Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/10—Carboxylix acids; Neutral salts thereof
  • C10M2207/22—Acids obtained from polymerised unsaturated acids
  • C10M2207/226—Acids obtained from polymerised unsaturated acids used as thickening agents
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/28—Amides; Imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
  • C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
  • C10M2219/066—Thiocarbamic type compounds
  • C10M2219/068—Thiocarbamate metal salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
  • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
  • C10M2223/04—Phosphate esters
  • C10M2223/045—Metal containing thio derivatives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
  • C10M2229/04—Siloxanes with specific structure
  • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/02—Viscosity; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/04—Molecular weight; Molecular weight distribution
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/04—Detergent property or dispersant property
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/54—Fuel economy
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/252—Diesel engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
  • C10N2040/255—Gasoline engines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
  • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

• the present invention relates to a lubricating oil composition for internal combustion engines (hereinafter also referred to as engine oil). Specifically, the present invention relates to an engine oil that is excellent in fuel economy and cleanliness and that is particularly suitable for a diesel engine.
• An internal combustion engine is required to further improve fuel efficiency for environmental measures such as recent CO 2 emission regulations.
• lubricating oil In order to improve fuel efficiency by using lubricating oil, it has been practiced to reduce the viscous resistance by reducing the use viscosity (see, for example, Patent Document 1).
• lubrication of internal combustion engines has the necessary viscosity and is naturally limited.
• the internal combustion engine oil is also used as a hydraulic pressure source for driving a valve, and a certain viscosity is required for maintaining the hydraulic pressure. For this reason, there was a limit in reducing the viscosity. To overcome this, heat management for internal combustion engines is being introduced.
• the required viscosity can be further reduced by lowering the maximum operating temperature of the internal combustion engine oil according to the purpose and conditions of use of the internal combustion engine, or by reducing the hydraulic pressure required for the pump by improving the internal combustion engine pump. It becomes. As a result, fuel consumption can be further reduced.
• the drastic reduction in the base oil viscosity increases the consumption of engine oil due to an increase in the amount of evaporation, and also makes it impossible to secure the necessary viscosity especially in the high shear rate region, increasing the risk of poor lubrication.
• the present invention has been made in view of such circumstances, and provides a lubricating oil composition for an internal combustion engine that is excellent in function as an engine oil of an internal combustion engine incorporating heat management, and particularly excellent in fuel saving and cleanliness. The purpose is to do.
• the present invention relates to (A) a base oil having a kinematic viscosity at 100 ° C. of 3.0 to 5.0 mm 2 / s, and (B) boronated succinimide as a boron element amount based on the total amount of the composition. 0.007% by weight or more, the content as a succinimide-based ashless dispersant is 5% by weight or less, (C) 0.5% by weight or more of a phenolic antioxidant, and (D) a weight average HTHS viscosity at 150 ° C.
• the lubricating oil composition for internal combustion engines is characterized by having an HTHS viscosity of 4.8 mPa ⁇ s or less and a viscosity index of 180 or more.
• the present invention also provides the above-described lubricating oil composition for internal combustion engines, wherein the ratio of the boronated succinimide to the non-boronated succinimide is 1.0 to 3.0 by weight. Moreover, this invention is that ratio of the total content of the boronated succinimide which is (B) component with respect to content of the viscosity index improver which is (D) component, and non-boronated succinimide is 6 or less.
• the above-described lubricating oil composition for internal combustion engines wherein the ratio of the boronated succinimide to the non-boronated succinimide is 1.0 to 3.0 by weight. Moreover, this invention is that ratio of the total content of the boronated succinimide which is (B) component with respect to content of the viscosity index improver which is (D) component, and non-boronated succinimide is 6 or less.
• a lubricating oil composition for an internal combustion engine that is excellent in function as an engine oil of an internal combustion engine incorporating heat management, and particularly excellent in fuel efficiency and cleanliness.
• the lubricating oil composition of the present invention is It can be suitably used for gasoline internal combustion engines, motorcycle internal combustion engines, diesel internal combustion engines, and gas internal combustion engines for motorcycles, automobiles, power generation, cogeneration, etc., and further, a fuel having a sulfur content of 50 mass ppm or less is used. Not only can it be suitably used for various internal combustion engines, but it is also useful for various internal combustion engines for ships and outboard motors.
