WO2011111795A1 - 潤滑油組成物 - Google Patents
潤滑油組成物 Download PDFInfo
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- WO2011111795A1 WO2011111795A1 PCT/JP2011/055699 JP2011055699W WO2011111795A1 WO 2011111795 A1 WO2011111795 A1 WO 2011111795A1 JP 2011055699 W JP2011055699 W JP 2011055699W WO 2011111795 A1 WO2011111795 A1 WO 2011111795A1
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- 0 CC(CC*)C(N(C(C)(C)*)C(C)=O)=O Chemical compound CC(CC*)C(N(C(C)(C)*)C(C)=O)=O 0.000 description 5
- FFVFNEVZDBBJPR-UHFFFAOYSA-N CCCCNC(NCCSCCNC(NCCCC)=S)=S Chemical compound CCCCNC(NCCSCCNC(NCCCC)=S)=S FFVFNEVZDBBJPR-UHFFFAOYSA-N 0.000 description 1
- TYXCIRTZWQJIBD-UHFFFAOYSA-N CNC(NCCSCCNC(NC)=S)=S Chemical compound CNC(NCCSCCNC(NC)=S)=S TYXCIRTZWQJIBD-UHFFFAOYSA-N 0.000 description 1
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- 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
- C10M141/08—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 sulfur-, selenium- or tellurium-containing compound
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- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
- C10M103/02—Carbon; Graphite
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- C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
- C10M103/04—Metals; Alloys
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
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- C10M2203/1025—Aliphatic fractions used as base material
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- C10M2215/24—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions having hydrocarbon substituents containing thirty or more carbon atoms, e.g. nitrogen derivatives of substituted succinic acid
- C10M2215/28—Amides; Imides
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Definitions
- the present invention relates to a lubricating oil composition. More particularly, the present invention relates to a lubricating oil composition that is particularly useful for internal combustion engines such as gasoline engines, diesel engines, and gas engines.
- an oxidation catalyst In current engines such as automobiles, an oxidation catalyst, a three-way catalyst, a NO x storage-type reduction catalyst, a diesel particulate filter (DPF), and the like are used 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 in order to prevent deterioration of the device. Yes.
- zinc dithiophosphate has been used for many years as an antiwear and antioxidant for internal combustion engine lubricants used in gasoline engines, diesel engines, gas engines, etc. It is considered an important essential additive for lubricating oils.
- zinc dithiophosphate generates sulfuric acid and phosphoric acid when decomposed, the basic compound in the engine oil is consumed to promote deterioration of the lubricating oil, and the oil renewal period may be extremely shortened.
- zinc dithiophosphate may become sludge under high temperature conditions and deteriorate cleanliness inside the engine.
- zinc dithiophosphate contains a large amount of phosphorus and sulfur as well as a metal (zinc) in the molecule, it is considered to cause an adverse effect on the exhaust gas purification device. Therefore, it is desired to develop a lubricating oil composition having excellent wear resistance without using zinc dithiophosphate.
- Patent Documents 1 to 3 describe lubricating oil additives and lubricating oil compositions mainly composed of a disulfide compound having a specific structure.
- Patent Document 4 describes a triazine compound as a lubricant additive.
- Patent Document 5 describes a lubricating oil containing a thiadiazole compound.
- the present invention has been made in view of the above circumstances, and an object thereof is to provide a lubricating oil composition that is excellent in deposit resistance, corrosion resistance, and wear resistance even with low phosphorus content and low sulfated ash content. is there.
- a lubricating oil composition comprising a base oil and a succinimide compound and at least one selected from the following (A) to (C): (A) A sulfur-containing compound represented by the following general formula (I).
- R 1 and R 2 are each independently a hydrogen atom; a hydrocarbon group having 1 to 50 carbon atoms selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group and an aryl group;
- a hydrogen atom represents a heteroatom-containing group having 1 to 50 carbon atoms, which contains an atom selected from an oxygen atom, a nitrogen atom and a sulfur atom, and each Y independently represents —O—, —S—, —SO—.
- R 3 to R 12 are each independently a hydrogen atom; a hydrocarbon group having 1 to 50 carbon atoms selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group and an aryl group;
- a hydrogen atom represents a heteroatom-containing group having 1 to 50 carbon atoms, which contains an atom selected from an oxygen atom, a nitrogen atom and a sulfur atom, and each Y independently represents —O—, —S—, —SO—.
- x and y each independently represents 0.
- Integers of ⁇ 2, u and r each independently represent an integer of 0 to 3, t and w each independently represent an integer of 0 to 3.
- v represents an integer of 0 to 5.
- P is 1
- v is an integer of 0 to 3.
- n and m are each independently 0 or 1
- k is an integer of 0 to 3, and when p is 0, x, y, n , M and v are not simultaneously 0.
- R 13 to R 16 are each independently a hydrogen atom bonded to a carbon atom; a hydrocarbon group having 1 to 50 carbon atoms; an amino group, an amide group, an ether group, a thioether group.
- a lubricating oil composition that is excellent in deposit resistance, corrosion resistance and wear resistance even with low phosphorus content and low sulfated ash content.
- the lubricating oil composition of the present invention is characterized in that a base oil is blended with a succinimide compound and one or more selected from the following (A) to (C).
- 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 carrying out 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.
- polyolefins and polyol esters are particularly preferable.
- the said mineral oil may be used individually by 1 type as a base oil, and may be used in combination of 2 or more type.
- the said synthetic oil may be used 1 type and may be used in combination of 2 or more type.
- one or more mineral oils and one or more synthetic oils may be used in combination.
- the viscosity of the base oil is not particularly limited, but the kinematic viscosity at 100 ° C. is preferably in the range of 2 to 30 mm 2 / s, more preferably in the range of 3 to 15 mm 2 / s, and still more preferably in the range of 4 to The range is 10 mm 2 / s.
- the kinematic viscosity at 100 ° C. is 2 mm 2 / s or more, the evaporation loss is small, and when it is 30 mm 2 / s or less, the power loss due to the viscous resistance is suppressed, and the fuel efficiency improvement effect is obtained.
- % 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.
- a more preferable% C A is 1.0 or less, further 0.5 or less, and 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.
- a base oil having a viscosity index of 70 or more has a small viscosity change due to a change in temperature.
- succinimide compound examples include a monotype succinimide compound represented by the following general formula (IV) or a bis type succinimide compound represented by the following general formula (V). It is done.
- R 17 , R 19 and R 22 are each an alkenyl group or alkyl group having a number average molecular weight of 500 to 4,000, and R 19 and R 22 are the same or different. May be.
- the number average molecular weights of R 17 , R 19 and R 22 are preferably 1,000 to 4,000. If the number average molecular weight of R 17 , R 19 and R 22 is 500 or more, the solubility in the base oil is good, and if it is 4,000 or less, the dispersibility does not deteriorate.
- R 18 , R 20 and R 21 are each an alkylene group having 2 to 5 carbon atoms, R 20 and R 21 may be the same or different, r is an integer of 1 to 10, and s is 0 or an integer of 1 to 10 is shown.
- 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 view of dispersibility and solubility in base oil.
- alkenyl group examples include a polybutenyl group, a polyisobutenyl group, and an ethylene-propylene copolymer
- alkyl group is a hydrogenated form 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.
- succinimide compound an alkenyl succinimide compound such as polybutenyl succinimide or an alkyl succinimide compound is preferably used.
- the alkenyl succinimide compound or the alkyl succinimide compound is generally an alkenyl succinic anhydride obtained by reaction of polyolefin and maleic anhydride, or an alkyl succinic anhydride obtained by hydrogenating it, and a polyamine. 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 forming the polyolefin one or two or more kinds of ⁇ -olefins having 2 to 8 carbon atoms can be mixed and used, and a mixture of isobutene and 1-butene 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.
