WO2021187370A1 - 潤滑油組成物、過給機搭載ディーゼルエンジン、及び潤滑油組成物の使用方法 - Google Patents
潤滑油組成物、過給機搭載ディーゼルエンジン、及び潤滑油組成物の使用方法 Download PDFInfo
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- WO2021187370A1 WO2021187370A1 PCT/JP2021/010097 JP2021010097W WO2021187370A1 WO 2021187370 A1 WO2021187370 A1 WO 2021187370A1 JP 2021010097 W JP2021010097 W JP 2021010097W WO 2021187370 A1 WO2021187370 A1 WO 2021187370A1
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- lubricating oil
- oil composition
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- 0 CCC(C)N(*)*C(C)(CC)N(C(CC1*)=O)C1=O Chemical compound CCC(C)N(*)*C(C)(CC)N(C(CC1*)=O)C1=O 0.000 description 2
Classifications
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- 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
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- 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
- 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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- 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/26—Carboxylic acids; Salts thereof
- C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
- C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
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- 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
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/76—Esters containing free hydroxy or carboxyl groups
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/44—Five-membered ring containing nitrogen and carbon only
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- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
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- C10M135/10—Sulfonic acids or derivatives thereof
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- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
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- C10M139/06—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing atoms of elements not provided for in groups C10M127/00 - C10M137/00 having a metal-to-carbon bond
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- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B39/00—Component parts, details, or accessories relating to, driven charging or scavenging pumps, not provided for in groups F02B33/00 - F02B37/00
- F02B39/14—Lubrication of pumps; Safety measures therefor
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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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- 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
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
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- 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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- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
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- C10M2215/26—Amines
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- C10M2215/28—Amides; Imides
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- C10M2215/30—Heterocyclic compounds
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- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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- C10M2223/045—Metal containing thio derivatives
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- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C10N2030/52—Base number [TBN]
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- C10N2040/252—Diesel engines
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- C10N2040/25—Internal-combustion engines
- C10N2040/252—Diesel engines
- C10N2040/253—Small diesel engines
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- 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, a diesel engine equipped with a supercharger to which the lubricating oil composition is applied, and a method of using the lubricating oil composition.
- the supercharger installed in the diesel engine equipped with a supercharger has a structure that makes it easy to suck in mist-ized engine oil because the temperature of the supercharger becomes high. Therefore, the mist floating around the turbocharger is likely to be formed around the turbocharger as a deposit. As the engine displacement increases, the turbocharger becomes hotter and the amount of mist-ized engine oil taken in increases, so that the formation of deposits tends to increase. The formed deposit causes harmful effects such as lowering the efficiency of the turbocharger.
- Patent Document 1 describes a fraction having a boiling point of 500 to 550 ° C. of 14% by mass or more and a boiling point of 550 ° C. for the purpose of providing a lubricating oil composition having improved performance of suppressing deposit formation.
- a lubricating oil composition containing 5% by mass or more of a fraction exceeding the above amount is disclosed.
- a new lubricating oil composition that can be suitably applied to lubrication of a diesel engine equipped with a supercharger is required.
- a base oil contains a non-boron-modified succinimide and a boron-modified succinimide in a predetermined ratio, and further, as a metal-based cleaning agent, a metal-based cleaning agent having a base value of a predetermined value or less is used.
- a lubricating oil composition containing or containing an amine-based antioxidant in a content of a predetermined value or less.
- [1] Contains a base oil (A), a non-boron-modified succinimide (B), a boron-modified succinimide (C), a metal-based cleaning agent (D), and an antioxidant (E).
- the content ratio [B / N] of the boron atom derived from the component (C) and the nitrogen atom derived from the component (B) and the component (C) is 0.30 or less in terms of mass ratio.
- a lubricating oil composition that satisfies at least one of the following requirements (I) and (II).
- the component (D) contains a metal-based cleaning agent (D1) having a base value of less than 100 mgKOH / g.
- -Requirement (II) The component (E) contains an amine-based antioxidant (E1), and the content of the component (E1) is 1.00% by mass or less based on the total amount of the lubricating oil composition. .. [2]
- the component (B) is selected from monoimide succinate (B1) represented by the following general formula (b-1) and bisimide succinate (B2) represented by the following general formula (b-2).
- RA , RA1 and RA2 are independently alkenyl groups having a mass average molecular weight (Mw) of 500 to 3000.
- R B, R B1 and R B2 are each independently an alkylene group having 2 to 5 carbon atoms.
- RC and RC1 are independent hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, or groups represented by-(AO) n- H (however, A is an independent group having 1 to 10 carbon atoms). It is an alkylene group of 2 to 4 and n is an integer of 1 to 10).
- x1 is an integer of 1 to 10
- x2 is an integer of 0 to 10.
- the lubricating oil composition of one preferred embodiment of the present invention has a high effect of suppressing the formation of deposits, it can be suitably applied to lubrication of a diesel engine equipped with a supercharger.
- the kinematic viscosity and the viscosity index mean values measured or calculated in accordance with JIS K2283: 2000.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, and are specifically described in Examples. Means the value measured by the method.
- the contents of metal atoms alkali metal atoms, alkaline earth metal atoms, zinc atoms, etc.
- phosphorus atoms and boron atoms mean values measured in accordance with JPI-5S-38-2003.
- the content of nitrogen atom means a value measured according to JIS K2609.
- the lubricating oil composition of the present invention contains a base oil (A), a non-boron-modified succinic acid imide (B), a boron-modified succinate imide (C), a metal-based cleaning agent (D), and an antioxidant (E).
- the content ratio [B / N] of the boron atom derived from the component (C) to the nitrogen atom derived from the components (B) and (C) should be 0.30 or less in terms of mass ratio.
- the lubricating oil composition of the present invention satisfies at least one of the following requirements (I) and (II).
- the component (D) contains a metal-based cleaning agent (D1) having a base value of less than 100 mgKOH / g.
- the component (E) contains an amine-based antioxidant (E1), and the content of the component (E1) is 1.00% by mass or less based on the total amount of the lubricating oil composition. ..
- the lubricating oil composition of the present invention Since the lubricating oil composition of the present invention is prepared so as to satisfy the above requirements, it has a high effect of suppressing the formation of deposits (hereinafter, also referred to as "deposit resistance"), and is particularly continuous in a high temperature environment. It is possible to effectively develop excellent deposit resistance even when used in various ways. That is, in the lubricating oil composition of the present invention, it is contained together with the component (C), and the content ratio [B / N] is adjusted to be 0.30 or less so that the boron of the component (C) can be obtained. It is said that the formation of the resulting deposit is effectively suppressed, and the dispersibility is improved so that the performance of each component when the components (D) and (E) are blended can be more effectively expressed.
- the performance of the component (D1) and the component (E1) is effective. It is considered that it can be expressed as a lubricating oil composition having improved deposit resistance. From the viewpoint of obtaining a lubricating oil composition having further improved deposit resistance, it is preferable that the lubricating oil composition of one aspect of the present invention satisfies both the above requirements (I) and (II).
- the content ratio [B / N] of the boron atom derived from the component (C) and the nitrogen atom derived from the components (B) and (C). Is 0.30 or less in terms of mass ratio, but is preferably 0.28 or less, more preferably 0.26 or less, still more preferably 0.25 or less, still more preferably 0.24 or less, and particularly preferably 0. It is .22 or less, preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.07 or more, still more preferably 0.09 or more, and particularly preferably 0.11 or more.
- the content ratio [B / N] is preferably 0.01 to 0.30, more preferably 0.01 to 0.28, more preferably 0.05 to 0.26, and further in terms of mass ratio. It is preferably 0.07 to 0.25, more preferably 0.09 to 0.24, and particularly preferably 0.11 to 0.22.
- the total content of the nitrogen atoms derived from the component (B) and the component (C) is preferably based on the total amount (100% by mass) of the lubricating oil composition. 0.040 to 0.300% by mass, more preferably 0.045 to 0.250% by mass, further preferably 0.050 to 0.200% by mass, still more preferably 0.055 to 0.170% by mass, Particularly preferably, it is 0.060 to 0.150% by mass. Further, the total content of the nitrogen atoms derived from the component (B) and the component (C) is 0.062% by mass or more and 0.065% by mass based on the total amount (100% by mass) of the lubricating oil composition.
- the base value of the component (D1) defined in the requirement (I) is less than 100 mgKOH / g, preferably 90 mgKOH / g or less, more preferably 85 mgKOH / g or less. More preferably 80 mgKOH / g or less, still more preferably 75 mgKOH / g or less, particularly preferably 70 mgKOH / g or less, and further preferably 65 mgKOH / g or less, 60 mgKOH / g or less, 50 mgKOH / g or less, 40 mgKOH / g or less, Alternatively, it may be 30 mgKOH / g or less.
- the base value of the component (D1) specified in the requirement (I) is 0 mgKOH / g or more, but 5 mgKOH / g or more, 10 mgKOH / g or more, 15 mgKOH / g or more, 20 mgKOH / g or more, 25 mgKOH / g or more. , 30 mgKOH / g or more, 35 mgKOH / g or more, or 40 mgKOH / g or more.
- the base values of the component (D1) specified in the requirement (I) and the component (D2) described later are defined in JIS K2501 "Petroleum products and lubricating oil-neutralization value test method". It means the base value by the "perchloric acid method" measured according to.
- the content of the component (D1) in terms of metal atom is based on the total amount (100% by mass) of the lubricating oil composition. It is preferably 0.001 to 0.080% by mass, more preferably 0.005 to 0.060% by mass, still more preferably 0.007 to 0.050% by mass, and even more preferably 0.010 to 0.040% by mass. %, Especially preferably 0.012 to 0.035% by mass.
- the content of the component (D1) in terms of metal atom is 0.015% by mass or more, 0.017% by mass or more, or 0. It may be 020% by mass or more, and may be 0.032% by mass or less, 0.030% by mass or less, or 0.027% by mass or less.
- the content of the component (E1) is 1.00% by mass or less based on the total amount (100% by mass) of the lubricating oil composition.
- it is preferably 0.90% by mass or less, more preferably 0.80% by mass or less, still more preferably 0.70% by mass or less, still more preferably 0.65% by mass or less, and particularly preferably 0.60% by mass.
- % Or less more preferably 0.55% by mass or less, or 0.50% by mass or less, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.
- the content of the component (E1) is preferably 0.01 to 1.00% by mass based on the total amount (100% by mass) of the lubricating oil composition. More preferably 0.01 to 0.90% by mass, more preferably 0.05 to 0.80% by mass or less, still more preferably 0.10 to 0.70% by mass, still more preferably 0.15 to 0. It is 65% by mass, particularly preferably 0.20 to 0.60% by mass.
