WO2014136970A1 - 潤滑油組成物 - Google Patents
潤滑油組成物 Download PDFInfo
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- WO2014136970A1 WO2014136970A1 PCT/JP2014/056068 JP2014056068W WO2014136970A1 WO 2014136970 A1 WO2014136970 A1 WO 2014136970A1 JP 2014056068 W JP2014056068 W JP 2014056068W WO 2014136970 A1 WO2014136970 A1 WO 2014136970A1
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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
- C10M141/12—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 compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- 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
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/028—Overbased salts thereof
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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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- C10M2207/28—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
- C10M2209/084—Acrylate; Methacrylate
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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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- C10M2215/223—Five-membered rings containing nitrogen and carbon only
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/28—Amides; Imides
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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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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- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/066—Organic compounds derived from inorganic acids or metal salts derived from Mo or W
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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C10N2030/42—Phosphor free or low phosphor content compositions
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- C10N2040/25—Internal-combustion engines
Definitions
- the present invention relates to a lubricating oil composition used for internal combustion engines such as diesel engines, gasoline engines, gas engines, and hybrid vehicle engines.
- pistons made of aluminum alloy have a thermal and mechanical endurance temperature of about 350 ° C. and a large amount of thermal expansion. Therefore, there is an improvement in response to the recent demand for higher output and lower fuel consumption of automobile engines.
- a cast iron piston having a thermal and mechanical endurance temperature of up to about 400 ° C. is partially employed.
- the cast iron piston has higher durability than a piston made of an aluminum alloy and also has good seizure resistance because graphite contained in the cast iron has self-lubricating properties.
- cast iron pistons are more likely to cause engine performance degradation because they have higher wear and lower cleanliness due to the high temperature near the piston top dead center than aluminum alloys.
- the present invention can prevent deterioration in engine performance even when used in an internal combustion engine for automobiles that can achieve higher output and lower fuel consumption by increasing the thermal and mechanical durability temperatures than in the past.
- An object of the present invention is to provide a lubricating oil composition capable of satisfying both the durability and the durability.
- the present inventor can solve the above-mentioned problems by mixing them under specific conditions in a lubricating oil composition having a base oil, a dispersant, and a metallic detergent. As a result, the present invention has been completed.
- the lubricating oil composition according to the present invention comprises a base oil containing at least one selected from mineral oil and synthetic oil, having a viscosity index of 120 or more, and a paraffin content by ring analysis of 70% or more, and (A ) A dispersant containing at least one compound selected from alkenyl succinimide, alkenyl succinimide borate, alkyl succinimide, and alkyl succinimide borate, and (B) alkali metal sulfonate, alkali A metal detergent containing at least one compound selected from metal phenate, alkali metal salicylate, alkaline earth metal sulfonate, alkaline earth metal phenate, and alkaline earth metal salicylate, and component (A) Is 0.01% by mass or more and 0.10% by mass or less in terms of nitrogen content based on the total composition And (B) component is contained in an amount of 0.01% by mass or more and 0.3% by mass or less in terms of metal content based
- the method for producing a lubricating oil composition according to the present invention includes a base oil containing at least one selected from mineral oil and synthetic oil, having a viscosity index of 120 or more and a paraffin content by ring analysis of 70% or more.
- the present invention it is possible to prevent deterioration in engine performance even when used in an internal combustion engine for automobiles that can achieve higher output and lower fuel consumption by increasing the thermal and mechanical durability temperatures than in the past. It is possible to provide a lubricating oil composition capable of satisfying both of the above durability.
- the lubricating oil composition comprises a base oil containing at least one selected from mineral oil and synthetic oil, having a viscosity index of 120 or more and a paraffin content by ring analysis of 70% or more, and (A) alkenyl A dispersant containing at least one compound selected from succinimide, alkenyl succinimide borate, alkyl succinimide, and alkyl succinimide borate, and (B) alkali metal sulfonate, alkali metal phenate And a metal detergent containing at least one compound selected from alkali metal salicylates, alkaline earth metal sulfonates, alkaline earth metal phenates, and alkaline earth metal salicylates.
- the component (A) is contained in an amount of 0.01% by mass or more and 0.10% by mass or less in terms of nitrogen content based on the total composition amount, and the component (B) is 0.01 mass in terms of metal content based on the total amount of composition. % To 0.3% by mass.
- 1 or more types of compounds chosen from the boride of this alkenyl succinimide in the (A) component, and the boride of the alkyl succinimide are contained, and the mass ratio of the boron and nitrogen contained in (A) component is contained.
- a certain B / N ratio is 0.5 or more.
- the phosphorus content on the basis of the total composition amount is 100 mass ppm or more and 1200 mass ppm or less, and the sulfated ash content on the basis of the total composition amount is 1.1 mass% or less.
- the lubricating oil composition according to the present invention may be simply referred to as “the present composition”.
- the base oil of the composition may be mineral oil or synthetic oil.
- 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 can be desolvated, solvent extracted, hydrocracked, solvent dewaxed, catalytic dehydrated.
- Mineral oil refined by one or more treatments such as wax, hydrorefining, or the like, or mineral oil produced by isomerizing wax, GTL WAX, and the like.
- Synthetic oils include, for example, polybutene, polyolefins [ ⁇ -olefin homopolymers and copolymers (eg, ethylene- ⁇ -olefin copolymers)], various esters (eg, polyol esters, dibasic acid esters, phosphorus Acid ester, etc.), various ethers (eg, polyphenyl ether), polyglycol, alkylbenzene, alkylnaphthalene and the like.
- polyolefins and polyol esters are particularly preferred from the viewpoints of viscosity characteristics, solubility of additives, and compatibility with seal rubbers.
- one kind of the mineral oil may be used, or two or more kinds may be used in combination.
- 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 usually, 2 mm 2 / s or more 30 mm 2 / s or less, preferably 3 mm 2 / s or more 15 mm 2 / s or less, particularly preferably 4 mm 2 / s or more 10 mm 2 / s or less.
- 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.
- the base oil has a paraffin content (may be described as% CP) by ring analysis of 70% or more.
- % CP is less than 70%, the oxidation stability is poor, and an increase in acid value and sludge are likely to occur.
- the% CP is preferably 80% or more.
- the viscosity index of the base oil is 120 or more. Preferably, it is 125 or more, more preferably 130 or more.
- the base oil having a viscosity index of less than 120 has a large viscosity change due to a change in temperature, and a fuel efficiency improvement effect at a low temperature is reduced.
- the component (A) is a dispersant containing one or more compounds selected from alkenyl succinimides, alkenyl succinimide borides, alkyl succinimides, and alkyl succinimide borides.
- the component (A) is an alkenyl succinimide, an alkenyl succinimide borate, an alkyl succinimide, and an alkyl succinimide borate, and the alkenyl succinimide borate.
- alkyl succinimide borides is essential.
- a high temperature detergency is improved because a component contains the boride of an alkenyl succinimide or an alkyl succinimide.
- the succinimide includes a monoimide structure and a bisimide structure.
- the monoimide structure includes both a structure based on a single alkenyl or alkyl succinic acid monoimide and a structure based on a boride of alkenyl or alkyl succinic monoimide.
- Examples of the alkenyl or alkyl succinic acid monoimide include alkenyl or alkyl succinic acid monoimide represented by the following formula (1).