- diamines such as ethylenediamine, propylenediamine, butylenediamine, and pentylenediamine
- diethylenetriamine triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di (methylethylene) triamine, dibutylenetriamine
- polyalkylene polyamines such as tributylenetetramine and pentapentylenehexamine
- piperazine derivatives such as aminoethy
- the succinimide compound in addition to the alkenyl or alkyl succinimide compound, a boron derivative thereof and / or a compound 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 make 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 usually in the range of 0.05 to 5% by mass, preferably 0.1 to 3% by mass as boron.
- the blending amount of the succinimide compound is preferably in the range of 0.5 to 15% by mass, more preferably in the range of 1 to 10% by mass, and further preferably 3 to 7% by mass based on the total amount of the lubricating oil composition. % Range.
- the blending amount of the succinimide compound is 0.5% by mass or more, the deposit resistance of the lubricating oil composition is sufficiently improved.
- the low temperature fluidity of the lubricating oil composition is obtained. Will greatly improve.
- the component (A) is a sulfur-containing compound represented by the following general formula (I), and the component (B) is a sulfur compound represented by the following general formula (II).
- R 1 and R 2 are each independently a hydrogen atom; a hydrocarbon group having 1 to 50 carbon atoms selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group and an aryl group;
- a hydrogen atom represents a heteroatom-containing group having 1 to 50 carbon atoms, which contains an atom selected from an oxygen atom, a nitrogen atom and a sulfur atom, and each Y independently represents —O—, —S—, —SO—.
- R 3 to R 12 are each independently a hydrogen atom; a hydrocarbon group having 1 to 50 carbon atoms selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group and an aryl group;
- a hydrogen atom represents a heteroatom-containing group having 1 to 50 carbon atoms, which contains an atom selected from an oxygen atom, a nitrogen atom and a sulfur atom, and each Y independently represents —O—, —S—, —SO—.
- the alkyl group represented by R 1 to R 12 is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 24 carbon atoms.
- Specific examples of the alkyl group include, for example, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups. And various octadecyl groups and various icosyl groups.
- the alkyl group may be substituted with an aromatic group, and examples thereof include a benzyl group and a phenethyl group.
- the cycloalkyl group represented by R 1 to R 12 is preferably a cycloalkyl group having 3 to 30 carbon atoms, and more preferably a cycloalkyl group having 3 to 24 carbon atoms.
- cycloalkyl group examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a diethylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylethylcyclohexyl group.
- a diethylcyclohexyl group examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a diethylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, and
- the cycloalkyl group may be substituted with an aromatic group, and examples thereof include a phenylcyclopentyl group and a phenylcyclohexyl group.
- the alkenyl group represented by R 1 to R 12 is preferably an alkenyl group having 2 to 30 carbon atoms, and more preferably an alkenyl group having 2 to 24 carbon atoms.
- alkenyl group examples include, for example, vinyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methylvinyl group, 1-methylallyl group, 1,1-dimethylallyl group, 2 -Methylallyl group, nonenyl group, decenyl group, octadecenyl group and the like.
- the alkenyl group may be substituted with an aromatic group.
- the cycloalkenyl group represented by R 1 to R 12 is preferably a cycloalkenyl group having 3 to 30 carbon atoms, and more preferably a cycloalkenyl group having 3 to 24 carbon atoms.
- cycloalkenyl group examples include a cyclobutenyl group and a methylcyclobutenyl group.
- the cycloalkenyl group may be substituted with an aromatic group.
- the aryl group represented by R 1 to R 12 is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 24 carbon atoms.
- Specific examples of the aryl group include phenyl group, tolyl group, xylyl group, naphthyl group, butylphenyl group, octylphenyl group, nonylphenyl group and the like.
- Y independently represents —O—, —S—, —SO—, —SO 2 —, — (C ⁇ O) O—, — (C ⁇ O) NH.
- X1 and X2 are integers of 1 to 3, and 1 is preferable.
- n is each independently an integer of 1 to 5, preferably 1 or 2.
- Examples of the sulfur-containing compound represented by the general formula (I) include compounds represented by the following formulas.
- x represents an integer of 1 to 3.
- sulfur-containing compound represented by the general formula (II) include tetramethyl dithiomalate, tetraethyl dithiomalate, tetra-1-propyl dithiomalate, tetra-2-propyl dithiomalate, and tetra-1-butyl dithiomalate.
- Disulfide tetramethyl thiomalate, tetraethyl thiomalate, tetra-1-propyl thiomalate, tetra-2-propyl thiomalate, tetra-1-butyl thiomalate, tetra-2-butyl thiomalate, tetraisobutyl thiomalate, thiomalate Tetra-1-hexyl, tethiothiomalate -1-octyl, tetra-1- (2-ethyl) hexyl thiomalate, tetra-1- (3,5,5-trimethyl) hexyl thiomalate, tetra-1-decyl thiomalate, tetra-1-dodecyl thiomalate , Tetra-1-hexadecyl thiomalate, tetra-1-octadecyl thio
- the component (C) is a heterocyclic compound that may have a double bond in the cyclic portion represented by the following general formula (III), or the heterocyclic compound, a boron compound, a molybdenum compound, and a silicon compound. It is a reaction product with a selected compound.
- X 1 , X 2 , X 3 and X 4 each independently represent N or NH, O or S, and p represents 0 or 1.
- x and y each independently represents 0.
- Integers of ⁇ 2, u and r each independently represent an integer of 0 to 3, t and w each independently represent an integer of 0 to 3.
- v represents an integer of 0 to 5.
- P is 1, v is an integer of 0 to 3.
- n and m are each independently 0 or 1
- k is an integer of 0 to 3, and when p is 0, x, y, n , M and v are not simultaneously 0.
- R 13 to R 16 are each independently a hydrogen atom bonded to a carbon atom; a hydrocarbon group having 1 to 50 carbon atoms; an amino group, an amide group, an ether group, a thioether group. , A functional group having 1 to 50 carbon atoms selected from a dithioether group and a carboxyl group; or selected from the functional groups That shows the total hydrocarbon group having a carbon number of 1 to 150 having at least one substituent, and when p is 0, R 13 and R 14 are not a hydrogen atom at the same time, when p is 1, R 13 R 16 is not simultaneously a hydrogen atom Y 1 and Y 2 are each independently a hydrogen atom, halogen atom, amino group, amide group, hydroxyl group, carbonyl group, aldehyde group, carboxyl group, ester group and ether A functional group having 1 to 50 carbon atoms selected from the group; or a hydrocarbon group or heterocycle having a total carbon number of 1 to 150 which may have at least
- X 1 , X 2 , and X 3 each independently represent N, NH, O, or S.
- x and y each independently represents an integer of 0 to 2
- v represents an integer of 0 to 5.
- n and m are each independently 0 or 1, and x, y, n, m and v are not 0 simultaneously.
- R 13 and R 14 are each independently selected from a hydrogen atom bonded to a carbon atom; a hydrocarbon group having 1 to 50 carbon atoms; an amino group, an amide group, an ether group, a thioether group, a dithioether group, and a carboxyl group A functional group having 1 to 50 carbon atoms; or a hydrocarbon group having 1 to 150 carbon atoms having at least one substituent selected from the functional groups, and R 13 and R 14 are simultaneously hydrogen atoms. There is nothing.
- X 1 , X 2 , X 3 and X 4 each independently represent N, NH, O or S.
- x and y are each independently an integer of 0 to 2
- u and r are each independently an integer of 0 to 3
- t and w are each independently an integer of 0 to 3.
- v represents an integer of 0 to 3.
- n and m are each independently 0 or 1
- k is an integer of 0 to 3
- R 13 to R 16 are each independently a hydrogen atom bonded to a carbon atom; a hydrocarbon group having 1 to 50 carbon atoms; A functional group having 1 to 50 carbon atoms selected from an amino group, an amide group, an ether group, a thioether group, a dithioether group and a carboxyl group; or all carbons having at least one substituent selected from the functional groups Represents a hydrocarbon group of 1 to 150, and R 13 to R 16 do not simultaneously become hydrogen atoms.