- the lubricating oil composition according to one aspect of the present invention preferably further contains at least one of a viscosity index improver (F) and an abrasion resistant agent (G), and the viscosity index improver (F) and the abrasion resistant agent. It is more preferable to contain (G) together. Further, the lubricating oil composition according to one aspect of the present invention further contains additives for lubricating oil other than the components (B) to (G), if necessary, as long as the effects of the present invention are not impaired. You may.
- the total content of the components (A) to (E) is preferably 55% by mass or more based on the total amount (100% by mass) of the lubricating oil composition. It is more preferably 65% by mass or more, further preferably 70% by mass or more, still more preferably 75% by mass or more, and particularly preferably 80% by mass or more.
- the total content of the components (A) to (G) is preferably 60% by mass or more based on the total amount (100% by mass) of the lubricating oil composition. It is more preferably 70% by mass or more, further preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
- Base oil examples include one or more selected from mineral oils and synthetic oils.
- Mineral oils include, for example, atmospheric residual oil obtained by atmospheric distillation of crude oils such as paraffin crude oil, intermediate base crude oil, and naphthenic crude oil; and distillate oil obtained by vacuum distillation of these atmospheric residual oils. Examples thereof include refined oils obtained by subjecting the distillate oil to one or more refining treatments such as solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, and hydrorefining.
- Examples of the synthetic oil include poly such as an ⁇ -olefin homopolymer or an ⁇ -olefin copolymer (for example, an ⁇ -olefin copolymer having 8 to 14 carbon atoms such as an ethylene- ⁇ -olefin copolymer).
- Examples thereof include synthetic oil (GTL) obtained by isomerizing the produced wax (GTL wax (Gas To Liquids WAX)).
- the component (A) used in one aspect of the present invention includes mineral oils classified into Group 2 and Group 3 of the API (American Petroleum Institute) base oil category, and one or more selected from synthetic oils. Is preferable.
- the kinematic viscosity of the component (A) used in one aspect of the present invention at 100 ° C. is preferably 2.0 to 20.0 mm 2 / s, more preferably 2.0 to 15.0 mm 2 / s, and even more preferably 2.0 to 15.0 mm 2 / s. It is 3.0 to 12.0 mm 2 / s, more preferably 3.2 to 9.0 mm 2 / s, and particularly preferably 3.5 to 7.0 mm 2 / s.
- the viscosity index of the component (A) used in one aspect of the present invention is appropriately set according to the use of the lubricating oil composition, but is preferably 70 or more, more preferably 80 or more, still more preferably 90 or more. , More preferably 100 or more, and particularly preferably 110 or more.
- the kinematic viscosity and viscosity index of the mixed oil are preferably in the above ranges.
- the content of the component (A) is preferably 30 to 98% by mass, more preferably 40 to 95% based on the total amount (100% by mass) of the lubricating oil composition. It is by mass, more preferably 50 to 93% by mass, even more preferably 60 to 90% by mass, and particularly preferably 65 to 87% by mass.
- the lubricating oil composition of the present invention contains a non-boron-modified succinimide (B).
- the component (B) may be used alone or in combination of two or more.
- the component (B) used in one embodiment of the present invention includes alkenylsuccinic acid monoimide (B1) represented by the following general formula (b-1) and alkenylsuccinic acid represented by the following general formula (b-2). It is preferably at least one selected from bisimide (B2).
- RA , RA1 and RA2 are independently alkenyls having a weight average molecular weight (Mw) of 500 to 3000 (preferably 1000 to 3000). Is the basis.
- alkenyl group include a polybutenyl group, a polyisobutenyl group, an ethylene-propylene copolymer and the like, and a polybutenyl group or a polyisobutenyl group is preferable.
- R B, R B1 and R B2 are each independently an alkylene group having 2 to 5 carbon atoms.
- RC and RC1 are independent hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, or groups represented by-(AO) n- H (however, A is an independent group having 1 to 10 carbon atoms). It is an alkylene group of 2 to 4 and n is an integer of 1 to 10).
- x1 is an integer of 1 to 10, preferably an integer of 2 to 5, and more preferably 3 or 4.
- x2 is an integer of 0 to 10, preferably an integer of 1 to 5, and more preferably an integer of 2 to 4.
- RC and RC1 in the above general formulas (b-1) and (b-2) are not hydrogen atoms but alkyl groups having 1 to 10 carbon atoms or -(AO) It is preferable that the compound is a group represented by n-H.
- the component (B) used in one aspect of the present invention is monoimide alkenyl succinate (B1) represented by the general formula (b-1). ) Is preferably included.
- the content of the component (B) in terms of nitrogen atom is preferably 0.005 to 0. Based on the total amount (100% by mass) of the lubricating oil composition. 120% by mass, more preferably 0.007 to 0.100% by mass, still more preferably 0.010 to 0.080% by mass, even more preferably 0.015 to 0.070% by mass, particularly preferably 0.020. It is ⁇ 0.065% by mass.
- the lubricating oil composition of the present invention contains a boron-modified succinimide (C) together with the component (B).
- the component (C) may be used alone or in combination of two or more.
- the component (C) is contained together with the component (B) to obtain a content ratio [B / N] of the boron atom derived from the component (C) and the nitrogen atom derived from the components (B) and (C). It is used to adjust to 0.30 or less. Then, the content ratio [B / N] can be adjusted to 0.30 or less to obtain a lubricating oil composition having excellent deposit resistance.
- the component (C) used in one aspect of the present invention may be boron-modified monoimide succinate or boron-modified bisimide succinate. Specific examples thereof include a boron-modified product of monoimide alkenyl succinate represented by the general formula (b-1) and a boron-modified product of bisimide alkenyl succinate represented by the general formula (b-2).
- the ratio [B / N] of the boron atom and the nitrogen atom constituting the component (C) used in one aspect of the present invention is preferably 0.10 to 0.90, more preferably 0.15 to the mass ratio. It is 0.80, more preferably 0.20 to 0.70, even more preferably 0.25 to 0.60, and particularly preferably 0.30 to 0.50.
- the content of the boron atom derived from the component (C) is preferably 0.001 to 0. Based on the total amount (100% by mass) of the lubricating oil composition. 070% by mass, more preferably 0.003 to 0.060% by mass, still more preferably 0.006 to 0.050% by mass, even more preferably 0.008 to 0.040% by mass, particularly preferably 0.010. It is ⁇ 0.035% by mass.
- the content of the boron atom derived from the component (C) is 0.011% by mass or more, 0.012% by mass or more, or 0.013% by mass based on the total amount (100% by mass) of the lubricating oil composition. % Or more, and 0.032% by mass or less, 0.030% by mass or less, 0.027% by mass or less, 0.025% by mass or less, 0.023% by mass or less, or 0.020% by mass or less. May be.
- the content of the component (C) in terms of nitrogen atom is preferably 0.015 to 0. Based on the total amount (100% by mass) of the lubricating oil composition. 180% by mass, more preferably 0.020 to 0.150% by mass, still more preferably 0.025 to 0.120% by mass, even more preferably 0.030 to 0.100% by mass, particularly preferably 0.032. It is ⁇ 0.085% by mass.
- the lubricating oil composition of one aspect of the present invention may contain an ashless dispersant other than the components (B) and (C) as long as the effects of the present invention are not impaired.
- examples of such other ashless dispersants include monoimide succinate, bisimide succinate, benzylamine, succinate ester, and boron-modified products thereof.
- the content of the ashless dispersant other than the components (B) and (C) is the component (B) and ( With respect to the total of 100 parts by mass of C), preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, still more preferably 0 to 10 parts by mass, still more preferably 0 to 5 parts by mass, particularly preferably. It is 0 to 1 part by mass.
- the lubricating oil composition of the present invention contains a metal-based cleaning agent (D).
- a metal-based cleaning agent (D) By containing the component (D), the clean dispersibility is improved, and a lubricating oil composition having excellent deposit resistance can be obtained.
- the component (D) may be used alone or in combination of two or more.
- the component (D) used in one embodiment of the present invention is at least one selected from metal salicylate, metal phenate, and metal sulfonate, which contains a metal atom selected from an alkali metal atom and an alkaline earth metal atom. Is preferable. As the metal atom, sodium, calcium, magnesium, or barium is preferable, and calcium is more preferable. That is, the component (D) is preferably a calcium-based cleaning agent.
- the metal sulfonate is preferably a compound represented by the following general formula (d-1), and the metal salicylate is preferably a compound represented by the following general formula (d-2) as the metal phenate. Is preferably a compound represented by the following general formula (d-3).
- M is a metal atom selected from alkali metals and alkaline earth metals, and sodium, calcium, magnesium, or barium is preferable, and calcium is more preferable.
- M' is an alkaline earth metal, preferably calcium, magnesium, or barium, and more preferably calcium.
- y is an integer of 0 or more, preferably an integer of 0 to 3.
- p is a valence of M, which is 1 or 2.
- R is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
- Examples of the hydrocarbon group that can be selected as R include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 ring-forming carbon atoms, and 6 to 18 ring-forming carbon atoms. Examples thereof include an aryl group of 7 to 18, an alkylaryl group having 7 to 18 carbon atoms, and an arylalkyl group having 7 to 18 carbon atoms.
- the component (D) contains a metal-based cleaning agent (D1) having a base value of less than 100 mgKOH / g.
- the component (D1) preferably contains at least one selected from metal sulfonate and metal salicylate, and more preferably contains at least calcium sulfonate or calcium sulfonate.
- the total content ratio of the metal sulfonate (preferably calcium sulfonate) and the metal salicylate (preferably calcium salicylate) in the component (D1) is contained in the lubricating oil composition.
- the component (D1) Based on the total amount (100% by mass) of the component (D1), preferably 50 to 100% by mass, more preferably 60 to 100% by mass, still more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, Particularly preferably, it is 90 to 100% by mass.
- the component (D) preferably contains a metal-based cleaning agent (D2) having a base value of 100 mgKOH / g or more together with the component (D1).
- the content ratio of the component (D1) to the component (D2) [(D1) / (D2)] is a mass ratio in terms of metal atoms, preferably 1/99 to 50. / 50, more preferably 1.5 / 98.5 to 40/60, even more preferably 2/98 to 30/70, even more preferably 2.5 / 97.5 to 25/75, particularly preferably 3 / It is 97 to 20/80.
- the component (D) includes the component (D2).
- the base value of the component (D2) used in one embodiment of the present invention is 100 mgKOH / g or more, preferably 110 mgKOH / g or more, more preferably 120 mgKOH / g or more, still more preferably 150 mgKOH / g or more, still more preferably.
- the base value of the component (D2) is preferably 100 to 600 mgKOH / g, more preferably 110 to 600 mgKOH / g, more preferably 120 to 550 mgKOH / g, still more preferably 150 to 500 mgKOH / g, and even more preferably. It is 180 to 450 mgKOH / g, particularly preferably 200 to 400 mgKOH / g.