- the bisimide structure includes both a structure based on an alkenyl or alkyl succinic acid bisimide alone and a structure based on a boride of an alkenyl or alkyl succinic acid bisimide.
- Examples of the alkenyl or alkyl succinic acid bisimide include alkenyl or alkyl succinic acid bisimide represented by the following formula (2).
- R 1 , R 3 and R 4 are alkenyl groups or alkyl groups, and the mass average molecular weights are preferably 500 or more and 3,000 or less, respectively, more preferably 1 3,000 to 3,000.
- the mass average molecular weight of R 1 , R 3 and R 4 described above is 500 or more, the solubility in the base oil increases, and when it is 3,000 or less, the effect of cleanliness can be expected.
- R 3 and R 4 may be the same or different.
- R 2 , R 5 and R 6 are each an alkylene group having 2 to 5 carbon atoms, and R 5 and R 6 may be the same or different.
- m represents an integer of 1 to 10
- n represents 0 or an integer of 1 to 10.
- n is preferably 1 to 4, more preferably 2 to 3. Unlike monoimide, when n is 1 or more, high-temperature cleanability is even better, and when n is 4 or less, solubility in base oil is even better.
- 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 preferably obtained as a mixture of 1-butene and isobutene or a polymer of high-purity isobutene.
- a representative example of a suitable alkyl group is a hydrogenated polybutenyl group or polyisobutenyl group.
- the alkenyl or alkyl succinimide is usually obtained by reacting an alkenyl succinic anhydride obtained by reacting a polyolefin with maleic anhydride, or an alkyl succinic anhydride obtained by hydrogenating it with a polyamine.
- the succinic monoimide and succinic bisimide described above can be produced by changing the reaction ratio of alkenyl succinic anhydride or alkyl succinic anhydride and polyamine.
- ⁇ -olefins having 2 to 8 carbon atoms can be mixed and used, but a mixture of isobutene and 1-butene is preferably used. be able to.
- polyamines include ethylenediamine, propylenediamine, butylenediamine, pentylenediamine and other single diamines, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di (methylethylene) triamine, dibutylenetriamine, triethylene
- polyalkylene polyamines such as butylenetetramine and pentapentylenehexamine
- piperazine derivatives such as aminoethylpiperazine.
- the boride of an alkenyl or alkyl succinimide can be used for the boride of an alkenyl or alkyl succinimide.
- the above polyamine and boron oxide, boron halide, boric acid, boric anhydride, boric acid ester, ammonium boric acid It is obtained by reacting with an intermediate obtained by reacting a boron compound such as a salt and imidizing.
- the mass ratio (Nm / Nb) of nitrogen derived from the monoimide structure and nitrogen derived from the bisimide structure is 0.5 or less, preferably 0.4 or less.
- Engine durability can be improved as mass ratio (Nm / Nb) is 0.5 or less.
- one or more compounds selected from alkenyl succinimide, alkenyl succinimide borate, alkyl succinimide, and alkyl succinimide borate have a nitrogen content based on the total amount of the composition. It is contained 0.01% by mass or more and 0.10% by mass or less in terms of conversion. More preferably, they are 0.02 mass% or more and 0.09 mass% or less, More preferably, they are 0.03 mass% or more and 0.08 mass% or less. When this compound is less than 0.01% by mass in terms of nitrogen content, the high-temperature cleanability is deteriorated, and when it exceeds 0.10% by mass, the oxidation stability is deteriorated.
- the mass ratio (B / N ratio) of boron and nitrogen constituting the boride of alkenyl or alkyl succinimide in component (A) is 0.5 or more, preferably 0.6 or more, more preferably 0.8 or more.
- B / N ratio is 0.5 or more, the high-temperature cleanability is greatly improved.
- High temperature detergency is exhibited when the boron content derived from the boride of alkenyl or alkyl succinimide in the component (A) is a certain amount or more. If the boron content derived from the alkenyl or alkyl succinimide borate in the component (A) is 0.01% by mass or more and 0.06% by mass or less on the basis of the total amount of the composition, sufficient high-temperature cleanliness is obtained. can get. Preferably, they are 0.02 mass% or more and 0.05 mass% or less.
- Component (B) of the lubricating oil composition according to the present invention is one selected from alkali metal sulfonates, alkali metal phenates, alkali metal salicylates, alkaline earth metal sulfonates, alkaline earth metal phenates, and alkaline earth metal salicylates. It is a metallic detergent containing the above compounds. Of these, the component (B) is preferably at least one of an alkali metal sulfonate and an alkaline earth metal sulfonate.
- 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.
- magnesium salts, calcium salts and the like can be mentioned, among which calcium salts are preferably used.
- Alkaline earth metal phenates include alkylphenols, alkylphenol sulfides, alkaline earth metal salts of Mannich reaction products of alkylphenols, particularly magnesium salts, calcium salts, and the like. Of these, calcium salts are preferably used.
- alkaline earth metal salicylates examples include alkaline earth metal salts of alkyl salicylic acid, particularly magnesium salts and 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 an alkyl group having 6 to 18 carbon atoms, which may be linear or branched. These may also be primary alkyl groups, secondary alkyl groups or tertiary alkyl groups.
- Alkaline earth metal sulfonates, alkaline earth metal phenates and alkaline earth metal salicylates include the above-mentioned alkyl aromatic sulfonic acids, alkylphenols, alkylphenol sulfides, Mannich reactants of alkylphenols, alkyl salicylic acids, etc. from magnesium and calcium.
- Neutral alkaline earth metal sulfonates, neutral alkaline earth metal phenates and neutral alkaline earths obtained by direct reaction with one or more selected alkaline earth metal bases such as oxides or hydroxides of alkaline earth metals Metallic salicylates are included.
- Alkaline earth metal sulfonates, alkaline earth metal phenates, and alkaline earth metal salicylates include the above-mentioned alkyl aromatic sulfonic acids, alkylphenols, alkylphenol sulfides, Mannich reactants of alkylphenols, alkylsalicylic acids, etc., once as sodium salts. Further, neutral alkaline earth metal sulfonates, neutral alkaline earth metal phenates and neutral alkaline earth metal salicylates obtained by substituting alkali metal salts such as potassium salts with alkaline earth metal salts are included.
- alkaline earth metal sulfonates, alkaline earth metal phenates and alkaline earth metal salicylates include neutral alkaline earth metal sulfonates, neutral alkaline earth metal phenates and neutral alkaline earth metal salicylates, and excess alkali Basic alkaline earth metal sulfonates, basic alkaline earth metal phenates, and basic alkaline earth metal salicylates obtained by heating an earth metal salt or an alkaline earth metal base in the presence of water are included.
- alkaline earth metal sulfonates, alkaline earth metal phenates and alkaline earth metal salicylates include neutral alkaline earth metal sulfonates, neutral alkaline earth metal phenates and neutral alkaline earths in the presence of carbon dioxide. Also included are overbased alkaline earth metal sulfonates, overbased alkaline earth metal phenates and overbased alkaline earth metal salicylates obtained by reacting metal salicylates with alkaline earth metal carbonates or borates. It is.
- the alkaline earth metal sulfonate, alkaline earth metal phenate and alkaline earth metal salicylate can be used in combination of one or more selected from the above.