- Y 1 and Y 2 in the general formula (III) are each independently selected from hydrogen atom; halogen atom; amino group, amide group, hydroxyl group, carbonyl group, aldehyde group, carboxyl group, ester group and ether group.
- R 13 to R 16 in the general formula (III) are preferably a hydrogen atom or a hydrocarbon group having 1 to 150 carbon atoms, a thioether group or a dithioether group, more preferably a hydrocarbon group having 1 to 150 carbon atoms. It is.
- a hydrocarbon group such as a polybutene group, which may be linear or branched, saturated or unsaturated.
- hydrocarbons having 8 to 30 carbon atoms such as octyl, 2-ethylhexyl, decyl, dodecyl, dodecenyl, tetradecene, tetradecenyl, hexadecene, hexadecenyl, octadecyl, octadecenyl, oleyl, stearyl, isostearyl, dococenyl, decentrimer group, etc. It is a group.
- the heterocyclic compound represented by the general formula (III) is, for example, pyridine, pyrrole, pyrimidine, pyrazole, pyridazine, imidazole, pyrazine, triazine, triazole, tetrazole, oxazole, oxadiazole, thiazole, which is the basic skeleton of the heterocyclic ring.
- the reaction of (a) and (b) is carried out at room temperature to 200 ° C, preferably 50 to 150 ° C.
- the reaction may be performed without a catalyst or in the presence of a catalyst.
- organic solvents such as hexane, toluene, xylene, tetrahydrofuran (THF), dimethylformamide (DMF), can also be used, for example.
- a triazole compound is obtained by a reaction of a corresponding amine compound and a diacyl hydrazine, or a reaction of a corresponding aminoguanidine derivative and an acid derivative.
- a thiadiazole compound is obtained by a reaction of a corresponding sulfur compound and a diacyl hydrazine. Further, it can also be obtained by forming a heterocyclic ring by a trimerization reaction of a corresponding nitrile compound.
- the basic skeleton of the heterocyclic ring is a saturated or unsaturated compound in which one ring has a total number of nitrogen and / or oxygen and / or sulfur of 1 to 4.
- Such cyclic compounds include pyridine, pyrrole, pyrimidine, pyrazole, pyridazine, imidazole, pyrazine, triazine, triazole, tetrazole, oxazole, oxadiazole, thiazole, thiadiazole, furan, dioxane, pyran, thiophene and their derivatives. Can be mentioned.
- pyridine, pyrrole, pyrimidine, pyrazole, pyridazine, imidazole, pyrazine, triazine, triazole, tetrazole, oxazole, oxadiazole, thiadiazole, furan, dioxane, pyran, and derivatives thereof may be mentioned.
- These may be monocyclic compounds as described above, for example, polycyclic cyclic compounds such as indole, indazole, benzotriazole, benzimidazole, purine, quinoline, isoquinoline, naphthyridine, carbazole, naphthimidazole, etc. It doesn't matter.
- a hydrocarbon group or an amine, amide, alcohol, ketone, aldehyde, carboxylic acid, ester, ether, thioether, dithioether, halogen or a hydrocarbon compound containing them may be added to the heterocyclic compound as a functional group.
- Hydrocarbon groups or amines, amides, alcohols, ketones, aldehydes, carboxylic acids, esters, ethers, thioethers, dithioethers and hydrocarbon compounds containing them may be added.
- Examples of functional groups added to the heterocyclic compound include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups; amino groups, methylamino groups, ethylamino groups, dimethylamino groups, Substituted or unsubstituted amino groups such as diethylamino group and aminomethyl group; carbamoyl group; hydroxyl group, hydroxymethyl group, hydroxyethyl group; carboxymethyl group, carboxyethyl group; ethoxyl group, propoxyl group; methoxycarbonyl group, ethoxycarbonyl Group: methylcarbonyl group, ethylcarbonyl group; acetoxyl group, propoxyl group, butyroylxyl group; formyl group; halogen; sulfide group such as alkylthio group, alkyldithio group, disulfide group; diethylenetriamine, triethylenet
- alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; substituted or unsubstituted amino groups such as amino group, methylamino group, ethylamino group, dimethylamino group and diethylamino group Groups; sulfide groups such as alkylthio groups and alkyldithio groups, and disulfide groups.
- Examples of the compound (b) include 2-decyl-1-bromotetradecane, 2-butyl-1-bromooctane, 2-pentyl-1-bromononane, 2-hexyl-1-bromodecane, 2-heptyl-1-bromoundecane, 2-octyl-1-bromododecane, 2-nonyl-1-bromotridecane, 2,4-dioctyl-1-bromotetradecane, bromopolybutane, bromooctane, bromododecane, bromododecane, bromotetradecane, bromohexadecane, bromo Bromine compounds such as octadecane, bromoeicosane, bromodocosane, bromotetracosane, bromoheptadecene, bromoisostearyl, 2-decyl-1-chlorotetradecane, 2-but
- the cyclic structure moiety when p is 0 or the two cyclic structure moieties when p is 1 is derived from the compound (a). At least one of Y 1 and Y 2 is derived from the compound (b).
- the reaction product of the heterocyclic compound represented by the general formula (III) and the boric compound, which is the antiwear agent of the present invention has a molar ratio of boron compound to the heterocyclic compound obtained as described above. It is obtained by reacting at a ratio of 1: 0.01 to 10, preferably at a ratio of 1: 0.05 to 5.
- the reaction between the heterocyclic compound and the boron compound is carried out at 50 to 250 ° C., preferably 100 to 200 ° C.
- a solvent for example, an organic solvent such as hydrocarbon oil, hexane, heptane, octane, toluene, xylene or the like can be used.
- boron compound for example, boron oxide, boron halide, boric acid, boric anhydride, boric acid ester and the like can be used.
- the reaction product of the heterocyclic compound represented by the general formula (III) and the molybdenum compound, which is the antiwear agent of the present invention contains a molybdenum compound with respect to the heterocyclic compound obtained as described above. It is obtained by reacting at a molar ratio of 1: 0.01 to 10, preferably at a ratio of 1: 0.05 to 5.
- the reaction between the heterocyclic compound and the molybdenum compound is carried out at 50 to 250 ° C., preferably 100 to 200 ° C.
- a solvent for example, an organic solvent such as hydrocarbon oil, hexane, heptane, octane, toluene, xylene or the like can be used.
- the molybdenum compound for example, molybdenum oxide, molybdenum halide, molybdic acid, or the like can be used.
- the reaction product of the heterocyclic compound represented by the general formula (III) and the silicon compound, which is the antiwear agent of the present invention contains a silicon compound with respect to the heterocyclic compound obtained as described above. It is obtained by reacting at a molar ratio of 1: 0.01 to 10, preferably at a ratio of 1: 0.05 to 5.
- the reaction between the heterocyclic compound and the silicon compound is carried out at 50 to 250 ° C., preferably 100 to 200 ° C.
- a solvent for example, an organic solvent such as hydrocarbon oil, hexane, heptane, octane, toluene, xylene or the like can be used.
- the silicon compound for example, silicon oxide, silicon halide, silicic acid, silicate ester and the like can be used.
- the above components (A) to (C) may be used singly or in combination of two or more.
- the blending amount of the components (A) and (B) is preferably 0.01 to 5.0% by mass, more preferably 0.1 to 2.0% by mass based on the total amount of the composition. By being 0.01 mass% or more, sufficient deposit resistance and abrasion resistance are usually obtained, and when it exceeds 5.0 mass%, an effect commensurate with the added amount may not be obtained.
