Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
  • C10M107/02—Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/02—Sulfurised compounds
• • 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
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/02—Sulfurised compounds
  • C10M135/04—Hydrocarbons
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M151/00—Lubricating compositions characterised by the additive being a macromolecular compound containing sulfur, selenium or tellurium
  • C10M151/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
  • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
  • C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms 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
  • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
  • C10M2205/17—Fisher Tropsch reaction products
  • C10M2205/173—Fisher Tropsch reaction products 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/023—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds 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
  • 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
  • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
• • 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
  • C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
  • C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
• • 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
  • C10M2221/00—Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2221/04—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2221/041—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds involving sulfurisation of macromolecular compounds, e.g. polyolefins
• • 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
  • C10M2223/047—Thioderivatives not containing metallic elements
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/02—Viscosity; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/04—Molecular weight; Molecular weight distribution
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—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
  • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives

Definitions

• the present invention relates to a lubricating oil composition.
• the present invention relates to a lubricating oil composition for automobiles having a reduced viscosity that can be applied to a differential gear.
• Lubricating oil compositions are used in a wide variety of applications such as automobiles and machines. In recent years, lowering the viscosity of automotive lubricating oil compositions has been demanded from the viewpoint of fuel efficiency. However, lowering the viscosity of the lubricating oil composition affects the oil film forming ability. In particular, in the field of automotive gear oils, and more particularly in lubricating oils used for differential gears, reducing the viscosity of the lubricating oil causes problems such as the occurrence of wear on bearings and the occurrence of scoring on gear tooth surfaces. Therefore, it was difficult to cope with the low viscosity. Therefore, it is hoped to develop a gear oil composition for automobiles, particularly a differential gear oil composition, which can suppress wear on bearings and the like under conditions where oil film formation is difficult at high temperatures even with low viscosity oil. It is rare.
• the inventors of the present invention can reduce the viscosity of a lubricating oil by using a low-viscosity base oil and a high-viscosity base oil in advance, and at the same time, can achieve bearing fatigue life characteristics and fuel economy that are particularly affected by oil film forming ability.
• the invention described in Japanese Patent Application Laid-Open No. 2007-039480 has been made.
• the lubricating oil composition described in Japanese Patent Application Laid-Open No. 2007-039480 has insufficient wear prevention properties for bearings and the like and scoring properties for gear tooth surfaces and the like.
• Japanese Patent Application Laid-Open No. 2014-012855 discloses specific acidic phosphoric acid alkyl esters, dialkylamines and / or trialkylamines, specific sulfur compounds containing no -S-S-S- or higher polysulfur bond, and Lubricating oil compositions optionally comprising certain thiophosphate trihydrocarbyl esters are disclosed.
• the lubricating oil composition described in Japanese Patent Application Laid-Open No. 2014-012855 relates to a wind power booster oil composition that requires seizure resistance and fatigue resistance, and there is no description regarding scoring.
• the present invention has an object to provide a lubricating oil composition capable of suppressing the occurrence of wear on bearings and the like and scoring on gear tooth surfaces and the like even when the viscosity is lowered.
• the present inventors have found that the above problem can be achieved by blending a specific amount of an extreme pressure agent having a specific amount of active sulfur into the lubricating oil composition, and have achieved the present invention.
• the present invention provides a lubricating oil composition
• a lubricating oil composition comprising a lubricating base oil and a sulfur-based extreme pressure agent, wherein the active sulfur content of the extreme pressure agent is 5 to 30% by mass, and the extreme pressure agent is a lubricating oil.
• the lubricating oil composition is provided, wherein the lubricating oil composition is contained in the composition in an amount of 5 to 15% by mass based on the total mass of the composition.
• Preferred embodiments of the present invention further have at least one of the following features (1) to (7).
• the sulfur-based extreme pressure agent is a sulfurized olefin.
• the lubricating oil composition has a kinematic viscosity at 100 ° C. of 5 to 15 mm 2 / s.
• At least one part of the lubricating base oil is a Fischer-Tropsch derived base oil.
• At least one part of the lubricating base oil is a poly- ⁇ -olefin (PAO) base oil.
• PAO poly- ⁇ -olefin
• the lubricant base oil has a kinematic viscosity 5 ⁇ 15 mm 2 / s at 100 ° C..
