiphenylamine alkyl group: butyl group and octyl group
  • lubricating oil compositions of the present invention were prepared according to the compositions shown in Tables 1 to 3. .
  • solubility tests of additives were performed. In the solubility test, each component containing the additive was collected in a mixing container at room temperature, mixed with heating and stirring at 80 ° C, and the dissolution state of the additive (presence or absence of insoluble components) was checked visually at predetermined intervals. It was done by observation.
  • lubricating oil compositions (Comparative Examples 1 to 12) were prepared according to the compositions shown in Table 4 by a conventional method. Then, a solubility test was performed in the same manner as described above, and evaluation was performed in the same manner. Tables 1 to 4 show these evaluation results. ⁇
  • Alkyl diph L-nilamine (alkyl group: butyl group, octyl group) 13) OCP average molecular weight: 150,000 14) polyalkylene glycol
  • Alkyl group butyl group, phosphorus content: 13.2 mass ⁇ 1 ⁇ 2, zinc content: 13 mass%, sulfur content: 0 mass%
  • Alkyl group 1,3 dimethylbutyl group, phosphorus content: 13.8 mass%, zinc content: 18.7 mass%
  • Alkyl group 2-ethylhexyl group, phosphorus content: 9.1% by mass, calcium content: 5.8% by mass
  • Alkyl group 2-ethylhexyl group, phosphorus content: 8.8% by mass, zinc content: 9.1% by mass
  • Alkyl diphenylamine (alkyl group: butyl group and octyl group)
  • the lubricating oil composition containing the lubricating oil additive of the present invention disappeared after 16 hours and completely dissolved.
  • the lubricating oil composition containing the lubricating oil additive of the present invention obtained by using the ashless dispersant as the component (B) is: After 2 hours, the insoluble matter had disappeared, indicating that it was completely dissolved in a short time. It has been confirmed that the lubricating oil composition thus obtained has no problem in storage stability. It has been confirmed that zinc dialkyl monothiophosphate (Note 7 in Table 4) can be oil-solubilized by the same method, and that a lubricating oil composition can be manufactured in a short time.
  • the lubricating oil composition of the present invention has the same anti-wear properties as compared with the case where zinc dialkyldithiophosphate is used, and has a long drain property such as oxidation stability and base number maintenance property, and has a high temperature. Cleanliness, low friction, copper corrosion, etc. can be significantly improved, and the sulfur content is 0.3% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, particularly substantially A low-sulfur lubricating oil composition containing no sulfur can be obtained, and the above-described various characteristics can be obtained in an internal combustion engine using gasoline having a sulfur content of 10 mass ppm or less and natural gas having a sulfur content of 1 mass ppm or less. About performance Have also confirmed.
  • the lubricating oil additive of the present invention makes it possible to completely dissolve a metal salt of a phosphorus compound that is insoluble or has low solubility in a lubricating oil in a short period of time in a lubricating oil.
  • a lubricating oil composition is prepared using an ashless dispersant or an additive obtained by pre-dissolving or reacting with a salt of an aliphatic amine as an amine compound, the lubricating oil composition can be manufactured in a time as short as a normal lubricating oil composition. It is possible to do. Therefore, the present invention can provide a lubricating oil additive which is extremely useful for industrially mass-producing a lubricating oil composition having the above-described excellent performance, and a method for producing the same.

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Abstract

Cette invention concerne un additif pour huile de graissage que l'on obtient en conférant la solubilité dans l'huile à (A) un sel de métal de composé phosphoré spécifique insoluble ou peu soluble dans des huiles de graissage, ceci en dissolvant ou en faisant réagir le sel (A) dans ou avec (B) un composé amine.
PCT/JP2003/008337 2002-06-28 2003-06-30 Additif pour huile de graissage, composition d'huile de graissage le renfermant et procede de fabrication dudit additif WO2004003118A1 (fr)