- the blending amount of the component (C) is 0.01 to 20% by mass, preferably 0.05 to 15% by mass, more preferably 0.1 to 10% by mass, based on the total amount of the composition. By making the blending amount 0.01% by mass or more, deposit resistance and wear resistance are exhibited, and by making the blending amount 20% by mass or less, an increase in cost is avoided and the original characteristics of the lubricating base oil are possessed. Can be prevented.
- additives may be blended within a range that does not impair the effect.
- the additive include an antioxidant, a metallic detergent, a viscosity index improver, a pour point depressant, a metal deactivator, a rust inhibitor, and an antifoaming agent.
- the antioxidant which does not contain phosphorus is preferable, for example, a phenolic antioxidant, an amine antioxidant, a molybdenum amine complex antioxidant, a sulfur type antioxidant, etc. are mentioned.
- 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 monoalkyl diphenylamines such as monooctyldiphenylamine and monononyldiphenylamine; 4,4′-dibutyldiphenylamine, 4,4′-dipentyldiphenylamine, 4,4′-dihexyldiphenylamine 4,4′-diheptyldiphenylamine, 4,4′-dioctyldiphenylamine, dialkyldiphenylamines such as 4,4′-dinonyldiphenylamine; tetrabutyldiphenylamine, tetrahexyldiphenylamine; polyoctyldiphenylamine, tetranonyldiphenylamine, etc.
- monoalkyl diphenylamines such as monooctyldiphenylamine and monononyldiphenylamine
- Alkyldiphenylamines and ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, and further butylphenyl- ⁇ -naphthylamine, pentylphenyl- ⁇ - Fuchiruamin, hexylphenyl - ⁇ - naphthylamine, heptylphenyl - ⁇ - naphthylamine, octylphenyl - ⁇ - naphthylamine, alkylated phenyl - ⁇ - naphthylamine, such as nonylphenyl - ⁇ - naphthylamine; and the like.
- dialkyldiphenylamine type and naphthylamine type are preferred.
- Examples of the molybdenum amine complex-based antioxidant include hexavalent molybdenum compounds, specifically those obtained by reacting molybdenum trioxide and / or molybdic acid with an amine compound, for example, in JP-A-2003-252887.
- a compound obtained by the described production method can be used. Although it does not restrict
- alkyl group having 1 to 30 carbon atoms such as methylamine, ethylamine, dimethylamine, diethylamine, methylethylamine, methylpropylamine and the like (these alkyl groups may be linear or branched).
- alkanol groups may be linear or branched; methylenediamine, ethylenediamine, propylene diene And alkylenediamines having 1 to 30 carbon atoms such as butylene diamine; polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine; undecyldiethylamine, undecyldiethanolamine, dodecyldipropanolamine , Oleyldiethanolamine, oleylpropylenediamine, stearyltetraethylenepentamine and other monoamines, diamines, polyamines having an alkyl or alkenyl group having 8 to 20 carbon atoms, and heterocyclic compounds such as imidazoline; alkylene oxides of these compounds And adducts; and mixtures thereof.
- Examples thereof include sulfur-containing molybdenum complexes of succinimide described in JP-B-3-22438 and JP-A-2004-2866. Specifically, the following steps (m) and (n) Can be manufactured.
- step (m) The product of step (m) is subjected to at least one stripping or sulfiding step or both steps.
- the molybdenum complex is diluted with isooctane and measured with a UV-visible spectrophotometer in a quartz cell having an optical path length of 1 centimeter with a constant molybdenum concentration of 0.00025 g molybdenum per g diluted molybdenum complex, a wavelength of 350 Taking sufficient time to give a molybdenum complex having an absorbance at the nanometer of less than 0.7, and maintaining the temperature of the reaction mixture in the stripping or sulfiding step below about 120 ° C.
- the molybdenum complex can also be produced by the following steps (o), (p) and (q).
- the product obtained is at a temperature of about 120 ° C. or less, the molar ratio of sulfur to molybdenum is about 1: 1 or less, and the molybdenum complex diluted with isooctane is diluted with 0 molybdenum / g molybdenum complex.
- 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 in the range of 0.1 to 5% by mass and more preferably in the range of 0.1 to 3% by mass based on the total amount of the composition.
- the compounding amount of the molybdenum complex is preferably 10 to 1000 ppm by mass, more preferably 30 to 800 ppm by mass, and further preferably 50 to 500 ppm by mass in terms of molybdenum based on the total amount of the composition.
- 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. Examples thereof include a mixture of two or more selected from the inside.
- 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, particularly a magnesium salt, and And / or calcium salts, among which calcium salts are preferably used.
- alkaline earth metal phenate 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 salicylates 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 is preferably an alkyl group having 4 to 30 carbon atoms, more preferably a linear or branched alkyl group having 6 to 18 carbon atoms, which are linear or branched. But you can. 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
- the metal detergent used in the present invention is preferably an alkaline earth metal salicylate or alkaline earth metal phenate for the purpose of reducing the sulfur content in the composition, and more preferably an overbased salicylate or an overbased phenate, In particular, overbased calcium salicylate is preferred.
- the total base number of the metal detergent used in the present invention is preferably in the range of 10 to 500 mgKOH / g, more preferably in the range of 15 to 450 mgKOH / g, and one or more selected from these are used in combination. be able to.
- 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 invention is not particularly limited in its metal ratio, and usually 20 or less can be used singly or in combination of two or more, but preferably the metal ratio is 3 or less. It is particularly preferable to use a metal detergent having a viscosity of 1.5 or less, particularly preferably 1.2 or less, because it is excellent in oxidation stability, base number maintenance, high-temperature cleanability and the like.
- the metal ratio here is expressed by the valence of the metal element in the metal-based detergent ⁇ the metal element content (mol%) / the soap group content (mol%).
- the metal elements are calcium, magnesium, and the like.
- the soap group means a sulfonic acid group, a phenol group, a salicylic acid group, and the like.
- the blending amount of the metallic detergent is preferably in the range of 0.01 to 20% by mass, more preferably in the range of 0.1 to 10% by mass, and 0.5 to 5% by mass based on the total amount of the lubricating oil composition.
- the range of is more preferable.
- 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
- the metal type detergent contains said prescribed amount, you may use it individually or in combination of 2 or more types.
- overbased calcium salicylate or overbased calcium phenate is particularly preferable in the metal detergent, and the polybutenyl succinic acid bisimide is particularly preferable in the ashless dispersant.
- the total base number of the overbased calcium salicylate and the overbased calcium phenate is preferably in the range of 100 to 500 mgKOH / g, more preferably in the range of 200 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 in the range of 0.5 to 15% by mass, more preferably in the range of 1 to 10% by mass, 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 5000 to 50,000.
- the blending amount of the pour point depressant is preferably in the range of 0.1 to 2 mass%, more preferably in the range of 0.1 to 1 mass%, based on the total amount of the lubricating oil composition, from the viewpoint of the blending effect.
- the metal deactivator examples include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.
- the compounding amount of the metal deactivator is preferably in the range of 0.01 to 3% by mass, more preferably in the range of 0.01 to 1% by mass, based on the total amount of the lubricating oil composition.
- rust preventive examples include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinate, polyhydric alcohol ester and the like.
- the blending amount of these rust inhibitors is preferably in the range of 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of the blending effect.
- the antifoaming agent examples include silicone oil, fluorosilicone oil, and fluoroalkyl ether.
- the blending amount is 0.00 on the basis of the total amount of the lubricating oil composition from the viewpoint of balance of antifoaming effect and economy.
- the range of 005 to 0.5% by mass is preferable, and the range of 0.01 to 0.2% by mass is more preferable.
- a friction modifier In the lubricating oil composition of the present invention, a friction modifier, an antiwear agent, and an extreme pressure agent may be further blended as necessary.
- this friction modifier refers to compounds other than the polar group containing compound which is an essential component of this invention.