• the lubricating oil composition is a lubricating oil composition for a transmission.
• the lubricating oil composition is a differential gear lubricating oil composition.
• the lubricating oil composition of the present invention can suppress the occurrence of wear on bearings and scoring on gear tooth surfaces even when the viscosity is lowered.
• the lubricating oil composition of the present invention can be suitably used as a lubricating oil for automobiles, and further suitable as a transmission gear oil and a differential gear oil.
• Lubricating oil base oil The lubricating oil base oil in the present invention is not particularly limited, and conventionally known lubricating oil base oils can be used.
• Examples of the lubricating base oil include mineral base oils, synthetic base oils, and mixed base oils thereof.
• Mineral oil base oils include highly refined paraffinic mineral oils (high viscosity index mineral oil base oils obtained by subjecting hydrorefined oil, catalytic isomerized oil, etc. to solvent dewaxing or hydrodewaxing, etc. ) Is preferred.
• mineral base oils other than the above include, for example, raffinates obtained by solvent refining using lube oil as an aromatic extraction solvent such as phenol and furfural, hydrogen such as cobalt and molybdenum using silica-alumina as a carrier.
• hydrotreated oil obtained by hydrotreating using a hydrotreating catalyst For example, 100 neutral oil, 150 neutral oil, 500 neutral oil, etc. can be mentioned.
• Examples of synthetic base oils include base oils obtained from hydrocracking and hydroisomerization of raw materials such as waxes obtained from Fischer-Tropsch synthesis from natural gas such as methane (so-called Fischer-Tropsch derived) Base oil), poly- ⁇ -olefin base oil (PAO), polybutene, alkylbenzene, polyol ester, polyglycol ester, dibasic acid ester, phosphate ester, and silicon oil. Of these, Fischer-Tropsch derived base oils and poly- ⁇ -olefin (PAO) base oils are preferred.
• base oils obtained from hydrocracking and hydroisomerization of raw materials such as waxes obtained from Fischer-Tropsch synthesis from natural gas such as methane (so-called Fischer-Tropsch derived) Base oil), poly- ⁇ -olefin base oil (PAO), polybutene, alkylbenzene, polyol ester, polyglycol ester, dibasic acid ester, phosphate ester,
• the lubricating base oil is selected from the above mineral base oil, the above synthetic base oil, or a combination thereof, one kind may be used alone, or two or more kinds may be used in combination.
• two or more kinds of lubricating base oils are used in combination, they may be mineral base oils, synthetic base oils, or a combination of mineral oil base oils and synthetic base oils, and the mode is not limited.
• a combination of a mineral base oil and a synthetic base oil is suitable.
• a mineral base oil and a synthetic base oil are used in combination, at least one selected from a Fischer-Tropsch derived base oil and a poly- ⁇ -olefin (PAO) base oil is used as the synthetic base oil.
• the preferred mode of combined use is (1) A combination of mineral oil base oil and Fischer-Tropsch derived base oil, (2) A combination of a mineral oil base oil and a poly- ⁇ -olefin (PAO) base oil, (3) A combination of mineral base oil, Fischer-Tropsch derived base oil and poly- ⁇ -olefin (PAO) base oil, or (4) Fischer-Tropsch derived base oil and poly- ⁇ -olefin (PAO). ) Combination with base oil.
• a combination of (3) mineral oil base oil, Fischer-Tropsch derived base oil, and poly- ⁇ -olefin (PAO) base oil is particularly preferable.
• the mineral oil base oil is not limited to those produced by the above production method, but preferably has a kinematic viscosity at 100 ° C. of 2 to 35 mm 2 / s, more preferably 2 to 20 mm 2 / s. More preferably, it is 3 to 10 mm 2 / s.
• the Fischer-Tropsch derived base oil is not particularly limited, but preferably has a kinematic viscosity at 100 ° C. of 2 to 40 mm 2 / s, more preferably 2 to 20 mm 2 / s, and still more preferably 2 It should be ⁇ 10 mm 2 / s.
• the poly- ⁇ -olefin (PAO) base oil is not particularly limited, but examples thereof include 1-octene oligomer, 1-decene oligomer, ethylene- ⁇ -olefin oligomer, ethylene-propylene oligomer, isobutene oligomer and hydrogen thereof. Can be used.
