WO2007021014A1 - Lubricant oil composition - Google Patents

Lubricant oil composition Download PDF

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Publication number
WO2007021014A1
WO2007021014A1 PCT/JP2006/316274 JP2006316274W WO2007021014A1 WO 2007021014 A1 WO2007021014 A1 WO 2007021014A1 JP 2006316274 W JP2006316274 W JP 2006316274W WO 2007021014 A1 WO2007021014 A1 WO 2007021014A1
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WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
acid
metal
metal salt
Prior art date
Application number
PCT/JP2006/316274
Other languages
French (fr)
Japanese (ja)
Inventor
Hitoshi Komatsubara
Shigeki Matsui
Original Assignee
Nippon Oil Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=37757664&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2007021014(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Nippon Oil Corporation filed Critical Nippon Oil Corporation
Priority to CN2006800375881A priority Critical patent/CN101283079B/en
Priority to EP06782833A priority patent/EP1918356B1/en
Publication of WO2007021014A1 publication Critical patent/WO2007021014A1/en
Priority to US12/026,670 priority patent/US20080139424A1/en

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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
    • 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
    • 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
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/146—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings having carboxyl groups bound to carbon atoms of six-membeered aromatic rings having a hydrocarbon substituent of thirty or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbasedsulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • 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
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/106—Thiadiazoles
    • 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
    • C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
    • C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
    • C10M2219/108—Phenothiazine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/041—Triaryl phosphates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/042—Metal salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/043—Ammonium or amine salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/049—Phosphite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • 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
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/52—Base number [TBN]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/74—Noack Volatility
    • 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
    • C10N2030/76—Reduction of noise, shudder, or vibrations
    • 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
    • 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
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
    • C10N2040/045—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for continuous variable transmission [CVT]
    • 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 suitable for a transmission having a slip-controlled wet clutch, and more specifically, when a specific salicylate-based detergent is used, an excellent metal preform and metal belt.
  • a clear, slip-controlled wet clutch and metal belt that have anti-wear and initial anti-shoulder performances and can maintain the anti-shudder performance for a long period of time.
  • Recent automatic transmissions are desired to be lighter and smaller, and as the combined engine increases in output, the power transmission capacity is being improved.
  • the lubricating oil used in these materials is required to have high lubrication performance, that is, performance that prevents wear on the surfaces of bearings, gears, and the like.
  • the torque transmitted between the metal pulley and the metal belt is increasing with the increase in engine output.
  • a high transmission torque capacity is required, and the ability to prevent wear on the metal surface between the metal bouley and the metal belt is particularly required.
  • Patent Document 1 includes a specific amount of calcium salicylate and SP-based extreme pressure agent, a specific amount of succinic acid imide and boron-containing ashless dispersant, which has excellent anti-shudder life and fatigue life.
  • a long-lasting transmission lubricant composition is disclosed in Patent Document 2 as an essential component of an organic acid metal salt having a specific structure, an antiwear agent, and a succinic acid imide containing fluorine.
  • Patent Document 3 includes calcium salicylate and phosphorus-based antiwear agent.
  • Patent Document 4 Incorporates a friction modifier and a dispersion-type viscosity index improver, which achieves both high metal-to-metal friction coefficient and anti-shudder properties for the slip control mechanism, and can be used for a long time.
  • Oil In Patent Document 4 a dithiocarbamate compound, a condensate of a branched fatty acid having 8 to 30 carbon atoms and an amine, and an amine-based antioxidant are blended to provide excellent anti-shudder performance.
  • Patent Document 5 contains calcium sulfonate and phosphite, as well as a sarcosine derivative or a reaction product of carboxylic acid and amino acid.
  • An automatic transmission oil composition that has anti-shudder performance against a capping device and has long life performance against a belt type CVT device is disclosed in Patent Document 6 as a specific alkali.
  • a slip controller that contains a specific amount of earth metal sulfonate. It is excellent in oxidation stability as a built-in automatic transmission.
  • Automatic transmission fluid composition is disclosed having a long-term durability performance is sustained by.
  • the transmission has a slip control type wet clutch, especially in a continuously variable transmission in which a metal boule and a metal belt are in contact with each other under severe conditions, it is unique to the slip control type wet clutch. There is no disclosure or suggestion of a solution to prevent long-term shudder over time
  • Patent Document 1 Japanese Laid-Open Patent Publication No. 2 2003-1 1 3 3 91
  • Patent Document 2 Japanese Patent Laid-Open No. 2 0 0 1-3 2 3 2 92
  • Patent Document 3 Japanese Patent Laid-Open No. 2 00 0-3-5 5 6 95
  • Patent Document 4 Japanese Patent Application Laid-Open No. 11-500 0 7
  • Patent Document 5 Japanese Patent Application Laid-Open No. 10-3020 692
  • Patent Document 6 Japanese Patent Laid-Open No. 10-2 5 4 8 7
  • Patent Document 7 Japanese Laid-Open Patent Publication No. 20 0 4 1 6 7 8 12
  • the object of the present invention is to provide an excellent metal boot and metal belt wear resistance and the first shader even when a monoalkyl type salicylate detergent is used.
  • Non-slip control wet clutch, metal pulley, and gold-metal continuously variable transmission that have anti-slip performance and can maintain anti-shudder performance for a long period of time, continuously variable transmission with slip-control start clutch
  • a lubricating oil composition suitable for a machine is provided.
  • the lubricating base oil contains (A) a monoalkyl salicylic acid metal salt having a composition ratio of 85 to 100 mo 1% and a dialkyl salicylic acid ⁇ salt having a composition ratio of 0 to 15 mo 1%.
  • R 1 is a linear or branched alkyl group having 1 to 30 carbon atoms
  • R 2 is a hydrogen atom or a linear or branched group having 1 to 24 carbon atoms.
  • Each represents a branched alkyl group
  • a and b each independently represent 1, 2 or 3.
  • the lubricating oil composition comprises a friction modifier, particularly an amine friction modifier and / or a fatty acid friction modifier. It is preferable that an agent is included.
  • the lubricating oil composition preferably contains calcium sulfonate and / or magnesium sulfonate.
  • the lubricating oil composition preferably contains a non-boron ashless dispersant and / or a boron ashless dispersant.
  • the alkyl salicylic acid metal salt is a secondary monoalkyl type alkyl salicylic acid metal salt.
  • the lubricating oil composition is preferably for a continuously variable transmission having a metal pulley and a metal belt.
  • the slip control type wet clutch is a slip control type start clutch.
  • the present invention also relates to a continuously variable transmission having a metal pulley and a metal belt, and a method for lubricating a Z or slip control type wet clutch, characterized by using the lubricating oil composition.
  • the present invention is described in detail below.
  • the lubricating base oil in the lubricating oil composition of the present invention is not particularly limited, and mineral oil base oils and synthetic base oils used for ordinary lubricating oils can be used.
  • mineral base oils lubricating oil fractions obtained by depressurizing and distilling atmospheric residual oil obtained by atmospheric distillation of crude oil can be desolvated, solvent extracted, and hydrocracked.
  • synthetic base oils specifically, polybutene or a hydride; 1- Okute N'ori Goma, 1 Desen'ori sesame Chief poly - a Orebuin or its hydrogenated product; Jito Li decyl glutarate, di one 2 -Ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, and 2-diethyl oleyl sebacate-neopentinolegrinole enoestole, trimethylone lepropan caprylate, trimethy mouthful Polypropane esters such as lepropane pelargonate, pentaerythritol, 2-ethylenolehexanoate, and pentaerythritol pelargonate; aromatic synthetic oils such as alkylnaphthalene, alkylbenzene, and aromatic ester, or mixtures thereof it can.
  • 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, and a mixed oil of one or more mineral base oils and one or more synthetic base oils. '.
  • 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 It is desirable to adjust to mm 2 / s, particularly preferably 3 to 4.5 mm 2 / s.
  • Lubrication When the kinematic viscosity of the oil base oil at 100 ° C exceeds 8 mm 2 / s, the low-temperature viscosity characteristics deteriorate, while when the kinematic viscosity is less than 2 mm 2 s, lubrication Insufficient oil film formation at the location is inferior in lubricity, and the evaporation loss of the lubricating base oil is increased, 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 even more preferably 0. 0 1% by mass or less is desirable. '
  • the amount of evaporation loss of the lubricating base oil is not particularly limited, but the NOACK evaporation amount is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, and particularly preferably Is preferably adjusted to 2 2 to 35 mass%.
  • the NO ACK evaporation amount here means the evaporation amount measured according to CECL—40—T-87.
  • the kinematic viscosity at 100 ° C. is 1.5 to 3.5 mm 2 / s, preferably 2 to 3.2 mm 2 / s, more preferably 2 5-3 mm 2 / s, and the sulfur content is not more than 0.05% by mass, preferably not more than 0.01% by mass, more preferably not more than 0.05% by mass, NO AC K Evaporation amount is 20 to 80% by mass, preferably 30 to 65% by mass, more preferably 30 to
  • sulfur content is not more than 0.05 mass%, preferably not more than 0.01 mass%, more preferably not more than 0.00 mass%, 1 ⁇ 0 0 Evaporation amount of 5 to 20% by mass, preferably 10 to 18% by mass, more preferably 12 to 16% by mass of base oil.
  • 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 0.0 5 to 1 Mass%, preferably 0.;!
  • NOACK evaporation amount is 10 mass% or less, preferably 5 mass% or less, more preferably 3
  • a small amount, for example, 5 to 30% by mass of a base oil having a mass% or less may be mixed.
  • the component (A) specified in the lubricating oil composition of the present invention has a composition ratio of monoalkyl salicylic acid metal salt of 85 to 100 mol% and a composition ratio of dialkyl salicylic acid metal salt of 0 to An alkyl salicylic acid metal salt having a composition ratio of 15 to 1 mo and a 3-alkyl salicylic acid metal salt of 40 to 100 mo 1%, and Z or a (per) salt basic salt thereof.
  • the monoalkyl salicylic acid metal salt here means an alkyl salicylic acid metal salt having one alkyl group, such as 3 monoalkyl salicylic acid gold horse salt, 4 monoalkyl salicylic acid metal salt, 5-alkyl salicylic acid metal salt, and the like.
  • the composition ratio of the salt is alkyl salicylic acid metal salt 10 0 mo 1. /.
  • 8 5 to 10 0 mo 1%, preferably 8 8 to 9 8 In ol%, more preferably 90 to 9 5 mo 1%, an alkyl salicylic acid metal salt other than a monoalkyl salicylic acid metal salt for example, the constituent ratio of the dialkyl salicylic acid metal salt is 0 to 15 mo 1%, preferably 2 to 12 mo 1%, more preferably 5 to 1 O HI O 1%.
  • the composition ratio of the 3-alkyl salicylic acid metal salt is 40 to 100 mol%, preferably 45 to 80 mol 1%, more preferably 5 to 100 mol 1 metal alkyl salt. 0 to 60 mol%.
  • the total composition ratio of 4-alkyl salicylic acid metal salt and 5-alkyl salicylic acid metal salt is the same as that for alkyl salicylic acid metal salt 10%, except for 3 -alkyl salicylic acid metal salt and dialkyl salicylic acid metal salt. 0 to 60 mo 1%, preferably 20 to 50 mo 1%, more preferably 30 to 45 mo 1%.
  • composition ratio of 3 —alkyl salicylate By making the composition ratio of 3 —alkyl salicylate more than 40 mo 1%, 5 The composition ratio of the monoalkyl salicylic acid metal salt can be made relatively low, and the oil solubility can be improved.
  • the alkyl group in the alkyl salicylic acid metal salt constituting the component (A) has 10 to 40 carbon atoms, preferably 10 to 1'9 carbon atoms or 20 to 30 carbon atoms, more preferably Is an alkyl group having 14 to 18 carbon atoms or 20 to 26 carbon atoms, particularly preferably an alkyl group having 14 to 1'8 carbon atoms.
  • alkyl group having 10 to 40 carbon atoms examples include decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, C-alkyl of 10 to 4 Q such as icosyl group, hecosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, and triacontyl group Group.
  • alkyl groups may be linear or branched, and may be a primary alkyl group or a secondary alkyl group.
  • a secondary alkyl group is particularly preferred from the viewpoint of easily obtaining a metal salt of salicylic acid that satisfies the definition of the component (A).
  • examples of the metal in the alkyl salicylic acid metal salt include alkali metals such as sodium and rhodium, alkaline earth metals such as calcium and magnesium, and are preferably calcium and magnesium, and are preferably calcium. Particularly preferred.
  • the component (A) of the present invention can be produced by a known method and the like, and is not particularly limited.
  • 1 mol 1 sentence is more than 1 mol 1 phenol, ethylene, propylene, butene, etc.
  • a method of alkylating with a straight chain ⁇ -olefin such as an ethylene polymer and carboxylating with carbon dioxide gas, etc., or salicylic acid
  • Alkylic salicylic acid mainly composed of monoalkyl salicylic acid obtained by a method of alkylation using 1 or more lmo 1 or more olefins, preferably linear ⁇ -olefins, to Reaction with a metal base such as an oxide or hydroxide of a strong metal or alkaline earth metal, or an alkaline metal salt such as a sodium salt or a strong lithium salt It is further obtained by such be substituted Al force Li metal salts and Al force Li earth metal salts.
  • the reaction ratio of phenol or salicylic acid to olefin is preferably, for example, 1: 1 to 1.15 (molar ratio), more preferably 1: 1.05 to 1: 1 (molar ratio).
  • the composition ratio of monoalkyl salicylic acid metal salt and dialkyl salicyl acid metal salt can be controlled to the desired ratio, and by using linear ⁇ -olefin as the olefin, 3-alkyl
  • the metal salicylic acid metal salt, 5-alkylsalicylic acid metal salt and the like can be easily controlled to a desired ratio as in the component ( ⁇ ) specified in the present application, and an alkylsalicylic acid metal salt having a secondary primary alkyl which is preferable in the present invention.
  • olefins When branched olefins are used as olefins, it is easy to obtain only 5-alkylsalicylic acid metal salts, but oil-soluble by mixing 3-alkylsalicylic acid metal salts, etc. so as to form the component (ii) of the present application. This is an undesirable method because the manufacturing process is diversified.
  • the component (ii) of the present invention comprises an alkali metal or alkaline earth gold salicylate (neutral salt) obtained as described above, and an excess of alkali metal or alkaline earth.
  • Metal salt or Al-strength metal Base obtained by heating metal genus or Al-strength earth metal base (hydroxide or oxide of Al-strength metal or Al-strength earth metal) in the presence of water.
  • Over-base obtained by reacting the above-mentioned neutral salt with a base such as hydroxide of alkaline metal or alkaline metal in the presence of organic salt, carbon dioxide gas, boric acid or borate Sexual salts are also included.
  • 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 is 1. It is desirable to use 0 to 20% by mass, preferably 2.0 to 16% by mass.
  • the most preferable component (A) specified in the present invention is that the composition ratio of the monoalkyl salicylic acid metal salt is 85 to 95 mo 1% and the dialkyl salicylic acid metal salt The composition ratio is 5 to 15 mo 1%, 3
  • the composition ratio of monoalkyl salicylic acid metal salt is 50 to 60 mo 1%
  • the composition ratio of 4-alkyl salicylic acid metal salt and 5-alkyl salicylic acid metal salt is 3 Alkyl salicylic acid metal salt that is 5 to 4 5 mo 1%, and / or (per) basic salt thereof.
  • the alkyl group here is particularly preferably a secondary monoalkyl group. '
  • the base number of component (A) is usually 0 to 500 mg KOH / g, preferably 20 to 45 mg KOH / g, particularly preferably 100 to 300 mg KOH Zg.
  • the base number here means the base number by the perchloric acid method measured in accordance with 7. of JISK 25.0 1 “Neutralization of petroleum products and lubricants”. .
  • the content of the component (ii) is converted to metal elements based on the total amount of the lubricating oil composition in terms of wear prevention, initial shudder prevention performance, and maintenance performance. in preferably 0.00 5 to 0.5 wt%, preferably 0.0 1 to 0.2 mass 0/0, more preferably 0.0 2 to 0.1% by weight, particularly preferably 0.0 It is 2-0.05 mass%, and it is better that the content is relatively small.
  • the component ( ⁇ ) in the lubricating oil composition of the present invention is a nitrogen compound represented by the general formula (1). , C
  • R 1 represents a linear or branched alkyl group having 1 to 30 carbon atoms, preferably 6 to 24 carbon atoms, and more preferably 6 to 12 carbon atoms.
  • R 2 represents a hydrogen atom or a linear or branched alkyl group having 1 to 24 carbon atoms, preferably a hydrogen atom or 1 to 12 carbon atoms, more preferably 6 to 12 carbon atoms.
  • a and b are each independently 1, 2 or 3, preferably 1 or 2, and more preferably a and b are both 2.
  • linear or branched alkyl group having 1 to 30 carbon atoms represented by R 1 include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n —Ptyl group, isobutyl group, sec-butynole group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadel Group, hexadecyl group, heptadecyl group, 'octadecyl group, nonadecyl group, icosyl / le group, hencosyl group, docosyl group, tricosyl group, tetracosyl group, pentaco'syl group, hexacosyl group, h
  • R 1 is an alkyl group having 6 to 24 carbon atoms and R 2 is hydrogen because it can further improve the maintenance performance of wear prevention performance and anti-shudder performance. More preferably, it is an atom or an alkyl group having 1 to 24 carbon atoms, and a and b are 1 or 2, and R 1 and R 2 are 6 to L carbon atoms, preferably 6 to 10 carbon atoms. Particularly preferred is a case in which a and b are both 2.
  • a nitrogen compound represented by the general formula (1) is a 2, 5_bis (alkylthio) having a straight or branched alkyl group having 6 to 24 carbon atoms — 1 , 3, 4-thiadiazole, straight chain or branched alkyl group having 6 to 24 carbon atoms, 2, 5 bis (alkyldithio) — 1, 3, 3, 4-thiadiazole, straight chain having 6 to 24 carbon atoms Or 2- (alkylthio) 1-5-mercapto 1,3,4-thiadiazole, having a branched alkyl group. 2; (alkyldithio) having a linear or branched alkyl group having 6 to 24 carbon atoms. ) — 5— Lucapto 1, 3, 4-thiadiazole and mixtures thereof.
  • 2,5-bis (alkyldithio) 1,1,4-thiadiazole is particularly preferable.
  • the content of the nitrogen compound represented by the general formula (1) is preferably 0.005 to 0.5 mass%, more preferably, based on the total amount of the composition. 0.0 1 to 0.2 mass 0/0, more preferably from 0.02 to 0.1 5% by weight, particularly preferably 0.0 3 to 0.1 4% by weight.
  • the component (C) in the lubricating oil composition of the present invention is a phosphorus wear inhibitor.
  • the phosphorus antiwear agent is not particularly limited as long as it contains phosphorus in the molecule.
  • the phosphorus compound represented by the following general formula (2) or general formula (3) Salt is not particularly limited as long as it contains phosphorus in the molecule.
  • the phosphorus compound represented by the following general formula (2) or general formula (3) Salt is not particularly limited as long as it contains phosphorus in the molecule.
  • the phosphorus compound represented by the following general formula (2) or general formula (3) Salt is represented by the following general formula (2) or general formula (3) Salt.
  • X 1 , X 2 , X 3 , X 4 , X 5, and X 6 each independently represent an oxygen atom or a sulfur atom.
  • 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • hydrocarbon group having 1 to 30 carbon atoms represented by the above R 3 to R 8 include: an alkyl group, an alkyl group, an alkenyl group, an allyl substitution, and an alkyl group. , Aryl groups, alkyl-substituted aryl groups, and aryl alkyl groups.
  • alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nor group, decyl group, undecyl group, dodecyl group.
