WO2010029945A1 - Additive for oil and lubricating oil composition containing same - Google Patents

Additive for oil and lubricating oil composition containing same Download PDF

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Publication number
WO2010029945A1
WO2010029945A1 PCT/JP2009/065758 JP2009065758W WO2010029945A1 WO 2010029945 A1 WO2010029945 A1 WO 2010029945A1 JP 2009065758 W JP2009065758 W JP 2009065758W WO 2010029945 A1 WO2010029945 A1 WO 2010029945A1
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Prior art keywords
compound
substituent
optionally substituted
same
lubricating oil
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PCT/JP2009/065758
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French (fr)
Japanese (ja)
Inventor
卓 大原
幸宏 磯貝
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協和発酵ケミカル株式会社
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Priority to JP2010528736A priority Critical patent/JPWO2010029945A1/en
Publication of WO2010029945A1 publication Critical patent/WO2010029945A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/14—Containing carbon-to-nitrogen double bounds, e.g. guanidines, hydrazones, semicarbazones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • 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
    • C10M2223/042—Metal salts thereof
    • 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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/02—Bearings
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives

Definitions

  • the present invention relates to an additive for oils used in a lubricating oil composition or the like.
  • Zinc phosphate compounds such as zinc dialkyldithiophosphate are known as wear reducing agents used in lubricating oil compositions used in engines and transmissions for automobiles, bearings, and the like (Non-patent Document 1). Since the zinc phosphate compound cannot impart sufficient friction resistance to oils such as a lubricating oil composition alone, it is used in combination with a friction modifier.
  • Patent Document 1 discloses a lubricating oil composition for protecting silver which contains a reaction product of C5-C60 carboxylic acid and guanidine and does not contain a zinc dihydrocarbyl dithiophosphate.
  • Patent Documents 2 and 3 disclose a lubricant composition containing a reaction product of C5-C60 carboxylic acid and guanidine.
  • a functional liquid containing a compound such as a urea derivative, guanidine or guanidine acetate is disclosed in Patent Document 4, and zinc dialkyldithiophosphate is exemplified as one of additives that can be included in the functional liquid.
  • a compound such as a urea derivative, guanidine or guanidine acetate
  • zinc dialkyldithiophosphate is exemplified as one of additives that can be included in the functional liquid.
  • the friction resistance and wear resistance of the functional fluid are not sufficient.
  • a cotton spinning oil characterized by containing a cationic surfactant having an amidine group, such as stearylguanidine acetate, is known (Patent Document 5).
  • An object of the present invention is to provide an additive for oils that imparts excellent friction resistance or excellent wear resistance to oils such as lubricating oil compositions.
  • the present invention provides the following (1) to (25).
  • X 1 and X 2 are the same or different and each represents a sulfur atom or an oxygen atom
  • R 1 and R 2 are the same or different and each represents an optionally substituted alkyl or substituent.
  • An alkenyl that may have, an aryl that may have a substituent, an cycloalkyl that may have a substituent, or a cycloalkenyl that may have a substituent, and two R 1 , Two R 2 s , two X 1 s and two X 2 s may be the same or different
  • a zinc phosphate compound having the structure represented by formula (II):
  • R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are each a hydrogen atom, an optionally substituted alkyl, an optionally substituted alkenyl or Represents an aralkyl which may have a substituent, and R 4 and R 5 or R 6 and R 7 together with the adjacent nitrogen atom each represents an aliphatic heterocyclic group which may have a substituent.
  • R 3 , R 4 , R 5 , R 6 and R 7 do not represent a hydrogen atom at the same time, or a guanidine compound or a salt thereof. .
  • R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are a hydrogen atom, an optionally substituted alkyl or an optionally substituted alkenyl.
  • At least one of R 3 , R 4 , R 5 , R 6 and R 7 may have a substituent, an alkyl having 12 to 30 carbon atoms, or an optionally substituted carbon
  • X 1 and X 2 are the same or different and each represents a sulfur atom or an oxygen atom
  • R 1 and R 2 are the same or different and each represents an optionally substituted alkyl or substituent.
  • An alkenyl that may have, an aryl that may have a substituent, an cycloalkyl that may have a substituent, or a cycloalkenyl that may have a substituent, and two R 1 , Two R 2 s , two X 1 s and two X 2 s may be the same or different
  • a zinc phosphate compound having the structure represented by formula (II):
  • R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are each a hydrogen atom, an optionally substituted alkyl, an optionally substituted alkenyl or Represents an aralkyl which may have a substituent, and R 4 and R 5 or R 6 and R 7 together with the adjacent nitrogen atom each represents an aliphatic heterocyclic group which may have a substituent.
  • R 3 , R 4 , R 5 , R 6 and R 7 do not represent hydrogen atoms at the same time
  • an oil containing a reaction product with a salt thereof Additives are not represent hydrogen atoms at the same time
  • R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are a hydrogen atom, an optionally substituted alkyl or an optionally substituted alkenyl.
  • the additive for oils as described in (7). At least one of R 3 , R 4 , R 5 , R 6 and R 7 may have a substituent, an alkyl having 12 to 30 carbon atoms, or an optionally substituted carbon
  • Lubricating oil base oil is mineral oil, poly- ⁇ -olefin, fatty acid ester, aromatic ester, polyalkylene glycol, phosphate ester, silicone, silicate ester, polyphenyl ether, alkylbenzene, synthetic naphthene, gas two
  • the lubricating oil composition according to (13) which is at least one selected from the group consisting of liquid (GTL), fluorocarbon, ionic liquid, vegetable oil, and animal oil.
  • X 1 and X 2 are the same or different and each represents a sulfur atom or an oxygen atom
  • R 1 and R 2 are the same or different and each represents an optionally substituted alkyl or substituent.
  • An alkenyl that may have, an aryl that may have a substituent, an cycloalkyl that may have a substituent, or a cycloalkenyl that may have a substituent, and two R 1 , Two R 2 s , two X 1 s and two X 2 s may be the same or different
  • a zinc phosphate compound having the structure represented by formula (II)
  • R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are each a hydrogen atom, an optionally substituted alkyl, an optionally substituted alkenyl or Represents an aralkyl which may have a substituent, and R 4 and R 5 or R 6 and R 7 together with the adjacent nitrogen atom each represents an aliphatic heterocyclic group which may have a substituent.
  • R 3 , R 4 , R 5 , R 6 and R 7 do not simultaneously represent a hydrogen atom) or a salt thereof (ii) represented by formula (I) Reaction product (18) R 3 , R 4 , R 5 , R 6 and R 7 of a zinc phosphate compound having the structure: and a guanidine compound represented by formula (II) or a salt thereof are the same or different , Hydrogen atom, optionally substituted alkyl or The lubricating oil composition according to (17), which is alkenyl which may have a substituent.
  • At least one of R 3 , R 4 , R 5 , R 6 and R 7 may have a substituent, an alkyl having 12 to 30 carbon atoms, or an optionally substituted carbon
  • Lubricating oil base oil is mineral oil, poly- ⁇ -olefin, fatty acid ester, aromatic ester, polyalkylene glycol, phosphate ester, silicone, silicate ester, polyphenyl ether, alkylbenzene, synthetic naphthene, gas two
  • the lubricating oil composition according to any one of (17) to (22) which is at least one selected from the group consisting of liquid (GTL), fluorocarbon, ionic liquid, vegetable oil, and animal oil.
  • examples of the alkyl include linear or branched alkyl having 1 to 30 carbon atoms, specifically, methyl, ethyl, propyl, Isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, 1-ethylpropyl, hexyl, isohexyl, 1-methylpentyl, 1-ethylbutyl, heptyl, 1- Methylhexyl, 1-ethylpentyl, octyl, 1-eth
  • alkenyl examples include linear or branched alkenyl having 2 to 30 carbon atoms, and specifically, vinyl, allyl, isopropenyl, butenyl, isobutenyl, 2-methylpropenyl, pentenyl, 1-methyl-2 -Butenyl, 1-ethyl-2-propenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, butyloctenyl, octylbutenyl, tridecenyl, tetradecenyl, butyldecenyl, hexyloctenyl, hexyldecenyl, heptadecenyl, octadecenyl, dodecylhexenyl, dodecylhexenyl Examples include decenyl, eicosenyl, octyldodecenyl, t
  • aryl examples include aryl having 6 to 14 carbon atoms, and specific examples include phenyl, naphthyl, azulenyl, anthryl and the like.
  • cycloalkyl examples include cycloalkyl having 3 to 7 carbon atoms, and specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
  • Examples of cycloalkenyl include cycloalkenyl having 3 to 7 carbon atoms, and specific examples include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl and the like.
  • Examples of aralkyl include aralkyl having 7 to 30 carbon atoms, and specifically include benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, phenylheptyl, phenyloctyl, phenylnonyl, phenyldecyl. , Phenylundecyl, phenyldodecyl, naphthylmethyl, naphthylethyl and the like.
  • Examples of the aliphatic heterocyclic ring of the aliphatic heterocyclic group formed by R 4 and R 5 or R 6 and R 7 together with the adjacent nitrogen atom include, for example, the number of carbon atoms containing at least one nitrogen atom Examples include 3 to 10 aliphatic heterocycles, and specific examples include a piperidine ring, a pyrrolidine ring, and a morpholine ring. Examples of the substituent for alkyl and alkenyl include the same or different 1 to 3 substituents, specifically, hydroxy, alkoxy, alkoxyalkoxy, alkyl-substituted or unsubstituted amino, mercapto, alkylthio and the like. .
  • Alkyl parts of alkoxy, alkoxyalkoxy, alkyl-substituted amino and alkylthio are as defined above.
  • the alkyl-substituted amino is amino substituted with two alkyls
  • the two alkyls may be the same or different.
  • the alkylene part of alkoxyalkoxy has the same meaning as that obtained by removing one hydrogen atom from the alkyl.
  • Examples of the substituent of the aryl, cycloalkyl, cycloalkenyl, aralkyl and aliphatic heterocyclic group include, for example, the same or different 1 to 5 substituents, specifically, hydroxy, alkyl, alkoxy, nitro, cyano, Examples include alkyl-substituted or unsubstituted amino, mercapto, alkylthio and the like.
  • alkyl, alkoxy, alkyl-substituted amino and alkylthio are as defined above.
  • R 1 and R 2 are the same or different and each may have an optionally substituted alkyl group having 3 to 14 carbon atoms or an optionally substituted group having 3 to 14 carbon atoms.
  • Alkenyl is preferred.
  • the substituent of the alkyl having 3 to 14 carbon atoms has the same meaning as the substituent of the alkyl
  • the substituent of alkenyl having 3 to 14 carbons has the same meaning as the substituent of the alkenyl.
  • Specific examples of the alkyl having 3 to 14 carbon atoms include those having 3 to 14 carbon atoms among the alkyls exemplified above.
  • Specific examples of the alkenyl having 3 to 14 carbon atoms include those having 3 to 14 carbon atoms among the alkenyls exemplified above.
  • Examples of the compound (I) include a compound represented by the formula (I), a salt of a compound represented by the formula (I) and zinc oxide, and the like.
  • the compound (I) those in which two X 1 and two X 2 are all the same and are an oxygen atom or a sulfur atom are preferred, and all of two X 1 and two X 2 are the same and are a sulfur atom Is more preferable.
  • Examples of the compound (I) in which two X 1 and two X 2 are all the same and are oxygen atoms include, for example, formula (Ia)
  • R 1 and R 2 have the same meanings as described above, and y represents 0 or 1/3).
  • compound (II) or a salt thereof at least one of R 3 , R 4 , R 5 , R 6 and R 7 has an optionally substituted alkyl having 12 to 30 carbon atoms or a substituent.
  • the alkenyl having 12 to 30 carbon atoms which may be optionally substituted is preferable, and the alkyl having 16 to 18 carbon atoms which may be substituted or the alkenyl having 16 to 18 carbon atoms which may be optionally substituted.
  • the alkyl substituent having 12 to 30 carbon atoms and the alkyl substituent having 16 to 18 carbon atoms have the same meaning as the above alkyl substituent, and the alkenyl having 12 to 30 carbon atoms and the substituent having 16 to 18 carbon atoms are substituted Is synonymous with the substituent of the said alkenyl.
  • Specific examples of the alkyl having 12 to 30 carbon atoms and the alkyl having 16 to 18 carbon atoms include those having 12 to 30 and 16 to 18 carbon atoms among the alkyls exemplified above.
  • Specific examples of the alkenyl having 12 to 30 carbon atoms and the alkenyl having 16 to 18 carbon atoms include those having 12 to 30 and 16 to 18 carbon atoms among the alkenyls exemplified above.
  • H m A represents m protons and an anion represented by A m ⁇ when completely ionized.
  • A represents an m-valent group obtained by removing m hydrogen atoms from the acid
  • p represents 1 when m is 1
  • p is 1 or more when m is an integer of 2 or more.
  • a salt represented by any one of integers equal to or less than m).
  • H m A includes formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, n-octylic acid, 2-ethylhexylic acid, isononanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, oleic acid, Carboxylic acids such as stearic acid and isostearic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, octadecenylsulfonic acid and other sulfonic acids, sulfuric acid, nitric acid, hydrochloric acid, carbonic acid, boron Examples thereof include acid and phosphoric acid, and carbonic acid and boric acid are preferable.
  • reaction product of compound (I) with compound (II) or a salt thereof examples include, for example, compound (I), a mixture of compound (II) or a salt thereof and diethyl ether in a molar amount twice that of compound (I). And a reaction product obtained by refluxing for 1 hour.
  • the reaction product of the compound (I) and the compound (II) or a salt thereof may be referred to as a reaction product (X).
  • Compound (I) can be obtained as a commercial product, or can be obtained by a known method such as JP-A 63-99082 or Journal of Organic Chemistry, 1956, Vol. 21, p. It can obtain by manufacturing according to the method as described in 705 grade
  • a mixture of compound (Ib-2i) and compound (Ib-2ii), a mixture of compound (Ib-3i) and compound (Ib-3ii), compound (Ib- Preferred examples of compound (I) include a mixture of 4i) and compound (Ib-4ii), a mixture of compound (Ib-5i) and compound (Ib-5ii), and the like.
  • An example of a method for producing compound (II) or a salt thereof is shown in the following formula.
  • R 3 , R 4 , R 5 , R 6 , R 7 , A, m and p are as defined above, Y represents an oxygen atom or a sulfur atom, and R 8 has 1 to 4 carbon atoms.
  • H n B represents an acid dissociated into n protons and an anion represented by B n ⁇ when completely ionized, and B represents an n valence obtained by removing n hydrogen atoms from the acid.
  • alkyl having 1 to 4 carbon atoms include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and the like, and methyl and ethyl are preferable.
  • Examples of the acid represented by H n B include the acids exemplified above as specific examples of H m A.
  • Examples of the alkali metal include sodium and potassium.
  • Compound (V) is described in, for example, Bioorganic Medicinal Chemistry, 2003, Vol. 11, p. According to the method described in 1283 and the like, it can be produced by reacting compound (III) and compound (IV) in a solvent at 20 to 200 ° C. for 0.5 to 24 hours.
  • Compound (III) can be obtained as a commercial product, for example, Journal of American Chemical Society, 1952, vol. 74, p. 4271 or Organic Synthesis, 1963, vol. 4, p. It can obtain by manufacturing according to the method of 645, etc.
  • Compound (IV) can be obtained as a commercial product, or can be obtained, for example, by manufacturing according to the method described in US Pat. No. 4,409,399 or JP-B-38-21353.
  • the solvent examples include hydrocarbons such as hexane, decane, tetradecane, toluene, xylene, alcohols such as methanol, ethanol, isopropyl alcohol, and butanol, ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, methoxybenzene, and diphenyl ether, methylene chloride Halogenated hydrocarbons such as dichloroethane, chloroform, chlorobenzene and dichlorobenzene, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, dimethyl sulfoxide, mixed solvents thereof, etc. Hydrocarbons are preferred.
  • hydrocarbons such as hexane, decane, tetradecane, toluene, xylene
  • alcohols such as methanol, ethanol, isopropyl alcohol, and butanol
  • ethers such as
  • the compound (IV) is preferably used in an amount of 0.2 to 20 equivalents, more preferably 0.5 to 10 equivalents, relative to the compound (III).
  • the compound (V) may be purified by methods usually used in organic synthetic chemistry (such as various chromatographic methods, recrystallization methods, and distillation methods).
  • organic synthetic chemistry such as various chromatographic methods, recrystallization methods, and distillation methods.
  • one of the two or more kinds of compounds (V) may be isolated by the above-described purification method or the like.
  • the mixture is a raw material of a reaction product of a salt of compound (I) and compound (II), a raw material of an additive for oils containing a salt of compound (I) and compound (II), or an addition for the oils You may use as a raw material of the lubricating oil composition obtained by mixing an agent and lubricating base oil.
  • compound (V) can also be converted to a salt of another compound (II) [eg, compound (VI) and the like].
  • a method for converting compound (V) into compound (VI) for example, compound (V) and M n B (wherein, M, n and B are as defined above) in a solvent ⁇ 10
  • examples thereof include a method for producing compound (VI) by reacting at -100 ° C. for 0.1-24 hours.
  • M n B is preferably used in an amount of 0.2 to 20 equivalents, more preferably 0.5 to 10 equivalents, relative to compound (V).
  • the solvent include the solvents exemplified above, and a mixture of the solvent and water.
  • the compound (VI) may be purified by methods usually used in organic synthetic chemistry (various chromatographic methods, recrystallization methods, distillation methods, etc.).
  • one of the two or more kinds of compounds (VI) may be isolated by the above purification method or the like.
  • the mixture is a raw material of a reaction product of a salt of compound (I) and compound (II), a raw material of an additive for oils containing a salt of compound (I) and compound (II), or an addition for the oils You may use as a raw material of the lubricating oil composition obtained by mixing an agent and lubricating base oil.
  • Compound (II) can be produced, for example, by reacting compound (V) with a base at ⁇ 10 to 100 ° C. for 0.1 to 24 hours in a solvent.
  • the base include inorganic bases such as sodium hydroxide, potassium hydroxide, and cesium hydroxide.
  • the base is preferably used in an amount of 0.2 to 200 equivalents, more preferably 0.5 to 100 equivalents, relative to compound (V).
  • the solvent examples include the solvents exemplified above, and a mixture of the solvent and water.
  • the compound (II) may be purified by methods usually used in organic synthetic chemistry (such as various chromatographic methods, recrystallization methods, and distillation methods).
  • Compound (VI) can also be produced by reacting compound (II) with H n B (wherein n and B are as defined above).
  • R 3 , R 4 , and R 5 are the same and are a hydrogen atom
  • compounds (II) in which R 3 , R 4 , and R 5 are the same and are a hydrogen atom can be synthesized according to, for example, the method described in US Pat. No. 2,425,341, such as NHR 6a R 7a
  • R 6a and R 7a are the same or different and each represents a hydrogen atom, an alkyl having a substituent, an alkenyl optionally having a substituent, or an aralkyl optionally having a substituent.
  • R 6a and R 7a may be combined with the adjacent nitrogen atom to form an optionally substituted aliphatic heterocyclic group, provided that R 6a and R 7a are simultaneously hydrogen atoms.
  • the alkyl which may have a substituent the alkenyl which may have a substituent, the aralkyl which may have a substituent and the substituent formed together with the adjacent nitrogen atom
  • the aliphatic heterocyclic group optionally having the same meaning as defined above.
  • the amine salt include hydrochloride, hydrobromide, sulfate, nitrate, and the like.
  • NHR 6a R 7a can be obtained as a commercial product, or can be obtained, for example, according to the method described in US Pat. No. 4,409,399 or Japanese Patent Publication No. 38-21353.
  • a mixture of compound (VI-1a) and compound (VI-1b), a mixture of compound (VI-2a) and compound (VI-2b), compound (VI- A mixture of 3a) and compound (VI-3b) is also a preferred specific example of compound (II) or a salt thereof.
  • the geometric isomerism (E or Z) of the carbon-carbon double bond in compound (VI-2a) and compound (VI-2b) is not particularly limited.
  • a compound obtained by reacting compound (II) or a salt thereof with a boron compound is converted between compound (I) and compound (II) or a salt thereof instead of compound (II) or a salt thereof.
  • boron compound examples include borate salts such as ammonium borate, monomethyl borate, dimethyl borate, trimethyl borate, monoethyl borate, diethyl borate, triethyl borate, monopropyl borate, dipropyl borate, boron
  • boric acid esters such as tripropyl acid, monobutyl borate, dibutyl borate, tributyl borate, mono-2-ethylhexyl borate, di-2-ethylhexyl borate, tri-2-ethylhexyl borate, and the like.
  • Reactant (X) can be produced, for example, by reacting compound (I) with compound (II) or a salt thereof in a solvent such as diethyl ether at 0 to 120 ° C. for 0.1 to 30 hours. it can. It is preferable to use the compound (II) or a salt thereof in an amount of 0.1 to 10 times the amount of the compound (I).
  • Compound (I) can be used alone or in admixture of two or more. Among them, it is preferable to use a compound (Ib) in which y is 0 and a compound (Ib) in which y is 1/3. Compound (II) or a salt thereof can be used alone or in admixture of two or more.
  • the reaction product (X) may be purified by methods commonly used in organic synthetic chemistry (such as various chromatographic methods, recrystallization methods, and distillation methods). When a mixture of compound (I) and / or compound (II) or a salt thereof and reactant (X) is obtained, the mixture is used as a raw material for an additive for oils containing reactant (X) May be.
  • Compound (I) can be used alone or in admixture of two or more. Among them, it is preferable to use a compound (Ib) in which y is 0 and a compound (Ib) in which y is 1/3. Moreover, compound (II) or its salt can be used individually or in mixture of 2 or more types.
  • the oil additive containing compound (I) and compound (II) or a salt thereof may be used alone if it is prepared to contain compound (I) and compound (II) or a salt thereof.
  • the additive may be a combination of a plurality of additives.
  • the additive for oils is a combination of a plurality of additives, and the combination of the plurality of additives includes an additive containing compound (I) and an addition containing compound (II) or a salt thereof. It is preferable to contain an agent.
  • the additive for oils containing the reactant (X) may be a single additive or a combination of a plurality of additives. It may be.
  • the additive for oils of the present invention may contain other components in addition to the compound (I), the compound (II) or a salt thereof and the reaction product (X).
  • Other components include, for example, commonly used oil additives [for example, detergent dispersants, antioxidants, wear reducing agents (antiwear agents, anti-seizure agents, extreme pressure agents, etc.), friction Adjustment agents, oiliness agents, rust inhibitors, gas phase rust inhibitors, pour point depressants, viscosity index improvers, thickeners, preservatives, antifoaming agents, demulsifiers, dyes, fragrances, etc.] Is mentioned.
  • oil additives for example, detergent dispersants, antioxidants, wear reducing agents (antiwear agents, anti-seizure agents, extreme pressure agents, etc.), friction Adjustment agents, oiliness agents, rust inhibitors, gas phase rust inhibitors, pour point depressants, viscosity index improvers, thickeners, preservatives, antifoaming agents, demulsifiers, dyes, fragrances, etc.
  • each of the plurality of additives includes, for example, one or more selected from those exemplified above as the other components You may go out.
  • a lubricating oil composition obtained by mixing an additive for oils containing compound (I) and compound (II) or a salt thereof and a lubricating base oil includes, for example, compound (I) and compound (I) II) or a salt thereof, a lubricating base oil, and optional components can be obtained by mixing simultaneously or in any order.
  • Specific methods for preparing the lubricating oil composition include, for example, a method of adding Compound (I), Compound (II) or a salt thereof and an optional component to a lubricating base oil, Compound (I) and a lubricating base. The method of adding compound (II) or its salt to the composition obtained by mixing oil and arbitrary components is mentioned.
  • Examples of the lubricating base oil include natural base oils and synthetic base oils.
