WO2010147016A1 - 潤滑油組成物 - Google Patents
潤滑油組成物 Download PDFInfo
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- WO2010147016A1 WO2010147016A1 PCT/JP2010/059623 JP2010059623W WO2010147016A1 WO 2010147016 A1 WO2010147016 A1 WO 2010147016A1 JP 2010059623 W JP2010059623 W JP 2010059623W WO 2010147016 A1 WO2010147016 A1 WO 2010147016A1
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- oil composition
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
- C10M135/10—Sulfonic acids or derivatives thereof
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/287—Partial esters
- C10M2207/289—Partial esters containing free hydroxy groups
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
- C10M2215/064—Di- and triaryl amines
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- 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
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- 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
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- C10M2229/02—Unspecified siloxanes; Silicones
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- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C10N2030/42—Phosphor free or low phosphor content compositions
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Definitions
- the present invention relates to a lubricating oil composition, and more particularly, to a lubricating oil composition that is excellent in wear resistance, high-temperature cleanliness, and base number maintenance even with low phosphorus content, low sulfur content, and low sulfated ash content.
- zinc dithiophosphate (Zn-DTP) has been used for many years as an anti-wear and antioxidant agent for lubricating oils for internal combustion engines used in gasoline engines, diesel engines, gas engines, etc. Is considered an important essential additive.
- this zinc dithiophosphate contains a large amount of phosphorus and sulfur as well as metal (zinc) in the molecule, the decomposition product of zinc dithiophosphate generates sulfuric acid and phosphoric acid. For this reason, zinc dithiophosphate may consume basic compounds in engine oil to accelerate the deterioration of lubricating oil, and may shorten the oil renewal period extremely. Means).
- an oxidation catalyst a three-way catalyst, a NOx occlusion-type reduction catalyst, a diesel particulate filter (DPF), and the like are used in current automobile engines to purify exhaust gas.
- These exhaust gas purification devices are known to be adversely affected by the metal, phosphorus and sulfur components in engine oil, and it is necessary to reduce these components from the standpoint of measures against deterioration of the device. ing. Therefore, the basic performance (wear resistance, cleanliness, base number maintenance) required for lubricating oil for internal combustion engines even with low metal content (ie low sulfated ash content), low phosphorus content, and even low sulfur content. Therefore, there is a strong demand for lubricating oil for internal combustion engines.
- Patent Document 1 proposes a lubricating oil composition containing a specific phosphorus-containing phenolic antioxidant.
- phosphorus-containing phenolic antioxidants have room for further improvement in order to solve the above-mentioned problems such as insufficient solubility in base oils.
- Patent Document 2 for the purpose of improving the dispersibility of the base oil and extending the oil exchange period, a specific aromatic group is bonded to the base oil through a sulfonamide bond. A technique for directly modifying base oil is also disclosed.
- the present invention provides a lubricating oil composition that is excellent in wear resistance, high-temperature cleanability, and base number maintenance, even with low phosphorus content, low sulfur content, and low metal content (low sulfated ash content). Is intended to be provided at low cost.
- a lubricating oil composition comprising a base oil and a sulfonamide compound represented by the following general formula (1).
- R 1 is one selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group;
- R 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl groups, substituted or unsubstituted (It is one selected from an aryl group and a substituted or unsubstituted heteroaryl group, and R 2 and R 3 may be bonded to form a ring structure or a condensed ring structure.)
- R 2 and R 3 are a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted
- the lubricating oil composition according to ⁇ 1> which is one selected from an alkynyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group.
- R 2 and R 3 in the general formula (1) has a substituent
- the substituent is each independently a hydrocarbon group having 1 to 20 carbon atoms ⁇ 1> or The lubricating oil composition according to ⁇ 2>.
- R 2 and R 3 in the general formula (1) is an unsubstituted alkyl group, an unsubstituted cycloalkyl group, an unsubstituted alkenyl group, an unsubstituted alkynyl group, or an unsubstituted aryl
- R 1 represents an unsubstituted alkyl group, an unsubstituted cycloalkyl group, an unsubstituted alkenyl group, an unsubstituted alkynyl group, an unsubstituted aryl group, and an unsubstituted heteroaryl.
- the lubricating oil composition according to any one of ⁇ 1> to ⁇ 4>, which is one selected from a group.
- ⁇ 6> The lubricating oil composition according to any one of ⁇ 1> to ⁇ 5>, wherein the phosphorus content is 0.12% by mass or less based on the composition, and the sulfated ash content is 1.2% by mass or less. is there.
- ⁇ 7> The lubricating oil composition according to any one of ⁇ 1> to ⁇ 6>, which is a lubricating oil composition for an internal combustion engine.
- a lubricating oil composition that is excellent in wear resistance, high-temperature cleanability, and base number maintainability even at low phosphorus content, low sulfur content, and low metal content (low sulfated ash content) is provided at low cost. can do.
- the lubricating oil composition of the present embodiment is characterized in that a sulfonamide compound represented by the general formula (1) is blended with a base oil.
- Base oil There is no restriction
- the mineral oil for example, a lubricating oil fraction obtained by distillation under reduced pressure of atmospheric residual oil obtained by atmospheric distillation of crude oil, solvent removal, solvent extraction, hydrocracking, solvent dewaxing, contact Mineral oil refined by performing one or more treatments such as dewaxing, hydrorefining, etc., or mineral oil produced by isomerizing wax, GTL WAX, and the like.
- examples of the synthetic oil include polybutene, polyolefin [ ⁇ -olefin homopolymer and copolymer (eg, ethylene- ⁇ -olefin copolymer)], and various esters (eg, polyol ester, dibasic acid). Ester, phosphate ester, etc.), various ethers (eg, polyphenyl ether), polyglycol, alkylbenzene, alkylnaphthalene and the like. Of these synthetic oils, polyolefins and polyol esters are particularly preferable.
- the mineral oil may be used alone or in combination of two or more.
- the said synthetic oil may be used 1 type and may be used in combination of 2 or more type. Further, one or more mineral oils and one or more synthetic oils may be used in combination.
- kinematic viscosity at 100 ° C. of preferably not more than 2 mm 2 / s or more 30 mm 2 / s, more preferably be less 3 mm 2 / s or more 15 mm 2 / s More preferably, it is 4 mm 2 / s or more and 10 mm 2 / s or less.
- the kinematic viscosity at 100 ° C. is 2 mm 2 / s or more, the evaporation loss is small. Further, when the kinematic viscosity at 100 ° C. is not more than 30 mm 2 / s, the power loss due to viscosity resistance is restricted, thereby improving fuel efficiency.
- % by ring analysis C A content of sulfur is preferably used include: 50 ppm by mass 3.0.
- the% C A by ring analysis shows a proportion of aromatic content calculated by ring analysis n-d-M method (percentage).
- the sulfur content is a value measured according to JIS K2541.
- a base oil having a% CA of 3.0 or less and a sulfur content of 50 mass ppm or less provides a lubricating oil composition having good oxidation stability and capable of suppressing an increase in acid value and sludge formation. be able to.
- More preferable% C A is 1.0 or less, and further preferably 0.5 or less.
- a more preferable sulfur content is 30 mass ppm or less.
- the viscosity index of the base oil is preferably 70 or more, more preferably 100 or more, and still more preferably 120 or more.
- the base oil having a viscosity index of 70 or more has a small change in viscosity due to a change in temperature.
- a sulfonamide compound represented by the following general formula (1) is blended.