  • alkyl groups such as a group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group (these alkyl groups may be linear or branched).
  • Examples of the cycloalkyl group include a cycloalkyl group having 5 to 7 carbon atoms such as a cyclopentyl group, a cyclohexyl group, and a cyclopentyl group.
  • Examples of the alkylcycloalkyl group include, for example, a methylcyclopentyl group, a dimethylcyclopentinole group, a methinoreethyl / recyclopentyl / re group, a ethenorecloclopentyl group, a methylcyclohexyl group, a dimethinorecyclohexyl group, and a methylethynoleic mouth.
  • Alkyl cycloalkyl groups having 6 to 11 carbon atoms such as xyle groups, jetty / recix hexinoles groups, methino leschi heptisoles groups, dimethylcycloheptyl groups, methylethyl heptyl heptyl groups, ethynolecic butyl groups, etc.
  • the substitution position of the group to the cycloalkyl group is also arbitrary. '
  • alkenyl groups examples include butyr, pentenyl, hexyl, heptenyl, octul, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,
  • An alkenyl group such as a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, and a .octadecenyl group (the alkenyl group may be linear or branched, and the position of the double bond is arbitrary) Can do.
  • aryl group examples include aryl groups such as a phenyl group and a naphthyl group.
  • alkylaryl group examples include, for example, a tolyl group, a xylyl group, an ethi / lephenyl group, a propi / refenine / le group, a petit / lephenisole group, a pentylphenyl group, a hexylphenyl group, and a heptylphenyl group.
  • Octylphenyl group, nonylphenyl group, decylph each alkylaryl group having 7 to 18 carbon atoms such as nyl group, undecylphenyl group, dodecylphenyl group, etc. (the alkyl group may be linear or branched)
  • substitution position on the aryl group is also arbitrary. , '
  • arylalkyl group examples include a benzyl group, a phenylethyl group, a phenisolepropinole group, a phenenolevbutizole group, a pheny / repentinole group, and a phenenohexoxy.
  • each arylalkyl group having 7 to 12 carbon atoms such as an alkyl group (these alkyl groups may be linear or branched).
  • the hydrocarbon group having 1 to 30 carbon atoms represented by R 3 r ⁇ R 8 is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms. More preferred is an alkyl group having 4 to 20 carbon atoms, and still more preferred is an alkynole group having 6 to 18 carbon atoms.
  • Examples of the phosphorus compound represented by the general formula (2) include phosphorous acid, monothiophosphorous acid, dithiophosphorous acid, trithiophosphorous acid; and one hydrocarbon group having 1 to 30 carbon atoms.
  • phosphorous acid diester having two hydrocarbon groups having 1 to 30 carbon atoms, monothio Phosphite diester, dithiophosphite diester, trithiophosphite diester;
  • phosphite triester having three hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphite triester, dithiophosphite And acid triesters, trithiophosphorous acid triesters; and mixtures thereof.
  • Examples of the phosphorus compound represented by the general formula (3) include: phosphoric acid, monothiophosphoric acid, dithiophosphoric acid, trithiophosphoric acid, tetrathiophosphoric acid; phosphoric acid having one hydrocarbon group having 1 to 30 carbon atoms. Monoester, monothiophosphoric acid monoester, dithiophosphoric acid monoester, trithiophosphoric acid monoester, tetrathiophosphoric acid monoester; 'above.
  • one or more of X 1 , X 2 and X 3 are preferably oxygen atoms, and two or more Is more preferably an oxygen atom, and most preferably all three are oxygen atoms.
  • one or more of X 4 , X 5 and X 6 are preferably oxygen atoms, and two or more Oxygen atom More preferably, all three are oxygen atoms.
  • the phosphorus compound may be an ammonia, a hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms.
  • an amine compound having only a hydroxyl group-containing hydrocarbon group in the molecule a nitrogen compound such as an alkylene oxide adduct of the amine compound, or a metal oxide, metal hydroxide, metal carbonate, metal chloride
  • a salt obtained by neutralizing a part or all of the remaining acidic hydrogen by the action of a metal base such as
  • nitrogen compound examples include: ammonia; monomethylamine, monoethinoreamine, monopropi / reamine, monoptinoreamine, monopentinoreamine, monohexylamine, monoheptyl / reamine, monooctyl / reamine, monolaurinoreamine, Monostearylamine, Monooleylamine Dimethylamine, Methylethylamine, Jetylamine, Methylpropylamine, Ethylpropylamine, Dipropylamine, Methylbutylamine, Ethylbutyramine, Propylptylamine, Dibutylamine, Dipentenoreamin , Dihexenoreamine, diheptinoreamin, dioctylamine and other alkyls or alkenylamines (the alkyl group or alkenyl group may be linear or branched); monomethano ⁇ ⁇ Luamine, Monoethanol 7 Reamine, Monopropano
  • the metal in the above metal base include alkali metals such as lithium, sodium, force lithium and cesium, alkaline earth metals such as calcium, magnesium and barium, zinc, copper, iron, lead, Examples include heavy metals such as nickel, silver, manganese, and molybdenum. Among these, the strength of calcium, magnesium, etc. Li earth metal and zinc are preferred.
  • components (C) can be used alone or in combination of two or more. .
  • phosphorous acid phosphoric acid
  • Preferred is one or a mixture of two or more selected from esters or phosphate esters, and an amine salt in which an alkylamine having an alkyl group having 1 to 18 carbon atoms is allowed to act.
  • Phosphorous acid, 4 to 4 carbon atoms One or a mixture of two or more selected from phosphites having 20 alkyl groups is more preferable, and it is particularly preferable to contain a phosphite diester having an alkyl group having 4 to 8 carbon atoms.
  • the content of the component (C) is usually based on the total amount of the composition.
  • the phosphorus element concentration is preferably 0.0 0 1 to 0.
  • Mass 0/0 more preferably 0.0 0 5 to 0.0 8 wt%, more preferably 0.
  • the mass ratio of the content of the component (A) at the metal element concentration (M) to the content (P) of the phosphorus element concentration of the component (C) on the basis of the total amount of the composition ((M) / (P)) is not particularly limited, but is preferably 0.1 to 250, preferably 0.5 to 50, more preferably 0.8 to 5, particularly preferably 1. ⁇ 3.
  • the mass ratio of the content of the component (B) to the content (P) of the component (C) at the phosphorus element concentration ((B) / (P )) is not particularly limited, but is preferably 0.1 to 2500, preferably 0.5 to 50, more preferably 1 to 10 and particularly preferably 1.5 to 5.
  • (C) Component content in phosphorus element concentration (P)
  • the mass ratio of (A) 'component and (B) component to the above ranges makes it possible to prevent wear and prevent initial shading. It is possible to obtain a composition that has excellent anti-blocking performance and can easily maintain anti-shudder performance for a long time. You can.
  • the combined use of the (A) component, the (B) component and the (C) component provides excellent anti-wear properties and initial anti-shoulder performance and long anti-shudder performance.
  • Additives that can be added include, for example, metallic detergents other than component (A), ashless dispersant, friction modifier, antioxidant, extreme pressure additive, antiwear agent, viscosity index improver, and anti-wrinkle Agents, corrosion inhibitors, pour point depressants, rubber swelling agents, antifoaming agents, and coloring agents. These can be used alone or in combination.
  • metallic detergents other than the component (A) include salicylate detergents, sulfonate detergents, and phenate detergents that do not fall under the component (A).
  • Examples of salicylate detergents not corresponding to the component (A) include alkyl salicylic acid metal salts having a composition ratio of dialkyl salicylic acid metal salt having two alkyl groups having 10 to 40 carbon atoms of 15 mo 1% or more. Z or its (over) basic salt, dialkyl salicylic acid metal salt having an alkyl group having 1 to 9 carbon atoms and an alkyl group having 10 to 40 carbon atoms and Z or its (over) basic salt, Examples include alkyl salicylic acid metal salts and / or (over) basic salts thereof in which the composition ratio of the 3-alkyl salicylic acid metal salt is less than 40 mo 1%.
  • examples of the metal include Al-strength metal and Al-strength earth metal. ..
  • the sulfonate detergent examples include alkyl aromatic sulfonic acids obtained by sulfonating alkyl aromatic compounds having a molecular weight of 100 to 1500, preferably 20:00 to 700. Of these, alkaline earth metal salts, particularly magnesium salts and Z or calcium salts are preferably used. Specific examples of the alkyl aromatic sulfonic acids include so-called petroleum sulfonic acids and synthetic sulfonic acids.
  • the alkyl aromatic compound in the lubricating oil fraction of mineral oil is sulfonated.
  • Synthetic sulfonic acids are, for example, by-produced from an alkylbenzene production plant that is a raw material for detergents, and polylevine is alkylated into benzene.
  • a sulfonated alkylbenzene having a linear or branched alkyl group obtained by sulfination, or a sulfonated dinonylnaphthalene may be used.
  • the sulfonating agent for sulfonating these alkyl aromatic compounds is not particularly limited, but usually fuming sulfuric acid or sulfuric acid is used.
  • the phenate detergent include reacting sulfur with an alkylphenol having at least one linear or branched alkyl group having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms.
  • the base number of the metal detergent other than the component (A) is usually 0 to 500 mg KOH / g, preferably 20 to 450 mg KOH / g.
  • a metal detergent other than the component (A) when a metal detergent other than the component (A) is used, a calcium sulfonate detergent having a base number of 0 to 500 mg KOH / g, preferably 100 to 40 Omg KOH / g. It is particularly preferable to use one or more selected from magnesium sulfonate detergents. By using these sulfonate detergents in combination, it is possible to obtain a composition with a very good balance of anti-wear effect, anti-shudder property, and maintainability.
  • a metallic detergent other than the component (A) when a metallic detergent other than the component (A) is contained, its content is not particularly limited, but is usually from 0.00 to 1 to 5 on the basis of the total amount of the product. % By weight, preferably 0.05 to 1% by weight, particularly preferably 0.1 to 0.5% by weight.
  • any compound usually used as an ashless dispersant for lubricating oil can be used.
  • a nitrogen-containing compound such as succinic acid, benzylamine, polyamine, or a derivative thereof having at least one alkyl group or alkenyl group having 40 to 40 carbon atoms, preferably 60 to 350 carbon atoms in the molecule, or Examples include modified products.
  • the alkyl group having 40 to 400 carbon atoms and the alkenyl group may be linear or branched.
  • olefin oligomers such as propylene, 1-butene and isobutylene, and ethylene.
  • Propylene coco Examples include branched alkyl groups and branched alkenyl groups derived from ligomer. If the alkyl group or alkenyl group has less than 40 carbon atoms, the solubility of the compound in the lubricating base oil will be reduced, while if the alkyl group or alkenyl group has more than 400 carbon atoms, the composition The low-temperature fluidity of things deteriorates.
  • Examples of the derivatives or modified products of nitrogen-containing compounds mentioned as examples of the above ashless dispersant include, for example, nitrogen-containing compounds such as those described above, monocarboxylic acids having 2 to 30 carbon atoms (fatty acids, etc.), Shu Neutralize some or all of the remaining amino groups and Z or imino groups by the action of polycarboxylic acids having 2 to 30 carbon atoms such as acid, phthalic acid, trimellitic acid, and pyromellitic acid.
  • acid-modified compound boric acid is allowed to act on the nitrogen-containing compound as described above to neutralize part or all of the remaining amino group and / or imino group;
  • boron-modified compound by reacting phosphoric acid or phosphorous acid with a nitrogen-containing compound as described above, some or all of the remaining amino group and Z or imino group are neutralized, Amidified, so-called Two modified compounds selected from sulfur-modified compounds obtained by allowing a sulfur compound to act on a nitrogen-containing compound as described above; and acid-modified, boron-modified, phosphorus-modified, and sulfur-modified compounds as described above. Examples thereof include modified compounds that combine the above modifications.
  • lubricating oil composition of the present invention one kind or two or more kinds of compounds arbitrarily selected from these can be used in any amount, but the content thereof is usually the lubricating oil composition. '0.1 to 10% by mass based on the total amount.
  • the lubricating oil composition of the present invention preferably contains a non-boron-based ashless dispersant and / or a boron-containing ash-dispersed agent, and these ashless dispersants may be succinic acid-based ashless dispersants. More preferred.
  • the content of the non-boron ashless dispersant and / or the fluorine-containing ashless dispersant is preferably 0.1 to 10% by mass, more preferably 3 to 6% by mass, based on the total amount of the lubricating oil composition.
  • the non-boron ashless dispersant is preferably 10% by mass or less, more preferably 1 to 6% by mass, and particularly preferably 2 to 4% by mass.
  • the mass ratio of the content of the boron-containing ashless dispersant to the total content of the non-boron-based ashless dispersant and the content of the boron-containing ashless dispersant is preferably from 0.1 to 1, More preferably, it is 0.15-0.5, Most preferably, it is 0.2-0.3.
  • 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 straight chain having 6 to 30 carbon atoms.
  • Examples include amine-based friction modifiers, imide-based friction modifiers, amide-based friction modifiers, and fatty acid-based friction modifiers having at least one chain alkyl group or straight-chain alkenyl group in the molecule.
  • amine friction modifier examples include linear or branched carbon atoms having 6 to 30 carbon atoms, preferably linear aliphatic monoamines, linear or branched, and preferably linear.
  • an aliphatic amine-based friction modifier such as an alkylene oxide adduct of the aliphatic amine or the like.
  • the imid friction modifier one or two linear or branched, preferably branched hydrocarbon groups having 6 to 30 carbon atoms, preferably 8 to 18 carbon atoms.
  • the mono- and / or psuccinic acid imide, and the succinic acid imide is reacted with one or more selected from boric acid, phosphoric acid, a carboxylic acid having 1 to 20 carbon atoms, or a sulfur-containing compound.
  • succinic acid-based friction modifiers such as succinic acid imide-modified compounds.
  • Amid-based friction modifiers include linear or branched, preferably linear, branched fatty acids with 7 to 31 carbon atoms, ammonia, aliphatic monoamines or aliphatic polyamines, etc. Examples thereof include fatty acid amide friction modifiers.
  • fatty acid friction modifier examples include linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms, and esters of the fatty acids with aliphatic monohydric alcohols or aliphatic polyhydric alcohols. Fatty acid esters, alkaline earth metal salts of the fatty acids (magnesium salts, calcium salts, etc.) and fatty acid metal salts such as zinc salts.
  • the above-mentioned imide friction modifiers particularly succinic acid imide friction modifiers, not only increase the friction coefficient of wet clutches and improve power transmission efficiency, but also significantly improve the anti-shudder life. It is effective for.
  • aliphatic amine friction modifiers and fatty acid friction modifiers are particularly preferably used because the initial anti-shattering property is remarkably improved.
  • these aliphatic amine-based friction modifier and z or fatty acid-based friction modifier are particularly preferable to contain
  • the mass ratio is not particularly limited, but is preferably 1: 5 to 5: 1, more preferably in terms of excellent speed change characteristics. Is 1: 3 to 3: 1, particularly preferably 1: 2 to 2: 1.
  • one kind or two or more kinds of compounds arbitrarily selected from these friction modifiers can be contained in any amount, but usually the content thereof is the lubricating oil composition. It is 0.01 to 5.0% by mass on a basis, preferably 0.03 to 3.0% by mass.
  • Antioxidants that can be used are those generally used in lubricating oils, such as funinol compounds and amine compounds.
  • alkylphenols such as 2-6-g-tert-butyl / le-4-methylphenol, and methylene-1,4-bisphenol (2,6-ditert-butyl-4-methylenophenol).
  • Bisphenols naphthylamines such as phenyl-alpha ⁇ -naphthylamine, dialkyldiphenylamines, (3,5-di-tert-petityl-4-hydroxyphenyl) 'fatty acids (propionic acid etc.) and monovalent or Polyhydric alcohols, for example, esters with methanol, octadecanol, 1, 6 hexadiol ⁇ /, neopentinoglycol ⁇ thiojetylene glycolol, triethyleneglycol ', pentaerythritol, Examples include organometallic antioxidants such as phenothiazines, molybdenite copper, zinc, and mixtures of these. .
  • One or two or more compounds arbitrarily selected from these can be contained in any amount, but usually the content is 0.0 on the basis of the total amount of the lubricating oil composition. ⁇ 5. 0 mass 0/0. '
  • phenol-based antioxidants and amine- or amine-based antioxidants are used because they can easily maintain anti-shudder performance for a longer period of time. It is preferable to use an amine-based antioxidant and anti-oxidant 3 ⁇ 4r in combination.
  • the mass ratio when a phenolic antioxidant and a amine antioxidant are used in combination is preferably 1: 5 to L0: 1, more preferably 1: 1 to 8: 1, and even more preferable. Or 2: 1 to 6: 1.
  • any compound usually used as an extreme pressure additive for lubricating oils can be used.
  • sulfur compounds One or two or more compounds arbitrarily selected from these can be contained in any amount, but usually the content is from 0.001 to 5 based on the total amount of the lubricating oil composition. 0% by mass. +
  • the viscosity index improver is a so-called non-dispersion type viscosity index improver such as a copolymer of one or more monomers selected from various methacrylates or a hydrogenated product thereof. Or a so-called dispersion type viscosity index improver obtained by copolymerizing various methacrylic acid esters containing a nitrogen compound.
  • specific examples of other viscosity index improvers include non-dispersed or dispersed ethylene mono- ⁇ -olefin copolymers (examples of ⁇ -olefin include propylene, 1-butene and 1-pentene) or the like.
  • the number average molecular weight of the viscosity index improver is, for example, 5 00 0 to 1 5 0 0 0 0, preferably 5 0 0 0 3 5 in the case of dispersed and non-dispersed polymethacrylates.
  • 0 0 0 is polyisobutylene or a hydride thereof
  • a polymer or a hydride thereof a polymer having a molecular weight of 80,000 to 1,500, preferably 300,000 to 1,200 is preferable.
  • one kind or two or more kinds of compounds arbitrarily selected from these viscosity index improvers can be contained in any amount, but usually the content is 0.1 to 20.0% by mass based on the lubricating oil composition.
  • anti-tacking agents examples include alkelle succinic acid and alkenyl succinic acid ester. , Polyhydric alcohol ester, petroleum sulphonate, dinonylnaphthalene sulfonate and the like.
  • corrosion inhibitor examples include benzotriazole-based, tolyltriazole-based, and -imidazolazole-based compounds.
  • pour point depressant examples include polymetatalate 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 from 0.05 to 0.2% by mass, and the content of the antifoaming agent is 0.0% based on the total amount of the composition.
  • the content of 0-5 to 0.01% by mass and the other additives is about 0 to 0.05 to 10% by mass, respectively.
  • the kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is usually 2 to 25 mm 2 / s, preferably 3 to 8 mm 2 Z s, more preferably 4 to 7 mm 2 / s, more preferably Is ⁇ It is.
  • the lubricating oil composition of the present invention has an excellent metal pulley and metal belt wear resistance and initial anti-shudder performance, and can maintain the anti-shudder performance for a long period of time.
  • a metal belt particularly a lubricating oil composition suitable for a continuously variable transmission having a wet starting clutch.
  • a lubricating oil that requires an anti-wear property or an improved wet clutch property specifically, an automobile
  • It can also be suitably used as a lubricating oil for automatic transmissions such as construction machinery and agricultural machinery, manual transmissions, and differential gears.
  • suitable for industrial gear oils, automobiles such as motorcycles and automobiles, gasoline engines for power generation and marine use, lubricants for diesel engines and gas engines, turbine oils, compressor oils, etc. be able to.
  • monoalkyl salicylate detergents have excellent initial anti-shatter performance, they do not only inhibit the anti-wear effect of phosphorus additives, but also include slip-controlled wet-type cleaners.