- the component (D2) preferably contains metal salicylate, and more preferably calcium salicylate.
- the content ratio of the metal salicylate (preferably calcium salicylate) in the component (D2) is the total amount (100% by mass) of the component (D2) contained in the lubricating oil composition. ), It is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, further preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, and particularly preferably 90 to 100% by mass. ..
- the content of the component (D) in terms of metal atom is preferably 0.010 to 0.600 based on the total amount (100% by mass) of the lubricating oil composition. Mass%, more preferably 0.030 to 0.500% by mass, still more preferably 0.060 to 0.450% by mass, even more preferably 0.100 to 0.400% by mass, particularly preferably 0.130 to 0.130 to It is 0.300% by mass.
- the lubricating oil composition of the present invention contains an antioxidant (E). By containing the component (E), the oxidative stability is improved, and a lubricating oil composition having excellent deposit resistance can be obtained.
- the component (E) may be used alone or in combination of two or more.
- Examples of the component (E) used in one aspect of the present invention include amine-based antioxidants, phenol-based antioxidants, molybdenum-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.
- the component (E) contains an amine-based antioxidant (E1).
- the amine-based antioxidant include diphenylamine and diphenylamine-based antioxidants such as alkylated diphenylamine having an alkyl group having 3 to 20 carbon atoms; ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, and alkyl having 3 to 20 carbon atoms.
- Examples include naphthylamine-based antioxidants having a group such as substituted phenyl- ⁇ -naphthylamine; and the like.
- the component (E) preferably contains a phenolic antioxidant (E2) together with the component (E1). Further, even when the above requirement (II) is not satisfied, the component (E) preferably contains a phenolic antioxidant.
- the phenolic antioxidant include 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, and the like.
- the content ratio of the component (E1) to the component (E2) [(E1) / (E2)] is a mass ratio, preferably 0.01 to 0.60, more preferably. Is 0.03 to 0.50, more preferably 0.05 to 0.40, still more preferably 0.07 to 0.35, and particularly preferably 0.10 to 0.30.
- the content of the component (E2) is preferably 0.1 to 7.0% by mass, more preferably 0.1 to 7.0% by mass, based on the total amount (100% by mass) of the lubricating oil composition.
- the content of the component (E) is preferably 0.1 to 8.0% by mass based on the total amount (100% by mass) of the lubricating oil composition. It is preferably 0.5 to 7.2% by mass, more preferably 0.8 to 6.7% by mass, still more preferably 1.2 to 5.2% by mass, and particularly preferably 1.6 to 4.7% by mass. %.
- the lubricating oil composition of one aspect of the present invention preferably further contains a viscosity index improver (F).
- a lubricating oil composition having excellent fuel efficiency can be obtained.
- the component (F) may be used alone or in combination of two or more.
- the content of the component (F) is preferably 0.1 to 10.0% by mass, more preferably, based on the total amount (100% by mass) of the lubricating oil composition. Is 0.5 to 8.0% by mass, more preferably 0.7 to 6.0% by mass, even more preferably 1.0 to 4.0% by mass, and particularly preferably 1.2 to 2.5% by mass. Is.
- the component (F) used in one embodiment of the present invention preferably contains at least one selected from a comb-shaped polymer (F1) and an olefin-based copolymer (F2), and has a lubricating oil composition with further improved deposit resistance. From the viewpoint of the product, it is preferable to contain both the comb-shaped polymer (F1) and the olefin-based copolymer (F2).
- the content ratio of the component (F2) to the component (F1) [(F2) / (F1)] is a mass ratio, and lubrication with further improved deposit resistance.
- it is preferably 0.90 or less, more preferably 0.80 or less, still more preferably 0.70 or less, still more preferably 0.60 or less, and further improve shear stability.
- it is preferably 0.05 or more, more preferably 0.10 or more, still more preferably 0.12 or more, still more preferably 0.15 or more.
- the content ratio of the component (F2) to the component (F1) [(F2) / (F1)] is preferably 0.05 to 0.90, more preferably 0. It is 10 to 0.80, more preferably 0.12 to 0.70, and even more preferably 0.15 to 0.60.
- the comb-shaped polymer which is the component (F1) used in one aspect of the present invention may be a polymer having a structure having a large number of three-pronged branch points in the main chain having high molecular weight side chains.
- a polymer having at least a structural unit (X1) derived from a macromonomer (x1) is preferable.
- This structural unit (X1) corresponds to the above-mentioned "high molecular weight side chain".
- the above-mentioned "macromonomer (x1)” means a high molecular weight monomer having a polymerizable functional group, and is preferably a high molecular weight monomer having a polymerizable functional group at the terminal.
- the content of the constituent unit (X1) is preferably 0.5 to 20 mol% based on the total amount (100 mol%) of the constituent units of the component (F1). It is more preferably 0.7 to 10 mol%, still more preferably 0.9 to 5 mol%.
- the content of each structural unit in the component (F1) and the component (F2) means a value calculated by analyzing the 13 C-NMR quantitative spectrum.
- the number average molecular weight (Mn) of the macromonomer (x1) is preferably 300 or more, more preferably 400 or more, further preferably 500 or more, and preferably 100,000 or less, more preferably 50,000 or less. , More preferably 20,000 or less. That is, the number average molecular weight (Mn) of the macromonomer (x1) is preferably 300 to 100,000, more preferably 400 to 50,000, and even more preferably 500 to 20,000.
- the macromonomer (x1) may have, for example, one or more repeating units represented by the following general formulas (i) to (iii) in addition to the above-mentioned polymerizable functional group.
- R b1 is a linear or branched alkylene group having 1 to 10 carbon atoms.
- R b2 is a linear or branched alkylene group having 2 to 4 carbon atoms.
- R b3 is a hydrogen atom or a methyl group.
- R b4 is a linear or branched alkyl group having 1 to 10 carbon atoms.
- the macromonomer (x1) is preferably a polymer having a repeating unit represented by the general formula (i), and R b1 in the general formula (i) is 1,2. More preferably, it is a polymer having a repeating unit (X1-1) which is at least one of a-butylene group and a 1,4-butylene group.
- the content of the repeating unit (X1-1) is preferably 1 to 100 mol%, more preferably 20 to 95 mol%, still more preferably, based on the total amount (100 mol%) of the constituent units of the macromonomer (x1). Is 40 to 90 mol%, more preferably 50 to 80 mol%.
- the macromonomer (x1) is a copolymer having two or more repeating units selected from the general formulas (i) to (iii)
- the form of copolymerization is a block copolymer. It may be a random copolymer or a random copolymer.
- the component (F1) used in one embodiment of the present invention may be a copolymer composed of only a structural unit (X1) derived from one type of macromonomer (x1), or is derived from two or more types of macromonomers (x1). It may be a copolymer having a structural unit (X1). Further, the component (F1) used in one embodiment of the present invention has a structural unit (X1) derived from the macromonomer (x1) and a structural unit (X2) derived from a monomer other than the macromonomer (x1). It may be a copolymer.
- a side chain containing a structural unit (X1) derived from a macromonomer (x1) is used as opposed to a main chain containing a structural unit (X2) derived from a monomer (x2).
- a copolymer having the above is preferable.
- Examples of the monomer (x2) include alkyl (meth) acrylate, nitrogen atom-containing vinyl monomer, hydroxyl group-containing vinyl monomer, phosphorus atom-containing monomer, aliphatic hydrocarbon-based vinyl monomer, and alicyclic type.
- Hydrocarbon-based vinyl monomers, vinyl esters, vinyl ethers, vinyl ketones, epoxy group-containing vinyl monomers, halogen element-containing vinyl monomers, unsaturated polycarboxylic acid esters, (di) alkyl fumarate, ( D) Alkyl maleate, aromatic hydrocarbon-based vinyl monomer and the like can be mentioned.
- the monomer (x2) a monomer other than the phosphorus atom-containing monomer and the aromatic hydrocarbon-based vinyl monomer is preferable, and the monomer represented by the following general formula (a1), alkyl (meth). ) It is more preferable to contain at least one selected from acrylate and a hydroxyl group-containing vinyl monomer, and further preferably to contain at least a hydroxyl group-containing vinyl monomer (x2-d).
- R b11 is a hydrogen atom or a methyl group.
- R b12 is a single bond, linear or branched alkylene group having 1 to 10 carbon atoms, -O-, or -NH-.
- R b13 is a linear or branched alkylene group having 2 to 4 carbon atoms.
- n represents an integer of 1 or more (preferably an integer of 1 to 20, more preferably an integer of 1 to 5).
- the plurality of R b13s may be the same or different, and the (R b13 O) n portion may be a random bond or a block bond.
- R b14 is a linear or branched alkyl group having 1 to 60 carbon atoms (preferably 10 to 50, more preferably 20 to 40).
- the weight average molecular weight (Mw) of the component (F1) used in one embodiment of the present invention is preferably 200,000 or more, more preferably 250,000 or more, from the viewpoint of obtaining a lubricating oil composition having further improved deposit resistance. More preferably 300,000 or more, still more preferably 350,000 or more, particularly preferably 450,000 or more, and preferably 1 million or less, more preferably 900,000 or less, still more preferably 800,000 or less, even more preferably. Is 750,000 or less, particularly preferably 700,000 or less.
- the weight average molecular weight (Mw) of the component (F1) is preferably 200,000 to 1,000,000, more preferably 250,000 to 900,000, still more preferably 300,000 to 800,000, and even more preferably 350,000 to 750,000. , Particularly preferably 450,000 to 700,000.
- the molecular weight distribution (Mw / Mn) of the component (F1) used in one embodiment of the present invention has a lubricating oil composition with further improved deposit resistance.
- Mn indicates the number average molecular weight of the component (F1)
- Mn indicates the number average molecular weight of the component (F1)
- Mn indicates the number average molecular weight of the component (F1)
- Mn indicates the number average molecular weight of the component (F1)
- Mn indicates the number average molecular weight of the component (F1)
- Mn indicates the number average molecular weight of the component (F1)
- Mn indicates the number average molecular weight of the component (F1)
- Mn indicates the number average molecular weight of the component (F1)
- Mn indicates the number average molecular weight of the component (F1)
- Mn indicates the number average molecular weight of the component (F1)
- Mn indicates the number average molecular weight of the component (F1)
- Mn indicates the number average molecular weight of
- the molecular weight distribution (Mw / Mn) of the component (F1) is preferably 1.01 to 8.00, more preferably 1.02 to 7.00, still more preferably 1.05 to 6.00, and further. It is preferably 1.07 to 4.00, particularly preferably 1.10 to 3.00.
- the SSI (shear stability index) of the component (F1) used in one aspect of the present invention is preferably 100 or less, more preferably 80 or less, from the viewpoint of obtaining a lubricating oil composition having further improved deposit resistance. It is more preferably 70 or less, still more preferably 60 or less, and particularly preferably 50 or less.