• lubricating base oil in the lubricating oil composition of the present invention either mineral oil or synthetic oil can be used.
• a mineral oil base oil a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and / or vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, Paraffinic mineral oil, or normal paraffinic base oil, isoparaffinic base oil, etc., refined by combining one or more of refining treatments such as catalytic dewaxing, hydrorefining, sulfuric acid washing, clay treatment, etc.
• a base oil whose kinematic viscosity at 100 ° C. satisfies the above conditions can be used.
• Preferred examples of the lubricating base oil according to the present invention include the following base oils (1) to (8) as raw materials, and the raw oil and / or the lubricating oil fraction recovered from the raw oil
• recovering lubricating oil fractions can be mentioned.
• a wax such as slack wax obtained by a lubricant dewaxing step and / or a synthetic wax (Fischer-Tropsch wax, GTL wax, etc.) obtained by a gas-liquid (GTL) process or the like.
• DAO de-oiling oil
• MHC Mild hydrocracking treatment oil
• the above-mentioned predetermined purification methods include hydrorefining such as hydrocracking and hydrofinishing; solvent refining such as furfural solvent extraction; dewaxing such as solvent dewaxing and catalytic dewaxing; acid clay and activated clay White clay refining; chemical (acid or alkali) cleaning such as sulfuric acid cleaning and caustic soda cleaning are preferred.
• one of these purification methods may be performed alone, or two or more may be combined.
• the order in particular is not restrict
• the lubricating base oil according to the present invention is obtained by subjecting a base oil selected from the above base oils (1) to (8) or a lubricating oil fraction recovered from the base oil to a predetermined treatment.
• the following base oil (9) or (10) is particularly preferred.
• the base oil selected from the above base oils (1) to (8) or the lubricating oil fraction recovered from the base oil is hydrocracked and recovered from the product or the product by distillation or the like. Hydrocracked mineral oil obtained by subjecting a lubricating oil fraction to dewaxing treatment such as solvent dewaxing or catalytic dewaxing, or distillation after the dewaxing treatment.
• a base oil selected from the base oils (1) to (8) or a lubricating oil fraction recovered from the base oil is hydroisomerized and recovered from the product or the product by distillation or the like.
• Hydroisomerized mineral oil obtained by subjecting the lubricating oil fraction to dewaxing treatment such as solvent dewaxing or catalytic dewaxing, or distillation after the dewaxing treatment.
• a solvent refining treatment and / or a hydrofinishing treatment step may be further provided as necessary at a convenient step.
• the catalyst used in the hydrocracking and hydroisomerization is not particularly limited, but a composite oxide having cracking activity (for example, silica alumina, alumina boria, silica zirconia, etc.) or one or more of the composite oxides is used.
• a hydrocracking catalyst having a carrier combined with a binder and combined with a metal having hydrogenation ability for example, one or more metals such as Group VIa metal or Group VIII metal in the periodic table
• a hydroisomerization catalyst in which a support containing zeolite for example, ZSM-5, zeolite beta, SAPO-11, etc.
• the hydrocracking catalyst and the hydroisomerization catalyst may be used in combination by stacking or mixing.
• the reaction conditions in the hydrocracking and hydroisomerization are not particularly limited, but the hydrogen partial pressure is 0.1 to 20 MPa, the average reaction temperature is 150 to 450 ° C., the LHSV is 0.1 to 3.0 hr ⁇ 1 , the hydrogen / oil ratio. 50 to 20000 scf / b is preferable.
• Kinematic viscosity at 100 ° C. of the lubricating base oil of the invention must be at less 5.0 mm 2 / s, preferably 4.5 mm 2 / s or less, particularly preferably 4.2 mm 2 / s or less It is.
• the kinematic viscosity needs to be 3.0 mm 2 / s or more, preferably 3.4 mm 2 / s or more, and more preferably 3.7 mm 2 / s or more.
• the kinematic viscosity at 100 ° C. refers to the kinematic viscosity at 100 ° C. defined in ASTM D-445. When the 100 ° C.