  • the anti-shudder performance of the latch could not be maintained for a long time, the combination of the (B) component and the (C) component with the (A) component of the present invention allowed the metal pulley and metal belt to It is possible to suppress wear in the continuously variable transmission that is in contact, and to prevent the shudder specific to the slip control type wet clutch for a long period of time.
  • Each lubricating oil composition shown in Examples 1 to 6 in Table 1 and each lubricating oil composition shown in Comparative Examples 1 to 3 for comparison were prepared and shown below.
  • the ratio of base oil is based on the total amount of base oil, and the amount of each additive is based on the total amount of composition.
  • LVFA low-duty truck
  • contact pressure 1.5MPa
  • other conditions are evaluated in accordance with JASO.M 34 9-98, dd V from 2 rp m. To 200 rpm Was measured.
  • d No d V indicates a positive value, and the larger the value, the better the initial anti-shudder performance. If d ⁇ / d V is negative, the anti-shudder performance is greatly deteriorated.
  • each lubricating oil composition was deteriorated at 150 ° C for 72 hours according to JIS-K 2 5 14 Then, organic iron containing iron ions was prepared by dissolving 300 mass ppm as iron.
  • di iZd V was measured by the same method as in (1). As d / iZdV shows a positive value and the value is larger, the iron content due to the metal pulley and metal belt dissolves into the lubricating oil after long-term use. Even so, the anti-shudder performance in the wet clutch can be maintained for a long time.
  • Hydrocracking base oil 100 ° C kinematic viscosity 2.6mm 2 / s, viscosity index 105, NOACK evaporation 52 mass%, S content 0.1 mass% or less

Abstract

Disclosed is a lubricant oil composition which has an excellent preventive property on the abrasion of a metal pulley or a metal belt and an excellent initial shudder preventing property, can exert a shudder preventing property for a prolonged period of time, and is suitable for use in a continuously variable transmission with a sliding-controlled wet clutch and a metal belt. A lubricant oil composition comprising (A) alkylsalicylic acid metal salts composed of 85-100 mol% of a monoalkylsalicylic acid metal salt, 0-15 mol% of a dialkylsalicylic acid metal salt and 40-100 mol% of a 3-alkylsalicylic acid metal salt, each based on the total amount of the composition, and/or a (per)basic salt thereof; (B) a specific nitrogen compound, and (C) a phosphorus-containing anti-abrasion agent in a lubricant base oil.

Description

.潤 滑 油 組 成 物  Lubricating oil composition
[技術分野] [Technical field]
本発明は、 滑り制御式湿式クラツチを有する変速機用に好適な潤滑油組成物に 関し、 詳しくは、 特定のサリシレート系清浄剤を使用した場合に、 優れた金属プ 一リー及ぴ金属ベルトの摩耗防止性と初期シャダ一防止性能を有すると共にシャ ダー防止性能を長期間維持しうる明、 滑り制御式湿式クラッチと金属ベルト、 特に 湿式の発進クラッチを有する無段変速機に好適な変速機用潤滑油組成物に関する 田  The present invention relates to a lubricating oil composition suitable for a transmission having a slip-controlled wet clutch, and more specifically, when a specific salicylate-based detergent is used, an excellent metal preform and metal belt. A clear, slip-controlled wet clutch and metal belt that have anti-wear and initial anti-shoulder performances and can maintain the anti-shudder performance for a long period of time. Especially suitable for continuously variable transmissions with wet start clutches. Field concerning lubricating oil composition
[背景技術] 書 [Background]
最近の自動変速機は軽量小型化が望まれており、 組み合わされるエンジンの高 出力化に伴い、 動力伝達能力の向上が追求されている。 そのため、， これらに使用 される潤滑油には、 高い潤滑性能、 すなわち、 ベアリング、 歯車等の表面におけ る摩耗等を防止する性能が要求される。 また、 金属ベルト式無段変速機において もエンジンの高出力化に伴い、 金属プーリ一と金属ベルト間で伝達される トルク は増大しており、 そのため、 これらに'使用される潤滑油.には高い伝達トルク容量 が要求されると共に、 金属ブーリーと金属ベルト間の金属表面における摩耗等を 防止する性能が特に要求される。  Recent automatic transmissions are desired to be lighter and smaller, and as the combined engine increases in output, the power transmission capacity is being improved. For this reason, the lubricating oil used in these materials is required to have high lubrication performance, that is, performance that prevents wear on the surfaces of bearings, gears, and the like. Also, in the metal belt type continuously variable transmission, the torque transmitted between the metal pulley and the metal belt is increasing with the increase in engine output. A high transmission torque capacity is required, and the ability to prevent wear on the metal surface between the metal bouley and the metal belt is particularly required.
一方、' これら自動変速機や無段変速機には、 .トルク 'コンパ タに内蔵されてい るロックアップクラッチを低速で滑らせる制御 （スリ ップロックアップ制御） を 有するものがあるが、 これによつて、 エンジンのトルク変動を吸収して乗り心地 を向上させながら、 エンジントルクを効率よく変速機構へ伝達する とができる ように改良が進められている。 また、 一部の無段変速機には、 湿式の発進クラッ チを備えたものがあり、 該発進クラツチを初めは滑らせてから結合することで停 止状態からの発進をスム ズに行う、 所謂滑り制御が行われている。. これらの口 ックアップクラツチや発進クラツチ等の滑り制御が行,われる変速機に用いられる 潤滑油には、 優れた初期シャダ一防止性能と、 これを長期間維持する性能が要求 されている。 こう した中、 ロックアップクラッチの摩擦特性を良好に維持し、 初期シャダ一 防止性能と、 これを長期間維持させるために、 摩擦調整剤、 金属系清浄剤、 無灰 分散剤、 摩耗防止剤などを最適化した変速機油組成物が開示されている （特許文. 献：！〜 6参照）。 On the other hand, some of these automatic transmissions and continuously variable transmissions have a control (slip lockup control) that causes the lockup clutch built in the torquer to slide at a low speed. Improvements are being made so that engine torque can be efficiently transmitted to the transmission mechanism while absorbing the torque fluctuations of the engine and improving ride comfort. In addition, some continuously variable transmissions are equipped with a wet start clutch, and the start clutch is smoothly slid and then combined to smoothly start from a stopped state. So-called slip control is performed. Lubricating oils used in transmissions that perform slip control of these clutches, starting clutches, etc., are required to have excellent initial shudder prevention performance and performance to maintain this for a long period of time. Under these circumstances, in order to maintain the friction characteristics of the lock-up clutch well and to prevent initial shuddering and maintain this for a long period of time, friction modifiers, metal detergents, ashless dispersants, antiwear agents, etc. An optimized transmission oil composition has been disclosed (see Patent Documents:! ~ 6).
例えば、 特許文献 1には、 特定のカルシウムサリシレートと S P系極圧剤、 特 定のコハク酸イミ ド及ぴホウ素含有無灰分散剤を特定量含有する、 シャダ一防止 寿命に優れ、 かつ疲労寿命が長いという優れた性能を有する変速機用潤滑油組成 物が、 特許文献 2には、 特定の構造を有する有機酸金属塩、 摩耗防止剤、 及ぴホ ゥ素含有コハク酸イミ ドを必須成分として配合じた、 高い金属間摩擦係数とス リ ップ制御機構に対するシャダ一防止性を両立する無段変速機用潤滑油組成物が、 特許文献 3には、 カルシウムサリ シレート、 りん系摩耗防止剤、 摩擦調整剤、 及 ぴ分散型粘度指数向上剤を配合した、 高い金属間摩擦係数とス リ ップ制御機構に 対するシャダ一防止性を両立し、 長期にわたって使用可能な無段変速機用潤滑油 組成物が、 特許文献 4には、 ジチォカーバメート化合物、 及び炭素数 8〜3 0を 有する分岐鎖状脂肪酸とァミンの縮合物、更にはァミン系酸化防止剤を配合した、 シャダ一防止性能に優れ、 かつシャダ一防止寿命の長い潤滑油組成物が、 特許文 献 5には、 カルシウムスルホネート及び亜リン酸エステル類、 更に、 サルコシン 誘導体あるいはカルボン酸とアミ の反応生成物を配合.した、 スリップロックァ ップ装置 対してシャダ一防止寿命の性能を有し、 ベルト式 C V T装置に対して スクラッチソィ.ズ防止長寿命の性能を有する自動変速機油組成物が、 特許文献 6 には、 特定のアルカリ土類金属スルホネ トを特定量含有する、 スリ ップ制御機 '構付自動変速機用として酸化安定性に優れると共に、 シャダ一振動防止性能およ ぴ長期間の使用によってもその性能が持続される長期耐久性を有する自動変速機 油組成物が開示されている。  For example, Patent Document 1 includes a specific amount of calcium salicylate and SP-based extreme pressure agent, a specific amount of succinic acid imide and boron-containing ashless dispersant, which has excellent anti-shudder life and fatigue life. A long-lasting transmission lubricant composition is disclosed in Patent Document 2 as an essential component of an organic acid metal salt having a specific structure, an antiwear agent, and a succinic acid imide containing fluorine. A lubricating oil composition for a continuously variable transmission that combines a high coefficient of friction between metals and an anti-shudder property with respect to a slip control mechanism is disclosed in Patent Document 3, which includes calcium salicylate and phosphorus-based antiwear agent. Incorporates a friction modifier and a dispersion-type viscosity index improver, which achieves both high metal-to-metal friction coefficient and anti-shudder properties for the slip control mechanism, and can be used for a long time. Oil In Patent Document 4, a dithiocarbamate compound, a condensate of a branched fatty acid having 8 to 30 carbon atoms and an amine, and an amine-based antioxidant are blended to provide excellent anti-shudder performance. , And a long-life prevention oil composition, Patent Document 5 contains calcium sulfonate and phosphite, as well as a sarcosine derivative or a reaction product of carboxylic acid and amino acid. An automatic transmission oil composition that has anti-shudder performance against a capping device and has long life performance against a belt type CVT device is disclosed in Patent Document 6 as a specific alkali. A slip controller that contains a specific amount of earth metal sulfonate. It is excellent in oxidation stability as a built-in automatic transmission. Automatic transmission fluid composition is disclosed having a long-term durability performance is sustained by.
しかしながら、 本発明者らの検討によると、 金属系清浄剤としてスルホネート 系清浄剤を使用した場合には初期シャダ一防止性が未だ不十分であり、 また、 サ リシレート系清浄剤、 中でも、 モノアルキルタイプのサリシレート系清浄剤を用 いた場合には、 初期シャダ一防止性能には優れるもの,の、 余属プーリーと金属べ ルトが厳しい条件で接触する無段変速機において摩耗や鉄イオン等の金属イオン の溶出が多く発生しやすく、 また、 上記特許文献に挙げられた摩擦調整剤を配合 してもシャダ一防止性能を十分に維持することが困難であることが判明した。 なお、 特許文献 7に 、 モノアルキルタイプのサリシレー ト系清浄剤はリン系 添加剤の摩耗防止効果を阻害するため、 特定のアミ ド化合物を併用することで内 燃機関の動弁系摩耗防止性能を向上できることが開示されているが、 滑り制御式 湿式クラツチを有する変速機、 特に金属ブーリーと金属ベルトが厳しい条件で接 触する無段変速機において摩耗を抑制し、 滑り制御式湿式クラツチに特有のシャ ダーを長期間に渡り防止するための解決方法については開示も示唆もされていな レ、 However, according to the study by the present inventors, when a sulfonate detergent is used as a metal detergent, the initial anti-shattering property is still insufficient, and a salicylate detergent, especially a monoalkyl When using a type of salicylate-based detergent, the initial shudder prevention performance is excellent, but metal such as wear and iron ions is used in continuously variable transmissions where the extra pulley and metal belt are in contact under severe conditions. Elution of ions is likely to occur, and the friction modifier listed in the above patent document is included. Even so, it has been found that it is difficult to maintain sufficient anti-shudder performance. In Patent Document 7, the monoalkyl-type salicylate detergent inhibits the anti-wear effect of phosphorus-based additives. Although it is disclosed that the transmission has a slip control type wet clutch, especially in a continuously variable transmission in which a metal boule and a metal belt are in contact with each other under severe conditions, it is unique to the slip control type wet clutch. There is no disclosure or suggestion of a solution to prevent long-term shudder over time
( 1 ) 特許文献 1 ：特開 2 0 0 3 ― 1 1 3 3 9 1号公報  (1) Patent Document 1: Japanese Laid-Open Patent Publication No. 2 2003-1 1 3 3 91
( 2) 特許文献 2 ：特開 2 0 0 1 ― 3 2 3 2 9 2号公報  (2) Patent Document 2: Japanese Patent Laid-Open No. 2 0 0 1-3 2 3 2 92
( 3) 特許文献 3 ：特開 2 0 0 0 ― 3 5 5 6 9 5号公報  (3) Patent Document 3: Japanese Patent Laid-Open No. 2 00 0-3-5 5 6 95
(4) 特許文献 4 ：特開平 1 1― 5 0 0 7 7号公報  (4) Patent Document 4: Japanese Patent Application Laid-Open No. 11-500 0 7
(5 ) 特許文献 5 ：特開平 1 0— 3 0 6 2 9 2号公報  (5) Patent Document 5: Japanese Patent Application Laid-Open No. 10-3020 692
(6 ) 特許文献 6 ：特開平 1 0— 2 5 4 8 7号公報  (6) Patent Document 6: Japanese Patent Laid-Open No. 10-2 5 4 8 7
( 7) 特許文献 7 ：特開 2 0 0 4一 6 7 8 1 2号公報  (7) Patent Document 7: Japanese Laid-Open Patent Publication No. 20 0 4 1 6 7 8 12
[発明の開示] ' ' [Disclosure of the Invention] ''
本発明の課題は、 以上のような事情に鑑み、. モノアルキルタイプのサリシレー ト系清浄剤を用いた場合でも、 優れた金属ブーリ一及び金属ベルトの摩耗防止性 と初斯シャ 'ダ一.防止性能を有すると共にシャダ一防止性能を長期間維持しうる、 滑り制御式湿式クラッチと金属プーリー及ぴ金.属ベルトを備えた無段変速機、 に滑り制御式発進クラッチを備えた無段変速機に好適な潤滑油組成物を提供する ことである。 '  In view of the circumstances as described above, the object of the present invention is to provide an excellent metal boot and metal belt wear resistance and the first shader even when a monoalkyl type salicylate detergent is used. Non-slip control wet clutch, metal pulley, and gold-metal continuously variable transmission that have anti-slip performance and can maintain anti-shudder performance for a long period of time, continuously variable transmission with slip-control start clutch A lubricating oil composition suitable for a machine is provided. '
本発明者らは、 上記課題を解決するために鋭意検討した結果、 特定のサリシレ 一ト系清浄剤、 特定の窒素化合物及ぴリン系摩耗防止剤を併用することで上記課 題を改善できることを見出し、 本発明を完成するに至った。  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be improved by using a specific salicylate detergent, a specific nitrogen compound and a phosphorus wear inhibitor in combination. The headline, the present invention has been completed.
すなわち本発明は、潤滑油基油に、 （A) モノアルキルサリチル酸金属塩の構成 比が 8 5〜 1 0 0 m o 1 %、 ジアルキルサリチル酸^属塩の構成比が 0〜 1 5 m o 1 %であって、 3—アルキルサリチル酸金属塩の構成比が 4 0〜1 0 0 m o 1 %であるアルキルサリチル酸金属塩、 及び 又はその （過） 塩基性塩と、 （B) 一般式 （ 1 ) で示される窒素化合物及び （C ) リン系摩耗防止剤を含むことを特 徴とする、 滑り制御式湿式クラツチを有する変速機用に好適な潤滑油組成物にあ る。 That is, according to the present invention, the lubricating base oil contains (A) a monoalkyl salicylic acid metal salt having a composition ratio of 85 to 100 mo 1% and a dialkyl salicylic acid ^ salt having a composition ratio of 0 to 15 mo 1%. An alkyl salicylic acid metal salt having a composition ratio of 3-alkylsalicylic acid metal salt of 40 to 100 mo 1%, and / or a (per) basic salt thereof, (B) A lubricating oil composition suitable for a transmission having a slip-controlled wet clutch, characterized by comprising a nitrogen compound represented by the general formula (1) and (C) a phosphorus-based antiwear agent.
N—— N N—— N
1 II II 9 ,ハ 1 II II 9, Ha
R1— (S)a-CN ,C— (S)b-R2 (1 ) R 1 — (S) a -C N , C— (S) b -R 2 (1)
s  s
(一般式 （ 1 ) において、 R 1は、 炭素数 1 〜 3 0の直鎖状又は分枝状のアルキ ル基、 R 2は、 水素原子又は炭素数 1 〜 2 4の直 ¾状又は分枝状のアルキル基を それぞれ示し、 a及び bはそれぞれ個別に 1 、 2又は 3を示す。） また、 前記潤滑油組成物は、 摩擦調整剤、 特にアミン系摩擦調整剤及び 又は 脂肪酸系摩擦調整剤を含むことが好ましい。 (In the general formula (1), R 1 is a linear or branched alkyl group having 1 to 30 carbon atoms, R 2 is a hydrogen atom or a linear or branched group having 1 to 24 carbon atoms. Each represents a branched alkyl group, and a and b each independently represent 1, 2 or 3.) Also, the lubricating oil composition comprises a friction modifier, particularly an amine friction modifier and / or a fatty acid friction modifier. It is preferable that an agent is included.
また、 前記潤滑油組成物は、 カルシウムスルホネート及び 又はマグネシウム スルホネートを含有することが好ましい。  The lubricating oil composition preferably contains calcium sulfonate and / or magnesium sulfonate.
• また、 前記潤滑油組成物は、 非ホウ素系無灰分散剤及ぴ 又はホウ素系無灰分 散剤を含有することが好ましい。 '  • The lubricating oil composition preferably contains a non-boron ashless dispersant and / or a boron ashless dispersant. '
また、 前記アルキルサリチル酸金属塩がセカンダリ一アルキル型アルキルサリ チル酸金属塩であることが好ましい。  Moreover, it is preferable that the alkyl salicylic acid metal salt is a secondary monoalkyl type alkyl salicylic acid metal salt.
また、 前記潤滑油組成物は金属プーリーと金属ベルトを有する無段変速機用で あることが好ましい。  The lubricating oil composition is preferably for a continuously variable transmission having a metal pulley and a metal belt.
また、 前記滑り制御式湿式クラツチが滑り制御式発進クラツチであることが好 ましい。  Further, it is preferable that the slip control type wet clutch is a slip control type start clutch.
また、 本発明は、 前記潤滑油組成物を用いることを特徴とする金属プーリーと 金属ベルトを有する無段変速機及び Z又は滑り制御式湿式クラツチの潤滑方法に 関する。 以下本発明について詳述する。  The present invention also relates to a continuously variable transmission having a metal pulley and a metal belt, and a method for lubricating a Z or slip control type wet clutch, characterized by using the lubricating oil composition. The present invention is described in detail below.
本発明の潤滑油組成物における潤滑油基油としては特に制限はなく、 通常の潤 滑油に使用される鉱油系基油、 合成系基油が使用できる。 鉱油系基油としては、 具体的には、 原油を常圧蒸留して得られる常圧残油を減 圧蒸留して得られた潤滑油留分を、 溶剤脱れき、 溶剤抽出、 水素化分解、 溶剤脱 ろう、 水素化精製等の処理を 1つ以上行って精製したもの、 あるいはワックス異 性化鉱油、 GT L WAX (ガストウリキッドワックス） を異性化する手法で製 造される基油等が例示できる。 The lubricating base oil in the lubricating oil composition of the present invention is not particularly limited, and mineral oil base oils and synthetic base oils used for ordinary lubricating oils can be used. Specifically, as mineral base oils, lubricating oil fractions obtained by depressurizing and distilling atmospheric residual oil obtained by atmospheric distillation of crude oil can be desolvated, solvent extracted, and hydrocracked. , Solvent dewaxing, refined by one or more treatments such as hydrorefining, or base oil produced by isomerizing wax-differentiated mineral oil, GT L WAX (Gast Liquid Wax), etc. Can be illustrated.