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AU2003244023A AU2003244023A1 (en) 2002-06-28 2003-06-30 Lubricating oil additive, lubricating oil composition containing the same, and process for producing the same
JP2004517339A JP4532268B2 (ja) 2002-06-28 2003-06-30 潤滑油添加剤、これを含有する潤滑油組成物及びその製造方法
CN038173549A CN1671828B (zh) 2002-06-28 2003-06-30 润滑油添加剂,包含这种添加剂的润滑油组合物,以及这种添加剂和组合物的生产方法
EP03736321A EP1516911A4 (fr) 2002-06-28 2003-06-30 Additif pour huile de graissage, composition d'huile de graissage le renfermant et procede de fabrication dudit additif
US11/020,087 US7732385B2 (en) 2002-06-28 2004-12-22 Lubricating oil additives, lubricating oil compositions containing such additives and processes for producing such additives and compositions

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JP2017002300A (ja) * 2015-06-11 2017-01-05 株式会社オートネットワーク技術研究所 金属表面コーティング用組成物および端子付き被覆電線
JP2020526641A (ja) * 2017-07-14 2020-08-31 シェブロン・オロナイト・カンパニー・エルエルシー 硫黄リン非含有亜鉛化合物を含有する潤滑油組成物、および直接噴射火花点火式エンジンにおける低速早期着火を防止または低減する方法

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JP4515797B2 (ja) * 2004-03-19 2010-08-04 新日本石油株式会社 ディーゼルエンジン用潤滑油組成物
AR070686A1 (es) * 2008-01-16 2010-04-28 Shell Int Research Un metodo para preparar una composicion de lubricante
CN101323809B (zh) * 2008-08-12 2010-12-22 上海海联润滑材料科技有限公司 盾构专用抗磨液压油
CA2834569A1 (fr) * 2011-05-26 2012-11-29 The Lubrizol Corporation Melanges stabilises contenant des modificateurs de frottement
JP5843406B2 (ja) 2014-02-19 2016-01-13 株式会社オートネットワーク技術研究所 金属表面コーティング用組成物およびこれを用いた端子付き被覆電線
US9944879B2 (en) * 2014-10-08 2018-04-17 Afton Chemical Corporation Phosphorous-containing compounds and uses thereof
JP2023004315A (ja) * 2021-06-25 2023-01-17 Ｅｎｅｏｓ株式会社 内燃機関用潤滑油組成物
CN116042288A (zh) * 2021-10-28 2023-05-02 中国石油化工股份有限公司 润滑脂组合物及其制备方法和嘧啶类化合物和脂肪醇的应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1237581A (en) * 1968-05-17 1971-06-30 Mobil Oil Corp Coordinated complexes of nitrogenous compounds
EP0325977A1 (fr) * 1988-01-27 1989-08-02 The Elco Corporation Additifs de phosphite amine pour lubrifiant
JPH0320395A (ja) * 1989-03-08 1991-01-29 Daido Kagaku Kogyo Kk 潤滑防錆油組成物
JPH03258897A (ja) * 1990-03-07 1991-11-19 Daido Kagaku Kogyo Kk 熱間圧延油組成物
JPH0565493A (ja) * 1991-09-06 1993-03-19 Daido Kagaku Kogyo Kk アルミ合金又は非鉄金属の塑性加工潤滑剤
JPH10147788A (ja) * 1996-11-21 1998-06-02 Kagaku Gijutsu Shinko Jigyodan 水性冷間鍛造潤滑剤
JPH11323363A (ja) * 1998-05-21 1999-11-26 Daido Chem Ind Co Ltd 水性冷間鍛造潤滑剤
JP2002155291A (ja) * 2000-11-21 2002-05-28 Tonengeneral Sekiyu Kk 潤滑油組成物