- the SSI of the component (F1) is usually 0.1 or more, although there is no particular limitation on the lower limit.
- the SSI shear stability index
- SSI (%) (Kv 0 -Kv 1 ) / (Kv 0- Kv oil ) x 100
- Kv 0 is the value of the kinematic viscosity of the sample oil obtained by diluting the polymer component with mineral oil at 100 ° C.
- Kv 1 is the value of the sample oil obtained by diluting the polymer component with mineral oil. It is a value of kinematic viscosity at 100 ° C. after irradiation with ultrasonic waves for 30 minutes according to the output method according to the procedure of 5S-29-06.
- Kv oil is a value of the kinematic viscosity of the mineral oil used when diluting the polymer component at 100 ° C.
- the SSI value of the component (F1) changes depending on the structure of the comb-shaped polymer. Specifically, there is a tendency shown below, and the SSI value of the component (F1) can be easily adjusted by considering these matters.
- the following items are merely examples and can be adjusted by considering items other than these items.
- -The side chain of the comb-shaped polymer is composed of macromonomer (x1), and the content of the structural unit (X1) derived from the macromonomer (x1) is 0.5 based on the total amount (100 mol%) of the structural unit.
- Comb-shaped polymers having a molar% or more tend to have a low SSI value.
- the larger the molecular weight of the macromonomer (x1) constituting the side chain of the comb-shaped polymer the lower the SSI value tends to be.
- the content of the component (F1) is preferably 0.50 to 6.00% by mass, more preferably based on the total amount (100% by mass) of the lubricating oil composition. Is 0.85 to 5.00% by mass, more preferably 0.88 to 4.00% by mass, still more preferably 1.00 to 3.50% by mass, still more preferably 1.20 to 3.00% by mass. , Particularly preferably 1.45 to 2.50% by mass.
- the component (F2) used in one embodiment of the present invention is a copolymer having a structural unit derived from a monomer having an alkenyl group, and is, for example, 2 to 20 carbon atoms (preferably 2 to 16, more preferably 2 to 16 carbon atoms). Examples thereof include ⁇ -olefin copolymers of 2 to 14), and more specific examples thereof include ethylene- ⁇ -olefin copolymers, styrene-diene copolymers, and styrene-isoprene copolymers.
- the weight average molecular weight (Mw) of the component (F2) used in one embodiment of the present invention is preferably 200,000 or more, more preferably 300,000 or more, still more preferably 400,000 or more, still more preferably 500,000 or more, particularly preferably. Is 550,000 or more, preferably 1 million or less, more preferably 900,000 or less, still more preferably 800,000 or less, still more preferably 750,000 or less, and particularly preferably 700,000 or less. That is, the weight average molecular weight (Mw) of the component (F2) is preferably 200,000 to 1,000,000, more preferably 300,000 to 900,000, still more preferably 400,000 to 800,000, and even more preferably 500,000 to 750,000. , Particularly preferably 550,000 to 700,000.
- the molecular weight distribution (Mw / Mn) of the component (F2) used in one embodiment of the present invention is preferably 8.00 or less, more preferably 7. It is 0.00 or less, more preferably 6.00 or less, still more preferably 3.00 or less, particularly preferably 2.00 or less, and preferably 1.001 or more, more preferably 1.005 or more, still more preferable. Is 1.01 or more, more preferably 1.02 or more, and particularly preferably 1.03 or more.
- the molecular weight distribution (Mw / Mn) of the component (F2) is preferably 1.001 to 8.00, more preferably 1.005 to 7.00, still more preferably 1.01 to 6.00, and further. It is preferably 1.02 to 3.00, and particularly preferably 1.03 to 2.00.
- the SSI (shear stability index) of the component (F2) used in one embodiment of the present invention is preferably 60 or less, more preferably 40 or less, still more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15. It is as follows.
- the SSI of the component (F2) is usually 0.1 or more, although there is no particular limitation on the lower limit.
- the content of the component (F2) is preferably 0.10 to 2.00% by mass, more preferably based on the total amount (100% by mass) of the lubricating oil composition. Is 0.15 to 1.70% by mass, more preferably 0.17 to 1.50% by mass, still more preferably 0.20 to 1.20% by mass, and particularly preferably 0.25 to 1.00% by mass. Is.
- the component (F2) contains a star polymer (F21) from the viewpoint of obtaining a lubricating oil composition having good deposit resistance and shear stability.
- the content ratio of the component (F21) in the component (F2) is based on the total amount (100% by mass) of the component (F2) contained in the lubricating oil composition. It is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass.
- the star-shaped polymer which is the component (F21) used in one aspect of the present invention may be a polymer having a structure in which three or more chain polymers are bonded at one point.
- Examples of the chain polymer constituting the component (F21) include a copolymer of a vinyl aromatic monomer and a conjugated diene monomer, a hydride thereof, and the like.
- Examples of the vinyl aromatic monomer include styrene, alkyl-substituted styrene having 8 to 16 carbon atoms, alkoxy-substituted styrene having 8 to 16 carbon atoms, vinyl naphthalene, and alkyl-substituted vinyl naphthalene having 8 to 16 carbon atoms.
- Examples of the conjugated diene monomer include conjugated diene having 4 to 12 carbon atoms, and specifically, 1,3-butadiene, isoprene, piperylene, 4-methylpenta-1,3-diene, and 3,4-dimethyl-1. , 3-Hexadiene, 4,5-diethyl-1,3-octadiene and the like.
- the lubricating oil composition of one aspect of the present invention may contain other viscosity index improvers other than the components (F1) and (F2) as long as the effects of the present invention are not impaired.
- the content of the viscosity index improver other than the components (F1) and (F2) is preferably 100 parts by mass with respect to the total amount of the components (F1) and (F2) contained in the lubricating oil composition. It is 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, still more preferably 0 to 10 parts by mass, and even more preferably 0 to 1 part by mass.
- the lubricating oil composition of one aspect of the present invention preferably further contains an abrasion resistant agent (G).
- the component (G) may be used alone or in combination of two or more.
- Examples of the component (G) used in one embodiment of the present invention include zinc dialkyldithiophosphate (ZnDTP), zinc phosphate, zinc dithiocarbamate, molybdenum dithiocarbamate, molybdenum dithiophosphate, disulfides, olefin sulfides, and fats and oils sulfides. , Sulfurized esters, thiocarbonates, thiocarbamates, polysulfides and other sulfur-containing compounds; phosphite esters, phosphoric acid esters, phosphonic acid esters and phosphorus-containing compounds such as amine salts or metal salts thereof. Examples include sulfur and phosphorus-containing abrasion resistant agents such as thioaroic acid esters, thiophosphate esters, thiophosphonic acid esters, and amine salts or metal salts thereof.
- the component (G) contains zinc dialkyldithiophosphate (ZnDTP).
- ZnDTP zinc dialkyldithiophosphate
- Examples of zinc dithiophosphate include compounds represented by the following general formula (g-1).
- R 1 to R 4 independently represent hydrocarbon groups and may be the same or different from each other.
- the number of carbon atoms of the hydrocarbon group that can be selected as R 1 to R 4 is preferably 1 to 20, more preferably 1 to 16, still more preferably 3 to 12, and even more preferably 3 to 10.
- Alkyl groups such as group, phenyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group; octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group.
- cyclohexyl group dimethylcyclohexyl group, ethylcyclohexyl group, methylcyclohexylmethyl group, cyclohexylethyl group, propylcyclohexyl group, butylcyclohexyl group, heptylcyclohexyl group and other cycloalkyl groups; phenyl group, naphthyl group , Aryl groups such as anthracenyl group, biphenyl group, terphenyl group; alkylaryl groups such as tolyl group, dimethylphenyl group, butylphenyl group, nonylphenyl group, methylbenzyl group, dimethylnaphthyl group; phenylmethyl group, phenylethyl group , Arylalkyl groups such as diphenylmethyl group and the like.
- hydrocarbon group such as the hydrocarbon group
- the content of the component (G) is preferably 0.01 to 3.0% by mass, more preferably, based on the total amount (100% by mass) of the lubricating oil composition. Is 0.05 to 2.5% by mass, more preferably 0.10 to 2.0% by mass, and even more preferably 0.20 to 1.8% by mass.
- the content of ZnDTP in terms of zinc atom is the total amount (100 mass) of the lubricating oil composition. %) On a basis, preferably 0.01 to 1.0% by mass, more preferably 0.03 to 0.80% by mass, still more preferably 0.05 to 0.60% by mass, still more preferably 0.08. It is about 0.50% by mass, particularly preferably 0.10 to 0.40% by mass.
- the phosphorus atom equivalent content of ZnDTP is preferably 0.01 to 1.0% by mass, more preferably 0.02 to 0.70, based on the total amount (100% by mass) of the lubricating oil composition. It is by mass, more preferably 0.03 to 0.50% by mass, even more preferably 0.05 to 0.40% by mass, and particularly preferably 0.07 to 0.30% by mass.
- the lubricating oil composition of one aspect of the present invention may further contain additives for lubricating oil other than the components (B) to (G), if necessary, as long as the effects of the present invention are not impaired.
- additives for lubricating oil include pour point lowering agents, anti-emulsifiers, friction modifiers, corrosion inhibitors, metal deactivators, rust inhibitors, antistatic agents, defoamers and the like. ..
- Each of these additives for lubricating oil may be used alone or in combination of two or more.
- each of these additives for lubricating oil can be appropriately adjusted within a range that does not impair the effects of the present invention, but each addition is based on the total amount (100% by mass) of the lubricating oil composition. Independently for each agent, it is usually 0.001 to 15% by mass, preferably 0.005 to 10% by mass, and more preferably 0.01 to 5% by mass.
- the method for producing the lubricating oil composition according to one aspect of the present invention is not particularly limited, but from the viewpoint of productivity, the components (A), the components (B) to (E), and, if necessary, the components It is preferable that the method comprises a step of blending (F) to (G) and other additives for lubricating oil.
- the resin component such as the component (F) is preferably in the form of a solution dissolved in a diluting oil, and the solution is preferably blended with the component (A).
- the kinematic viscosity of the lubricating oil composition according to one aspect of the present invention at 40 ° C. is preferably 10 to 130 mm 2 / s, more preferably 20 to 115 mm 2 / s, still more preferably 25 to 100 mm 2 / s, and further. It is preferably 30 to 90 mm 2 / s, and particularly preferably 35 to 80 mm 2 / s.
- the kinematic viscosity at 100 ° C. for one embodiment of the lubricating oil composition of the present invention preferably 6.0 ⁇ 16.0mm 2 / s, more preferably 8.0 ⁇ 14.0mm 2 / s, more preferably 8 It is .5 to 13.5 mm 2 / s, more preferably 9.0 to 13.0 mm 2 / s, and particularly preferably 9.3 to 12.5 mm 2 / s.