• the poly- ⁇ -olefin (PAO) base oil preferably has a kinematic viscosity at 100 ° C. of 2 to 100 mm 2 / s, more preferably 2 to 50 mm 2 / s, and even more preferably 10 to 50 mm 2 / s. There should be.
• the kinematic viscosity of the lubricating base oil is not limited as long as the gist of the present invention is not impaired.
• the entire lubricating base oil preferably has a kinematic viscosity at 100 ° C. of 3 to 40 mm 2 / s, more preferably 4 to 20 mm 2 / s. Preferably it has 5 to 15 mm 2 / s, particularly preferably 8 to 15 mm 2 / s. If the kinematic viscosity at 100 ° C.
• the lubricating base oil exceeds the upper limit, it may be difficult to lower the viscosity of the lubricating oil composition, and it may be difficult to achieve fuel economy. Further, if the kinematic viscosity at 100 ° C. is less than the lower limit, fuel saving can be achieved, but it may be difficult to ensure wear prevention and scoring prevention.
• the lubricating oil composition of the present invention contains a sulfur-based extreme pressure agent as an essential component.
• the sulfur-based extreme pressure agent used in the present invention is required to have an active sulfur amount of 5 to 30% by mass, preferably 5 to 20% by mass, more preferably 5 to 18% by mass, and still more preferably 5%. -15% by mass, particularly preferably 8-12% by mass. If the amount of active sulfur exceeds the above upper limit, not only metal corrosion will occur, but it will be difficult to ensure wear prevention and scoring prevention.
• the lower limit of the amount of active sulfur is not particularly limited, but the above lower limit is preferable for ensuring extreme pressure.
• the amount of active sulfur is measured by the method prescribed in ASTM D1662. More specifically, the amount of active sulfur based on ASTM D1662 can be measured by the following procedure. 1. In a 200 ml beaker, put 50 g of a sample and 5 g of copper powder (purity 99% or more, particle size 75 ⁇ m or less), and heat to 150 ° C. while stirring with a stirrer (500 rpm). 2. When the temperature reaches 150 ° C., add 5 g of copper powder and stir for 30 minutes. 3. Stirring is stopped, and an ASTM D130-compliant copper plate is placed in a beaker and immersed for 10 minutes.
• ASTM D130-compliant copper plate is placed in a beaker and immersed for 10 minutes.
• the sulfur-based extreme pressure agent in the present invention is not particularly limited as long as it has the above-mentioned specific amount of active sulfur, and can be selected from known sulfur-based extreme pressure agents.
• it is at least one selected from sulfide compounds typified by sulfurized olefins and sulfurized esters typified by sulfurized fats and oils, and sulfurized olefins are particularly preferable.
• the sulfur-based extreme pressure agent used in the present invention is represented by, for example, the following general formula (1).
• R 1 and R 2 are each independently a monovalent substituent and contain at least one element of carbon, hydrogen, oxygen, and sulfur. Specific examples include saturated or unsaturated hydrocarbon groups having a straight chain structure or a branched structure having 1 to 40 carbon atoms, and may be aliphatic, aromatic, or araliphatic. Further, it may contain oxygen and / or sulfur atoms. R 1 and R 2 may be bonded. When there is one bond, for example, it is represented by the following general formula (2).
• x is an integer of 1 or more, preferably an integer of 1 to 12.
• x is preferably an integer of 1 to 10, more preferably an integer of 1 to 8, and particularly preferably an integer of 2 to 5.
• the sulfur-based extreme pressure agents represented by the general formulas (1) and (2) are usually not a single x, but a mixture of various sulfur numbers, in which compounds having specific sulfur numbers are active. It is thought to function as sulfur.
• sulfur-based extreme pressure agents are further described below.
• Sulfurized olefins are obtained by sulfiding olefins, and are collectively referred to as sulfide compounds including those obtained by sulfiding hydrocarbon-based raw materials other than olefins.
• sulfurized olefin include those obtained by sulfurizing olefins such as polyisobutylenes and terpenes with sulfur or other sulfurizing agents.