• kinematic viscosity of the lubricating base oil component exceeds 5.0 mm 2 / s, the low-temperature viscosity characteristics may be deteriorated, and sufficient fuel economy may not be obtained. 3.0 mm 2 / s If it is less than 1, the formation of the oil film at the lubrication site is insufficient, so that the lubricity is inferior, and the evaporation loss of the lubricating oil composition may be increased.
• the viscosity index of the lubricating base oil according to the present invention is preferably 120 or more. More preferably, it is 125 or more, More preferably, it is 130 or more, Most preferably, it is 140 or more. On the other hand, the viscosity index is preferably 160 or less. When the viscosity index is less than 120, not only the viscosity-temperature characteristics, thermal / oxidative stability, and volatilization prevention properties deteriorate, but also the friction coefficient tends to increase, and the wear prevention properties tend to decrease. . On the other hand, when the viscosity index exceeds 160, the low-temperature viscosity characteristics tend to deteriorate.
• the viscosity index in the present invention means a viscosity index measured according to JIS K 2283-1993.
• the sulfur content in the lubricating base oil according to the present invention depends on the sulfur content of the raw material.
• a raw material that does not substantially contain sulfur such as a synthetic wax component obtained by a Fischer-Tropsch reaction or the like
• a lubricating base oil that does not substantially contain sulfur can be obtained.
• the sulfur content is preferably 10 mass ppm or less, from the viewpoint of further improving thermal and oxidation stability and reducing sulfur content, and preferably 5 mass ppm or less. It is more preferable that it is not substantially contained.
• % C P of mineral lubricating base oil of the present invention is preferably 70 or more, more preferably 80 or more, more preferably 85 or more, and most preferably 90 or more. Moreover, Preferably it is 95 or less.
• the% C P of the lubricating base oil is less than 70, the viscosity-temperature characteristics, thermal / oxidative stability and friction characteristics tend to decrease, and when the additive is added to the lubricating base oil The effectiveness of the additive tends to decrease. Also from the viewpoint of solubility of additives, because it is preferable to contain 5% of% C N, preferably 95% or less.
• % C A of the lubricating base oil of the present invention is preferably 2 or less, more preferably 1 or less, more preferably 0.8 or less, particularly preferably 0.5 or less, and most preferably 0. If the% C A value of the lubricating base oil exceeds 2, the viscosity - temperature characteristic, thermal and oxidation stability and fuel efficiency tends to decrease.
• the% C P and% C A in the present invention obtained by a method according to ASTM D3238-85, respectively (n-d-M ring analysis), percentage of total number of carbon atoms of the paraffin carbon number, and the aromatic It means the percentage of the total number of group carbons.
• Examples of the synthetic base oil according to the present invention include poly ⁇ -olefins or hydrogenated products thereof, isobutene oligomers or hydrogenated products thereof, isoparaffins, alkylbenzenes, alkylnaphthalenes, etc. Among them, poly ⁇ -olefins are preferable.
• the poly ⁇ -olefin is typically an ⁇ -olefin oligomer or co-oligomer having 2 to 32 carbon atoms, preferably 6 to 16, particularly 1-octene oligomer, decene oligomer, 1-dodecene oligomer or co-oligomer. And their hydrides are preferred. If these are the same viscosity range as the mineral oil base oil mentioned above, what is marketed can be used.
• These synthetic base oils can be used alone or mixed with the mineral oil base oil described above. Moreover, there is no restriction
• the engine oil of the present invention contains a boronated succinimide as the component (B).
• a boronated succinimide as the component (B).
• a non-boronated succinimide means a succinimide before boronating the boronated succinimide.
• succinimide examples include succinimide having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms, or a derivative thereof.
• the alkyl group or alkenyl group has less than 40 carbon atoms, the solubility in the lubricating base oil tends to decrease.
• the alkyl group or alkenyl group has more than 400 carbon atoms, the lubricating oil for internal combustion engines The low temperature fluidity of the composition tends to deteriorate.
• the alkyl group or alkenyl group may be linear or branched, but specific examples thereof are derived from olefin oligomers such as propylene, 1-butene and isobutylene, and ethylene and propylene co-oligomers. And a branched alkyl group or a branched alkenyl group.
• succinimide monotype and / or bis type succinimide is preferably used.
• the method for producing succinimide is not particularly limited.
