Classifications

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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
  • C10M143/08—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
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  • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
  • C10M143/02—Polyethene
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
  • C10M143/10—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation containing aromatic monomer, e.g. styrene
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • 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
  • C10M2203/108—Residual fractions, e.g. bright stocks
  • C10M2203/1085—Residual fractions, e.g. bright stocks used as base material
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/022—Ethene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/026—Butene
• • C—CHEMISTRY; METALLURGY
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/04—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing aromatic monomers, e.g. styrene
• • 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
  • C10M2207/028—Overbased salts thereof
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C10M2207/26—Overbased carboxylic acid salts
  • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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  • 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
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/28—Amides; Imides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral 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
  • 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
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  • 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
  • C10N2020/073—Star shaped polymers
• • C—CHEMISTRY; METALLURGY
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  • 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
  • C10N2030/08—Resistance to extreme temperature
• • 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
  • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
• • 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
  • C10N2030/52—Base number [TBN]
• • 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

Definitions

• the present invention relates to a system lubricant composition for a crosshead type diesel engine.
• Crosshead diesel engines use cylinder oil that lubricates between the cylinder and piston, and system oil that controls lubrication and cooling of other parts.
• the cylinder oil is required to have a proper viscosity necessary for lubrication between the cylinder and the piston (piston ring) and a function of maintaining cleanliness necessary for proper movement of the piston and piston ring.
• this engine has a problem of cylinder corrosion due to acidic components such as sulfuric acid generated by combustion because high sulfur fuel is usually used because of its economic efficiency.
• the cylinder oil must have a function of neutralizing acidic components such as sulfuric acid to prevent corrosion.
• system oil unlike ordinary diesel engine oil, does not come into contact with combustion gas, is stored in a tank, and is supplied to bearings and the like by a circulation pump for lubrication and cooling. Since it is used over a long period of time, it is required to maintain an appropriate viscosity for a long period of time (for example, Patent Document 1).
• a circulation pump for lubrication and cooling. Since it is used over a long period of time, it is required to maintain an appropriate viscosity for a long period of time (for example, Patent Document 1).
• the viscosity of the system oil is increased by mixing the drip oil of the cylinder oil, and it has been a long-standing problem how to suppress the increase in the viscosity.
• due to the recent increase in environmental problems it has become important to prevent deterioration in fuel consumption due to increased friction loss at the bearing portion due to increased viscosity and reduction in heat exchange efficiency on the piston cooling surface. It was.
• the present invention is to provide a system lubricant composition for a crosshead type diesel engine that can prevent deterioration of fuel consumption by suppressing an increase in viscosity.
• the inventors of the present invention can balance the increase in the viscosity due to the drip oil and the decrease in the viscosity due to thermal decomposition of the polymer by adding the specific polymer.
• the present invention has been completed by finding that it is effective as a system lubricant composition for a crosshead type diesel engine. Specifically, a star polymer and / or olefin copolymer having a vinyl aromatic hydrocarbon structure in the molecule, which has excellent shear stability but is easily decomposed by heat, is used as a lubricant base oil. By blending, the polymer is decomposed on the piston cooling surface to reduce the viscosity of the system oil, offset the increase in viscosity due to the cylinder drip oil mixing, and suppress the deterioration of fuel consumption.
• the present invention relates to (A) (a-1) a star polymer having a vinyl aromatic hydrocarbon structure in the molecule and / or (a-2) ethylene / ⁇ based on mineral oil and / or synthetic oil.
• a crosshead type comprising a base number of 4 to 20 mgKOH / g and a kinematic viscosity at 100 ° C. of 7.5 to 15.0 mm 2 / s, comprising an olefin copolymer or a hydride thereof;
• the present invention relates to a system lubricating oil composition for diesel engines.
• the component (a-1) is a compound having a structure in which a diene polymer or copolymer is radially extended from a nucleus of a vinyl aromatic hydrocarbon located at the center of the molecule.
• the present invention relates to a system lubricant composition for a crosshead type diesel engine.
• the present invention also relates to the system lubricating oil composition for a crosshead type diesel engine as described above, wherein the vinyl aromatic hydrocarbon is divinylbenzene.
• the present invention also relates to the system lubricating oil composition for a crosshead type diesel engine as described above, wherein the diene polymer or copolymer is polyisoprene or isoprene-styrene copolymer.
