WO2009113234A1 - Composition d'huile lubrifiante - Google Patents

Composition d'huile lubrifiante Download PDF

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Publication number
WO2009113234A1
WO2009113234A1 PCT/JP2009/000406 JP2009000406W WO2009113234A1 WO 2009113234 A1 WO2009113234 A1 WO 2009113234A1 JP 2009000406 W JP2009000406 W JP 2009000406W WO 2009113234 A1 WO2009113234 A1 WO 2009113234A1
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Prior art keywords
mass
boronated
lubricating oil
alkyl
composition
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PCT/JP2009/000406
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English (en)
Japanese (ja)
Inventor
武藤明男
黒澤修
宮本大也
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新日本石油株式会社
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Publication of WO2009113234A1 publication Critical patent/WO2009113234A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/14—Chemical after-treatment of the constituents of the lubricating composition by boron or a compound containing boron

Definitions

  • the present invention relates to a lubricating oil composition, and in particular, a lubricating oil composition suitable for an automatic transmission and / or a continuously variable transmission capable of improving the anti-shudder property while maintaining a high intermetallic friction coefficient at high temperatures.
  • a lubricating oil composition suitable for an automatic transmission and / or a continuously variable transmission capable of improving the anti-shudder property while maintaining a high intermetallic friction coefficient at high temperatures.
  • Recent lightweight automatic transmissions and continuously variable transmissions are desired to be lighter and smaller, and as the combined engine increases in output, improvement in power transmission capability is being pursued.
  • continuously variable transmissions are required to improve the friction coefficient between the belt and pulley in order to reduce the pressure loss in the hydraulic pump caused by high engine output and tension on the metal belt.
  • a shift shock is applied to lubricating oil used in a transmission in which slip control is performed, such as a lock-up clutch incorporated in a torque converter and a wet start clutch used in some continuously variable transmissions.
  • Patent Documents 1 to 4 As a conventional transmission oil, in order to maintain a good coefficient of friction between metals between the belt and the pulley, to prevent the initial shudder and maintain this for a long period of time, a friction modifier, a metallic detergent, an ashless dispersant, Transmission oil compositions with optimized antiwear agents and the like have been proposed (see, for example, Patent Documents 1 to 4).
  • a friction modifier for example, an organic acid metal salt having a specific structure, an antiwear agent, and a boron-containing succinimide are blended as essential components, and both a high intermetal friction coefficient and anti-shudder properties for a slip control mechanism are achieved.
  • Patent Document 2 discloses a lubricating oil composition for a continuously variable transmission, which includes calcium salicylate, a phosphorus-based antiwear agent, a friction modifier, and a dispersion type viscosity index improver.
  • a lubricating oil composition for a continuously variable transmission that has both anti-shudder properties for the mechanism and can be used for a long period of time is disclosed in Patent Document 3 as calcium sulfonates and phosphites, and further sarcosine derivatives or carboxylic acids and amines.
  • Automatic transmission fluid composition having a performance of the clutch noise prevention long life is disclosed.
  • Patent Document 4 discloses an automatic transmission oil having excellent anti-suddering properties and a constant transmission torque capacity, which includes specific amounts of calcium salicylate and magnesium salicylate, specific friction modifiers, and boric acid-modified succinimide. ing.
  • an object of the present invention is to provide a lubricating oil composition having a high coefficient of friction between metals and excellent in transmission characteristics and anti-shudder performance and suitable as an automatic transmission oil and / or continuously variable transmission oil. Is to provide.
  • the present inventors have found that boronated alkyl succinimide and / or boronated alkenyl succinimide having a specific weight average molecular weight, and metal having a linear alkyl group
  • a lubricating oil composition containing a specific amount of a system detergent can improve the above problems, and has completed the present invention.
  • the present invention relates to (A) a boronated alkyl succinimide and / or a boronated alkenyl succinimide having a weight average molecular weight of 1,000 to 20,000 based on the total amount of the composition.
  • a lubricating oil composition which is.
  • (MeB) / (BoA) is preferably 1.0 to 7.0.
  • the lubricating oil composition of the present invention is a lubricating oil composition suitable as an automatic transmission oil and / or continuously variable transmission oil that has a high coefficient of friction between metals and is excellent in transmission characteristics and anti-shudder performance.
  • 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, Refined by performing one or more treatments such as hydroisomerization, solvent dewaxing, hydrorefining, etc., or base oil produced by isomerizing wax isomerized mineral oil, GTL WAX (gas-tuly wax) Can be illustrated.
  • GTL WAX gas-tuly wax
  • synthetic base oils include polybutene or hydrides thereof; poly- ⁇ -olefins such as 1-octene oligomers and 1-decene oligomers or hydrides thereof; ditridecyl glutarate, di-2-ethylhexyl adipate Diesters such as diisodecyl adipate, ditridecyl adipate and di-2-ethylhexyl sebacate; neopentyl glycol ester, trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, and pentaerythritol Examples thereof include polyol esters such as pelargonate; aromatic synthetic oils such as alkyl naphthalene, alkyl benzene, and aromatic esters, or mixtures thereof.