• an alkyl succinic acid or alkenyl succinic acid obtained by reacting a compound having an alkyl group or alkenyl group having 40 to 400 carbon atoms with maleic anhydride at 100 to 200 ° C. It can be obtained by reacting with a polyamine.
• the polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
• Boronation of succinimide is generally carried out by allowing boric acid to act on succinimide to neutralize part or all of the remaining amino group and / or imino group.
• methods for producing a boronated succinimide are disclosed in Japanese Patent Publication Nos. 42-8013, 42-8014, 51-52381, 51-130408, and the like. And the like.
• organic compounds such as alcohols, hexane, xylene, etc., light lubricating oil base oil, polyamine and polyalkenyl succinic acid (anhydride), boric acid, boric acid ester, or boron compounds such as borate can be obtained by mixing and heat-treating under appropriate conditions.
• the boric acid content of the boric acid succinimide thus obtained can usually be 0.1 to 45% by mass.
• the boron content in the boronated succinimide used in the present invention is not particularly limited, but is usually 0.1 to 3% by mass, preferably 0.2% by mass or more, more preferably 0.3% by mass. % Or more, more preferably 0.5 mass% or more. Moreover, Preferably it is 2 mass% or less, More preferably, it is 1.5 mass% or less, More preferably, it is 1 mass% or less. In the present invention, it is preferable to use a boronated succinimide having a boron content within this range, and it is particularly preferable to use a boron-containing bissuccinimide.
• the boron content exceeds 3% by mass, there is a concern not only about stability, but also the amount of boron in the composition becomes excessive, and there is a concern about an influence on the exhaust gas aftertreatment device with an increase in sulfated ash content. Therefore, it is not preferable. Further, when the boron content is less than 0.1% by mass, the effect of addition cannot be expected.
• a non-borated non-borated succinimide together with a boronated succinimide.
• the ratio of the boronated succinimide and the non-boronated succinimide is preferably used in the range of 1.0 to 3.0 by weight. More preferably, it is 1.2 or more, Preferably it is 2.6 or less, More preferably, it is 2.0 or less, More preferably, it is 1.5 or less.
• the ratio of boronated succinimide and non-boronated succinimide exceeds 3.0, not only is there concern about stability, but the amount of boron in the composition increases too much, increasing the amount of sulfated ash, exhaust gas This is not preferable because the influence on the post-processing apparatus is concerned.
• the ratio is less than 1.0, the effect of adding boronated succinimide cannot be expected.
• the reason why the mixed use is preferable is that the boronated succinimide alone has an unstable boronated compound and precipitates a borated product, and has an excellent balance of cleanliness.
• the content of the component (B) in the lubricating oil composition for internal combustion engines according to the present invention is required to be 0.007% by mass or more as the amount of boron element based on the total amount of the lubricating oil composition for internal combustion engines. Yes, preferably 0.01% by mass or more. Moreover, Preferably it is 0.1 mass% or less, More preferably, it is 0.05 mass% or less, More preferably, it is 0.02 mass% or less. If the amount is less than 0.007% by mass, the effect of boron cannot be expected, and if it exceeds 0.1% by mass, the composition lacks stability. In the present invention, the total content of boronated succinimide and non-borated succinimide is 5% by mass or less based on the total amount of the composition.
• the molecular weight of component (B) is determined by the carbon number of the alkyl group or alkenyl group and the structure of the polyamine, but the molecular weight is preferably 2500 or more, more preferably 3000 or more, and further preferably 3500 or more. Moreover, 10,000 or less are preferable, 7000 or less are more preferable, and 5000 or less are more preferable. If it is less than 2500, the cleansing effect is small, and if it exceeds 10,000, the low-temperature viscosity of the composition deteriorates.
• Boronated succinimide and non-boronated succinimide are generally provided in a state of being dissolved in a solvent corresponding to a lubricating base oil as a solvent.
• the content as used in the field of this invention is a net content as a compound which does not contain a solvent.
• succinimide dissolved in a solvent the effective concentration of succinimide in the solution is calculated, and the amount added is net succinimide.
• As a method of calculating the effective concentration for example, 1 to 2 grams of an additive solution containing the succinimide is accurately weighed in a sax-like rubber having a capacity of 50 ml using natural rubber as a raw material.