• the present invention further comprises at least one selected from (B) a metal-based detergent, (C) a zinc dialkyldithiophosphate, (D) a rust inhibitor and (E) an ashless dispersant.
• the present invention relates to a system lubricant composition for a crosshead type diesel engine as described above.
• the present invention also relates to the system lubricating oil composition for a crosshead type diesel engine as described above, wherein the base oil has a kinematic viscosity at 100 ° C. of 3.5 to 9.3 mm 2 / s.
• system lubricating oil composition for a crosshead type diesel engine of the present invention By using the system lubricating oil composition for a crosshead type diesel engine of the present invention, an increase in the viscosity of the system oil can be suppressed, and as a result, deterioration of fuel consumption can be prevented.
• the lubricating base oil used in the system lubricating oil composition for a crosshead type diesel engine of the present invention (hereinafter referred to as the lubricating oil composition of the present invention) is not particularly limited, and mineral oil, synthetic oil or a mixture thereof is used. can do.
• the lubricating oil fraction obtained by subjecting the crude oil to atmospheric distillation obtained under reduced pressure is subjected to solvent removal, solvent extraction, hydrocracking, Produced by one or more processes such as solvent dewaxing, hydrorefining, etc., or manufactured by a method of isomerizing GTL WAX (Gas Liquid Wax) produced by wax isomerized mineral oil, Fischer-Tropsch process, etc.
• GTL WAX Gas Liquid Wax
• synthetic base oils include polybutene or hydrides thereof; poly ⁇ -olefins such as 1-octene oligomers and 1-decene oligomers or hydrides thereof; ethylene and carbon having a weight average molecular weight of 8,000 or less.
• Copolymers with ⁇ -olefins of 3 to 30 diesters such as ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate; trimethylolpropane caprylate, Polyol ester such as trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate; copolymer of dicarboxylic acid such as dibutyl maleate and ⁇ -olefin having 2 to 30 carbon atoms; alkyl naphthalene Alkylbenzene, can be exemplified aromatic synthetic oils, and mixtures thereof and aromatic esters.
• diesters such as ditridecyl glutarate, di-2-ethylhexyl
• a mineral base oil or a synthetic base oil may be used alone or in combination of two or more, or a mineral oil base oil may be used.
• One type or two or more types of base oils and one or more types of synthetic base oils can be mixed and used.
• Kinematic viscosity at 100 ° C. of the lubricating base oil of the present invention is preferably 9.3 mm 2 / s or less, more preferably 8.5 mm 2 / s, more preferably not more than 8.0 mm 2 / s.
• the kinematic viscosity at 100 ° C. is preferably 3.5 mm 2 / s or more, more preferably 3.8 mm 2 / s or more, and still more preferably 4.0 mm 2 / s or more.
• the kinematic viscosity at 100 ° C. here refers to the kinematic viscosity at 100 ° C. as defined in ASTM D-445.
• the kinematic viscosity at 40 ° C. of the lubricating base oil according to the present invention is not particularly limited, but is preferably 150 mm 2 / s or less, more preferably 120 mm 2 / s or less, and still more preferably 90 mm 2 / s or less.
• the kinematic viscosity at 40 ° C. is preferably 15 mm 2 / s or more, more preferably 20 mm 2 / s or more, and further preferably 25 mm 2 / s or more.
• the viscosity index of the lubricating base oil according to the present invention is preferably 85 or more, more preferably 90 or more, and still more preferably 95 or more.
• the upper limit of the viscosity index is not particularly limited, and normal paraffin, slack wax, GTL wax, etc., or isoparaffin mineral oil obtained by isomerizing these can also be used.
• the viscosity index in the present invention means a viscosity index measured according to JIS K 2283-1993.
• the lubricating oil composition of the present invention comprises (a-1) a star polymer having a vinyl aromatic hydrocarbon structure in the molecule and / or (a-2) an ethylene / ⁇ -olefin copolymer as component (A). Or the hydride is contained as an essential component.
• the star polymer having a vinyl aromatic hydrocarbon structure in the molecule of the component (a-1) specifically refers to a number (two or more) dienes from the nucleus of the vinyl aromatic hydrocarbon located at the center of the molecule.
• This is a compound having a structure in which the arms of the polymer or copolymer are radially extended.