  • the above mineral base oil, the above synthetic base oil, or an arbitrary mixture of two or more selected from these can be used.
  • examples thereof include one or more mineral base oils, one or more synthetic base oils, a mixed oil of one or more mineral base oils and one or more synthetic base oils, and the like.
  • the kinematic viscosity of the lubricating base oil used in the present invention is not particularly limited, but the kinematic viscosity at 100 ° C. is preferably 2 to 8 mm 2 / s, more preferably 2.5 to 6 mm 2 / s, particularly preferably. Is preferably adjusted to 3 to 4.5 mm 2 / s.
  • the kinematic viscosity at 100 ° C. of the lubricating base oil exceeds 8 mm 2 / s, the low-temperature viscosity characteristic deteriorates.
  • the kinematic viscosity is less than 2 mm 2 / s, an oil film is formed at the lubrication point. Insufficient lubrication results in poor lubricity and increases the evaporation loss of the lubricating base oil, which is not preferable.
  • the sulfur content of the lubricating base oil used in the present invention is not particularly limited, but is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and further preferably 0.01% by mass or less. It is desirable to be.
  • the evaporation loss amount of the lubricating base oil is not particularly limited, but the NOACK evaporation amount is preferably adjusted to 10 to 50% by mass, more preferably 20 to 40% by mass, and particularly preferably 22 to 35% by mass. It is desirable that By using a lubricating base oil having a NOACK evaporation amount adjusted to the above range, both low temperature characteristics and wear resistance can be achieved.
  • the NOACK evaporation amount means an evaporation amount measured according to CEC L-40-T-87.
  • the lubricating base oil in the present invention include a kinematic viscosity at 100 ° C. of 1.5 to 3.5 mm 2 / s, preferably 2 to 3.2 mm 2 / s, more preferably 2.5 to 3 mm 2.
  • the sulfur content is 0.05% by mass or less, preferably 0.01% by mass or less, more preferably 0.005% by mass or less
  • the NOACK evaporation is 20 to 80% by mass, preferably 30%.
  • sulfur content is 0.05% by mass or less, preferably 0.01% by mass or less, more preferably 0.005% by mass or less
  • NOACK evaporation is 5 to 20% by mass.
  • % Preferably 10 18% by mass, more preferably 12-16% by mass of base oil mixed in a mass ratio of 10:90 to 90:10, preferably 25:75 to 75:25, more preferably 40:60 to 60:40
  • the kinematic viscosity, the sulfur content, and the NOACK evaporation amount of the mixed base oil at 100 ° C.
  • the mixed base oil further has a kinematic viscosity at 100 ° C. of 6 mm 2 / s or more, preferably 10 to 35 mm 2 / s, and a sulfur content of 0.05 to 1% by mass, preferably 0.1 to 0. 0.7% by mass, more preferably 0.2 to 0.6% by mass, and a NOACK evaporation amount of 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less. You may mix 30 mass%.
  • the component (A) used in the lubricating oil composition of the present invention comprises (a1) boronated alkyl succinimide and / or boronated alkenyl succinimide (hereinafter referred to as (a1) having a weight average molecular weight of 1,000 to 20,000.
  • Component is also referred to as a boronated succinimide derivative), or (a1) a boronated alkyl succinimide and / or a boronated alkenyl succinimide and (a2) a non-borated alkyl succinimide and / or a non-borated
  • component (a2) is also referred to as non-borated succinimide derivative.
  • the alkenyl group or alkyl group in the alkyl succinimide or alkenyl succinimide has 40 to 400 carbon atoms and a number average molecular weight of 550 to 6000, which may be linear or branched, but may be branched. Specifically, a branched alkyl group having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms derived from an olefin oligomer such as propylene, 1-butene or isobutylene, or a co-oligomer of ethylene and propylene is preferably used. Alkenyl group and the like.
  • the high molecular weight alkenyl group or alkyl group is preferably polybutene (polyisobutene), more preferably polybutene (polyisobutene) having a number average molecular weight of 800 to 5,000.
  • alkyl succinimide or alkenyl succinimide used in the lubricating oil composition of the present invention include compounds represented by the following general formula (1) or (2), or a mixture thereof. In addition, in a mixture, what contains many monostructures shown by Formula (1) is used preferably.
  • R 1 to R 3 each independently represents an alkyl group or an alkenyl group having 40 to 400 carbon atoms, a is 1 to 10, preferably 2 to 5, and b is 0 to 10 or 1. Shows ⁇ 5 integer.
  • the boronated succinimide derivative is obtained by allowing a boron compound such as boric acid to act on the succinimide derivative represented by the above general formula (1) or (2), thereby remaining amino groups and / or imino groups.