- the above-mentioned neutral salts, basic salts, overbased salts and mixtures thereof can be used, and in particular, one of overbased salicylates, overbased phenates, and overbased sulfonates. Mixing the above with neutral sulfonate is preferable in terms of cleanliness and wear resistance inside the engine.
- Metal-based detergents are usually commercially available in a state diluted with a light lubricating base oil or the like and are available. It is desirable to use a metal-based detergent having a metal content of 1.0 to 20% by mass, preferably 2.0 to 16% by mass.
- the base number of the component (B) is preferably 10 mgKOH / g or more and 600 mgKOH / g or less, more preferably 20 mgKOH / g or more and 500 mgKOH / g or less.
- the total base number referred to here is JIS K2501 “Petroleum products and lubricating oils-Neutralization number test method”. Means the total base number by potentiometric titration method (base number / perchloric acid method) measured according to the above.
- metal ratio is 3 or less, More preferably, 1. It is particularly preferable to use a metal detergent of 5 or less, particularly preferably 1.2 or less, as an essential component because it is excellent in oxidation stability, base number maintenance, high-temperature cleanability, and the like.
- the metal ratio here is represented by the valence of the metal element in the metal-based detergent ⁇ metal element content (mol%) / soap group content (mol%), and the metal elements include calcium, magnesium, and the like.
- the soap group means a sulfonic acid group, a phenol group, a salicylic acid group, and the like.
- the component (B) is preferably 0.3% by mass or less in order to reduce the sulfated ash content to 1.1% by mass or less.
- the compounding quantity of (B) component is contained 0.01 mass% or more and 0.3 mass% or less in conversion of the metal content in the composition whole quantity standard.
- sodium sulfonate is added to the component (B) based on the total amount of the lubricating oil composition. It is contained at 05 mass% or less.
- magnesium sulfonate is contained in an amount of 0.05% by mass or less of metal based on the total amount of the lubricating oil composition.
- the sulfur content is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and still more preferably 0.2% by mass or less based on the total amount of the composition. 1% by mass or less. When the sulfur content is 0.3% by mass or less, the performance deterioration of the exhaust gas purification catalyst can be effectively suppressed.
- composition further preferably contains zinc dialkyldithiophosphate (hereinafter also referred to as “ZnDTP”) as component (C).
- ZnDTP zinc dialkyldithiophosphate
- Examples of the component (C) include ZnDTP represented by the following formula (3).
- R 11 , R 12 , R 13 and R 14 are alkyl substituted with a primary or secondary alkyl group having 3 to 22 carbon atoms or an alkyl group having 3 to 18 carbon atoms. It is a substituent selected from an aryl group, and they may be the same as or different from each other.
- these ZnDTPs may be used singly or in combination of two or more, and in particular, those having a secondary alkyl group zinc dithiophosphate as a main component. In order to improve wear resistance, it is preferable.
- Specific examples of ZnDTP include zinc dipropyldithiophosphate, zinc dibutyldithiophosphate, zinc dipentyldithiophosphate, zinc dihexyldithiophosphate, zinc diisopentyldithiophosphate, zinc diethylhexyldithiophosphate, zinc dioctyldithiophosphate, dinonyldithiophosphate.
- Zinc zinc didecyl dithiophosphate, zinc didodecyl dithiophosphate, zinc dipropylphenyl dithiophosphate, zinc dipentylphenyl dithiophosphate, zinc dipropylmethylphenyl dithiophosphate, zinc dinonylphenyl dithiophosphate, zinc didodecylphenyl dithiophosphate, di Examples include zinc dodecylphenyl dithiophosphate.
- an antioxidant In the lubricating oil composition according to the present invention, an antioxidant, a viscosity index improver, a pour point depressant, a rust inhibitor, a metal deactivator, if necessary, as long as the effects of the present invention are not impaired. Antifoaming agents, antiwear agents, extreme pressure agents, and other additives may be added. ⁇ Antioxidant> As the antioxidant, a phenol-based or amine-based antioxidant can be used.
- phenolic antioxidant examples include octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate; 4,4′-methylenebis (2,6-di-t-butylphenol); 4,4′-bis (2,6-di-t-butylphenol); 4,4′-bis (2-methyl-6-t-butylphenol); 2,2′-methylenebis (4-ethyl-6-t) -Butylphenol); 2,2'-methylenebis (4-methyl-6-t-butylphenol); 4,4'-butylidenebis (3-methyl-6-t-butylphenol); 4,4'-isopropylidenebis (2 , 6-di-t-butylphenol); 2,2′-methylenebis (4-methyl-6-nonylphenol); 2,2′-isobutylidenebis (4,6-dimethylphenol); '-Methylenebis (4-methyl-6-cyclohexylphenol); 2,6-di-t-
- amine antioxidants include monoalkyl diphenylamines such as monooctyl diphenylamine and monononyl diphenylamine; 4,4′-dibutyldiphenylamine, 4,4′-dipentyldiphenylamine, 4,4′-dihexyldiphenylamine, 4 Dialkyldiphenylamines such as 4,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine; polyalkyldiphenylamines such as tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, tetranonyldiphenylamine Systems; and those of the naphthylamine type, specifically ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine
- a molybdenum amine antioxidant may be further added.
- a hexavalent molybdenum compound specifically, a product obtained by reacting molybdenum trioxide and / or molybdic acid with an amine compound, for example, the production described in JP-A-2003-252887
- the compound obtained by the method can be used. 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 Amines and alkylenediamines having 1-30 carbon atoms such as butylenediamine; polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine; undecyldiethylamine, undecyldiethanolamine, dodecyldipropanolamine , Oleyldiethanolamine, oleylpropylenediamine, stearyltetraethylenepentamine and other monoamines, diamines, polyamines having a C8-20 alkyl group or alkenyl group, and heterocyclic compounds such as imidazoline; alkylene oxides of these compounds Additives; and mixtures thereof.
- Examples thereof include a sulfur-containing molybdenum complex of succinimide described in JP-B-3-22438 and JP-A-2004-2866.
- the amount of the antioxidant described above is preferably 0.3% by mass or more and 3% by mass or less based on the total amount of the composition. Moreover, 0.4 mass% or more and 3 mass% or less are more preferable, 0.4 mass% or more and 2 mass% or less are still more preferable, and 0.5 mass% or more and 2 mass% or less are especially preferable. If the antioxidant is 0.3% by mass or more based on the total amount of the composition, an increase in the acid value can be suppressed, and if it is 3% by mass or less, solubility in the lubricating base oil can be ensured.
- Viscosity index improver examples include polymethacrylate, dispersed polymethacrylate, olefin copolymer (for example, ethylene-propylene copolymer), dispersed olefin copolymer, styrene copolymer (for example, Styrene-diene copolymer, styrene-isoprene copolymer, etc.).
- the blending amount of these viscosity index improvers is 0.5% by mass or more and 15% by mass or less, preferably 1% by mass or more and 10% by mass or less, based on the total amount of the composition, from the viewpoint of the blending effect.
- pour point depressant examples include ethylene-vinyl acetate copolymer, condensate of chlorinated paraffin and naphthalene, condensate of chlorinated paraffin and phenol, polymethacrylate, polyalkylstyrene, and the like. Polymethacrylate having a molecular weight of 5,000 or more and 50,000 or less is preferably used. These are used in a proportion of 0.1% by mass or more and 5% by mass or less based on the total amount of the composition.