- the viscosity index of the lubricating oil composition according to one aspect of the present invention is preferably 90 or more, more preferably 100 or more, still more preferably 110 or more, and even more preferably 130 or more.
- the SAE viscosity grade of the lubricating oil composition according to one aspect of the present invention is preferably 0W-30 or 5W-30. In these SAE viscosity grades, various performances can be sufficiently exhibited when applied to lubrication of a diesel engine mounted on a supercharger.
- the acid value of the lubricating oil composition according to one aspect of the present invention is preferably 0.30 to 4.00 mgKOH / g, more preferably 0.70 to 3.50 mgKOH / g, and even more preferably 1.20 to 3. It is 20 mgKOH / g, more preferably 1.50 to 3.00 mgKOH / g.
- the acid value of the lubricating oil composition means a value measured according to JIS K2501: 2003 (potentiometric titration method).
- the base value of the lubricating oil composition according to one aspect of the present invention is preferably 2.0 to 12.0 mgKOH / g, more preferably 4.0 to 11.0 mgKOH / g, and even more preferably 5.0 to 10. It is 0 mgKOH / g, more preferably 7.0 to 9.5 mgKOH / g.
- the base value of the lubricating oil composition means a value measured in accordance with JIS K2501: 2003 (perchloric acid method).
- the content of the boron atom of the lubricating oil composition according to one aspect of the present invention is preferably 0.001 to 0.070% by mass, more preferably 0.003 to 0.060, based on the total amount of the lubricating oil composition. It is by mass, more preferably 0.006 to 0.050% by mass, even more preferably 0.008 to 0.040% by mass, and particularly preferably 0.010 to 0.035% by mass. Further, the content of the boron atom of the lubricating oil composition of one aspect of the present invention is 0.011% by mass or more and 0.012% by mass or more based on the total amount (100% by mass) of the lubricating oil composition. , 0.013% by mass or more, and 0.032% by mass or less, 0.030% by mass or less, 0.027% by mass or less, 0.025% by mass or less, 0.023% by mass or less, or It may be 0.020% by mass or less.
- the content of the nitrogen atom in the lubricating oil composition according to one aspect of the present invention is preferably 0.025 to 0.400% by mass, more preferably 0.030 to 0.300, based on the total amount of the lubricating oil composition. It is by mass, more preferably 0.040 to 0.250% by mass, even more preferably 0.050 to 0.200% by mass, and particularly preferably 0.060 to 0.170% by mass. Further, the content of the nitrogen atom of the lubricating oil composition of one aspect of the present invention is 0.070% by mass or more and 0.080% by mass or more based on the total amount (100% by mass) of the lubricating oil composition. , 0.090% by mass or more, or 0.100% by mass or more, and 0.160% by mass or less, 0.150% by mass or less, 0.140% by mass or less, or 0.130% by mass or less. May be good.
- the lubricating oil composition of one aspect of the present invention has a high effect of suppressing the formation of deposits, and therefore can be suitably applied to lubrication of a diesel engine equipped with a supercharger.
- the amount of deposits generated when a hot tube test is performed on the lubricating oil composition of one aspect of the present invention at a temperature of 300 ° C. in a glass tube in accordance with JPI-5S-55-99 is preferably 40.0 mg.
- the amount of deposits generated when the above hot tube test is performed is an index of the amount of deposit generated with the use of the lubricating oil composition over time, and the smaller the value of the amount of deposits, the more deposits are formed even with the use over time. It can be said that it is a lubricating oil composition having a high effect of suppressing the above.
- the amount of caulking generated when the above panel caulking test is performed is an index of the amount of deposit generated in the lubricating oil composition in a high temperature environment, and the smaller the value of the deposit amount, the more the lubricating oil composition is used in a high temperature environment. It can be said that this is a lubricating oil composition having a high effect of suppressing the formation of deposits.
- the detailed measurement method and measurement conditions of the hot tube test and the panel caulking test are as described in Examples described later.
- the present invention may also provide the following [1] and [2].
- [1] A diesel engine equipped with a supercharger to which the above-mentioned lubricating oil composition of one aspect of the present invention is applied.
- [2] A method for using a lubricating oil composition, which applies the lubricating oil composition according to one aspect of the present invention to lubricate a diesel engine mounted on a supercharger.
- Examples 1 to 8, Comparative Examples 1 to 3 Various additives were blended with the base oil according to the types and blending amounts shown in Tables 1 and 2, and lubricating oil compositions were prepared respectively.
- the amounts of the viscosity index improvers shown in Tables 1 and 2 are in terms of active ingredients (solid content equivalent) excluding the mass of the diluted oil, even if they are mixed in a state of being dissolved in the diluted oil. The blending amount is described.
- the details of the base oil and various additives used in the preparation of each lubricating oil composition are as follows.
- R A is an alkenyl group having Mw500 ⁇ 3000 in the non-boron-modified succinic acid bisimide
- -Phenolic antioxidant C7-C9 alkyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate
- ⁇ Other additives> -Additive mixture A mixture of additives containing a pour point lowering agent and a defoaming agent together with a friction modifier and a metal inactivating agent.