  • the boronated succinimide derivative is superior to the non-borated product in terms of thermal and oxidation stability.
  • Examples of the boron compound that acts on the compound represented by the general formula (1) or (2) include boric acid, borates, and borate esters.
  • a succinimide derivative in which a boron compound is allowed to act is preferably used because of its excellent heat resistance and oxidation stability.
  • Component (A) is a boronated succinimide derivative such as a monocarboxylic acid having 2 to 30 carbon atoms (fatty acid, etc.) or a polycarbon having 2 to 30 carbon atoms such as oxalic acid, phthalic acid, trimellitic acid or pyromellitic acid. It may be modified with one or more selected from phosphorus-containing acids such as carboxylic acid, phosphoric acid and phosphorous acid, and sulfur-containing compounds.
  • Component (A) in the lubricating oil composition of the present invention includes (a1) a boronated succinimide derivative, or (a1) a mixture of a boronated succinimide derivative and (a2) a non-borated succinimide derivative. Either may be used, but a combination of (a1) a boronated succinimide derivative and (a2) a non-borated succinimide derivative is preferred.
  • the weight average molecular weight of the component (A) in the lubricating oil composition of the present invention is 1000 to 20000, preferably 2000 to 15000, more preferably 3000 to 10,000, and still more preferably 3000 to 7000.
  • the weight average molecular weight is less than 1000, the molecular weight of the non-polar alkyl group or alkenyl group is small, the sludge dispersibility is poor, and the polar amine group which may become an active site for oxidative degradation is relatively May increase and the oxidation stability may be inferior.
  • the weight average molecular weight exceeds 20000, the low-temperature viscosity characteristics may be deteriorated.
  • the weight average molecular weight means that two columns of GHSHR-M (7.8 mm ID ⁇ 30 cm) manufactured by Tosoh Corporation are used in series with a 150-CALC / GPC apparatus manufactured by Waters, and tetrahydrofuran is used as a solvent. , Temperature 23 ° C., flow rate 1 mL / min, sample concentration 1% by mass, sample injection amount 75 ⁇ L, and weight average molecular weight in terms of polystyrene measured with a detector differential refractometer (RI).
  • RI detector differential refractometer
  • the content of the component (A) in the lubricating oil composition of the present invention is required to be 0.005% by mass or more, preferably 0.007% by mass as the boron content (BoA) based on the total amount of the composition. As mentioned above, Most preferably, it is 0.01 mass or more. Moreover, it is necessary that it is 0.1 mass% or less as a boron amount (BoA), Preferably it is 0.09 mass% or less, More preferably, it is 0.08 mass% or less, Most preferably, it is 0.07 mass% or less. is there.
  • the boron content exceeds 0.1% by mass, the balance between the shudder prevention life and the speed change characteristics may be deteriorated. On the other hand, if the boron content is less than 0.005% by mass, the friction coefficient between metals may not be increased while maintaining the shudder prevention life and the speed change characteristics.
  • the content of the component (A) is 0.01 to 0.4% by mass, preferably 0.02 to 0.3% by mass, more preferably 0.03% as the nitrogen amount based on the total amount of the composition. 0.25% by mass, most preferably 0.04 to 0.2% by mass. When the amount of nitrogen exceeds 0.4% by mass, it may be difficult to increase the anti-shudder life.
  • the content of (a2) a non-boronated succinimide derivative is usually the amount of nitrogen. 0.005 to 0.4 mass%, preferably 0.01 to 0.2 mass%, particularly preferably 0.05 to 0.08 mass%.
  • the component (B) in the lubricating oil composition of the present invention is a metal detergent having a linear alkyl group having 6 to 60 carbon atoms derived from an ethylene oligomer and having a base number of 100 to 500 mgKOH / g.
  • a metal detergent having a linear alkyl group having 6 to 60 carbon atoms derived from an ethylene oligomer and having a base number of 100 to 500 mgKOH / g.
  • the metal detergent one or more selected from the group consisting of a sulfonate detergent, a salicylate detergent, a phenate detergent, and the like can be used.
  • Examples of the sulfonate detergent used in the present invention include an alkali metal salt of a linear alkyl aromatic sulfonic acid obtained by sulfonating a linear alkyl aromatic compound having a molecular weight of 100 to 1500, preferably 200 to 700, or Alkaline earth metal salts can be mentioned, and particularly, magnesium salts and / or calcium salts, particularly calcium salts are preferably used.
  • the alkyl group is preferably a linear alkyl group having 6 to 60 carbon atoms, more preferably a linear alkyl group having 10 to 40 carbon atoms, and particularly preferably a linear alkyl group having 15 to 30 carbon atoms.
  • alkyl groups are linear and may be either a primary alkyl group or a secondary alkyl group, but a secondary alkyl group is particularly preferable.