- rust preventive examples include petroleum sulfonate, alkylbenzene sulfonate, dinonyl naphthalene sulfonate, alkenyl succinate, polyhydric alcohol ester and the like.
- the blending amount of these rust preventives is 0.01% by mass or more and 1% by mass or less, preferably 0.05% by mass or more and 0.5% by mass or less based on the total amount of the composition from the viewpoint of the blending effect. .
- Metal deactivator examples include benzotriazole, tolyltriazole, thiadiazole, imidazole, and pyrimidine compounds. Of these, benzotriazole compounds are preferred.
- the compounding amount of these metal deactivators is preferably 0.01% by mass or more and 0.1% by mass or less, more preferably 0.03% by mass or more and 0% by mass based on the total amount of the composition from the viewpoint of blending effect. 0.05% by mass or less.
- Antifoaming agent examples include silicone oil, fluorosilicone oil, fluoroalkyl ether, and the like, and 0.005% by mass or more and 0.1% by mass based on the total amount of the composition from the viewpoint of balance between defoaming effect and economy. % Or less is preferable.
- Antiwear or extreme pressure agents include zinc dithiophosphate, zinc phosphate, zinc dithiocarbamate, molybdenum dithiocarbamate, molybdenum dithiophosphate, disulfides, sulfurized olefins, sulfurized fats and oils, sulfurized esters, thiocarbonates, thiocarbonates Sulfur-containing compounds such as carbamates and polysulfides; Phosphorous esters, phosphate esters, phosphonate esters, and phosphorus-containing compounds such as amine salts or metal salts thereof; thiophosphite esters, thiophosphoric acid Examples include sulfur and phosphorus-containing antiwear agents such as esters, thiophosphonic acid esters, and amine salts or metal salts thereof.
- the blending amount of the other antiwear agent is 600 mass ppm or less in terms of element as zinc based on the total amount of the lubricating oil composition.
- they are 0 mass ppm or more and 500 mass ppm or less, More preferably, they are 0 mass ppm or more and 400 mass ppm or less.
- the compounding quantity of another antiwear agent or extreme pressure agent is 500 mass ppm or less in terms of element as phosphorus on the basis of the total amount of the lubricating oil composition.
- they are 0 mass ppm or more and 400 mass ppm or less, More preferably, they are 0 mass ppm or more and 300 mass ppm or less.
- the blending amount of zinc is 600 mass ppm or less and the blending amount of phosphorus is 500 mass ppm or less, the basic compound in the lubricating oil composition, for example, engine oil is consumed, and the oil renewal period becomes extremely short. There is no.
- the phosphorus content based on the total amount of the composition is 100 mass ppm or more and 1200 mass ppm or less. If the amount of phosphorus is less than 100 ppm by mass, the wear resistance will be insufficient. On the other hand, if the phosphorus content exceeds 1200 ppm by mass, poisoning of exhaust gas to the purification catalyst cannot be sufficiently suppressed.
- the phosphorus content is preferably 200 ppm to 1100 ppm, more preferably 300 ppm to 1000 ppm, and particularly preferably 400 ppm to 900 ppm.
- the sulfated ash content based on the total amount of the composition is 1.1% by mass or less. If the sulfated ash content exceeds 1.1 mass%, the amount of ash deposited on the DPF filter increases in the diesel engine, the ash content of the DPF filter tends to clog, and the life of the DPF filter is shortened. From the viewpoint of further improving the oxidation stability, base number maintenance, and high-temperature cleanability of the lubricating oil composition, the sulfated ash content is more preferably 0.2% by mass or more, and particularly 0.3% by mass or more. Thus, a composition capable of maintaining the base number and the high temperature cleanliness for a longer period can be obtained.
- the sulfated ash refers to the ash that has been made constant by adding sulfuric acid to the carbonized residue produced by burning the sample and heating it. Usually, to know the approximate amount of the metal additive in the lubricating oil composition. Used for. Specifically, JIS K 2272 [5. It is measured by the method specified in the sulfate ash test method].
- the lubricating oil composition according to the present invention is not only excellent in high-temperature cleanliness, but also has good compatibility with fluororubber seals frequently used in the engine, so that it is a gasoline engine, diesel engine, gas engine, and hybrid vehicle engine. It can use suitably for internal combustion engines, such as. Examples of the internal combustion engine include a general internal combustion engine manufactured using a material such as an aluminum alloy material, a nickel chromium alloy material, a carbon steel material, or a chromium molybdenum steel material.
- the lubricating oil composition according to the present invention includes: In particular, it can be suitably used for lubricating an internal combustion engine in which at least the piston head is made of cast iron material.
- the method for producing a lubricating oil composition includes a base oil containing at least one selected from mineral oil and synthetic oil, having a viscosity index of 120 or more and a paraffin content by ring analysis of 70% or more.
- the component (B) is contained in an amount of 0.01% by mass to 0.3% by mass in terms of the metal content based on the total amount of the composition, and the boronated product of the alkenyl succinimide and the alkyl succinic acid in the component (A) Contains one or more compounds selected from imide boride, B / N ratio, which is a mass ratio of boron and nitrogen contained in component (A), is 0.5 or more, and contains phosphorus in the composition based on the total amount
- a method for producing a lubricating oil composition by blending such that the amount is 100 mass ppm or more and 1200 mass ppm or less and the sulfated ash content is 1.1 mass% or less based on the total amount of the composition. is there.
- the manufacturing method of the lubricating oil composition according to the present embodiment further includes an antioxidant, a viscosity index improver, a pour point depressant, a rust inhibitor, a metal Activators, antifoaming agents, antiwear agents, extreme pressure agents, and other additives are blended.
- (A) component and (B) component are added to the base oil, and further, an antioxidant, a viscosity index improver, a pour point depressant, a rust inhibitor, and a metal inert as necessary.
- the lubricating oil composition obtained by blending the agent, the antifoaming agent, the antiwear agent, the extreme pressure agent, and further other additives contains these various blended additives.
- the lubricating oil composition may be converted into another compound by reacting at least a part of these various additives.
- Sample oils of lubricating oil compositions were prepared using the following base oils, dispersants, metal-based detergents, and other additives, and the characteristics and properties of these sample oils were measured by the evaluation methods described below. The results are shown in Tables 1 and 2.
- Base oil hydrorefined base oil, 40 ° C. kinematic viscosity 21 mm 2 / s, 100 ° C.
- Viscosity index improver A polymethacrylate, weight average molecular weight 420,000, resin amount 39% by mass
- Phenol antioxidant octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate
- Amine antioxidant dialkyldiphenylamine, nitrogen content 4.62% by mass
- Zinc dithiophosphate Zn content 9.0% by mass, phosphorus content 8.2% by mass, sulfur content 17.1% by mass, alkyl group; mixture of secondary butyl group and secondary hexyl group
- Agent A Neutral calcium sulfonate, base number (perchloric acid method) 20 mgKOH / g, calcium content 1.8% by mass, sulfur content 1.8% by mass
- Metal detergent B neutral calcium sulfon
- High temperature cleanliness evaluation method (hot tube test)> High temperature cleanability was evaluated by a hot tube test according to JPI-5S-55-99. Specifically, the sample oil was continuously supplied into a glass tube having an inner diameter of 2 mm at a flow rate of 0.31 mL / h and air at a flow rate of 10 mL / min for 16 hours. The temperature of the glass tube was kept at 280 ° C. Thereafter, the mass of the deposit adhered to the glass tube was measured. The evaluation is 10 steps, and the higher the score, the smaller the mass of deposit deposits and the better the high temperature cleanliness.