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3491133A (en) * 1964-03-06 1970-01-20 Cities Service Res & Dev Co Metal organo phosphates and amine salts thereof
US4981602A (en) * 1988-06-13 1991-01-01 The Lubrizol Corporation Lubricating oil compositions and concentrates
CN1101666A (zh) * 1993-10-12 1995-04-19 张仁鹏 一种复合润滑剂的制备方法
ES2124002T3 (es) * 1994-07-11 1999-01-16 Exxon Chemical Patents Inc Dispersantes a base de aditivos de succinimida derivados de poliamida pesada utilizados para aceite lubricante.
US5763372A (en) * 1996-12-13 1998-06-09 Ethyl Corporation Clean gear boron-free gear additive and method for producing same
JP4663843B2 (ja) * 2000-03-29 2011-04-06 Ｊｘ日鉱日石エネルギー株式会社 潤滑油組成物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1237581A (en) * 1968-05-17 1971-06-30 Mobil Oil Corp Coordinated complexes of nitrogenous compounds
EP0325977A1 (fr) * 1988-01-27 1989-08-02 The Elco Corporation Additifs de phosphite amine pour lubrifiant
JPH0320395A (ja) * 1989-03-08 1991-01-29 Daido Kagaku Kogyo Kk 潤滑防錆油組成物
JPH03258897A (ja) * 1990-03-07 1991-11-19 Daido Kagaku Kogyo Kk 熱間圧延油組成物
JPH0565493A (ja) * 1991-09-06 1993-03-19 Daido Kagaku Kogyo Kk アルミ合金又は非鉄金属の塑性加工潤滑剤
JPH10147788A (ja) * 1996-11-21 1998-06-02 Kagaku Gijutsu Shinko Jigyodan 水性冷間鍛造潤滑剤
JPH11323363A (ja) * 1998-05-21 1999-11-26 Daido Chem Ind Co Ltd 水性冷間鍛造潤滑剤
JP2002155291A (ja) * 2000-11-21 2002-05-28 Tonengeneral Sekiyu Kk 潤滑油組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1516911A4 *

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7563752B2 (en) 2002-08-05 2009-07-21 Nippon Oil Corporation Lubricating oil compositions
US7625847B2 (en) 2002-08-05 2009-12-01 Nippon Oil Corporation Lubricating oil compositions
JPWO2005035701A1 (ja) * 2003-10-09 2006-12-21 出光興産株式会社 潤滑油添加剤及び潤滑油組成物
JP4734117B2 (ja) * 2003-10-09 2011-07-27 出光興産株式会社 潤滑油添加剤及び潤滑油組成物
US7645726B2 (en) 2004-12-10 2010-01-12 Afton Chemical Corporation Dispersant reaction product with antioxidant capability
JP4573758B2 (ja) * 2004-12-10 2010-11-04 アフトン・ケミカル・コーポレーション 抗酸化性を有する分散剤反応生成物
JP2006169519A (ja) * 2004-12-10 2006-06-29 Afton Chemical Corp 抗酸化性を有する分散剤反応生成物
TWI423995B (zh) * 2005-06-22 2014-01-21 Nippon Polyurethane Kogyo Kk A reaction catalyst for forming a isocyanurate link, and a method for producing the modified polyisocyanate mixture containing the isocyanurate link thereof
JP2008231192A (ja) * 2007-03-19 2008-10-02 Nippon Oil Corp 潤滑油組成物
WO2011099195A1 (fr) 2010-02-12 2011-08-18 Ｊｘ日鉱日石エネルギー株式会社 Composition d'additif lubrifiant
CN102753665A (zh) * 2010-02-12 2012-10-24 吉坤日矿日石能源株式会社 润滑油用添加剂组合物
CN104194896A (zh) * 2014-08-30 2014-12-10 广西大学 一种蓖麻基高速齿轮泵油的组合物
CN104194895A (zh) * 2014-08-31 2014-12-10 广西大学 一种燃用油焦浆发动机油组合物
JP2017002300A (ja) * 2015-06-11 2017-01-05 株式会社オートネットワーク技術研究所 金属表面コーティング用組成物および端子付き被覆電線
JP2020526641A (ja) * 2017-07-14 2020-08-31 シェブロン・オロナイト・カンパニー・エルエルシー 硫黄リン非含有亜鉛化合物を含有する潤滑油組成物、および直接噴射火花点火式エンジンにおける低速早期着火を防止または低減する方法
JP7221271B2 (ja) 2017-07-14 2023-02-13 シェブロン・オロナイト・カンパニー・エルエルシー 硫黄リン非含有亜鉛化合物を含有する潤滑油組成物、および直接噴射火花点火式エンジンにおける低速早期着火を防止または低減する方法

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EP1516911A4 (fr) 2005-09-14
JP4532268B2 (ja) 2010-08-25
EP1516911A1 (fr) 2005-03-23
CN102268317B (zh) 2013-09-18
AU2003244023A1 (en) 2004-01-19
CN1671828A (zh) 2005-09-21
JPWO2004003118A1 (ja) 2005-10-27
CN102268317A (zh) 2011-12-07

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