- the prepared lubricating oil composition was measured or calculated for 40 ° C. kinematic viscosity, 100 ° C. kinematic viscosity, viscosity index, acid value, and base value according to the above method, and the following evaluation was performed. These results are shown in Tables 1 and 2.
- Hot tube test A hot tube test based on JPI-5S-55-99 was performed on the prepared lubricating oil composition. Specifically, in a glass tube having an inner diameter of 2 mm whose mass has been measured in advance, while maintaining the temperature of the glass tube at 300 ° C., the prepared lubricating oil composition is poured into the glass tube at a flow rate of 0.3 mL / hour. The flow rate was 10 mL / min for 16 hours. Then, the mass of the glass tube after the test was measured, and the difference from the mass of the glass tube before the test was calculated as the amount of deposits (unit: mg) adhering to the inside of the glass tube. It can be said that the smaller the amount of deposits, the higher the effect of suppressing the formation of deposits.
- the lubricating oil compositions prepared in Examples 1 to 8 had a smaller amount of deposits in the hot tube test and a smaller amount of caulking in the panel caulking test than the lubricating oil compositions of Comparative Examples 1 to 3. It can be seen that the effect of suppressing the formation of deposits is high. On the other hand, the lubricating oil compositions prepared in Comparative Examples 1 to 3 have a large amount of at least one of the amount of deposits in the hot tube test and the amount of caulking in the panel caulking test, and there is room for improvement in the effect of suppressing the formation of deposits. became.
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Abstract
Description
例えば、特許文献1には、デポジットの形成を抑制する性能を向上させた潤滑油組成物の提供を目的として、沸点500~550℃を有する留分を14質量%以上、及び、沸点が550℃を超える留分を5質量%以上含有する潤滑油組成物が開示されている。
[1]基油(A)、非ホウ素変性コハク酸イミド(B)、ホウ素変性コハク酸イミド(C)、金属系清浄剤(D)、及び酸化防止剤(E)を含有し、
成分(C)に由来するホウ素原子と、成分(B)及び成分(C)に由来する窒素原子との含有量比[B/N]が、質量比で、0.30以下であり、
下記要件(I)及び(II)の少なくとも一方を満たす、潤滑油組成物。
・要件(I):成分(D)が、塩基価100mgKOH/g未満の金属系清浄剤(D1)を含む。
・要件(II):成分(E)が、アミン系酸化防止剤(E1)を含み、成分(E1)の含有量が、前記潤滑油組成物の全量基準で、1.00質量%以下である。
[2]成分(B)が、下記一般式(b-1)で表されるコハク酸モノイミド(B1)、及び下記一般式(b-2)で表されるコハク酸ビスイミド(B2)から選ばれる少なくとも1種である、上記[1]に記載の潤滑油組成物。
RB、RB1及びRB2は、それぞれ独立して、炭素数2~5のアルキレン基である。
RC及びRC1は、それぞれ独立して、水素原子、炭素数1~10のアルキル基、又は-(AO)n-Hで表される基(ただし、Aは、それぞれ独立して、炭素数2~4のアルキレン基であり、nは1~10の整数である)である。
x1は、1~10の整数であり、x2は、0~10の整数である。〕
[3]要件(I)及び(II)を共に満たす、上記[1]又は[2]に記載の潤滑油組成物。
[4]要件(I)で規定する成分(D1)の金属原子換算での含有量が、前記潤滑油組成物の全量基準で、0.005~0.080質量%である、上記[1]~[3]のいずれか一項に記載の潤滑油組成物。
[5]酸化防止剤(E)が、フェノール系酸化防止剤(E2)を含有する、上記[1]~[4]のいずれか一項に記載の潤滑油組成物。
[6]成分(E1)と成分(E2)との含有量比〔(E1)/(E2)〕が、質量比で、0.01~0.60である、上記[5]に記載の潤滑油組成物。
[7]さらに粘度指数向上剤(F)を含有し、
成分(F)が、櫛形ポリマー(F1)及びオレフィン系共重合体(F2)の少なくとも一方を含む、上記[1]~[6]のいずれか一項に記載の潤滑油組成物。
[8]成分(F)が、櫛形ポリマー(F1)及びオレフィン系共重合体(F2)を共に含み、
成分(F1)に対する成分(F2)の含有量比〔(F2)/(F1)〕が、質量比で、0.90以下である、上記[7]に記載の潤滑油組成物。
[9]成分(F2)が、星形ポリマー(F21)を含む、上記[8]に記載の潤滑油組成物。
[10]さらに耐摩耗剤(G)を含有する、上記[1]~[9]のいずれか一項に記載の潤滑油組成物。
[11]前記潤滑油組成物のSAE粘度グレードが、0W-30又は5W-30である、上記[1]~[10]のいずれか一項に記載の潤滑油組成物。
[12]前記潤滑油組成物が、過給機搭載ディーゼルエンジンに用いられる、上記[1]~[11]のいずれか一項に記載の潤滑油組成物。
[13]上記[1]~[12]のいずれか一項に記載の潤滑油組成物を適用した、過給機搭載ディーゼルエンジン。
[14]上記[1]~[12]のいずれか一項に記載の潤滑油組成物を過給機搭載ディーゼルエンジンの潤滑に適用する、潤滑油組成物の使用方法。
本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、ゲルパーミエーションクロマトグラフィー(GPC)法で測定される標準ポリスチレン換算の値であり、具体的には実施例に記載の方法により測定された値を意味する。
本明細書において、金属原子(アルカリ金属原子、アルカリ土類金属原子、亜鉛原子等)、リン原子及びホウ素原子の含有量は、JPI-5S-38-2003に準拠して測定した値を意味し、窒素原子の含有量は、JIS K2609に準拠して測定した値を意味する。
本発明の潤滑油組成物は、基油(A)、非ホウ素変性コハク酸イミド(B)、ホウ素変性コハク酸イミド(C)、金属系清浄剤(D)、及び酸化防止剤(E)を含有し、成分(C)に由来するホウ素原子と成分(B)及び(C)に由来する窒素原子との含有量比[B/N]が、質量比で、0.30以下となるように調製している。
その上で、本発明の潤滑油組成物は、下記要件(I)及び(II)の少なくとも一方を満たす。
・要件(I):成分(D)が、塩基価100mgKOH/g未満の金属系清浄剤(D1)を含む。
・要件(II):成分(E)が、アミン系酸化防止剤(E1)を含み、成分(E1)の含有量が、前記潤滑油組成物の全量基準で、1.00質量%以下である。
つまり、本発明の潤滑油組成物において、成分(C)と共に含有すると共に、上記含有量比[B/N]を0.30以下となるように調製することで、成分(C)のホウ素に起因したデポジットの形成も効果的に抑制すると共に、成分(D)及び(E)を配合した際の各成分が有する性能をより効果的に発現させ得るように、分散性を向上させていると考えられる。そのように添加剤の分散性が向上させた溶液中で、要件(I)及び(II)の少なくとも一方を満たすように調整することで、成分(D1)及び成分(E1)が有する性能を効果的に発現させて、耐デポジット性を向上させた潤滑油組成物となり得ると考えられる。
なお、耐デポジット性をより向上させた潤滑油組成物とする観点から、本発明の一態様の潤滑油組成物は、上記要件(I)及び(II)を共に満たすことが好ましい。
つまり、当該含有量比[B/N]は、質量比で、好ましくは0.01~0.30、より好ましくは0.01~0.28、より好ましくは0.05~0.26、更に好ましくは0.07~0.25、より更に好ましくは0.09~0.24、特に好ましくは0.11~0.22である。
また、成分(B)及び成分(C)に由来する窒素原子の合計含有量は、当該潤滑油組成物の全量(100質量%)基準で、さらに、0.062質量%以上、0.065質量%以上、0.067質量%以上、又は0.070質量%以上としてもよく、また、0.140質量%以下、0.130質量%以下、0.120質量%以下、0.110質量%以下、又は0.100質量%以下としてもよい。
また、要件(I)で規定する成分(D1)の塩基価は、0mgKOH/g以上であるが、5mgKOH/g以上、10mgKOH/g以上、15mgKOH/g以上、20mgKOH/g以上、25mgKOH/g以上、30mgKOH/g以上、35mgKOH/g以上、又は40mgKOH/g以上としてもよい。
なお、要件(I)で規定する成分(D1)及び後述の成分(D2)の塩基価は、JIS K2501「石油製品および潤滑油-中和価試験方法」の7.に準拠して測定される「過塩素酸法」による塩基価を意味する。
なお、成分(D1)の金属原子換算での含有量は、当該潤滑油組成物の全量(100質量%)基準で、さらに、0.015質量%以上、0.017質量%以上、又は0.020質量%以上としてもよく、また、0.032質量%以下、0.030質量%以下、又は0.027質量%以下としてもよい。
つまり、要件(II)を満たす潤滑油組成物において、成分(E1)の含有量は、前記潤滑油組成物の全量(100質量%)基準で、好ましくは0.01~1.00質量%、より好ましくは0.01~0.90質量%、より好ましくは0.05~0.80質量%以下、更に好ましくは0.10~0.70質量%、より更に好ましくは0.15~0.65質量%、特に好ましくは0.20~0.60質量%である。
また、本発明の一態様の潤滑油組成物は、本発明の効果を損なわない範囲で、必要に応じて、成分(B)~(G)以外の他の潤滑油用添加剤をさらに含有してもよい。
本発明の一態様で用いる成分(A)である基油としては、鉱油及び合成油から選ばれる1種以上が挙げられる。
鉱油としては、例えば、パラフィン系原油、中間基系原油、ナフテン系原油等の原油を常圧蒸留して得られる常圧残油;これらの常圧残油を減圧蒸留して得られる留出油;当該留出油を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱ろう、接触脱ろう、及び水素化精製等の精製処理を1つ以上施して得られる精製油;等が挙げられる。
なお、本発明の一態様において、成分(A)として、2種以上の基油を組み合わせた混合油を用いる場合、当該混合油の動粘度及び粘度指数が上記範囲であることが好ましい。
本発明の潤滑油組成物は、非ホウ素変性コハク酸イミド(B)を含有する。
成分(B)は、単独で用いてもよく、2種以上を併用してもよい。
本発明の一態様で用いる成分(B)としては、下記一般式(b-1)で表されるアルケニルコハク酸モノイミド(B1)、及び下記一般式(b-2)で表されるアルケニルコハク酸ビスイミド(B2)から選ばれる少なくとも1種であることが好ましい。
RB、RB1及びRB2は、それぞれ独立して、炭素数2~5のアルキレン基である。
RC及びRC1は、それぞれ独立して、水素原子、炭素数1~10のアルキル基、又は-(AO)n-Hで表される基(ただし、Aは、それぞれ独立して、炭素数2~4のアルキレン基であり、nは1~10の整数である)である。
x1は、1~10の整数であり、好ましくは2~5の整数、より好ましくは3又は4である。
x2は、0~10の整数であり、好ましくは1~5の整数、より好ましくは2~4の整数である。
なお、耐デポジット性をより向上させた潤滑油組成物とする観点から、本発明の一態様で用いる成分(B)は、前記一般式(b-1)で表されるアルケニルコハク酸モノイミド(B1)を少なくとも含むことが好ましい。