- ⁇ Initial film formation test> Using a Kamata four-ball tester, a rotating ball and a fixed ball are electrically insulated completely by a lubricating oil film in a test time of 180 seconds under conditions of an oil temperature of 80 ° C., a rotation speed of 500 rpm, and a load of 0.0480 MPa. Time was evaluated as the film formation time. The shorter the film formation time, the better the initial film formation ability and the better the wear resistance.
- ⁇ Load bearing performance test> Using an Iwata four-ball tester, under an oil temperature of 80 ° C.
- the load was increased by 0.196 MPa every 3 minutes from the initial load of 0.048 MPa, and the load was applied to 0.288 MPa to rotate.
- the load at which the sphere and the fixed sphere are electrically conducted completely was evaluated as a complete contact load. The larger the value of the complete contact load, the better the load bearing performance.
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Abstract
Description
自動車用エンジンの高出力を図ると、エンジンにおける燃焼温度及び圧力は上昇する傾向にある。特に、ディーゼルエンジンでは、高温における耐性及び剛性、耐熱亀裂性などが求められるため、エンジンを堅強に設計する必要がある。しかし、低燃費化のためには、エンジンの軽量化が求められる。
そこで従来、ディーゼルエンジン用ピストンには、軽量化のために、JIS AC8A等のアルミニウム合金が用いられてきた。また、アルミニウム合金を用いたディーゼルエンジンの潤滑に適する潤滑油組成物が開発されている(例えば、特許文献1参照)。
鋳鉄ピストンは、アルミニウム合金からなるピストンに比べて耐久性が高いうえに、鋳鉄に含まれる黒鉛が自己潤滑性を有するため、耐焼付性も良好である。しかし、鋳鉄ピストンは、アルミニウム合金に比べて、ピストン上死点近縁が高温になることで、摩耗が大きく清浄性にも劣ることから、エンジンの性能低下を引き起こし易いことが懸念される。
そこで、本発明は、従来よりも熱的及び機械的耐久温度を高めて高出力化及び低燃費化を実現し得る自動車用内燃機関に用いてもエンジンの性能低下を防止でき、エンジン性能とエンジンの耐久性とを両立できる潤滑油組成物を提供することを目的とする。
本発明に係る潤滑油組成物は、鉱油及び合成油から選ばれる少なくとも1つを含み、粘度指数が120以上であり、環分析によるパラフィン分が70%以上である基油と、(A)アルケニルコハク酸イミド、アルケニルコハク酸イミドのホウ素化物、アルキルコハク酸イミド、及びアルキルコハク酸イミドのホウ素化物から選ばれる1種以上の化合物が含まれる分散剤と、(B)アルカリ金属スルフォネート、アルカリ金属フェネート、アルカリ金属サリチレート、アルカリ土類金属スルフォネート、アルカリ土類金属フェネート、及びアルカリ土類金属サリチレートから選ばれる1種以上の化合物が含まれる金属系清浄剤と、を有する。
(A)成分は、組成全量基準における窒素含有量換算で0.01質量%以上0.10質量%以下含まれ、(B)成分は、組成物全量基準における金属含有量換算で0.01質量%以上0.3質量%以下含まれる。
また、(A)成分中における該アルケニルコハク酸イミドのホウ素化物及びアルキルコハク酸イミドのホウ素化物から選ばれる1種以上の化合物が含まれ、(A)成分に含まれるホウ素と窒素の質量比であるB/N比が0.5以上である。さらに、潤滑油組成物においては、組成物全量基準におけるリン含有量が100質量ppm以上1200質量ppm以下であり、組成物全量基準における硫酸灰分が1.1質量%以下である。本発明に係る潤滑油組成物を、以下、単に「本組成物」という場合がある。
本組成物の基油は、鉱油でも合成油でもよい。この鉱油や合成油の種類に制限はなく、従来、潤滑油組成物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。
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。
合成油としては、例えば、ポリブテン、ポリオレフィン[α-オレフィン単独重合体や共重合体(例えばエチレン-α-オレフィン共重合体)など]、各種のエステル(例えば、ポリオールエステル、二塩基酸エステル、リン酸エステルなど),各種のエーテル(例えば、ポリフェニルエーテルなど)、ポリグリコール、アルキルベンゼン、アルキルナフタレンなどが挙げられる。これらの合成油のうち、粘度特性、添加剤の溶解性およびシールゴムへの適合性の観点より特にポリオレフィン、ポリオールエステルが好ましい。
本発明では、上記鉱油を1種用いてもよく、2種以上を組み合わせて用いてもよい。また、上記合成油を1種用いてもよく、2種以上を組み合わせて用いてもよい。さらには、鉱油1種以上と合成油1種以上とを組み合わせて用いてもよい。
基油の粘度については特に制限はなく、潤滑油組成物の用途に応じて選択できる。基油の粘度は、100℃における動粘度が、通常、2mm2/s以上30mm2/s以下、好ましくは3mm2/s以上15mm2/s以下、特に好ましくは4mm2/s以上10mm2/s以下である。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。
さらに、基油の粘度指数は、120以上である。好ましくは、125以上、さらに好ましくは、130以上である。この粘度指数が120未満の基油は、温度の変化による粘度変化が大きく、低温における燃費改善効果が低減する。
(A)成分は、アルケニルコハク酸イミド、アルケニルコハク酸イミドのホウ素化物、アルキルコハク酸イミド、及びアルキルコハク酸イミドのホウ素化物から選ばれる1種以上の化合物が含まれる分散剤である。
(A)成分は、アルケニルコハク酸イミド、アルケニルコハク酸イミドのホウ素化物、アルキルコハク酸イミド、及びアルキルコハク酸イミドのホウ素化物から選ばれる1種以上の化合物のうち、アルケニルコハク酸イミドのホウ素化物又はアルキルコハク酸イミドのホウ素化物のいずれか一方を必須とする。(A)成分がアルケニルコハク酸イミド又はアルキルコハク酸イミドのホウ素化物を含むことにより、高温清浄性が高められる。
本実施形態においてコハク酸イミドは、モノイミド構造及びビスイミド構造を含む。
モノイミド構造としては、アルケニル若しくはアルキルコハク酸モノイミド単体に基づく構造と、アルケニル若しくはアルキルコハク酸モノイミドのホウ素化物に基づく構造の双方が含まれる。アルケニル若しくはアルキルコハク酸モノイミドとしては、例えば、下記式(1)で示されるアルケニル若しくはアルキルコハク酸モノイミドが挙げられる。