  • the linear alkyl aromatic sulfonic acid is produced from, for example, an alkyl benzene having a linear alkyl group, which is produced as a by-product from an alkyl benzene production plant that is a raw material for detergents or is obtained by alkylating polyolefin into benzene. Sulfonated or alkylnaphthalene sulfonated.
  • the sulfonating agent for sulfonating these linear alkyl aromatic compounds is not particularly limited, but usually fuming sulfuric acid or sulfuric acid is used.
  • the above linear alkyl aromatic sulfonic acid may be directly reacted with an alkaline earth metal base such as magnesium and / or calcium alkaline earth metal oxide or hydroxide.
  • an alkaline earth metal base such as magnesium and / or calcium alkaline earth metal oxide or hydroxide.
  • neutral alkaline earth metal sulfonates obtained by replacing alkali metal salts such as sodium salts and potassium salts with alkaline earth metal salts once can be given.
  • the sulfonate detergent used in the present invention it is preferable to use a calcium sulfonate detergent or a magnesium sulfonate detergent, and it is particularly preferable to use a calcium sulfonate detergent in that it exhibits a high coefficient of friction between metals. .
  • the salicylate detergent used in the present invention is a metal salt of salicylic acid having 1 to 2 linear alkyl groups having 1 to 60 carbon atoms (wherein the alkyl group has 6 to 60 carbon atoms in total), preferably an alkali metal salt or Alkaline earth metal salts, more preferably magnesium salts and / or calcium salts, particularly preferably calcium salts are used.
  • the alkyl salicylic acid has a constituent ratio of the monoalkyl salicylic acid metal salt of 85 to 100 mol%, a constituent ratio of the dialkyl salicylic acid metal salt of 0 to 15 mol%, and a constituent ratio of the 3-alkyl salicylic acid metal salt of 40 to 100 mol%.
  • a metal salt and / or a (over) basic salt thereof is preferred in that the anti-shudder life can be further improved.
  • the monoalkyl salicylic acid metal salt here means an alkyl salicylic acid metal salt having one alkyl group such as a 3-alkyl salicylic acid metal salt, a 4-alkyl salicylic acid metal salt, a 5-alkyl salicylic acid metal salt, and the like.
  • the composition ratio of the salt is 85 to 100 mol%, preferably 88 to 98 mol%, more preferably 90 to 95 mol% with respect to 100 mol% of the alkylsalicylic acid metal salt, and an alkylsalicylic acid metal salt other than the monoalkylsalicylic acid metal salt, for example,
  • the constituent ratio of the metal salt of dialkyl salicylic acid is 0 to 15 mol%, preferably 2 to 12 mol%, more preferably 5 to 10 mol%.
  • the constituent ratio of the 3-alkyl salicylic acid metal salt is 40 to 100 mol%, preferably 45 to 80 mol%, more preferably 50 to 60 mol% with respect to 100 mol% of the alkyl salicylic acid metal salt.
  • the total composition ratio of the 4-alkyl salicylic acid metal salt and the 5-alkyl salicylic acid metal salt corresponds to the composition ratio excluding the above-mentioned 3-alkyl salicylic acid metal salt and dialkyl salicylic acid metal salt with respect to 100 mol% of the alkyl salicylic acid metal salt. And 0 to 60 mol%, preferably 20 to 50 mol%, more preferably 30 to 45 mol%.
  • a composition having both wear prevention properties and low-temperature characteristics can be obtained.
  • the composition ratio of 3-alkyl salicylate 40 mol% or more the composition of the metal salt of 5-alkyl salicylic acid The ratio can be made relatively low, and the oil solubility can be improved.
  • the alkyl group in the linear alkyl salicylic acid metal salt preferably has 10 to 40 carbon atoms, more preferably 10 to 19 carbon atoms or 20 to 30 carbon atoms, still more preferably 14 to 18 carbon atoms or 20 to 26 carbon atoms. And particularly preferably a linear alkyl group having 14 to 18 carbon atoms.
  • These alkyl groups are linear and may be either a primary alkyl group or a secondary alkyl group, but a secondary alkyl group is particularly preferable.
  • examples of the metal in the linear alkyl salicylic acid metal salt include alkaline earth metals such as calcium and magnesium, and the calcium salt and the magnesium salt are preferable, and the calcium salt is particularly preferable.
  • the salicylate-based detergent of the present invention can be produced by a known method and the like, and is not particularly limited.
  • the salicylate-based detergent is a straight chain such as an ethylene polymer having 10 to 40 carbon atoms and 1 mol or more per 1 mol of phenol.
  • Monoalkyl salicylic acid obtained by alkylation using a chain ⁇ -olefin and carboxylation with carbon dioxide or the like, or alkylation using 1 mol or more of the linear ⁇ -olefin with respect to 1 mol of salicylic acid, etc.
  • Alkyl salicylic acid as the main component is reacted with a metal base such as an alkali metal or alkaline earth metal oxide or hydroxide, or an alkali metal salt such as a sodium salt or potassium salt, or an alkali metal salt. It is obtained by substituting with an alkaline earth metal salt.