  • Examples of natural base oils include mineral oil, vegetable oil, and animal oil.
  • Examples of the mineral oil include paraffinic crude oil, intermediate crude oil, and naphthenic crude oil. Further, refined oils obtained by refining them by distillation or the like can also be used.
  • Synthetic base oils include, for example, poly- ⁇ -olefins (polybutene, polypropylene, ⁇ -olefin oligomers having 8 to 14 carbon atoms, etc.), fatty acid esters (fatty acid monoesters, fatty acid esters of polyhydric alcohols, aliphatic polybasic acids) Ester), aromatic ester (aromatic monoester, aromatic ester of polyhydric alcohol, aromatic polybasic acid ester, etc.), polyalkylene glycol, phosphate ester, silicone, silicate ester, polyphenyl ether, alkylbenzene, Synthetic naphthene, gas-to-liquid (GTL), fluorocarbon, ionic liquid and the like can be mentioned.
  • poly- ⁇ -olefins polybutene, polypropylene, ⁇ -olefin oligomers having 8 to 14 carbon atoms, etc.
  • fatty acid esters fatty acid monoesters, fatty acid esters of polyhydric alcohol
  • Lubricating oil base oil is (1) mineral oil, poly- ⁇ -olefin, fatty acid ester, aromatic ester, polyalkylene glycol, phosphate ester, silicone, silicate ester, polyphenyl ether, alkylbenzene, synthetic naphthene, gas two It is preferably at least one selected from the group consisting of liquid (GTL), fluorocarbon, ionic liquid, vegetable oil, and animal oil.
  • GTL liquid
  • Mineral oil poly- ⁇ -olefin, fatty acid ester, polyalkylene glycol, phosphorus More preferably, it is at least one selected from the group consisting of acid esters, silicones, silicate esters, polyphenyl ethers, alkylbenzenes, synthetic naphthenes, gas-to-liquid (GTL) and vegetable oils.
  • the molar ratio of compound (I) to compound (II) or a salt thereof is preferably 0.1 to 10 [compound (I) / compound (II) or a salt thereof].
  • the use of compound (I) with respect to the total amount of the lubricating oil composition so that the phosphorus content in the lubricating oil composition is in the range of 0.001 to 0.1% by mass with respect to the total amount of the lubricating oil composition It is preferable to adjust the amount.
  • the amount of compound (II) or a salt thereof used is preferably 0.001 to 500 mmol, more preferably 0.01 to 300 mmol, more preferably 0.1 to 1 kg of the lubricating oil composition. It is preferably ⁇ 100 mmol.
  • the optional component examples include additives usually used in lubricating oil compositions, and specific examples of the additive include, for example, detergent dispersants, antioxidants, wear reducing agents (antiwear agents). Anti-seizure agent, extreme pressure agent, etc.), friction modifier, oiliness agent, rust preventive agent, gas phase rust preventive agent, pour point depressant, viscosity index improver, thickener, antiseptic, antifoaming agent, Examples include demulsifiers, dyes, and fragrances.
  • the amount of these additives used is preferably 0.001 to 5% by mass in the lubricating oil composition.
  • a lubricating oil composition obtained by mixing an additive for oils containing compound (I) and compound (II) or a salt thereof and a lubricating base oil is the following (i) and / or (ii) And a lubricating base oil.
  • (I) Compound (I) and Compound (II) or a salt thereof (ii) Reactant (X)
  • the lubricating oil composition containing the (i) and / or the (ii) has excellent friction resistance or excellent wear resistance.
  • the lubricating oil composition obtained by mixing the additive for oils containing the reactant (X) and the lubricating base oil includes, for example, the reactant (X), the lubricating base oil, and optional components. Can be obtained by mixing at the same time or in any order.
  • the lubricating base oil and the optional components are as defined above.
  • Use amount of reactant (X) with respect to the total amount of the lubricating oil composition so that the phosphorus content in the lubricating oil composition is in the range of 0.001 to 0.1 mass% with respect to the total amount of the lubricating oil composition Is preferably adjusted.
  • the amount of the optional component used is that when preparing a lubricating oil composition obtained by mixing an additive for oils containing compound (I) and compound (II) or a salt thereof, and a lubricating base oil. It is the same as that.
  • the lubricating oil composition of the present invention includes, for example, engine oil, automatic transmission oil, continuously variable transmission oil, gear oil, power steering oil, shock absorber oil, turbine oil, hydraulic oil, refrigeration oil, rolling oil, bearing oil, metal It can be used for processing lubricants, sliding surface oils, greases, biological lubricants, and the like.
  • oil additive of the present invention with other oils such as fuel oil, it is possible to impart excellent friction resistance or excellent wear resistance to other oils.
  • fuel oil examples include biodiesel fuel.
  • the amount of compound (I) used when mixing an oil additive containing compound (I) and compound (II) or a salt thereof with fuel oil is 0.00001-10.
  • the content is preferably mass%, more preferably 0.00001 to 1 mass%.
  • the amount of compound (II) or a salt thereof used when mixing an oil additive containing compound (I) and compound (II) or a salt thereof with fuel oil is 0 per 1 kg of fuel oil. It is preferably 0.001 to 500 mmol, more preferably 0.01 to 300 mmol, and further preferably 0.1 to 100 mmol.
  • the amount of the reactant (X) used when mixing the oil additive containing the reactant (X) and the fuel oil is preferably 0.00001 to 10% by mass with respect to the fuel oil. It is more preferably 0.00001 to 1% by mass.
  • the precipitated white solid was collected by filtration with a centrifuge, washed with diethyl ether, and dried under reduced pressure at 50 ° C. to obtain 17.79 g of 9-octadecenylguanidine sulfate.
  • N-ethyl-S-methylisothiourea hydrogen iodide 4.00 g, octadecylamine 4.82 g (manufactured by Tokyo Chemical Industry Co., Ltd.) and methanol 20 ml were mixed and stirred at 60 to 70 ° C. for 6.5 hours. After cooling the reaction solution to 15 ° C., the solvent was distilled off from the reaction solution. 20 ml of diethyl ether was added to the residue, stirred and filtered, the solvent was distilled off from the filtrate, 50 ml of hexane was added to the residue, recrystallization was performed, the solid was collected by filtration, dried at 40 ° C. under reduced pressure, and N-ethyl- 4.27 g of N′-octadecylguanidine hydrogen iodide was obtained.
  • N-ethyl-N′-octadecylguanidine hydrogen iodide 2.50 g, methylene chloride 100 ml and 1 wt% aqueous sodium carbonate solution 100 ml were mixed and stirred at 15 to 25 ° C. for 0.5 hour. The reaction mixture is separated, and the organic layer is washed with saturated brine, dehydrated over anhydrous magnesium sulfate and filtered. The solvent is evaporated from the filtrate, and the residue is dried under reduced pressure at 50 ° C. to give compound (VI-3). 1.47 g of a crude product was obtained.
  • a solution obtained by mixing 45.5 g of hexadecylamine hydrochloride, 2.0 g of hexadecylamine, 40 ml of butanol and 11 ml of distilled water was heated to 93 ° C., and 13.9 g of cyanamide (manufactured by Kanto Chemical Co., Inc.) and 53 ml of distilled water were used.
  • An aqueous solution obtained by mixing was added dropwise to the solution, and the mixture was stirred at 92 ° C. for 7 hours.
  • the solvent was distilled off from the reaction solution to obtain 68.6 g of hexadecylguanidine hydrochloride.
  • a solution obtained by mixing 35.1 g of dodecylamine hydrochloride, 1.5 g of dodecylamine, 30 ml of butanol and 8 ml of distilled water was heated to 94 ° C., and 13.6 g of cyanamide (manufactured by Kanto Chemical Co., Inc.) and 40 ml of distilled water were added.
  • the aqueous solution obtained by mixing was added dropwise to the solution, and the mixture was stirred at 95 ° C. for 12.5 hours.
  • the solvent was distilled off from the reaction solution to obtain 51.4 g of dodecylguanidine hydrochloride.
  • the mixture was filtered, and 115 ml of a 10 wt% aqueous sodium hydroxide solution was added dropwise to the filtrate at 20-25 ° C.
  • the reaction solution and 10.2 g of activated carbon were mixed and stirred at 20-25 ° C. for 15 minutes.
  • the mixture was filtered, an aqueous solution obtained by mixing 42.2 g of zinc chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 30 ml of distilled water was added to the filtrate at 20-25 ° C., and the mixture was added at 20-25 ° C. for 0.5 hour. Stir.
  • the obtained compound (Ib-2) was a mixture of the compound (Ib-2i) and the compound (Ib-2ii).
  • the mixture was filtered, and 120 ml of a 10% by weight aqueous sodium hydroxide solution was added dropwise to the filtrate at 20-25 ° C.
  • the reaction solution and 10.2 g of activated carbon were mixed and stirred at 20 to 25 ° C. for 10 minutes.
  • the mixture was filtered, an aqueous solution obtained by mixing 23.0 g of zinc chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 17 ml of distilled water was added to the filtrate at 20-25 ° C., and the mixture was stirred at 20-25 ° C. for 3 hours. did.
  • the precipitated crystals were collected by filtration, washed with distilled water, and dried under reduced pressure at 35 ° C. to obtain 60.3 g of a crude compound (Ib-3i).
  • the obtained compound (Ib-4) was a mixture of the compound (Ib-4i) and the compound (Ib-4ii).
  • the molar ratio of compound (Ib-4i) to compound (Ib-4ii) in compound (Ib-4) was determined.
  • Molar ratio; Compound (Ib-4i) / Compound (Ib-4ii) 95.5 / 4.5 1 H-NMR (CDCl 3 , ⁇ ppm); 0.90 (m, 24H), 1.20-1.50 (m, 32H), 1.67 (m, 4H), 4.08 (m, 8H)
  • reaction solution and 5.6 g of zinc chloride (Wako Pure Chemical Industries, Ltd.) were mixed and stirred at 50 ° C. for 1 hour.
  • the reaction solution was mixed with 200 ml of hexane, stirred at room temperature for 10 minutes, and then separated.
  • the aqueous layer was extracted twice with 100 ml of hexane, and the combined organic layer was dehydrated with anhydrous sodium sulfate and filtered.
  • the solvent was distilled off from the filtrate, and the residue was recrystallized with a tetrahydrofuran-ethanol mixed solvent to give compound (Ib- 45.4 g of a crude product of 4) was obtained.
  • 31 P-NMR (CDCl 3 , ⁇ ppm); 108.0 The 31 P-NMR measurement results of zinc didodecyldithiophosphate are shown below. 31 P-NMR (CDCl 3 , ⁇ ppm); 99.6
  • Compound (I) includes compound (Ia-1), compound (Ib-1) [Zinc dialkyldithiophosphate manufactured by LUBRIZOL; LUBRIZOL 1095, phosphorus content 9.42% by mass, sulfur content 20.20% by mass, zinc Content 10.41% by mass], compound (Ib-2), (Ib-3i), (Ib-4) or (Ib-5) was used.
  • the compound (II), (II-2), (II-3), (VI-1), (VI-2) or (VI-3) was used as the compound (II) or a salt thereof.
  • the reactant (X) the reactant (X-1), (X-2) or (X-3) was used.
  • the cleaning dispersant a succinimide type ashless dispersant (LUBRIZOL 6401 manufactured by LUBRIZOL, nitrogen content 0.36% by mass) was used.
  • a calcium sulfonate metal detergent (LUBRIZOL 6477C manufactured by LUBRIZOL, total base number 302 mgKOH / g, calcium content 11.98% by mass) was used.
  • antioxidant IRGANOX L57 manufactured by Ciba Specialty Chemicals was used.
  • Example 6 0.5 parts by weight of antioxidant 1 and 0.5 parts by weight of antioxidant 2 were added sequentially to 99.0 parts by weight of the lubricating base oil at 10 to 30 ° C. to obtain 100.0 parts by weight of solution (C-1).
  • Got a part. 87.0 parts by mass of lubricant base oil, 0.5 parts by mass of antioxidant 1, 0.5 parts by mass of antioxidant 2, 8.0 parts by mass of cleaning dispersant 1 and 4.0 parts by mass of cleaning dispersant 2 Were sequentially added at 10 to 30 ° C. to obtain 100.0 parts by mass of a solution (C-2).
  • Example 7 Example 6 except that 0.2 part by mass of the compound (II-3) was used instead of 0.3 part by mass of the compound (II-2), and the amount of the solution (C-1) used was 49.0 parts by mass. The same operation was carried out to obtain 100.0 parts by mass of a lubricating oil composition having the mixing ratio shown in Table 1.
  • Example 8 Compound (Ib-1) is used in place of 0.8 part by mass, Compound (Ib-2) is used in 0.6 part by mass, Compound (II-1) is used in place of Compound (II-2), and Solution (C— The same operation as in Example 6 was performed except that the amount used in 1) was changed to 49.1 parts by mass to obtain 100.0 parts by mass of a lubricating oil composition having a mixing ratio shown in Table 1.
  • Example 9 Example 6 except that 0.6 part by mass of compound (Ib-2) was used instead of 0.8 part by mass of compound (Ib-1) and the amount of solution (C-1) used was 49.1 parts by mass. The same operation was carried out to obtain 100.0 parts by mass of a lubricating oil composition having the mixing ratio shown in Table 1.
  • Example 10 Compound (Ib-1) 0.7 parts by mass instead of 0.8 parts by mass, Compound (II-2) instead of Compound (II-2), Compound (II-1)
  • the same operation as in Example 6 was performed except that the amount used in 1) was changed to 49.0 parts by mass to obtain 100.0 parts by mass of a lubricating oil composition having a mixing ratio shown in Table 1.
  • Example 11 Table 2 shows the same procedure as in Example 6, except that compound (Ib-4) is used instead of compound (Ib-1) and compound (II-1) is used instead of compound (II-2). 100.0 parts by mass of the lubricating oil composition having the described mixing ratio was obtained.
  • Example 12 The compound (Ib-1) is used in an amount of 1.0 part by mass instead of the compound (Ib-1) in an amount of 1.0 part by mass, the compound (II-1) is used in place of the compound (II-2), The same operation as in Example 6 was performed except that the amount used in 1) was changed to 48.7 parts by mass to obtain 100.0 parts by mass of a lubricating oil composition having a mixing ratio shown in Table 2.
  • Example 13 Compound (Ib-1) 0.2 parts by mass instead of 0.8 parts by mass, Compound (II-2) instead of Compound (II-2), Compound (II-1)
  • the same operation as in Example 6 was performed except that the amount used in 1) was changed to 49.5 parts by mass to obtain 100.0 parts by mass of a lubricating oil composition having a mixing ratio shown in Table 2.
  • Example 14 92.5 parts by mass of lubricant base oil, 0.5 parts by mass of antioxidant 1, 0.5 parts by mass of antioxidant 2, 4.0 parts by mass of detergent 1 and 2.0 parts by mass of detergent 2 Were added sequentially at 10-30 ° C. 0.5 parts by mass of the reaction product (X-1) was added to the obtained solution, and the mixture was stirred at 70 to 90 ° C. for 1 hour to obtain 100.0 parts by mass of the lubricating oil composition having the mixing ratio shown in Table 2. Obtained.
  • Example 15 The same operation as in Example 14 was carried out except that the compound (X-2) was used in place of the reactant (X-1) to obtain 100.0 parts by mass of a lubricating oil composition having the mixing ratio shown in Table 2. .
  • Example 16 Example 14 except that 0.8 parts by mass of the reactant (X-3) was used instead of 0.5 parts by mass of the reactant (X-1), and the amount of the lubricating base oil used was 92.2 parts by mass. The same operation was performed to obtain 100.0 parts by mass of a lubricating oil composition having a mixing ratio shown in Table 2.
  • a shell type four-ball friction tester (manufactured by Takachiho Seiki Co., Ltd.) was used as a tester.
  • the wear scar diameter was the average value of all three fixed spheres in the vertical and horizontal directions.
  • Table 5 shows the friction scar diameters of the lubricating oil compositions obtained in Examples 1 and 3 and Comparative Example 1.

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Abstract

An additive for oils is provided which comprises a zinc phosphate compound having a structure represented by formula (I) (wherein X1 and X2 are the same or different and each represents sulfur or oxygen, and R1 and R2 are the same or different and each represents an optionally substituted alkyl, etc., provided that the two R1’s, two R2’s, two X1’s, and two X2’s each may be the same or different) and either a guanidine compound represented by formula (II) (wherein R3, R4, R5, R6, and R7 are the same or different and each represents hydrogen, an optionally substituted alkyl, etc., provided that not all of R3, R4, R5, R6, and R7 are hydrogen) or a salt thereof.

Description

油類用添加剤およびこれを含有する潤滑油組成物Additive for oil and lubricating oil composition containing the same
　本発明は、潤滑油組成物などに用いる油類用添加剤などに関する。 The present invention relates to an additive for oils used in a lubricating oil composition or the like.
　自動車などのエンジンおよび変速機、軸受けなどに用いる潤滑油組成物に用いる摩耗低減剤として、ジアルキルジチオリン酸亜鉛などのリン酸亜鉛化合物が知られている（非特許文献１）。該リン酸亜鉛化合物は潤滑油組成物などの油類に対して十分な耐摩擦特性を単独では付与できないので、摩擦調整剤と併用して用いられる。
　特許文献１にＣ５－Ｃ６０カルボン酸とグアニジンなどとの反応生成物を含有し、ジヒドロカルビルジチオリン酸亜鉛化合物を含まない、銀を保護するための潤滑油組成物が開示されている。特許文献２および３にＣ５－Ｃ６０カルボン酸とグアニジンなどとの反応生成物を含有する潤滑剤組成物が開示されている。 Zinc phosphate compounds such as zinc dialkyldithiophosphate are known as wear reducing agents used in lubricating oil compositions used in engines and transmissions for automobiles, bearings, and the like (Non-patent Document 1). Since the zinc phosphate compound cannot impart sufficient friction resistance to oils such as a lubricating oil composition alone, it is used in combination with a friction modifier.
Patent Document 1 discloses a lubricating oil composition for protecting silver which contains a reaction product of C5-C60 carboxylic acid and guanidine and does not contain a zinc dihydrocarbyl dithiophosphate. Patent Documents 2 and 3 disclose a lubricant composition containing a reaction product of C5-C60 carboxylic acid and guanidine.
　尿素誘導体、グアニジンまたはグアニジンアセテートなどの化合物を含有する機能液が特許文献４に開示されており、該特許文献には該機能液に含むことができる添加剤の一つとしてジアルキルジチオリン酸亜鉛が例示されている。しかし、該機能液の耐摩擦特性および耐摩耗特性は十分ではない。
　ステアリルグアニジン酢酸塩などのアミジン基を有するカチオン型界面活性剤を含有することを特徴とする綿紡績用油剤が知られている（特許文献５）。 A functional liquid containing a compound such as a urea derivative, guanidine or guanidine acetate is disclosed in Patent Document 4, and zinc dialkyldithiophosphate is exemplified as one of additives that can be included in the functional liquid. Has been. However, the friction resistance and wear resistance of the functional fluid are not sufficient.
A cotton spinning oil characterized by containing a cationic surfactant having an amidine group, such as stearylguanidine acetate, is known (Patent Document 5).
米国特許第４９４８５２３号明細書US Pat. No. 4,948,523 特開２００２－１２９１８４号公報JP 2002-129184 A 特開２００３－１０５３６８号公報JP 2003-105368 A 特開昭６３－３０８０９６号公報JP-A-63-308096 特開昭６３－２３５５７９号公報JP-A 63-235579
　本発明の目的は、潤滑油組成物などの油類に優れた耐摩擦特性または優れた耐摩耗特性を付与する油類用添加剤などを提供することにある。 An object of the present invention is to provide an additive for oils that imparts excellent friction resistance or excellent wear resistance to oils such as lubricating oil compositions.
　本発明は、以下の（１）～（２５）を提供する。
（１）式（Ｉ） The present invention provides the following (1) to (25).
(1) Formula (I)
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
（式中、Ｘ１およびＸ２は、同一または異なって、硫黄原子または酸素原子を表し、Ｒ１およびＲ２は、同一または異なって、置換基を有していてもよいアルキル、置換基を有していてもよいアルケニル、置換基を有していてもよいアリール、置換基を有していてもよいシクロアルキルまたは置換基を有していてもよいシクロアルケニルを表し、２つのＲ１、２つのＲ２、２つのＸ１および２つのＸ２のそれぞれは同一または異なっていてもよい）で表される構造を有するリン酸亜鉛化合物と、式（ＩＩ） (In the formula, X 1 and X 2 are the same or different and each represents a sulfur atom or an oxygen atom, and R 1 and R 2 are the same or different and each represents an optionally substituted alkyl or substituent. An alkenyl that may have, an aryl that may have a substituent, an cycloalkyl that may have a substituent, or a cycloalkenyl that may have a substituent, and two R 1 , Two R 2 s , two X 1 s and two X 2 s may be the same or different), and a zinc phosphate compound having the structure represented by formula (II):
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
（式中、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７は、同一または異なって、水素原子、置換基を有していてもよいアルキル、置換基を有していてもよいアルケニルまたは置換基を有していてもよいアラルキルを表し、Ｒ４とＲ５またはＲ６とＲ７が隣接する窒素原子と一緒になってそれぞれ置換基を有していてもよい脂肪族複素環基を形成してもよい。但し、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７が同時に水素原子を表すことはない）で表されるグアニジン化合物またはその塩とを含有する油類用添加剤。
（２）Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７が、同一または異なって、水素原子、置換基を有していてもよいアルキルまたは置換基を有していてもよいアルケニルである（１）に記載の油類用添加剤。
（３）Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７のうち、少なくとも一つが置換基を有していてもよい炭素数１２～３０のアルキルまたは置換基を有していてもよい炭素数１２～３０のアルケニルである（１）または（２）に記載の油類用添加剤。
（４）式（ＩＩ）で表されるグアニジン化合物またはその塩が、式（ＩＩ）で表されるグアニジン化合物の炭酸塩である（１）～（３）のいずれかに記載の油類用添加剤。
（５）２つのＸ１および２つのＸ２のすべてが同一で硫黄原子である（１）～（４）のいずれかに記載の油類用添加剤。
（６）Ｒ１およびＲ２が、同一または異なって、置換基を有していてもよい炭素数３～１４のアルキルまたは置換基を有していてもよい炭素数３～１４のアルケニルである（１）～（５）のいずれかに記載の油類用添加剤。
（７）式（Ｉ） (Wherein R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are each a hydrogen atom, an optionally substituted alkyl, an optionally substituted alkenyl or Represents an aralkyl which may have a substituent, and R 4 and R 5 or R 6 and R 7 together with the adjacent nitrogen atom each represents an aliphatic heterocyclic group which may have a substituent. Provided that R 3 , R 4 , R 5 , R 6 and R 7 do not represent a hydrogen atom at the same time, or a guanidine compound or a salt thereof. .
(2) R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are a hydrogen atom, an optionally substituted alkyl or an optionally substituted alkenyl. The additive for oils as described in (1).
(3) At least one of R 3 , R 4 , R 5 , R 6 and R 7 may have a substituent, an alkyl having 12 to 30 carbon atoms, or an optionally substituted carbon The additive for oils according to (1) or (2), which is alkenyl having several 12 to 30.
(4) The oil addition according to any one of (1) to (3), wherein the guanidine compound represented by the formula (II) or a salt thereof is a carbonate of the guanidine compound represented by the formula (II). Agent.
(5) The additive for oils according to any one of (1) to (4), wherein all of two X 1 and two X 2 are the same and are sulfur atoms.
(6) R 1 and R 2 are the same or different and may be an optionally substituted alkyl group having 3 to 14 carbon atoms or an optionally substituted alkenyl group having 3 to 14 carbon atoms. (1) The additive for oils according to any one of (5).