- the sulfonamide compound as a component of the lubricating oil composition, even if the phosphorus content, sulfur content and metal content are reduced, it is possible to obtain the effect of improving the wear resistance, the high temperature cleanliness and the base number maintainability. .
- R 1 is one selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group;
- 2 and R 3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, substituted or unsubstituted It is one selected from an aryl group and a substituted or unsubstituted heteroaryl group, and R 2 and R 3 may be bonded to form a ring structure or a condensed ring structure.
- the alkyl group includes linear and branched alkyl groups.
- Preferred alkyl groups are those containing 1 to 20 carbon atoms, including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and the like.
- the alkyl group may be substituted with a substituent. More preferably, the alkyl group has 4 to 18 carbon atoms.
- substituents include a halogen atom, hydroxy group, amino group, nitro group, cyano group, alkyl group, alkenyl group, cycloalkyl group, alkoxy group, aromatic hydrocarbon group, aromatic heterocyclic group, Aralkyl group, aryloxy group, alkoxycarbonyl group, fluorinated alkyl group, fluorinated aryl group, carboxyl group, isocyanate group, thioisocyanate group, imino group, sulfone group, thiocarboxyl group, carbonyl group, thiocarbonyl group, formyl group , Thioformyl group, silanol group, hydrocarbyloxy group, nitrile group, pyridyl group, amide group, imide group, imidazolyl group, ammonium group, hydrazo group, azo group, diazo group, ketimine group, epoxy group, thioepoxy group, oxycarbonyl group (
- substituted or unsubstituted alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group.
- the cycloalkyl group includes a polycyclic cyclic alkyl group.
- Preferred cycloalkyl groups are those having a structure in which the ring is composed of 3 to 7 carbon atoms, including cyclopropyl, cyclopentyl, cyclohexyl, and the like.
- the cycloalkyl group may be substituted with a substituent. The substituent is the same as that described for the alkyl group.
- Examples of the substituted or unsubstituted cycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a diethylcyclopentyl group, a phenylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylethylcyclohexyl group, and a diethylcyclohexyl group.
- the alkenyl group includes both linear and branched alkenyl groups. Preferred alkenyl groups are those containing 2 to 20 carbon atoms. In addition, the alkenyl group may be substituted with a substituent. The substituent is the same as that described for the alkyl group. The alkenyl group preferably has 4 to 18 carbon atoms.
- Examples of the substituted or unsubstituted alkenyl group include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 1-methylvinyl group, styryl group, 2,2-diphenylvinyl group, 1,2-diphenylvinyl group, 1-methylallyl group, 1,1-dimethylallyl group, 2-methylallyl group, 1-phenylallyl group, 2-phenylallyl group, 3-phenylallyl Group, 3,3-diphenylallyl group, 1,2-dimethylallyl group, 1-phenyl-1-butenyl group, and 3-phenyl-1-butenyl group.
- the alkynyl group includes both a linear alkynyl group and a branched alkynyl group.
- Preferred alkynyl groups are those containing 2 to 40 carbon atoms.
- the alkynyl group may be substituted with a substituent.
- the substituent is the same as that described for the alkyl group. More preferably, the alkynyl group has 4 to 18 carbon atoms.
- substituted or unsubstituted alkynyl group examples include ethynyl group, methylethynyl group, 2-propynyl group, 3-butynyl group, 1-methyl-2-propynyl group, and phenylethynyl group.
- the aryl group includes a monocyclic group and a polycyclic group.
- Polycyclic groups are those in which two carbons are shared by two adjacent rings, which are fused, and at least one ring is an aromatic ring, for example, the other ring is A cycloalkyl ring, a cycloalkenyl ring, an aryl ring, a heterocycle, and a heteroaromatic ring.
- the aryl group may be substituted with a substituent. The substituent is the same as that described for the alkyl group.
- Examples of the unsubstituted aryl group include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3 Examples thereof include -phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, and 4-pyrenyl group.
- Examples of the substituted aryl group include tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, and decyl.
- An alkylaryl group having 7 to 18 carbon atoms such as a phenyl group, an undecylphenyl group, and a dodecylphenyl group (the alkyl group may be linear or branched, and the substitution position on the aryl group is arbitrary); Can be mentioned.
- examples of the unsubstituted aryl group include 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p -Terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p -Tolyl group, pt-butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, Examples include a 4′-methylbiphenylyl group and a 4 ′′ -t-butyl-p-terphenyl-4-yl group.
- heteroaryl group examples include monocyclic heteroaromatic groups that may contain 1 to 3 heteroatoms, and specifically include pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, Groups such as pyrazine and pyrimidine are mentioned.
- a heteroaryl group includes a polycyclic heteroaromatic group having two or more rings in which two atoms are shared in two adjacent rings (the rings are fused), wherein at least one The ring is heteroaryl, for example, the other ring can be a cycloalkyl ring, cycloalkenyl ring, aryl ring, heterocycle, and / or heteroaromatic ring.
- the aryl group may be substituted with a substituent. The substituent is the same as that described for the alkyl group.
- substituted or unsubstituted heteroaryl group examples include 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofurany
- R 2 and R 3 may be bonded to form a ring structure or a condensed ring structure.
- the ring in the case of forming the ring structure include a cyclohexane ring and a cyclopentane ring.
- the condensed ring in the case of forming the condensed ring structure include a naphthalene ring, a fluorene ring, an acenaphthene ring, a quinoline ring, Examples include a purine ring and a quinuclidine ring.
- R 2 or R 3 when the group described above is R 2 or R 3 , at least one of them is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group. It is preferably one selected from a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group. Specific examples include a case where one of R 2 and R 3 is a hydrogen atom and the other is one of the above groups. When R 2 and R 3 are both hydrogen atoms, the polarity of the sulfonamide compound is considered to be relatively large, which may be unfavorable in that the dispersibility or solubility in the base oil may decrease.
- the substituent when the above-described group has R 2 and R 3 having a substituent, the substituent is preferably a hydrocarbon group having 1 to 20 carbon atoms.
- the hydrocarbon group means any one of an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aromatic hydrocarbon group, and an aralkyl group. If the substituents in R 2 and R 3 contain not carbon atoms but other atoms other than carbon and hydrogen, the structure is complicated and not only a problem in terms of production process and production cost, but also the compound itself The stability of the may also decrease.
- the hydrocarbon group preferably has 4 to 18 carbon atoms, and more preferably 4 to 8 carbon atoms.
- R 2 and R 3 when the above-described groups are R 2 and R 3 , at least one of them is an unsubstituted alkyl group, an unsubstituted cycloalkyl group, an unsubstituted alkenyl group, or an unsubstituted alkynyl group.
- R 2 and R 3 are any of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group because dispersibility of the sulfonamide compound in the base oil is improved.
- R 2 and R 3 are any of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heteroaryl group because dispersibility of the sulfonamide compound in the base oil is improved.
- the unsubstituted group is more preferably an aryl group, a heteroaryl group, or an alkyl group, and further preferably an alkyl group, from the viewpoint of oxidation stability.
- R 1 described above is preferably one selected from an unsubstituted alkyl group, an unsubstituted cycloalkyl group, an unsubstituted aryl group, and an unsubstituted heteroaryl group.
- R 1 has a substituent, not only is it disadvantageous in the production of the compound, but the compound as a whole becomes large and the effect may be reduced.
- the unsubstituted group is more preferably an aryl group or a heteroaryl group from the viewpoint of production cost.