  • a metal base such as an alkali metal or alkaline earth metal oxide or hydroxide, or an alkali metal salt such as a sodium salt or potassium salt, or an alkali metal salt. It is obtained by substituting with an alkaline earth metal salt.
  • the reaction ratio of phenol or salicylic acid and ⁇ -olefin is preferably controlled to, for example, 1: 1 to 1.15 (molar ratio), more preferably 1: 1.05 to 1.1 (molar ratio).
  • the constituent ratio of the monoalkyl salicylic acid metal salt and the dialkyl salicylic acid metal salt can be controlled to a desired ratio.
  • the composition ratio of the 3-alkyl salicylic acid metal salt, the 5-alkyl salicylic acid metal salt and the like can be easily controlled to a desired ratio, and an alkyl having a secondary alkyl which is preferable in the present invention. Since salicylic acid metal salt can be obtained as a main component, it is particularly preferable.
  • the composition ratio of the monoalkyl salicylic acid metal salt is 85 to 95 mol% and the composition ratio of the dialkyl salicylic acid metal salt is 5 to 15 mol% from the viewpoint of excellent initial shudder prevention performance.
  • the alkyl group here is particularly preferably a secondary alkyl group.
  • the phenate-type metal detergent used in the present invention is an alkali metal salt or alkaline earth metal salt of an alkylphenol, alkylphenol sulfide, or Mannich reaction product of alkylphenol, and particularly preferably a calcium salt or a magnesium salt.
  • the alkyl group of the phenate-based metal detergent is a straight-chain saturated or unsaturated alkyl having 6 to 21 carbon atoms.
  • the carbon number of the alkyl group is preferably 9 to 18, more preferably 9 to 15. If the carbon number is shorter than 6, the solubility in the lubricating base oil may be inferior. If the carbon number is longer than 21, Manufacture is difficult and heat resistance may be inferior.
  • Examples of the metal detergent that can be used in the present invention include the neutral (normal salt) alkaline earth metal sulfonate, neutral (normal salt) alkaline earth metal salicylate, and neutral (normal salt) alkaline earth metal. Heat not only phenates, but also neutral alkaline earth metal sulfonates, neutral alkaline earth metal salicylates and neutral alkaline earth metal phenates and excess alkaline earth metal salts and alkaline earth metal bases in the presence of water.
  • a solvent an aliphatic hydrocarbon solvent such as hexane, an aromatic hydrocarbon solvent such as xylene, a light lubricating base oil, etc.
  • the metal content thereof is 1.0 to It is desirable to use 20% by mass, preferably 2.0 to 16% by mass.
  • the metal-based detergent used in the present invention is usually commercially available in a state diluted with a light lubricating base oil or the like, and can be obtained, but generally the metal content thereof is 1.0-20. It is desirable to use one having a mass%, preferably 2.0 to 16 mass%.
  • the base number of the metallic detergent used in the present invention is required to be 100 to 500 mgKOH / g, preferably 150 to 450 mgKOH / g, more preferably 200 to 400 mgKOH, in view of a high coefficient of friction between metals. / G.
  • the base number referred to here is JIS K2501 “Petroleum products and lubricating oils-Neutralization number test method”. It means the base number by the perchloric acid method measured according to the above.
  • the metal ratio of component (B) in the present invention is not particularly limited, and usually 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 it is 10 or less.
  • the metal ratio means the valence of the metal element in the metal detergent ⁇ the metal element content (mol%) / the soap group content (mol%).
  • the metal element means calcium, magnesium or the like
  • the soap group means a sulfonic acid group, a salicylic acid group, or a phenol group.
  • the content of the component (B) is required to be 0.01% by mass or more, preferably 0.02% by mass as a metal amount (MeB) based on the total amount of the composition. % Or more, more preferably 0.03% by mass or more, and particularly preferably 0.04% by mass.
  • the content of the component (B) needs to be 0.5% by mass or less, preferably 0.4% by mass or less, more preferably 0.8% by mass or less as the metal amount (MeB) on the basis of the entire composition. 3% by mass or less, particularly preferably 0.2% by mass or less.
  • the mass ratio ((MeB) / (BoA)) of the content of the component (A) and the component (B) in the lubricating oil composition of the present invention is preferably 1.0 or more, more preferably 1 .2 or more, more preferably 1.4 or more, particularly preferably 1.6 or more, and most preferably 1.8 or more.
  • (MeB) / (BoA) is preferably 7.0 or less, more preferably 6.5 or less, still more preferably 6.2 or less, particularly preferably 5.8 or less, and most preferably 5. 5 or less.
  • the lubricating oil composition of the present invention can obtain a lubricating oil composition having a good balance between the metal-to-metal friction coefficient, the speed change characteristics, and the anti-shudder performance by the above-described configuration.