(7) Formula (I)
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
（式中、Ｘ１およびＸ２は、同一または異なって、硫黄原子または酸素原子を表し、Ｒ１およびＲ２は、同一または異なって、置換基を有していてもよいアルキル、置換基を有していてもよいアルケニル、置換基を有していてもよいアリール、置換基を有していてもよいシクロアルキルまたは置換基を有していてもよいシクロアルケニルを表し、２つのＲ１、２つのＲ２、２つのＸ１および２つのＸ２のそれぞれは同一または異なっていてもよい）で表される構造を有するリン酸亜鉛化合物と、式（ＩＩ） (In the formula, X 1 and X 2 are the same or different and each represents a sulfur atom or an oxygen atom, and R 1 and R 2 are the same or different and each represents an optionally substituted alkyl or substituent. An alkenyl that may have, an aryl that may have a substituent, an cycloalkyl that may have a substituent, or a cycloalkenyl that may have a substituent, and two R 1 , Two R 2 s , two X 1 s and two X 2 s may be the same or different), and a zinc phosphate compound having the structure represented by formula (II):
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
（式中、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７は、同一または異なって、水素原子、置換基を有していてもよいアルキル、置換基を有していてもよいアルケニルまたは置換基を有していてもよいアラルキルを表し、Ｒ４とＲ５またはＲ６とＲ７が隣接する窒素原子と一緒になってそれぞれ置換基を有していてもよい脂肪族複素環基を形成してもよい。但し、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７が同時に水素原子を表すことはない）で表されるグアニジン化合物またはその塩との反応物を含有する油類用添加剤。
（８）Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７が、同一または異なって、水素原子、置換基を有していてもよいアルキルまたは置換基を有していてもよいアルケニルである（７）に記載の油類用添加剤。
（９）Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７のうち、少なくとも一つが置換基を有していてもよい炭素数１２～３０のアルキルまたは置換基を有していてもよい炭素数１２～３０のアルケニルである（７）または（８）に記載の油類用添加剤。
（１０）式（ＩＩ）で表されるグアニジン化合物またはその塩が、式（ＩＩ）で表されるグアニジン化合物の炭酸塩である（７）～（９）のいずれかに記載の油類用添加剤。 (Wherein R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are each a hydrogen atom, an optionally substituted alkyl, an optionally substituted alkenyl or Represents an aralkyl which may have a substituent, and R 4 and R 5 or R 6 and R 7 together with the adjacent nitrogen atom each represents an aliphatic heterocyclic group which may have a substituent. Provided that R 3 , R 4 , R 5 , R 6 and R 7 do not represent hydrogen atoms at the same time) or an oil containing a reaction product with a salt thereof Additives.
(8) R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are a hydrogen atom, an optionally substituted alkyl or an optionally substituted alkenyl. The additive for oils as described in (7).
(9) At least one of R 3 , R 4 , R 5 , R 6 and R 7 may have a substituent, an alkyl having 12 to 30 carbon atoms, or an optionally substituted carbon The additive for oils according to (7) or (8), which is alkenyl having several 12 to 30.
(10) The oil addition according to any one of (7) to (9), wherein the guanidine compound represented by the formula (II) or a salt thereof is a carbonate of the guanidine compound represented by the formula (II). Agent.
（１１）２つのＸ１および２つのＸ２のすべてが同一で硫黄原子である（７）～（１０）のいずれかに記載の油類用添加剤。
（１２）Ｒ１およびＲ２が、同一または異なって、置換基を有していてもよい炭素数３～１４のアルキルまたは置換基を有していてもよい炭素数３～１４のアルケニルである（７）～（１１）のいずれかに記載の油類用添加剤。
（１３）（１）～（１２）のいずれかに記載の油類用添加剤と潤滑油基油とを混合して得られる潤滑油組成物。
（１４）潤滑油基油が、鉱物油、ポリ－α－オレフィン、脂肪酸エステル、芳香族エステル、ポリアルキレングリコール、リン酸エステル、シリコーン、ケイ酸エステル、ポリフェニルエーテル、アルキルベンゼン、合成ナフテン、ガスツーリキッド（ＧＴＬ）、フルオロカーボン、イオン液体、植物油、および獣油からなる群より選ばれる１種以上である（１３）に記載の潤滑油組成物。
（１５）潤滑油基油がポリ－α－オレフィンを含有する（１３）に記載の潤滑油組成物。
（１６）潤滑油組成物中のリンの含量が０．００１～０．１質量％である（１３）～（１５）のいずれかに記載の潤滑油組成物。
（１７）下記（ｉ）および／または下記（ｉｉ）と、潤滑油基油とを含有する潤滑油組成物。
（ｉ）式（Ｉ） (11) The additive for oils according to any one of (7) to (10), wherein all of two X 1 and two X 2 are the same and are sulfur atoms.
(12) R 1 and R 2 are the same or different and may be an optionally substituted alkyl having 3 to 14 carbons or an optionally substituted alkenyl having 3 to 14 carbons (7) The additive for oils according to any one of (11).
(13) A lubricating oil composition obtained by mixing the additive for oils according to any one of (1) to (12) and a lubricating base oil.
(14) Lubricating oil base oil is mineral oil, poly-α-olefin, fatty acid ester, aromatic ester, polyalkylene glycol, phosphate ester, silicone, silicate ester, polyphenyl ether, alkylbenzene, synthetic naphthene, gas two The lubricating oil composition according to (13), which is at least one selected from the group consisting of liquid (GTL), fluorocarbon, ionic liquid, vegetable oil, and animal oil.
(15) The lubricating oil composition according to (13), wherein the lubricating base oil contains a poly-α-olefin.
(16) The lubricating oil composition according to any one of (13) to (15), wherein the content of phosphorus in the lubricating oil composition is 0.001 to 0.1% by mass.
(17) A lubricating oil composition comprising the following (i) and / or the following (ii) and a lubricating base oil.
(I) Formula (I)
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
（式中、Ｘ１およびＸ２は、同一または異なって、硫黄原子または酸素原子を表し、Ｒ１およびＲ２は、同一または異なって、置換基を有していてもよいアルキル、置換基を有していてもよいアルケニル、置換基を有していてもよいアリール、置換基を有していてもよいシクロアルキルまたは置換基を有していてもよいシクロアルケニルを表し、２つのＲ１、２つのＲ２、２つのＸ１および２つのＸ２のそれぞれは同一または異なっていてもよい）で表される構造を有するリン酸亜鉛化合物および式（ＩＩ） (In the formula, X 1 and X 2 are the same or different and each represents a sulfur atom or an oxygen atom, and R 1 and R 2 are the same or different and each represents an optionally substituted alkyl or substituent. An alkenyl that may have, an aryl that may have a substituent, an cycloalkyl that may have a substituent, or a cycloalkenyl that may have a substituent, and two R 1 , Two R 2 s , two X 1 s and two X 2 s may be the same or different) and a zinc phosphate compound having the structure represented by formula (II)
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
（式中、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７は、同一または異なって、水素原子、置換基を有していてもよいアルキル、置換基を有していてもよいアルケニルまたは置換基を有していてもよいアラルキルを表し、Ｒ４とＲ５またはＲ６とＲ７が隣接する窒素原子と一緒になってそれぞれ置換基を有していてもよい脂肪族複素環基を形成してもよい。但し、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７が同時に水素原子を表すことはない）で表されるグアニジン化合物またはその塩
（ｉｉ）式（Ｉ）で表される構造を有するリン酸亜鉛化合物と式（ＩＩ）で表されるグアニジン化合物またはその塩との反応物
（１８）Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７が、同一または異なって、水素原子、置換基を有していてもよいアルキルまたは置換基を有していてもよいアルケニルである（１７）に記載の潤滑油組成物。
（１９）Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７のうち、少なくとも一つが置換基を有していてもよい炭素数１２～３０のアルキルまたは置換基を有していてもよい炭素数１２～３０のアルケニルである（１７）または（１８）に記載の潤滑油組成物。
（２０）式（ＩＩ）で表されるグアニジン化合物またはその塩が、式（ＩＩ）で表されるグアニジン化合物の炭酸塩である（１７）～（１９）のいずれかに記載の潤滑油組成物。 (Wherein R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are each a hydrogen atom, an optionally substituted alkyl, an optionally substituted alkenyl or Represents an aralkyl which may have a substituent, and R 4 and R 5 or R 6 and R 7 together with the adjacent nitrogen atom each represents an aliphatic heterocyclic group which may have a substituent. Provided that R 3 , R 4 , R 5 , R 6 and R 7 do not simultaneously represent a hydrogen atom) or a salt thereof (ii) represented by formula (I) Reaction product (18) R 3 , R 4 , R 5 , R 6 and R 7 of a zinc phosphate compound having the structure: and a guanidine compound represented by formula (II) or a salt thereof are the same or different , Hydrogen atom, optionally substituted alkyl or The lubricating oil composition according to (17), which is alkenyl which may have a substituent.
(19) At least one of R 3 , R 4 , R 5 , R 6 and R 7 may have a substituent, an alkyl having 12 to 30 carbon atoms, or an optionally substituted carbon The lubricating oil composition according to (17) or (18), which is alkenyl having several 12 to 30.
(20) The lubricating oil composition according to any one of (17) to (19), wherein the guanidine compound represented by the formula (II) or a salt thereof is a carbonate of the guanidine compound represented by the formula (II). .
（２１）２つのＸ１および２つのＸ２のすべてが同一で硫黄原子である（１７）～（２０）のいずれかに記載の潤滑油組成物。
（２２）Ｒ１およびＲ２が、同一または異なって、置換基を有していてもよい炭素数３～１４のアルキルまたは置換基を有していてもよい炭素数３～１４のアルケニルである（１７）～（２１）のいずれかに記載の潤滑油組成物。
（２３）潤滑油基油が、鉱物油、ポリ－α－オレフィン、脂肪酸エステル、芳香族エステル、ポリアルキレングリコール、リン酸エステル、シリコーン、ケイ酸エステル、ポリフェニルエーテル、アルキルベンゼン、合成ナフテン、ガスツーリキッド（ＧＴＬ）、フルオロカーボン、イオン液体、植物油、および獣油からなる群より選ばれる１種以上である（１７）～（２２）のいずれかに記載の潤滑油組成物。
（２４）潤滑油基油がポリ－α－オレフィンを含有する（１７）～（２２）のいずれかに記載の潤滑油組成物。
（２５）潤滑油組成物中のリンの含量が０．００１～０．１質量％である（１７）～（２４）のいずれかに記載の潤滑油組成物。 (21) The lubricating oil composition according to any one of (17) to (20), wherein all of two X 1 and two X 2 are the same and are sulfur atoms.
(22) R 1 and R 2 are the same or different and each may be an optionally substituted alkyl having 3 to 14 carbons or an optionally substituted alkenyl having 3 to 14 carbons (17) The lubricating oil composition according to any one of (21).
(23) Lubricating oil base oil is mineral oil, poly-α-olefin, fatty acid ester, aromatic ester, polyalkylene glycol, phosphate ester, silicone, silicate ester, polyphenyl ether, alkylbenzene, synthetic naphthene, gas two The lubricating oil composition according to any one of (17) to (22), which is at least one selected from the group consisting of liquid (GTL), fluorocarbon, ionic liquid, vegetable oil, and animal oil.
(24) The lubricating oil composition according to any one of (17) to (22), wherein the lubricating base oil contains a poly-α-olefin.
(25) The lubricating oil composition according to any one of (17) to (24), wherein the content of phosphorus in the lubricating oil composition is 0.001 to 0.1% by mass.
　本発明によれば、潤滑油組成物などの油類に優れた耐摩擦特性または優れた耐摩耗特性を付与する油類用添加剤などを提供できる。 According to the present invention, it is possible to provide an additive for oils that imparts excellent friction resistance or excellent wear resistance to oils such as lubricating oil compositions.
　以下、式（Ｉ）で表される構造を有する化合物を化合物（Ｉ）といい、式（ＩＩ）で表される化合物を化合物（ＩＩ）という。他の式番号の化合物についても同様である。
　式（Ｉ）および式（ＩＩ）中の各基の定義において、アルキルとしては、例えば、直鎖または分岐の炭素数１～３０のアルキルが挙げられ、具体的には、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチル、ペンチル、イソペンチル、ネオペンチル、ｔｅｒｔ－ペンチル、１－メチルブチル、１－エチルプロピル、ヘキシル、イソヘキシル、１－メチルペンチル、１－エチルブチル、ヘプチル、１－メチルヘキシル、１－エチルペンチル、オクチル、１－エチルヘキシル、２－エチルヘキシル、１－メチルヘプチル、ノニル、１－メチルオクチル、３，５，５－トリメチルヘキシル、デシル、１－メチルノニル、１－プロピルヘプチル、ウンデシル、１－メチルデシル、ドデシル、１－メチルウンデシル、２－ブチルオクチル、トリデシル、１－メチルドデシル、イソトリデシル、テトラデシル、２－ブチルデシル、２－ヘキシルオクチル、ヘキサデシル、２－ヘキシルデシル、ヘプタデシル、オクタデシル、２－オクチルデシル、２－ヘキシルドデシル、エイコシル、２－オクチルドデシル、ドコシル、テトラコシル、２－デシルテトラデシル、２－ドデシルヘキサデシル、トリアコンチルなどが挙げられる。 Hereinafter, a compound having a structure represented by formula (I) is referred to as compound (I), and a compound represented by formula (II) is referred to as compound (II). The same applies to the compounds of other formula numbers.
In the definition of each group in the formula (I) and the formula (II), examples of the alkyl include linear or branched alkyl having 1 to 30 carbon atoms, specifically, methyl, ethyl, propyl, Isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, 1-ethylpropyl, hexyl, isohexyl, 1-methylpentyl, 1-ethylbutyl, heptyl, 1- Methylhexyl, 1-ethylpentyl, octyl, 1-ethylhexyl, 2-ethylhexyl, 1-methylheptyl, nonyl, 1-methyloctyl, 3,5,5-trimethylhexyl, decyl, 1-methylnonyl, 1-propylheptyl, Undecyl, 1-methyldecyl, dodecyl, 1-methyl Undecyl, 2-butyloctyl, tridecyl, 1-methyldodecyl, isotridecyl, tetradecyl, 2-butyldecyl, 2-hexyloctyl, hexadecyl, 2-hexyldecyl, heptadecyl, octadecyl, 2-octyldecyl, 2-hexyldecyl, eicosyl, Examples thereof include 2-octyldodecyl, docosyl, tetracosyl, 2-decyltetradecyl, 2-dodecylhexadecyl, triacontyl and the like.
　アルケニルとしては、例えば、直鎖または分岐の炭素数２～３０のアルケニルが挙げられ、具体的には、ビニル、アリル、イソプロペニル、ブテニル、イソブテニル、２－メチルプロペニル、ペンテニル、１－メチル－２－ブテニル、１－エチル－２－プロペニル、オクテニル、ノネニル、デセニル、ウンデセニル、ドデセニル、ブチルオクテニル、オクチルブテニル、トリデセニル、テトラデセニル、ブチルデセニル、ヘキシルオクテニル、ヘキシルデセニル、ヘプタデセニル、オクタデセニル、ドデシルヘキセニル、デシルオクテニル、イソオクタデセニル、エイコセニル、オクチルドデセニル、テトラコセニル、デシルテトラデセニル、トリアコンテニル、ドデシルオクタデセニルなどが挙げられる。 Examples of alkenyl include linear or branched alkenyl having 2 to 30 carbon atoms, and specifically, vinyl, allyl, isopropenyl, butenyl, isobutenyl, 2-methylpropenyl, pentenyl, 1-methyl-2 -Butenyl, 1-ethyl-2-propenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, butyloctenyl, octylbutenyl, tridecenyl, tetradecenyl, butyldecenyl, hexyloctenyl, hexyldecenyl, heptadecenyl, octadecenyl, dodecylhexenyl, dodecylhexenyl Examples include decenyl, eicosenyl, octyldodecenyl, tetracocenyl, decyltetradecenyl, triacontenyl, dodecyloctadecenyl and the like.
　アリールとしては、例えば、炭素数６～１４のアリールが挙げられ、具体的には、フェニル、ナフチル、アズレニル、アントリルなどが挙げられる。
　シクロアルキルとしては、例えば、炭素数３～７のシクロアルキルが挙げられ、具体的には、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチルなどが挙げられる。 Examples of aryl include aryl having 6 to 14 carbon atoms, and specific examples include phenyl, naphthyl, azulenyl, anthryl and the like.
Examples of cycloalkyl include cycloalkyl having 3 to 7 carbon atoms, and specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
　シクロアルケニルとしては、例えば、炭素数３～７のシクロアルケニルが挙げられ、具体的には、シクロプロペニル、シクロブテニル、シクロペンテニル、シクロヘキセニル、シクロヘプテニルなどが挙げられる。
　アラルキルとしては、例えば、炭素数７～３０のアラルキルが挙げられ、具体的には、ベンジル、フェニルエチル、フェニルプロピル、フェニルブチル、フェニルペンチル、フェニルヘキシル、フェニルヘプチル、フェニルオクチル、フェニルノニル、フェニルデシル、フェニルウンデシル、フェニルドデシル、ナフチルメチル、ナフチルエチルなどが挙げられる。 Examples of cycloalkenyl include cycloalkenyl having 3 to 7 carbon atoms, and specific examples include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl and the like.
Examples of aralkyl include aralkyl having 7 to 30 carbon atoms, and specifically include benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, phenylheptyl, phenyloctyl, phenylnonyl, phenyldecyl. , Phenylundecyl, phenyldodecyl, naphthylmethyl, naphthylethyl and the like.
　Ｒ４とＲ５、またはＲ６とＲ７が隣接する窒素原子と一緒になってそれぞれ形成される脂肪族複素環基の脂肪族複素環としては、例えば、少なくとも窒素原子を一つ含む炭素数３～１０個の脂肪族複素環が挙げられ、具体的には、ピペリジン環、ピロリジン環、モルホリン環などが挙げられる。
　アルキルおよびアルケニルの置換基としては、例えば、同一または異なって１～３個の置換基、具体的には、ヒドロキシ、アルコキシ、アルコキシアルコキシ、アルキル置換または非置換のアミノ、メルカプト、アルキルチオなどが挙げられる。アルコキシ、アルコキシアルコキシ、アルキル置換のアミノおよびアルキルチオのアルキル部分は前記アルキルと同義である。なお、アルキル置換のアミノが２つのアルキルで置換されたアミノである場合、該２つのアルキルは同一でも異なっていてもよい。アルコキシアルコキシのアルキレン部分は前記アルキルから水素原子を一つ除いたものと同義である。 Examples of the aliphatic heterocyclic ring of the aliphatic heterocyclic group formed by R 4 and R 5 or R 6 and R 7 together with the adjacent nitrogen atom include, for example, the number of carbon atoms containing at least one nitrogen atom Examples include 3 to 10 aliphatic heterocycles, and specific examples include a piperidine ring, a pyrrolidine ring, and a morpholine ring.
Examples of the substituent for alkyl and alkenyl include the same or different 1 to 3 substituents, specifically, hydroxy, alkoxy, alkoxyalkoxy, alkyl-substituted or unsubstituted amino, mercapto, alkylthio and the like. . Alkyl parts of alkoxy, alkoxyalkoxy, alkyl-substituted amino and alkylthio are as defined above. When the alkyl-substituted amino is amino substituted with two alkyls, the two alkyls may be the same or different. The alkylene part of alkoxyalkoxy has the same meaning as that obtained by removing one hydrogen atom from the alkyl.
　アリール、シクロアルキル、シクロアルケニル、アラルキルおよび脂肪族複素環基の置換基としては、例えば、同一または異なって１～５個の置換基、具体的には、ヒドロキシ、アルキル、アルコキシ、ニトロ、シアノ、アルキル置換または非置換のアミノ、メルカプト、アルキルチオなどが挙げられる。ここで、アルキル、アルコキシ、アルキル置換のアミノおよびアルキルチオは、それぞれ前記と同義である。 Examples of the substituent of the aryl, cycloalkyl, cycloalkenyl, aralkyl and aliphatic heterocyclic group include, for example, the same or different 1 to 5 substituents, specifically, hydroxy, alkyl, alkoxy, nitro, cyano, Examples include alkyl-substituted or unsubstituted amino, mercapto, alkylthio and the like. Here, alkyl, alkoxy, alkyl-substituted amino and alkylthio are as defined above.
　式（Ｉ）において、Ｒ１およびＲ２が、同一または異なって、置換基を有していてもよい炭素数３～１４のアルキルまたは置換基を有していてもよい炭素数３～１４のアルケニルであるのが好ましい。ここで、炭素数３～１４のアルキルの置換基は前記アルキルの置換基と同義であり、炭素数３～１４のアルケニルの置換基は前記アルケニルの置換基と同義である。炭素数３～１４のアルキルの具体例としては、例えば、前記に例示したアルキルのうち炭素数が３～１４であるものなどが例示される。炭素数３～１４のアルケニルの具体例としては、例えば、前記に例示したアルケニルのうち炭素数が３～１４であるものなどが例示される。 In the formula (I), R 1 and R 2 are the same or different and each may have an optionally substituted alkyl group having 3 to 14 carbon atoms or an optionally substituted group having 3 to 14 carbon atoms. Alkenyl is preferred. Here, the substituent of the alkyl having 3 to 14 carbon atoms has the same meaning as the substituent of the alkyl, and the substituent of alkenyl having 3 to 14 carbons has the same meaning as the substituent of the alkenyl. Specific examples of the alkyl having 3 to 14 carbon atoms include those having 3 to 14 carbon atoms among the alkyls exemplified above. Specific examples of the alkenyl having 3 to 14 carbon atoms include those having 3 to 14 carbon atoms among the alkenyls exemplified above.
　化合物（Ｉ）としては、例えば、式（Ｉ）で表される化合物、式（Ｉ）で表される化合物と酸化亜鉛との塩などが挙げられる。
　化合物（Ｉ）において、２つのＸ１および２つのＸ２のすべてが同一で酸素原子または硫黄原子であるものが好ましく、２つのＸ１および２つのＸ２のすべてが同一で硫黄原子であるものがより好ましい。 Examples of the compound (I) include a compound represented by the formula (I), a salt of a compound represented by the formula (I) and zinc oxide, and the like.
In the compound (I), those in which two X 1 and two X 2 are all the same and are an oxygen atom or a sulfur atom are preferred, and all of two X 1 and two X 2 are the same and are a sulfur atom Is more preferable.
　化合物（Ｉ）のうち２つのＸ１および２つのＸ２のすべてが同一で酸素原子であるものとしては、例えば、式（Ｉａ） Examples of the compound (I) in which two X 1 and two X 2 are all the same and are oxygen atoms include, for example, formula (Ia)
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
（式中、Ｒ１およびＲ２はそれぞれ前記と同義である）で表される化合物などが挙げられる。
　化合物（Ｉ）のうち２つのＸ１および２つのＸ２のすべてが同一で硫黄原子であるものとしては、例えば、式（Ｉｂ） (Wherein, R 1 and R 2 are as defined above) and the like.
Examples of the compound (I) in which all two X 1 and two X 2 are the same and are a sulfur atom include, for example, the compound of the formula (Ib)
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
（式中、Ｒ１およびＲ２はそれぞれ前記と同義であり、ｙは０または１／３を表す）で表される化合物などが挙げられる。
　化合物（ＩＩ）またはその塩において、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７のうち少なくとも一つが置換基を有していてもよい炭素数１２～３０のアルキルまたは置換基を有していてもよい炭素数１２～３０のアルケニルであるのが好ましく、置換基を有していてもよい炭素数１６～１８のアルキルまたは置換基を有していてもよい炭素数１６～１８のアルケニルであるのがより好ましい。ここで、炭素数１２～３０のアルキルおよび炭素数１６～１８のアルキルの置換基は前記アルキルの置換基と同義であり、炭素数１２～３０のアルケニルおよび炭素数１６～１８のアルケニルの置換基は前記アルケニルの置換基と同義である。炭素数１２～３０のアルキルおよび炭素数１６～１８のアルキルの具体例としては、例えば、前記に例示したアルキルのうち炭素数が１２～３０および１６～１８であるものなどが例示される。炭素数１２～３０のアルケニルおよび炭素数１６～１８のアルケニルの具体例としては、例えば、前記に例示したアルケニルのうち炭素数が１２～３０および１６～１８であるものなどが例示される。 (Wherein, R 1 and R 2 have the same meanings as described above, and y represents 0 or 1/3).