ビスイミド構造も同様に、アルケニル若しくはアルキルコハク酸ビスイミド単体に基づく構造と、アルケニル若しくはアルキルコハク酸ビスイミドのホウ素化物に基づく構造の双方が含まれる。アルケニル若しくはアルキルコハク酸ビスイミドとしては、例えば、下記式(2)で示されるアルケニル若しくはアルキルコハク酸ビスイミドが挙げられる。
上記したR1、R3およびR4の質量平均分子量が500以上であると、基油への溶解性が高くなり、3,000以下であると、清浄性の効果が期待できる。R3およびR4は同一でも異なっていてもよい。
R2、R5およびR6は、それぞれ炭素数2~5のアルキレン基であり、R5およびR6は同一でも異なっていてもよい。mは1~10の整数を示し、nは0または1~10の整数を示す。ここで、mは、好ましくは2~5、より好ましくは3~4である。mが2以上であると、より一層良好な高温清浄性を与えることができ、mが5以下であると、基油に対する溶解性がより一層良好となる。
上記式(2)において、nは好ましくは1~4であり、より好ましくは2~3である。モノイミドと異なり、nが1以上であると、高温清浄性がより一層良好であり、nが4以下であると、基油に対する溶解性がより一層良好となる。
一方、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、およ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を挙げることができる。
例えば、上記の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。
本発明に係る潤滑油組成物の(B)成分は、アルカリ金属スルフォネート、アルカリ金属フェネート、アルカリ金属サリチレート、アルカリ土類金属スルフォネート、アルカリ土類金属フェネート、及びアルカリ土類金属サリチレートから選ばれる1種以上の化合物が含まれる金属系清浄剤である。(B)成分としては、これらのなかでも、アルカリ金属スルフォネート又はアルカリ土類金属スルフォネートの少なくともいずれか一方であることが好ましい。
アルカリ土類金属フェネートとしては、アルキルフェノール、アルキルフェノールサルファイド、アルキルフェノールのマンニッヒ反応物のアルカリ土類金属塩、特に、マグネシウム塩、カルシウム塩等が挙げられ、中でもカルシウム塩が好ましく用いられる。
アルカリ土類金属サリシレートとしては、アルキルサリチル酸のアルカリ土類金属塩、特に、マグネシウム塩、カルシウム塩等が挙げられ、中でもカルシウム塩が好ましく用いられる。
アルカリ土類金属系清浄剤を構成するアルキル基としては、炭素数4~30のものが好ましく、より好ましくは6~18のアルキル基であり、これらは直鎖状でも分枝状でもよい。これらはまた1級アルキル基、2級アルキル基または3級アルキル基でもよい。
アルカリ土類金属スルフォネート、アルカリ土類金属フェネート及びアルカリ土類金属サリシレートは、上述したものから選ばれる1種または2種以上を併用することができる。
また、潤滑油組成物の硫酸灰分を1.1質量%以下に低減するという観点から、より好ましくは、(B)成分に、ナトリウムスルフォネートが該潤滑油組成物全量基準で金属量0.05質量%以下含まれることである。または、マグネシウムスルフォネートが該潤滑油組成物全量基準で金属量0.05質量%以下含まれることである。
本発明に係る潤滑油組成物においては、硫黄含有量が組成物全量基準で0.3質量%以下であることが好ましく、0.2質量%以下であることがより好ましく、さらに好ましくは0.1質量%以下である。硫黄含有量が0.3質量%以下であると、排出ガスの浄化触媒の性能低下を効果的に抑えることができる。
本組成物には、さらに(C)成分として、ジアルキルジチオリン酸亜鉛(以下、「ZnDTP」とも記載する。)が好ましく配合される。(C)成分としては、例えば、下記式(3)で示されるZnDTPが挙げられる。
ZnDTPの具体例としては、ジプロピルジチオリン酸亜鉛、ジブチルジチオリン酸亜鉛、ジペンチルジチオリン酸亜鉛、ジヘキシルジチオリン酸亜鉛、ジイソペンチルジチオリン酸亜鉛、ジエチルヘキシルジチオリン酸亜鉛、ジオクチルジチオリン酸亜鉛、ジノニルジチオリン酸亜鉛、ジデシルジチオリン酸亜鉛、ジドデシルジチオリン酸亜鉛、ジプロピルフェニルジチオリン酸亜鉛、ジペンチルフェニルジチオリン酸亜鉛、ジプロピルメチルフェニルジチオリン酸亜鉛、ジノニルフェニルジチオリン酸亜鉛、ジドデシルフェニルジチオリン酸亜鉛、ジドデシルフェニルジチオリン酸亜鉛等が挙げられる。
本発明に係る潤滑油組成物には、本発明の効果を損なわない範囲で、必要に応じて、酸化防止剤、粘度指数向上剤、流動点降下剤、防錆剤、金属不活性化剤、消泡剤、耐摩耗剤、極圧剤、さらに他の添加剤を添加してもよい。
<酸化防止剤>
酸化防止剤としては、フェノール系やアミン系などの酸化防止剤を用いることができる。
フェノール系酸化防止剤としては、例えば、オクタデシル-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;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およびエステル基含有フェノール系のものが好適である。
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。具体的には、モノアミン、ジアミン、ポリアミンおよ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、およ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、およ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のアルキル基また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;およびこれらの混合物等が例示できる。また、特公平3-22438号公報および特開2004-2866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。
粘度指数向上剤としては、例えば、ポリメタクリレート、分散型ポリメタクリレート、オレフィン系共重合体(例えば、エチレン-プロピレン共重合体など)、分散型オレフィン系共重合体、スチレン系共重合体(例えば、スチレン-ジエン共重合体、スチレン-イソプレン共重合体など)などが挙げられる。これら粘度指数向上剤の配合量は、配合効果の点から、組成物全量基準で、0.5質量%以上15質量%以下であり、好ましくは1質量%以上10質量%以下である。
流動点降下剤としては、エチレン-酢酸ビニル共重合体、塩素化パラフィンとナフタレンとの縮合物、塩素化パラフィンとフェノールとの縮合物、ポリメタクリレート、ポリアルキルスチレン等が挙げられ、例えば、質量平均分子量が5,000以上50,000以下のポリメタクリレートが好ましく用いられる。これらは、組成物全量基準で、0.1質量%以上5質量%以下の割合で使用される。
防錆剤としては、石油スルフォネート、アルキルベンゼンスルフォネート、ジノニルナフタレンスルフォネート、アルケニルコハク酸エステル、多価アルコールエステル等が挙げられる。これら防錆剤の配合量は、配合効果の点から、組成物全量基準で、0.01質量%以上1質量%以下であり、好ましくは0.05質量%以上0.5質量%以下である。
金属不活性化剤(銅腐食防止剤)としては、例えば、ベンゾトリアゾール系、トリルトリアゾール系、チアジアゾール系、イミダゾール系およびピリミジン系化合物等が挙げられる。この中でベンゾトリアゾール系化合物が好ましい。金属不活性化剤を配合することでエンジン部品の金属腐食および酸化劣化を抑制することができる。これら金属不活性化剤の配合量は、配合効果の点から、組成物全量基準で、好ましくは0.01質量%以上0.1質量%以下であり、より好ましくは0.03質量%以上0.05質量%以下である。