• the engine oil of the present invention contains a phenolic antioxidant as the component (C).
• phenol-based ashless antioxidant include 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-Butylphenol), 4,4'-bis (2-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl- 6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-isopropylidenebis (2,6-di-tert-butylphenol), 2,2′- Methylene bis (4-methyl-6-nonylphenol), 2,2'-isobutylidene bis (4,6-dimethylphenol), 2,2'-methylene bis (4-methyl) 6-cyclohexylphenol), 2,6-di-tert-but
• a hydroxyphenyl group-substituted ester antioxidant (octyl-3- (3,5-di-tert-butyl-4-hydroxy) which is an ester of a hydroxyphenyl group-substituted fatty acid and an alcohol having 4 to 12 carbon atoms.
• Phenyl) propionate, octyl-3- (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate, etc.) and bisphenol ashless antioxidants are preferred, and hydroxyphenyl group-substituted ester antioxidants are more preferred .
• a phenol compound having a molecular weight of 240 or more is preferable because it has a high decomposition temperature and exhibits its effect even under higher temperature conditions.
• an amine-based ashless antioxidant may be further contained.
• examples of amine-based ashless antioxidants include phenyl- ⁇ -naphthylamine, alkylphenyl- ⁇ -naphthylamine, and dialkyldiphenylamine.
• the engine oil of this invention contains the viscosity index improver whose ratio of a weight average molecular weight and PSSI is 1.2 * 10 ⁇ 4 > or more as a component (D).
• the weight average molecular weight (M w ) of the viscosity index improver according to the present invention is preferably 600,000 or less, more preferably 500,000 or less, and even more preferably 460,000 or less. Moreover, it is preferable that it is 10,000 or more, More preferably, it is 50,000 or more, More preferably, it is 100,000 or more, Especially preferably, it is 200,000 or more. If the weight average molecular weight is less than 10,000, the effect of improving the viscosity index when dissolved in a lubricating base oil is small, resulting in poor fuel economy and low temperature viscosity characteristics, and may increase costs.
• the PSSI (Permanent Cystability Index) of the viscosity index improver according to the present invention is preferably 20 or less, more preferably 17 or less, still more preferably 16 or less, and particularly preferably 15 or less.
• PSSI Permanent Cystability Index
• PSSI is less than 1, the viscosity index improvement effect when dissolved in a lubricating base oil is small, and it is not only inferior in fuel efficiency and low-temperature viscosity characteristics, but also may increase costs. Is preferably 1 or more.
• the weight average molecular weight and PSSI ratio of viscosity index improver according to the present invention is required to be 1.2 ⁇ 10 4 or more, preferably 1.5 ⁇ 10 4 or more, further Preferably it is 2.0 ⁇ 10 4 or more. If M W / PSSI is below 1.2 ⁇ 10 4, there is a possibility that fuel saving properties and low-temperature startability i.e. viscosity temperature characteristics and low temperature viscosity characteristics are deteriorated.
• viscosity index improvers include non-dispersed or dispersed ester group-containing viscosity index improvers, non-dispersed or dispersed poly (meth) acrylate viscosity index improvers, and styrene-diene hydrogenation.
• the content of the viscosity index improver of the component (D) in the lubricating oil composition of the present invention is preferably 0.1 to 5% by mass, more preferably 0.5% by mass, based on the total amount of the composition. As mentioned above, More preferably, it is 1.0 mass% or more. Moreover, it is preferable that it is 3 mass% or less, More preferably, it is 2 mass% or less. If the content is less than 0.1% by mass, the low temperature characteristics may be insufficient, and if the content exceeds 5% by mass, the shear stability of the composition may be deteriorated.
• the viscosity index improver is also usually provided in a dissolved state in a solvent equivalent to a lubricating base oil as in the case of the succinimide described above, but the content referred to in the present invention does not include the solvent. Net content.
• the ratio of the total content of the boronated succinimide and the non-boronated succinimide as the component (B) to the content of the viscosity index improver as the component (D) is 6 or less. That is, the ratio of the total content of the boronated succinimide and the non-boronated succinimide as the component (B) to the content of the viscosity index improver as the component (D) is limited. This is because both the component (D) and the component (B) affect the increase in the viscosity of the composition, but the component (B) has a great influence on the increase in the low-temperature viscosity. This is because it is necessary to suppress the contribution of the component B).