• sulfide compounds other than sulfurized olefins include diisobutyl disulfide, dioctyl polysulfide, di-tert-butyl polysulfide, diisobutyl polysulfide, dihexyl polysulfide, di-tert-nonyl polysulfide, didecyl polysulfide, didodecyl polysulfide, diisobutylene polysulfide, Examples thereof include octenyl polysulfide and dibenzyl polysulfide.
• Sulfurized fats and oils are reaction products of fats and sulfur, and are obtained by sulfidizing animal and vegetable fats and oils such as lard, beef tallow, whale oil, palm oil, coconut oil and rapeseed oil as fats and oils. .
• This reaction product is not a single substance species but a mixture of various substances, and the chemical structure itself is not necessarily clear.
• sulfurized esters are obtained by sulfurizing ester compounds obtained by reaction of various organic acids (saturated fatty acids, unsaturated fatty acids, dicarboxylic acids, aromatic carboxylic acids, etc.) with various alcohols with sulfur or other sulfurizing agents. Can be obtained.
• various organic acids saturated fatty acids, unsaturated fatty acids, dicarboxylic acids, aromatic carboxylic acids, etc.
• sulfur or other sulfurizing agents can be obtained.
• the chemical structure itself is not always clear.
• the content of the sulfur-based extreme pressure agent is 5% by mass to 15% by mass, preferably 6% by mass to 12% by mass, based on the total mass of the lubricating oil composition. It is also a feature of the present invention that the content of the sulfur-based extreme pressure agent is larger than that of the lubricating oil composition. If the content exceeds the above upper limit value, thermal oxidation stability is lowered and sludge is likely to be generated, and in addition, metal corrosion is likely to occur, which is not preferable. Moreover, when content is less than the said lower limit, since scoring prevention property falls, it is unpreferable.
• the lubricating oil composition of the present invention may further contain a phosphorous extreme pressure agent and / or a sulfur-containing phosphorous extreme pressure agent as optional components. it can.
• the sulfur element contained in the sulfur-containing phosphorus-based extreme pressure agent here is not sulfur (active sulfur) measured by ASTM D1662, and the extreme-pressure agent is distinguished from the above-described sulfur-based extreme pressure agent. It is.
• the phosphorus-based extreme pressure agent and the sulfur-containing phosphorus-based extreme pressure agent are not particularly limited and may be conventionally known ones.
• the phosphoric acid ester and the acidic phosphoric acid ester are represented by (R 1 O) a P ( ⁇ O) (OH) 3-a .
• a is 0, 1, 2, or 3;
• R 1 is independently a monovalent hydrocarbon group having 4 to 30 carbon atoms.
• the phosphite and acidic phosphite are represented by (R 2 O) b P ( ⁇ O) (OH) 2 -b H.
• b is 0, 1 or 2;
• R 2 is independently a monovalent hydrocarbon group having 4 to 30 carbon atoms.
• R 3 , R 4 and R 5 are a hydrogen atom or a monovalent hydrocarbon group having 4 to 30 carbon atoms.
• R 3 , R 4 and R 5 are hydrogen atoms, an acidic thiophosphate is formed.
• X 1 , X 2 , X 3 and X 4 are each independently an oxygen atom or a sulfur atom. However, at least one of X 1 , X 2 , X 3 and X 4 is a sulfur atom.
• R 6 and R 7 are each independently a hydrogen atom or a monovalent hydrocarbon group having 4 to 30 carbon atoms.
• one of R 6 and R 7 is a hydrogen atom, it is an acidic thiophosphate.
• X 5 , X 6 and X 7 are each independently an oxygen atom or a sulfur atom. Provided that at least one of X 5, X 6 and X 7 is a sulfur atom.
• the phosphoric acid ester and acidic phosphoric acid ester are preferably phosphoric acid monoalkyl ester, phosphoric acid dialkyl ester, and phosphoric acid trialkyl ester, but are not limited thereto.
• the phosphite and acidic phosphite are preferably a monoalkyl phosphite and a dialkyl phosphite, but are not limited thereto.
• the thiophosphoric acid ester and the acidic thiophosphoric acid ester are preferably a thiophosphoric acid monoalkyl ester, a thiophosphoric acid dialkyl ester, and a thiophosphoric acid trialkyl ester, but are not limited thereto.
• the thiophosphite is preferably a thiophosphite monoalkyl ester and a thiophosphite dialkyl ester, but is not limited thereto.