合成系基油としては、 具体的には、 ポリブテン又はその水素化物 ； 1—ォクテ ンオリ ゴマー、 1—デセンオリ ゴマ一等のポリ― aーォレブイン又はその水素化 物 ； ジト リデシルグルタレート、 ジ一 2—ェチルへキシルアジペート、 ジイソデ シルアジペート、 ジト リデシルアジペート、 及ぴジー 2—ェチルへキシルセバケ ― ト等のジエステノレ ； ネオペンチノレグリ コーノレエステノレ、 ト リメチローノレプロパ ンカプリ レート、 ト リメチ口一ルプロパンペラルゴネート、 ペンタエリスリ トー ノレ一 2—ェチノレへキサノエート、 及ぴペンタエリスリ トールペラルゴネート等の ポリオールエステル ； アルキルナフタレン、 アルキルベンゼン、 及び芳香族エス テル等の芳香族系合成油又はこれらの混合物等が例示できる。 As synthetic base oils, specifically, polybutene or a hydride; 1- Okute N'ori Goma, 1 Desen'ori sesame Chief poly - a Orebuin or its hydrogenated product; Jito Li decyl glutarate, di one 2 -Ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, and 2-diethyl oleyl sebacate-neopentinolegrinole enoestole, trimethylone lepropan caprylate, trimethy mouthful Polypropane esters such as lepropane pelargonate, pentaerythritol, 2-ethylenolehexanoate, and pentaerythritol pelargonate; aromatic synthetic oils such as alkylnaphthalene, alkylbenzene, and aromatic ester, or mixtures thereof it can.
本発明における潤滑油基油としては、 上記鉱油系基油、 上記合成系基油又ばこ れらの中から選ばれる 2種以上の任意混合物等が使用できる。 例えば、 1種以上 の鉱油系基油、 1種以上の合成系基油、 1種以上の鉱油系基油と 1種以上の合成 系基油との混合油等を挙げることができる。 ' .  As the lubricating base oil in the present invention, 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, and a mixed oil of one or more mineral base oils and one or more synthetic base oils. '.
本発明において用いる潤滑油基油の動粘度は特に制限はないが、 その 1 0 0°C での動粘度は、 好ましくは 2'〜 8 mm.2 / s、 より好ましくは 2. 5〜 6 mm2/ s、 特に好ましくは 3〜 4. 5 mm2/ sに調整してなることが望ましい。 潤滑 '油基油の 1 0 0 °Cでの動粘度が 8 mm2/ sを越える場合は、 低温粘度特性が悪 化し、 一方、 その動粘度が 2 mm2, s未満の場合は、 潤滑箇所での油膜形成が 不十分であるため潤滑性に劣り、 また潤滑油基油の蒸発損失が大きくなるため、 それぞれ好ましくない。 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 It is desirable to adjust to mm 2 / s, particularly preferably 3 to 4.5 mm 2 / s. Lubrication 'When the kinematic viscosity of the oil base oil at 100 ° C exceeds 8 mm 2 / s, the low-temperature viscosity characteristics deteriorate, while when the kinematic viscosity is less than 2 mm 2 s, lubrication Insufficient oil film formation at the location is inferior in lubricity, and the evaporation loss of the lubricating base oil is increased, which is not preferable.
また、 本発明において用いる潤滑油基油の硫黄含有量に特に制限はないが、 好 ましくは 0. 1質量％以下、 より好ましくは 0. 0 5質量％以下、 さらに纾まし くは 0. 0 1質量％以下であることが望ましい。 '  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 even more preferably 0. 0 1% by mass or less is desirable. '
潤滑油基油の蒸発損失量としては、 特に制限はないが、 NOACK蒸発量で、 好ましくは 1 0〜 5 0質量％、 より好ましくは 2 0〜4 0質量％、 特に好ましく は 2 2 ~ 3 5質量％に調整してなることが望ましい。 NO AC K蒸発量が上記範 囲に調整された潤滑油基油を使用することで低温特性と摩耗防止性を両立しうる。 なお、 ここでいう NO A C K蒸発量とは、. C E C L— 4 0— T一 8 7に準拠し て測定される蒸発量を意味する。 The amount of evaporation loss of the lubricating base oil is not particularly limited, but the NOACK evaporation amount is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, and particularly preferably Is preferably adjusted to 2 2 to 35 mass%. By using a lubricating base oil whose NO AC K evaporation amount is adjusted within the above range, both low temperature characteristics and wear resistance can be achieved. The NO ACK evaporation amount here means the evaporation amount measured according to CECL—40—T-87.
本発明における潤滑油基油の具体例としては、 1 0 0 °Cにおける動粘度が 1. 5〜 3. 5 mm2/ s、 好ましくは 2〜 3. 2 mm2/ s、 さらに好ましくは 2. 5〜 3 mm2/ sであり、 硫黄含有量が 0. 0 5質量％以下、 好ましくは 0. 0 1質量％以下、 さらに好ましくは 0. 0 0 5質量％以下であり、 NO AC K蒸発 量が 2 0 ~ 8 0質量％、 好ましくは 3 0〜 6 5質量％、 さらに好ましくは 3 0〜As a specific example of the lubricating base oil in the present invention, the kinematic viscosity at 100 ° C. is 1.5 to 3.5 mm 2 / s, preferably 2 to 3.2 mm 2 / s, more preferably 2 5-3 mm 2 / s, and the sulfur content is not more than 0.05% by mass, preferably not more than 0.01% by mass, more preferably not more than 0.05% by mass, NO AC K Evaporation amount is 20 to 80% by mass, preferably 30 to 65% by mass, more preferably 30 to
5 5質量％の基油と、 1 0 0 °Cにおける動粘度が 3. 5〜 6 mm2/ s、 好まし くは 3. 8〜 4. 5 mm 2/ s、 さらに好ましくは 3. 9〜 4 · 3 mm2/ s、 硫 黄含有量が 0. 0 5質量％以下、 好ましくは 0. 0 1質量％以下、 さらに好まし くは 0. 0 0 5質量％以下であり、 1^0 0 蒸発量が 5〜 2 0質量％、 好まし くは 1 0〜 1 8質量％、 さらに好ましくは 1 2〜 1 6質量％の基油とを 1 0 : 9 0 ~ 9 0 ： 1 0、 好ましくは 2 5 : 7 5〜 7 5 : 2 5、 さらに好ましくは 4 0 ：5 5% by mass base oil and kinematic viscosity at 100 ° C of 3.5 to 6 mm 2 / s, preferably 3.8 to 4.5 mm 2 / s, more preferably 3.9 ~ 4 · 3 mm 2 / s, sulfur content is not more than 0.05 mass%, preferably not more than 0.01 mass%, more preferably not more than 0.00 mass%, 1 ^ 0 0 Evaporation amount of 5 to 20% by mass, preferably 10 to 18% by mass, more preferably 12 to 16% by mass of base oil. , Preferably 2 5: 7 5 to 7 5: 2 5, more preferably 4 0:
6 0〜·6 0 ： 4 0の質量比で混合し、 混合基油の 1 0 0°Cにおける動粘度、 硫 含有量及び NO AC K蒸発量をそれぞれ上記範囲とすることが好ましい。 これに より変速機油組成物として好適な低温特性と潤滑性能を両立しうる組成物を得る ことできる。 It is preferable to mix at a mass ratio of 60 to 60:40, and to make the kinematic viscosity, sulfur content, and NO AC K evaporation amount of the mixed base oil at 100 ° C. within the above ranges. As a result, it is possible to obtain a composition that can satisfy both low temperature characteristics and lubricating performance suitable as a transmission oil composition.
, なお、上記混合基油には、 さらに 1 0 0°Cにおける動粘度が 6 mm2/ s以上、 好ましくは 1 0〜 3 5 mm2/ s、 硫黄含有量が 0. .0 5〜 1質量％、 好ましく は 0. ；!〜 0. 7質量％、 さらに好ましくは 0. 2〜 0. 6質量％、 NOACK 蒸発量が 1 0質量％以下、 好ましくは 5質量％以下、 さらに好ましくは 3質量％ 以下の基油を少量、 例えば 5〜 3 0質量％混合しても良い。 本発明の潤滑油組成物において特定される （A) 成分は、 モノアルキルサリチ ル酸金属塩の構成比が 8 5〜 1 0 0m o 1 %、 ジアルキルサリチル酸金属塩の構 成比が 0 ~ 1 5 m o 1 %であって、 3—アルキルサリチル酸金属塩の構成比が 4 0〜 1 0 0 m o 1 %であるアルキルサリチル酸金属塩、 及ぴ Z又はその （過） 塩 基性塩である。 ここでいうモノアルキルサリチル酸金属塩は、 3一アルキルサリチル酸金馬塩、 4一アルキルサリチル酸金属塩、 5—アルキルサリチル酸金属塩等のアルキル基 を 1つ有するアルキルサリチル酸金属塩を意味し、 モノアルキルサリチル酸金属 塩の構成比は、 アルキルサリチル酸金属塩 1 0 0 m o 1 。/。に対し、 8 5〜 1 0 0 m o 1 %、好ましくは 8 8〜 9 8 In o l %、さらに好ましくは 9 0〜 9 5 m o 1 % であり、 モノアルキルサリチル酸金属塩以外のアルキルサリチル酸金属塩、 例え ばジアルキルサリチル酸金属塩の構成比は、 0〜 1 5 m o 1 %、 好ましくは 2〜 1 2 m o 1 %、 さらに好ましく は 5〜 1 O HI O 1 %である。 In addition, 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 0.0 5 to 1 Mass%, preferably 0.;! To 0.7 mass%, more preferably 0.2 to 0.6 mass%, NOACK evaporation amount is 10 mass% or less, preferably 5 mass% or less, more preferably 3 A small amount, for example, 5 to 30% by mass of a base oil having a mass% or less may be mixed. The component (A) specified in the lubricating oil composition of the present invention has a composition ratio of monoalkyl salicylic acid metal salt of 85 to 100 mol% and a composition ratio of dialkyl salicylic acid metal salt of 0 to An alkyl salicylic acid metal salt having a composition ratio of 15 to 1 mo and a 3-alkyl salicylic acid metal salt of 40 to 100 mo 1%, and Z or a (per) salt basic salt thereof. The monoalkyl salicylic acid metal salt here means an alkyl salicylic acid metal salt having one alkyl group, such as 3 monoalkyl salicylic acid gold horse salt, 4 monoalkyl salicylic acid metal salt, 5-alkyl salicylic acid metal salt, and the like. The composition ratio of the salt is alkyl salicylic acid metal salt 10 0 mo 1. /. In contrast, 8 5 to 10 0 mo 1%, preferably 8 8 to 9 8 In ol%, more preferably 90 to 9 5 mo 1%, an alkyl salicylic acid metal salt other than a monoalkyl salicylic acid metal salt, For example, the constituent ratio of the dialkyl salicylic acid metal salt is 0 to 15 mo 1%, preferably 2 to 12 mo 1%, more preferably 5 to 1 O HI O 1%.
また、 3—アルキルサリチル酸金属塩の構成比は、 アルキルサリチル酸金属塩 1 0 0 m o 1 %に対し、 4 0〜 1 0 0 m o l %、好ましくは 4 5〜 8 0 m o 1 %、 さらに好ましくは 5 0〜 6 0 m o l %である。 なお、 4—アルキルサリチル酸金 属塩及び 5—アルキルサリチル酸金属塩の合計の構成比は、 アルキルサリチル酸 金属塩 1 0 0 m o 1 %に対し、 上記 3 —アルキルサリチル酸金属塩、 ジアルキル サリチル酸金属塩を除いた構成比に相当し、 0〜 6 0 m o 1 %、 好ましくは 2 0 〜 5 0 m o 1 %、 さらに好ましく は 3 0〜4 5 m o 1 %である。 ジアルキルサリ チル酸金属塩を少量含むことで摩耗防止性と低温特性を両立した組成物を得るこ とができ、 3 —アルキルサリ シレー トの構成比を' 4 0 m o 1 %以上とすることで、 5 一アルキルサリチル酸金属塩の構成比を相対的に低くすることができ、 油溶性 を向上させることができる。  The composition ratio of the 3-alkyl salicylic acid metal salt is 40 to 100 mol%, preferably 45 to 80 mol 1%, more preferably 5 to 100 mol 1 metal alkyl salt. 0 to 60 mol%. The total composition ratio of 4-alkyl salicylic acid metal salt and 5-alkyl salicylic acid metal salt is the same as that for alkyl salicylic acid metal salt 10%, except for 3 -alkyl salicylic acid metal salt and dialkyl salicylic acid metal salt. 0 to 60 mo 1%, preferably 20 to 50 mo 1%, more preferably 30 to 45 mo 1%. By containing a small amount of a metal salt of dialkyl salicylate, it is possible to obtain a composition that has both anti-wear properties and low-temperature properties. By making the composition ratio of 3 —alkyl salicylate more than 40 mo 1%, 5 The composition ratio of the monoalkyl salicylic acid metal salt can be made relatively low, and the oil solubility can be improved.
また、 （A)成分を構成するアルキルサリチル酸金属塩におけるアルキル基と し ては、 炭素数 1 0〜 4 0、 好ましくは炭素数 1 0〜 1 '9又は炭素数 2 0〜 3 0、 さらに好ましくは炭素数 1 4〜 1 8又は炭素数 2 0〜 2 6のアルキル基、 特に好 ましくは炭素数 1 4 ~ 1' 8のアルキル基である。 炭素数 1 0〜4 0'のアルキル基 と しては、 デシル基、 ゥンデシル基、 ドデシル基、 ト リデシル基、 テ トラデシル 基、 ペンタデシル基、 へキサデシル基、 ヘプタデシル基、 ォクタデシル基、 ノナ デシル基、 ィコシル基、 ヘンィコシル基、 ドコシル基、 ト リ コシル基、 テ トラコ シル基、 ペンタコシル基、 ヘキサコシル基、 ヘプタコシル基、 ォクタコシル基、 ノナコシル基、 及ぴトリアコンチル基等の炭素数 1 0〜 4 Qの'アルキル基が挙げ られる。 これらアルキル基は直鎖状であっても分枝状であっても良く、 プライマ リーアルキル基、 セカンダリーアルキル基であっても良いが、 本発明においては ( A ) 成分の規定を満たすサリチル酸金属塩を得やすい点で、 セカンダリーアル キル基であることが特に好ましい。 In addition, the alkyl group in the alkyl salicylic acid metal salt constituting the component (A) has 10 to 40 carbon atoms, preferably 10 to 1'9 carbon atoms or 20 to 30 carbon atoms, more preferably Is an alkyl group having 14 to 18 carbon atoms or 20 to 26 carbon atoms, particularly preferably an alkyl group having 14 to 1'8 carbon atoms. Examples of the alkyl group having 10 to 40 carbon atoms include decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, C-alkyl of 10 to 4 Q such as icosyl group, hecosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, and triacontyl group Group. These alkyl groups may be linear or branched, and may be a primary alkyl group or a secondary alkyl group. A secondary alkyl group is particularly preferred from the viewpoint of easily obtaining a metal salt of salicylic acid that satisfies the definition of the component (A).
また、 アルキルサリチル酸金属塩における金属としては、 ナトリウム、 力リ ウ ム等のアルカリ金属、 カルシウム、 マグネシウム等のアルカリ土類金属等が挙げ られ、 カルシウム、 マグネシウムであることが好ましく、 カルシウムであること が特に好ましい。  Further, examples of the metal in the alkyl salicylic acid metal salt include alkali metals such as sodium and rhodium, alkaline earth metals such as calcium and magnesium, and are preferably calcium and magnesium, and are preferably calcium. Particularly preferred.
本発明の （A ) 成分は、 公知の方法等で製造することができ、 特に制限はない が、 例えば、 フエノール 1 m o 1 に対し 1 m o 1文はそれ以上の、 エチレン、 プ ロピレン、 ブテン等の重合体又は共重合体等の炭素数 1 0〜4 0のォレフイン、 好ましくはエチレン重合体等の直鎖 α—ォレフインを用いてアルキレーシヨンし、 炭酸ガス等でカルボキシレーションする方法、 あるいはサリチル酸 1 m ο 1に対 し l m o 1又はそれ以上の当該ォレフィン、 好ましくは当該直鎖 α—ォレフィ ン を用いてアルキレーションする方法等により得たモノアルキルサリチル酸を主成 分とするアルキルサリチル酸に、 アル力リ金属又はアル力リ土類金属の酸化物や 水酸化物等の金属塩基と反応させたり、 又はナトリ ゥム塩や力リ ゥム塩等のアル 力リ金属塩としたり、 さらにアル力リ金属塩をアル力リ土類金属塩と置換させる こと等により得られる。 ここで、 フエノール又はサリチル酸とォレフィ ンの反応 割合を、好ましくは、 例えば 1 ： 1〜 1 . 1 5 (モル比）、.より好ましくは 1 ： 1 . 0 5 ~ 1 ： 1 (モル比） に制御することでモノアルキルサリチル酸金属塩とジァ ルキルサリチル.酸金属塩の構成比を所望の割合に制御することができ、 また、 ォ レフインとして直鎖 α —ォレフインを用いることで、 ' 3—アルキルサリチル酸金 属塩、 5—アルキルサリチル酸金属塩等の構成比を本願特定の （Α ) 成分のよう な所望の割合に制御しやすくなるとともに、 本発明において好ましいセカンダリ 一アルキルを有するアルキルサリチル酸金属塩を主成分として得ることができる ため特に好ましい。 なお、 ォレフィンとして分岐ォレフィンを用いた場合には、 ほぼ 5—アルキルサリチル酸金属塩のみを得やすいが、 本願 （Α ) 成分の構成と なるように 3—アルキルサリチル酸金属塩等を混合して油溶性を改善する必要が あり、 製造プロセスが多様化するため好ましくない方法である'。  The component (A) of the present invention can be produced by a known method and the like, and is not particularly limited. For example, 1 mol 1 sentence is more than 1 mol 1 phenol, ethylene, propylene, butene, etc. A method of alkylating with a straight chain α-olefin such as an ethylene polymer and carboxylating with carbon dioxide gas, etc., or salicylic acid Alkylic salicylic acid mainly composed of monoalkyl salicylic acid obtained by a method of alkylation using 1 or more lmo 1 or more olefins, preferably linear α-olefins, to Reaction with a metal base such as an oxide or hydroxide of a strong metal or alkaline earth metal, or an alkaline metal salt such as a sodium salt or a strong lithium salt It is further obtained by such be substituted Al force Li metal salts and Al force Li earth metal salts. Here, the reaction ratio of phenol or salicylic acid to olefin is preferably, for example, 1: 1 to 1.15 (molar ratio), more preferably 1: 1.05 to 1: 1 (molar ratio). By controlling, the composition ratio of monoalkyl salicylic acid metal salt and dialkyl salicyl acid metal salt can be controlled to the desired ratio, and by using linear α-olefin as the olefin, 3-alkyl The metal salicylic acid metal salt, 5-alkylsalicylic acid metal salt and the like can be easily controlled to a desired ratio as in the component (Α) specified in the present application, and an alkylsalicylic acid metal salt having a secondary primary alkyl which is preferable in the present invention. It is particularly preferable because it can be obtained as a main component. When branched olefins are used as olefins, it is easy to obtain only 5-alkylsalicylic acid metal salts, but oil-soluble by mixing 3-alkylsalicylic acid metal salts, etc. so as to form the component (ii) of the present application. This is an undesirable method because the manufacturing process is diversified.