In compound (II) or a salt thereof, at least one of R 3 , R 4 , R 5 , R 6 and R 7 has an optionally substituted alkyl having 12 to 30 carbon atoms or a substituent. The alkenyl having 12 to 30 carbon atoms which may be optionally substituted is preferable, and the alkyl having 16 to 18 carbon atoms which may be substituted or the alkenyl having 16 to 18 carbon atoms which may be optionally substituted. It is more preferable that Here, the alkyl substituent having 12 to 30 carbon atoms and the alkyl substituent having 16 to 18 carbon atoms have the same meaning as the above alkyl substituent, and the alkenyl having 12 to 30 carbon atoms and the substituent having 16 to 18 carbon atoms are substituted Is synonymous with the substituent of the said alkenyl. Specific examples of the alkyl having 12 to 30 carbon atoms and the alkyl having 16 to 18 carbon atoms include those having 12 to 30 and 16 to 18 carbon atoms among the alkyls exemplified above. Specific examples of the alkenyl having 12 to 30 carbon atoms and the alkenyl having 16 to 18 carbon atoms include those having 12 to 30 and 16 to 18 carbon atoms among the alkenyls exemplified above.
　化合物（ＩＩ）の塩としては、例えば、式（Ｖ） As a salt of compound (II), for example, formula (V)
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
（式中、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７はそれぞれ前記と同義であり、ＨｍＡは完全に電離したときｍ個のプロトンとＡｍ-で表されるアニオンとに解離する酸を表し、Ａは該酸からｍ個の水素原子を除いたｍ価の基を表し、ｍが１のときｐは１を表し、ｍが２以上の整数であるときｐは１以上ｍ以下である整数のうちのいずれかを表す）で表される塩などが挙げられる。 (Wherein R 3 , R 4 , R 5 , R 6 and R 7 have the same meanings as described above, and H m A represents m protons and an anion represented by A m− when completely ionized. Represents a dissociating acid, A represents an m-valent group obtained by removing m hydrogen atoms from the acid, p represents 1 when m is 1, and p is 1 or more when m is an integer of 2 or more. and a salt represented by any one of integers equal to or less than m).
　ＨｍＡとしては、ギ酸、酢酸、プロピオン酸、ブタン酸、ペンタン酸、ヘキサン酸、ｎ－オクチル酸、２－エチルヘキシル酸、イソノナン酸、デカン酸、ドデカン酸、テトラデカン酸、ヘキサデカン酸、オレイン酸、ステアリン酸、イソステアリン酸、などのカルボン酸、メタンスルホン酸、トリフルオロメタンスルホン酸、ベンゼンスルホン酸、ｐ－トルエンスルホン酸、オクタデセニルスルホン酸などのスルホン酸、硫酸、硝酸、塩酸、炭酸、ホウ酸、リン酸などが挙げられ、中でも炭酸およびホウ酸が好ましい。 H m A includes formic acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, n-octylic acid, 2-ethylhexylic acid, isononanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, oleic acid, Carboxylic acids such as stearic acid and isostearic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, octadecenylsulfonic acid and other sulfonic acids, sulfuric acid, nitric acid, hydrochloric acid, carbonic acid, boron Examples thereof include acid and phosphoric acid, and carbonic acid and boric acid are preferable.
　化合物（Ｉ）と化合物（ＩＩ）またはその塩との反応物としては、例えば、化合物（Ｉ）、化合物（Ｉ）に対して２倍モル量の化合物（ＩＩ）またはその塩およびジエチルエーテルの混合物を１時間還流することにより得られる反応物などが挙げられる。以後、化合物（Ｉ）と化合物（ＩＩ）またはその塩との反応物を反応物（Ｘ）ということもある。
　化合物（Ｉ）は市販品として入手するか、公知の方法、例えば特開昭６３－９９０８２号公報またはＪｏｕｒｎａｌ ｏｆ　Ｏｒｇａｎｉｃ　Ｃｈｅｍｉｓｔｒｙ、１９５６年、第２１巻、ｐ．７０５などに記載の方法に準じて製造することにより得ることができる。 Examples of the reaction product of compound (I) with compound (II) or a salt thereof include, for example, compound (I), a mixture of compound (II) or a salt thereof and diethyl ether in a molar amount twice that of compound (I). And a reaction product obtained by refluxing for 1 hour. Hereinafter, the reaction product of the compound (I) and the compound (II) or a salt thereof may be referred to as a reaction product (X).
Compound (I) can be obtained as a commercial product, or can be obtained by a known method such as JP-A 63-99082 or Journal of Organic Chemistry, 1956, Vol. 21, p. It can obtain by manufacturing according to the method as described in 705 grade | etc.,.
　化合物（Ｉ）の好ましい具体例を以下に示す。 Preferred specific examples of compound (I) are shown below.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　上記の式で表される化合物の他に、化合物（Ｉｂ－２ｉ）と化合物（Ｉｂ－２ｉｉ）との混合物、化合物（Ｉｂ－３ｉ）と化合物（Ｉｂ－３ｉｉ）との混合物、化合物（Ｉｂ－４ｉ）と化合物（Ｉｂ－４ｉｉ）との混合物、化合物（Ｉｂ－５ｉ）と化合物（Ｉｂ－５ｉｉ）との混合物なども化合物（Ｉ）の好ましい具体例として挙げられる。
　化合物（ＩＩ）またはその塩の製造法の例を、以下の式に示す。 In addition to the compound represented by the above formula, a mixture of compound (Ib-2i) and compound (Ib-2ii), a mixture of compound (Ib-3i) and compound (Ib-3ii), compound (Ib- Preferred examples of compound (I) include a mixture of 4i) and compound (Ib-4ii), a mixture of compound (Ib-5i) and compound (Ib-5ii), and the like.
An example of a method for producing compound (II) or a salt thereof is shown in the following formula.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
（式中、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ａ、ｍおよびｐはそれぞれ前記と同義であり、Ｙは酸素原子または硫黄原子を表し、Ｒ８は炭素数１～４のアルキルを表し、ＨｎＢは完全に電離したときｎ個のプロトンとＢｎ-で表されるアニオンとに解離する酸を表し、Ｂは該酸からｎ個の水素原子を除いたｎ価の基を表し、ｎが１のときｑは１を表し、ｎが２以上の整数であるときｑは１以上ｎ以下である整数のうちのいずれかを表し、ＡとＢとは同一ではなく、Ｍはアルカリ金属を表す）
　炭素数１～４のアルキルの具体例としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチルなどが挙げられ、中でもメチルおよびエチルが好ましい。 Wherein R 3 , R 4 , R 5 , R 6 , R 7 , A, m and p are as defined above, Y represents an oxygen atom or a sulfur atom, and R 8 has 1 to 4 carbon atoms. H n B represents an acid dissociated into n protons and an anion represented by B n− when completely ionized, and B represents an n valence obtained by removing n hydrogen atoms from the acid. When n is 1, q represents 1, and when n is an integer of 2 or more, q represents one of integers of 1 to n, and A and B are not the same , M represents an alkali metal)
Specific examples of the alkyl having 1 to 4 carbon atoms include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and the like, and methyl and ethyl are preferable.
　ＨｎＢで表される酸としては、例えば、ＨｍＡの具体例として前記に例示した酸が例示される。
　アルカリ金属としては、例えば、ナトリウム、カリウムなどが挙げられる。
　化合物（Ｖ）は、例えば、Ｂｉｏｏｒｇａｎｉｃ　Ｍｅｄｉｃｉｎａｌ　Ｃｈｅｍｉｓｔｒｙ、２００３年、第１１巻、ｐ．１２８３などに記載の方法に準じて、化合物（ＩＩＩ）と化合物（ＩＶ）とを、溶媒中２０～２００℃で０．５～２４時間反応させることにより製造することができる。 Examples of the acid represented by H n B include the acids exemplified above as specific examples of H m A.
Examples of the alkali metal include sodium and potassium.
Compound (V) is described in, for example, Bioorganic Medicinal Chemistry, 2003, Vol. 11, p. According to the method described in 1283 and the like, it can be produced by reacting compound (III) and compound (IV) in a solvent at 20 to 200 ° C. for 0.5 to 24 hours.
　化合物（ＩＩＩ）は市販品として入手するか、例えば、Ｊｏｕｒｎａｌ ｏｆ　Ａｍｅｒｉｃａｎ　Ｃｈｅｍｉｃａｌ　Ｓｏｃｉｅｔｙ、１９５２年、第７４巻、ｐ．４２７１またはＯｒｇａｎｉｃ　Ｓｙｎｔｈｅｓｉｓ、１９６３年、第４巻、ｐ．６４５に記載の方法などに準じて製造することにより得ることができる。
　化合物（ＩＶ）は市販品として入手するか、例えば、米国特許第４４０９３９９号明細書または特公昭３８－２１３５３号公報に記載の方法などに準じて製造することにより得ることができる。 Compound (III) can be obtained as a commercial product, for example, Journal of American Chemical Society, 1952, vol. 74, p. 4271 or Organic Synthesis, 1963, vol. 4, p. It can obtain by manufacturing according to the method of 645, etc.
Compound (IV) can be obtained as a commercial product, or can be obtained, for example, by manufacturing according to the method described in US Pat. No. 4,409,399 or JP-B-38-21353.
　溶媒としては、例えば、ヘキサン、デカン、テトラデカン、トルエン、キシレンなどの炭化水素、メタノール、エタノール、イソプロピルアルコール、ブタノールなどのアルコール、ジエチルエーテル、ジブチルエーテル、テトラヒドロフラン、メトキシベンゼン、ジフェニルエーテルなどのエーテル、塩化メチレン、ジクロロエタン、クロロホルム、クロロベンゼン、ジクロロベンゼンなどのハロゲン化炭化水素、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミドなどのアミド、ジメチルスルホキシド、これらの混合溶媒などが挙げられ、中でもアルコールおよびハロゲン化炭化水素が好ましい。 Examples of the solvent include hydrocarbons such as hexane, decane, tetradecane, toluene, xylene, alcohols such as methanol, ethanol, isopropyl alcohol, and butanol, ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, methoxybenzene, and diphenyl ether, methylene chloride Halogenated hydrocarbons such as dichloroethane, chloroform, chlorobenzene and dichlorobenzene, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, dimethyl sulfoxide, mixed solvents thereof, etc. Hydrocarbons are preferred.
　化合物（ＩＩＩ）に対して、化合物（ＩＶ）を０．２～２０当量使用することが好ましく、０．５～１０当量使用することがより好ましい。
　反応後、必要に応じて、化合物（Ｖ）を有機合成化学で通常用いられる方法（各種クロマトグラフィー法、再結晶法、蒸留法など）で精製してもよい。
　２種類以上の化合物（Ｖ）が反応により生成する場合、前記の精製方法などにより該２種類以上の化合物（Ｖ）の一つを単離してもよく、該２種類以上の化合物（Ｖ）の混合物を、化合物（Ｉ）と化合物（ＩＩ）の塩との反応物の原料、化合物（Ｉ）と化合物（ＩＩ）の塩とを含有する油類用添加剤の原料、または該油類用添加剤と潤滑油基油とを混合して得られる潤滑油組成物の原料として使用してもよい。 The compound (IV) is preferably used in an amount of 0.2 to 20 equivalents, more preferably 0.5 to 10 equivalents, relative to the compound (III).
After the reaction, if necessary, the compound (V) may be purified by methods usually used in organic synthetic chemistry (such as various chromatographic methods, recrystallization methods, and distillation methods).
When two or more kinds of compounds (V) are produced by the reaction, one of the two or more kinds of compounds (V) may be isolated by the above-described purification method or the like. The mixture is a raw material of a reaction product of a salt of compound (I) and compound (II), a raw material of an additive for oils containing a salt of compound (I) and compound (II), or an addition for the oils You may use as a raw material of the lubricating oil composition obtained by mixing an agent and lubricating base oil.
　必要に応じて、化合物（Ｖ）を、別の化合物（ＩＩ）の塩［例えば、化合物（ＶＩ）など］に変換することもできる。
　化合物（Ｖ）を化合物（ＶＩ）に変換する方法としては、例えば、化合物（Ｖ）とＭｎＢ（式中、Ｍ、ｎおよびＢは、それぞれ前記と同義である）とを溶媒中－１０～１００℃で０．１～２４時間反応させることにより化合物（ＶＩ）を製造する方法などが挙げられる。 If necessary, compound (V) can also be converted to a salt of another compound (II) [eg, compound (VI) and the like].
As a method for converting compound (V) into compound (VI), for example, compound (V) and M n B (wherein, M, n and B are as defined above) in a solvent −10 Examples thereof include a method for producing compound (VI) by reacting at -100 ° C. for 0.1-24 hours.
　化合物（Ｖ）に対して、ＭｎＢを０．２～２０当量使用することが好ましく、０．５～１０当量使用することがより好ましい。
　溶媒としては、例えば、前記に例示した溶媒、該溶媒と水との混合物などが挙げられる。
　反応後、必要に応じて、化合物（ＶＩ）を有機合成化学で通常用いられる方法（各種クロマトグラフィー法、再結晶法、蒸留法など）で精製してもよい。 M n B is preferably used in an amount of 0.2 to 20 equivalents, more preferably 0.5 to 10 equivalents, relative to compound (V).
Examples of the solvent include the solvents exemplified above, and a mixture of the solvent and water.
After the reaction, if necessary, the compound (VI) may be purified by methods usually used in organic synthetic chemistry (various chromatographic methods, recrystallization methods, distillation methods, etc.).
　２種類以上の化合物（ＶＩ）が反応により生成する場合、前記の精製方法などにより該２種類以上の化合物（ＶＩ）の一つを単離してもよく、該２種類以上の化合物（ＶＩ）の混合物を、化合物（Ｉ）と化合物（ＩＩ）の塩との反応物の原料、化合物（Ｉ）と化合物（ＩＩ）の塩とを含有する油類用添加剤の原料、または該油類用添加剤と潤滑油基油とを混合して得られる潤滑油組成物の原料として使用してもよい。 When two or more kinds of compounds (VI) are produced by the reaction, one of the two or more kinds of compounds (VI) may be isolated by the above purification method or the like. The mixture is a raw material of a reaction product of a salt of compound (I) and compound (II), a raw material of an additive for oils containing a salt of compound (I) and compound (II), or an addition for the oils You may use as a raw material of the lubricating oil composition obtained by mixing an agent and lubricating base oil.
　化合物（ＩＩ）は、例えば、化合物（Ｖ）と塩基とを溶媒中－１０～１００℃で０．１～２４時間反応させることにより製造することができる。
　塩基としては、例えば、水酸化ナトリウム、水酸化カリウム、水酸化セシウムなどの無機塩基などが挙げられる。
　化合物（Ｖ）に対して、塩基を０．２～２００当量使用することが好ましく、０．５～１００当量使用することがより好ましい。 Compound (II) can be produced, for example, by reacting compound (V) with a base at −10 to 100 ° C. for 0.1 to 24 hours in a solvent.
Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, and cesium hydroxide.
The base is preferably used in an amount of 0.2 to 200 equivalents, more preferably 0.5 to 100 equivalents, relative to compound (V).
　溶媒としては、例えば、前記に例示した溶媒、該溶媒と水との混合物などが挙げられる。
　反応後、必要に応じて、化合物（ＩＩ）を有機合成化学で通常用いられる方法（各種クロマトグラフィー法、再結晶法、蒸留法など）で精製してもよい。
　化合物（ＩＩ）とＨｎＢ（式中、ｎおよびＢはそれぞれ前記と同義である）とを反応させることにより化合物（ＶＩ）を製造することもできる。 Examples of the solvent include the solvents exemplified above, and a mixture of the solvent and water.
After the reaction, if necessary, the compound (II) may be purified by methods usually used in organic synthetic chemistry (such as various chromatographic methods, recrystallization methods, and distillation methods).
Compound (VI) can also be produced by reacting compound (II) with H n B (wherein n and B are as defined above).
　また、化合物（ＩＩ）のうちＲ３、Ｒ４、およびＲ５が同一で水素原子であるものは、例えば、米国特許第２４２５３４１号明細書に記載の方法などに準じて、ＮＨＲ６ａＲ７ａ（式中、Ｒ６ａおよびＲ７ａは、同一または異なって、水素原子、置換基を有していてもよいアルキル、置換基を有していてもよいアルケニルまたは置換基を有していてもよいアラルキルを表し、Ｒ６ａとＲ７ａが隣接する窒素原子と一緒になって置換基を有していてもよい脂肪族複素環基を形成してもよい。但し、Ｒ６ａおよびＲ７ａが同時に水素原子を表すことはない）で表されるアミンの塩と、シアナミドとを反応させることにより製造することもできる。ここで、置換基を有していてもよいアルキル、置換基を有していてもよいアルケニル、置換基を有していてもよいアラルキルおよび隣接する窒素原子と一緒になって形成される置換基を有していてもよい脂肪族複素環基は、それぞれ前記と同義である。アミンの塩としては、例えば、塩酸塩、臭化水素塩、硫酸塩、硝酸塩などが挙げられる。ＮＨＲ６ａＲ７ａは市販品として入手するか、例えば米国特許第４４０９３９９号明細書または特公昭３８－２１３５３号公報に記載の方法などに準じて製造することにより得ることができる。 In addition, compounds (II) in which R 3 , R 4 , and R 5 are the same and are a hydrogen atom can be synthesized according to, for example, the method described in US Pat. No. 2,425,341, such as NHR 6a R 7a ( In the formula, R 6a and R 7a are the same or different and each represents a hydrogen atom, an alkyl having a substituent, an alkenyl optionally having a substituent, or an aralkyl optionally having a substituent. R 6a and R 7a may be combined with the adjacent nitrogen atom to form an optionally substituted aliphatic heterocyclic group, provided that R 6a and R 7a are simultaneously hydrogen atoms. Can also be produced by reacting a salt of an amine represented by Here, the alkyl which may have a substituent, the alkenyl which may have a substituent, the aralkyl which may have a substituent and the substituent formed together with the adjacent nitrogen atom The aliphatic heterocyclic group optionally having the same meaning as defined above. Examples of the amine salt include hydrochloride, hydrobromide, sulfate, nitrate, and the like. NHR 6a R 7a can be obtained as a commercial product, or can be obtained, for example, according to the method described in US Pat. No. 4,409,399 or Japanese Patent Publication No. 38-21353.
　以下に、化合物（ＩＩ）またはその塩の好ましい具体例を示す。 Hereinafter, preferred specific examples of the compound (II) or a salt thereof will be shown.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　上記の式で表される化合物の他に、化合物（ＶＩ－１ａ）と化合物（ＶＩ－１ｂ）との混合物、化合物（ＶＩ－２ａ）と化合物（ＶＩ－２ｂ）との混合物、化合物（ＶＩ－３ａ）と化合物（ＶＩ－３ｂ）との混合物なども、化合物（ＩＩ）またはその塩の好ましい具体例として挙げられる。
　化合物（ＶＩ－２ａ）および化合物（ＶＩ－２ｂ）における炭素－炭素２重結合の幾何異性（ＥまたはＺ）は特に限定されない。 In addition to the compound represented by the above formula, a mixture of compound (VI-1a) and compound (VI-1b), a mixture of compound (VI-2a) and compound (VI-2b), compound (VI- A mixture of 3a) and compound (VI-3b) is also a preferred specific example of compound (II) or a salt thereof.
The geometric isomerism (E or Z) of the carbon-carbon double bond in compound (VI-2a) and compound (VI-2b) is not particularly limited.
　化合物（ＩＩ）またはその塩とホウ素化合物とを反応させて得られる化合物（例えば、ホウ素錯体など）を、化合物（ＩＩ）またはその塩の代わりに化合物（Ｉ）と化合物（ＩＩ）またはその塩との反応物の原料、化合物（Ｉ）と化合物（ＩＩ）またはその塩とを含有する油類用添加剤の原料、あるいは該油類用添加剤と潤滑油基油とを混合して得られる潤滑油組成物の原料としてとして用いてもよい。 A compound obtained by reacting compound (II) or a salt thereof with a boron compound (for example, a boron complex) is converted between compound (I) and compound (II) or a salt thereof instead of compound (II) or a salt thereof. Lubricant obtained by mixing the raw material of the reaction product, the raw material of the additive for oils containing the compound (I) and the compound (II) or a salt thereof, or the lubricating oil base oil and the additive for oils You may use as a raw material of an oil composition.
　ホウ素化合物としては、例えば、ホウ酸アンモニウムなどのホウ酸塩、ホウ酸モノメチル、ホウ酸ジメチル、ホウ酸トリメチル、ホウ酸モノエチル、ホウ酸ジエチル、ホウ酸トリエチル、ホウ酸モノプロピル、ホウ酸ジプロピル、ホウ酸トリプロピル、ホウ酸モノブチル、ホウ酸ジブチル、ホウ酸トリブチル、ホウ酸モノ２－エチルヘキシル、ホウ酸ジ２－エチルヘキシル、ホウ酸トリ２－エチルヘキシルなどのホウ酸エステルなどが挙げられる。 Examples of the boron compound include borate salts such as ammonium borate, monomethyl borate, dimethyl borate, trimethyl borate, monoethyl borate, diethyl borate, triethyl borate, monopropyl borate, dipropyl borate, boron Examples thereof include boric acid esters such as tripropyl acid, monobutyl borate, dibutyl borate, tributyl borate, mono-2-ethylhexyl borate, di-2-ethylhexyl borate, tri-2-ethylhexyl borate, and the like.
　反応物（Ｘ）は、例えば、化合物（Ｉ）と化合物（ＩＩ）またはその塩とをジエチルエーテルなどの溶媒中、０～１２０℃で、０．１～３０時間反応させることにより製造することができる。
　化合物（Ｉ）に対して、化合物（ＩＩ）またはその塩を０．１～１０倍モル量使用することが好ましい。 Reactant (X) can be produced, for example, by reacting compound (I) with compound (II) or a salt thereof in a solvent such as diethyl ether at 0 to 120 ° C. for 0.1 to 30 hours. it can.
It is preferable to use the compound (II) or a salt thereof in an amount of 0.1 to 10 times the amount of the compound (I).
　化合物（Ｉ）は単独で、または２種以上を混合して使用できる。中でも、化合物（Ｉｂ）のうちｙが０であるものと、化合物（Ｉｂ）のうちｙが１／３であるものとを混合して使用するのが好ましい。化合物（ＩＩ）またはその塩は単独で、または２種以上を混合して使用できる。
　反応後、必要に応じて、反応物（Ｘ）を有機合成化学で通常用いられる方法（各種クロマトグラフィー法、再結晶法、蒸留法など）で精製してもよい。化合物（Ｉ）および／または化合物（ＩＩ）またはその塩と、反応物（Ｘ）との混合物が得られたとき、該混合物を反応物（Ｘ）を含有する油類用添加剤の原料として使用してもよい。 Compound (I) can be used alone or in admixture of two or more. Among them, it is preferable to use a compound (Ib) in which y is 0 and a compound (Ib) in which y is 1/3. Compound (II) or a salt thereof can be used alone or in admixture of two or more.
After the reaction, if necessary, the reaction product (X) may be purified by methods commonly used in organic synthetic chemistry (such as various chromatographic methods, recrystallization methods, and distillation methods). When a mixture of compound (I) and / or compound (II) or a salt thereof and reactant (X) is obtained, the mixture is used as a raw material for an additive for oils containing reactant (X) May be.