• phosphate ester As phosphate ester, phosphite ester, thiophosphate ester, and thiophosphite ester, more specifically, monooctyl phosphate, dioctyl phosphate, trioctyl phosphate, monooctyl phosphite, dioctyl phosphite, Monooctyl thiophosphate, dioctyl thiophosphate, trioctyl thiophosphate, monooctyl thiophosphite, dioctyl thiophosphite, monododecyl phosphate, dododecyl phosphate, tridodecyl phosphate, monododecyl phosphite, didodecyl phosphite, Monododecyl thiophosphate, didodecyl thiophosphate, tridodec
• alkylamine salts and alkenylamine salts of the above compounds which are partial esters can also be suitably used. That is, an amine salt of an acidic phosphate ester, an amine salt of an acidic phosphite ester, an amine salt of an acidic thiophosphate ester, or an amine salt of an acidic thiophosphite ester can be used, but is not limited thereto. is not.
• the amine of the amine salt is represented by R 8 R 9 R 10 N, having a linear structure or a branched chain of R 8, R 9 and R 10 are each independently hydrogen or a C 1-20 saturated or unsaturated A saturated aliphatic hydrocarbon group, and more specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a nonyl group, a dodecyl group, a propenyl group, a butenyl group, an oleyl group, and the like.
• the phosphorus extreme pressure agent and the sulfur-containing phosphorus extreme pressure agent can be used alone or in combination of two or more. In the case of combination, for example, the following embodiments are exemplified, but the invention is not limited thereto.
• (1) Thiophosphate amine salt and phosphate ester amine salt In particular, a combination of a thiophosphate ester amine salt having an alkyl group and a phosphate ester amine salt having an alkyl group, (2) Thiophosphate ester amine salt and phosphate ester In particular, a combination of a thiophosphate ester amine salt having an alkyl group and a phosphate ester having an alkyl group, (3) Phosphate ester amine salt and thiophosphate ester In particular, a combination of a phosphate ester amine salt having an alkyl group and a thiophosphate ester having an alkyl group, (4) Thiophosphate ester and phosphate ester In particular,
• the addition amount of the phosphorus-based extreme pressure agent and the sulfur-containing phosphorus-based extreme pressure agent is not limited, and may be appropriately adjusted. For example, it is preferably 10% by mass or less, more preferably 1 to 8% by mass, and further preferably 2 to 6% by mass with respect to the total mass of the lubricating oil composition. If the content exceeds the above upper limit value, scoring prevention property on the tooth surface or the like may be deteriorated, which is not preferable. When the content is equal to or more than the lower limit value relative to the mass of the entire lubricating oil composition, it further contributes to wear prevention performance.
• Ashless dispersant may further contain an ashless dispersant.
• a conventionally known ashless dispersant may be used and is not particularly limited. Examples thereof include nitrogen-containing compounds having 40 to 400 carbon atoms and at least one alkyl group or alkenyl group having a straight chain structure or a branched structure in the molecule or derivatives thereof, or modified products of alkenyl succinimide. .
• Ashless dispersants may be used alone or in combination of two or more.
• a borated ashless dispersant can also be used.
• the boronated ashless dispersant is a borated version of any ashless dispersant used in lubricating oils. Boronation is generally performed by allowing boric acid to act on an imide compound to neutralize part or all of the remaining amino group and / or imino group.
• the carbon number of the alkyl group or alkenyl group is preferably 40 to 400, more preferably 60 to 350.
• the solubility of the compound in the lubricating base oil tends to decrease.
• the carbon number of an alkyl group and an alkenyl group exceeds the said upper limit, it exists in the tendency for the low-temperature fluidity
• the alkyl group and alkenyl group may have a straight chain structure or a branched structure.
• Preferred embodiments include, for example, oligomers of olefins such as propylene, 1-butene and isobutylene, branched alkyl groups or branched alkenyl groups derived from ethylene and propylene co-oligomers, and the like.
• the alkenyl succinimide is a reaction product of one end of a polyamine and succinic anhydride, a so-called monotype succinimide, and a reaction product of both ends of the polyamine and succinic anhydride, so-called bis-type. And succinimide.
• the lubricating oil composition of the present invention may contain one of monotype and bistype, or may contain both.