本発明の （Α ) 成分は、 上記のようにして得られたアルカリ金属又はアルカリ 土類金サリシレート （中性塩） に、 さらに過剰のアルカリ金属又はアルカリ土類 金属塩やアル力リ金.属又はアル力リ土類金属塩基 （アル力リ金属又はアル力リ土 類金属の水酸化物や酸化物） を水の存在下で加熱することにより得られる塩基性 塩や、 炭酸ガス又はホウ酸若しくはホウ酸塩の存在下で上記中性塩をアル力リ金 属又はアル力リ土類金属の水酸化物等の塩基と反応させることにより得られる過 塩基性塩も含まれる。 The component (ii) of the present invention comprises an alkali metal or alkaline earth gold salicylate (neutral salt) obtained as described above, and an excess of alkali metal or alkaline earth. Metal salt or Al-strength metal. Base obtained by heating metal genus or Al-strength earth metal base (hydroxide or oxide of Al-strength metal or Al-strength earth metal) in the presence of water. Over-base obtained by reacting the above-mentioned neutral salt with a base such as hydroxide of alkaline metal or alkaline metal in the presence of organic salt, carbon dioxide gas, boric acid or borate Sexual salts are also included.
なお、 これらの反応は、 通常、 溶媒 （へキサン等の脂肪族炭化水素溶剤、 キシ レン等の芳香族炭化水素溶剤、 軽質潤滑油基油等） 中で行われ、 その金属含有量 が 1. 0〜 2 0質量％、 好ましくは 2. 0〜 1 6質量％のものを用いるのが望ま しい。  These reactions are usually carried out in a solvent (an aliphatic hydrocarbon solvent such as hexane, an aromatic hydrocarbon solvent such as xylene, a light lubricating base oil, etc.), and the metal content is 1. It is desirable to use 0 to 20% by mass, preferably 2.0 to 16% by mass.
本発明において特定される （A) 成分として最も好ましいものとしては、 初期 シャダ一防止性能に優れる点から、 モノアルキルサリチル酸金属塩の構成比が 8 5〜 9 5 m o 1 %、 ジアルキルサリチル酸金属塩の構成比が 5〜 1 5 m o 1 %、 3一アルキルサリチル酸金属塩の構成比が 5 0〜 6 0 m o 1 %、 4—アルキルサ リチル酸金属塩及ぴ 5—アルキルサリチル酸金属塩の構成比が 3 5〜 4 5 m o 1 %であるアルキルサリチル酸金属塩、 及び 又はその （過） 塩基性塩である。 ここでいうアルキル基としては、 セカンダリ一アルキル基であることが特に好ま しい。 '  The most preferable component (A) specified in the present invention is that the composition ratio of the monoalkyl salicylic acid metal salt is 85 to 95 mo 1% and the dialkyl salicylic acid metal salt The composition ratio is 5 to 15 mo 1%, 3 The composition ratio of monoalkyl salicylic acid metal salt is 50 to 60 mo 1%, the composition ratio of 4-alkyl salicylic acid metal salt and 5-alkyl salicylic acid metal salt is 3 Alkyl salicylic acid metal salt that is 5 to 4 5 mo 1%, and / or (per) basic salt thereof. The alkyl group here is particularly preferably a secondary monoalkyl group. '
本発明において、 （A) 成分の塩基価は、 通常 0〜500 m g KOH/ g , 好ま しくは 2 0〜4 5 0mg KOH/ g、 特に好ましくは 1 00〜3 00mg KOH Zgであり'、 こ.れらの中から選ばれる 1種又は 2種以上併用することができる。 なお、 ここでいう塩基価とは、 J I S K 2 5.0 1 「'石油製品及ぴ潤滑油一中和 '価試験法」 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。  In the present invention, the base number of component (A) is usually 0 to 500 mg KOH / g, preferably 20 to 45 mg KOH / g, particularly preferably 100 to 300 mg KOH Zg. One or more selected from these can be used in combination. The base number here means the base number by the perchloric acid method measured in accordance with 7. of JISK 25.0 1 “Neutralization of petroleum products and lubricants”. .
本発明の潤滑油組成物において、 （Α)成分の含有量は、摩耗防止性と初期シャ ダー防止性能、 その維持性能の点から、 潤滑油組成物全量を基準とレて、 金属元 素換算で好ましくは 0. 00 5〜0. 5質量％、 好ましくは 0. 0 1〜0. 2質 量0 /0、 さらに好ましくは 0. 0 2〜0. 1質量％、特に好ましくは 0. 0 2〜0· 0 5質量％であり、 含有量が比較的少ない方が良い。 本発明の潤滑油組成物における （Β) 成分は、 一般式 （1 ) で表される窒素化合 物である。 ，ハ In the lubricating oil composition of the present invention, the content of the component (ii) is converted to metal elements based on the total amount of the lubricating oil composition in terms of wear prevention, initial shudder prevention performance, and maintenance performance. in preferably 0.00 5 to 0.5 wt%, preferably 0.0 1 to 0.2 mass 0/0, more preferably 0.0 2 to 0.1% by weight, particularly preferably 0.0 It is 2-0.05 mass%, and it is better that the content is relatively small. The component (油) in the lubricating oil composition of the present invention is a nitrogen compound represented by the general formula (1). , C
(1 ) (1)
Figure imgf000011_0001
上記一般式 （ 1 ) において、 R 1は、炭素数 1〜 3 0、 好ましくは炭素数 6〜 2 4、 さらに好ましくは炭素数 6〜 1 2の直鎖状又は分枝状のアルキル基を示す。 R 2は水 素原子又は炭素数 1〜 2 4、 好ましくは水素原子又は炭素数 1〜 1 2、 さらに好ま しくは炭素数 6〜 1 2の直鎖状又は分枝状のアルキル基を示す。 a及ぴ bは、 それ ぞれ個別に、 1、 2又は 3であり、 好ましく は 1又は 2であり、 さらに好ましくは a及ぴ bが共に 2である。
Figure imgf000011_0001
In the above general formula (1), R 1 represents a linear or branched alkyl group having 1 to 30 carbon atoms, preferably 6 to 24 carbon atoms, and more preferably 6 to 12 carbon atoms. . R 2 represents a hydrogen atom or a linear or branched alkyl group having 1 to 24 carbon atoms, preferably a hydrogen atom or 1 to 12 carbon atoms, more preferably 6 to 12 carbon atoms. a and b are each independently 1, 2 or 3, preferably 1 or 2, and more preferably a and b are both 2.
上記 R 1で示される炭素数 1〜 3 0の直鎖状又は分枝状のアルキル基と しては、 具 体的には例えば、 メチル基、 ェチル基、 n—プロピル基、 イソプロピル基、 n—プ チル基、 イソブチル基、 s e c—ブチノレ基、 t e r t—ブチル基、 ペンチル基、 へ キシル基、 ォクチル基、 ノニル基、 デシル基、 ゥンデシル基、 ドデシル基、 トリデ シル基、 テ トラデシル基、 ペンタデ ル基、 へキサデシル基、 ヘプタデシル基、'ォ クタデシル基、 ノナデシル基、 ィコシ /レ基、 ヘンィコシル基、 ドコシル基、 トリ コ シル基、 テ トラコシル基、 ペンタコ'シル基、 へキサコシル基、 ヘプタコシル基、 ォ クタ シル基、 ノナコシル基、 ト リアコンチル基 （これらは直鎖状でも分枝状でも よい） 等を挙げることができる。 また R 2で示される炭素数 1〜 2 4の直鎖状又は分 枝状のアルキル基としても、 上記 R 1で例示した炭素数 1〜 2 4のアルキル基等が挙 げられる。 . Specific examples of the linear or branched alkyl group having 1 to 30 carbon atoms represented by R 1 include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n —Ptyl group, isobutyl group, sec-butynole group, tert-butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadel Group, hexadecyl group, heptadecyl group, 'octadecyl group, nonadecyl group, icosyl / le group, hencosyl group, docosyl group, tricosyl group, tetracosyl group, pentaco'syl group, hexacosyl group, heptacosyl group, Examples include a tacacyl group, a nonacosyl group, a triacontyl group (which may be linear or branched). Further, even linear or branched alkyl group having a carbon number of 1-2 4 represented by R 2, exemplified such as an alkyl group having a carbon number of 1-2 4 above R 1 can be mentioned up. .
一般式 （ 1 ) で表される金素化合物において、 摩耗防止性能とシャダ一防止性能 の維持性能をより向上できることから、 R 1は炭素数 6〜 2 4のアルキル基であり、 R 2は水素原子又は炭素数 1〜 2 4のアルキル基であり、 かつ a及び bが 1又は 2で ある場合がより好ましく、 R 1及ぴ R 2が炭素数 6〜： L 2、 好ましくは 6〜 1 0のァ ルキル基であり、 a及び bが共に 2.である場合が特に好ましい。 In the metal compound represented by the general formula (1), R 1 is an alkyl group having 6 to 24 carbon atoms and R 2 is hydrogen because it can further improve the maintenance performance of wear prevention performance and anti-shudder performance. More preferably, it is an atom or an alkyl group having 1 to 24 carbon atoms, and a and b are 1 or 2, and R 1 and R 2 are 6 to L carbon atoms, preferably 6 to 10 carbon atoms. Particularly preferred is a case in which a and b are both 2.
—般式 （ 1 ) で表される'窒素化合物と して好ましいものと しては、 炭素数 6〜 2 4の直鎖又は分枝アルキル基を有する、 2， 5 _ビス 〈アルキルチオ） — 1 , 3 , 4ーチアジアゾール、 炭素数 6〜 2 4の直鎖又は分技アルキル基を有する、 2， 5 一ビス （アルキルジチォ） — 1 , 3 , 4—チアジアゾール、 炭素数 6〜 2 4の直鎖 又は分枝アルキル基.を有する、 2— （アルキルチオ） 一 5—メルカプト一 1 , 3， 4ーチアジアゾール、 .炭.素数 6〜 24の直鎖又は分枝アルキル基を有する、 2— （ァ ルキルジチォ） — 5— ルカプト一 1 , 3, 4—チアジアゾール及びこれらの混合 物等が挙げられる。 これらの中でも、 2, 5—ビス (アルキルジチォ) 一 1， 3, 4ーチアジアゾールが特に好ましい。 — Preferred as a nitrogen compound represented by the general formula (1) is a 2, 5_bis (alkylthio) having a straight or branched alkyl group having 6 to 24 carbon atoms — 1 , 3, 4-thiadiazole, straight chain or branched alkyl group having 6 to 24 carbon atoms, 2, 5 bis (alkyldithio) — 1, 3, 3, 4-thiadiazole, straight chain having 6 to 24 carbon atoms Or 2- (alkylthio) 1-5-mercapto 1,3,4-thiadiazole, having a branched alkyl group. 2; (alkyldithio) having a linear or branched alkyl group having 6 to 24 carbon atoms. ) — 5— Lucapto 1, 3, 4-thiadiazole and mixtures thereof. Among these, 2,5-bis (alkyldithio) 1,1,4-thiadiazole is particularly preferable.
本発明の潤滑油組成物において、 一般式 （1) で示される窒素化合物の含有量は、 組成物全量基準で 0. 0 0 5〜0. 5質量％であることが好ましく、 よ り好ましく は 0. 0 1〜0. 2質量0 /0、 さらに好ましく は 0. 02〜0. 1 5質量％であり、 特に好ましくは 0. 0 3〜0. 1 4質量％である。 当該窒素化合物の含有量を上記 範囲とすることで摩耗防止性とシャダ一防止性能の維持性能を長期間にわたり維持 しゃすくなる。 本発明の潤滑油組成物における （C) 成分は、 リ ン系摩耗防止剤である。 In the lubricating oil composition of the present invention, the content of the nitrogen compound represented by the general formula (1) is preferably 0.005 to 0.5 mass%, more preferably, based on the total amount of the composition. 0.0 1 to 0.2 mass 0/0, more preferably from 0.02 to 0.1 5% by weight, particularly preferably 0.0 3 to 0.1 4% by weight. By keeping the content of the nitrogen compound in the above range, the maintenance performance of anti-wear and anti-shudder performance can be maintained over a long period of time. The component (C) in the lubricating oil composition of the present invention is a phosphorus wear inhibitor.
リ ン系摩耗防止剤としては、 分子中にリ ンを含むものであれば特に制限はない が、 例えば、 下記一般式 （2) 又は一般式 （3) で示されるリ ン化合物又は れ らの塩が挙げられる。
Figure imgf000012_0001
The phosphorus antiwear agent is not particularly limited as long as it contains phosphorus in the molecule. For example, the phosphorus compound represented by the following general formula (2) or general formula (3) Salt.
Figure imgf000012_0001
Figure imgf000012_0002
上記一般式 （2) 及び （3) において、 X1、 X2、 X3、 X4、 X5.及ぴ X6は、 それぞれ個別に、 酸素原子又は硫黄原子を示す。 3、 R4、 R5、 R6、 R7及ぴ R8は、 それぞれ個別に、 水素原子又は炭素数 1〜 30の炭化水素基を示す。
Figure imgf000012_0002
In the above general formulas (2) and (3), X 1 , X 2 , X 3 , X 4 , X 5, and X 6 each independently represent an oxygen atom or a sulfur atom. 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
上記 R3〜R8で表される炭素数 1 ~ 3 0の炭化水素基と しては、 具体的には、. アルキル基、シク口アルキル基、アルケニル基、アル ル置換、シク口アルキル基、 ァリール基、 アルキル置換ァリール基、 及ぴァリールアルキル基を挙げることが できる。 上記アルキル基と .しては、 例えば、 メチル基、 ェチル基、 プロピル基、 ブチル 基、 ペンチル基、 へキ、 ル基、 ヘプチル基、 ォクチル基、 ノ -ル基、 デシル基、 ゥンデシル基、 ドデシル基、 ト リデシル基、 テ トラデシル基、 ペンタデシル基、 へキサデシル基、 ヘプタデシル基、 ォクタデシル基等のアルキル基 （これらアル キル基は直鎖状でも分枝状でもよい） を挙げることができる。 Specific examples of the hydrocarbon group having 1 to 30 carbon atoms represented by the above R 3 to R 8 include: an alkyl group, an alkyl group, an alkenyl group, an allyl substitution, and an alkyl group. , Aryl groups, alkyl-substituted aryl groups, and aryl alkyl groups. Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nor group, decyl group, undecyl group, dodecyl group. And alkyl groups such as a group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group (these alkyl groups may be linear or branched).
上記シクロアルキル基と しては、 例えば、 シクロペンチル基、 シクロへキシル 基、 シク口へプチル基等の炭素数 5〜 7のシク口アルキル基を挙げることができ る。 また上記アルキルシクロアルキル基と しては、 例えば、 メチルシクロペンチ ル基、 ジメチルシクロペンチノレ基、 メチノレエチ /レシクロペンチ/レ基、 ジェチノレシ クロペンチル基、 メチルシクロへキシル基、 ジメチノレシクロへキシル基、 メチル ェチノレシク口へキシ レ基、ジェチ /レシク口へキシノレ基、メチノレシク口へプチゾレ基、 ジメチルシクロへプチル基、 メチルェチルシク口へプチル基、 ジェチノレシク口へ プチル基等の炭素数 6〜 1 1のアルキルシクロアルキル基 （アルキル基のシクロ アルキル基への置換位置も任意である） を挙げ.ることができる。 '  Examples of the cycloalkyl group include a cycloalkyl group having 5 to 7 carbon atoms such as a cyclopentyl group, a cyclohexyl group, and a cyclopentyl group. Examples of the alkylcycloalkyl group include, for example, a methylcyclopentyl group, a dimethylcyclopentinole group, a methinoreethyl / recyclopentyl / re group, a ethenorecloclopentyl group, a methylcyclohexyl group, a dimethinorecyclohexyl group, and a methylethynoleic mouth. Alkyl cycloalkyl groups having 6 to 11 carbon atoms such as xyle groups, jetty / recix hexinoles groups, methino leschi heptisoles groups, dimethylcycloheptyl groups, methylethyl heptyl heptyl groups, ethynolecic butyl groups, etc. The substitution position of the group to the cycloalkyl group is also arbitrary. '
上記ァルケ-ル基と しては、 例えば、 ブテュル基、 ペンテニル基、 へキセ ル 基、 ヘプテニル基、 ォクテュル基、 ノネニル基、 デセニル基、 ゥンデセニル基、 ドデセニル基、 ト リデセニル基、.テ トラデセニル基、 ペンタデセニル基、 へキサ デセニル基、 ヘプタデセニル基、.ォクタデセニル基等のアルケニル基 （これらァ ルケ二ル¾は直鎖状でも分枝状でもよく、 また二重結合の位置も任意である） を 挙げることができる。  Examples of the above alkenyl groups include butyr, pentenyl, hexyl, heptenyl, octul, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, An alkenyl group such as a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, and a .octadecenyl group (the alkenyl group may be linear or branched, and the position of the double bond is arbitrary) Can do.
上記ァリール基と しては、 例えば、 フ ニル基、 ナフチル基等のァリール基を. '挙げることができる。 また上記アルキルァリール基と しては、例えば、 ト リル基、 キシリル基、 ェチ/レフェニル基、 プロピ /レフェ二/レ基、 プチ/レフェニゾレ基、 ペン チルフエニル基、 へキシルフェニル基、 ヘプチルフエニル基、 ォクチルフェニル 基、 ノニルフヱニル基、 デシルフ： ニル基、 ゥンデシルフヱニル基、 ドデシルフ ヱニル基等の炭素数 7〜 1 8の各アルキルァリール基 （アルキル基は直鎖状でも 分枝状でもよく、 またァリール基への置換位置も任意である） を挙げることがで さる。 ， '  Examples of the aryl group include aryl groups such as a phenyl group and a naphthyl group. Examples of the alkylaryl group include, for example, a tolyl group, a xylyl group, an ethi / lephenyl group, a propi / refenine / le group, a petit / lephenisole group, a pentylphenyl group, a hexylphenyl group, and a heptylphenyl group. , Octylphenyl group, nonylphenyl group, decylph: each alkylaryl group having 7 to 18 carbon atoms such as nyl group, undecylphenyl group, dodecylphenyl group, etc. (the alkyl group may be linear or branched) In addition, the substitution position on the aryl group is also arbitrary. , '
上記ァリールアルキル基と しては、 例えば、 ベンジル基、 フエニルェチル基、 フエニゾレプロピノレ基、 フエニノレブチゾレ基、 フエ二/レペンチノレ基、 フエ二ノレへキシ ル基等の炭素数 7〜 1 2の各ァリールアルキル基 （これらアルキル基は直鎖状で も分枝状でもよい） を挙げることができる。 Examples of the arylalkyl group include a benzyl group, a phenylethyl group, a phenisolepropinole group, a phenenolevbutizole group, a pheny / repentinole group, and a phenenohexoxy. And each arylalkyl group having 7 to 12 carbon atoms such as an alkyl group (these alkyl groups may be linear or branched).
上記 R 3 r^ R 8で表される炭素数 1〜 3 0の炭化水素基は.、炭素数 1〜 3 0のァ ルキル基又は炭素数 6〜 2 4のァリ一ル基であることが好ましく、 より好ましく は炭素数 4〜 2 0のアルキル基であり、 更に好ましくは炭素数 6〜 1 8のアルキ ノレ基である。 The hydrocarbon group having 1 to 30 carbon atoms represented by R 3 r ^ R 8 is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms. More preferred is an alkyl group having 4 to 20 carbon atoms, and still more preferred is an alkynole group having 6 to 18 carbon atoms.