　化合物（Ｉ）と化合物（ＩＩ）またはその塩とを含有する油類用添加剤において、化合物（Ｉ）は単独で、または２種以上を混合して使用できる。中でも、化合物（Ｉｂ）のうちｙが０であるものと、化合物（Ｉｂ）のうちｙが１／３であるものとを混合して使用するのが好ましい。また、化合物（ＩＩ）またはその塩は単独で、または２種以上を混合して使用できる。 In the additive for oils containing Compound (I) and Compound (II) or a salt thereof, Compound (I) can be used alone or in admixture of two or more. Among them, it is preferable to use a compound (Ib) in which y is 0 and a compound (Ib) in which y is 1/3. Moreover, compound (II) or its salt can be used individually or in mixture of 2 or more types.
　化合物（Ｉ）と化合物（ＩＩ）またはその塩とを含有する油類用添加剤は、化合物（Ｉ）と化合物（ＩＩ）またはその塩とを含有するように調製されたものであれば、単独の添加剤であってもよく、複数の添加剤の組みあわせであってもよい。中でも、該油類用添加剤が複数の添加剤の組みあわせであって、該複数の添加剤の組み合わせが化合物（Ｉ）を含有する添加剤と、化合物（ＩＩ）またはその塩を含有する添加剤とを含有するのが好ましい。 The oil additive containing compound (I) and compound (II) or a salt thereof may be used alone if it is prepared to contain compound (I) and compound (II) or a salt thereof. The additive may be a combination of a plurality of additives. In particular, the additive for oils is a combination of a plurality of additives, and the combination of the plurality of additives includes an additive containing compound (I) and an addition containing compound (II) or a salt thereof. It is preferable to contain an agent.
　反応物（Ｘ）を含有する油類用添加剤は、反応物（Ｘ）を含有するように調製されたものであれば、単独の添加剤であってもよく、複数の添加剤の組みあわせであってもよい。
　本発明の油類用添加剤は、化合物（Ｉ）、化合物（ＩＩ）またはその塩および反応物（Ｘ）以外に、その他の成分を含有していてもよい。その他の成分しては、例えば、通常用いられている油類用添加剤［例えば、清浄分散剤、酸化防止剤、摩耗低減剤（耐摩耗剤、焼付き防止剤、極圧剤など）、摩擦調整剤、油性剤、防錆剤、気相防錆剤、流動点降下剤、粘度指数向上剤、増粘剤、防腐剤、消泡剤、抗乳化剤、染料、香料など］に用いられるものなどが挙げられる。 As long as the additive for oils containing the reactant (X) is prepared so as to contain the reactant (X), it may be a single additive or a combination of a plurality of additives. It may be.
The additive for oils of the present invention may contain other components in addition to the compound (I), the compound (II) or a salt thereof and the reaction product (X). Other components include, for example, commonly used oil additives [for example, detergent dispersants, antioxidants, wear reducing agents (antiwear agents, anti-seizure agents, extreme pressure agents, etc.), friction Adjustment agents, oiliness agents, rust inhibitors, gas phase rust inhibitors, pour point depressants, viscosity index improvers, thickeners, preservatives, antifoaming agents, demulsifiers, dyes, fragrances, etc.] Is mentioned.
　本発明の油類用添加剤が複数の添加剤の組みあわせであるとき、該複数の添加剤のそれぞれが、例えば、その他の成分として前記に例示したものの中から選ばれる１種以上などを含んでいてもよい。
　本発明の油類用添加剤を潤滑油組成物などの油類に添加することにより、潤滑油組成物などの油類に優れた耐摩擦特性または優れた耐摩耗特性を付与することができる。 When the additive for oils of the present invention is a combination of a plurality of additives, each of the plurality of additives includes, for example, one or more selected from those exemplified above as the other components You may go out.
By adding the additive for oils of the present invention to oils such as lubricating oil compositions, it is possible to impart excellent friction resistance or excellent wear resistance characteristics to oils such as lubricating oil compositions.
　化合物（Ｉ）と化合物（ＩＩ）またはその塩とを含有する油類用添加剤と、潤滑油基油とを混合して得られる潤滑油組成物は、例えば、化合物（Ｉ）と、化合物（ＩＩ）またはその塩と、潤滑油基油と、任意成分とを、同時にまたは任意の順序で混合することにより得ることができる。該潤滑油組成物を調製する具体的な方法としては、例えば、化合物（Ｉ）、化合物（ＩＩ）またはその塩および任意成分を潤滑油基油に添加する方法、化合物（Ｉ）と潤滑油基油と任意成分とを混合して得られる組成物に化合物（ＩＩ）またはその塩を添加する方法などが挙げられる。 A lubricating oil composition obtained by mixing an additive for oils containing compound (I) and compound (II) or a salt thereof and a lubricating base oil includes, for example, compound (I) and compound (I) II) or a salt thereof, a lubricating base oil, and optional components can be obtained by mixing simultaneously or in any order. Specific methods for preparing the lubricating oil composition include, for example, a method of adding Compound (I), Compound (II) or a salt thereof and an optional component to a lubricating base oil, Compound (I) and a lubricating base. The method of adding compound (II) or its salt to the composition obtained by mixing oil and arbitrary components is mentioned.
　潤滑油基油としては、例えば、天然基油、合成基油などが挙げられる。
　天然基油としては、例えば、鉱物油、植物油、獣油などが挙げられる。
　鉱物油としては、例えば、パラフィン基系原油、中間基系原油、ナフテン基系原油などが挙げられる。また、これらを蒸留などにより精製した精製油も使用可能である。
　合成基油としては、例えば、ポリ－α－オレフィン（ポリブテン、ポリプロピレン、炭素数８～１４のα－オレフィンオリゴマーなど）、脂肪酸エステル（脂肪酸モノエステル、多価アルコールの脂肪酸エステル、脂肪族多塩基酸エステルなど）、芳香族エステル（芳香族モノエステル、多価アルコールの芳香族エステル、芳香族多塩基酸エステルなど）、ポリアルキレングリコール、リン酸エステル、シリコーン、ケイ酸エステル、ポリフェニルエーテル、アルキルベンゼン、合成ナフテン、ガスツーリキッド（ＧＴＬ）、フルオロカーボン、イオン液体などが挙げられる。 Examples of the lubricating base oil include natural base oils and synthetic base oils.
Examples of natural base oils include mineral oil, vegetable oil, and animal oil.
Examples of the mineral oil include paraffinic crude oil, intermediate crude oil, and naphthenic crude oil. Further, refined oils obtained by refining them by distillation or the like can also be used.
Synthetic base oils include, for example, poly-α-olefins (polybutene, polypropylene, α-olefin oligomers having 8 to 14 carbon atoms, etc.), fatty acid esters (fatty acid monoesters, fatty acid esters of polyhydric alcohols, aliphatic polybasic acids) Ester), aromatic ester (aromatic monoester, aromatic ester of polyhydric alcohol, aromatic polybasic acid ester, etc.), polyalkylene glycol, phosphate ester, silicone, silicate ester, polyphenyl ether, alkylbenzene, Synthetic naphthene, gas-to-liquid (GTL), fluorocarbon, ionic liquid and the like can be mentioned.
　潤滑油基油が、（１）鉱物油、ポリ－α－オレフィン、脂肪酸エステル、芳香族エステル、ポリアルキレングリコール、リン酸エステル、シリコーン、ケイ酸エステル、ポリフェニルエーテル、アルキルベンゼン、合成ナフテン、ガスツーリキッド（ＧＴＬ）、フルオロカーボン、イオン液体、植物油、および獣油からなる群より選ばれる１種以上であるのが好ましく、（２）鉱物油、ポリ－α－オレフィン、脂肪酸エステル、ポリアルキレングリコール、リン酸エステル、シリコーン、ケイ酸エステル、ポリフェニルエーテル、アルキルベンゼン、合成ナフテン、ガスツーリキッド（ＧＴＬ）および植物油からなる群より選ばれる１種以上であるのがより好ましい。 Lubricating oil base oil is (1) mineral oil, poly-α-olefin, fatty acid ester, aromatic ester, polyalkylene glycol, phosphate ester, silicone, silicate ester, polyphenyl ether, alkylbenzene, synthetic naphthene, gas two It is preferably at least one selected from the group consisting of liquid (GTL), fluorocarbon, ionic liquid, vegetable oil, and animal oil. (2) Mineral oil, poly-α-olefin, fatty acid ester, polyalkylene glycol, phosphorus More preferably, it is at least one selected from the group consisting of acid esters, silicones, silicate esters, polyphenyl ethers, alkylbenzenes, synthetic naphthenes, gas-to-liquid (GTL) and vegetable oils.
　化合物（Ｉ）と化合物（ＩＩ）またはその塩とのモル比は、０．１～１０［化合物（Ｉ）／化合物（ＩＩ）またはその塩］であるのが好ましい。また、潤滑油組成物中のリンの含量が潤滑油組成物の全量に対して０．００１～０．１質量％の範囲になるように、潤滑油組成物の全量に対する化合物（Ｉ）の使用量を調整することが好ましい。化合物（ＩＩ）またはその塩の使用量は、潤滑油組成物１ｋｇに対して０．００１～５００ミリモルであるのが好ましく、０．０１～３００ミリモルであるのがより好ましく、さらには０．１～１００ミリモルであるのが好ましい。 The molar ratio of compound (I) to compound (II) or a salt thereof is preferably 0.1 to 10 [compound (I) / compound (II) or a salt thereof]. The use of compound (I) with respect to the total amount of the lubricating oil composition so that the phosphorus content in the lubricating oil composition is in the range of 0.001 to 0.1% by mass with respect to the total amount of the lubricating oil composition It is preferable to adjust the amount. The amount of compound (II) or a salt thereof used is preferably 0.001 to 500 mmol, more preferably 0.01 to 300 mmol, more preferably 0.1 to 1 kg of the lubricating oil composition. It is preferably ˜100 mmol.
　任意成分としては、例えば、潤滑油組成物に通常用いられている添加剤などが挙げられ、該添加剤の具体例としては、例えば、清浄分散剤、酸化防止剤、摩耗低減剤（耐摩耗剤、焼付き防止剤、極圧剤など）、摩擦調整剤、油性剤、防錆剤、気相防錆剤、流動点降下剤、粘度指数向上剤、増粘剤、防腐剤、消泡剤、抗乳化剤、染料、香料などが挙げられる。これらの添加剤の使用量は、潤滑油組成物中、それぞれ０．００１～５質量％であるのが好ましい。 Examples of the optional component include additives usually used in lubricating oil compositions, and specific examples of the additive include, for example, detergent dispersants, antioxidants, wear reducing agents (antiwear agents). Anti-seizure agent, extreme pressure agent, etc.), friction modifier, oiliness agent, rust preventive agent, gas phase rust preventive agent, pour point depressant, viscosity index improver, thickener, antiseptic, antifoaming agent, Examples include demulsifiers, dyes, and fragrances. The amount of these additives used is preferably 0.001 to 5% by mass in the lubricating oil composition.
　化合物（Ｉ）と化合物（ＩＩ）またはその塩とを含有する油類用添加剤と潤滑油基油とを混合して得られる潤滑油組成物は、下記の（ｉ）および／または（ｉｉ）と潤滑油基油とを含有する。
　（ｉ）化合物（Ｉ）および化合物（ＩＩ）またはその塩
　（ｉｉ）反応物（Ｘ）
　前記（ｉ）および／または前記（ｉｉ）を含有する潤滑油組成物は、優れた耐摩擦特性または優れた耐摩耗特性を有する。 A lubricating oil composition obtained by mixing an additive for oils containing compound (I) and compound (II) or a salt thereof and a lubricating base oil is the following (i) and / or (ii) And a lubricating base oil.
(I) Compound (I) and Compound (II) or a salt thereof (ii) Reactant (X)
The lubricating oil composition containing the (i) and / or the (ii) has excellent friction resistance or excellent wear resistance.
　反応物（Ｘ）を含有する油類用添加剤と潤滑油基油とを混合して得られる潤滑油組成物は、例えば、反応物（Ｘ）と、潤滑油基油と、任意成分とを、同時にまたは任意の順序で混合することにより得ることができる。ここで、潤滑油基油および任意成分は、それぞれ前記と同義である。
　潤滑油組成物中のリンの含量が潤滑油組成物の全量に対して０．００１～０．１質量％の範囲になるように、潤滑油組成物の全量に対する反応物（Ｘ）の使用量を調整することが好ましい。 The lubricating oil composition obtained by mixing the additive for oils containing the reactant (X) and the lubricating base oil includes, for example, the reactant (X), the lubricating base oil, and optional components. Can be obtained by mixing at the same time or in any order. Here, the lubricating base oil and the optional components are as defined above.
Use amount of reactant (X) with respect to the total amount of the lubricating oil composition so that the phosphorus content in the lubricating oil composition is in the range of 0.001 to 0.1 mass% with respect to the total amount of the lubricating oil composition Is preferably adjusted.
　任意成分の使用量は、化合物（Ｉ）と化合物（ＩＩ）またはその塩とを含有する油類用添加剤と、潤滑油基油とを混合して得られる潤滑油組成物を調製するときのそれと同様である。
　本発明の潤滑油組成物は、例えば、エンジン油、自動変速機油、無段変速機油、ギヤ油、パワーステアリング油、ショックアブソーバ油、タービン油、作動油、冷凍機油、圧延油、軸受油、金属加工用潤滑油、摺動面油、グリース、生体潤滑剤などに使用することができる。 The amount of the optional component used is that when preparing a lubricating oil composition obtained by mixing an additive for oils containing compound (I) and compound (II) or a salt thereof, and a lubricating base oil. It is the same as that.
The lubricating oil composition of the present invention includes, for example, engine oil, automatic transmission oil, continuously variable transmission oil, gear oil, power steering oil, shock absorber oil, turbine oil, hydraulic oil, refrigeration oil, rolling oil, bearing oil, metal It can be used for processing lubricants, sliding surface oils, greases, biological lubricants, and the like.
　また、本発明の油類用添加剤と燃料油などの他の油類とを混合することにより、他の油類に優れた耐摩擦特性または優れた耐摩耗特性を付与することもできる。
　燃料油としては、バイオディーゼル燃料などが挙げられる。
　化合物（Ｉ）と化合物（ＩＩ）またはその塩とを含有する油類用添加剤と、燃料油とを混合するときの化合物（Ｉ）の使用量は、燃料油に対して０．００００１～１０質量％であるのが好ましく、０．００００１～１質量％であるのがより好ましい。 Also, by mixing the oil additive of the present invention with other oils such as fuel oil, it is possible to impart excellent friction resistance or excellent wear resistance to other oils.
Examples of the fuel oil include biodiesel fuel.
The amount of compound (I) used when mixing an oil additive containing compound (I) and compound (II) or a salt thereof with fuel oil is 0.00001-10. The content is preferably mass%, more preferably 0.00001 to 1 mass%.
　化合物（Ｉ）と化合物（ＩＩ）またはその塩とを含有する油類用添加剤と、燃料油とを混合するときの化合物（ＩＩ）またはその塩の使用量は、燃料油１ｋｇに対して０．００１～５００ミリモルであるのが好ましく、０．０１～３００ミリモルであるのがより好ましく、さらには０．１～１００ミリモルであるのが好ましい。
　反応物（Ｘ）を含有する油類用添加剤と燃料油とを混合するときの反応物（Ｘ）の使用量は、燃料油に対して０．００００１～１０質量％であるのが好ましく、０．００００１～１質量％であるのがより好ましい。 The amount of compound (II) or a salt thereof used when mixing an oil additive containing compound (I) and compound (II) or a salt thereof with fuel oil is 0 per 1 kg of fuel oil. It is preferably 0.001 to 500 mmol, more preferably 0.01 to 300 mmol, and further preferably 0.1 to 100 mmol.
The amount of the reactant (X) used when mixing the oil additive containing the reactant (X) and the fuel oil is preferably 0.00001 to 10% by mass with respect to the fuel oil. It is more preferably 0.00001 to 1% by mass.
　以下、合成例、実施例、比較例および試験例により、本発明をさらに具体的に説明する。
　合成例および試験例中の測定データは、以下の測定機器、測定手法により得た。
・　核磁気共鳴スペクトル
　１Ｈ－ＮＭＲ；テトラメチルシランを内部標準物として使用：ＧＳＸ－４００（４００ＭＨｚ；日本電子社製）。 Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples, comparative examples, and test examples.
The measurement data in the synthesis examples and the test examples were obtained by the following measuring instruments and measuring methods.
Nuclear magnetic resonance spectrum 1 H-NMR; using tetramethylsilane as an internal standard: GSX-400 (400 MHz; manufactured by JEOL Ltd.).
　３１Ｐ－ＮＭＲ；リン酸トリフェニルを内部標準物として使用：ＪＮＭ－ＥＣＡ５００（２０２．５ＭＨｚ；日本電子社製）。
（２）動摩擦係数の測定（耐摩擦特性の評価）：曽田式振子型摩擦試験機（神鋼造機社製）
（３）摩耗痕径の測定（耐摩耗特性の評価）：シェル式四球摩擦試験機（高千穂精機社製、エア圧加重方式）
　合成例９～１１において、活性炭は日本エンバイロケミカル社製白鷺Ｐを用いた。 31 P-NMR; using triphenyl phosphate as an internal standard: JNM-ECA500 (202.5 MHz; manufactured by JEOL Ltd.).
(2) Measurement of coefficient of dynamic friction (evaluation of friction resistance): Iwata-type pendulum type friction tester (manufactured by Shinko Engineering Co., Ltd.)
(3) Measurement of wear scar diameter (evaluation of wear resistance): Shell type four-ball friction tester (manufactured by Takachiho Seiki Co., Ltd., air pressure load method)
In Synthesis Examples 9 to 11, white activated carbon P manufactured by Nippon Enviro Chemical Co., Ltd. was used as the activated carbon.
[合成例１]　オクタデシルグアニジン［化合物（ＩＩ－１）］の合成
　メチルイソチオ尿素硫酸塩５．００ｇ（東京化成工業社製）、オクタデシルアミン１１．１０ｇ（東京化成工業社製；オクタデシルアミンを８０％以上含む）およびメタノール１０ｍｌを混合し、６０～７０℃で２．０時間攪拌した。反応液を１５℃まで冷却後、析出した白色固体を濾取した。この白色固体にジエチルエーテル１００ｍｌを加え、３０～４０℃で４時間リスラリーした。白色固体を濾取し、ジエチルエーテルで洗浄し、５０℃で減圧乾燥して、オクタデシルグアニジン硫酸塩１０．４０ｇを得た。 [Synthesis Example 1] Synthesis of Octadecylguanidine [Compound (II-1)] 5.00 g of methylisothiourea sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.), 11.10 g of octadecylamine (manufactured by Tokyo Chemical Industry Co., Ltd .; 80% or more of octadecylamine) And 10 ml of methanol were mixed and stirred at 60 to 70 ° C. for 2.0 hours. The reaction solution was cooled to 15 ° C., and the precipitated white solid was collected by filtration. 100 ml of diethyl ether was added to this white solid and reslurried at 30-40 ° C. for 4 hours. The white solid was collected by filtration, washed with diethyl ether, and dried under reduced pressure at 50 ° C. to obtain 10.40 g of octadecylguanidine sulfate.
　オクタデシルグアニジン硫酸塩２．７９ｇ、テトラヒドロフラン８０ｍｌ、メタノール２０ｍｌおよび２５重量％水酸化ナトリウム水溶液３０ｍｌを混合し、窒素雰囲気下、６０～７０℃で１．０時間攪拌した。反応液を１５℃まで冷却後、溶媒を留去し、析出した白色固体を濾取し、蒸留水、アセトンで順次洗浄し、５０℃で減圧乾燥して化合物（ＩＩ－１）１．７９ｇを得た。
１Ｈ－ＮＭＲ（ＣＦ３ＣＯＯＤ，δｐｐｍ）；０．８２（ｔ，３Ｈ），１．０５－１．４５（ｍ，３０Ｈ），１．５９－１．７０（ｍ，２Ｈ），３．２０（ｔ，２Ｈ）
元素分析；
実測値（％）Ｃ：７３．３５、Ｈ：１３．０６、Ｎ：１３．５９、Ｓ：０．００ 2.79 g of octadecylguanidine sulfate, 80 ml of tetrahydrofuran, 20 ml of methanol and 30 ml of 25 wt% aqueous sodium hydroxide solution were mixed and stirred at 60 to 70 ° C. for 1.0 hour under a nitrogen atmosphere. After cooling the reaction solution to 15 ° C., the solvent was distilled off, and the precipitated white solid was collected by filtration, washed successively with distilled water and acetone, and dried under reduced pressure at 50 ° C. to obtain 1.79 g of compound (II-1). Obtained.
1 H-NMR (CF 3 COOD, δ ppm); 0.82 (t, 3H), 1.05-1.45 (m, 30H), 1.59-1.70 (m, 2H), 3.20 (T, 2H)
Elemental analysis;
Actual value (%) C: 73.35, H: 13.06, N: 13.59, S: 0.00
 [合成例２]　オクタデシルグアニジン炭酸塩［化合物（ＶＩ－１）］の合成
　オクタデシルグアニジン硫酸塩１．００ｇ、テトラヒドロフラン２０ｍｌおよび５重量％炭酸ナトリウム水溶液１５ｍｌを混合し、６０～７０℃で０．５時間攪拌した。反応液を１５℃まで冷却後、析出した白色固体を濾取し、蒸留水、アセトンで順次洗浄し、５０℃で減圧乾燥して化合物（ＶＩ－１）０．８１ｇを得た。
１Ｈ－ＮＭＲ（ＣＦ３ＣＯＯＤ，δｐｐｍ）；０．８７（ｔ，３Ｈ），１．１０－１．５０（ｍ，３０Ｈ），１．６５－１．７５（ｍ，２Ｈ），３．２５（ｍ，２Ｈ）
元素分析；
実測値（％）Ｃ：６６．５７、Ｈ：１１．７８、Ｎ：１１．８３、Ｓ：０．００ [Synthesis Example 2] Synthesis of Octadecylguanidine Carbonate [Compound (VI-1)] 1.00 g of octadecylguanidine sulfate, 20 ml of tetrahydrofuran and 15 ml of 5 wt% aqueous sodium carbonate solution were mixed and mixed at 60 to 70 ° C for 0.5 hour. Stir. After cooling the reaction solution to 15 ° C., the precipitated white solid was collected by filtration, washed successively with distilled water and acetone, and dried under reduced pressure at 50 ° C. to obtain 0.81 g of compound (VI-1).
1 H-NMR (CF 3 COOD, δ ppm); 0.87 (t, 3H), 1.10-1.50 (m, 30H), 1.65-1.75 (m, 2H), 3.25 (M, 2H)
Elemental analysis;
Actual value (%) C: 66.57, H: 11.78, N: 11.83, S: 0.00
[合成例３]　９－オクタデセニルグアニジン炭酸塩［化合物（ＶＩ－２）］の合成
　メチルイソチオ尿素硫酸塩８．９９ｇ（東京化成工業社製）、９－オクタデセニルアミン２１．７３ｇ（アルドリッチ社製；９－オクタデセニルアミンを７０％以上含む）およびメタノール３０ｍｌを混合し、６０～７０℃で４．５時間攪拌した。反応液を１５℃まで冷却後、反応液から溶媒を留去し、残渣にジエチルエーテル１２０ｍｌを加えた。析出した白色固体を遠心分離器により濾取し、ジエチルエーテルで洗浄し、５０℃で減圧乾燥して９－オクタデセニルグアニジン硫酸塩１７．７９ｇを得た。 [Synthesis Example 3] Synthesis of 9-octadecenylguanidine carbonate [Compound (VI-2)] 8.99 g of methylisothiourea sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.), 21.73 g of 9-octadecenylamine (Aldrich) Made by the company; containing 70% or more of 9-octadecenylamine) and 30 ml of methanol were mixed and stirred at 60 to 70 ° C. for 4.5 hours. After cooling the reaction solution to 15 ° C., the solvent was distilled off from the reaction solution, and 120 ml of diethyl ether was added to the residue. The precipitated white solid was collected by filtration with a centrifuge, washed with diethyl ether, and dried under reduced pressure at 50 ° C. to obtain 17.79 g of 9-octadecenylguanidine sulfate.