- the blending amount of the friction modifier is preferably in the range of 0.01 to 2% by mass, more preferably in the range of 0.01 to 1% by mass, 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, and disulfides (represented by general formula (I) or (II) used in the present invention).
- dibenzyl disulfide sulfur-containing compounds such as sulfurized olefins, sulfurized fats and oils, sulfurized esters, thiocarbonates, thiocarbamates, polysulfides; Phosphorus esters, phosphate esters, phosphonate esters, and phosphorus-containing compounds such as amine salts or metal salts thereof; thiophosphite esters, thiophosphate esters, thiophosphonate esters, and amines thereof Sulfur and phosphorus containing antiwear agents such as salts or metal salts; That.
- sulfur-containing compounds such as sulfurized olefins, sulfurized fats and oils, sulfurized esters, thiocarbonates, thiocarbamates, polysulfides; Phosphorus esters, phosphate esters, phosphonate esters, and phosphorus-containing compounds such as amine salts or metal salts thereof; thiophosphite esters, thiophosphate esters
- the lubricating oil composition of the present invention is composed of the above-mentioned composition, but preferably satisfies the following as its properties.
- the sulfated ash content (JIS K2272) is 0.6% by mass or less, more preferably 0.1% by mass or less.
- the phosphorus content (JIS-5S-38-92) is 0.05% by mass or less, more preferably 0.02% by mass or less, and still more preferably 0% by mass. In addition to the above, it is more preferable to satisfy the following.
- Sulfur content (JIS K2541) is 0.4 mass% or less, More preferably, it is 0.2 mass% or less.
- the boron content is 0.4% by mass or less, more preferably 0.2% by mass or less.
- the lubricating oil composition of the present invention that satisfies these 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 invention uses polybutenyl succinimide in combination with the above components (A) to (C), and as a result of this combination, no deposit resistance is obtained when each is used alone. Sex is expressed. Therefore, it is possible to obtain a lubricating oil composition having a sufficiently excellent lubricating performance without blending zinc dithiophosphate, which has been conventionally used as a lubricating oil additive, and to achieve the properties such as sulfate ash. It becomes easy.
- the lubricating oil composition of the present invention is preferably 2 or less in a copper plate corrosion test (measurement conditions: 100 ° C., 3 hours) specified in JIS K 2513. If the copper plate corrosion test is 2 or less, the heat resistance of the hydraulic fluid composition is good and has the effect of suppressing the generation of sludge. A copper plate corrosion test of 1 is more preferable.
- the lubricating oil composition of the present invention can be preferably used as a lubricating oil for internal combustion engines such as motorcycles, automobiles, gasoline engines for power generation, marine use, diesel engines, gas engines, etc., and has a low phosphorus content and low sulfur content. Therefore, it is particularly suitable for an internal combustion engine equipped with an exhaust gas purification device.
- the lubricating oil composition of the present invention is also suitably used in applications other than those described above.
- the lubricating oil composition of the present invention exhibits excellent wear resistance and friction reduction effects, for example, an internal combustion engine, an automatic transmission, a continuously variable transmission, a manual transmission, a power steering, a shock absorber, and a compressor Used for lubrication of refrigerant compressors, refrigerators, hydraulic pumps, clutch pulleys and the like.
- the lubricating oil composition of the present invention comprises an internal combustion engine oil, an automatic transmission oil, a continuously variable transmission oil, a manual transmission oil, a power steering oil, a shock absorber oil, a compressor oil, a refrigerating machine oil, a hydraulic pump oil, and a clutch pulley lubrication. It can be used for oil and grease.
- Hot tube test The test temperature was set to 300 ° C., and the other conditions were measured in accordance with JPI-5S-55-99. In accordance with JPI-5S-55-99, the glass tube after the test was evaluated in 11 stages from 0 (black) to 10 (colorless). The higher the number, the better the deposit resistance.
- Copper plate corrosion test The test temperature was 100 ° C., the test time was 3 hours, and the other conditions were evaluated according to JIS K 2513 in the following four stages. The lower the number, the better the corrosion resistance.
- Lubricating oil compositions were prepared by blending the base oils and additives shown in Tables 1 and 2 in the proportions shown in Tables 1 and 2. The properties, composition and performance of the composition are shown in Tables 1 and 2.
- Base oil hydrorefined base oil, 40 ° C. kinematic viscosity 21 mm 2 / s, 100 ° C. kinematic viscosity 4.5 mm 2 / s, viscosity index 127,% C A 0.0, sulfur content less than 20 ppm by mass, NOACK evaporation Amount 13.3% by mass
- Polybutenyl succinic acid monoimide number average molecular weight of polybutenyl group 1000, nitrogen content 1.76% by mass, boron content 1.9% by mass
- Zinc dialkyldithiophosphate Zn content 9.0% by mass, phosphorus content 8.2% by mass, sulfur content 17.1% by mass, alkyl group; mixture compound A of secondary butyl group and secondary hexyl group : Bis (n-octoxycarbonylmethyl) disulfide, sulfur content 15.2%
- Compound B bis (tridecyloxycarbonylethyl) sulfide, sulfur content 5.4%
- Compound C
- the lubricating oil compositions of Examples 1 to 13 are synergistic by combining polybutenyl succinic acid monoimide with a sulfur-containing compound, a heterocyclic compound or a reaction product thereof.
- the effect shows high deposit resistance, and also shows good corrosion resistance and a low wear scar diameter value.
- the effect of the present invention expressed by the above combined use is that polybutenyl succinic acid monoimide, sulfur-containing compound, heterocyclic compound or reaction product thereof Are not expressed even when used alone.
- the lubricating oil composition excellent in deposit resistance, corrosion resistance, and abrasion resistance is obtained.
- the lubricating oil composition of the present invention can be particularly preferably used as a lubricating oil composition for internal combustion engines such as gasoline engines, diesel engines, and gas engines.