  • a known lubricating oil additive can be added for the purpose of further imparting necessary performance as a product.
  • additives that can be added include ashless dispersants other than the component (A), phosphorus-based antiwear agents, metal-based detergents other than the component (B), friction modifiers, antioxidants, extreme pressure additives, and viscosity.
  • Examples thereof include an index improver, a metal deactivator, a rust inhibitor, a corrosion inhibitor, a pour point depressant, a rubber swelling agent, an antifoaming agent, and a colorant. These can be used alone or in combination of several kinds.
  • any compound usually used as an ashless dispersant for lubricating oil can be used.
  • nitrogen-containing compounds such as succinimide, benzylamine, and polyamine, or derivatives or modified products thereof having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms in the molecule.
  • the alkyl group or alkenyl group having 40 to 400 carbon atoms may be linear or branched, and specific examples include olefin oligomers such as propylene, 1-butene and isobutylene, and ethylene and propylene.
  • Examples include branched alkyl groups and branched alkenyl groups derived from co-oligomers.
  • the carbon number of the alkyl group or alkenyl group is less than 40, the solubility of the compound in the lubricating base oil decreases, whereas when the carbon number of the alkyl group or alkenyl group exceeds 400, the low temperature fluidity of the composition Gets worse.
  • the ashless dispersant other than the component (A) may have either a mono structure represented by the formula (1) or a bis structure as represented by the formula (2), but includes many mono structures. Those are preferred.
  • lubricating oil composition of the present invention one or two or more compounds arbitrarily selected from these can be used in any amount, but the content is usually the total amount of the lubricating oil composition.
  • the reference is 0.1 to 10% by mass, preferably 1 to 6% by mass.
  • the phosphorus antiwear agent is not particularly limited as long as it contains phosphorus in the molecule.
  • phosphate monoesters, phosphate diesters, phosphates having a hydrocarbon group having 1 to 30 carbon atoms are available.
  • hydrocarbon group having 1 to 30 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group, an alkyl-substituted cycloalkyl group, an aryl group, an alkyl-substituted aryl group, and an arylalkyl group.
  • One type or two or more types can be arbitrarily blended.
  • phosphites or phosphate esters having an alkyl group having 4 to 20 carbon atoms or an (alkyl) aryl group having 6 to 12 carbon atoms, and those having 1 carbon atom.
  • Preferred is one or a mixture of two or more selected from amine salts in which an alkylamine having an alkyl group of ⁇ 18 is allowed to act, and a phosphite ester having an alkyl group of 4 to 20 carbon atoms such as dibutyl phosphite, phenyl
  • a phosphite ester having an alkyl group of 4 to 20 carbon atoms such as dibutyl phosphite
  • phenyl One or a mixture of two or more selected from phosphites having a (alkyl) aryl group having 6 to 12 carbon atoms such as phosphite is more preferable, and (alkyl) having 6 to 12 carbon atoms such as diphenylphosphite It is particularly preferable to contain a phosphorous acid diester having an aryl group.
  • the content of the phosphorus-based antiwear agent is usually 0.01 to 5% by mass based on the total amount of the composition, but the phosphorus element concentration is preferably 0.001 to 0.1% by mass. %, More preferably 0.005 to 0.09 mass%, still more preferably 0.01 to 0.08 mass%, particularly preferably 0.02 to 0.07 mass%.
  • the metallic detergent other than the component (B) one or more selected from the group consisting of general sulfonates having a branched alkyl group, salisheets and phenates can be used.
  • the base number of the metal detergent other than the component (B) is usually 0 to 500 mgKOH / g, preferably 20 to 450 mgKOH / g.
  • the content is not particularly limited, but is usually 0.01 to 5% by mass based on the total amount of the composition, preferably Is 0.05 to 1% by mass, more preferably 0.1 to 0.5% by mass.
  • any compound usually used as a friction modifier for lubricating oils can be used, but an alkyl group or alkenyl group having 6 to 30 carbon atoms, particularly a linear alkyl group having 6 to 30 carbon atoms.
  • amine-based friction modifiers, imide-based friction modifiers, amide-based friction modifiers, fatty acid-based friction modifiers, and the like that have at least one linear alkenyl group in the molecule.
  • the amine-based friction modifier include linear or branched, preferably linear aliphatic monoamines having 6 to 30 carbon atoms, and linear or branched, preferably linear chains having 6 to 30 carbon atoms.
  • Aliphatic aliphatic alkanolamines linear or branched, preferably linear aliphatic polyamines, or aliphatic amine friction modifiers such as alkylene oxide adducts of these aliphatic amines.
  • the imide-based friction modifier include mono- and / or mono- and / or mono- and / or branched hydrocarbon groups having 6 to 30 carbon atoms, preferably 8 to 18 carbon atoms.