• Vinyl aromatic hydrocarbons located at the center of the molecule include divinylbenzene, trivinylbenzene, tetravinylbenzene, divinylortho-, meta- or para-xylene, trivinylortho-, meta- or para-xylene, tetravinyl.
• Ortho-, meta- or para-xylene, divinylnaphthalene, divinylethylbenzene, divinylbiphenyl, diisobutenylbenzene, diisopropenylbenzene, diisopropenylbiphenyl and the like can be mentioned. Of these, divinylbenzene is preferred.
• the diene monomer constituting the diene polymer or copolymer preferably has 4 to 12 carbon atoms.
• 1,3-butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl- Examples include 1,3-hexadiene and 4,5-diethyl-1,3-octadiene. Of these, 1,3-butadiene and isoprene are preferred.
• Examples of the diene polymer or copolymer serving as the arm of the star polymer include diene homopolymers such as polyisoprene and diene comopolymers such as isoprene-butadiene copolymer.
• copolymer of diene and another monomer other than diene for example, isoprene / styrene copolymer.
• the copolymer may be a random copolymer or a block copolymer.
• the weight average molecular weight (M W ) of the star polymer having a vinyl aromatic hydrocarbon structure in the molecule (a-1) used as the component (A) is preferably 10,000 or more, Preferably it is 50,000 or more, More preferably, it is 100,000 or more. Moreover, it is preferable that it is 1,000,000 or less, More preferably, it is 800,000 or less, More preferably, it is 500,000 or less.
• the weight average molecular weight is less than 10,000, not only the viscosity adjustment effect may not be sufficiently exhibited, but also the cost may increase, and when the weight average molecular weight exceeds 1,000,000. Since the shear stability is poor, the viscosity adjusting effect may not be exhibited in the same manner.
• the PSSI (Permanent Cysability Index) of the star polymer having a vinyl aromatic hydrocarbon structure in the molecule (a-1) used in the present invention is preferably 1 to 40, more preferably 1 to 35, still more preferably 1 to 30, particularly preferably 1 to 25.
• PSSI exceeds 40, since shear stability is bad, there exists a possibility that the viscosity adjustment effect cannot fully be exhibited.
• PSSI is less than 1, there exists a possibility that the viscosity adjustment effect cannot be exhibited similarly.
• PSSI Perst al.
• ASTM D 6022-01 Standard Practice for Calculation of Permanent Shear Stability Index
• ASTM D 6278-02 Test Metohd for Shear Stability of Polymer Containing Fluids Using a European Diesel. It means the permanent shear stability index of the polymer calculated based on the data measured by the Injector Apparatus).
• the (a-2) component ethylene / ⁇ -olefin copolymer or its hydride is a copolymer of ethylene and ⁇ -olefin or a hydrogenated compound thereof.
• Specific examples of the ⁇ -olefin include propylene, isobutylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like.
• the ethylene- ⁇ -olefin copolymer is not only a so-called non-dispersed type composed of only hydrocarbons, but also a so-called dispersed type ethylene- ⁇ -olefin copolymer obtained by reacting a polar compound such as a nitrogen-containing compound with the copolymer. Can be used. Among these, it is most preferable to use an ethylene-propylene copolymer.
• the weight average molecular weight (M w ) of the (a-2) ethylene / ⁇ -olefin copolymer or hydride thereof used as the component (A) in the present invention is preferably 10,000 or more, more preferably It is 20,000 or more, More preferably, it is 50,000 or more. Moreover, it is preferable that it is 500,000 or less, More preferably, it is 400,000 or less, More preferably, it is 300,000 or less.
• the weight average molecular weight is less than 10,000, not only the viscosity adjustment effect may not be sufficiently exhibited, but also the cost may increase.
• the weight average molecular weight exceeds 500,000 shear stability is achieved. Similarly, the viscosity adjustment effect may not be exhibited due to poor properties.
• the PSSI (Permanent Cystability Index) of the (a-2) ethylene / ⁇ -olefin copolymer or hydride thereof used in the present invention is preferably 1 to 75, more preferably 3 to 50, still more preferably 5 to 30, particularly preferably 10 to 28.
• PSSI exceeds 75, since shear stability is bad, there exists a possibility that the viscosity adjustment effect at the time of adding to system oil cannot be exhibited.
• PSSI is less than 1, there exists a possibility that the viscosity adjustment effect cannot be exhibited similarly.