　９－オクタデセニルグアニジン硫酸塩１０．００ｇ、塩化メチレン５００ｍｌおよび５重量％炭酸ナトリウム水溶液１４０ｍｌを１５～２５℃で１．０時間反応させた。反応液を分液し、有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで脱水後、濾過し、濾液から溶媒を留去し、残渣を５０℃で減圧乾燥して化合物（ＶＩ－２）９．１１ｇを得た。
１Ｈ－ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）；０．８８（ｔ，３Ｈ），１．２０－１．４１（ｍ，２２Ｈ），１．５８－１．６５（ｍ，２Ｈ），１．９３－２．０２（ｍ，４Ｈ），３．１５（ｂｒ，２Ｈ），５．３０－５．３８（ｍ，２Ｈ），６．５８－７．２３（
ｂｒ，３Ｈ），７．７３（ｓ，１Ｈ）
元素分析；
実測値（％）Ｃ：６５．０６、Ｈ：１１．２１、Ｎ：１１．５９、Ｓ：０．００ 10.00 g of 9-octadecenylguanidine sulfate, 500 ml of methylene chloride and 140 ml of 5 wt% aqueous sodium carbonate solution were reacted at 15-25 ° C for 1.0 hour. The reaction mixture is separated, and the organic layer is washed with saturated brine, dehydrated over anhydrous magnesium sulfate and filtered. The solvent is evaporated from the filtrate, and the residue is dried under reduced pressure at 50 ° C. to give compound (VI-2). 9.11 g was obtained.
1 H-NMR (CDCl 3 , δ ppm); 0.88 (t, 3H), 1.20-1.41 (m, 22H), 1.58-1.65 (m, 2H), 1.93- 2.02 (m, 4H), 3.15 (br, 2H), 5.30-5.38 (m, 2H), 6.58-7.23 (
br, 3H), 7.73 (s, 1H)
Elemental analysis;
Actual value (%) C: 65.06, H: 11.21, N: 11.59, S: 0.00
[合成例４]　Ｎ－エチル－Ｎ’－オクタデシルグアニジン炭酸塩［化合物（ＶＩ－３）］の合成
　エチルチオ尿素６．９２ｇ（アルドリッチ社製）、ヨウ化メタン１１．１５ｇ（東京化成工業社製）およびメタノール１０ｍｌを混合し、６０～７０℃で４．０時間攪拌した。反応液から溶媒を留去し、Ｎ－エチル－Ｓ－メチルイソチオ尿素ヨウ化水素塩１６．２８ｇを得た。 [Synthesis Example 4] Synthesis of N-ethyl-N'-octadecylguanidine carbonate [Compound (VI-3)] 6.92 g of ethylthiourea (manufactured by Aldrich), 11.15 g of methane iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) And 10 ml of methanol were mixed and stirred at 60 to 70 ° C. for 4.0 hours. The solvent was distilled off from the reaction solution to obtain 16.28 g of N-ethyl-S-methylisothiourea hydrogen iodide salt.
　Ｎ－エチル－Ｓ－メチルイソチオ尿素ヨウ化水素塩４．００ｇ、オクタデシルアミン４．８２ｇ（東京化成工業社製）およびメタノール２０ｍｌを混合し、６０～７０℃で６．５時間攪拌した。反応液を１５℃まで冷却後、反応液から溶媒を留去した。残渣にジエチルエーテル２０ｍｌを加えて攪拌し、濾過し、濾液から溶媒を留去し、残渣にヘキサン５０ｍｌを加え再結晶を行い、固体を濾取し、４０℃で減圧乾燥してＮ－エチル－Ｎ’－オクタデシルグアニジンヨウ化水素塩４．２７ｇを得た。 N-ethyl-S-methylisothiourea hydrogen iodide 4.00 g, octadecylamine 4.82 g (manufactured by Tokyo Chemical Industry Co., Ltd.) and methanol 20 ml were mixed and stirred at 60 to 70 ° C. for 6.5 hours. After cooling the reaction solution to 15 ° C., the solvent was distilled off from the reaction solution. 20 ml of diethyl ether was added to the residue, stirred and filtered, the solvent was distilled off from the filtrate, 50 ml of hexane was added to the residue, recrystallization was performed, the solid was collected by filtration, dried at 40 ° C. under reduced pressure, and N-ethyl- 4.27 g of N′-octadecylguanidine hydrogen iodide was obtained.
　Ｎ－エチル－Ｎ’－オクタデシルグアニジンヨウ化水素塩２．５０ｇ、塩化メチレン１００ｍｌおよび１重量％炭酸ナトリウム水溶液１００ｍｌを混合し、１５～２５℃で０．５時間攪拌した。反応液を分液し、有機層を飽和食塩水で洗浄し、無水硫酸マグネシウムで脱水後、濾過し、濾液から溶媒を留去し、残渣を５０℃で減圧乾燥して化合物（ＶＩ－３）の粗体１．４７ｇを得た。 N-ethyl-N′-octadecylguanidine hydrogen iodide 2.50 g, methylene chloride 100 ml and 1 wt% aqueous sodium carbonate solution 100 ml were mixed and stirred at 15 to 25 ° C. for 0.5 hour. The reaction mixture is separated, and the organic layer is washed with saturated brine, dehydrated over anhydrous magnesium sulfate and filtered. The solvent is evaporated from the filtrate, and the residue is dried under reduced pressure at 50 ° C. to give compound (VI-3). 1.47 g of a crude product was obtained.
　この粗体１．００ｇをシリカゲルカラムクロマトグラフィーにより精製して化合物（ＶＩ－３）０．５４ｇを得た。
１Ｈ－ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）；０．８８（ｔ，３Ｈ），１．００－１．４８（ｍ，３１Ｈ），１．５５－１．６９（ｍ，２Ｈ），１．７１－２．２０（ｍ，２Ｈ），２．８５－３．４１（ｍ，４Ｈ），６．８５－７．５５（ｂｒ，３Ｈ）
元素分析；
実測値（％）Ｃ：６７．２７、Ｈ：１１．７７、Ｎ：９．９２、Ｓ：０．００
[合成例５]　９－オクタデセニル尿素（比較化合物Ｐ）の合成 1.00 g of this crude product was purified by silica gel column chromatography to obtain 0.54 g of compound (VI-3).
1 H-NMR (CDCl 3 , δ ppm); 0.88 (t, 3H), 1.00-1.48 (m, 31H), 1.55-1.69 (m, 2H), 1.71- 2.20 (m, 2H), 2.85-3.41 (m, 4H), 6.85-7.55 (br, 3H)
Elemental analysis;
Actual value (%) C: 67.27, H: 11.77, N: 9.92, S: 0.00
[Synthesis Example 5] Synthesis of 9-octadecenyl urea (Comparative Compound P)
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　９－オクタデセニルアミン１６．５ｇ（アルドリッチ社製；９－オクタデセニルアミンを７０％以上含む）および尿素１８．５ｇ（和光純薬工業社製）を混合し、１６０℃で３．０時間攪拌した。反応液を１５℃まで冷却し、塩化メチレン５０ｍｌを加え、蒸留水で洗浄した。無水硫酸マグネシウムで脱水後、濾過し、濾液から溶媒を留去し、残渣を５０℃で減圧乾燥して比較化合物Ｐの粗体８．７０ｇを得た。 16.5 g of 9-octadecenylamine (manufactured by Aldrich; containing 70% or more of 9-octadecenylamine) and 18.5 g of urea (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed and heated at 160 ° C. for 3.0 hours. Stir. The reaction solution was cooled to 15 ° C., added with 50 ml of methylene chloride, and washed with distilled water. After dehydration with anhydrous magnesium sulfate, filtration was performed, the solvent was distilled off from the filtrate, and the residue was dried under reduced pressure at 50 ° C. to obtain 8.70 g of a crude product of Comparative Compound P.
　この粗体１．５０ｇをシリカゲルカラムクロマトグラフィーにより精製して比較化合物Ｐ０．８１ｇを得た。
１Ｈ－ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）；０．８８（ｔ，３Ｈ），１．０５－１．３８（ｍ，２２Ｈ），１．３８－１．５５（ｍ，２Ｈ），１．９０－２．０５（ｍ，４Ｈ），３．０５－３．１５（ｍ，２Ｈ），４．７５－４．８０（ｂｒ，２Ｈ），５．０８－５．１８（ｂｒ，１Ｈ），５．２５－５．４５（ｍ，２Ｈ）
元素分析；
実測値（％）Ｃ：７３．６０、Ｈ：１２．１３、Ｎ：９．０１、Ｓ：０．００ 1.50 g of this crude product was purified by silica gel column chromatography to obtain 0.81 g of Comparative Compound P.
1 H-NMR (CDCl 3 , δ ppm); 0.88 (t, 3H), 1.05-1.38 (m, 22H), 1.38-1.55 (m, 2H), 1.90- 2.05 (m, 4H), 3.05-3.15 (m, 2H), 4.75-4.80 (br, 2H), 5.08-5.18 (br, 1H), 5. 25-5.45 (m, 2H)
Elemental analysis;
Actual value (%) C: 73.60, H: 12.13, N: 9.01, S: 0.00
[合成例６]ジブチルリン酸亜鉛［化合物（Ｉａ－１）］の合成
　リン酸ジブチル５４．８ｇ（東京化成工業社製）、酸化亜鉛１０．０ｇ（和光純薬工業社製）およびヘキサン１５０ｍｌ（和光純薬工業社製）の混合物を５時間還流させた。反応液から溶媒を留去し、残渣にエタノールと水との混合溶媒を加え再結晶を行い、固体を濾取し、６０℃で減圧乾燥してジブチルリン酸亜鉛５４．５ｇを得た。
１Ｈ－ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）：０．９１（ｂｒ，１２Ｈ），１．３８（ｂｒ，８Ｈ），１．５８（ｂｒ，８Ｈ），３．９１（ｂｒ，８Ｈ） [Synthesis Example 6] Synthesis of zinc dibutyl phosphate [Compound (Ia-1)] 54.8 g of dibutyl phosphate (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.0 g of zinc oxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 150 ml of hexane (Japanese sum) A mixture of Koyo Pure Chemical Industries, Ltd.) was refluxed for 5 hours. The solvent was distilled off from the reaction solution, and a mixed solvent of ethanol and water was added to the residue for recrystallization. The solid was collected by filtration and dried under reduced pressure at 60 ° C. to obtain 54.5 g of zinc dibutyl phosphate.
1 H-NMR (CDCl 3 , δ ppm): 0.91 (br, 12H), 1.38 (br, 8H), 1.58 (br, 8H), 3.91 (br, 8H)
［合成例７］ヘキサデシルグアニジン［化合物（ＩＩ－２）］の合成
　ヘキサデシルアミン４０．０ｇ（東京化成工業社製；ヘキサデシルアミンを９０％以上含む）とテトラヒドロフラン６７ｍｌとを混合して得た溶液に３５重量％塩酸１９．０ｇを加え、混合物を４５℃で１時間攪拌した。反応液から溶媒を留去してヘキサデシルアミン塩酸塩４５．５ｇを得た。 [Synthesis Example 7] Synthesis of hexadecylguanidine [Compound (II-2)] Obtained by mixing 40.0 g of hexadecylamine (manufactured by Tokyo Chemical Industry Co., Ltd .; containing 90% or more of hexadecylamine) and 67 ml of tetrahydrofuran. To the solution was added 19.0 g of 35 wt% hydrochloric acid and the mixture was stirred at 45 ° C. for 1 hour. The solvent was distilled off from the reaction solution to obtain 45.5 g of hexadecylamine hydrochloride.
　ヘキサデシルアミン塩酸塩４５．５ｇ、ヘキサデシルアミン２．０ｇ、ブタノール４０ｍｌおよび蒸留水１１ｍｌを混合して得た溶液を９３℃まで加熱し、シアナミド１３．９ｇ（関東化学社製）と蒸留水５３ｍｌとを混合して得た水溶液を該溶液に滴下し、混合物を９２℃で７時間攪拌した。反応液から溶媒を留去してヘキサデシルグアニジン塩酸塩６８．６ｇを得た。 A solution obtained by mixing 45.5 g of hexadecylamine hydrochloride, 2.0 g of hexadecylamine, 40 ml of butanol and 11 ml of distilled water was heated to 93 ° C., and 13.9 g of cyanamide (manufactured by Kanto Chemical Co., Inc.) and 53 ml of distilled water were used. An aqueous solution obtained by mixing was added dropwise to the solution, and the mixture was stirred at 92 ° C. for 7 hours. The solvent was distilled off from the reaction solution to obtain 68.6 g of hexadecylguanidine hydrochloride.
　ヘキサデシルグアニジン塩酸塩６８．６ｇおよびテトラヒドロフラン２８０ｍｌを混合して得た溶液を５８℃まで加熱し、２５重量％水酸化ナトリウム水溶液２８０．０ｇを該溶液に加え、混合物を１時間還流した。反応液を１３℃まで冷却後、析出した結晶を濾取し、蒸留水で洗浄し、６０℃で減圧乾燥して化合物（ＩＩ－２）４０．８ｇを得た。
１Ｈ－ＮＭＲ（ＣＤ３ＯＤ，δｐｐｍ）；０．９０（ｔ，３Ｈ），１．２０－１．４１（ｍ，２６Ｈ），１．５５（ｍ，２Ｈ），３．１０（ｔ，２Ｈ） A solution obtained by mixing 68.6 g of hexadecylguanidine hydrochloride and 280 ml of tetrahydrofuran was heated to 58 ° C., 280.0 g of 25 wt% aqueous sodium hydroxide solution was added to the solution, and the mixture was refluxed for 1 hour. After cooling the reaction solution to 13 ° C., the precipitated crystals were collected by filtration, washed with distilled water, and dried under reduced pressure at 60 ° C. to obtain 40.8 g of compound (II-2).
1 H-NMR (CD 3 OD, δ ppm); 0.90 (t, 3H), 1.20-1.41 (m, 26H), 1.55 (m, 2H), 3.10 (t, 2H) )
［合成例８］ドデシルグアニジン［化合物（ＩＩ－３）］の合成
　ドデシルアミン３０．０ｇ（東京化成工業社製）とテトラヒドロフラン５０ｍｌとを混合して得た溶液に３５重量％塩酸１８．６ｇを加え、混合物を２５～３１℃で１時間攪拌した。反応液から溶媒を留去してドデシルアミン塩酸塩３５．１ｇを得た。 [Synthesis Example 8] Synthesis of dodecylguanidine [compound (II-3)] To a solution obtained by mixing 30.0 g of dodecylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50 ml of tetrahydrofuran was added 18.6 g of 35 wt% hydrochloric acid. The mixture was stirred at 25-31 ° C. for 1 hour. The solvent was distilled off from the reaction solution to obtain 35.1 g of dodecylamine hydrochloride.
　ドデシルアミン塩酸塩３５．１ｇ、ドデシルアミン１．５ｇ、ブタノール３０ｍｌおよび蒸留水８ｍｌを混合して得た溶液を９４℃まで加熱し、シアナミド１３．６ｇ（関東化学社製）と蒸留水４０ｍｌとを混合して得た水溶液を該溶液に滴下し、混合物を９５℃で１２．５時間攪拌した。反応液から溶媒を留去し、ドデシルグアニジン塩酸塩５１．４ｇを得た。 A solution obtained by mixing 35.1 g of dodecylamine hydrochloride, 1.5 g of dodecylamine, 30 ml of butanol and 8 ml of distilled water was heated to 94 ° C., and 13.6 g of cyanamide (manufactured by Kanto Chemical Co., Inc.) and 40 ml of distilled water were added. The aqueous solution obtained by mixing was added dropwise to the solution, and the mixture was stirred at 95 ° C. for 12.5 hours. The solvent was distilled off from the reaction solution to obtain 51.4 g of dodecylguanidine hydrochloride.
　ドデシルグアニジン塩酸塩５１．４ｇおよびテトラヒドロフラン２１０ｍｌを混合して得た溶液を５５℃まで加熱し、２５重量％水酸化ナトリウム水溶液２００．０ｇを該溶液に加え、混合物を１時間還流した。反応液を８℃まで冷却後、析出した結晶を濾取し、結晶を蒸留水で洗浄し、６０℃で減圧乾燥して化合物（ＩＩ－３）２７．０ｇを得た。
１Ｈ－ＮＭＲ（ＣＤ３ＯＤ，δｐｐｍ）；０．９０（ｔ，３Ｈ），１．２０－１．４１（ｍ，１８Ｈ），１．５５（ｍ，２Ｈ），３．１０（ｔ，２Ｈ） A solution obtained by mixing 51.4 g of dodecylguanidine hydrochloride and 210 ml of tetrahydrofuran was heated to 55 ° C., 200.0 g of 25 wt% aqueous sodium hydroxide solution was added to the solution, and the mixture was refluxed for 1 hour. After cooling the reaction solution to 8 ° C., the precipitated crystals were collected by filtration, washed with distilled water, and dried under reduced pressure at 60 ° C. to obtain 27.0 g of compound (II-3).
1 H-NMR (CD 3 OD, δ ppm); 0.90 (t, 3H), 1.20-1.41 (m, 18H), 1.55 (m, 2H), 3.10 (t, 2H) )
［合成例９］ジイソプロピルジチオリン酸亜鉛［化合物（Ｉｂ－２）］の合成
　７５℃まで加熱した２－プロパノール５４．１ｇ（和光純薬工業社製）に五硫化二リン５０．１ｇ（アルドリッチ社製）を分割して添加した後、混合物を７８～８０℃で８時間攪拌した。反応液を室温まで冷却し、反応液と活性炭１０．０ｇとを混合し、室温で１時間攪拌した。混合物を濾過し、１０重量％水酸化ナトリウム水溶液１１５ｍｌを濾液に２０～２５℃で滴下した。反応液と活性炭１０．２ｇとを混合し、２０～２５℃で１５分間攪拌した。混合物を濾過し、塩化亜鉛４２．２ｇ（和光純薬工業社製）と蒸留水３０ｍｌを混合して得た水溶液を濾液に２０～２５℃で加え、混合物を２０～２５℃で０．５時間攪拌した。反応液にジエチルエーテル８００ｍｌおよび蒸留水１００ｍｌを加え、分液し、水層をジエチルエーテルで抽出した。合わせた有機層を蒸留水で３回洗浄し、無水硫酸ナトリウムで脱水後、濾過し、濾液から溶媒を留去して化合物（Ｉｂ－２）５３．９ｇを得た。 [Synthesis Example 9] Synthesis of zinc diisopropyldithiophosphate [Compound (Ib-2)] 54.1 g (manufactured by Wako Pure Chemical Industries, Ltd.) of 2-propanol heated to 75 ° C. and 50.1 g of diphosphorus pentasulfide (manufactured by Aldrich) ) Was added in portions, and the mixture was stirred at 78-80 ° C. for 8 hours. The reaction solution was cooled to room temperature, and the reaction solution and 10.0 g of activated carbon were mixed and stirred at room temperature for 1 hour. The mixture was filtered, and 115 ml of a 10 wt% aqueous sodium hydroxide solution was added dropwise to the filtrate at 20-25 ° C. The reaction solution and 10.2 g of activated carbon were mixed and stirred at 20-25 ° C. for 15 minutes. The mixture was filtered, an aqueous solution obtained by mixing 42.2 g of zinc chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 30 ml of distilled water was added to the filtrate at 20-25 ° C., and the mixture was added at 20-25 ° C. for 0.5 hour. Stir. To the reaction solution, 800 ml of diethyl ether and 100 ml of distilled water were added, followed by liquid separation, and the aqueous layer was extracted with diethyl ether. The combined organic layers were washed with distilled water three times, dehydrated with anhydrous sodium sulfate and filtered, and the solvent was distilled off from the filtrate to obtain 53.9 g of compound (Ib-2).
　得られた化合物（Ｉｂ－２）は、化合物（Ｉｂ－２ｉ）と化合物（Ｉｂ－２ｉｉ）との混合物であった。化合物（Ｉｂ－２）中の化合物（Ｉｂ－２ｉ）と化合物（Ｉｂ－２ｉｉ）とのモル比を特開平５－９３１９６号公報記載の滴定法により求めた。
　モル比；化合物（Ｉｂ－２ｉ）／化合物（Ｉｂ－２ｉｉ）＝９９．１／０．９
１Ｈ－ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）；１．４１（ｍ，２４Ｈ），４．８８（ｍ，４Ｈ） The obtained compound (Ib-2) was a mixture of the compound (Ib-2i) and the compound (Ib-2ii). The molar ratio of compound (Ib-2i) to compound (Ib-2ii) in compound (Ib-2) was determined by the titration method described in JP-A No. 5-93196.
Molar ratio; Compound (Ib-2i) / Compound (Ib-2ii) = 99.1 / 0.9
1 H-NMR (CDCl 3 , δ ppm); 1.41 (m, 24H), 4.88 (m, 4H)
［合成例１０］ジ－ｔｅｒｔ－ブチルジチオリン酸亜鉛［化合物（Ｉｂ－３ｉ）］の合成
　８０℃まで加熱した２－ブタノール６６．８ｇ（和光純薬工業社製）に五硫化二リン５０．０ｇ（アルドリッチ社製）を分割して添加した後、混合物を９０～９５℃で７時間攪拌した。反応液を室温まで冷却し、活性炭１０．０ｇを反応液に加え、混合物を室温で０．５時間攪拌した。混合物を濾過し、１０重量％水酸化ナトリウム水溶液１２０ｍｌを濾液に２０～２５℃で滴下した。反応液と活性炭１０．２ｇとを混合し、２０～２５℃で１０分間攪拌した。混合物を濾過し、塩化亜鉛２３．０ｇ（和光純薬工業社製）と蒸留水１７ｍｌを混合して得た水溶液を濾液に２０～２５℃で添加し、混合物を２０～２５℃で３時間攪拌した。析出した結晶を濾取し、蒸留水で洗浄し、３５℃で減圧乾燥して化合物（Ｉｂ－３ｉ）の粗体６０．３ｇを得た。 [Synthesis Example 10] Synthesis of zinc di-tert-butyldithiophosphate [compound (Ib-3i)] 66.8 g of 2-butanol (manufactured by Wako Pure Chemical Industries, Ltd.) heated to 80 ° C. and 50.0 g of diphosphorus pentasulfide (Aldrich) was added in portions and the mixture was stirred at 90-95 ° C. for 7 hours. The reaction solution was cooled to room temperature, 10.0 g of activated carbon was added to the reaction solution, and the mixture was stirred at room temperature for 0.5 hour. The mixture was filtered, and 120 ml of a 10% by weight aqueous sodium hydroxide solution was added dropwise to the filtrate at 20-25 ° C. The reaction solution and 10.2 g of activated carbon were mixed and stirred at 20 to 25 ° C. for 10 minutes. The mixture was filtered, an aqueous solution obtained by mixing 23.0 g of zinc chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 17 ml of distilled water was added to the filtrate at 20-25 ° C., and the mixture was stirred at 20-25 ° C. for 3 hours. did. The precipitated crystals were collected by filtration, washed with distilled water, and dried under reduced pressure at 35 ° C. to obtain 60.3 g of a crude compound (Ib-3i).