- the sulfonamide compound which can be used by this embodiment is illustrated.
- the sulfonamide compound include benzenesulfonamide, 2-methylbenzenesulfonamide, 4-methylbenzenesulfonamide, 2-chlorobenzenesulfonamide, 4-chlorobenzenesulfonamide, 2,5-dichlorobenzenesulfonamide, 3,5- Dichlorobenzenesulfonamide, 2-bromobenzenesulfonamide, 4-bromobenzenesulfonamide, 2-nitrobenzenesulfonamide, 3-nitrobenzenesulfonamide, 4-nitrobenzenesulfonamide, 4-hydroxybenzenesulfonamide, naphthalenesulfonamide, 5- Hydroxynaphthalenesulfonamide, benzenesulfone methylamide, benzenesulfone ethylamide, benzenesulfonanilide,
- R 1 , R 2 and R 3 in the general formula (1) are preferable, and in particular, N-butylbenzenesulfonamide and N -Butyl-4-methylbenzenesulfonamide and the like are preferably used from the viewpoint of performance and cost.
- these sulfonamide compounds represented by the general formula (1) may be used singly or in combination of two or more.
- the amount of the sulfonamide compound represented by the general formula (1) is preferably 0.01% by mass or more and 5% by mass or less, and 0.05% by mass or more and 3% by mass or less based on the composition. More preferably, it is more preferably 0.1% by mass or more and 2% by mass or less.
- the blending amount of the sulfonamide compound represented by the general formula (1) is less than 0.01% by mass, performances such as wear resistance, high temperature cleanliness and base number maintenance may not be sufficiently exhibited.
- the blending amount exceeds 5% by mass the deterioration of the automobile exhaust gas purification catalyst accompanying an increase in the sulfur content in the composition may not be suppressed.
- the lubricating oil composition of the present embodiment further includes an antioxidant, an ashless dispersant, a metallic detergent, a viscosity index improver, a pour point depressant, a metal deactivator, a rust inhibitor, and an anti-oxidant. It is preferable that at least one additive selected from foaming agents is blended.
- the antioxidant which does not contain phosphorus is preferable, for example, a phenolic antioxidant, an amine type antioxidant, a molybdenum amine complex type
- phenolic antioxidants include 4,4′-methylenebis (2,6-di-t-butylphenol), 4,4′-bis (2,6-di-t-butylphenol), 4,4 ′.
- amine antioxidant examples include monoalkyldiphenylamines such as monooctyldiphenylamine and monononyldiphenylamine; 4,4′-dibutyldiphenylamine, 4,4′-dipentyldiphenylamine, 4,4′-dihexyldiphenylamine Dialkyldiphenylamines such as 4,4′-diheptyldiphenylamine, 4,4′-dioctyldiphenylamine, and 4,4′-dinonyldiphenylamine; tetrabutyldiphenylamine, tetrahexyldiphenylamine; tetraoctyldiphenylamine, and tetranonyldiphenylamine Polyalkyldiphenylamines; and ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, butylphenyl- ⁇ -naphth
- Examples of the molybdenum amine complex-based antioxidant include hexavalent molybdenum compounds. Specific examples include molybdenum trioxide and / or a compound obtained by reacting molybdic acid with an amine compound; A compound obtained by the production method described in JP-A-2525287 can be used. Although it does not restrict
- an alkyl group having 1 to 30 carbon atoms such as methylamine, ethylamine, dimethylamine, diethylamine, methylethylamine, and methylpropylamine (these alkyl groups may be linear or branched).
- sulfur-based antioxidant examples include phenothiazine, pentaerythritol-tetrakis- (3-laurylthiopropionate), didodecyl sulfide, dioctadecyl sulfide, didodecylthiodipropionate, dioctadecylthiodipropionate, Examples include myristyl thiodipropionate, dodecyl octadecyl thiodipropionate, and 2-mercaptobenzimidazole.
- phenol-based antioxidants and amine-based antioxidants are preferable from the viewpoint of reducing metal content and sulfur content.
- the said antioxidant may be used individually by 1 type, and 2 or more types may be mixed and used for it.
- a mixture of one or more phenolic antioxidants and one or more amine antioxidants is preferable.
- the blending amount of the antioxidant is usually preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, based on the total amount of the composition.
- any ashless dispersant used in lubricating oils can be used.
- a monotype succinimide compound represented by the following general formula (2) or the following general formula A bis-type succinimide compound represented by (3) is mentioned.
- the general formula (2), in (3), R 6, R 8 and R 9, respectively, an alkenyl group or an alkyl group having a number average molecular weight of 500 ⁇ 4,000, R 8 and R 9 are different and the same It may be.
- the number average molecular weight of R 6 , R 8 and R 9 is preferably 1,000 to 4,000. If the number average molecular weight of R 6 , R 8 and R 9 is 500 or more, the solubility in the base oil is good, and if it is 4,000 or less, the cleanliness may not be lowered.
- R 7 , R 10 and R 11 are each an alkylene group having 2 to 5 carbon atoms, and R 10 and R 11 may be the same or different.
- r represents an integer of 1 to 10, and s represents 0 or an integer of 1 to 10.
- the r is preferably 2 to 5, more preferably 3 to 4.
- s is preferably 1 to 4, more preferably 2 to 3. If s is in the above range, it is preferable in terms of cleanliness and solubility in base oil.
- alkenyl group examples include a polybutenyl group, a polyisobutenyl group, and an ethylene-propylene copolymer
- examples of the alkyl group include hydrogenated groups thereof.
- suitable alkenyl groups include polybutenyl or polyisobutenyl groups.
- the polybutenyl group is obtained by polymerizing a mixture of 1-butene and isobutene or high-purity isobutene.
- a representative example of a suitable alkyl group is a hydrogenated polybutenyl group or polyisobutenyl group.
- the above alkenyl succinimide compound or alkyl succinimide compound is usually an alkenyl succinic anhydride obtained by the reaction of polyolefin and maleic anhydride, or an alkyl succinic anhydride obtained by hydrogenating it. It can manufacture by making it react.
- the mono-type succinimide compound and the bis-type succinimide compound can be produced by changing the reaction ratio of the alkenyl succinic anhydride or alkyl succinic anhydride and polyamine.
- olefin monomer for forming the polyolefin one or two or more kinds of ⁇ -olefins having 2 to 8 carbon atoms can be used, and a mixture of isobutene and butene-1 is preferably used. Can do.
- polyamines examples include single diamines such as ethylenediamine, propylenediamine, butylenediamine, and pentylenediamine; diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di (methylethylene) triamine, dibutylenetriamine And polyalkylene polyamines such as tributylenetetramine and pentapentylenehexamine; piperazine derivatives such as aminoethylpiperazine and the like.
- a boron derivative thereof and / or one obtained by modifying these with an organic acid may be used.
- the boron derivative of the alkenyl or alkyl succinimide compound those produced by a conventional method can be used. For example, after reacting the polyolefin with maleic anhydride to form an alkenyl succinic anhydride, the above polyamine and boron oxide, boron halide, boric acid, boric anhydride, boric acid ester, ammonium salt of boric acid It can be obtained by reacting with an intermediate obtained by reacting a boron compound such as, and imidizing.
- the boron content in the boron derivative is not particularly limited, but is preferably in the range of 0.05 to 5% by mass, more preferably in the range of 0.1 to 3% by mass as boron.
- the blend amount of the ashless dispersant is preferably 0.5% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass or less, and further preferably 3% by mass, based on the total amount of the lubricating oil composition. It is 7 mass% or less.