• the content of the component (A) in the lubricating oil composition of the present invention is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, further preferably 3 to 12% by mass, based on the total amount of the composition. Most preferably, it is 4 to 10% by mass. If the content is less than 1% by mass, the effect of adjusting the viscosity may not be sufficiently exhibited. If the content exceeds 20% by mass, the handling property may be deteriorated and the lubricating oil production work may be adversely affected. In addition, there is a possibility that deposits are generated due to deterioration of the polymer and the cleanliness is deteriorated.
• the ethylene / ⁇ -olefin copolymer or hydride thereof is usually provided in a state diluted with 10 to 90% by mass of mineral oil.
• the lubricating oil composition of the present invention further contains at least one selected from (B) a metal-based detergent, (C) a zinc dialkyldithiophosphate, (D) a rust inhibitor and (E) an ashless dispersant. It is preferable.
• metal detergent use one or more metal detergents selected from phenate detergents, sulfonate detergents, salicylate detergents, carboxylate detergents and phosphonate detergents. Can do.
• the phenate-type metal detergent contains, for example, an alkylphenol having a structure represented by the following formulas (1) to (3), an alkylphenol sulfide, an alkaline earth metal salt of a Mannich reaction product of an alkylphenol, or a (over) basic salt thereof. It is a phenate metal detergent.
• alkaline earth metal include magnesium, barium, and calcium. Magnesium or calcium is preferable, and calcium is particularly preferable.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 may be the same or different and each has 4 to 30 carbon atoms, preferably Represents a 6-18 linear or branched alkyl group. If the carbon number is shorter than 4, the solubility in the lubricating base oil may be poor. If the carbon number is longer than 30, the production is difficult and the heat resistance may be poor.
• R 1 to R 7 include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, etc.
• M 1 , M 2 and M 3 each represent an alkaline earth metal, preferably calcium and / or magnesium, x, y and z each independently represent an integer of 1 to 3, and m represents 0, 1 or 2 , N represents 0 or 1.
• the sulfonate detergent examples include an alkali metal salt or an alkaline earth metal salt of an alkyl aromatic sulfonic acid obtained by sulfonating an alkyl aromatic compound having a molecular weight of 300 or more, preferably 400 to 700, and / or its ( Per) basic salts can be used.
• the alkali metal or alkaline earth metal examples include sodium, potassium, magnesium, barium, and calcium. Magnesium and / or calcium are preferable, and calcium is particularly preferably used.
• alkyl aromatic sulfonic acid examples include so-called petroleum sulfonic acid and synthetic sulfonic acid.
• the petroleum sulfonic acid here, generally used is a product obtained by sulfonating an alkyl aromatic compound of a lubricating oil fraction of mineral oil, or so-called mahoganic acid produced as a by-product when white oil is produced.
• a sulfonated alkylbenzene having a linear or branched alkyl group which is obtained as a by-product from an alkylbenzene production plant that is a raw material of a detergent or is obtained by alkylating polyolefin with benzene, is obtained.
• alkylnaphthalene such as dinonylnaphthalene.
• the sulfonating agent for sulfonating these alkyl aromatic compounds is not particularly limited, but usually fuming sulfuric acid or anhydrous sulfuric acid is used.
• the salicylate detergent examples include alkali metal or alkaline earth metal salicylate having one hydrocarbon group having 1 to 19 carbon atoms and / or (over) basic salt thereof, and one hydrocarbon group having 20 to 40 carbon atoms.
• Alkali metal or alkaline earth metal salicylate and / or (over) basic salt thereof alkali metal or alkaline earth metal salicylate having two or more hydrocarbon groups having 1 to 40 carbon atoms and / or ( Per) basic salts (these hydrocarbon groups may be the same or different).
• the alkali metal or alkaline earth metal include sodium, potassium, magnesium, barium, and calcium. Magnesium and / or calcium are preferable, and calcium is particularly preferably used.
• the base number of the metal detergent (B) used in the present invention is preferably in the range of 50 to 500 mgKOH / g, more preferably in the range of 100 to 450 mgKOH / g, and 150 to 350 mgKOH / g. More preferably, it is the range. If the base number of the metal detergent is less than 50 mgKOH / g, there is a risk that corrosion wear will increase due to insufficient acid neutralization, and if it exceeds 500 mgKOH / g, there may be a problem in solubility. There is.