一般式 （2 ) で表されるリン化合物としては、 例えば、 亜リン酸、 モノチォ亜 リン酸、 ジチォ亜リン酸、 トリチォ亜リン酸；上記炭素数 1〜3 0の炭化水素基 を 1つ有する亜リン酸モノエステル、 モノチォ亜'リン酸モノエステル、 ジチォ亜 リン酸モノエステル、 トリチォ亜リン酸モノエステル ；上記炭素数 1〜 3 0の炭 化水素基を 2つ有する亜リン酸ジエステル、 モノチォ亜リン酸ジエステル、 ジチ ォ亜リン酸ジエステル、 トリチォ亜リン酸ジエステル ；上記炭素数 1〜 3 0の炭 化水素基を 3つ有する亜リン酸トリエステル、 モノチォ亜リン酸トリエステル、 ジチォ亜リン酸トリエステル、 トリチォ亜リン酸トリエステル ；及ぴこれらの混 合物を挙げることができる。  Examples of the phosphorus compound represented by the general formula (2) include phosphorous acid, monothiophosphorous acid, dithiophosphorous acid, trithiophosphorous acid; and one hydrocarbon group having 1 to 30 carbon atoms. Phosphorous acid monoester, monothio'phosphoric acid monoester, dithiophosphorous acid monoester, trithiophosphorous acid monoester; phosphorous acid diester having two hydrocarbon groups having 1 to 30 carbon atoms, monothio Phosphite diester, dithiophosphite diester, trithiophosphite diester; phosphite triester having three hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphite triester, dithiophosphite And acid triesters, trithiophosphorous acid triesters; and mixtures thereof.
一般式 （3 ) で表されるリン化合物としては、 例えば、. リン酸、 モノチォリン 酸、 ジチォリン酸、 トリチォリン酸、 テトラチォリン酸；上記炭素数 1〜 3 0の 炭化水素基を 1つ有するリ ン酸モノ.エステル、 モノチォ.リ ン酸モノエステル、 ジ チォリ ン酸モノエステル、 ト リチォリ ン酸モノエステル、 テ トラチォリ ン酸モノ エステル； '上記.炭素数 1〜 3 0の炭化水素基を 2つ有するリン酸ジエステル、 モ ノチオリン酸ジエステル、ジチォリ ン酸ジエステル、 ト'リチオリン酸ジエステル、 'テ トラチォリン酸ジエステル ；上記炭素数 1〜 3 0の炭化水素基を 3つ有するリ ン酸ト リエステル、 モノチォリン酸ト リエステル、 ジチォリ ン酸トリエステル、 トリチオリン酸トリエステル、 テトラチォリン酸トリエステル；及びこれらの混 合物を挙げることができる。 '  Examples of the phosphorus compound represented by the general formula (3) include: phosphoric acid, monothiophosphoric acid, dithiophosphoric acid, trithiophosphoric acid, tetrathiophosphoric acid; phosphoric acid having one hydrocarbon group having 1 to 30 carbon atoms. Monoester, monothiophosphoric acid monoester, dithiophosphoric acid monoester, trithiophosphoric acid monoester, tetrathiophosphoric acid monoester; 'above. 2 hydrocarbon groups having 1 to 30 carbon atoms Phosphoric acid diester, monothiophosphoric acid diester, dithiophosphoric acid diester, g'lithiophosphoric acid diester, 'tetrathiophosphoric acid diester; phosphoric acid triester having three hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphoric acid Reesters, dithiophosphoric acid triesters, trithiophosphoric acid triesters, tetrathiophosphoric acid triesters; and these Mention may be made of mixtures. '
本発明においては、上記一般式（2 )で表されるリン化合物のうち、 （ 2 )式中、 X 1、 X 2、 X 3の 1個以上が酸素原子であることが好ましく、 2個以上が酸素原 子であることがさらに好ましく、 3個全てが酸素原子 あるこ'とが最も好ましい。 また、 上記一般式 （3 ) で表されるリ ン化合物のうち、 （3 ) 式中、 X 4、 X 5、 X 6のうち 1個以上が酸素原子であることが好ましく、 2個以上が酸素原子であ ることがさらに好ましく、 3個全てが酸素原子であることが最も好ましい。 In the present invention, among the phosphorus compounds represented by the general formula (2), in the formula (2), one or more of X 1 , X 2 and X 3 are preferably oxygen atoms, and two or more Is more preferably an oxygen atom, and most preferably all three are oxygen atoms. Among the phosphorus compounds represented by the general formula (3), in the formula (3), one or more of X 4 , X 5 and X 6 are preferably oxygen atoms, and two or more Oxygen atom More preferably, all three are oxygen atoms.
また、 一般式 （2 ) .又は （3 ) で表されるリ ン化合物の塩としては、 リ ン化合 物にアンモニ.ァゃ、 炭素数 1〜 1 8、 好ましくは 1 ~ 8の炭化水素基又はヒ ドロ キシル基含有炭化水素基のみを分子中に有するアミン化合物、 該ァミン化合物の アルキレンォキサイ ド付加物等の窒素化合物、 あるいは金属酸化物、 金属水酸化 物、 金属炭酸塩、 金属塩化物等の金属塩基を作用させて、 残存する酸性水素の一 部又は全部を中和した塩を挙げることができる。  In addition, as a salt of the phosphorus compound represented by the general formula (2) or (3), the phosphorus compound may be an ammonia, a hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms. Or an amine compound having only a hydroxyl group-containing hydrocarbon group in the molecule, a nitrogen compound such as an alkylene oxide adduct of the amine compound, or a metal oxide, metal hydroxide, metal carbonate, metal chloride And a salt obtained by neutralizing a part or all of the remaining acidic hydrogen by the action of a metal base such as
上記窒素化合物としては、 具体的には、 アンモニア ； モノメチルァミ ン、 モノ ェチノレアミン、 モノプロピ /レアミン、 モノプチノレアミン、 モノペンチノレアミン、 モノへキシルァミン、 モノへプチ/レアミン、 モノォクチ/レアミン、 モノラウリノレ ァミン、 モノステアリルァミン、 モノォレイルアミンジメチルァミン、 メチルェ チルァミン、 ジェチルァミン、 メチルプロピルァミン、 ェチルプロピルァミン、 ジプロピルァミン、 メチルブチルァミン、 ェチルブチルァミン、 プロピルプチル ァミン、 ジブチルァミン、 ジペンチノレアミ ン、 ジへキシノレアミン、 ジヘプチノレア ミン、 ジォクチルァミン等のアルキル又はアルケニルァミン （アルキル基又はァ ルケ二ル基は直鎖状でも分技状でもよい）；モノメタノ ^~ルァミン、 モノエタノー 7レアミン、 モノプロパノールアミシ、 モノプタノールァミン、 モノペンタノ一ノレ ァミン、 モノへキサノールァミン、 モノへプダノールァミン、 モノォクタノール ァミン、 モノノナノールァミン、 ジメタノールァミン、 メタノールエタノールァ ミン、 ジェ'タノ.一ルァミン、 メタノールプロパノールァミン、 エタノールプロパ ノーノレアミ ン、 ジプロパノーノレアミ ン、 メタノーノレブタノ一ノレアミ ン、 エタノー ルブタノールァミン、 プロパノールブタノ一ルァミン、 ジブタノールァミン、 ジ ペンタノールァミ ン、 ジへキサノ一 /レアミ ン、 ジヘプタノールアミ ン、 ジォクタ ノールァミン等のアル力ノールァミン （アル力ノ一ル基は直鎖状でも分枝状でも よレ、） ； これらアルキルァミン、 アルカノールァミンにエチレンォキサイ ド等のァ ルキレンォキサイ ドを付加物；及びこれらの混合物等が例示できる。  Specific examples of the nitrogen compound include: ammonia; monomethylamine, monoethinoreamine, monopropi / reamine, monoptinoreamine, monopentinoreamine, monohexylamine, monoheptyl / reamine, monooctyl / reamine, monolaurinoreamine, Monostearylamine, Monooleylamine Dimethylamine, Methylethylamine, Jetylamine, Methylpropylamine, Ethylpropylamine, Dipropylamine, Methylbutylamine, Ethylbutyramine, Propylptylamine, Dibutylamine, Dipentenoreamin , Dihexenoreamine, diheptinoreamin, dioctylamine and other alkyls or alkenylamines (the alkyl group or alkenyl group may be linear or branched); monomethano ^ ~ Luamine, Monoethanol 7 Reamine, Monopropanol Amishi, Monoptanolamine, Monopentanol Monoamine, Monohexanolamine, Monoheptanolamine, Monooctanolamine, Monononanolamine, Dimethanolamine, Methanolethanolamine, Jet 'Tano-mono-lamine, methanol-propanolamine, ethanol-propanolamine, di-propanolanolamine, methanol-butanolamine-amine, ethanolbutanolamine, propanolbutanolamine, dibutanolamine, dipentanolamine, Alkylamines such as dihexanoyl / reamin, diheptanolamine, dioctanolamine, etc. (the alkyl group can be linear or branched); , § Rukirenokisai de adducts such as ethylene O wherein de the alkanol § Min; and mixtures thereof and the like.
上記金属塩基における金属としては、 具体的には、 リチウム、 ナトリ ウム、 力 リ ウム、 セシウム等のアルカリ金属、 カルシウム、 マグネ ウム、 バリ ウム等の アルカリ土類金属、 亜鉛、 銅、 鉄、 鉛、 ニッケル、 銀、 マンガン、 モリブデン等 の重金属等が挙げられる。 これらの中ではカルシウム、 マグネシウム等のアル力 リ土類金属及び亜鉛が好ましい。 Specific examples of the metal in the above metal base include alkali metals such as lithium, sodium, force lithium and cesium, alkaline earth metals such as calcium, magnesium and barium, zinc, copper, iron, lead, Examples include heavy metals such as nickel, silver, manganese, and molybdenum. Among these, the strength of calcium, magnesium, etc. Li earth metal and zinc are preferred.
これらの （C) 成分は、 1種類あるいは 2種類以上を任意に配合することがで さる。 . .  These components (C) can be used alone or in combination of two or more. .
本発明における （C) 成分のうち、 より好ましいものとしては、 亜リン酸、 リ ン酸、 炭素数 4〜 20のアルキル基又は炭素数 6〜 1 2の （アルキル） ァリール 基を有する亜リン酸エステル若しくはリン酸エステル、 及ぴこれらに炭素数 1〜 1 8のアルキル基を有するアルキルァミンを作用させたァミン塩から選ばれる 1 種又は 2種以上の混合物が好ましく、 亜リン酸、 炭素数 4〜 20のアルキル基を 有する亜リン酸エステルから選ばれる 1種又は 2種以上の混合物がより好ましく、 炭素数 4〜8のアルキル基を有する亜リン酸ジエステルを含有することが特に好 ましい。  Among the components (C) in the present invention, more preferred are phosphorous acid, phosphoric acid, phosphorous acid having an alkyl group having 4 to 20 carbon atoms or an (alkyl) aryl group having 6 to 12 carbon atoms. Preferred is one or a mixture of two or more selected from esters or phosphate esters, and an amine salt in which an alkylamine having an alkyl group having 1 to 18 carbon atoms is allowed to act. Phosphorous acid, 4 to 4 carbon atoms One or a mixture of two or more selected from phosphites having 20 alkyl groups is more preferable, and it is particularly preferable to contain a phosphite diester having an alkyl group having 4 to 8 carbon atoms.
本発明の潤滑油組成物において （C) 成分の含有量は、 組成物全量基準で通常 In the lubricating oil composition of the present invention, the content of the component (C) is usually based on the total amount of the composition.
0. 0 1〜 5質量％であるが、 リン元素濃度として、好ましくは 0. 0 0 1〜0.Although it is 0 to 1-5 mass%, the phosphorus element concentration is preferably 0.0 0 1 to 0.
1質量0 /0、 より好ましくは 0. 0 0 5〜0. 0 8質量％、 さらに好ましくは 0.1 Mass 0/0, more preferably 0.0 0 5 to 0.0 8 wt%, more preferably 0.
0 1〜0. 0 6質量0 /0、 特に好ましくは 0. 0 2〜0. 0 5質量0 /0である。 （C) 成分の含有量を上記範囲とすることで、 摩耗防止性及び初期シャダ一防止性能に 優れると共に、 シャダ一防止性能を長期間維持じゃすい組成物を得ることができ る。 0 1 to 0.0 6 wt 0/0, and particularly preferably from 0.0 2 to 0.0 5 weight 0/0. By setting the content of the component (C) within the above range, it is possible to obtain an easy-to-wear composition that is excellent in anti-wear properties and initial anti-shoulder performance and maintains anti-shudder performance for a long period of time.
なお、 本発明の潤滑油組成物において、 組成物全量基準で （C) 成分のリン元 素濃度 の含有量 （P) に対する （A) 成分の金属元素濃度 （M) での含有量の 質量比 （（M) / (P)) には特に制限はないが、 好ましくは 0. 1〜2 50、 好 'ましくは 0. 5〜50、 さらに好ましくは 0. 8〜5、 特に好ましくは 1〜3で ある。  In the lubricating oil composition of the present invention, the mass ratio of the content of the component (A) at the metal element concentration (M) to the content (P) of the phosphorus element concentration of the component (C) on the basis of the total amount of the composition ((M) / (P)) is not particularly limited, but is preferably 0.1 to 250, preferably 0.5 to 50, more preferably 0.8 to 5, particularly preferably 1. ~ 3.
また、 本発明の潤滑油組成物において、 組成物全量基準で （C) 成分のリン元 素濃度での含有量 （P) に対する （B) 成分の含有量の質量比 （（B) / (P)) には特に制限はないが、 好ましくは 0. 1〜 2 5 0、 好ましくは 0. 5〜5 0、 さらに好ましくは 1〜 1 0、 特に好ましくは 1. 5〜5である。  In the lubricating oil composition of the present invention, the mass ratio of the content of the component (B) to the content (P) of the component (C) at the phosphorus element concentration ((B) / (P )) Is not particularly limited, but is preferably 0.1 to 2500, preferably 0.5 to 50, more preferably 1 to 10 and particularly preferably 1.5 to 5.
(C) 成分のリン元素濃度での含有量 （P) に対す,る （A)'成分及ぴ （B) 成 分のそれぞれの質量比を上記範囲とすることで、 摩耗防止性及び初期シャダ一防 止性能に優れると共に、 シャダ一防止性能を長期間維持しやすい組成物を得るこ とができる。 本発明の潤滑油組成物には、 （A ) 成分、 （B ) 成分及ぴ （C ) 成分を併用する ことで摩耗防止性及ぴ初期シャダ一防止性能に優れると共に、 シャダ一防止性能 を長期間維持できる組成物を得ることができるが、 その性能をさらに高める目的 で、 又は潤滑油組成物として必要な性能をさらに付与する目的で、 公知の潤滑油 添加剤を加えることができる。 添加できる添加剤としては、 例えば、 （A ) 成分以 外の金属系清浄剤、 無灰分散剤、 摩擦調整剤、 酸化防止剤、 極圧添加剤、 摩耗防 止剤、 粘度指数向上剤、 鳍止め剤、 腐食防止剤、 流動点降下剤、 ゴム膨潤剤、 消 泡剤、 着色剤等を挙げることができる。 これらは単独で、 あるいは数種類組合せ て用いることができる。 (C) Component content in phosphorus element concentration (P) The mass ratio of (A) 'component and (B) component to the above ranges makes it possible to prevent wear and prevent initial shading. It is possible to obtain a composition that has excellent anti-blocking performance and can easily maintain anti-shudder performance for a long time. You can. In the lubricating oil composition of the present invention, the combined use of the (A) component, the (B) component and the (C) component provides excellent anti-wear properties and initial anti-shoulder performance and long anti-shudder performance. Although a composition that can be maintained for a period of time can be obtained, a known lubricating oil additive can be added for the purpose of further enhancing its performance or for the purpose of further imparting the performance required as a lubricating oil composition. Additives that can be added include, for example, metallic detergents other than component (A), ashless dispersant, friction modifier, antioxidant, extreme pressure additive, antiwear agent, viscosity index improver, and anti-wrinkle Agents, corrosion inhibitors, pour point depressants, rubber swelling agents, antifoaming agents, and coloring agents. These can be used alone or in combination.
( A ) 成分以外の金属系清浄剤としては、 （A ) 成分に該当しないサリシレート 系清浄剤、 スルホネート系清浄剤、 フエネート系清浄剤等が挙げられる。  Examples of metallic detergents other than the component (A) include salicylate detergents, sulfonate detergents, and phenate detergents that do not fall under the component (A).
( A ) 成分に該当しないサリシレート系清浄剤としては、 例えば、 炭素数 1 0 〜 4 0のアルキル基を 2つ有するジアルキルサリチル酸金属塩の構成比が 1 5 m o 1 %以上のアルキルサリチル酸金属塩及ぴ Z又はその （過） 塩基性塩、 炭素数 1〜 9のアルキル基と炭素数 1 0〜 4 0のアルキル基を有するジアルキルサリチ ル酸金属塩及び Z又はその （過） 塩基性塩、 3—アルキルサリチル酸金属塩の構 成比が 4 0 m o 1 %未満であるアルキルサリチル酸金属塩及び/又はその （過） 塩基性塩等'が挙.げられる。 ここで金属としてはアル力リ金属又はアル力リ土類金 属等が挙げられる。 . . '  Examples of salicylate detergents not corresponding to the component (A) include alkyl salicylic acid metal salts having a composition ratio of dialkyl salicylic acid metal salt having two alkyl groups having 10 to 40 carbon atoms of 15 mo 1% or more. Z or its (over) basic salt, dialkyl salicylic acid metal salt having an alkyl group having 1 to 9 carbon atoms and an alkyl group having 10 to 40 carbon atoms and Z or its (over) basic salt, Examples include alkyl salicylic acid metal salts and / or (over) basic salts thereof in which the composition ratio of the 3-alkyl salicylic acid metal salt is less than 40 mo 1%. Here, examples of the metal include Al-strength metal and Al-strength earth metal. ..
また、 スルホネート系清浄剤としては、 例えば、 分子量 1 0 0〜 1 5 0 0、 好 ましくは 2 0 0〜 7 0 0のアルキル芳香族化合物をスルホン化することによって 得られるアルキル芳香族スルホン酸のアル力リ土類金属塩、 特にマグネシウム塩 及ぴ Z又はカルシウム塩が好ましく用いられ、 アルキル芳香族スルホン酸として は、 具体的にはいわゆる石油スルホン酸や合成スルホン酸等が挙げられる。  Examples of the sulfonate detergent include alkyl aromatic sulfonic acids obtained by sulfonating alkyl aromatic compounds having a molecular weight of 100 to 1500, preferably 20:00 to 700. Of these, alkaline earth metal salts, particularly magnesium salts and Z or calcium salts are preferably used. Specific examples of the alkyl aromatic sulfonic acids include so-called petroleum sulfonic acids and synthetic sulfonic acids.
石油スルホン酸としては、 一般に鉱油の潤滑油留分のアルキル芳香族化合物を スルホン化したものゃホワイ トオイル製造時に副生する、 いわゆるマホガニー酸 等が用いられる。 また合成スルホン酸としては、 例えば、 洗剤の原料となるアル キルベンゼン製造プラントから副生したり、 ポリォレブインをベンゼンにアルキ ル化することにより得られる、 直鎖状や分枝状のアルキル基を有するアルキルべ ンゼンを原料とし、 これをスルホン化したもの、 あるいはジノニルナフタレンを スルホン化したもの等が用いられる。 またこれらアルキル芳香族化合物をスルホ ン化する際のスルホン化剤としては特に制限はないが、 通常、 発煙硫酸や硫酸が 用いられる。 As the petroleum sulfonic acid, what is commonly referred to as mahoganic acid produced as a by-product during manufacture of white oil is used if the alkyl aromatic compound in the lubricating oil fraction of mineral oil is sulfonated. Synthetic sulfonic acids are, for example, by-produced from an alkylbenzene production plant that is a raw material for detergents, and polylevine is alkylated into benzene. For example, a sulfonated alkylbenzene having a linear or branched alkyl group obtained by sulfination, or a sulfonated dinonylnaphthalene may be used. The sulfonating agent for sulfonating these alkyl aromatic compounds is not particularly limited, but usually fuming sulfuric acid or sulfuric acid is used.