- the blending amount is less than 0.5% by mass, the effect of maintaining the base number at high temperatures is small.
- the blending amount exceeds 15% by mass, the low-temperature fluidity of the lubricating oil composition is greatly deteriorated. Therefore, each is not preferable.
- any alkaline earth metal detergent used for lubricating oil can be used, for example, alkaline earth metal sulfonate, alkaline earth metal phenate, alkaline earth metal salicylate, and these.
- alkaline earth metal sulfonate alkaline earth metal phenate
- alkaline earth metal salicylate alkaline earth metal salicylate
- alkaline earth metal sulfonate examples include an alkaline earth metal salt of an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound having a molecular weight of 300 to 1,500, preferably 400 to 700,
- a magnesium salt and / or a calcium salt can be used, and among them, a calcium salt is preferably used.
- alkaline earth metal phenates examples include alkylphenols, alkylphenol sulfides, alkaline earth metal salts of Mannich reaction products of alkylphenols, particularly magnesium salts and / or calcium salts, among which calcium salts are particularly preferably used.
- alkaline earth metal salicylate examples include alkaline earth metal salts of alkyl salicylic acid, particularly magnesium salts and / or calcium salts, among which calcium salts are preferably used.
- the alkyl group constituting the alkaline earth metal detergent preferably has 4 to 30 carbon atoms, and these may be linear or branched.
- the alkyl group is more preferably a linear or branched alkyl group having 6 to 18 carbon atoms. These may also be primary alkyl groups, secondary alkyl groups or tertiary alkyl groups.
- alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate the above-mentioned alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, Mannich reaction product of alkylphenol, alkylsalicylic acid, etc. are directly added to magnesium and / or Or it reacts with alkaline earth metal bases such as calcium alkaline earth metal oxides and hydroxides, or once is converted to an alkali metal salt such as sodium salt or potassium salt and then substituted with alkaline earth metal salt, etc.
- alkaline earth metal bases such as calcium alkaline earth metal oxides and hydroxides
- neutral alkaline earth metal sulfonates, neutral alkaline earth metal phenates and neutral alkaline earth metal salicylates obtained by In addition, neutral alkaline earth metal sulfonate, neutral alkaline earth metal phenate, neutral alkaline earth metal salicylate and excess alkaline earth metal salt or alkaline earth metal base can be obtained by heating in the presence of water.
- Overbased alkaline earth metal sulfonates, overbased alkaline earth metal phenates and overbased alkaline earth metal salicylates obtained by reacting alkaline earth metal salicylates with alkaline earth metal carbonates or borates Is also included.
- alkaline earth metal salicylate and alkaline earth metal phenate are preferable for the purpose of reducing sulfur content in the composition, and overbased salicylate and overbased phenate are particularly preferable.
- overbased calcium salicylate is preferred.
- the total base number of the metal detergent used in the present embodiment is preferably 10 mgKOH / g or more and 500 mgKOH / g or less, more preferably 15 mgKOH / g or more and 450 mgKOH / g or less, and one or two selected from these These can be used together.
- the total base number referred to here is JIS K 2501 “Petroleum products and lubricants—neutralization number test method”. Means the total base number by potentiometric titration method (base number / perchloric acid method) measured according to the above.
- the metal detergent used in the present embodiment is not particularly limited in the metal ratio, and usually 20 or less can be used singly or in combination of two or more, preferably the metal ratio is 3 or less, It is particularly preferable to use a metal detergent of 1.5 or less, particularly 1.2 or less, because it is more excellent in oxidation stability, base number maintenance, high temperature cleanability and the like.
- the metal ratio referred to here is represented by (metal element valence) ⁇ (metal element content (mol%)) / (soap group content (mol%)) in a metal-based detergent.
- the element means calcium, magnesium or the like
- the soap group means a sulfonic acid group, a phenol group, a salicylic acid group, or the like.
- the blending amount of the metallic detergent is preferably 0.01% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, and 0.5% by mass based on the total amount of the lubricating oil composition. More preferably, the content is 5% by mass or less.
- the blending amount is less than 0.01% by mass, it is difficult to obtain performances such as high-temperature cleanliness, oxidation stability, and base number maintenance, which is not preferable.
- it is 20% by mass or less an effect commensurate with the amount added is usually obtained, but the upper limit of the amount of the metallic detergent is as low as possible regardless of the above range. It is important to do.
- the metal content of the lubricating oil composition that is, the sulfated ash content can be reduced to prevent the deterioration of the exhaust gas purification device of the automobile.
- a metal type detergent contains said prescribed amount, you may use it individually or in combination of 2 or more types.
- the metal detergent, ashless dispersant, and the like may be used as a dispersibility improver for the sulfonamide compound.
- overbased calcium salicylate or overbased calcium phenate is particularly preferable among the metal detergents
- the polybutenyl succinic acid bisimide is particularly preferable among the ashless dispersants.
- the total base number of the overbased calcium salicylate and the overbased calcium phenate is preferably from 100 mgKOH / g to 500 mgKOH / g, more preferably from 200 mgKOH / g to 500 mgKOH / g.
- the viscosity index improver examples include polymethacrylate, dispersed polymethacrylate, olefin copolymer (eg, ethylene-propylene copolymer), dispersed olefin copolymer, styrene copolymer (eg, Styrene-diene copolymer, styrene-isoprene copolymer, etc.).
- the blending amount of the viscosity index improver is preferably 0.5% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass or less based on the total amount of the lubricating oil composition from the viewpoint of the blending effect.
- pour point depressant examples include polymethacrylate having a weight average molecular weight of about 5,000 to 50,000.
- the blending amount of the pour point depressant is preferably 0.1% by mass or more and 2% by mass or less, more preferably 0.1% by mass or more and 1% by mass or less, based on the total amount of the lubricating oil composition, from the viewpoint of blending effect. is there.
- the metal deactivator examples include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.
- the compounding amount of the metal deactivator is preferably 0.01% by mass or more and 3% by mass or less, more preferably 0.01% by mass or more and 1% by mass or less, based on the total amount of the lubricating oil composition.
- rust inhibitor examples include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinate, and polyhydric alcohol ester.
- the blending amount of these rust preventives is preferably 0.01% by weight or more and 1% by weight or less, more preferably 0.05% by weight or more and 0.5% by weight, based on the total amount of the lubricating oil composition, from the viewpoint of blending effects. It is as follows.
- the antifoaming agent examples include silicone oil, fluorosilicone oil, and fluoroalkyl ether, and the blending amount thereof is 0.00 on the basis of the total amount of the lubricating oil composition from the viewpoint of balance between the antifoaming effect and economy.
- 005 mass% or more and 0.5 mass% or less are preferable, More preferably, they are 0.01 mass% or more and 0.2 mass% or less.
- the lubricating oil composition of this embodiment may further contain a friction modifier, an antiwear agent, and an extreme pressure agent.
- a friction reducing agent any compound usually used as a friction reducing agent for lubricating oils can be used.
- it has at least one alkyl group or alkenyl group having 6 to 30 carbon atoms in the molecule.
- Ashless friction reducing agents such as fatty acid esters, fatty acid amides, fatty acids, aliphatic alcohols, aliphatic amines, and aliphatic ethers.
- the blending amount of the friction reducing agent is preferably 0.01% by mass or more and 2% by mass or less, more preferably 0.01% by mass or more and 1% by mass or less, based on the total amount of the lubricating oil composition.