• the base number referred to here is JIS K2501 “Petroleum products and lubricants-Neutralization number test method”. Means the base number measured by the perchloric acid method according to the above.
• the metal ratio of the metallic detergent is not particularly limited, but the lower limit is 1 or more, preferably 2 or more, particularly preferably 2.5 or more, and the upper limit is preferably 20 or less, more preferably 15 or less, particularly preferably. Is preferably 10 or less.
• the metal ratio referred to here is represented by (B) the valence of the metal element in the metal-based detergent ⁇ metal element content (mol%) / soap group content (mol%).
• Alkaline earth metals such as calcium and magnesium and soap groups mean phenol groups.
• composition of the present invention when (B) a metallic detergent is used, its content is usually 0.5 to 15% by mass, preferably 1 to 12% by mass, particularly preferably based on the total amount of the composition. 1.5 to 10% by mass.
• the lubricating oil composition of the present invention preferably contains (C) zinc dialkyldithiophosphate represented by the following general formula (4).
• R 1 , R 2 , R 3 and R 4 may be the same or different, and each independently represents an alkyl group having 1 to 30 carbon atoms or an alkylaryl group having 7 to 30 carbon atoms. Yes, the alkyl group may be linear or branched, and may be primary or secondary.
• (C) component dithiophosphate zinc the conventional arbitrary methods are employable and it does not restrict
• it can be synthesized by reacting an alcohol having an alkyl group corresponding to R 1 , R 2 , R 3 and R 4 with diphosphorus pentasulfide to produce dithiophosphoric acid and neutralizing it with zinc oxide. it can.
• (C) zinc dithiophosphate when used, its content is preferably 0.005 to 0.12% by mass as phosphorus element content based on the total amount of the composition. More preferred is 0.01 to 0.10% by mass, and further more preferred is 0.02 to 0.08% by mass. If it is less than 0.005% by mass, the extreme pressure and gear characteristics required for system oil cannot be obtained, and if it exceeds 0.12% by mass, the seal ring and oil slaver ring of the bearing and stuffing box may be corroded. is there.
• the lubricating oil composition of the present invention preferably contains (D) a rust inhibitor.
• a rust inhibitor examples include sulfonates (salts such as sodium, calcium and barium), succinic acid derivatives, organic acid esters such as fatty acid esters and sorbitan acid esters, and carboxylates (sodium such as stearic acid and naphthenic acid). , Magnesium, barium, zinc, etc.), polyhydric alcohol partial esters such as sorbitan monoester and pentaerythritol monoester, oxidized paraffin (oxidized wax), carboxylic acid, phosphate ester and the like, and sulfonate is preferred.
• a rust inhibitor when used, its content is preferably 0.005 to 5% by mass based on the total amount of the composition.
• the lubricating oil composition of the present invention preferably contains (E) an ashless dispersant.
• an ashless dispersant any ashless dispersant used in lubricating oils can be used.
• the alkyl group or alkenyl group may be linear or branched, but preferred examples include those derived from olefin oligomers such as propylene, 1-butene and isobutylene, and copolymers derived from ethylene and propylene. Examples thereof include a branched alkyl group and a branched alkenyl group.
• succinimide shown by the following Formula or its boron modified product is preferable.
• R 1 represents an alkyl or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms
• h represents an integer of 1 to 5, preferably 2 to 4.
• R 2 and R 3 each independently represent an alkyl group or an alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms, and particularly preferably a polybutenyl group.
• I represents an integer of 0 to 4, preferably 1 to 3.
• the content thereof is preferably 1 to 8% by mass based on the total amount of the composition.
• the lubricating oil composition of the present invention is an optional component commonly used in lubricating oils depending on its purpose in order to further improve its performance or to add other required performance in addition to the above configuration.
• Further additives can be added.
• additives include additives such as antioxidants, extreme pressure agents, corrosion inhibitors, demulsifiers, metal deactivators, pour point depressants, and antifoaming agents.
• Antioxidants include phenolic antioxidants such as DBPC, bisphenol and hindered phenol, amine antioxidants such as diphenylamine and N-phenyl- ⁇ -naphthylamine, and metal antioxidants such as copper and molybdenum Is mentioned.