　この粗体６０．３ｇとエタノール３００ｍｌを混合し、混合物中の不溶物を濾別し、濾液に蒸留水５４ｍｌを加え、溶液を氷浴で１時間冷却し、析出した結晶を濾取し、蒸留水で洗浄し、３０℃で減圧乾燥して化合物（Ｉｂ－３ｉ）１６．７ｇを得た。
１Ｈ－ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）；０．９７（ｔ，１２Ｈ），１．４８（ｄ，１２Ｈ），１．６８（ｍ，８Ｈ），４．６６（ｍ，４Ｈ） 60.3 g of this crude product and 300 ml of ethanol were mixed, insoluble matter in the mixture was filtered off, 54 ml of distilled water was added to the filtrate, the solution was cooled in an ice bath for 1 hour, and the precipitated crystals were collected by filtration and distilled. Washing with water and drying under reduced pressure at 30 ° C. gave 16.7 g of compound (Ib-3i).
1 H-NMR (CDCl 3 , δ ppm); 0.97 (t, 12H), 1.48 (d, 12H), 1.68 (m, 8H), 4.66 (m, 4H)
［合成例１１］ビス（２－エチルヘキシル）ジチオリン酸亜鉛［化合物（Ｉｂ－４）］の合成
　ジチオリン酸Ｓ－水素＝Ｏ，Ｏ－ビス（２－エチルヘキシル）（ＳＣ有機化学社製Ｐｈｏｓｌｅｘ　ＤＴ－８）３０．０ｇに１０重量％水酸化ナトリウム水溶液３７ｍｌを２１～３９℃で滴下した。反応液にエタノール６０ｍｌおよび活性炭３．０ｇを加え、混合物を２６℃で４５分間攪拌した。混合物を濾過し、塩化亜鉛５．８ｇ（和光純薬工業社製）と蒸留水２０ｍｌを混合して得た水溶液を濾液に２３～２５℃で添加し、混合物を２０～２５℃で７０分間攪拌した。反応液にジエチルエーテル１４０ｍｌを加え、分液した。有機層を蒸留水で２回洗浄し、無水硫酸ナトリウムで脱水後、濾過し、濾液から溶媒を留去した。残渣をヘキサン１５０ｍｌに溶解し、メタノール１５０ｍｌで３回抽出し、合わせたメタノール層から溶媒を留去して化合物（Ｉｂ－４）１３．２ｇを得た。 Synthesis Example 11 Synthesis of Zinc Bis (2-ethylhexyl) dithiophosphate [Compound (Ib-4)] Dithiophosphate S-hydrogen = O, O-bis (2-ethylhexyl) (Phoslex DT-8 manufactured by SC Organic Chemical Co., Ltd.) ) 37 ml of a 10% by weight aqueous sodium hydroxide solution was added dropwise to 30.0 g at 21-39 ° C. 60 ml of ethanol and 3.0 g of activated carbon were added to the reaction solution, and the mixture was stirred at 26 ° C. for 45 minutes. The mixture was filtered, an aqueous solution obtained by mixing 5.8 g of zinc chloride (manufactured by Wako Pure Chemical Industries, Ltd.) and 20 ml of distilled water was added to the filtrate at 23-25 ° C., and the mixture was stirred at 20-25 ° C. for 70 minutes. did. 140 ml of diethyl ether was added to the reaction solution, and the solution was separated. The organic layer was washed twice with distilled water, dehydrated with anhydrous sodium sulfate, filtered, and the solvent was distilled off from the filtrate. The residue was dissolved in 150 ml of hexane, extracted three times with 150 ml of methanol, and the solvent was distilled off from the combined methanol layers to obtain 13.2 g of compound (Ib-4).
　得られた化合物（Ｉｂ－４）は、化合物（Ｉｂ－４ｉ）と化合物（Ｉｂ－４ｉｉ）との混合物であった。合成例９と同様の方法により、化合物（Ｉｂ－４）中の化合物（Ｉｂ－４ｉ）と化合物（Ｉｂ－４ｉｉ）とのモル比を求めた。
　モル比；化合物（Ｉｂ－４ｉ）／化合物（Ｉｂ－４ｉｉ）＝９５．５／４．５
１Ｈ－ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）；０．９０（ｍ，２４Ｈ），１．２０－１．５０（ｍ，３２Ｈ），１．６７（ｍ，４Ｈ），４．０８（ｍ，８Ｈ） The obtained compound (Ib-4) was a mixture of the compound (Ib-4i) and the compound (Ib-4ii). In the same manner as in Synthesis Example 9, the molar ratio of compound (Ib-4i) to compound (Ib-4ii) in compound (Ib-4) was determined.
Molar ratio; Compound (Ib-4i) / Compound (Ib-4ii) = 95.5 / 4.5
1 H-NMR (CDCl 3 , δ ppm); 0.90 (m, 24H), 1.20-1.50 (m, 32H), 1.67 (m, 4H), 4.08 (m, 8H)
［合成例１２］ジドデシルジチオリン酸亜鉛［化合物（Ｉｂ－５）］の合成
　９０℃まで加熱したドデカノール３２．７ｇ（和光純薬工業社製）に五硫化二リン９．８ｇ（アルドリッチ社製）を分割して添加した後、混合物を１２０℃で５時間攪拌した。反応液を室温まで冷却し、１０重量％水酸化ナトリウム水溶液３３ｍｌおよびメタノール３０ｍｌを反応液に２０～２５℃で加え、混合物を５０℃で１時間攪拌した。反応液と塩化亜鉛５．６ｇ（和光純薬工業社製）を混合し、５０℃で１時間攪拌した。反応液にヘキサン２００ｍｌを加えて室温で１０分間攪拌した後、分液した。水層をヘキサン１００ｍｌで２回抽出し、合わせた有機層を無水硫酸ナトリウムで脱水後、濾過し、濾液から溶媒を留去し、残渣をテトラヒドロフラン－エタノール混合溶媒で再結晶して化合物（Ｉｂ－４）の粗体３５．４ｇを得た。 [Synthesis Example 12] Synthesis of zinc didodecyl dithiophosphate [compound (Ib-5)] 32.7 g of dodecanol heated to 90 ° C (manufactured by Wako Pure Chemical Industries, Ltd.) and 9.8 g of diphosphorus pentasulfide (manufactured by Aldrich) Was added in portions and the mixture was stirred at 120 ° C. for 5 hours. The reaction solution was cooled to room temperature, 33 ml of a 10 wt% aqueous sodium hydroxide solution and 30 ml of methanol were added to the reaction solution at 20-25 ° C., and the mixture was stirred at 50 ° C. for 1 hour. The reaction solution and 5.6 g of zinc chloride (Wako Pure Chemical Industries, Ltd.) were mixed and stirred at 50 ° C. for 1 hour. The reaction solution was mixed with 200 ml of hexane, stirred at room temperature for 10 minutes, and then separated. The aqueous layer was extracted twice with 100 ml of hexane, and the combined organic layer was dehydrated with anhydrous sodium sulfate and filtered. The solvent was distilled off from the filtrate, and the residue was recrystallized with a tetrahydrofuran-ethanol mixed solvent to give compound (Ib- 45.4 g of a crude product of 4) was obtained.
　この粗体１７．０ｇをヘキサン８５ｍｌに溶解し、溶液をメタノール８５ｍｌで抽出し、メタノール層から溶媒を留去して化合物（Ｉｂ－５）１．４ｇを得た。
　得られた化合物（Ｉｂ－５）は、化合物（Ｉｂ－５ｉ）と化合物（Ｉｂ－５ｉｉ）との混合物であった。合成例９と同様の方法により、化合物（Ｉｂ－５）中の化合物（Ｉｂ－５ｉ）と化合物（Ｉｂ－５ｉｉ）とのモル比を求めた。 17.0 g of this crude product was dissolved in 85 ml of hexane, the solution was extracted with 85 ml of methanol, and the solvent was distilled off from the methanol layer to obtain 1.4 g of compound (Ib-5).
The obtained compound (Ib-5) was a mixture of the compound (Ib-5i) and the compound (Ib-5ii). In the same manner as in Synthesis Example 9, the molar ratio of compound (Ib-5i) to compound (Ib-5ii) in compound (Ib-5) was determined.
　モル比；化合物（Ｉｂ－５ｉ）／化合物（Ｉｂ－５ｉｉ）＝９２．６／７．４
１Ｈ－ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）；０．９０（ｍ，１２Ｈ），１．２１－１．４３（ｍ，７２Ｈ），１．７４（ｍ，８Ｈ），４．１８（ｍ，８Ｈ） Molar ratio; Compound (Ib-5i) / Compound (Ib-5ii) = 92.6 / 7.4
1 H-NMR (CDCl 3 , δ ppm); 0.90 (m, 12H), 1.21-1.43 (m, 72H), 1.74 (m, 8H), 4.18 (m, 8H)
［合成例１３］反応物（Ｘ－１）の合成
　オクタデシルグアニジン［化合物（ＩＩ－１）］１．２ｇ（４．０ミリモル）、ジイソプロピルジチオリン酸亜鉛［化合物（Ｉｂ－２）］１．０ｇ（２．０ミリモル）およびジエチルエーテル２０ｍｌの混合物を、１時間還流させた。反応液から溶媒を留去して反応物（Ｘ－１）２．２ｇを得た。
３１Ｐ－ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）；１０２．８
　ジイソプロピルジチオリン酸亜鉛の３１Ｐ－ＮＭＲ測定結果を以下に示す。
３１Ｐ－ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）；９２．７
　反応物（Ｘ－１）におけるリンの化学シフト値は、ジイソプロピルジチオリン酸亜鉛におけるそれと異なった。 Synthesis Example 13 Synthesis of Reactant (X-1) 1.2 g (4.0 mmol) of octadecylguanidine [Compound (II-1)], 1.0 g of zinc diisopropyldithiophosphate [Compound (Ib-2)] 2.0 mmol) and 20 ml of diethyl ether were refluxed for 1 hour. The solvent was distilled off from the reaction solution to obtain 2.2 g of a reaction product (X-1).
31 P-NMR (CDCl 3 , δ ppm); 102.8
The 31 P-NMR measurement results of zinc diisopropyldithiophosphate are shown below.
31 P-NMR (CDCl 3 , δ ppm); 92.7
The chemical shift value of phosphorus in the reactant (X-1) was different from that in zinc diisopropyldithiophosphate.
［合成例１４］反応物（Ｘ－２）の合成
　ヘキサデシルグアニジン［化合物（ＩＩ－２）］０．６ｇ（２．０ミリモル）、ジイソプロピルジチオリン酸亜鉛［化合物（Ｉｂ－２）］０．５ｇ（１．０ミリモル）およびジエチルエーテル１５ｍｌの混合物を、１時間還流させた。反応液から溶媒を留去して反応物（Ｘ－２）１．１ｇを得た。
３１Ｐ－ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）；１０２．６
［合成例１５］反応物（Ｘ－３）の合成
　オクタデシルグアニジン［化合物（ＩＩ－１）］０．３ｇ（１．０ミリモル）、ジドデシルジチオリン酸亜鉛［化合物（Ｉｂ－５）］０．５ｇ（０．５ミリモル）およびジエチルエーテル３０ｍｌの混合物を、１時間還流させた。反応液から溶媒を留去して反応物（Ｘ－３）０．８ｇを得た。
３１Ｐ－ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）；１０８．０
　ジドデシルジチオリン酸亜鉛の３１Ｐ－ＮＭＲ測定結果を以下に示す。
３１Ｐ－ＮＭＲ（ＣＤＣｌ３，δｐｐｍ）；９９．６ [Synthesis Example 14] Synthesis of Reactant (X-2) 0.6 g (2.0 mmol) of hexadecylguanidine [Compound (II-2)], 0.5 g of zinc diisopropyldithiophosphate [Compound (Ib-2)] A mixture of (1.0 mmol) and 15 ml of diethyl ether was refluxed for 1 hour. The solvent was distilled off from the reaction solution to obtain 1.1 g of a reaction product (X-2).
31 P-NMR (CDCl 3 , δ ppm); 102.6
[Synthesis Example 15] Synthesis of Reactant (X-3) 0.3 g (1.0 mmol) of octadecylguanidine [Compound (II-1)], 0.5 g of zinc didodecyldithiophosphate [Compound (Ib-5)] A mixture of (0.5 mmol) and 30 ml of diethyl ether was refluxed for 1 hour. The solvent was distilled off from the reaction solution to obtain 0.8 g of a reaction product (X-3).
31 P-NMR (CDCl 3 , δ ppm); 108.0
The 31 P-NMR measurement results of zinc didodecyldithiophosphate are shown below.
31 P-NMR (CDCl 3 , δ ppm); 99.6
［潤滑油組成物の調製］
　潤滑油基油としては、ポリ－α－オレフィン（イネオスオリゴマーズジャパン社製ＤＵＲＡＳＹＮ１６４、１００℃動粘度：３．９ｍｍ２／秒、粘度指数：１２２）を用いた。
　化合物（Ｉ）としては、化合物（Ｉａ－１）、化合物（Ｉｂ－１）［ＬＵＢＲＩＺＯＬ社製のジアルキルジチオリン酸亜鉛；ＬＵＢＲＩＺＯＬ　１０９５、リン含量９．４２質量％、硫黄含量２０．２０質量％、亜鉛含量１０．４１質量％］、化合物（Ｉｂ－２）、（Ｉｂ－３ｉ）、（Ｉｂ－４）または（Ｉｂ－５）を使用した。 [Preparation of lubricating oil composition]
As the lubricating base oil, poly-α-olefin (DURASYN164 manufactured by Ineos Oligomers Japan, 100 ° C. kinematic viscosity: 3.9 mm 2 / sec, viscosity index: 122) was used.
Compound (I) includes compound (Ia-1), compound (Ib-1) [Zinc dialkyldithiophosphate manufactured by LUBRIZOL; LUBRIZOL 1095, phosphorus content 9.42% by mass, sulfur content 20.20% by mass, zinc Content 10.41% by mass], compound (Ib-2), (Ib-3i), (Ib-4) or (Ib-5) was used.
　化合物（ＩＩ）またはその塩としては、化合物（ＩＩ－１）、（ＩＩ－２）、（ＩＩ－３）、（ＶＩ－１）、（ＶＩ－２）または（ＶＩ－３）を使用した。
　反応物（Ｘ）としては、反応物（Ｘ－１）、（Ｘ－２）または（Ｘ－３）を使用した。
　清浄分散剤１としては、コハク酸イミドタイプ無灰分散剤（ＬＵＢＲＩＺＯＬ社製ＬＵＢＲＩＺＯＬ　６４０１、窒素含量０．３６質量％）を使用した。 The compound (II), (II-2), (II-3), (VI-1), (VI-2) or (VI-3) was used as the compound (II) or a salt thereof.
As the reactant (X), the reactant (X-1), (X-2) or (X-3) was used.
As the cleaning dispersant 1, a succinimide type ashless dispersant (LUBRIZOL 6401 manufactured by LUBRIZOL, nitrogen content 0.36% by mass) was used.
　清浄分散剤２としては、カルシウムスルホネート系金属清浄剤（ＬＵＢＲＩＺＯＬ社製ＬＵＢＲＩＺＯＬ　６４７７Ｃ、全塩基価３０２ｍｇＫＯＨ／ｇ、カルシウム含量１１．９８質量％）を使用した。
　酸化防止剤１としては、チバ・スペシャリティ・ケミカルズ社製ＩＲＧＡＮＯＸ　Ｌ５７を使用した。 As the detergent dispersant 2, a calcium sulfonate metal detergent (LUBRIZOL 6477C manufactured by LUBRIZOL, total base number 302 mgKOH / g, calcium content 11.98% by mass) was used.
As antioxidant 1, IRGANOX L57 manufactured by Ciba Specialty Chemicals was used.
　酸化防止剤２としては、エーピーアイコーポレーション社製ヨシノックスＢＨＴを使用した。
［実施例１～５］
　潤滑油基油９１．９質量部に、酸化防止剤１　０．５質量部、酸化防止剤２　０．５質量部　、清浄分散剤１　４．０質量部および清浄分散剤２　２．０質量部を、１０～３０℃で順次加えた。得られた溶液に表１に記載の化合物（Ｉ）０．８質量部を加え、混合物を１０～９０℃で１時間攪拌した。得られた溶液に表１に記載の化合物（ＩＩ)またはその塩０．３質量部を加え、混合物を７０～９０℃で１時間攪拌して表１に記載の混合比の潤滑油組成物１００．０質量部を得た。 As the antioxidant 2, Yoshinox BHT manufactured by API Corporation was used.
[Examples 1 to 5]
91.9 parts by mass of lubricant base oil, 0.5 parts by mass of antioxidant 1, 0.5 parts by mass of antioxidant 2, 4.0 parts by mass of detergent 1 and 2.0 parts by mass of detergent 2 Were added sequentially at 10-30 ° C. To the obtained solution, 0.8 part by mass of Compound (I) shown in Table 1 was added, and the mixture was stirred at 10 to 90 ° C. for 1 hour. To the resulting solution, 0.3 part by mass of compound (II) or a salt thereof shown in Table 1 was added, and the mixture was stirred at 70 to 90 ° C. for 1 hour. 0.0 part by mass was obtained.
［実施例６］
　潤滑油基油９９．０質量部に、酸化防止剤１　０．５質量部および酸化防止剤２　０．５質量部を、１０～３０℃で順次加えて溶液（Ｃ－１）１００．０質量部を得た。
　潤滑油基油８７．０質量部に、酸化防止剤１　０．５質量部、酸化防止剤２　０．５質量部、清浄分散剤１　８．０質量部および清浄分散剤２　４．０質量部を、１０～３０℃で順次加えて溶液（Ｃ－２）１００．０質量部を得た。
　溶液（Ｃ－１）４８．９質量部に化合物（Ｉｂ－１）０．８質量部を加え、混合物を４０～９０℃で１時間攪拌した。得られた溶液に化合物（ＩＩ－２）０．３質量部を加え、混合物を７０～９０℃で１時間攪拌した。得られた溶液５０．０質量部と溶液（Ｃ－２）５０．０質量部とを混合し、７０～９０℃で１時間攪拌して表１に記載の混合比の潤滑油組成物１００．０質量部を得た。 [Example 6]
0.5 parts by weight of antioxidant 1 and 0.5 parts by weight of antioxidant 2 were added sequentially to 99.0 parts by weight of the lubricating base oil at 10 to 30 ° C. to obtain 100.0 parts by weight of solution (C-1). Got a part.
87.0 parts by mass of lubricant base oil, 0.5 parts by mass of antioxidant 1, 0.5 parts by mass of antioxidant 2, 8.0 parts by mass of cleaning dispersant 1 and 4.0 parts by mass of cleaning dispersant 2 Were sequentially added at 10 to 30 ° C. to obtain 100.0 parts by mass of a solution (C-2).
To 48.9 parts by mass of the solution (C-1), 0.8 part by mass of the compound (Ib-1) was added, and the mixture was stirred at 40 to 90 ° C. for 1 hour. To the obtained solution, 0.3 part by mass of compound (II-2) was added, and the mixture was stirred at 70 to 90 ° C. for 1 hour. 50.0 parts by mass of the obtained solution and 50.0 parts by mass of the solution (C-2) were mixed and stirred at 70 to 90 ° C. for 1 hour to obtain a lubricating oil composition 100. 0 parts by weight were obtained.
［実施例７］
　化合物（ＩＩ－２）０．３質量部の代わりに化合物（ＩＩ－３）０．２質量部を用い、溶液（Ｃ－１）の使用量を４９．０質量部にする以外は実施例６と同様な操作を行い、表１に記載の混合比の潤滑油組成物１００．０質量部を得た。
［実施例８］
　化合物（Ｉｂ－１）０．８質量部の代わりに化合物（Ｉｂ－２）０．６質量部を用い、化合物（ＩＩ－２）の代わりに化合物（ＩＩ－１）を用い、溶液（Ｃ－１）の使用量を４９．１質量部にする以外は実施例６と同様な操作を行い、表１に記載の混合比の潤滑油組成物１００．０質量部を得た。 [Example 7]
Example 6 except that 0.2 part by mass of the compound (II-3) was used instead of 0.3 part by mass of the compound (II-2), and the amount of the solution (C-1) used was 49.0 parts by mass. The same operation was carried out to obtain 100.0 parts by mass of a lubricating oil composition having the mixing ratio shown in Table 1.
[Example 8]
Compound (Ib-1) is used in place of 0.8 part by mass, Compound (Ib-2) is used in 0.6 part by mass, Compound (II-1) is used in place of Compound (II-2), and Solution (C— The same operation as in Example 6 was performed except that the amount used in 1) was changed to 49.1 parts by mass to obtain 100.0 parts by mass of a lubricating oil composition having a mixing ratio shown in Table 1.
［実施例９］
　化合物（Ｉｂ－１）０．８質量部の代わりに化合物（Ｉｂ－２）０．６質量部を用い、溶液（Ｃ－１）の使用量を４９．１質量部にする以外は実施例６と同様な操作を行い、表１に記載の混合比の潤滑油組成物１００．０質量部を得た。
［実施例１０］
　化合物（Ｉｂ－１）０．８質量部の代わりに化合物（Ｉｂ－３）０．７質量部を用い、化合物（ＩＩ－２）の代わりに化合物（ＩＩ－１）を用い、溶液（Ｃ－１）の使用量を４９．０質量部にする以外は実施例６と同様な操作を行い、表１に記載の混合比の潤滑油組成物１００．０質量部を得た。 [Example 9]
Example 6 except that 0.6 part by mass of compound (Ib-2) was used instead of 0.8 part by mass of compound (Ib-1) and the amount of solution (C-1) used was 49.1 parts by mass. The same operation was carried out to obtain 100.0 parts by mass of a lubricating oil composition having the mixing ratio shown in Table 1.
[Example 10]
Compound (Ib-1) 0.7 parts by mass instead of 0.8 parts by mass, Compound (II-2) instead of Compound (II-2), Compound (II-1) The same operation as in Example 6 was performed except that the amount used in 1) was changed to 49.0 parts by mass to obtain 100.0 parts by mass of a lubricating oil composition having a mixing ratio shown in Table 1.
［実施例１１］
　化合物（Ｉｂ－１）の代わりに化合物（Ｉｂ－４）を用い、化合物（ＩＩ－２）の代わりに化合物（ＩＩ－１）を用いる以外は実施例６と同様な操作を行い、表２に記載の混合比の潤滑油組成物１００．０質量部を得た。
［実施例１２］
　化合物（Ｉｂ－１）０．８質量部の代わりに化合物（Ｉｂ－５）１．０質量部を用い、化合物（ＩＩ－２）の代わりに化合物（ＩＩ－１）を用い、溶液（Ｃ－１）の使用量を４８．７質量部にする以外は実施例６と同様な操作を行い、表２に記載の混合比の潤滑油組成物１００．０質量部を得た。 [Example 11]
Table 2 shows the same procedure as in Example 6, except that compound (Ib-4) is used instead of compound (Ib-1) and compound (II-1) is used instead of compound (II-2). 100.0 parts by mass of the lubricating oil composition having the described mixing ratio was obtained.
[Example 12]
The compound (Ib-1) is used in an amount of 1.0 part by mass instead of the compound (Ib-1) in an amount of 1.0 part by mass, the compound (II-1) is used in place of the compound (II-2), The same operation as in Example 6 was performed except that the amount used in 1) was changed to 48.7 parts by mass to obtain 100.0 parts by mass of a lubricating oil composition having a mixing ratio shown in Table 2.