消泡剤としては、シリコーン油、フルオロシリコーン油およびフルオロアルキルエーテル等が挙げられ、消泡効果および経済性のバランスなどの点から、組成物全量に基づき、0.005質量%以上0.1質量%以下を配合させることが好ましい。
耐摩耗剤又は極圧剤としては、ジチオリン酸亜鉛、リン酸亜鉛、ジチオカルバミン酸亜鉛、ジチオカルバミン酸モリブデン、ジチオリン酸モリブデン、ジスルフィド類、硫化オレフィン類、硫化油脂類、硫化エステル類、チオカーボネート類、チオカーバメート類、ポリサルファイド類等の硫黄含有化合物;亜リン酸エステル類、リン酸エステル類、ホスホン酸エステル類、及びこれらのアミン塩又は金属塩等のリン含有化合物;チオ亜リン酸エステル類、チオリン酸エステル類、チオホスホン酸エステル類、及びこれらのアミン塩又は金属塩等の硫黄及びリン含有耐摩耗剤が挙げられる。
他の耐摩耗剤又は極圧剤を必要に応じて配合する場合、他の耐摩耗剤の配合量は、潤滑油組成物全量基準で、亜鉛として元素換算で600質量ppm以下である。好ましくは、0質量ppm以上500質量ppm以下、より好ましくは0質量ppm以上400質量ppm以下である。
また、他の耐摩耗剤又は極圧剤の配合量は、潤滑油組成物全量基準で、リンとして元素換算で500質量ppm以下である。好ましくは、0質量ppm以上400質量ppm以下、より好ましくは0質量ppm以上300質量ppm以下である。亜鉛の配合量が600質量ppm以下、リンの配合量が500質量ppm以下であると、潤滑油組成物中、例えば、エンジン油中の塩基性化合物を消耗し更油期間が極端に短くなることがない。
本発明に係る潤滑油組成物においては、組成物全量基準におけるリン含有量は、100質量ppm以上1200質量ppm以下である。前記リン量が100質量ppm未満であれば、耐摩耗性が不十分になる。一方、前記リン含有量が1200質量ppmを超えると、排出ガスの浄化触媒への被毒を十分に抑えることができない。
リン含有量は、好ましくは200質量ppm以上1100質量ppm以下、より好ましくは300質量ppm以上1000質量ppm以下、特に好ましくは400質量ppm以上900質量ppm以下である。
本発明に係る潤滑油組成物においては、組成物全量基準における硫酸灰分は、1.1質量%以下である。該硫酸灰分が1.1質量%を超えると、ディーゼルエンジンにおいて、DPFのフィルタに堆積する灰分量が増え、該DPFフィルタの灰分詰まりが起こりやすくなり、DPFフィルタの寿命が短くなる。
潤滑油組成物の酸化安定性や塩基価維持性、高温清浄性をより高める観点から、硫酸灰分は、より好ましくは、0.2質量%以上であり、特に、0.3質量%以上とすることで、より長期間塩基価および高温清浄性を維持できる組成物を得ることができる。
なお、この硫酸灰分とは、試料を燃焼して生じた炭化残留物に硫酸を加えて加熱し、恒量にした灰分をいい、通常、潤滑油組成物中の金属添加剤の大略量を知るために用いられる。具体的には、JIS K 2272[5.硫酸灰分試験方法]に規定される方法により測定される。
本実施形態に係る潤滑油組成物の製造方法は、鉱油及び合成油から選ばれる少なくとも1つを含み、粘度指数が120以上であり、環分析によるパラフィン分が70%以上である基油に、(A)アルケニルコハク酸イミド、アルケニルコハク酸イミドのホウ素化物、アルキルコハク酸イミド、及びアルキルコハク酸イミドのホウ素化物から選ばれる1種以上の化合物が含まれる分散剤と、(B)アルカリ金属スルフォネート、アルカリ金属フェネート、アルカリ金属サリチレート、アルカリ土類金属スルフォネート、アルカリ土類金属フェネート、及びアルカリ土類金属サリチレートから選ばれる1種以上の化合物が含まれる金属系清浄剤とを、(A)成分が組成全量基準における窒素含有量換算で0.01質量%以上0.10質量%以下含まれ、(B)成分が組成物全量基準における金属含有量換算で0.01質量%以上0.3質量%以下含まれ、(A)成分中における該アルケニルコハク酸イミドのホウ素化物及びアルキルコハク酸イミドのホウ素化物から選ばれる1種以上の化合物が含まれ、(A)成分に含まれるホウ素と窒素の質量比であるB/N比が0.5以上であり、組成物全量基準におけるリン含有量が100質量ppm以上1200質量ppm以下であり、組成物全量基準における硫酸灰分が1.1質量%以下であるように配合することにより、潤滑油組成物を製造することを特徴とする方法である。
[実施例及び比較例]
下記の基油、分散剤、金属系清浄剤、その他の添加剤を用いて潤滑油組成物の試料油を調製し、後述の評価方法により、これら試料油の特性及び性状を測定した。結果を第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、%CP 83、%CA0.0、硫黄含有量10質量ppm未満、NOACK蒸発量13.3質量%
粘度指数向上剤A:ポリメタクリレート、重量平均分子量420,000、樹脂量39質量%
フェノール系酸化防止剤:オクタデシル-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
アミン系酸化防止剤:ジアルキルジフェニルアミン、窒素含有量4.62質量%
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
金属系清浄剤A:中性カルシウムスルフォネート、塩基価(過塩素酸法)20mgKOH/g、カルシウム含有量1.8質量%、硫黄含有量1.8質量%
金属系清浄剤B:中性カルシウムスルフォネート、塩基価(過塩素酸法)22mgKOH/g、カルシウム含有量2.4質量%、硫黄含有量3.0質量%
金属系清浄剤C:過塩基性カルシウムスルフォネート、塩基価(過塩素酸法)308mgKOH/g、カルシウム含有量12質量%、硫黄含有量1.1質量%
金属系清浄剤D:過塩基性カルシウムスルフォネート、塩基価(過塩素酸法)320mgKOH/g、カルシウム含有量13質量%、硫黄含有量2.4質量%
金属系清浄剤E:過塩基性カルシウムスルフォネート、塩基価(過塩素酸法)450mgKOH/g、カルシウム含有量15質量%、硫黄含有量1.2質量%
金属系清浄剤F:過塩基性カルシウムスルフォネート、塩基価(過塩素酸法)500mgKOH/g、カルシウム含有量18.5質量%
金属系清浄剤G:過塩基性カルシウムフェネート、塩基価(過塩素酸法)200mgKOH/g、カルシウム含有量7.2質量%、硫黄含有量2.0質量%
金属系清浄剤H:過塩基性カルシウムフェネート、塩基価(過塩素酸法)255mgKOH/g、カルシウム含有量9.2質量%、硫黄含有量3.3質量%
金属系清浄剤I:過塩基性カルシウムフェネート、塩基価(過塩素酸法)400mgKOH/g、カルシウム含有量14質量%、硫黄含有量2質量%
金属系清浄剤J:中性カルシウムサリチレート、塩基価(過塩素酸法)64mgKOH/g、カルシウム含有量2.3質量%
金属系清浄剤K:過塩基性ナトリウムスルフォネート、塩基価(過塩素酸法)450mgKOH/g、ナトリウム含有量19.5質量%、硫黄含有量1.2質量%
金属系清浄剤L:過塩基性マグネシウムスルフォネート、塩基価(過塩素酸法)410mgKOH/g、マグネシウム含有量9.4質量%、硫黄含有量2.0質量%
金属系清浄剤M:過塩基性カルシウムサリシレート、塩基価(過塩素酸法)230mgKOH/g、カルシウム含有量7.9質量%
金属系清浄剤N:過塩基性カルシウムサリシレート、塩基価(過塩素酸法)290mgKOH/g、カルシウム含有量7.8質量%
無灰分散剤A:アルケニルコハク酸イミドのホウ素誘導体、ポリブテニル基の数平均分子量1000、窒素含有量1.8質量%、ホウ素含有量2.0質量%
無灰分散剤B:アルケニルコハク酸イミド、ポリブテニル基の数平均分子量2000、窒素含有量1.0質量%
メチルベンゾトリアゾール誘導体:1-[N,N-ビス(2-エチルヘキシル)アミノメチル]メチルベンゾトリアゾール