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Abstract
Description
しかし、ジチオリン酸亜鉛は、分解すると硫酸やリン酸を発生するため、エンジン油中の塩基性化合物を消耗し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。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することがある。さらに、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、排出ガス浄化装置への悪影響の原因となることが考えられる。したがって、ジチオリン酸亜鉛を使用しなくても耐摩耗性に優れる潤滑油組成物の開発が望まれる。
すなわち本発明は、
1.基油に、コハク酸イミド化合物と、下記(A)~(C)から選択される1種以上とを配合してなる潤滑油組成物、
(A)下記一般式(I)で表される硫黄含有化合物。
(B)下記一般式(II)で表される硫黄含有化合物。
(C)下記一般式(III)で表される環状部分に二重結合を有していてもよい複素環化合物、あるいは該複素環化合物と、ホウ素化合物、モリブデン化合物及びケイ素化合物から選ばれる化合物との反応生成物。
2.リン含有量が0.5質量%以下であり、かつ、硫酸灰分が0.6質量%以下である上記1記載の潤滑油組成物、
3.リン含有量が0質量%であり、かつ、硫酸灰分が0.1質量%以下である上記1又は2記載の潤滑油組成物、
4.前記一般式(I)において、X1が1である上記1~3のいずれかに記載の潤滑油組成物、及び
5.後処理装置が装着されたエンジンに用いられる上記1~4のいずれかに記載の潤滑油組成物、
を提供するものである。
本発明において用いる基油としては、特に制限はなく、従来、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、あるいはワックスや、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。
本発明においては、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く、また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、さらには0.5以下であり、またより好ましい硫黄分は30質量ppm以下である。
本発明におけるコハク酸イミド化合物としては、例えば、下記一般式(IV)で表されるモノタイプのコハク酸イミド化合物、又は下記一般式(V)で表されるビスタイプのコハク酸イミド化合物が挙げられる。
上記R17、R19及びR22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以下であれば分散性が低下する恐れがない。
さらに一般式(V)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、分散性及び基油に対する溶解性の点で好ましい。
コハク酸イミド化合物としては、ポリブテニルコハク酸イミド等のアルケニルコハク酸イミド化合物や、アルキルコハク酸イミド化合物が好ましく用いられる。
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、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、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と酸化ホウ素、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には、特に制限はないが、ホウ素として、通常、0.05~5質量%の範囲、好ましくは0.1~3質量%の範囲である。
コハク酸イミド化合物の配合量が0.5質量%以上であると、潤滑油組成物の耐デポジット性が十分に改善し、一方、15質量%以下であると、潤滑油組成物の低温流動性が大幅に改善する。
前記(A)成分は、下記一般式(I)で表される硫黄含有化合物であり、前記(B)成分は、下記一般式(II)で表される硫黄化合物である。
R1~R12で表されるシクロアルキル基は、炭素数3~30のシクロアルキル基が好ましく、炭素数3~24のシクロアルキル基がより好ましい。シクロアルキル基の具体例としては、シクロプロピル基、シクロペンチル基、シクロへキシル基、メチルシクロペンチル基、ジメチルシクロペンチル基、メチルエチルシクロペンチル基、ジエチルシクロペンチル基、メチルシクロヘキシル基、ジメチルシクロヘキシル基、メチルエチルシクロヘキシル基およびジエチルシクロヘキシル基等が挙げられる。また、シクロアルキル基は芳香族基で置換されていてもよく、例えばフェニルシクロペンチル基、フェニルシクロヘキシル基等が挙げられる。
R1~R12で表されるアルケニル基は、炭素数2~30のアルケニル基が好ましく、炭素数2~24のアルケニル基がより好ましい。アルケニル基の具体例としては、例えばビニル基、アリル基、1-ブテニル基、2-ブテニル基、3-ブテニル基、1-メチルビニル基、1-メチルアリル基、1,1-ジメチルアリル基、2-メチルアリル基、ノネニル基、デセニル基、オクタデセニル基等が挙げられる。また、アルケニル基は芳香族基で置換されていてもよい。
R1~R12で表されるシクロアルケニル基は、炭素数3~30のシクロアルケニル基が好ましく、炭素数3~24のシクロアルケニル基がより好ましい。シクロアルケニル基の具体例としては、シクロブテニル基、メチルシクロブテニル基等が挙げられる。また、シクロアルケニル基は芳香族基で置換されていてもよい。
R1~R12で表されるアリール基は、炭素数6~30のアリール基が好ましく、炭素数6~24のアリール基がより好ましい。アリール基の具体例としては、フェニル基、トリル基、キシリル基、ナフチル基、ブチルフェニル基、オクチルフェニル基、ノニルフェニル基等が挙げられる。
一般式(I)および(II)において、X1及びX2は1~3の整数であり、1が好ましい。nはそれぞれ独立に1~5の整数であり、1または2が好ましい。
(1)pが0の場合
X1、X2、及びX3は、それぞれ独立にNもしくはNH、O又はSを示す。
x及びyは、それぞれ独立に0~2の整数、vは0~5の整数を示す。
n及びmは、それぞれ独立に0又は1、x、y、n、m及びvは同時に0にはならない。
R13及びR14は、それぞれ独立に炭素原子に結合する水素原子;炭素数1~50の炭化水素基;アミノ基、アミド基、エーテル基、チオエーテル基、ジチオエーテル基及びカルボキシル基の中から選ばれる炭素数1~50の官能基;あるいは該官能基の中から選ばれる少なくとも一種の置換基を有する全炭素数1~150の炭化水素基を示し、R13及びR14は同時に水素原子になることはない。
(2)pが1の場合
X1、X2、X3及びX4は、それぞれ独立にNもしくはNH、O又はSを示す。
x及びyは、それぞれ独立に0~2の整数、u及びrは、それぞれ独立に0~3の整数、t及びwは、それぞれ独立に0~3の整数を示す。vは0~3の整数を示す。
n及びmは、それぞれ独立に0又は1、kは0~3の整数を示し、R13~R16は、それぞれ独立に炭素原子に結合する水素原子;炭素数1~50の炭化水素基;アミノ基、アミド基、エーテル基、チオエーテル基、ジチオエーテル基及びカルボキシル基の中から選ばれる炭素数1~50の官能基;あるいは該官能基の中から選ばれる少なくとも一種の置換基を有する全炭素数1~150の炭化水素基を示し、R13~R16は同時に水素原子になることはない。
さらに好ましくは、オクチル、2-エチルヘキシル、デシル、ドデシル、ドデセニル、テトラデセン、テトラデセニル、ヘキサデセン、ヘキサデセニル、オクタデシル、オクタデセニル、オレイル、ステアリル、イソステアリル、ドコセニル、デセントリマー基等の炭素数8~30の炭化水素基である。
一般式(III)で表される複素環化合物は、例えば、複素環の基本骨格となるピリジン、ピロール、ピリミジン、ピラゾール、ピリダジン、イミダゾール、ピラジン、トリアジン、トリアゾール、テトラゾール、オキサゾール、オキサジアゾール、チアゾール、チアジアゾール、フラン、ジオキサン、ピラン、チオフェンを基本骨格とする化合物及びそれらの誘導体(a)と炭素数10~200のアルキル基、アルケニル基、シクロアルキル基を有するハロゲン化合物、アミン化合物、アルコール類、メルカプト類、エポキシ化合物及びカルボキシル基等の官能基を有する化合物(b)とをモル比(a):(b)を1:5~5:1、好ましくは、1:2~2:1の割合で反応させて得ることができる。
(a)と(b)の反応は、室温~200℃、好ましくは50~150℃で行う。
反応は、無触媒でも触媒の存在下で行なってもよい。
また、反応を行うに際して溶剤、例えば、ヘキサン、トルエン、キシレン、テトラヒドロフラン(THF)、ジメチルホルムアミド(DMF)等の有機溶剤を使用することもできる。
また、例えば、トリアゾール化合物は、対応するアミン化合物とジアシルヒドラジンの反応、あるいは、対応するアミノグアニジン誘導体と酸誘導体の反応により、チアジアゾール化合物は、対応する硫黄化合物とジアシルヒドラジンの反応により、トリアジン化合物は、対応するニトリル化合物の三量化反応により、複素環を形成して得ることもできる。
このような環状化合物としては、ピリジン、ピロール、ピリミジン、ピラゾール、ピリダジン、イミダゾール、ピラジン、トリアジン、トリアゾール、テトラゾール、オキサゾール、オキサジアゾール、チアゾール、チアジアゾール、フラン、ジオキサン、ピラン、チオフェン及びそれらの誘導体が挙げられる。
より好ましくは、ピリジン、ピロール、ピリミジン、ピラゾール、ピリダジン、イミダゾール、ピラジン、トリアジン、トリアゾール、テトラゾール、オキサゾール、オキサジアゾール、チアジアゾール、フラン、ジオキサン、ピラン、及びそれらの誘導体が挙げられる。