［実施例１３］
　化合物（Ｉｂ－１）０．８質量部の代わりに化合物（Ｉｂ－２）０．２質量部を用い、化合物（ＩＩ－２）の代わりに化合物（ＩＩ－１）を用い、溶液（Ｃ－１）の使用量を４９．５質量部にする以外は実施例６と同様な操作を行い、表２に記載の混合比の潤滑油組成物１００．０質量部を得た。
［実施例１４］
　潤滑油基油９２．５質量部に、酸化防止剤１　０．５質量部、酸化防止剤２　０．５質量部、清浄分散剤１　４．０質量部および清浄分散剤２　２．０質量部を、１０～３０℃で順次加えた。得られた溶液に反応物（Ｘ－１）０．５質量部を加え、混合物を７０～９０℃で１時間攪拌して表２に記載の混合比の潤滑油組成物１００．０質量部を得た。 [Example 13]
Compound (Ib-1) 0.2 parts by mass instead of 0.8 parts by mass, Compound (II-2) instead of Compound (II-2), Compound (II-1) The same operation as in Example 6 was performed except that the amount used in 1) was changed to 49.5 parts by mass to obtain 100.0 parts by mass of a lubricating oil composition having a mixing ratio shown in Table 2.
[Example 14]
92.5 parts by mass of lubricant base oil, 0.5 parts by mass of antioxidant 1, 0.5 parts by mass of antioxidant 2, 4.0 parts by mass of detergent 1 and 2.0 parts by mass of detergent 2 Were added sequentially at 10-30 ° C. 0.5 parts by mass of the reaction product (X-1) was added to the obtained solution, and the mixture was stirred at 70 to 90 ° C. for 1 hour to obtain 100.0 parts by mass of the lubricating oil composition having the mixing ratio shown in Table 2. Obtained.
［実施例１５］
　反応物（Ｘ－１）の代わりに化合物（Ｘ－２）を用いる以外は実施例１４と同様な操作を行い、表２に記載の混合比の潤滑油組成物１００．０質量部を得た。
［実施例１６］
　反応物（Ｘ－１）０．５質量部の代わりに反応物（Ｘ－３）０．８質量部を用い、潤滑油基油の使用量を９２．２質量部にする以外は実施例１４と同様な操作を行い、表２に記載の混合比の潤滑油組成物１００．０質量部を得た。 [Example 15]
The same operation as in Example 14 was carried out except that the compound (X-2) was used in place of the reactant (X-1) to obtain 100.0 parts by mass of a lubricating oil composition having the mixing ratio shown in Table 2. .
[Example 16]
Example 14 except that 0.8 parts by mass of the reactant (X-3) was used instead of 0.5 parts by mass of the reactant (X-1), and the amount of the lubricating base oil used was 92.2 parts by mass. The same operation was performed to obtain 100.0 parts by mass of a lubricating oil composition having a mixing ratio shown in Table 2.
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
［比較例１］化合物（ＩＩ－１）の代わりに化合物Ｐを用いる以外は実施例１と同様にして潤滑油組成物を得た。
［比較例２］化合物（Ｉ－１ｂ）の代わりに化合物（Ｉ－１ａ）を用いる以外は比較例１と同様にして潤滑油組成物を得た。
　実施例１～１６、比較例１および２で得た潤滑油組成物中のリンの含量（計算値）は以下のとおりである。 [Comparative Example 1] A lubricating oil composition was obtained in the same manner as in Example 1 except that Compound P was used instead of Compound (II-1).
[Comparative Example 2] A lubricating oil composition was obtained in the same manner as in Comparative Example 1 except that the compound (I-1a) was used instead of the compound (I-1b).
The phosphorus contents (calculated values) in the lubricating oil compositions obtained in Examples 1 to 16 and Comparative Examples 1 and 2 are as follows.
　実施例１～１２、比較例１および２；０．０８質量％
　実施例１３；０．０２質量％
　実施例１４～１６；０．０３質量％
［試験例１］動摩擦係数の測定
　潤滑油組成物の４０℃、８０℃、１２０℃および１５０℃における動摩擦係数を曽田式振子型摩擦試験機（神鋼造機社製）を用いて測定した。動摩擦係数は振子の初期振幅、振動させた時の振幅および振動回数から算出した。 Examples 1 to 12, Comparative Examples 1 and 2; 0.08% by mass
Example 13; 0.02 mass%
Examples 14 to 16; 0.03% by mass
[Test Example 1] Measurement of Dynamic Friction Coefficient The dynamic friction coefficient at 40 ° C, 80 ° C, 120 ° C and 150 ° C of the lubricating oil composition was measured using an Iwata-type pendulum type friction tester (manufactured by Shinko Engineering Co., Ltd.). The dynamic friction coefficient was calculated from the initial amplitude of the pendulum, the amplitude when vibrating, and the number of vibrations.
　実施例１～１６、比較例１および２で得た潤滑油組成物の動摩擦係数を表３および表４に示す（但し、実施例５および比較例２の４０℃における動摩擦係数は測定していない）。 The dynamic friction coefficients of the lubricating oil compositions obtained in Examples 1 to 16 and Comparative Examples 1 and 2 are shown in Tables 3 and 4 (however, the dynamic friction coefficients at 40 ° C. of Example 5 and Comparative Example 2 were not measured). ).
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
　表３および表４において、動摩擦係数の値が小さいもの程、潤滑油組成物の耐摩擦特性が優れていることを表す。実施例１～４、６および７で得られた潤滑油組成物は比較例１で得られた潤滑油組成物に比べて、耐摩擦特性に優れることがわかる。また、実施例５で得られた潤滑油組成物は比較例２で得られた潤滑油組成物に比べて、耐摩擦特性に優れることがわかる。
［試験例２］摩耗痕径の測定
　（ＡＳＴＭ　Ｄ４１７２）規定の方法（荷重；４０ｋｇｆ、回転数；１２００ｒｐｍ、時間；６０分、温度；７５℃）に準じ試験を行い、試験後の摩耗痕径を測定した。試験機には、シェル式四球摩擦試験機（高千穂精機社製）を用いた。摩耗痕径は３つの固定球の垂直方向、水平方向全ての平均値とした。実施例１、３および比較例１で得た潤滑油組成物の摩擦痕径を表５に示す。 In Tables 3 and 4, the smaller the value of the dynamic friction coefficient, the better the friction resistance of the lubricating oil composition. It can be seen that the lubricating oil compositions obtained in Examples 1 to 4, 6 and 7 are superior in friction resistance to the lubricating oil composition obtained in Comparative Example 1. In addition, it can be seen that the lubricating oil composition obtained in Example 5 is superior in friction resistance compared to the lubricating oil composition obtained in Comparative Example 2.
[Test Example 2] Measurement of wear scar diameter (ASTM D4172) A test is performed according to the prescribed method (load: 40 kgf, rotation speed: 1200 rpm, time: 60 minutes, temperature: 75 ° C), and the wear scar diameter after the test is determined. It was measured. A shell type four-ball friction tester (manufactured by Takachiho Seiki Co., Ltd.) was used as a tester. The wear scar diameter was the average value of all three fixed spheres in the vertical and horizontal directions. Table 5 shows the friction scar diameters of the lubricating oil compositions obtained in Examples 1 and 3 and Comparative Example 1.
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024
　表５において、摩耗痕径の値が小さいもの程、潤滑油組成物の耐摩耗特性が優れていることを表す。実施例１および３で得られた潤滑油組成物は比較例１で得られた潤滑油組成物に比べて、耐摩耗特性に優れることがわかる In Table 5, the smaller the value of the wear scar diameter, the better the wear resistance of the lubricating oil composition. It can be seen that the lubricating oil compositions obtained in Examples 1 and 3 are superior in wear resistance properties as compared to the lubricating oil composition obtained in Comparative Example 1.
　本発明により、潤滑油組成物などの油類に優れた耐摩擦特性または優れた耐摩耗特性を付与する油類用添加剤などを提供できる。 According to the present invention, it is possible to provide an additive for oils that imparts excellent friction resistance or excellent wear resistance to oils such as lubricating oil compositions.

Claims (25)

  1. 　式（Ｉ）
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｘ１およびＸ２は、同一または異なって、硫黄原子または酸素原子を表し、Ｒ１およびＲ２は、同一または異なって、置換基を有していてもよいアルキル、置換基を有していてもよいアルケニル、置換基を有していてもよいアリール、置換基を有していてもよいシクロアルキルまたは置換基を有していてもよいシクロアルケニルを表し、２つのＲ１、２つのＲ２、２つのＸ１および２つのＸ２のそれぞれは同一または異なっていてもよい）で表される構造を有するリン酸亜鉛化合物と、式（ＩＩ）
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７は、同一または異なって、水素原子、置換基を有していてもよいアルキル、置換基を有していてもよいアルケニルまたは置換基を有していてもよいアラルキルを表し、Ｒ４とＲ５またはＲ６とＲ７が隣接する窒素原子と一緒になってそれぞれ置換基を有していてもよい脂肪族複素環基を形成してもよい。但し、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７が同時に水素原子を表すことはない）で表されるグアニジン化合物またはその塩とを含有する油類用添加剤。     Formula (I)
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, X 1 and X 2 are the same or different and each represents a sulfur atom or an oxygen atom, and R 1 and R 2 are the same or different and each represents an optionally substituted alkyl or substituent. An alkenyl that may have, an aryl that may have a substituent, an cycloalkyl that may have a substituent, or a cycloalkenyl that may have a substituent, and two R 1 , Two R 2 s , two X 1 s and two X 2 s may be the same or different), and a zinc phosphate compound having the structure represented by formula (II):
    Figure JPOXMLDOC01-appb-C000002
     (Wherein R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are each a hydrogen atom, an optionally substituted alkyl, an optionally substituted alkenyl or Represents an aralkyl which may have a substituent, and R 4 and R 5 or R 6 and R 7 together with the adjacent nitrogen atom each represents an aliphatic heterocyclic group which may have a substituent. Provided that R 3 , R 4 , R 5 , R 6 and R 7 do not represent a hydrogen atom at the same time, or a guanidine compound or a salt thereof. .
  2. 　Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７が、同一または異なって、水素原子、置換基を有していてもよいアルキルまたは置換基を有していてもよいアルケニルである請求項１に記載の油類用添加剤。 2. R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are a hydrogen atom, an optionally substituted alkyl or an optionally substituted alkenyl. Additives for oils according to 1.
  3. 　Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７のうち、少なくとも一つが置換基を有していてもよい炭素数１２～３０のアルキルまたは置換基を有していてもよい炭素数１２～３０のアルケニルである請求項１または２に記載の油類用添加剤。 At least one of R 3 , R 4 , R 5 , R 6 and R 7 may have a substituent having 12 to 30 carbon atoms, or may have a substituent having 12 to 12 carbon atoms. The additive for oils according to claim 1 or 2, which is 30 alkenyl.
  4. 　式（ＩＩ）で表されるグアニジン化合物またはその塩が、式（ＩＩ）で表されるグアニジン化合物の炭酸塩である請求項１～３のいずれかに記載の油類用添加剤。 The oil additive according to any one of claims 1 to 3, wherein the guanidine compound represented by the formula (II) or a salt thereof is a carbonate of the guanidine compound represented by the formula (II).
  5. 　２つのＸ１および２つのＸ２のすべてが同一で硫黄原子である請求項１～４のいずれかに記載の油類用添加剤。 The additive for oils according to any one of claims 1 to 4, wherein all of two X 1 and two X 2 are the same and are sulfur atoms.
  6. 　Ｒ１およびＲ２が、同一または異なって、置換基を有していてもよい炭素数３～１４のアルキルまたは置換基を有していてもよい炭素数３～１４のアルケニルである請求項１～５のいずれかに記載の油類用添加剤。 2. The R 1 and R 2 are the same or different and are optionally substituted alkyl having 3 to 14 carbon atoms or optionally substituted alkenyl having 3 to 14 carbon atoms. The additive for oils according to any one of 1 to 5.
  7. 　式（Ｉ）
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｘ１およびＸ２は、同一または異なって、硫黄原子または酸素原子を表し、Ｒ１およびＲ２は、同一または異なって、置換基を有していてもよいアルキル、置換基を有していてもよいアルケニル、置換基を有していてもよいアリール、置換基を有していてもよいシクロアルキルまたは置換基を有していてもよいシクロアルケニルを表し、２つのＲ１、２つのＲ２、２つのＸ１および２つのＸ２のそれぞれは同一または異なっていてもよい）で表される構造を有するリン酸亜鉛化合物と、式（ＩＩ）
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７は、同一または異なって、水素原子、置換基を有していてもよいアルキル、置換基を有していてもよいアルケニルまたは置換基を有していてもよいアラルキルを表し、Ｒ４とＲ５またはＲ６とＲ７が隣接する窒素原子と一緒になってそれぞれ置換基を有していてもよい脂肪族複素環基を形成してもよい。但し、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７が同時に水素原子を表すことはない）で表されるグアニジン化合物またはその塩との反応物を含有する油類用添加剤。     Formula (I)
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, X 1 and X 2 are the same or different and each represents a sulfur atom or an oxygen atom, and R 1 and R 2 are the same or different and each represents an optionally substituted alkyl or substituent. An alkenyl that may have, an aryl that may have a substituent, an cycloalkyl that may have a substituent, or a cycloalkenyl that may have a substituent, and two R 1 , Two R 2 s , two X 1 s and two X 2 s may be the same or different), and a zinc phosphate compound having the structure represented by formula (II):
    Figure JPOXMLDOC01-appb-C000004
     (Wherein R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are each a hydrogen atom, an optionally substituted alkyl, an optionally substituted alkenyl or Represents an aralkyl which may have a substituent, and R 4 and R 5 or R 6 and R 7 together with the adjacent nitrogen atom each represents an aliphatic heterocyclic group which may have a substituent. Provided that R 3 , R 4 , R 5 , R 6 and R 7 do not represent hydrogen atoms at the same time) or an oil containing a reaction product with a salt thereof Additives.
  8. 　Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７が、同一または異なって、水素原子、置換基を有していてもよいアルキルまたは置換基を有していてもよいアルケニルである請求項７に記載の油類用添加剤。 8. R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are a hydrogen atom, an optionally substituted alkyl or an optionally substituted alkenyl. Additives for oils according to 1.
  9. 　Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７のうち、少なくとも一つが置換基を有していてもよい炭素数１２～３０のアルキルまたは置換基を有していてもよい炭素数１２～３０のアルケニルである請求項７または８に記載の油類用添加剤。 At least one of R 3 , R 4 , R 5 , R 6 and R 7 may have a substituent, an alkyl having 12 to 30 carbons, or an optionally substituted carbon having 12 to The additive for oils according to claim 7 or 8, which is 30 alkenyl.
  10. 　式（ＩＩ）で表されるグアニジン化合物またはその塩が、式（ＩＩ）で表されるグアニジン化合物の炭酸塩である請求項７～９のいずれかに記載の油類用添加剤。 The oil additive according to any one of claims 7 to 9, wherein the guanidine compound represented by the formula (II) or a salt thereof is a carbonate of the guanidine compound represented by the formula (II).
  11. 　２つのＸ１および２つのＸ２のすべてが同一で硫黄原子である請求項７～１０のいずれかに記載の油類用添加剤。 The additive for oils according to any one of claims 7 to 10, wherein all of two X 1 and two X 2 are the same and are sulfur atoms.
  12. 　Ｒ１およびＲ２が、同一または異なって、置換基を有していてもよい炭素数３～１４のアルキルまたは置換基を有していてもよい炭素数３～１４のアルケニルである請求項７～１１のいずれかに記載の油類用添加剤。 R 1 and R 2 are the same or different and are optionally substituted alkyl having 3 to 14 carbon atoms or optionally substituted alkenyl having 3 to 14 carbon atoms. The additive for oils according to any one of to 11.
  13. 　請求項１～１２のいずれかに記載の油類用添加剤と潤滑油基油とを混合して得られる潤滑油組成物。 A lubricating oil composition obtained by mixing the additive for oils according to any one of claims 1 to 12 and a lubricating base oil.
  14. 　潤滑油基油が、鉱物油、ポリ－α－オレフィン、脂肪酸エステル、芳香族エステル、ポリアルキレングリコール、リン酸エステル、シリコーン、ケイ酸エステル、ポリフェニルエーテル、アルキルベンゼン、合成ナフテン、ガスツーリキッド（ＧＴＬ）、フルオロカーボン、イオン液体、植物油、および獣油からなる群より選ばれる１種以上である請求項１３に記載の潤滑油組成物。 Lubricating base oils are mineral oil, poly-α-olefin, fatty acid ester, aromatic ester, polyalkylene glycol, phosphate ester, silicone, silicate ester, polyphenyl ether, alkylbenzene, synthetic naphthene, gas-to-liquid (GTL) ), A fluorocarbon, an ionic liquid, a vegetable oil, and a veterinary oil. The lubricating oil composition according to claim 13.
  15. 　潤滑油基油がポリ－α－オレフィンを含有する請求項１３に記載の潤滑油組成物。 The lubricating oil composition according to claim 13, wherein the lubricating base oil contains a poly-α-olefin.
  16. 　潤滑油組成物中のリンの含量が０．００１～０．１質量％である請求項１３～１５のいずれかに記載の潤滑油組成物。 The lubricating oil composition according to any one of claims 13 to 15, wherein the content of phosphorus in the lubricating oil composition is 0.001 to 0.1 mass%.
  17. 　下記（ｉ）および／または下記（ｉｉ）と、潤滑油基油とを含有する潤滑油組成物。
    （ｉ）式（Ｉ）
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ｘ１およびＸ２は、同一または異なって、硫黄原子または酸素原子を表し、Ｒ１およびＲ２は、同一または異なって、置換基を有していてもよいアルキル、置換基を有していてもよいアルケニル、置換基を有していてもよいアリール、置換基を有していてもよいシクロアルキルまたは置換基を有していてもよいシクロアルケニルを表し、２つのＲ１、２つのＲ２、２つのＸ１および２つのＸ２のそれぞれは同一または異なっていてもよい）で表される構造を有するリン酸亜鉛化合物および式（ＩＩ）
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７は、同一または異なって、水素原子、置換基を有していてもよいアルキル、置換基を有していてもよいアルケニルまたは置換基を有していてもよいアラルキルを表し、Ｒ４とＲ５またはＲ６とＲ７が隣接する窒素原子と一緒になってそれぞれ置換基を有していてもよい脂肪族複素環基を形成してもよい。但し、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７が同時に水素原子を表すことはない）で表されるグアニジン化合物またはその塩
    （ｉｉ）式（Ｉ）で表される構造を有するリン酸亜鉛化合物と式（ＩＩ）で表されるグアニジン化合物またはその塩との反応物     A lubricating oil composition comprising the following (i) and / or the following (ii) and a lubricating base oil.
    (I) Formula (I)
    Figure JPOXMLDOC01-appb-C000005
     (In the formula, X 1 and X 2 are the same or different and each represents a sulfur atom or an oxygen atom, and R 1 and R 2 are the same or different and each represents an optionally substituted alkyl or substituent. An alkenyl that may have, an aryl that may have a substituent, an cycloalkyl that may have a substituent, or a cycloalkenyl that may have a substituent, and two R 1 , Two R 2 s , two X 1 s and two X 2 s may be the same or different) and a zinc phosphate compound having the structure represented by formula (II)
    Figure JPOXMLDOC01-appb-C000006
     (Wherein R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are each a hydrogen atom, an optionally substituted alkyl, an optionally substituted alkenyl or Represents an aralkyl which may have a substituent, and R 4 and R 5 or R 6 and R 7 together with the adjacent nitrogen atom each represents an aliphatic heterocyclic group which may have a substituent. Provided that R 3 , R 4 , R 5 , R 6 and R 7 do not simultaneously represent a hydrogen atom) or a salt thereof (ii) represented by formula (I) Reaction product of a zinc phosphate compound having the structure shown below and a guanidine compound represented by formula (II) or a salt thereof
  18. 　Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７が、同一または異なって、水素原子、置換基を有していてもよいアルキルまたは置換基を有していてもよいアルケニルである請求項１７に記載の潤滑油組成物。 R 3 , R 4 , R 5 , R 6 and R 7 are the same or different and are a hydrogen atom, an optionally substituted alkyl or an optionally substituted alkenyl. The lubricating oil composition described in 1.
  19. 　Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７のうち、少なくとも一つが置換基を有していてもよい炭素数１２～３０のアルキルまたは置換基を有していてもよい炭素数１２～３０のアルケニルである請求項１７または１８に記載の潤滑油組成物。 At least one of R 3 , R 4 , R 5 , R 6 and R 7 may have a substituent, an alkyl having 12 to 30 carbons, or an optionally substituted carbon having 12 to The lubricating oil composition according to claim 17 or 18, which is 30 alkenyl.
  20. 　式（ＩＩ）で表されるグアニジン化合物またはその塩が、式（ＩＩ）で表されるグアニジン化合物の炭酸塩である請求項１７～１９のいずれかに記載の潤滑油組成物。 The lubricating oil composition according to any one of claims 17 to 19, wherein the guanidine compound represented by the formula (II) or a salt thereof is a carbonate of the guanidine compound represented by the formula (II).
  21. 　２つのＸ１および２つのＸ２のすべてが同一で硫黄原子である請求項１７～２０のいずれかに記載の潤滑油組成物。 All of the two X 1 and two X 2 is a lubricating oil composition according to any one of claims 17 to 20 which is a sulfur atom at the same.
  22. 　Ｒ１およびＲ２が、同一または異なって、置換基を有していてもよい炭素数３～１４のアルキルまたは置換基を有していてもよい炭素数３～１４のアルケニルである請求項１７～２１のいずれかに記載の潤滑油組成物。 18. R 1 and R 2 are the same or different and each is optionally substituted alkyl having 3 to 14 carbons or optionally substituted alkenyl having 3 to 14 carbons. The lubricating oil composition as described in any one of 1 to 21.
  23. 　潤滑油基油が、鉱物油、ポリ－α－オレフィン、脂肪酸エステル、芳香族エステル、ポリアルキレングリコール、リン酸エステル、シリコーン、ケイ酸エステル、ポリフェニルエーテル、アルキルベンゼン、合成ナフテン、ガスツーリキッド（ＧＴＬ）、フルオロカーボン、イオン液体、植物油、および獣油からなる群より選ばれる１種以上である請求項１７～２２のいずれかに記載の潤滑油組成物。 Lubricating base oils are mineral oil, poly-α-olefin, fatty acid ester, aromatic ester, polyalkylene glycol, phosphate ester, silicone, silicate ester, polyphenyl ether, alkylbenzene, synthetic naphthene, gas-to-liquid (GTL) The lubricating oil composition according to any one of claims 17 to 22, which is at least one member selected from the group consisting of fluorocarbons, ionic liquids, vegetable oils, and animal oils.
  24. 　潤滑油基油がポリ－α－オレフィンを含有する請求項１７～２２のいずれかに記載の潤滑油組成物。 The lubricating oil composition according to any one of claims 17 to 22, wherein the lubricating base oil contains a poly-α-olefin.
  25. 　潤滑油組成物中のリンの含量が０．００１～０．１質量％である請求項１７～２４のいずれかに記載の潤滑油組成物。
    　     The lubricating oil composition according to any one of claims 17 to 24, wherein the content of phosphorus in the lubricating oil composition is 0.001 to 0.1 mass%.
PCT/JP2009/065758 2008-09-09 2009-09-09 Additive for oil and lubricating oil composition containing same WO2010029945A1 (en)

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JP2016169345A (en) * 2015-03-13 2016-09-23 デクセリアルズ株式会社 Ionic liquid, lubricant and magnetic recording medium
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WO2011055599A1 (en) * 2009-11-09 2011-05-12 出光興産株式会社 Detergent dispersant and lubricating oil composition
EP2500405A1 (en) * 2009-11-09 2012-09-19 Idemitsu Kosan Co., Ltd. Detergent dispersant and lubricating oil composition
JPWO2011055599A1 (en) * 2009-11-09 2013-03-28 出光興産株式会社 Cleaning dispersant and lubricating oil composition
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JP2017186556A (en) * 2016-04-08 2017-10-12 アフトン・ケミカル・コーポレーションＡｆｔｏｎ Ｃｈｅｍｉｃａｌ Ｃｏｒｐｏｒａｔｉｏｎ Lubricant additives and lubricant compositions having improved frictional characteristics

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