その他の添加剤:流動点降下剤及び消泡剤
(1)基油及び潤滑油組成物の動粘度
JIS K 2283に規定される「石油製品動粘度試験方法」に準拠して測定した。
(2)基油の粘度指数
JIS K 2283に規定される「石油製品動粘度試験方法」に準拠して測定した。
(3)基油の硫黄含有量
JIS K 2541に準拠して測定した。
(4)基油の%CA…環分析n-d-M法にて芳香族成分の割合(百分率)を算出した。
(5)基油の%CP…環分析n-d-M法にてパラフィン成分の割合(百分率)を算出した。
(6)基油のNOACK蒸発量
JPI-5S-41-2004に準拠して測定した。
(7)ホウ素含有量
JPI-5S-38-92に準拠して測定した。
(8)窒素含有量
JIS K2609に準拠して測定した。
(9)モリブデンおよびリン含有量
JPI-5S-38-92に準拠して測定した。
(10)硫酸灰分
JIS K2272に準拠して測定した。
<高温清浄性評価法(ホットチューブ試験)>
高温清浄性は、JPI-5S-55-99に準拠してホットチューブ試験で評価した。具体的には、内径2mmのガラス管中に試料油を0.31mL/hの流量で、空気を10mL/minの流量で16時間流し続けた。ガラス管の温度は280℃に保った。その後ガラス管中に付着したデポジット付着物の質量を測定した。評価は10段階であり、点数が高いほど、デポジット付着物の質量が少なく、高温清浄性に優れる。
<初期被膜形成試験>
曾田四球試験機を用いて、油温80℃、回転数500rpm、荷重0.0480MPaの条件で、試験時間180秒間で回転球と固定球とが潤滑油被膜にて電気的に完全に絶縁される時間を被膜形成時間として評価した。被膜形成時間が短いほど、初期被膜形成能力が優れ、耐摩耗性能に優れる。
<耐荷重性能試験>
曾田四球試験機を用いて、油温80℃、回転数500rpmの条件で、初期荷重0.048MPaから3分毎に荷重を0.196MPaずつ上昇させて、0.288MPaまで荷重を掛けて、回転球と固定球とが電気的に完全に導通する荷重を完全接触荷重として評価した。完全接触荷重の値が大きいほど、耐荷重性能に優れる。
表1の結果より、本発明の潤滑油組成物を用いた実施例では、ホットチューブ試験におけるデポジット付着量が少ないことから高温清浄性に優れていることがわかる。また、実施例の潤滑油組成物は、初期被膜形成試験における結果が良好であることから、ピストン上死点においても油膜切れが起こりにくく、耐摩耗性が良好であることがわかる。また、耐荷重性能にも優れる。
Claims (9)
- 鉱油及び合成油から選ばれる少なくとも1つを含み、粘度指数が120以上であり、環分析によるパラフィン分が70%以上である基油と、
(A)アルケニルコハク酸イミド、アルケニルコハク酸イミドのホウ素化物、アルキルコハク酸イミド、及びアルキルコハク酸イミドのホウ素化物から選ばれる1種以上の化合物が含まれる分散剤と、
(B)アルカリ金属スルフォネート、アルカリ金属フェネート、アルカリ金属サリチレート、アルカリ土類金属スルフォネート、アルカリ土類金属フェネート、及びアルカリ土類金属サリチレートから選ばれる1種以上の化合物が含まれる金属系清浄剤と、を有し、
(A)成分が組成全量基準における窒素含有量換算で0.01質量%以上0.10質量%以下含まれ、
(B)成分が組成物全量基準における金属含有量換算で0.01質量%以上0.3質量%以下含まれ、
(A)成分中における該アルケニルコハク酸イミドのホウ素化物及びアルキルコハク酸イミドのホウ素化物から選ばれる1種以上の化合物が含まれ、(A)成分に含まれるホウ素と窒素の質量比であるB/N比が0.5以上であり、
組成物全量基準におけるリン含有量が100質量ppm以上1200質量ppm以下であり、
組成物全量基準における硫酸灰分が1.1質量%以下である潤滑油組成物。 - (B)成分がアルキル金属スルフォネート又はアルカリ土類金属スルフォネートの少なくともいずれか一方であり、
(B)成分の塩基価が10mgKOH/g以上600mgKOH/g以下である請求項1に記載の潤滑油組成物。 - アミン系酸化防止剤、フェノール系酸化防止剤、及びモリブデンアミン系酸化防止剤から選ばれる酸化防止剤が該潤滑油組成物全量基準で0.3質量%以上3質量%以下含まれる請求項1又は2に記載の潤滑油組成物。
- 前記リン含有量が200質量ppm以上1100質量ppm以下である請求項1~3のいずれかに記載の潤滑油組成物。
- 前記B/N比が0.6以上である請求項1~4のいずれかに記載の潤滑油組成物。
- (B)成分として、ナトリウムスルフォネートが該潤滑油組成物全量基準で金属量0.05質量%以下含まれる請求項1~5のいずれかに記載の潤滑油組成物。
- (B)成分として、マグネシウムスルフォネートが該潤滑油組成物全量基準で金属量0.05質量%以下含まれる請求項1~5のいずれかに記載の潤滑油組成物。
- 内燃機関の潤滑に用いられる請求項1~7のいずれかに記載の潤滑油組成物。
- 少なくともピストンヘッドが鋳鉄材料で製造された内燃機関の潤滑に用いられる請求項8に記載の潤滑油組成物。
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US14/773,609 US20160024417A1 (en) | 2013-03-08 | 2014-03-07 | Lubricating-oil composition |
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CN201480012146.6A CN105189720A (zh) | 2013-03-08 | 2014-03-07 | 润滑油组合物 |
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EP (1) | EP2966155A4 (ja) |
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JP2020164747A (ja) * | 2019-03-29 | 2020-10-08 | 出光興産株式会社 | 潤滑油組成物 |
US11732207B2 (en) | 2020-08-31 | 2023-08-22 | Eneos Corporation | Lubricating oil composition for internal combustion engine |
US11987766B2 (en) | 2020-08-31 | 2024-05-21 | Eneos Corporation | Lubricating oil composition for internal combustion engine |
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Also Published As
Publication number | Publication date |
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US20160024417A1 (en) | 2016-01-28 |
JP2018199836A (ja) | 2018-12-20 |
JPWO2014136970A1 (ja) | 2017-02-16 |
CN105189720A (zh) | 2015-12-23 |
JP6507455B2 (ja) | 2019-05-08 |
EP2966155A1 (en) | 2016-01-13 |
CN109439401A (zh) | 2019-03-08 |
JP6676868B2 (ja) | 2020-04-08 |
EP2966155A4 (en) | 2016-11-23 |
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