本発明の潤滑油組成物は、成分(B)と共に、ホウ素変性コハク酸イミド(C)を含有する。
なお、成分(C)は、単独で用いてもよく、2種以上を併用してもよい。
成分(C)は、成分(B)と共に含有して、成分(C)に由来するホウ素原子と、成分(B)及び(C)に由来する窒素原子との含有量比[B/N]を0.30以下に調整するために用いられる。そして、当該含有量比[B/N]を0.30以下に調整して、耐デポジット性に優れた潤滑油組成物とすることができる。
具体的には、前記一般式(b-1)で表されるアルケニルコハク酸モノイミドのホウ素変性物及び前記一般式(b-2)で表されるアルケニルコハク酸ビスイミドのホウ素変性物が挙げられる。
成分(C)に由来するホウ素原子の含有量は、当該潤滑油組成物の全量(100質量%)基準で、さらに、0.011質量%以上、0.012質量%以上、又は0.013質量%以上としてもよく、また、0.032質量%以下、0.030質量%以下、0.027質量%以下、0.025質量%以下、0.023質量%以下、又は0.020質量%以下としてもよい。
本発明の一態様の潤滑油組成物は、本発明の効果を損なわない範囲で、成分(B)及び(C)以外の他の無灰系分散剤を含有してもよい。
このような他の無灰系分散剤としては、例えば、コハク酸モノイミド、コハク酸ビスイミド、ベンジルアミン、コハク酸エステル、及びこれらのホウ素変性物等が挙げられる。
本発明の潤滑油組成物は、金属系清浄剤(D)を含有する。成分(D)を含有することで、清浄分散性が向上し、耐デポジット性に優れた潤滑油組成物とすることができる。
成分(D)は、単独で用いてもよく、2種以上を併用してもよい。
なお、前記金属原子としては、ナトリウム、カルシウム、マグネシウム、又はバリウムが好ましく、カルシウムがより好ましい。つまり、成分(D)は、カルシウム系清浄剤であることが好ましい。
上記一般式(d-3)中、M’は、アルカリ土類金属であり、カルシウム、マグネシウム、又はバリウムが好ましく、カルシウムがより好ましい。yは、0以上の整数であり、好ましくは0~3の整数である。
上記一般式(d-1)~(d-3)中、pはMの価数であり、1又は2である。Rは、水素原子又は炭素数1~18の炭化水素基である。
Rとして選択し得る炭化水素基としては、例えば、炭素数1~18のアルキル基、炭素数1~18のアルケニル基、環形成炭素数3~18のシクロアルキル基、環形成炭素数6~18のアリール基、炭素数7~18のアルキルアリール基、炭素数7~18のアリールアルキル基等が挙げられる。
本発明の一態様の潤滑油組成物において、成分(D1)中の金属スルホネート(好ましくはカルシウムスルホネート)及び金属サリシレート(好ましくはカルシウムサリシレート)の合計含有割合としては、当該潤滑油組成物に含まれる成分(D1)の全量(100質量%)基準で、好ましくは50~100質量%、より好ましくは60~100質量%、更に好ましくは70~100質量%、より更に好ましくは80~100質量%、特に好ましくは90~100質量%である。
上記要件(I)を満たす場合、成分(D1)と成分(D2)との含有量比〔(D1)/(D2)〕は、金属原子換算での質量比で、好ましくは1/99~50/50、より好ましくは1.5/98.5~40/60、更に好ましくは2/98~30/70、より更に好ましくは2.5/97.5~25/75、特に好ましくは3/97~20/80である。
本発明の一態様で用いる成分(D2)の塩基価は、100mgKOH/g以上であるが、好ましくは110mgKOH/g以上、より好ましくは120mgKOH/g以上、更に好ましくは150mgKOH/g以上、より更に好ましくは180mgKOH/g以上、特に好ましくは200mgKOH/g以上であり、また、好ましくは600mgKOH/g以下、より好ましくは550mgKOH/g以下、更に好ましくは500mgKOH/g以下、より更に好ましくは450mgKOH/g以下、特に好ましくは400mgKOH/g以下である。
つまり、成分(D2)の塩基価は、好ましくは100~600mgKOH/g、より好ましくは110~600mgKOH/g、より好ましくは120~550mgKOH/g、更に好ましくは150~500mgKOH/g、より更に好ましくは180~450mgKOH/g、特に好ましくは200~400mgKOH/gである。
本発明の一態様の潤滑油組成物において、成分(D2)中の金属サリシレート(好ましくはカルシウムサリシレート)の含有割合としては、当該潤滑油組成物に含まれる成分(D2)の全量(100質量%)基準で、好ましくは50~100質量%、より好ましくは60~100質量%、更に好ましくは70~100質量%、より更に好ましくは80~100質量%、特に好ましくは90~100質量%である。
本発明の潤滑油組成物は、酸化防止剤(E)を含有する。成分(E)を含有することで、酸化安定性が向上し、耐デポジット性に優れた潤滑油組成物とすることができる。
成分(E)は、単独で用いてもよく、2種以上を併用してもよい。
アミン系酸化防止剤としては、例えば、ジフェニルアミン、炭素数3~20のアルキル基を有するアルキル化ジフェニルアミン等のジフェニルアミン系酸化防止剤;α-ナフチルアミン、フェニル-α-ナフチルアミン、炭素数3~20のアルキル基を有する置換フェニル-α-ナフチルアミン等のナフチルアミン系酸化防止剤;等が挙げられる。
また、上記要件(II)を満たさない場合においても、成分(E)は、フェノール系酸化防止剤を含むことが好ましい。
フェノール系酸化防止剤としては、例えば、2,6-ジ-t-ブチルフェノール、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、C7~C9アルキル-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、イソオクチル-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、オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート等のモノフェノール系酸化防止剤;4,4’-メチレンビス(2,6-ジ-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)等のジフェノール系酸化防止剤;ヒンダードフェノール系酸化防止剤;等を挙げられる。
本発明の一態様の潤滑油組成物は、さらに粘度指数向上剤(F)を含有することが好ましい。成分(F)を含有することで、省燃費性に優れた潤滑油組成物とすることができる。
成分(F)は、単独で用いてもよく、2種以上を併用してもよい。
つまり、以上の観点から、成分(F1)に対する成分(F2)の含有量比〔(F2)/(F1)〕は、質量比で、好ましくは0.05~0.90、より好ましくは0.10~0.80、更に好ましくは0.12~0.70、より更に好ましくは0.15~0.60である。
本発明の一態様で用いる成分(F1)である櫛形ポリマーとしては、高分子量の側鎖が出ている三叉分岐点を主鎖に数多くもつ構造を有する重合体であればよい。
なお、本発明において、上記の「マクロモノマー(x1)」とは、重合性官能基を有する高分子量モノマーのことを意味し、末端に重合性官能基を有する高分子量モノマーであることが好ましい。
なお、本明細書において、成分(F1)や成分(F2)における各構成単位の含有量は、13C-NMR定量スペクトルを解析して算出した値を意味する。
つまり、マクロモノマー(x1)の数平均分子量(Mn)は、好ましくは300~100,000、より好ましくは400~50,000、更に好ましくは500~20,000である。
上記一般式(ii)中、Rb2は、炭素数2~4の直鎖又は分岐鎖のアルキレン基である。
上記一般式(iii)中、Rb3は、水素原子又はメチル基である。Rb4は、炭素数1~10の直鎖又は分岐鎖のアルキル基である。
なお、上記一般式(i)~(iii)で表される繰り返し単位をそれぞれ複数有する場合には、複数のRb1、Rb2、Rb3、及びRb4は、それぞれ同一であってもよく、互いに異なるものであってもよい。
また、本発明の一態様で用いる成分(F1)は、マクロモノマー(x1)に由来する構成単位(X1)と共に、マクロモノマー(x1)以外の他のモノマーに由来する構成単位(X2)を有する共重合体であってもよい。
このような櫛形ポリマーの具体的な構造としては、モノマー(x2)に由来する構成単位(X2)を含む主鎖に対して、マクロモノマー(x1)に由来する構成単位(X1)を含む側鎖を有する共重合体が好ましい。
Rb12は、単結合、炭素数1~10の直鎖又は分岐鎖のアルキレン基、-O-、又は-NH-である。
Rb13は、炭素数2~4の直鎖又は分岐鎖のアルキレン基である。また、nは1以上の整数(好ましくは1~20の整数、より好ましくは1~5の整数)を示す。なお、nが2以上の整数の場合、複数のRb13は、同一であってもよく、異なっていてもよく、さらに、(Rb13O)n部分は、ランダム結合でもブロック結合でもよい。
Rb14は、炭素数1~60(好ましくは10~50、より好ましくは20~40)の直鎖又は分岐鎖のアルキル基である。
つまり、成分(F1)の重量平均分子量(Mw)は、好ましくは20万~100万、より好ましくは25万~90万、更に好ましくは30万~80万、より更に好ましくは35万~75万、特に好ましくは45万~70万である。
つまり、成分(F1)の分子量分布(Mw/Mn)は、好ましくは1.01~8.00、より好ましくは1.02~7.00、更に好ましくは1.05~6.00、より更に好ましくは1.07~4.00、特に好ましくは1.10~3.00である。
また、成分(F1)のSSIは、下限値の制限は特に無いが、通常0.1以上である。
計算式(1):SSI(%)=(Kv0-Kv1)/(Kv0-Kvoil)×100
・櫛形ポリマーの側鎖がマクロモノマー(x1)で構成され、当該マクロモノマー(x1)に由来する構成単位(X1)の含有量が、構成単位の全量(100モル%)基準で、0.5モル%以上である櫛形ポリマーは、SSIの値が低くなる傾向にある。
・櫛形ポリマーの側鎖を構成するマクロモノマー(x1)の分子量が大きくなるほど、SSIの値が低くなる傾向にある。
本発明の一態様で用いる成分(F2)としては、アルケニル基を有するモノマーに由来の構成単位を有する共重合体であって、例えば、炭素数2~20(好ましくは2~16、より好ましくは2~14)のα-オレフィンの共重合体が挙げられ、より具体的には、エチレン-α-オレフィン共重合体、スチレン-ジエン共重合体、スチレン-イソプレン共重合体等が挙げられる。
つまり、成分(F2)の重量平均分子量(Mw)は、好ましくは20万~100万、より好ましくは30万~90万、更に好ましくは40万~80万、より更に好ましくは50万~75万、特に好ましくは55万~70万である。
つまり、成分(F2)の分子量分布(Mw/Mn)は、好ましくは1.001~8.00、より好ましくは1.005~7.00、更に好ましくは1.01~6.00、より更に好ましくは1.02~3.00、特に好ましくは1.03~2.00である。
また、成分(F2)のSSIは、下限値の制限は特に無いが、通常0.1以上である。
本発明の一態様の潤滑油組成物において、成分(F2)中の成分(F21)の含有割合としては、当該潤滑油組成物に含まれる成分(F2)の全量(100質量%)基準で、好ましくは50~100質量%、より好ましくは70~100質量%、更に好ましくは80~100質量%、より更に好ましくは90~100質量%、特に好ましくは95~100質量%である。
また、成分(F21)を構成する鎖状高分子としては、例えば、ビニル芳香族モノマーと共役ジエンモノマーとの共重合体やその水素化物等が挙げられる。
ビニル芳香族モノマーとしては、例えば、スチレン、炭素数8~16のアルキル置換スチレン、炭素数8~16のアルコキシ置換スチレン、ビニルナフタレン、炭素数8~16のアルキル置換ビニルナフタレン等が挙げられる。
共役ジエンモノマーとしては、炭素数4~12の共役ジエンが挙げられ、具体的には、1,3-ブタジエン、イソプレン、ピペリレン、4-メチルペンタ-1,3-ジエン、3,4-ジメチル-1,3-ヘキサジエン、4,5-ジエチル-1,3-オクタジエン等が挙げられる。
本発明の一態様の潤滑油組成物は、本発明の効果を損なわない範囲で、成分(F1)及び(F2)以外の他の粘度指数向上剤を含有してもよい。
ただし、成分(F1)及び(F2)以外の他の粘度指数向上剤の含有量としては、潤滑油組成物に含まれる成分(F1)及び(F2)の全量100質量部に対して、好ましくは0~50質量部、より好ましくは0~30質量部、更に好ましくは0~10質量部、より更に好ましくは0~1質量部である。
本発明の一態様の潤滑油組成物は、さらに耐摩耗剤(G)を含有することが好ましい。
成分(G)は、単独で用いてもよく、2種以上を併用してもよい。
R1~R4として選択し得る炭化水素基の炭素数は、好ましくは1~20、より好ましくは1~16、更に好ましくは3~12、より更に好ましくは3~10である。
これらの中でも、R1~R4として選択し得る、当該炭化水素基としては、アルキル基が好ましく、第1級アルキル基又は第2級アルキル基がより好ましい。
また、ZnDTPのリン原子換算での含有量は、当該潤滑油組成物の全量(100質量%)基準で、好ましくは0.01~1.0質量%、より好ましくは0.02~0.70質量%、更に好ましくは0.03~0.50質量%、より更に好ましくは0.05~0.40質量%、特に好ましくは0.07~0.30質量%である。