• the ratio of the total content of the boronated succinimide and the non-boronated succinimide as the component (B) to the content of the viscosity index improver as the component (D) is 6 or less, preferably 5 or less, more preferably 4 or less, still more preferably 3.5 or less, and most preferably 3 or less.
• the lubricating oil composition for internal combustion engines according to the present invention may contain any additive generally used in lubricating oils depending on the purpose in order to further improve its performance.
• additives include metal detergents, friction modifiers, ashless dispersants other than the component (B), antiwear agents (or extreme pressure agents), antioxidants other than the component (C), and corrosion.
• additives such as inhibitors, rust inhibitors, demulsifiers, metal deactivators, and antifoaming agents.
• metal detergents include normal salts and / or basic salts such as alkali metal / alkaline earth metal sulfonate, alkali metal / alkaline earth metal phenate, and alkali metal / alkaline earth metal salicylate.
• alkali metal include sodium and potassium
• examples of the alkaline earth metal include magnesium, calcium and barium. Magnesium or calcium is preferable, and calcium is more preferable.
• any compound usually used as a friction modifier for lubricating oils can be used, and examples thereof include organic molybdenum compounds and ashless friction modifiers.
• organic molybdenum compound include molybdenum dithiocarbamate, molybdenum dithiophosphate, molybdenum-amine complex, molybdenum-succinimide complex, molybdenum salt of organic acid, molybdenum salt of alcohol, and the like.
• Examples of the ashless friction modifier include an amine compound having at least one alkyl group or alkenyl group having 6 to 30 carbon atoms, particularly a linear alkyl group or linear alkenyl group having 6 to 30 carbon atoms in the molecule, Examples include ashless friction modifiers such as fatty acid esters, fatty acid amides, fatty acids, aliphatic alcohols, and aliphatic ethers. Moreover, the various ashless friction modifiers illustrated by the international publication 2005/037967 pamphlet are mentioned. In the present invention, molybdenum dithiocarbamate is most preferable from the viewpoint that friction can be reduced most.
• any antiwear agent / extreme pressure agent used in lubricating oils can be used.
• sulfur-based, phosphorus-based, sulfur-phosphorus extreme pressure agents and the like can be used.
• zinc dialkyldithiophosphate (ZnDTP) phosphites, thiophosphites, dithiophosphites Acid esters, trithiophosphites, phosphate esters, thiophosphate esters, dithiophosphate esters, trithiophosphate esters, amine salts thereof, metal salts thereof, derivatives thereof, dithiocarbamate, zinc dithio
• Examples thereof include carbamates, disulfides, polysulfides, sulfurized olefins, and sulfurized fats and oils.
• addition of a sulfur-based extreme pressure agent is preferable, and zinc dialkyldithiophosphate is particularly preferable.
• corrosion inhibitor examples include benzotriazole, tolyltriazole, thiadiazole, or imidazole compounds.
• rust preventive examples include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.
• demulsifier examples include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, or polyoxyethylene alkyl naphthyl ether.
• metal deactivator examples include imidazoline, pyrimidine derivatives, alkylthiadiazole, mercaptobenzothiazole, benzotriazole or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis.
• metal deactivator examples include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, and ⁇ - (o-carboxybenzylthio) propiononitrile.
• antifoaming agent examples include silicone oil having a kinematic viscosity at 25 ° C. of 1,000 to 100,000 mm 2 / s, alkenyl succinic acid derivative, ester of polyhydroxy aliphatic alcohol and long chain fatty acid, methyl salicylate and o- Examples thereof include hydroxybenzyl alcohol.
• the respective contents are 0.01 to 10% by mass based on the total amount of the lubricating oil composition for internal combustion engines. preferable.
• the HTHS viscosity at 150 ° C. of the lubricating oil composition for an internal combustion engine of the present invention is 2.8 mPa ⁇ s or less, preferably 2.6 mPa ⁇ s or less, more preferably 2.4 mPa ⁇ s or less. Moreover, it is 2.0 mPa * s or more, Preferably it is 2.1 mPa * s or more, More preferably, it is 2,2 mPa * s or more. When the HTHS viscosity at 150 ° C. exceeds 2.8 mPa ⁇ s, sufficient fuel saving performance may not be obtained.