- antiwear or extreme pressure agent examples include zinc dithiophosphate, zinc phosphate, zinc dithiocarbamate, molybdenum dithiocarbamate, molybdenum dithiophosphate, disulfides, sulfurized olefins, sulfurized fats and oils, sulfurized esters, thiocarbonates, Sulfur-containing compounds such as thiocarbamates and polysulfides; phosphorous esters, phosphate esters and phosphonate esters, and phosphorus-containing compounds such as amine salts or metal salts thereof; thiophosphites, Examples thereof include thiophosphate esters, thiophosphonate esters, sulfur and phosphorus-containing antiwear agents such as amine salts or metal salts thereof.
- the blending amount should be such that the phosphorus, sulfur and metal content in the lubricating oil by adding the antiwear or extreme pressure agent is not excessive. It is necessary to keep in mind.
- the lubricating oil composition of the present embodiment is composed of the above composition, but preferably satisfies the following as its properties.
- the sulfated ash content (JIS K2272) is 1.2% by mass or less, more preferably 1.0% by mass or less, and particularly preferably 0.8% by mass or less.
- the phosphorus content (JIS-5S-38-92) is 0.12% by mass or less, more preferably 0.10% by mass or less, particularly preferably 0.09% by mass or less. In addition to the above, it is more preferable to satisfy the following.
- the sulfur content (JIS K2541) is 0.12% by mass or less, more preferably 0.10% by mass or less, and particularly preferably 0.08% by mass or less.
- the lubricating oil composition of the present embodiment satisfying such properties can suppress deterioration of an oxidation catalyst, a three-way catalyst, a NOx occlusion-type reduction catalyst, a diesel particulate filter (DPF), and the like of an automobile engine.
- the lubricating oil composition of the present embodiment enhances the basic performance required for the lubricating oil for internal combustion engines, such as wear resistance, high-temperature cleanability, and base number maintenance, even with such properties. Can do.
- the lubricating oil composition of the present embodiment is excellent in wear resistance, base number maintenance, and high temperature cleanliness, and therefore the oil replacement period can be prolonged. Therefore, the lubricating oil composition of the present embodiment can be preferably used as a lubricating oil for internal combustion engines such as motorcycles, automobiles, power generation, marine gasoline engines, diesel engines, gas engines, etc. Due to its low ash content, it is particularly suitable for an internal combustion engine equipped with an exhaust gas aftertreatment device.
- the lubricating composition of the present embodiment is a lubricating oil that requires oxidation stability, such as a lubricating oil for a drive system such as an automatic or manual transmission, grease, wet brake oil, hydraulic hydraulic oil, turbine It can also be suitably used as a lubricating oil such as oil, compressor oil, bearing oil, and refrigerator oil.
- Base number residual ratio (%) (base number of lubricating oil composition after test / base number of lubricating oil composition before test) ⁇ 100
- Example 1 The base oil and additives shown in Table 1 are blended in the proportions shown in Table 1 to prepare a lubricating oil composition for an internal combustion engine, and the properties, composition and performance of the composition are shown in Table 1.
- the lubricating oil compositions of the examples blended with the sulfonamide compound A have wear resistance, high-temperature cleanliness, and base number residue even with low phosphorus content and low sulfated ash content. It turns out that it is favorable (Example 1).
- the lubricating oil composition of Comparative Example 1 prepared by using zinc dialkyldithiophosphate instead of the sulfonamide compound A of Example and changing the blending amount of the metal detergent is that of Example 1.