• phenolic antioxidants such as DBPC
• bisphenol and hindered phenol amine antioxidants such as diphenylamine and N-phenyl- ⁇ -naphthylamine
• metal antioxidants such as copper and molybdenum Is mentioned.
• any extreme pressure agent / antiwear agent used for lubricating oil can be used.
• sulfur-based, phosphorus-based, sulfur-phosphorus extreme pressure agents and the like can be used.
• its content is preferably 0.05 to 5% by mass based on the total amount of the composition.
• corrosion inhibitor examples include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.
• demulsifier examples include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl naphthyl ether, and the like.
• 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, ⁇ - (o-carboxybenzylthio) propiononitrile.
• pour point depressant for example, a polymethacrylate polymer compatible with the lubricating base oil to be used can be used.
• the antifoaming agent examples include silicone oil having a kinematic viscosity at 25 ° C. of 100 to 100,000 mm 2 / s, alkenyl succinic acid derivative, ester of polyhydroxy aliphatic alcohol and long chain fatty acid, methyl salicylate and o- Hydroxybenzyl alcohol, aluminum stearate, potassium oleate, N-dialkyl-allylamine nitroaminoalkanol, aromatic amine salt of isoamyl octyl phosphate, alkylalkylene diphosphate, metal derivative of thioether, metal derivative of disulfide, aliphatic hydrocarbon Fluorine compounds, triethylsilane, dichlorosilane, alkylphenyl polyethylene glycol ether sulfide, fluoroalkyl ether and the like can be mentioned.
• the content is based on the total amount of the composition, and is usually 0.005 to 5% by mass for the corrosion inhibitor, the rust inhibitor, and the demulsifier,
• the metal deactivator is usually selected from the range of 0.005 to 1% by mass
• the antifoaming agent is usually selected from the range of 0.0005 to 1% by mass.
• the kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is required to be 7.5 mm 2 / s or more, preferably 9.3 mm 2 / s or more, more preferably 10 mm 2 / s or more is there.
• the kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is required to be 15.0 mm 2 / s or less, preferably 14.5 mm 2 / s or less, more preferably 12.5 mm 2 / s or less. It is.
• the base number of the lubricating oil composition of the present invention is required to be 4 to 20 mgKOH / g, the lower limit is preferably 5 mgKOH / g or more, more preferably 5.5 mgKOH / g or more, and the upper limit is preferably Is 15 mg KOH / g or less, more preferably 10 mg KOH / g or less.
• the base number is less than 4 mgKOH / g, the cleanliness may be insufficient, and when the base number exceeds 20 mgKOH / g, the contaminated contaminants may be difficult to remove with a cleaner.
• the lubricating oil composition of the present invention is not only used as a system oil for a crosshead type diesel engine, but also for a trunk piston type diesel engine, a gasoline engine for two-wheeled vehicles, four-wheeled vehicles, for power generation, cogeneration, etc., diesel It can also be suitably used for engines, gas engines and the like.
• Examples 1 to 18, Comparative Examples 1 to 4 As shown in Tables 1 and 2, lubricating oil compositions of the present invention (Examples 1 to 18) and comparative lubricating oil compositions (Comparative Examples 1 to 4) were prepared. About the obtained composition, the hot tube test was implemented and the result was similarly shown in Table 1 and Table 2. For Examples 1 to 7, 10 to 16, and Comparative Examples 1, 3, and 4, the polymer was added so that the kinematic viscosity at 100 ° C. of the composition was 11.5 mm 2 / s. The addition amount of the compound and the mixing ratio of the base oil were adjusted.
• the properties of the cylinder drip oil are as follows: kinematic viscosity (100 ° C.): 28.1 mm 2 / s, acid value: 7.5 mgKOH / g, base number (perchloric acid method): 24.1 mgKOH / g, pentane insoluble matter (A Method): 6.0% by mass.
• the lubricating oil composition of the present invention is not different from the comparative oil in the viscosity change when tested with 100% new oil, but when the cylinder drip oil is mixed. It can be seen that the increase in viscosity is smaller than that of the comparative oil.
• the lubricating oil composition of the present invention is excellent in fuel efficiency because of little increase in viscosity even when cylinder drip oil is mixed, and exhibits particularly excellent effects as a system lubricating oil composition for a crosshead type diesel engine. To do.

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• 2010
  • 2010-10-08 CN CN201080058637.6A patent/CN102686712B/zh active Active
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