  • succinic acid such as bissuccinimide, a succinimide-modified compound obtained by reacting succinimide with boric acid, phosphoric acid, carboxylic acid having 1 to 20 carbon atoms, or one or more selected from sulfur-containing compounds. Examples thereof include imide friction modifiers.
  • amide friction modifier examples include fatty acid amide friction modifiers such as amides of linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms and ammonia, aliphatic monoamines or aliphatic polyamines. Etc. can be illustrated.
  • fatty acid friction modifier examples include linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms, and fatty acids such as esters of the fatty acids with aliphatic monohydric alcohols or aliphatic polyhydric alcohols. Examples include esters, fatty acid metal salts such as alkaline earth metal salts (magnesium salts, calcium salts, etc.) and zinc salts of the fatty acids.
  • aliphatic amine friction modifiers and fatty acid friction modifiers can be particularly preferably used in order to significantly improve the initial shudder prevention property. It is particularly preferable to contain these aliphatic amine friction modifiers and / or fatty acid friction modifiers.
  • the mass ratio is not particularly limited, but is preferably 1: 5 to 5: 1, more preferably from the viewpoint of excellent transmission characteristics. It is 1: 3 to 3: 1, particularly preferably 1: 2 to 2: 1.
  • one or two or more compounds arbitrarily selected from these friction modifiers can be contained in any amount, but the content is usually based on the total amount of the lubricating oil composition. 0.01 to 5.0% by mass, preferably 0.03 to 3.0% by mass.
  • any phenolic compound or amine compound that is generally used in lubricating oils can be used.
  • alkylphenols such as 2,6-di-tert-butyl-4-methylphenol and bisphenols such as methylene-4,4-bisphenol (2,6-di-tert-butyl-4-methylphenol)
  • Naphthylamines such as phenyl- ⁇ -naphthylamine, dialkyldiphenylamines, (3,5-di-tert-butyl-4-hydroxyphenyl) fatty acid (propionic acid, etc.)
  • mono- or polyhydric alcohols such as methanol, Esters with octadecanol, 1,6 hexadiol, neopentyl glycol, thiodiethylene glycol, triethylene glycol, pentaerythritol, etc.
  • organometallic antioxidants such as phenothiazines, molybdenum, copper
  • one or two or more compounds arbitrarily selected from these can be contained in an arbitrary amount, and the content thereof is usually 0.01 to based on the total amount of the lubricating oil composition. 5.0% by mass.
  • the phenol-based antioxidant and the amine-based antioxidant are particularly easy to maintain the anti-shudder performance over a long period of time.
  • the mass ratio when the phenolic antioxidant and the amine antioxidant are used in combination is preferably 1: 5 to 10: 1, more preferably 1: 1 to 8: 1, and further preferably 2: 1 to 6: 1.
  • any compound usually used as an extreme pressure additive for lubricating oil can be used.
  • sulfur compounds such as dithiocarbamates, disulfides, sulfurized olefins, sulfurized fats and oils, etc. Etc.
  • one or two or more compounds arbitrarily selected from these can be contained in an arbitrary amount, and the content thereof is usually 0.01 to based on the total amount of the lubricating oil composition. 5.0% by mass.
  • the viscosity index improver examples include a so-called non-dispersed viscosity index improver such as a copolymer of one or more monomers selected from various methacrylic esters or a hydrogenated product thereof, or nitrogen. Examples thereof include a so-called dispersion type viscosity index improver obtained by copolymerizing various methacrylic esters containing a compound.
  • specific examples of other viscosity index improvers include non-dispersed or dispersed ethylene- ⁇ -olefin copolymers (the ⁇ -olefins include propylene, 1-butene, 1-pentene, etc.) or hydrogen thereof.
  • the molecular weight of these viscosity index improvers needs to be selected in consideration of shear stability.
  • the number average molecular weight of the viscosity index improver is, for example, 5000 to 150,000, preferably 5000 to 35000 in the case of dispersed and non-dispersed polymethacrylate, in the case of polyisobutylene or a hydride thereof. Is 800 to 5000, preferably 1000 to 4000.
  • ethylene- ⁇ -olefin copolymer or a hydride thereof 800 to 150,000, preferably 3000 to 12000 are preferable.
  • one or two or more compounds arbitrarily selected from these viscosity index improvers can be contained in any amount, but the content is usually based on the lubricating oil composition standard. 0.1 to 20.0% by mass.
  • metal deactivators include thiazole compounds and thiadiazole compounds, and thiadiazole compounds are preferably used.
  • thiadiazole compounds include 2,5-bis (alkylthio) -1,3,4-thiadiazole having 6 to 24 carbon atoms or a straight or branched alkyl group having 6 to 24 carbon atoms.
  • 2,5-bis (alkyldithio) -1,3,4-thiadiazole having a group 2- (alkylthio) -5-mercapto-1, having a linear or branched alkyl group having 6 to 24 carbon atoms
  • Examples thereof include 3,4-thiadiazole, 2- (alkyldithio) -5-mercapto-1,3,4-thiadiazole having a straight chain or branched alkyl group having 6 to 24 carbon atoms, and a mixture thereof.