- the wear resistance is equivalent, but the high-temperature cleanliness (hot tube test score) and the base number residual ratio are remarkably inferior.
- the lubricating oil composition of the comparative example 1 has also high sulfur content compared with the composition of an Example.
- the present invention can provide a lubricating oil composition that is excellent in wear resistance, high-temperature cleanability, and base number maintainability at a low cost even with low phosphorus content, low sulfur content, and low metal content (low sulfated ash content). it can. Moreover, this invention can provide the lubricating oil composition which has the more superior performance, without mix
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Abstract
Description
しかし、このジチオリン酸亜鉛は、分子中に金属分(亜鉛)とともに、リン分および硫黄分を多量に含んでいることから、ジチオリン酸亜鉛の分解物は硫酸やリン酸を発生する。そのため、ジチオリン酸亜鉛は、エンジン油中の塩基性化合物を消耗させて潤滑油の劣化を促進し、更油期間を極端に短くすることがある(この現象は、いわゆる塩基価維持性が不十分であることを意味する)。また、ジチオリン酸亜鉛は高温条件でスラッジ化し、エンジン内部の清浄性を悪化させることがあることも問題視されている。
このような状況から、ジチオリン酸亜鉛に代わる内燃機関用潤滑油に使用できる耐摩耗添加剤の出現が望まれている。
したがって、低金属分(すなわち、低硫酸灰分)、低リン分、さらには低硫黄分であっても内燃機関用潤滑油に要求される基本的な性能(耐摩耗性、清浄性、塩基価維持性など)を具備する内燃機関用潤滑油が切望されている。
すなわち、本発明は、
<1> 基油に、下記の一般式(1)で表されるスルホンアミド化合物を配合してなる潤滑油組成物である。
本実施形態の潤滑油組成物は、基油に、前記一般式(1)で表されるスルホンアミド化合物を配合してなることを特徴とする。
本実施形態において用いる基油としては、特に制限はなく、従来、内燃機関用潤滑油の基油として使用されている鉱油や合成油の中から任意のものを適宜選択して用いることができる。
前記鉱油としては、例えば、原油を常圧蒸留して得られる常圧残油を減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、接触脱ろう、水素化精製等のうちの1つ以上の処理を行って精製した鉱油、あるいはワックス、GTL WAXを異性化することによって製造される鉱油等が挙げられる。
本実施形態においては、基油として、前記鉱油は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。また、前記合成油を一種用いてもよく、二種以上を組み合わせて用いてもよい。更には、鉱油一種以上と合成油一種以上とを組み合わせて用いてもよい。
100℃における動粘度が2mm2/s以上であると蒸発損失が少ない。また100℃における動粘度が30mm2/s以下であると、粘性抵抗による動力損失が抑制され、燃費改善効果が得られる。
%CAが3.0以下で、硫黄分が50質量ppm以下の基油は、良好な酸化安定性を有し、酸価の上昇やスラッジの生成を抑制しうる潤滑油組成物を提供することができる。より好ましい%CAは1.0以下、さらに好ましくは0.5以下である。またより好ましい硫黄分は30質量ppm以下である。
本実施形態の潤滑油組成物には、下記一般式(1)で表されるスルホンアミド化合物が配合される。該スルホンアミド化合物を潤滑油組成物の成分として用いることにより、リン分、硫黄分及び金属分を低減しても、耐摩耗性、高温清浄性及び塩基価維持性を高める効果を得ることができる。
上記置換基としては具体的には、ハロゲン原子、ヒドロキシ基、アミノ基、ニトロ基、シアノ基、アルキル基、アルケニル基、シクロアルキル基、アルコキシ基、芳香族炭化水素基、芳香族複素環基、アラルキル基、アリールオキシ基、アルコキシカルボニル基、フッ素化アルキル基、フッ素化アリール基、カルボキシル基、イソシアネート基、チオイソシアネート基、イミノ基、スルホン基、チオカルボキシル基、カルボニル基、チオカルボニル基、ホルミル基、チオホルミル基、シラノール基、ヒドロカルビルオキシ基、ニトリル基、ピリジル基、アミド基、イミド基、イミダゾリル基、アンモニウム基、ヒドラゾ基、アゾ基、ジアゾ基、ケチミン基、エポキシ基、チオエポキシ基、オキシカルボニル基(エステル結合)、カルボニルチオ基(チオエステル結合)、オキシ基(エーテル結合)、グリシドキシ基、スルフィド基(チオエーテル結合)、ジスルフィド基、メルカプト基、ヒドロカルビルチオ基、スルホニル基、スルフィニル基、イミン残基、ヒドロカルビルオキシシリル基、及び有機スズ基などが挙げられる。
また前記ハロゲン原子としては、フッ素、塩素、臭素、及びヨウ素等が挙げられる。
また前記置換のアリール基としては、例えば、トリル基、キシリル基、エチルフェニル基、プロピルフェニル基、ブチルフェニル基、ペンチルフェニル基、ヘキシルフェニル基、ヘプチルフェニル基、オクチルフェニル基、ノニルフェニル基、デシルフェニル基、ウンデシルフェニル基、及びドデシルフェニル基等の炭素数7~18のアルキルアリール基(アルキル基は直鎖状でも分枝状でもよく、またアリール基への置換位置も任意である)が挙げられる。さらに前記無置換のアリール基としては、例えば2-ビフェニルイル基、3-ビフェニルイル基、4-ビフェニルイル基、p-ターフェニル-4-イル基、p-ターフェニル-3-イル基、p-ターフェニル-2-イル基、m-ターフェニル-4-イル基、m-ターフェニル-3-イル基、m-ターフェニル-2-イル基、o-トリル基、m-トリル基、p-トリル基、p-t-ブチルフェニル基、p-(2-フェニルプロピル)フェニル基、3-メチル-2-ナフチル基、4-メチル-1-ナフチル基、4-メチル-1-アントリル基、4’-メチルビフェニルイル基、及び4”-t-ブチル-p-ターフェニル-4-イル基が挙げられる。
R2及びR3が共に水素原子であると、スルホンアミド化合物の極性が比較的大きくなると考えられ、基油への分散性あるいは溶解性が低下する等の好ましくない場合がある。
R2及びR3における置換基が、上記炭化水素基でなく炭素、水素以外の他の原子を含むと、構造上複雑となり、製造プロセス、製造コストの面で問題となるだけでなく、化合物自体の安定性も低下する場合がある。
前記炭化水素基の炭素数は4~18であることがより好ましく、4~8であることがさらに好ましい。
R2及びR3がアルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基及びヘテロアリール基のいずれかであると、スルホンアミド化合物の基油への分散性が向上するため好ましいが、これらが置換基を有する場合には、化合物の製造上不利であるだけでなく、全体として化合物が大きくなり、添加の効果が低減する場合がある。
R1が置換基を有する場合には、化合物の製造上不利であるだけでなく、全体として化合物が大きくなり、効果が低減する場合がある。
またこの場合、前記無置換とする基としては、製造コストの観点から、アリール基、ヘテロアリール基とすることがより好ましい。
上記スルホンアミド化合物としては、ベンゼンスルホンアミド、2-メチルベンゼンスルホンアミド、4-メチルベンゼンスルホンアミド、2-クロロベンゼンスルホンアミド、4-クロロベンゼンスルホンアミド、2,5-ジクロロベンゼンスルホンアミド、3,5-ジクロロベンゼンスルホンアミド、2-ブロモベンゼンスルホンアミド、4-ブロモベンゼンスルホンアミド、2-ニトロベンゼンスルホンアミド、3-ニトロベンゼンスルホンアミド、4-ニトロベンゼンスルホンアミド、4-ヒドロキシベンゼンスルホンアミド、ナフタレンスルホンアミド、5-ヒドロキシナフタレンスルホンアミド、ベンゼンスルホンメチルアミド、ベンゼンスルホンエチルアミド、ベンゼンスルホンアニリド、ベンゼンスルホン-4-クロロアニリド、4-メチルベンゼンスルホンメチルアミド、4-メチルベンゼンスルホンエチルアミド、4-メチルベンゼンスルホンアニリド、4-メチルベンゼンスルホン-4-クロロアニリド、2-ニトロベンゼンスルホンメチルアミド、2-ニトロベンゼンスルホンエチルアミド、2-ニトロベンゼンスルホンアニリド、2-ニトロベンゼンスルホン-4-クロロアニリド、メタンスルホンアニリド、エタンスルホンアニリド、トリクロロメタンスルホンアニリド、トリフロロメタンスルホンアニリド、メタンスルホン-4-クロロアニリド、エタンスルホン-4-クロロアニリド、トリクロロメタンスルホン-4-クロロアニリド、トリフロロメタンスルホン-4-クロロアニリド、メタンスルホンナフタレンアミド、エタンスルホンナフタレンアミド、トリクロロメタンスルホンナフタレンアミド、トリフロロメタンスルホンナフタレンアミド、p-トルエンスルホンアミド、N-ブチルベンゼンスルホンアミド、N-ブチル-4-メチルベンゼンスルホンアミド、N-フェニル-4-ヒドロキシベンゼンスルホンアミド、5-ジメチルアミノ-1-ナフタレンスルホンアミド、2-アミノ-N-シクロヘキシル-N-メチルベンゼンスルホンアミド、N-(4-アミノフェニル)-4-メチルベンゼンスルホンアミド、4-(2-アミノエチル)ベンゼンスルホンアミド、N-(3-アミノフェニル)メタンスルホンアミド、N,N-ジオクチルメタンスルホンアミド、N,N-ジオクチルエタンスルホンアミド、及びN,N-ジブテニルメタンスルホンアミドなどを挙げることができる。