フエネート系清浄剤としては、 具体的には、 炭素数 4〜30、 好ましくは炭素 数 6〜 1 8の直鎖状又は分枝状のアルキル基を少なく とも 1個有するアルキルフ ェノールと硫黄を反応させて得られるアルキルフエノールサルフアイ ド又はこの アルキルフエノールとホルムアルデヒ ドを反応させて得られるアルキルフエノー ルのマンニッヒ反応生成物のアル力リ土類金属塩、 特にマグネシウム塩及ぴ Z又 はカルシウム塩等が好ましく用いられる。 . これら （A) 成分以外の金属系清浄剤の塩基価は、 通常 0〜 500 m g KOH /g、 好ましくは 20〜450mg KOH/gのものを使用することができる。 本発明においで （A) 成分以外の金属系清浄剤を使用する場合、 塩基価 0〜5 0 0 m g KOH/ g , 好ましく は 1 00〜4 0 Om g KOH/gのカルシウムス ルホネート系清浄剤、 マグネシウムスルホネート系清浄剤から選ばれる 1種又は 2種以上を併用することが特に好ましい。 これらスルホネート系清浄剤を併用す ることで摩耗防止効果、 シャダ一防止性及びその維持性.を髙度にパランス良く優 れた組成物を得ることができる。  Specific examples of the phenate detergent include reacting sulfur with an alkylphenol having at least one linear or branched alkyl group having 4 to 30 carbon atoms, preferably 6 to 18 carbon atoms. Alkyl phenol sulfide obtained by the reaction of the above, or Al-rich earth metal salt of the Mannich reaction product of alkyl phenol obtained by reacting this alkyl phenol with formaldehyde, especially magnesium salt and Z or calcium salt, etc. Is preferably used. The base number of the metal detergent other than the component (A) is usually 0 to 500 mg KOH / g, preferably 20 to 450 mg KOH / g. In the present invention, when a metal detergent other than the component (A) is used, a calcium sulfonate detergent having a base number of 0 to 500 mg KOH / g, preferably 100 to 40 Omg KOH / g. It is particularly preferable to use one or more selected from magnesium sulfonate detergents. By using these sulfonate detergents in combination, it is possible to obtain a composition with a very good balance of anti-wear effect, anti-shudder property, and maintainability.
.本発明の潤滑 ·油組成物において、 （ A )成分以外の金属系清浄剤を含有させる場 合、その含有量は特に限定されないが、組^ ¾物全量基準で通常 0. 0 1〜5質量％ 'であり、 好ましくは 0. 0 5〜 1質量％、 特に好ましくは 0. 1〜0. 5質量％ である。  In the lubricating oil composition of the present invention, when a metallic detergent other than the component (A) is contained, its content is not particularly limited, but is usually from 0.00 to 1 to 5 on the basis of the total amount of the product. % By weight, preferably 0.05 to 1% by weight, particularly preferably 0.1 to 0.5% by weight.
無灰分散剤としては、 潤滑油用の無灰分散剤として通常用いられる任意の化合 物が使用可能である。 例えば、 炭素数 40〜40ひ、 好ましくは 60〜3 50の アルキル基又はアルケニル基を分子中に少なく とも 1個有する、コハク酸ィミ ド、 ベンジルァミン、 ポリアミン等の含窒素化合物、 又はその誘導体若しくは変性品 等が挙げられる。 炭素数 40〜400のアルキル基 はァルケニル基は、 直鎖状 でも分枝状でもよく、 好ましいものとしては、 具体的には、 プロピレン、 1ーブ テン、 イソブチレン等のォレフィンのオリ ゴマーやエチレンとプロピレンのコォ リゴマーから誘導される分枝状アルキル基や分枝状アルケニル基等が挙げられる。 アルキル基又はアルケ ル基の炭素数が 4 0未満の場合は化合物の潤滑油基油に 対する溶解性が低下し、 一方、 アルキル基又はアルケニル基の炭素数が 4 0 0を 越える場合は、 組成物の低温流動性が悪化する。 As the ashless dispersant, any compound usually used as an ashless dispersant for lubricating oil can be used. For example, a nitrogen-containing compound such as succinic acid, benzylamine, polyamine, or a derivative thereof having at least one alkyl group or alkenyl group having 40 to 40 carbon atoms, preferably 60 to 350 carbon atoms in the molecule, or Examples include modified products. The alkyl group having 40 to 400 carbon atoms and the alkenyl group may be linear or branched. Specifically, preferred are olefin oligomers such as propylene, 1-butene and isobutylene, and ethylene. Propylene coco Examples include branched alkyl groups and branched alkenyl groups derived from ligomer. If the alkyl group or alkenyl group has less than 40 carbon atoms, the solubility of the compound in the lubricating base oil will be reduced, while if the alkyl group or alkenyl group has more than 400 carbon atoms, the composition The low-temperature fluidity of things deteriorates.
上記無灰分散剤の 1例として挙げた含窒素化合物の誘導体若しくは変性品とし ては、 例えば、 前述したような含窒素化合物に、 炭素数 2〜 3 0のモノカルボン 酸 （脂肪酸等） や、 シュゥ酸、 フタル酸、 トリメリ ッ ト酸、 ピロメリ ッ ト酸等の 炭素数 2 ~ 3 0のポリカルボン酸を作用させて、 残存するアミノ基及ぴ Z又はィ ミノ基の一部又は全部を中和したり、 アミ ド化した、 いわゆる酸変性化合物 ；前 述したような含窒素化合物にホウ酸を作用させて、 残存するアミノ基及び/又は ィミノ基の一部又は全部を中和したり、 アミ ド化した、 いわゆるホウ素変性化合 物 ；前述したような含窒素化合物にリン酸又は亜リン酸を作用させて、 残存する アミノ基及ぴ Z又はイミノ基の一部又は全部を中和したり、 アミ ド化した、 いわ ゆるリン変性化合物 ；前述したような含窒素化合物に硫黄化合物を作用させた硫 黄変性化合物 ；及び前述したような含窒素化合物に酸変性、 ホウ素変性、 リン変 性、 硫黄変性から選ばれた 2種以上の変性を組み合わせた変性化合物等が挙げら れる。  Examples of the derivatives or modified products of nitrogen-containing compounds mentioned as examples of the above ashless dispersant include, for example, nitrogen-containing compounds such as those described above, monocarboxylic acids having 2 to 30 carbon atoms (fatty acids, etc.), Shu Neutralize some or all of the remaining amino groups and Z or imino groups by the action of polycarboxylic acids having 2 to 30 carbon atoms such as acid, phthalic acid, trimellitic acid, and pyromellitic acid. Or so-called acid-modified compound; boric acid is allowed to act on the nitrogen-containing compound as described above to neutralize part or all of the remaining amino group and / or imino group; So-called boron-modified compound; by reacting phosphoric acid or phosphorous acid with a nitrogen-containing compound as described above, some or all of the remaining amino group and Z or imino group are neutralized, Amidified, so-called Two modified compounds selected from sulfur-modified compounds obtained by allowing a sulfur compound to act on a nitrogen-containing compound as described above; and acid-modified, boron-modified, phosphorus-modified, and sulfur-modified compounds as described above. Examples thereof include modified compounds that combine the above modifications.
本発明の潤滑油組成物には、 これらの中から任意に選ばれた 1種類あるいは 2 種類以上の化合物を任意の量で使用することができるが、 通常その含有量は、 潤 滑油組成物'全量基準で 0 . 1〜 1 0質量％である。  In the lubricating oil composition of the present invention, one kind or two or more kinds of compounds arbitrarily selected from these can be used in any amount, but the content thereof is usually the lubricating oil composition. '0.1 to 10% by mass based on the total amount.
本発明の潤滑油組成物においては、 非ホウ素.系無灰分散剤及ぴ 又はホウ素含 有無灰分散剤を含有することが好ましく、 これら無灰分散剤はコハク酸ィミ ド系 無灰分散剤であることがより好ましい。 非ホウ素系無灰分散剤及び/又はホゥ素 含有無灰分散剤の含有量は、 潤滑油組成物全量基準で、 好ましくは 0 . 1〜 1 0 質量％、 より好ましくは 3〜 6質量％であり、 これらを併用する場合は、 非ホウ 素系無灰分散剤では、好ましくは 1 0質量％以下、より好ましくは 1〜 6質量％、 特に好ましくは 2〜4質量％であり、 ホウ素含有無灰分散剤では、 好ましくは 6 質量％以下、 より好ましくは 0 . 0 1〜4質量％、 特に好まじくは 0 · 5〜 2質 量％である。 なお、 非ホウ素系無灰分散剤とホウ素含有無灰分散剤の含有量の合 計量に対するホウ素含有無灰分散剤の含有量の質量比は、好ましくは 0 . 1〜 1、 より好ましくは 0 . 1 5〜0 . 5、 特に好ましくは 0 . 2〜0 . 3である。 ホウ 素含有無灰分散剤を含むことにより摩耗防止性を高めることができるとともにホ ゥ素含有無灰分散剤を少量とすることでシャダ一防止性能及びその維持性能並び に変速特性にもパランス良く優れた組成物を得やすくなる。 The lubricating oil composition of the present invention preferably contains a non-boron-based ashless dispersant and / or a boron-containing ash-dispersed agent, and these ashless dispersants may be succinic acid-based ashless dispersants. More preferred. The content of the non-boron ashless dispersant and / or the fluorine-containing ashless dispersant is preferably 0.1 to 10% by mass, more preferably 3 to 6% by mass, based on the total amount of the lubricating oil composition. When these are used in combination, the non-boron ashless dispersant is preferably 10% by mass or less, more preferably 1 to 6% by mass, and particularly preferably 2 to 4% by mass. It is preferably 6% by mass or less, more preferably 0.01 to 4% by mass, and particularly preferably 0.5 to 2% by mass. The mass ratio of the content of the boron-containing ashless dispersant to the total content of the non-boron-based ashless dispersant and the content of the boron-containing ashless dispersant is preferably from 0.1 to 1, More preferably, it is 0.15-0.5, Most preferably, it is 0.2-0.3. By including a boron-containing ashless dispersant, wear resistance can be enhanced, and by reducing the amount of boron-containing ashless dispersant, anti-shudder performance and maintenance performance as well as gear shifting characteristics are excellent. It becomes easy to obtain a composition.
摩擦調整剤としては、 潤滑油用の摩擦調整剤として通常用いられる任意の化合 物が使用可能であるが、 炭素数 6〜 3 0のアルキル基又はアルケニル基、 特に炭 素数 6〜 3 0の直鎖アルキル基又は直鎖アルケニル基を分子中に少なく とも 1個 有する、 アミン系摩擦調整剤、 イミ ド系摩擦調整剁、 アミ ド系摩擦調整剤、 脂肪 酸系摩擦調整剤等が挙げられる。  As the friction modifier, 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 straight chain having 6 to 30 carbon atoms. Examples include amine-based friction modifiers, imide-based friction modifiers, amide-based friction modifiers, and fatty acid-based friction modifiers having at least one chain alkyl group or straight-chain alkenyl group in the molecule.
アミン系摩擦調整剤としては、 炭素数 6〜 3 0の直鎖状若しくは分枝状、 好ま しくは直鎖状の脂肪族モノアミン、 直鎖状若し.くは分枝状、 好ましくは直鎖状の 脂肪族ポリアミン、 又はこれら脂肪族ァミンのアルキレンォキシド付加物等の脂 肪族ァミン系摩擦調整剤等が例示できる。  Examples of the amine friction modifier include linear or branched carbon atoms having 6 to 30 carbon atoms, preferably linear aliphatic monoamines, linear or branched, and preferably linear. And an aliphatic amine-based friction modifier such as an alkylene oxide adduct of the aliphatic amine or the like.
ィミ ド系摩擦調整剤としては、 炭素数 6〜 3 0、 好ましくは、 炭素数 8〜 1 8 の直鎖状若しくは分枝状、 好ましくは分枝状の炭化水素基を 1つ又は 2つ有する モノ及び/又はピスコハク酸イミ ド、 当該コハク酸イミ ドにホウ酸やリン酸、 炭 素数 1〜 2 0のカルボン酸あるいほ硫黄含有化合物から選ばれる 1種又は 2種以 上を反応させたコハク酸イミ ド変性化合物等のコハク酸イミ ド系摩擦調整剤等が 例示できる。  As the imid friction modifier, one or two linear or branched, preferably branched hydrocarbon groups having 6 to 30 carbon atoms, preferably 8 to 18 carbon atoms. The mono- and / or psuccinic acid imide, and the succinic acid imide is reacted with one or more selected from boric acid, phosphoric acid, a carboxylic acid having 1 to 20 carbon atoms, or a sulfur-containing compound. Examples thereof include succinic acid-based friction modifiers such as succinic acid imide-modified compounds.
.アミ ド系摩擦.調整剤としては、 炭素数 7〜 3 1の直鎖状又は分枝状、 好ましく は直鎖状の脂肪酸とアンモニア、 脂肪族モノアミン又は脂肪族ポリアミンとのァ ミ ド等の脂肪酸アミ ド系摩擦調製剤等が例示できる。  Amid-based friction modifiers include linear or branched, preferably linear, branched fatty acids with 7 to 31 carbon atoms, ammonia, aliphatic monoamines or aliphatic polyamines, etc. Examples thereof include fatty acid amide friction modifiers.
脂肪酸系摩擦調整剤としては、 炭素数 7〜 3 1の直鎖状又は分枝状、 好ましく は直鎖状の脂肪酸、 該脂肪酸と脂肪族 1価アルコール又は脂肪族多価アルコール とのエステル等の脂肪酸エステル、 該脂肪酸のアルカリ土類金属塩 （マグネシゥ ム塩、 カルシウム塩等） や亜鉛塩等の脂肪酸金属塩等が挙げられる。  Examples of the fatty acid friction modifier include linear or branched, preferably linear fatty acids having 7 to 31 carbon atoms, and esters of the fatty acids with aliphatic monohydric alcohols or aliphatic polyhydric alcohols. Fatty acid esters, alkaline earth metal salts of the fatty acids (magnesium salts, calcium salts, etc.) and fatty acid metal salts such as zinc salts.
これらのうち、 上述のイミ ド系摩擦調整剤、 特にコハク酸イミ ド系摩擦調整剤 は湿式クラッチの摩擦係数を高め、 動力伝達効率を向上させるだけでなく、 シャ ダー防止寿命を格段に向上させるために有効である。  Of these, the above-mentioned imide friction modifiers, particularly succinic acid imide friction modifiers, not only increase the friction coefficient of wet clutches and improve power transmission efficiency, but also significantly improve the anti-shudder life. It is effective for.
また、 上述の摩擦調整剤のうち、 脂肪族ァミン系摩擦調整剤や脂肪酸系摩擦調 整剤、 特に脂肪酸金属塩は、 初期シャダ一防止性を格段に向上させるため特に好 ましく用いることができ、 本発明においては、 これら脂肪族ァミン系摩擦調整剤 及び z又は脂肪酸系摩擦調整剤を含有することが特に好ましい。 なお、 脂肪族ァ ミン系摩擦調整剤と脂肪酸系摩擦調整剤を併用する場合、 その質量比は特に制限 はないが、 変速特性に優れる点で、 好ましくは 1 ： 5〜5 ： 1、 より好ましくは 1 ： 3〜3 ： 1、 特に好ましくは 1 ： 2〜2 ： 1である。 Among the friction modifiers described above, aliphatic amine friction modifiers and fatty acid friction modifiers. A preparation, particularly a fatty acid metal salt, can be particularly preferably used because the initial anti-shattering property is remarkably improved. In the present invention, these aliphatic amine-based friction modifier and z or fatty acid-based friction modifier. It is particularly preferable to contain In addition, when the aliphatic amine friction modifier and the fatty acid friction modifier are used in combination, the mass ratio is not particularly limited, but is preferably 1: 5 to 5: 1, more preferably in terms of excellent speed change characteristics. Is 1: 3 to 3: 1, particularly preferably 1: 2 to 2: 1.
本発明においては、 これらの摩擦調整剤の中から任意に選ばれた 1種類あるい は 2種類以上の化合物を任意の量で含有させることができるが、 通常その含有量 は、 潤滑油組成物基準で 0 . 0 1〜5 . 0質量％、 好ましくは 0 . 0 3〜3 . 0 質量％である。  In the present invention, one kind or two or more kinds of compounds arbitrarily selected from these friction modifiers can be contained in any amount, but usually the content thereof is the lubricating oil composition. It is 0.01 to 5.0% by mass on a basis, preferably 0.03 to 3.0% by mass.
酸化防止剤としては、 フニノール系化合物ゃァミン系化合物等、 潤滑油に一般 的に使用されているものであれば使用可能である。  Antioxidants that can be used are those generally used in lubricating oils, such as funinol compounds and amine compounds.
具体的には、 2— 6—ジー t e r t一プチ/レー 4—メチルフエノ一ノレ等のアル キルフエノーゾレ類、 メチレン一 4、 4—ビスフエノール （ 2、 6 -ジ一 t e r t ーブチルー 4—メチノレフエノール） 等のビスフエノール類、 フエ二ルー α—ナフ チルアミン等のナフチルァミン類、 ジアルキルジフエ二ルァミン類、 （ 3、 5—ジ — t e r t —プチルー 4ーヒ ドロキシフエニル） '脂肪酸 （プロピオン酸等） と 1 価又は多価アルコール、 例えば、 メタノール、 ォクタデカノ一ル、 1、 6へキサ ジオー^/、 ネオペンチノレグリコー^^ チオジェチレングリコーノレ、 トリエチレン グリ コ一ル'、 ぺ.ンタエリスリ トール等とのエステル、 フエノチアジン類、 モリブ デンゃ銅、 亜鉛等の有機金属系酸化防止剤及びこれら'の混合物等を挙げることが 'できる。  Specific examples include alkylphenols such as 2-6-g-tert-butyl / le-4-methylphenol, and methylene-1,4-bisphenol (2,6-ditert-butyl-4-methylenophenol). Bisphenols, naphthylamines such as phenyl-alpha α-naphthylamine, dialkyldiphenylamines, (3,5-di-tert-petityl-4-hydroxyphenyl) 'fatty acids (propionic acid etc.) and monovalent or Polyhydric alcohols, for example, esters with methanol, octadecanol, 1, 6 hexadiol ^ /, neopentinoglycol ^^ thiojetylene glycolol, triethyleneglycol ', pentaerythritol, Examples include organometallic antioxidants such as phenothiazines, molybdenite copper, zinc, and mixtures of these. .
これらの中から任意に選ばれた 1種類あるいは 2種類以上の化合物は、 任意の 量を含有させることができるが、通常その含有量は、潤滑油組成物全量基準で 0 . 0 ：！〜 5 . 0質量0 /0である。 ' One or two or more compounds arbitrarily selected from these can be contained in any amount, but usually the content is 0.0 on the basis of the total amount of the lubricating oil composition. ~ 5. 0 mass 0/0. '
なお、 本発明においてはフエノール系酸化防止剤及ぴノ又はァミン系酸化防止 剤を使用することが好ましく、 特にシャダ一防止性能をより長期に渡り維持しや すい点でフエノール系酸化防止剤及ぴァミン系酸化防.止剤 ¾r併用することが好ま しい。 フエノール系酸化防止剤及ぴァミン系酸化防止剤を併用する場合の質量比 は、 好ましくは 1 ： 5〜： L 0 ： 1、 より好ましくは 1 ： 1〜 8 ： 1、 さらに好ま しくは 2 ： 1〜 6 ： .1である。 In the present invention, it is preferable to use phenol-based antioxidants and amine- or amine-based antioxidants. Particularly, phenol-based antioxidants and phenol-based antioxidants are used because they can easily maintain anti-shudder performance for a longer period of time. It is preferable to use an amine-based antioxidant and anti-oxidant ¾r in combination. The mass ratio when a phenolic antioxidant and a amine antioxidant are used in combination is preferably 1: 5 to L0: 1, more preferably 1: 1 to 8: 1, and even more preferable. Or 2: 1 to 6: 1.