これらは、前記した単環の環状化合物であっても、例えば、インドール、インダゾール、ベンゾトリアゾール、ベンゾイミダゾール、プリン、キノリン、イソキノリン、ナフチリジン、カルバゾール、ナフトイミダゾール等の多環の環状化合物であってもかまわない。
また、複素環化合物に官能基として炭化水素基又はアミン、アミド、アルコール、ケトン、アルデヒド、カルボン酸、エステル、エーテル、チオエーテル、ジチオエーテル、ハロゲン及びそれらを含む炭化水素化合物が付加したものでもよいが、炭化水素基又はアミン、アミド、アルコール、ケトン、アルデヒド、カルボン酸、エステル、エーテル、チオエーテル、ジチオエーテル及びそれらを含む炭化水素化合物が付加したものがよい。
複素環化合物に付加する官能基の例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等のアルキル基;アミノ基、メチルアミノ基、エチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、アミノメチル基等の置換もしくは無置換のアミノ基;カルバモイル基;水酸基、ヒドロキシメチル基、ヒドロキシエチル基;カルボキシメチル基、カルボキシエチル基;エトキシル基、プロポキシル基;メトキシカルボニル基、エトキシカルボニル基;メチルカルボニル基、エチルカルボニル基;アセトキシル基、プロピオキシル基、ブチロイルキシル基;ホルミル基;ハロゲン;アルキルチオ基、アルキルジチオ基等のスルフィド基、ジスルフィド基;ジエチレントリアミン、トリエチレンテトラアミン、テトラエチレンペンタアミン等のポリエチレンポリアミン残基;アミノエチルピペラジン残基等が挙げられる。
好ましくは、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等のアルキル基;アミノ基、メチルアミノ基、エチルアミノ基、ジメチルアミノ基、ジエチルアミノ基等の置換もしくは無置換のアミノ基;アルキルチオ基、アルキルジチオ基等のスルフィド基、ジスルフィド基等が挙げられる。
これらは単独で用いてもよいし、2種類以上の混合物として用いてもよい。
Y1及びY2のうちの少なくとも一方は、化合物(b)に由来する。
複素環化合物とホウ素化合物との反応は、50~250℃、好ましくは100~200℃で行なわれる。
反応を行うに際して溶剤、例えば、炭化水素油、ヘキサン、ヘプタン、オクタン、トルエン、キシレン等の有機溶剤を使用することもできる。
ホウ素化合物としては、例えば、酸化ホウ素、ハロゲン化ホウ素、ホウ酸、ホウ酸無水物、ホウ酸エステルなどを使用することができる。
複素環化合物とモリブデン化合物との反応は、50~250℃、好ましくは100~200℃で行なわれる。
反応を行うに際して溶剤、例えば、炭化水素油、ヘキサン、ヘプタン、オクタン、トルエン、キシレン等の有機溶剤を使用することもできる。
モリブデン化合物としては、例えば、酸化モリブデン、ハロゲン化モリブデン、モリブデン酸などを使用することができる。
複素環化合物とケイ素化合物との反応は、50~250℃、好ましくは100~200℃で行なわれる。
反応を行うに際して溶剤、例えば、炭化水素油、ヘキサン、ヘプタン、オクタン、トルエン、キシレン等の有機溶剤を使用することもできる。
ケイ素化合物としては、例えば、酸化ケイ素、ハロゲン化ケイ素、ケイ酸、ケイ酸エステルなどを使用することができる。
上記(A)及び(B)成分の配合量は、組成物全量基準で、0.01~5.0質量%が好ましく、0.1~2.0質量%がより好ましい。0.01質量%以上であることで、通常、十分な耐デポジット性及び耐摩耗性が得られ、5.0質量%を超えた場合、添加量に見合った効果が得られない場合がある。
上記(C)成分の配合量は、組成物全量基準で、0.01~20質量%、好ましくは、0.05~15質量%、より好ましくは、0.1~10質量%である。配合量を0.01質量%以上とすることにより、耐デポジット性及び耐摩耗性が発揮され、20質量%以下とすることにより、コスト増を避け、かつ、潤滑油基油が有する本来の特性を低下させることを防止することができる。
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、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]などが挙げられる。
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、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、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、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、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;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、具体的には、以下の工程(m)および(n)により製造することができる。
(m)酸性モリブデン化合物又はその塩と、コハク酸イミド、カルボン酸アミド、炭化水素モノアミン、炭化水素ポリアミン、マンニッヒ塩基、ホスホン酸アミド、チオホスホン酸アミド、リン酸アミド、分散剤型粘度指数向上剤およびそれらの混合物からなる群より選ばれた塩基性窒素化合物とを、反応温度を約120℃以下に維持して反応させてモリブデン錯体を形成する工程。
(n)(m)の工程の生成物を少なくとも一回のストリッピング又は硫化工程または両工程にかける。ただし、モリブデン錯体をイソオクタンで希釈して、希釈したモリブデン錯体g当りモリブデン0.00025gの一定モリブデン濃度として、UV-可視分光光度計で光路長1センチメートルの石英セルで測定したときに、波長350ナノメータにおける吸光度が0.7未満であるモリブデン錯体を与えるのに充分な時間をかけ、かつストリッピング又は硫化工程における反応混合物の温度を約120℃以下に維持する工程。
また、このモリブデン錯体は、以下の工程(o)、(p)および(q)によっても製造することができる。
(o)酸性モリブデン化合物又はその塩と、コハク酸イミド、カルボン酸アミド、炭化水素モノアミン、炭化水素ポリアミン、マンニッヒ塩基、ホスホン酸アミド、チオホスホン酸アミド、リン酸アミド、分散剤型粘度指数向上剤およびそれらの混合物からなる群より選ばれた塩基性窒素化合物とを、反応温度を約120℃以下に維持して反応させてモリブデン錯体を形成する工程。
(p)(o)の工程の生成物を約120℃以下の温度でストリッピングする工程。
(q)得られた生成物を約120℃以下の温度で、硫黄とモリブデンのモル比が約1:1かそれ以下で、そしてモリブデン錯体をイソオクタンで希釈して希釈したモリブデン錯体g当りモリブデン0.00025gの一定モリブデン濃度にして、UV-可視分光光度計で光路長1センチメートルの石英セルで測定したときに、波長350ナノメータにおける吸光度が0.7未満であるモリブデン錯体を与えるのに充分な時間をかけて、硫化する工程。
酸化防止剤の配合量は、組成物全量基準で、通常0.1~5質量%の範囲が好ましく、0.1~3質量%の範囲がより好ましい。また、モリブデン錯体の配合量は、組成物全量基準でモリブデン量換算により、10~1000質量ppmが好ましく、30~800質量ppmがより好ましく、50~500質量ppmがさらに好ましい。
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、金属元素とはカルシウム、マグネシウム等、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。
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、0.5~15質量%の範囲が好ましく、より好ましくは1~10質量%の範囲である。
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、0.1~2質量%の範囲が好ましく、より好ましくは0.1~1質量%の範囲である。
金属不活性剤の配合量は、潤滑油組成物全量基準で、0.01~3質量%の範囲が好ましく、より好ましくは0.01~1質量%の範囲である。
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、0.01~1質量%の範囲が好ましく、より好ましくは0.05~0.5質量%である。
(1)硫酸灰分(JIS K2272)が、0.6質量%以下、より好ましくは0.1質量%以下であること。かつ、
(2)リン含有量(JIS-5S-38-92)が、0.05質量%以下、より好ましくは0.02質量%以下、さらに好ましくは0質量%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、0.4質量%以下、より好ましくは0.2質量%以下であること。
(4)ホウ素含有量が、0.4質量%以下、より好ましくは0.2質量%以下であること。
これらの性状を満たす本発明の潤滑油組成物は、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。
例に限定されるものではない。
<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。
JPI-5S-38-92に準拠して測定した。
(2)硫黄含有量
JIS K 2541に準拠して測定した。
(3)ホウ素含有量
JPI-5S-38-92に準拠して測定した。
(4)硫酸灰分
JIS K 2272に準拠して測定した。
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。JPI-5S-55-99に準拠して、試験後のガラス管を0点(黒色)~10点(無色)の11段階にて評価した。数字が高い程、耐デポジット性が良好であることを示す。