一般式(1)で表されるスルホンアミド化合物の配合量が0.01質量%未満であると、耐摩耗性、高温清浄性及び塩基価維持性などの性能が十分に発現されない場合がある。一方、配合量が5質量%を越えると、組成物中の硫黄含有量の増大に伴う自動車排出ガス浄化触媒の劣化を抑制することができない場合がある。
フェノール系酸化防止剤としては、例えば、4,4’-メチレンビス(2,6-ジ-t-ブチルフェノール)、4,4’-ビス(2,6-ジ-t-ブチルフェノール)、4,4’-ビス(2-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-エチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、4,4’-ブチリデンビス(3-メチル-6-t-ブチルフェノール)、4,4’-イソプロピリデンビス(2,6-ジ-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-ノニルフェノール)、2,2’-イソブチリデンビス(4,6-ジメチルフェノール);2,2’-メチレンビス(4-メチル-6-シクロヘキシルフェノール)、2,6-ジ-t-ブチル-4-メチルフェノール、2,6-ジ-t-ブチル-4-エチルフェノール、2,4-ジメチル-6-t-ブチルフェノール、2,6-ジ-t-アミル-p-クレゾール、2,6-ジ-t-ブチル-4-(N,N’-ジメチルアミノメチルフェノール)、4,4’-チオビス(2-メチル-6-t-ブチルフェノール)、4,4’-チオビス(3-メチル-6-t-ブチルフェノール)、2,2’-チオビス(4-メチル-6-t-ブチルフェノール)、ビス(3-メチル-4-ヒドロキシ-5-t-ブチルベンジル)スルフィド、ビス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)スルフィド、n-オクチル-3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオネート、n-オクタデシル-3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオネート、及び2,2’-チオ[ジエチル-ビス-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]が挙げられる。
これらの中で、特にビスフェノール系及びエステル基含有フェノール系のものが好適である。
これらの中で、ジアルキルジフェニルアミン系及びナフチルアミン系のものが好適である。
前記6価のモリブデン化合物と反応させるアミン化合物としては特に制限されないが、具体的には、モノアミン、ジアミン、ポリアミン及びアルカノールアミンが挙げられる。より具体的には、メチルアミン、エチルアミン、ジメチルアミン、ジエチルアミン、メチルエチルアミン、及びメチルプロピルアミン等の炭素数1~30のアルキル基(これらのアルキル基は直鎖状でも分枝状でもよい)を有するアルキルアミン;エテニルアミン、プロペニルアミン、ブテニルアミン、オクテニルアミン、及びオレイルアミン等の炭素数2~30のアルケニル基(これらのアルケニル基は直鎖状でも分枝状でもよい)を有するアルケニルアミン;メタノールアミン、エタノールアミン、メタノールエタノールアミン、及びメタノールプロパノールアミン等の炭素数1~30のアルカノール基(これらのアルカノール基は直鎖状でも分枝状でもよい)を有するアルカノールアミン;メチレンジアミン、エチレンジアミン、プロピレンジアミン、及びブチレンジアミン等の炭素数1~30のアルキレン基を有するアルキレンジアミン;ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、及びペンタエチレンヘキサミン等のポリアミン;ウンデシルジエチルアミン、ウンデシルジエタノールアミン、ドデシルジプロパノールアミン、オレイルジエタノールアミン、オレイルプロピレンジアミン、及びステアリルテトラエチレンペンタミン等の上記モノアミン、ジアミン、ポリアミンに炭素数8~20のアルキル基又はアルケニル基を有する化合物やイミダゾリン等の複素環化合物;並びにこれらの化合物のアルキレンオキシド付加物及びこれらの混合物等が例示できる。
また、特公平3-22438号公報及び特開2004-2866号公報に記載されているコハク酸イミドの硫黄含有モリブデン錯体等が例示できる。
酸化防止剤の配合量は、組成物全量基準で、通常0.1質量%以上5質量%以下が好ましく、0.1質量%以上3質量%以下がより好ましい。
上記R6、R8及びR9の数平均分子量が500以上であれば、基油への溶解性が良好であり、4,000以下であれば清浄性が低下するおそれがない。
さらに一般式(3)において、sは好ましくは1~4、より好ましくは2~3である。sが上記範囲内であれば、清浄性及び基油に対する溶解性の点で好ましい。
また、好適なアルキル基の代表例は、ポリブテニル基又はポリイソブテニル基を水添したものである。
また、前記ポリアミンとしては、エチレンジアミン、プロピレンジアミン、ブチレンジアミン、及びペンチレンジアミン等の単一ジアミン;ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ジ(メチルエチレン)トリアミン、ジブチレントリアミン、トリブチレンテトラミン、及びペンタペンチレンヘキサミン等のポリアルキレンポリアミン;アミノエチルピペラジン等のピペラジン誘導体などを挙げることができる。
アルケニル若しくはアルキルコハク酸イミド化合物のホウ素誘導体は、常法により製造したものを使用することができる。例えば、前記ポリオレフィンを無水マレイン酸と反応させてアルケニルコハク酸無水物とした後、更に上記のポリアミン及び酸化ホウ素、ハロゲン化ホウ素、ホウ酸、ホウ酸無水物、ホウ酸エステル、ホウ素酸のアンモニウム塩等のホウ素化合物を反応させて得られる中間体と反応させてイミド化させることによって得られる。
このホウ素誘導体中のホウ素含有量は、特に制限はないが、ホウ素として、0.05~5質量%の範囲が好ましく、より好ましくは0.1~3質量%の範囲である。
配合量が0.5質量%未満の場合は、高温下における塩基価維持性に対する効果が少なく、一方、配合量が15質量%を越える場合は、潤滑油組成物の低温流動性が大幅に悪化するため、それぞれ好ましくない。
これらはまた1級アルキル基、2級アルキル基又は3級アルキル基でもよい。
なお、ここでいう全塩基価とは、JIS K 2501「石油製品及び潤滑油-中和価試験方法」の7.に準拠して測定される電位差滴定法(塩基価・過塩素酸法)による全塩基価を意味する。
なお、ここでいう金属比とは、金属系清浄剤における(金属元素の価数)×(金属元素含有量(モル%))/(せっけん基含有量(モル%))で表され、該金属元素とはカルシウム、マグネシウム等を意味し、該せっけん基とは、スルホン酸基、フェノール基及びサリチル酸基等を意味する。
配合量が0.01質量%未満の場合、高温清浄性や酸化安定性、塩基価維持性などの性能が得られにくくなるため好ましくない。一方、20質量%以下であれば、通常その添加量に見合った効果が得られるが、当該金属系清浄剤の配合量の上限については、上記の範囲に関わらず、配合量を可能な限り低くすることが肝要である。それによって、潤滑油組成物の金属分、すなわち硫酸灰分を少なくして、自動車の排出ガス浄化装置の劣化を防止することができる。
また、金属系清浄剤は、上記の規定量を含有する限り、単独又は二種以上を組み合わせて用いてもよい。
具体的には、前記金属系清浄剤の中では過塩基性カルシウムサリシレートまたは過塩基性カルシウムフェネートが、前記無灰系分散剤の中では前記ポリブテニルコハク酸ビスイミドが特に好ましい。なお、上記過塩基性カルシウムサリシレート及び過塩基性カルシウムフェネートの全塩基価は100mgKOH/g以上500mgKOH/g以下であることが好ましく、200mgKOH/g以上500mgKOH/g以下がより好ましい。
粘度指数向上剤の配合量は、配合効果の点から、潤滑油組成物全量基準で、0.5質量%以上15質量%以下が好ましく、より好ましくは1質量%以上10質量%以下である。
流動点降下剤の配合量は、配合効果の点から、潤滑油組成物全量基準で、0.1質量%以上2質量%以下が好ましく、より好ましくは0.1質量%以上1質量%以下である。