極圧添加剤としては、 潤滑油用の極圧添加剤として通常用いられる任意の化合 物が使用可能であるが、 例えば、 ジチォカーバメート類、 ジスルフイ ド類、 硫化 ォレフィ ン類、 硫化油脂類等の硫黄系化合物等が挙げられる。 これらの中から任 意に選ばれた 1種類あるいは 2種類以上の化合物は、 任意の量を含有させること ができるが、通常その含有量は、潤滑油組成物全量基準で 0. 0 1〜5. 0質量％ である。 +  As the extreme pressure additive, any compound usually used as an extreme pressure additive for lubricating oils can be used. For example, dithiocarbamates, disulfides, sulfurized olefins, sulfurized fats and oils, etc. And sulfur compounds. One or two or more compounds arbitrarily selected from these can be contained in any amount, but usually the content is from 0.001 to 5 based on the total amount of the lubricating oil composition. 0% by mass. +
粘度指数向上剤としては、 具体的には、 各種メタクリル酸エステルから選ばれ る 1種又は 2種以上のモノマーの共重合体若しぐはその水添物などのいわゆる非 分散型粘度指数向上剤、 又はさらに窒素化合物を含む各種メタクリル酸エステル を共重合させたいわゆる分散型粘度指数向上剤等が例示できる。 他の粘度指数向 上剤の具体例としては、 非分散型又は分散型エチレン一 α—ォレフィン共重合体 ( α—ォレフィンとしてはプロピレン、 1ーブテン、 1 一ペンテン等が例示でき る。） 又はその水素化物、 ポリイソプチレン又はその水添物、 スチレン一ジェン水 素化共重合体、 スチレン一無水マレイン酸エステル共重合体及ぴポリアルキルス チレン等を挙げることができる。 , これらの粘度指数向上剤の分子量は、 せん断安定性を考慮して選定することが 必要である。 具体的には、 粘度指数向上剤の数平均分子量は、 例えば、 分散型及 ぴ非分散型ポリメタクリ レートの場合では、 5 0 0 0〜 1 5 0 0 0 0、 好ましく は 5 0 0 0 3 5 0 0 0のものが、 ポリイソブチレン又はその水素化物の場合は 8 0 0〜 5 0 0 0、 好ましくは 1 0 0 0 ^ 4 0 .0 0の'ものが、 エチレン一 α—ォ ■レフィン共重合体又はその水素化物の場合は 8 0 0〜 1 5 0 0 0 0、 好ましくは 3 0 0 0〜 1 2 0 0 0のものが好ましい。 Specifically, the viscosity index improver is a so-called non-dispersion type viscosity index improver such as a copolymer of one or more monomers selected from various methacrylates or a hydrogenated product thereof. Or a so-called dispersion type viscosity index improver obtained by copolymerizing various methacrylic acid esters containing a nitrogen compound. Specific examples of other viscosity index improvers include non-dispersed or dispersed ethylene mono- α -olefin copolymers (examples of α-olefin include propylene, 1-butene and 1-pentene) or the like. Examples thereof include a hydride, polyisobutylene or a hydrogenated product thereof, a styrene monohydrogen hydride copolymer, a styrene monomaleic anhydride ester copolymer, and a polyalkylstyrene. Therefore, it is necessary to select the molecular weight of these viscosity index improvers in consideration of shear stability. Specifically, the number average molecular weight of the viscosity index improver is, for example, 5 00 0 to 1 5 0 0 0 0, preferably 5 0 0 0 3 5 in the case of dispersed and non-dispersed polymethacrylates. In the case of 0 0 0 is polyisobutylene or a hydride thereof, 8 0 0 to 5 0 0 0, preferably 1 0 0 0 ^ 4 0 0 In the case of a polymer or a hydride thereof, a polymer having a molecular weight of 80,000 to 1,500, preferably 300,000 to 1,200 is preferable.
またこれらの粘度指数向上剤の中でもエチレン一 ーォレフィン共重合体又は その水素化物を用いた場合には、 特にせん断安定性に優れた潤滑油組成物を得る ことができる。  Further, among these viscosity index improvers, when an ethylene / olefin copolymer or a hydride thereof is used, a lubricating oil composition having particularly excellent shear stability can be obtained.
本発明においては、 これらの粘度指数向上剤の中から任意に選ばれた 1種類あ るいは 2種類以上の化合物を任意の量で含有させるこ,とができるが、 通常その含 有量は、 潤滑油組成物基準で 0. 1〜2 0. 0質量％である。  In the present invention, one kind or two or more kinds of compounds arbitrarily selected from these viscosity index improvers can be contained in any amount, but usually the content is 0.1 to 20.0% by mass based on the lubricating oil composition.
鳍止め剤としては、 例えば、 ァルケエルコハク酸、 アルケニルコハク酸エステ ル、 多価アルコールエステル、 石油スノレホネ一 ト、 ジノニルナフタ レンスルホネ 一ト等を挙げることができる。 Examples of anti-tacking agents include alkelle succinic acid and alkenyl succinic acid ester. , Polyhydric alcohol ester, petroleum sulphonate, dinonylnaphthalene sulfonate and the like.
腐食防止剤としては、'例えば、ベンゾトリァゾール系、 ト リルトリァゾール系、 - ィミダゾール系の化合物等を挙げることができる。  Examples of the corrosion inhibitor include benzotriazole-based, tolyltriazole-based, and -imidazolazole-based compounds.
流動点降下剤としては、 例えば、 使用する潤滑油基油に適合するポリメタタリ レート系のポリマー等を挙げることができる。  Examples of the pour point depressant include polymetatalate polymers that are compatible with the lubricating base oil used.
ゴム膨潤剤としては、 芳香族系やエステル系のゴム膨潤剤等が挙げられる。 消泡剤としては、 例えば、 ジメチルシリコーンやフルォロシリコーン等のシリ コ一ン類を挙げることができる。  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.
これらの添加剤の含有量は任意であるが、 通常組成物全量基準で、 腐食防止剤 の含有量は 0 . 0 0 5〜0 . 2質量％、 消泡剤の含有量は 0 . 0 0 0 5〜0 . 0 1質量％、 その他の添加剤の含有量は、 それぞれ 0 - 0 0 5〜1 0質量％程度で ある。 本発明の潤滑油組成物の 1 0 0 °Cにおける動粘度は通常 2〜 2 5 m m 2 / s、 好ましくは 3〜 8 m m 2 Z s、 より好ましくは 4〜 7 m m 2 / s、 更に好ましくは δ
Figure imgf000023_0001
である。 The content of these additives is arbitrary, but the content of the corrosion inhibitor is usually from 0.05 to 0.2% by mass, and the content of the antifoaming agent is 0.0% based on the total amount of the composition. The content of 0-5 to 0.01% by mass and the other additives is about 0 to 0.05 to 10% by mass, respectively. The kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is usually 2 to 25 mm 2 / s, preferably 3 to 8 mm 2 Z s, more preferably 4 to 7 mm 2 / s, more preferably Is δ
Figure imgf000023_0001
It is.
本発明の潤滑油組成物は、 優れた金属プ一リー及び金属ベルトの摩耗防止性と 初期シャダ一防止性能を有すると共にシャダ一防止性能を長期間維持しうる、 滑 り制御式湿式ク.ラツチと金属ベルト、 特に湿式の発進クラツチを有する無段変速 機に好適な潤滑油組成物であるが、 摩耗防止性あるいは湿式クラツチ特性の向上 'が要求される潤滑油、 具体的には、 自動車、 建設機械、 農業機械等の自動変速機 用あるいは手動変速機、 ディファ レンシャルギヤ用の潤滑油としても好適に用い られる。 その他、 工業用ギヤ油、 二輪車、 四輪車等の自動車用、 発電用、 舶用等 のガソ リ ンエンジン、 ディーゼルエンジン、 ガスエンジン用の潤滑油、 タービン 油、 圧縮機油等にも好適に使用することができる。  The lubricating oil composition of the present invention has an excellent metal pulley and metal belt wear resistance and initial anti-shudder performance, and can maintain the anti-shudder performance for a long period of time. And a metal belt, particularly a lubricating oil composition suitable for a continuously variable transmission having a wet starting clutch. However, a lubricating oil that requires an anti-wear property or an improved wet clutch property, specifically, an automobile, It can also be suitably used as a lubricating oil for automatic transmissions such as construction machinery and agricultural machinery, manual transmissions, and differential gears. Also suitable for industrial gear oils, automobiles such as motorcycles and automobiles, gasoline engines for power generation and marine use, lubricants for diesel engines and gas engines, turbine oils, compressor oils, etc. be able to.
[産業上の利用可能性] , ' [Industrial Applicability], '
モノアルキルタイプのサリシレート系清浄剤は初期シャダ一防止性能に優れる ものの、 リ ン系添加剤の摩耗防止効果を阻害するだけでなく、 滑り制御式湿式ク ラッチのシャダー防止性能を長期間維持することができなかったが、 本発明の (A) 成分に、 （B) 成分及び （C) 成分を併用することで、 金属プーリーと金属 ベルトが厳しい条件で接触する無段変速機において摩耗を抑制し、 滑り制御式湿 式クラツチに特有のシャダ一を長期間に渡り防止することが可能となる。 Although monoalkyl salicylate detergents have excellent initial anti-shatter performance, they do not only inhibit the anti-wear effect of phosphorus additives, but also include slip-controlled wet-type cleaners. Although the anti-shudder performance of the latch could not be maintained for a long time, the combination of the (B) component and the (C) component with the (A) component of the present invention allowed the metal pulley and metal belt to It is possible to suppress wear in the continuously variable transmission that is in contact, and to prevent the shudder specific to the slip control type wet clutch for a long period of time.
[発明を実施するための最良の形態] [Best Mode for Carrying Out the Invention]
以下、本発明の内容を実施例およぴ比較例によってさらに具体的に説明する力 本発明はこれらに何ら限定されるものではない。  Hereinafter, the power to explain the contents of the present invention more specifically with reference to Examples and Comparative Examples The present invention is not limited to these.
(実施例 1〜 6及び比較例 1〜 3 ) (Examples 1 to 6 and Comparative Examples 1 to 3)
表 1の実施例 1〜 6に示す各潤滑油組成物及ぴ比較のため比較例 1〜 3に示す 各潤滑油組成物を調整し、 以下に示す （ 1) 初期シャダ一防止性能、 （ 2) シャダ 一防止性の維持性能及び （3) 摩耗防止性能を評価し、 その結果を表 1に併記し た。 基油の割合は基油全量基準、 各添加剤の添加量は組成物全量基準である。  Each lubricating oil composition shown in Examples 1 to 6 in Table 1 and each lubricating oil composition shown in Comparative Examples 1 to 3 for comparison were prepared and shown below. (1) Initial shudder prevention performance, (2 ) Evaluated the ability to maintain shatter resistance and (3) anti-wear performance, and the results are also shown in Table 1. The ratio of base oil is based on the total amount of base oil, and the amount of each additive is based on the total amount of composition.
( 1) 初期シャダ一防止性能 (1) Initial shudder prevention performance
LVFAを使用し、 面圧を 1. 5MP a としで、 その他の条件については J A S O . M 34 9 - 9 8に準拠して評価を行い、 2 r p m.から 2 0 0 r p mにおけ る d d Vを測定した。 d ノ d Vが正の数値を示し、 かつ数値が大きいほど 初期シャダ '一防.止性能に優れ、 d μ / d Vが負であればシャダ一防止性が大幅に 悪化する指標となる。  LVFA is used, the contact pressure is 1.5MPa, and other conditions are evaluated in accordance with JASO.M 34 9-98, dd V from 2 rp m. To 200 rpm Was measured. d No d V indicates a positive value, and the larger the value, the better the initial anti-shudder performance. If d μ / d V is negative, the anti-shudder performance is greatly deteriorated.
( 2 ) シャダ一防止性能の維持性  (2) Maintaining anti-shudder performance
金属プーリーと金属ベルトが厳しい条件で接触する無段変速機においては金属 の摩耗や鉄イオン等の溶出が多く、 特に本発明における （A) 成分を使用する場 合に顕著であり、 シャダ一防止性を維持しにくいことが判明したため、 長期使用 後の潤滑油として想定し、 評価油として各潤滑油組成物を J I S—K 2 5 14に '準拠して 1 5 0°Cで 7 2時間劣化させ、 鉄イオンを含む有機鉄を、 鉄分として 3 00質量 p p m溶解させたものを調製した。 各評価油,についで （ 1) と同様の方 法で d iZd Vを測定した。 d /iZdVが正の値を示し、かつ数値が大きいほど、 長期間使用により金属プーリーと金属ベルトに起因する鉄分が潤滑油中に溶出し たとしても湿式クラ.ツチにおけるシャダ一防止性能を長期間維持できるものであ る。 In continuously variable transmissions where metal pulleys and metal belts contact under severe conditions, metal wear and elution of iron ions, etc. are common, especially when the component (A) in the present invention is used. As a lubricant after long-term use, each lubricating oil composition was deteriorated at 150 ° C for 72 hours according to JIS-K 2 5 14 Then, organic iron containing iron ions was prepared by dissolving 300 mass ppm as iron. Next to each evaluated oil, di iZd V was measured by the same method as in (1). As d / iZdV shows a positive value and the value is larger, the iron content due to the metal pulley and metal belt dissolves into the lubricating oil after long-term use. Even so, the anti-shudder performance in the wet clutch can be maintained for a long time.
(3) 摩耗防止性  (3) Wear resistance
A S TM— D 4 1 7 2に準拠し、 四球摩耗痕径を測定した。 摩耗痕径が小さい ほど摩耗防止性に優れる。 表 1の結果から明らかな通り、 本発明にかかる実施例 1〜 6の組成物を使用し た場合、 初期シャダ一防止性能の目安である d ノ d Vが正の数値を示しかつ数 値が大きいものであり、その維持性能も格段なものである。また、摩耗痕径も 0. 5 Omm以下であり、摩耗防止性能.も優れていることがわかる。一方、 （A)〜（C) 成分のいずれかを使用しない場合（比較例 1〜 3)、初期シャダ一防止性及ぴ摩耗 防止性のいずれかが大幅に劣ることがわかる。 According to AS TM — D 4 1 7 2, the four-ball wear scar diameter was measured. The smaller the wear scar diameter, the better the wear resistance. As is apparent from the results in Table 1, when the compositions of Examples 1 to 6 according to the present invention were used, d No d V, which is a measure of initial anti-shudder performance, showed a positive value and the numerical value was It is large and its maintenance performance is also remarkable. In addition, the wear scar diameter is 0.5 Omm or less, indicating that the wear prevention performance is excellent. On the other hand, when any of the components (A) to (C) is not used (Comparative Examples 1 to 3), it can be seen that either the initial shudder prevention property or the wear prevention property is significantly inferior.
表 1 table 1
Figure imgf000026_0002
Figure imgf000026_0002
1) 水素化分解基油（100°C動粘度 2.6mm2/s、粘度指数 105、 NOACK蒸発量 52質量％、 S量 0.1質量％以下） 1) Hydrocracking base oil (100 ° C kinematic viscosity 2.6mm 2 / s, viscosity index 105, NOACK evaporation 52 mass%, S content 0.1 mass% or less)
2) 水素化分解基油（100°C動粘度 4.0mm2/s、粘度指数 125、 NOACK蒸発量 16質量％、 S量 0.1質量％以下） 2) Hydrocracked base oil (100 ° C kinematic viscosity 4.0mm 2 / s, viscosity index 125, NOACK evaporation 16% by mass, S amount 0.1% by mass or less)
アルキルサリチル酸 Ca塩の炭酸 Ga過塩基性塩 (塩基価 170mgKOH/g,Ca量 6.7質量％)  Alkalisalicylic acid Ca salt Carbonate Ga overbased salt (Base number 170mgKOH / g, Ca content 6.7% by mass)
4-アルキル： 4mo|o/0、 5-アルキル： 35mol%、 3,5-ジアルキル： 8mol% ル、アルキル基: C6〜G8アルキル基 4-alkyl: 4mo | o / 0 , 5-alkyl: 35mol%, 3,5-dialkyl: 8mol%, alkyl group: C6-G8 alkyl group
6) ジ -2 -ェチルへキシルフォスファイト（リン含有量 10.6質量0 /o)6) Di-2-ethylhexyl phosphite (phosphorus content 10.6 mass 0 / o)
8) ホウ酸変性ポリブテニルコハク酸イミド 8) Boric acid modified polybutenyl succinimide
10) マグネシウムスルフォネート（全塩基価 1 0OmgKOHZg)  10) Magnesium sulfonate (total base number 10OmgKOHZg)
12) 脂肪酸系 12) Fatty acid
Figure imgf000026_0001
14) ビスフエノール系 15) ポリジメチルシロキサン
Figure imgf000026_0001
14) Bisphenol-based 15) Polydimethylsiloxane

Claims

請 求 の 範 囲 The scope of the claims
1. 潤滑油基油に、 （A)モノアルキルサリチル酸金属塩の構成比が 8 5 〜 1 0 0 m o 1 %、 ジアルキルサリチル酸金属塩の構成比が 0〜 1 5 m o 1 %で あって、 3—アルキルサリチル酸金属塩の構成比が 4 0〜 1 0 0 m o 1 %である アルキルサリチル酸金属塩、及ぴノ又はその （過）塩基性塩と、 （B) —般式 （ 1 ) で示される窒素化合物及び （C) リン系摩耗防止剤を含むことを特徴とする、 滑 り制御式湿式クラツチを有する変速機用に好適な潤滑油組成物。 1. In the lubricating base oil, the composition ratio of (A) monoalkyl salicylic acid metal salt is 85 to 100 mo 1%, and the composition ratio of dialkyl salicylic acid metal salt is 0 to 15 mo 1%. —Alkyl salicylic acid metal salt having a composition ratio of alkyl salicylic acid metal salt of 40 to 10 0 mo 1%, and Pino or its (over) basic salt, and (B) —shown by general formula (1) A lubricating oil composition suitable for a transmission having a slip-controlled wet clutch, comprising a nitrogen compound and (C) a phosphorus-based antiwear agent.
(1)(1)
Figure imgf000027_0001
Figure imgf000027_0001
(一般式 （ 1 ) において、 R 1は、 炭素数 1〜 3 0の直鎖状又は分枝状のアルキ ル基、 R 2は、 水素原子又は炭素数 1〜 2 4の直鎖状又は分枝状のアルキル基を それぞれ示し、 a及ぴ. bはそれぞれ個別に 1、 2又は 3を示す。） (In the general formula (1), R 1 is a linear or branched alkyl group having 1 to 30 carbon atoms, R 2 is a hydrogen atom or a linear or branched group having 1 to 24 carbon atoms. Each represents a branched alkyl group, a and b are each independently 1, 2 or 3.)
2. 摩擦調整剤を含むことを特徴とする請求項 1に記載の潤滑油組成物。 2. The lubricating oil composition according to claim 1, further comprising a friction modifier.
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CN101283079A (en) 2008-10-08
JP5030402B2 (en) 2012-09-19
EP1918356A1 (en) 2008-05-07
EP1918356B1 (en) 2011-08-10
JP2007051178A (en) 2007-03-01
CN101283079B (en) 2013-02-06
EP1918356A4 (en) 2008-12-31

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