(6)銅板腐食試験
試験温度を100℃、試験時間を3時間とし、それ以外の条件はJIS K 2513に準拠し、下記4段階で評価した。数字が低いほど、耐腐食性が良好であることを示す。
1:わずかに変色
2:中程度に変色
3:濃く変色
4:腐食
(7)往復動摩擦試験
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0.042μm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10mm
・振動数:10Hz
・試験時間:30分
第1表及び第2表に示した基油及び添加剤を第1表及び第2表に示す割合で配合して、潤滑油組成物を調製した。その組成物の性状・組成及び性能を第1表及び第2表に示す。
基油: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、%CA0.0、硫黄含有量20質量ppm未満、NOACK蒸発量13.3質量%
ポリブテニルコハク酸モノイミド:ポリブテニル基の数平均分子量1000、窒素含有量1.76質量%、ホウ素含有量1.9質量%
ジアルキルジチオリン酸亜鉛:Zn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級ブチル基と第2級ヘキシル基の混合物
化合物A:ビス(n-オクトキシカルボニルメチル)ジスルフィド、硫黄含有量15.2%
化合物B:ビス(トリデシルオキシカルボニルエチル)スルフィド、硫黄含有量5.4%
化合物C:2,6-ジ-t-ブチル-4-(4,6-ビス(オクチルチオ)-1,3,5-トリアジン-2-イルアミノ)フェノール、硫黄含有量10.9%
化合物D:2,5-ビス(n-オクチルジチオ)-1,3,4-チアジアゾール、硫黄含有量33.5%
化合物E:5-(8-ヘプタデセニル)-3-アミノ-1,2,4-トリアゾール
化合物F:5-(8-ヘプタデセニル)-3-アミノ-1,2,4-トリアゾールのホウ酸反応物
化合物G:オレフィンサルファイド、硫黄含有量43%(日本ルーブリゾール製、商品名:Anglamol33)
化合物H:ジオクチルポリサルファイド、硫黄含有量39%(大日本インキ化学工業製、商品名:DAILUBE GS-440)
化合物I:硫化油脂、硫黄含有量10.4%
化合物J:メチレンビス(ジブチルジチオカーバメート)、硫黄含有量30.3%
また実施例1~13と比較例5~9との対比から分かるように、上記併用により発現する本願発明の効果は、ポリブテニルコハク酸モノイミド、硫黄含有化合物、複素環化合物又はその反応生成物をそれぞれ単独で用いても発現しない。
上記のように、ポリブテニルコハク酸イミドと、特定の硫黄含有化合物、特定の複素環化合物及びその反応生成物から選択される化合物とを併用することで、低リン分、低硫黄分、低硫酸灰分であっても耐デポジット性、耐腐食性及び耐摩耗性に優れる潤滑油組成物が得られる。
Claims (5)
- 基油に、コハク酸イミド化合物と、下記(A)~(C)から選択される1種以上とを配合してなる潤滑油組成物。
(A)下記一般式(I)で表される硫黄含有化合物。
(式中、R1及びR2はそれぞれ独立に、水素原子;アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基およびアリール基から選ばれる炭素数1~50の炭化水素基;またはこれらの炭化水素基中に酸素原子、窒素原子および硫黄原子から選ばれる原子を含んでなる炭素数1~50のヘテロ原子含有基を表す。Yはそれぞれ独立に、-O-、-S-、-SO-、-SO2-、-(C=O)O-、-(C=O)NH-、-O(C=O)NH-、-C(=O)-、-N(H)-、-NHCONH-、-N=N-、-NH-C(=NH)-NH-、-S-C(=O)-、-NH-C(=S)-および-NH-C(=S)-NH-から選ばれる二価の基を表す。X1は1~3の整数であり、nはそれぞれ独立に1~5の整数である。)
(B)下記一般式(II)で表される硫黄含有化合物。
(式中、R3~R12はそれぞれ独立に、水素原子;アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基およびアリール基から選ばれる炭素数1~50の炭化水素基;またはこれらの炭化水素基中に酸素原子、窒素原子および硫黄原子から選ばれる原子を含んでなる炭素数1~50のヘテロ原子含有基を表す。Yはそれぞれ独立に、-O-、-S-、-SO-、-SO2-、-(C=O)O-、-(C=O)NH-、-O(C=O)NH-、-C(=O)-、-N(H)-、-NHCONH-、-N=N-、-NH-C(=NH)-NH-、-S-C(=O)-、-NH-C(=S)-および-NH-C(=S)-NH-から選ばれる二価の基を表す。X2は1~3の整数である。)
(C)下記一般式(III)で表される環状部分に二重結合を有していてもよい複素環化合物、あるいは該複素環化合物と、ホウ素化合物、モリブデン化合物及びケイ素化合物から選ばれる化合物との反応生成物。
(一般式(III)中、X1、X2、X3及びX4は、それぞれ独立にNもしくはNH、O又はSを、pは0又は1を示す。x及びyは、それぞれ独立に0~2の整数、u及びrは、それぞれ独立に0~3の整数、t及びwは、それぞれ独立に0~3の整数を示す。pが0の場合、vは0~5の整数を示し、pが1の場合、vは0~3の整数を示す。n及びmは、それぞれ独立に0又は1、kは0~3の整数を示し、pが0の場合、x、y、n、m及びvは同時に0にはならない。R13~R16は、それぞれ独立に炭素原子に結合する水素原子;炭素数1~50の炭化水素基;アミノ基、アミド基、エーテル基、チオエーテル基、ジチオエーテル基及びカルボキシル基の中から選ばれる炭素数1~50の官能基;あるいは該官能基の中から選ばれる少なくとも一種の置換基を有する全炭素数1~150の炭化水素基を示し、pが0の場合、R13及びR14は同時に水素原子になることはなく、pが1の場合、R13~R16は同時に水素原子になることはない。Y1及びY2は、それぞれ独立に水素原子;ハロゲン原子;アミノ基、アミド基、水酸基、カルボニル基、アルデヒド基、カルボキシル基、エステル基及びエーテル基の中から選ばれる炭素数1~50の官能基;あるいは該官能基の中から選ばれる少なくとも一種の官能基を有していてもよい全炭素数が1~150の炭化水素基又はヘテロ環を示す。) - リン含有量が0.5質量%以下であり、かつ、硫酸灰分が0.6質量%以下である請求項1記載の潤滑油組成物。
- リン含有量が0質量%であり、かつ、硫酸灰分が0.1質量%以下である請求項1又は2記載の潤滑油組成物。
- 前記一般式(I)において、X1が1である請求項1~3のいずれかに記載の潤滑油組成物。
- 後処理装置が装着されたエンジンに用いられる請求項1~4のいずれかに記載の潤滑油組成物。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11753453.7A EP2546324B1 (en) | 2010-03-12 | 2011-03-10 | Lubricant composition |
| US13/583,738 US9309481B2 (en) | 2010-03-12 | 2011-03-10 | Lubricant composition |
| CN201180011349.XA CN102782103B (zh) | 2010-03-12 | 2011-03-10 | 润滑油组合物 |
| KR1020127023411A KR20130016210A (ko) | 2010-03-12 | 2011-03-10 | 윤활유 조성물 |
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| JP2010056646A JP2011190331A (ja) | 2010-03-12 | 2010-03-12 | 潤滑油組成物 |
| JP2010-056646 | 2010-03-12 |
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| Country | Link |
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| US (1) | US9309481B2 (ja) |
| EP (1) | EP2546324B1 (ja) |
| JP (1) | JP2011190331A (ja) |
| KR (1) | KR20130016210A (ja) |
| CN (1) | CN102782103B (ja) |
| WO (1) | WO2011111795A1 (ja) |
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| JPWO2019177125A1 (ja) * | 2018-03-14 | 2021-02-25 | 出光興産株式会社 | 潤滑油組成物 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20130016210A (ko) | 2013-02-14 |
| EP2546324A1 (en) | 2013-01-16 |
| EP2546324A4 (en) | 2016-06-29 |
| US9309481B2 (en) | 2016-04-12 |
| EP2546324B1 (en) | 2021-04-21 |
| US20130005624A1 (en) | 2013-01-03 |
| CN102782103B (zh) | 2015-04-29 |
| CN102782103A (zh) | 2012-11-14 |
| JP2011190331A (ja) | 2011-09-29 |
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