金属不活性剤の配合量は、潤滑油組成物全量基準で、0.01質量%以上3質量%以下が好ましく、より好ましくは0.01質量%以上1質量%以下である。
これら防錆剤の配合量は、配合効果の点から、潤滑油組成物全量基準で、0.01質量%以上1質量%以下が好ましく、より好ましくは0.05質量%以上0.5質量%以下である。
前記摩擦低減剤としては、潤滑油用の摩擦低減剤として通常用いられている任意の化合物が使用可能であり、例えば、炭素数6~30のアルキル基又はアルケニル基を分子中に少なくとも1個有する、脂肪酸エステル、脂肪酸アミド、脂肪酸、脂肪族アルコール、脂肪族アミン、及び脂肪族エーテル等の無灰摩擦低減剤が挙げられる。
摩擦低減剤の配合量は、潤滑油組成物全量基準で0.01質量%以上2質量%以下が好ましく、より好ましくは0.01質量%以上1質量%以下である。
(1)硫酸灰分(JIS K2272)が、1.2質量%以下、より好ましくは1.0質量%以下、特に好ましくは0.8質量%以下であること。かつ、
(2)リン含有量(JIS-5S-38-92)が、0.12質量%以下、より好ましくは0.10質量%以下、特に好ましくは0.09質量%以下であること。
さらに、上記に加えて以下を満たすことがより好ましい。
(3)硫黄含有量(JIS K2541)が、0.12質量%以下、より好ましくは0.10質量%以下、特に好ましく0.08質量%以下であること。
このような性状を満たす本実施形態の潤滑油組成物は、自動車エンジンの酸化触媒、三元触媒、NOx吸蔵型還元触媒、ディーゼルパティキュレートフィルター(DPF)等の劣化を抑制できる。また、本実施形態の潤滑油組成物は、このような性状であっても、耐摩耗性、高温清浄性、塩基価維持性などの内燃機関用潤滑油に要求される基本的性能を高めることができる。
<性状、性能の測定方法>
以下の実施例、比較例における潤滑油組成物の性状及び性能は、次の方法によって求めた。
(1)動粘度
JIS K 2283に準拠して測定した。
(2)カルシウム、及びリンの含有量
JPI-5S-38-92に準拠して測定した。
(3)亜鉛の含有量
JPI-5S-38-92に準拠して測定した。
(4)硫黄含有量
JIS K 2541に準拠して測定した。
(5)硫酸灰分
JIS K 2272に準拠して測定した。
(6)銅溶出量
JPI-5S-38-92に準拠して測定した。
(7)塩基価
JIS K 2501に準拠して測定した。
往復動摩擦試験機にて、試験板として硬度(HRC)が61、表面の十点平均粗さ(Rz)が0.004μmで、大きさが3.9mm×38mm×58mmのSUJ-2製板、試験球として直径が10mmのSUJ-2製ボールを用い、下記の試験条件で摩耗試験を行った。摩耗試験後、試験球の摩耗痕径を測定した。摩耗試験後の試験球の摩耗痕径が小さいほど、耐摩耗性が優れていることを示す。
-試験条件-
・試験温度:100℃
・荷重:200N
・振幅:15mm
・振動数:10Hz
・試験時間:30分
試験温度は300℃に設定し、その他の条件については、JPI-5S-55-99に準拠して測定した。試験後の評点はJPI-5S-55-99に準拠してテストチューブに付着したラッカーを0点(黒色)~10点(無色)の11段階にて評価した。なお、数字が大きいほど堆積物が少なく高温清浄性が良好であることを示す。
JIS K2514-1996に準拠して内燃機関用潤滑油酸化安定度試験(Indiana Stirring Oxidation Test)を、下記の試験条件で実施した。
-試験条件-
・試験温度:165.5℃
・回転数:1300rpm
・試験時間:96時間
・触媒:銅板及び鉄板
上記試験後、油の塩基価、銅量(銅溶出量)を測定した。塩基価残存率は以下の式で算出した。なお、塩基価残存率が大きいほどロングドレン性に優れており、更油交換期間が長いことを示す。また、銅溶出量は多いほど、銅含有金属への影響が大きく、金属が腐食し易いことを表す。
塩基価残存率(%)=(試験後の潤滑油組成物の塩基価/試験前の潤滑油組成物の塩基価)×100
第1表に示した基油及び添加剤を第1表に示す割合で配合して、内燃機関用潤滑油組成物を調製し、その組成物の性状・組成及び性能を第1表に示す。
1):水素化精製基油(40℃動粘度:21mm2/s、100℃動粘度:4.5mm2/s、粘度指数:127、%CA:0、硫黄分20質量ppm未満、NOACK試験蒸発量:13.3質量%)
2):ポリメタクリレート(重量平均分子量:420000、樹脂量:39質量%)
3):ポリアルキルメタクリレート(重量平均分子量:6000)
4):過塩基性カルシウムサリシレート(塩基価(過塩素酸法):225mgKOH/g、Ca含有量:7.8質量%、硫黄含有量:0.3質量%)
5):ポリブテニルコハク酸ビスイミド(ポリブテニル基の平均分子量:2000、窒素含有量:0.99質量%)
6):n-オクタデシル-3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオネート
7):ジアルキルジフェニルアミン(窒素含有量:4.62質量%)
8):亜鉛含有量:9.0質量%、リン含有量:8.2質量%、硫黄含有量:17.1質量%、アルキル基:第2級ブチル基及び第2級ヘキシル基の混合物
9):N-ブチルベンゼンスルホンアミド(大八化学社製、商品名「BM-4」)
10):シリコーン系消泡剤
なお表中、リン含有量、亜鉛含有量における「-」は検出感度以下であることを示す。
これに対して、実施例のスルホンアミド化合物Aに代えてジアルキルジチオリン酸亜鉛を用い、かつ金属系清浄剤の配合量を変更して調製した比較例1の潤滑油組成物は、実施例1の内燃機関用潤滑油組成物に比べて、耐摩耗性は同等であるが、高温清浄性(ホットチューブ試験の評点)及び塩基価残存率が著しく劣っている。また、比較例1の潤滑油組成物は、実施例の組成物と比較して、硫黄分含有量も高いことがわかる。
したがって、本発明の潤滑油組成物は、ガソリンエンジン、ディーゼルエンジン、ガスエンジンなど、内燃機関用潤滑油組成物として広くかつ有効に利用することができる。
Claims (7)
- 基油に、下記の一般式(1)で表されるスルホンアミド化合物を配合してなる潤滑油組成物。
- 前記一般式(1)におけるR2及びR3の少なくともいずれかが、置換もしくは無置換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換のアルケニル基、置換もしくは無置換のアルキニル基、置換もしくは無置換のアリール基及び置換もしくは無置換のヘテロアリール基から選択される1種である請求項1に記載の潤滑油組成物。
- 前記一般式(1)におけるR2及びR3の少なくともいずれかが置換基を有する場合、該置換基が、それぞれ独立に炭素数が1~20の炭化水素基である請求項1または2に記載の潤滑油組成物。
- 前記一般式(1)におけるR2及びR3の少なくともいずれかが、無置換のアルキル基、無置換のシクロアルキル基、無置換のアルケニル基、無置換のアルキニル基、無置換のアリール基及び無置換のヘテロアリール基から選択される1種である請求項1または2に記載の潤滑油組成物。
- 前記一般式(1)におけるR1が、無置換のアルキル基、無置換のシクロアルキル基、無置換のアリール基及び無置換のヘテロアリール基から選択される1種である請求項1~4のいずれかに記載の潤滑油組成物。
- リン含有量が組成物基準で0.12質量%以下であり、かつ硫酸灰分が1.2質量%以下である請求項1~5のいずれかに記載の潤滑油組成物。
- 内燃機関用潤滑油組成物である請求項1~6のいずれかに記載の潤滑油組成物。
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JP6718273B2 (ja) * | 2016-03-23 | 2020-07-08 | シェルルブリカンツジャパン株式会社 | 電子制御機器を配した油圧作動機用潤滑油組成物 |
BR112018067519B1 (pt) * | 2016-03-24 | 2022-05-03 | Shell Internationale Research Maatschappij B.V | Composição de óleo lubrificante |
US11193081B2 (en) | 2016-05-24 | 2021-12-07 | The Lubrizol Corporation | Seal swell agents for lubricating compositions |
CN109496228B (zh) * | 2016-05-24 | 2021-11-05 | 路博润公司 | 用于润滑组合物的密封溶胀剂 |
CA3178672A1 (en) * | 2020-06-09 | 2021-12-16 | Stanley GUNAWAN | Inverting surfactants for inverse emulsions |
CN116042294B (zh) * | 2021-10-28 | 2024-05-17 | 中国石油化工股份有限公司 | 适用于柴油发动机的润滑油组合物及其制备方法和应用 |
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