  • 2,5-bis (alkyldithio) -1,3,4-thiadiazole is particularly preferable.
  • the content of these metal deactivators is 0.005 to 0.5% by mass based on the total amount of the composition.
  • Examples of the rust inhibitor include alkenyl succinic acid, alkenyl succinic acid ester, polyhydric alcohol ester, petroleum sulfonate, dinonyl naphthalene sulfonate and the like.
  • Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, and imidazole compounds.
  • Examples of the pour point depressant include polymethacrylate polymers that are compatible with the lubricating base oil used.
  • Examples of rubber swelling agents include aromatic and ester rubber swelling agents.
  • Examples of the antifoaming agent include silicones such as dimethyl silicone and fluorosilicone.
  • the content of these additives is arbitrary, but the content of the corrosion inhibitor is usually 0.005 to 0.2% by mass and the content of the antifoaming agent is 0.0005 to 0.00% based on the total amount of the composition.
  • the content of 01% by mass and other additives is about 0.005 to 10% by mass, respectively.
  • Kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is usually 2 ⁇ 25mm 2 / s, preferably 3 ⁇ 15mm 2 / s, more preferably 4 ⁇ 10mm 2 / s, more preferably 5 ⁇ 7 mm 2 / s.
  • the lubricating oil composition of the present invention is a lubricating oil composition suitable as an automatic transmission oil / or continuously variable transmission oil that has a high coefficient of friction between metals and is excellent in transmission characteristics and anti-shudder performance.
  • the lubricating oil composition of the present invention is also excellent in performance as a transmission oil other than those described above, and is used as a lubricating oil for automatic transmissions such as automobiles, construction machines, and agricultural machines or for differential gears for manual transmissions. Are also preferably used.
  • it can be suitably used for industrial gear oils, automobiles such as motorcycles and automobiles, gasoline engines for power generation and marine use, diesel engines, lubricating oils for gas engines, turbine oils, compressor oils, etc. it can.
  • Examples 1 and 2 and Comparative Examples 1 to 3 Each lubricating oil composition shown in Examples 1 and 2 of Table 1 (adjusted to 100 ° C. kinematic viscosity 7 mm 2 / s) and each lubricating oil composition shown in Comparative Examples 1 to 3 for comparison were prepared and shown below.
  • the ratio of the base oil is based on the total amount of the base oil, and the amount of each additive is based on the total amount of the composition.
  • ⁇ 1 a friction coefficient at a sliding speed of 1 m / s
  • ⁇ 2 a friction coefficient at a sliding speed of 2 m / s
  • v1 a sliding speed of 1 m / s
  • v2 a sliding speed of 2 m / s.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

L'invention porte sur une composition d'huile lubrifiante dont le coefficient de friction métal sur métal est élevé, les propriétés anti-vibration excellentes et qui peut être utilisée comme huile de transmission automatique et/ou à variation continue. La composition d'huile lubrifiante est caractérisée en ce qu'elle comprend une huile de base lubrifiante et les matières suivantes (A) et (B) incorporées à l'huile de base lubrifiante : (A) 0,005 à 0,1 % en masse de bore (BoA) et 0,01 à 0,4 % en masse d'azote de la quantité totale de la composition ; de (a1) un alkylsuccinimide boré et/ou un alcénylsuccinimide boré de masse moléculaire moyenne en poids de 1 000 à 20 000 ou d'un mélange de (a1) un alkylsuccinimide boré et/ou un alcénylsuccinimide boré avec (a2) un alkylsuccinimide non boré et/ou un alcénylsuccinimide non boré ; et (B) 0,01 à 0,5 % en masse de métal (MeB) de la quantité totale de la composition, d'un agent de nettoyage métallique contenant un groupe alkyle à chaîne droite ayant 6 à 60 atomes de carbone issu d'un oligomère de l'éthylène et un indice de base de 100 à 500 mg de KOH/g.
PCT/JP2009/000406 2008-03-10 2009-02-03 Composition d'huile lubrifiante WO2009113234A1 (fr)

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WO2014156307A1 (fr) * 2013-03-29 2014-10-02 Ｊｘ日鉱日石エネルギー株式会社 Composition d'huile lubrifiante pour une transmission automatique
WO2016170813A1 (fr) * 2015-04-22 2016-10-27 出光興産株式会社 Fluide de transmission automatique

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KR101438916B1 (ko) * 2012-11-02 2014-09-11 현대자동차주식회사 저온에서 윤활 성능이 우수한 그리이스 조성물
JP6940274B2 (ja) 2016-01-21 2021-09-22 Ｅｍｇルブリカンツ合同会社 潤滑油組成物

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WO2016170813A1 (fr) * 2015-04-22 2016-10-27 出光興産株式会社 Fluide de transmission automatique

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