• the HTHS viscosity at 150 ° C. means a high temperature high shear viscosity at 150 ° C. as defined in ASTM D4683.
• the lubricating oil composition for internal combustion engines of the present invention has an HTHS viscosity at 100 ° C. of 4.8 mPa ⁇ s or less.
• the pressure is preferably 4.7 mPa ⁇ s or less, more preferably 4.6 mPa ⁇ s or less, and particularly preferably 4.5 mPa ⁇ s or less.
• the HTHS viscosity at 100 ° C. exceeds 4.8 mPa ⁇ s, sufficient fuel saving performance may not be obtained.
• the HTHS viscosity at 100 ° C. is less than 3.9 mPa ⁇ s, the engine hydraulic pressure may be insufficient, so that it is preferably 3.9 mPa ⁇ s or more.
• the HTHS viscosity at 100 ° C. means a high temperature high shear viscosity at 100 ° C. as defined in ASTM D6616.
• the HTHS viscosity (150 ° C.) / HTHS viscosity (100 ° C.) is preferably 0.45 or more, more preferably 0.47 or more, further preferably 0.49 or more, and most preferably 0.51 or more. This is because the lower the HTHS viscosity (100 ° C.) with respect to the HTHS viscosity (150 ° C.), the better the fuel economy.
• the kinematic viscosity at 100 ° C. of the lubricating oil composition for an internal combustion engine according to the present invention is preferably 8 mm 2 / s or less, more preferably 7.5 mm 2 / s or less, further preferably 7 mm 2 / s or less, Most preferably, it is 6.8 mm 2 / s or less.
• the kinematic viscosity at 100 ° C. of the lubricating oil composition for internal combustion engines according to the present invention is preferably 4 mm 2 / s or more, more preferably 5 mm 2 / s or more, further preferably 6 mm 2 / s or more, Most preferably, it is 6.3 mm 2 / s or more.
• the kinematic viscosity at 100 ° C. in the present invention refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445.
• the kinematic viscosity at 100 ° C. is less than 4 mm 2 / s, there is a risk of insufficient lubricity, and when it exceeds 8 mm 2 / s, the necessary low temperature viscosity and sufficient fuel saving performance may not be obtained. is there.
• the viscosity index of the lubricating oil composition for internal combustion engines according to the present invention is 180 or more. More preferably, it is 190 or more, More preferably, it is 200 or more, Especially preferably, it is 210 or more, Most preferably, it is 220 or more.
• the viscosity index of the lubricating oil composition for an internal combustion engine according to the present invention is less than 180, it may be difficult to improve fuel economy while maintaining the HTHS viscosity at 150 ° C., and ⁇ 35 It may be difficult to reduce the low-temperature viscosity at 0 ° C.
• the viscosity index of the lubricating oil composition for internal combustion engines according to the present invention is greater than 300, the evaporability may be deteriorated, and the solubility of the additive and the compatibility with the sealing material may be insufficient. It is preferable that the number is 300 or less because there is a possibility that a problem due to the above may occur.
• Examples 1 to 5 Lubricating oil compositions of the present invention (Examples 1 to 5) and comparative lubricating oil compositions (Comparative Examples 1 to 5) were prepared, and a hot tube test was performed on each lubricating oil composition. The results are shown in Table 1.
• the test method conforms to JPI 5S-55-99, and the test conditions are a sample amount of 10 g, a test temperature of 300 ° C., and a test time of 16 hours.
• the lubricating oil compositions of Examples 1 to 5 containing all of the components (A) to (D) were changed to the lubricating oil compositions of Comparative Examples 1 and 2 not containing the component (B).
• the HTHS viscosity at 100 ° C. is low and the fuel economy is excellent.
• the HTT test score is high and the cleanliness is excellent.

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• 2013
  • 2013-07-02 US US14/414,126 patent/US20150210954A1/en not_active Abandoned
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  • 2013-07-02 JP JP2014524749A patent/JP6043791B2/ja active Active
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• 2015
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