本発明の一態様の潤滑油組成物は、本発明の効果を損なわない範囲で、必要に応じて、更に成分(B)~(G)以外の潤滑油用添加剤を含有してもよい。
このような潤滑油用添加剤としては、例えば、流動点降下剤、抗乳化剤、摩擦調整剤、腐食防止剤、金属不活性化剤、防錆剤、帯電防止剤、消泡剤等が挙げられる。
これらの潤滑油用添加剤は、それぞれ、単独で用いてもよく、2種以上を併用してもよい。
本発明の一態様の潤滑油組成物の製造方法としては、特に制限はないが、生産性の観点から、成分(A)に、成分(B)~(E)、並びに必要に応じて、成分(F)~(G)及び他の潤滑油用添加剤を配合する工程を有する、方法であることが好ましい。
なお、成分(F)等の樹脂成分は、成分(A)との相溶性の観点から、希釈油に溶解された溶液の形態とし、当該溶液を成分(A)に配合することが好ましい。
本発明の一態様の潤滑油組成物の40℃における動粘度としては、好ましくは10~130mm2/s、より好ましくは20~115mm2/s、更に好ましくは25~100mm2/s、より更に好ましくは30~90mm2/s、特に好ましくは35~80mm2/sである。
なお、本明細書において、潤滑油組成物の酸価は、JIS K2501:2003(電位差滴定法)に準拠して測定された値を意味する。
なお、本明細書において、潤滑油組成物の塩基価は、JIS K2501:2003(過塩素酸法)に準拠して測定された値を意味する。
また、本発明の一態様の潤滑油組成物のホウ素原子の含有量は、当該潤滑油組成物の全量(100質量%)基準で、さらに、0.011質量%以上、0.012質量%以上、又は0.013質量%以上としてもよく、また、0.032質量%以下、0.030質量%以下、0.027質量%以下、0.025質量%以下、0.023質量%以下、又は0.020質量%以下としてもよい。
また、本発明の一態様の潤滑油組成物の窒素原子の含有量は、当該潤滑油組成物の全量(100質量%)基準で、さらに、0.070質量%以上、0.080質量%以上、0.090質量%以上、又は0.100質量%以上としてもよく、また、0.160質量%以下、0.150質量%以下、0.140質量%以下、又は0.130質量%以下としてもよい。
以上のとおり、本発明の一態様の潤滑油組成物は、デポジットの形成の抑制効果が高いため、過給機搭載ディーゼルエンジンの潤滑に好適に適用し得る。
本発明の一態様の潤滑油組成物に対して、JPI-5S-55-99に準拠してガラス管内の温度300℃でホットチューブ試験を行った際に生じる堆積物量は、好ましくは40.0mg以下、より好ましくは35mg以下、より好ましくは30mg以下、更に好ましくは20mg以下、更に好ましくは10mg以下、より更に好ましくは6.5mg以下、より更に好ましくは5.0mg以下、特に好ましくは4.0mg以下である。
また、本発明の一態様の潤滑油組成物に対して、Fed. Test Method Std. 791-3462に準拠し、パネル温度350℃、油温100℃の条件下で、スプラッシュ時間を3時間、停止時間はなしで、パネルコーキング試験を行った際に生じたコーキング量は、好ましくは400mg以下、より好ましくは385mg以下、より好ましくは345mg以下、更に好ましくは320mg以下、更に好ましくは300mg以下、より更に好ましくは250mg以下、より更に好ましくは200mg以下、特に好ましくは170mg以下である。
上記のホットチューブ試験を行った際に生じる堆積物量は、潤滑油組成物の経時的使用に伴い発生するデポジット量の指標となり、当該堆積物量の値が小さいほど、経時的使用によってもデポジットの形成の抑制効果が高い潤滑油組成物であるといえる。
また、上記のパネルコーキング試験を行った際に生じるコーキング量は、潤滑油組成物を高温環境下で発生するデポジット量の指標となり、当該堆積物量の値が小さいほど、高温環境下での使用によってもデポジットの形成の抑制効果が高い潤滑油組成物であるといえる。
なお、上記のホットチューブ試験及びパネルコーキング試験の詳細な測定方法及び測定条件は、後述の実施例の記載のとおりである。
[1]上述の本発明の一態様の潤滑油組成物を適用した、過給機搭載ディーゼルエンジン。
[2]上述の本発明の一態様の潤滑油組成物を過給機搭載ディーゼルエンジンの潤滑に適用する、潤滑油組成物の使用方法。
JIS K2283:2000に準拠して測定及び算出した。
(2)カルシウム原子、ホウ素原子、亜鉛原子、リン原子の含有量
JPI-5S-38-2003に準拠して測定した。
(3)窒素原子の含有量
JIS K2609に準拠して測定した。
(4)重量平均分子量(Mw)、数平均分子量(Mn)、
ゲル浸透クロマトグラフ装置(アジレント社製、「1260型HPLC」)を用いて、下記の条件下で測定し、標準ポリスチレン換算にて測定した値を用いた。
(測定条件)
・カラム:「Shodex LF404」を2本、順次連結したもの。
・カラム温度:35℃
・展開溶媒:クロロホルム
・流速:0.3mL/min
また、測定した重量平均分子量(Mw)と数平均分子量(Mn)との比〔Mw/Mn〕を分子量分布として算出した。
(5)SSI(せん断安定性指数)
測定対象となる重合体に希釈油である鉱油を加えて試料油を調製し、当該試料油及び当該鉱油を用いて、JPI-5S-29-06に準拠して測定した。
具体的には、対象となる重合体について、前記計算式(1)中のKv0、Kv1、Kvoilの各値を測定して、当該計算式(1)より算出した。
(6)塩基価
JIS K2501:2003(過塩素酸法)に準拠して測定した。
(7)酸価
JIS K2501:2003(電位差滴定法)に準拠して測定した。
表1及び2に示す種類及び配合量にて、基油に、各種添加剤を配合し、潤滑油組成物をそれぞれ調製した。なお、表1及び2に記載された粘度指数向上剤の配合量は、希釈油で溶解された状態で配合したとしても、当該希釈油の質量を除いた有効成分換算(固形分換算)での配合量を記載している。
また、それぞれの潤滑油組成物の調製に使用した、基油及び各種添加剤の詳細は以下のとおりである。
・100N鉱油:API基油カテゴリーのグループ3に分類されるパラフィン系鉱油、40℃動粘度=18.4mm2/s、100℃動粘度=4.1mm2/s、粘度指数=125。
・非ホウ素変性コハク酸イミド(1):前記一般式(b-1)又は(b-2)で表される非ホウ素変性コハク酸イミド、窒素原子(N)含有量=1.0質量%。
・非ホウ素変性コハク酸イミド(2):前記一般式(b-2)中のRAがMw500~3000のアルケニル基、RCが水素原子ある非ホウ素変性コハク酸ビスイミド、窒素原子(N)含有量=1.15質量%。
・ホウ素変性コハク酸イミド:前記一般式(b-1)又は(b-2)で表されるコハク酸イミドのホウ素変性物、ホウ素原子(B)含有量=0.49質量%、窒素原子(N)含有量=1.50質量%、B/N=0.33。
・中性Caスルホネート:塩基価(過塩素酸法)=17mgKOH/gのカルシウムスルホネート、Ca原子含有量=2.4質量%。
・中性Caサリシレート:塩基価(過塩素酸法)=64mgKOH/gのカルシウムサリシレート、Ca原子含有量=2.3質量%。
・過塩基性Caサリシレート:塩基価(過塩素酸法)=225mgKOH/gのカルシウムサリシレート、Ca原子含有量=8.0質量%。
・アミン系酸化防止剤:4,4’-ジノニルフェニルアミン、窒素原子含有量=4.6質量%。
・フェノール系酸化防止剤:C7~C9アルキル-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
・櫛形ポリマー:Mw=60万、Mw/Mn=2.4、SSI=49である櫛形ポリマー。
・星形ポリマー(OCP):Mw=58万、Mw/Mn=1.1、SSI=14である星形ポリマー。
・ZnDTP:第2級アルキルジチオリン酸亜鉛、P含有量=7.0質量%、Zn原子含有量=8.3質量%。
・添加剤混合物:摩擦調整剤及び金属不活性化剤と共に、流動点降下剤、及び消泡剤を含む添加剤の混合物。
調製した潤滑油組成物に対して、JPI-5S-55-99に準拠したホットチューブ試験を行った。具体的には、予め質量を測定した内径2mmのガラス管に、ガラス管の温度を300℃に保ちながら、そのガラス管内に、調製した潤滑油組成物を流量0.3mL/時間で、空気を流量10mL/分で16時間流し続けた。そして、試験後のガラス管の質量を測定し、試験前のガラス管の質量との差を、ガラス管内に付着した堆積物量(単位:mg)として算出した。当該堆積物量が少ない潤滑油組成物ほど、デポジットの形成の抑制効果が高いといえる。
Fed. Test Method Std. 791-3462に準拠し、パネルコーキング試験機を用いて、パネル温度350℃、油温100℃の条件下で、スプラッシュ時間を3時間、停止時間はなしで、調製した潤滑油組成物を連続的にパネルへ散布した。試験終了後、パネルの重量を測定し、試験前のパネル重量との差から、パネルに付着したコーキング量を測定した。当該コーキング量が少ない潤滑油組成物ほど、デポジットの形成の抑制効果が高いといえる。
Claims (14)
- 基油(A)、非ホウ素変性コハク酸イミド(B)、ホウ素変性コハク酸イミド(C)、金属系清浄剤(D)、及び酸化防止剤(E)を含有し、
成分(C)に由来するホウ素原子と、成分(B)及び成分(C)に由来する窒素原子との含有量比[B/N]が、質量比で、0.30以下であり、
下記要件(I)及び(II)の少なくとも一方を満たす、潤滑油組成物。
・要件(I):成分(D)が、塩基価100mgKOH/g未満の金属系清浄剤(D1)を含む。
・要件(II):成分(E)が、アミン系酸化防止剤(E1)を含み、成分(E1)の含有量が、前記潤滑油組成物の全量基準で、1.00質量%以下である。 - 成分(B)が、下記一般式(b-1)で表されるコハク酸モノイミド(B1)、及び下記一般式(b-2)で表されるコハク酸ビスイミド(B2)から選ばれる少なくとも1種である、請求項1に記載の潤滑油組成物。
〔上記一般式(b-1)及び(b-2)中、RA、RA1及びRA2は、それぞれ独立して、質量平均分子量(Mw)が500~3000のアルケニル基である。
RB、RB1及びRB2は、それぞれ独立して、炭素数2~5のアルキレン基である。
RC及びRC1は、それぞれ独立して、水素原子、炭素数1~10のアルキル基、又は-(AO)n-Hで表される基(ただし、Aは、それぞれ独立して、炭素数2~4のアルキレン基であり、nは1~10の整数である)である。
x1は、1~10の整数であり、x2は、0~10の整数である。〕 - 要件(I)及び(II)を共に満たす、請求項1又は2に記載の潤滑油組成物。
- 要件(I)で規定する成分(D1)の金属原子換算での含有量が、前記潤滑油組成物の全量基準で、0.005~0.080質量%である、請求項1~3のいずれか一項に記載の潤滑油組成物。
- 酸化防止剤(E)が、フェノール系酸化防止剤(E2)を含有する、請求項1~4のいずれか一項に記載の潤滑油組成物。
- 成分(E1)と成分(E2)との含有量比〔(E1)/(E2)〕が、質量比で、0.01~0.60である、請求項5に記載の潤滑油組成物。
- さらに粘度指数向上剤(F)を含有し、
成分(F)が、櫛形ポリマー(F1)及びオレフィン系共重合体(F2)の少なくとも一方を含む、請求項1~6のいずれか一項に記載の潤滑油組成物。 - 成分(F)が、櫛形ポリマー(F1)及びオレフィン系共重合体(F2)を共に含み、
成分(F1)に対する成分(F2)の含有量比〔(F2)/(F1)〕が、質量比で、0.90以下である、請求項7に記載の潤滑油組成物。 - 成分(F2)が、星形ポリマー(F21)を含む、請求項8に記載の潤滑油組成物。
- さらに耐摩耗剤(G)を含有する、請求項1~9のいずれか一項に記載の潤滑油組成物。
- 前記潤滑油組成物のSAE粘度グレードが、0W-30又は5W-30である、請求項1~10のいずれか一項に記載の潤滑油組成物。
- 前記潤滑油組成物が、過給機搭載ディーゼルエンジンに用いられる、請求項1~11のいずれか一項に記載の潤滑油組成物。
- 請求項1~12のいずれか一項に記載の潤滑油組成物を適用した、過給機搭載ディーゼルエンジン。
- 請求項1~12のいずれか一項に記載の潤滑油組成物を過給機搭載ディーゼルエンジンの潤滑に適用する、潤滑油組成物の使用方法。
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| JP2009102486A (ja) * | 2007-10-22 | 2009-05-14 | Idemitsu Kosan Co Ltd | 潤滑油組成物 |
| JP2010100707A (ja) * | 2008-10-22 | 2010-05-06 | Idemitsu Kosan Co Ltd | 内燃機関用潤滑油組成物 |
| JP2019178296A (ja) * | 2018-03-30 | 2019-10-17 | 出光興産株式会社 | 潤滑油組成物、及び潤滑油組成物の使用方法 |
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| US20230122231A1 (en) | 2023-04-20 |
| JP7618645B2 (ja) | 2025-01-21 |
| CN115244159A (zh) | 2022-10-25 |
| US12570921B2 (en) | 2026-03-10 |
| JPWO2021187370A1 (ja) | 2021-09-23 |
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