• the above-mentioned modified product of alkenyl succinimide is, for example, a product obtained by modifying alkenyl succinimide with a boron compound (hereinafter sometimes referred to as boronated succinimide).
• Modifying with a boron compound means boronation.
• a boronated succinimide may be used individually by 1 type, or may use 2 or more types together. When used in combination, it may be a combination of two or more of boronated succinimides. Moreover, both a monotype and a bis type may be included, the combined use of monotypes, or the combined use of bistypes may be sufficient.
• a boronated succinimide and a non-borated succinimide may be used in combination.
• boronated succinimide methods for producing a boronated succinimide are disclosed in JP-B-42-8013 and JP-A-42-8014, JP-A-51-52381, JP-A-51-130408, and the like. And the like.
• organic compounds such as alcohols, hexane, xylene, etc., light lubricating oil base oil, polyamine and polyalkenyl succinic acid (anhydride), boric acid, boric acid ester, or boron compounds such as borate can be obtained by mixing and heat-treating under appropriate conditions.
• the boron content contained in the boronated succinimide thus obtained can usually be 0.1 to 4% by mass.
• a boron-modified compound of an alkenyl succinimide compound is particularly preferable because of excellent heat resistance, antioxidant properties, and antiwear properties.
• the boron content contained in the boronated ashless dispersant is not particularly limited. Usually, it is 0.1 to 3% by mass with respect to the mass of the ashless dispersant. As one aspect of the present invention, the boron content in the ashless dispersant is preferably 0.2% by mass or more, more preferably 0.4% by mass or more, and preferably 2.5% by mass or less. More preferably, it is 2.3 mass% or less, More preferably, it is 2.0 mass% or less.
• the boronated ashless dispersant is preferably a boronated succinimide, and particularly preferably a boronated bissuccinimide.
• the borated ashless dispersant has a boron / nitrogen mass ratio (B / N ratio) of 0.1 or more, preferably 0.2 or more, preferably less than 1.0, more preferably 0.8 or less. What has is preferable.
• the content of the ashless dispersant in the composition may be adjusted as appropriate. For example, it is preferably 0.01 to 20% by mass, more preferably 0.1 to the mass of the entire lubricating oil composition. ⁇ 10% by mass. If the content of the ashless dispersant is less than the above lower limit, the sludge dispersibility may be insufficient. Moreover, when content exceeds the said upper limit, there exists a possibility of deteriorating a specific rubber material or making low temperature fluidity worse.
• the lubricating oil composition of the present invention includes, as other additives other than the above components (A) to (D), a viscosity index improver, an antioxidant, a metallic detergent, and a friction modifier. , Corrosion inhibitors, rust inhibitors, demulsifiers, metal deactivators, antifoaming agents, and pour point depressants.
• a thickener examples include metal soap and metal salt.
• the viscosity index improver for example, a polymer or copolymer of one or more monomers selected from various methacrylic acid esters, or a hydride thereof, a so-called non-dispersed viscosity index improver, or So-called dispersible viscosity index improvers copolymerized with various methacrylic esters containing nitrogen compounds, non-dispersed or dispersed ethylene- ⁇ -olefin copolymers (for propylene, 1-butene, 1-pentene as ⁇ -olefins) Or a hydride thereof, a polyisobutylene or a hydride thereof, a hydride of a styrene-diene copolymer, a styrene-maleic anhydride ester copolymer, and a polyalkylstyrene.
• the viscosity index improver has a weight average molecular weight of usually 5,000 to 1,000,000, preferably 100,000 to 900,000 in the case of dispersed and non-dispersed polymethacrylates.
• isobutylene or a hydride thereof usually 800 to 5,000, preferably 1,000 to 4,000, and in the case of an ethylene- ⁇ -olefin copolymer or a hydride thereof, usually 800 to 500,000, Those having a viscosity of 3,000 to 200,000 are preferably used.
• a lubricating oil composition having particularly excellent shear stability can be obtained.
• One or two or more compounds arbitrarily selected from the above viscosity index improvers can be contained in any amount.
• the content of the viscosity index improver in the lubricating oil composition is 0.01 to 20% by mass, preferably 0.02 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total amount of the composition. is there.
• Antioxidants may be those commonly used in lubricating oils, for example, ashless antioxidants such as phenolic antioxidants and amine antioxidants and organometallic antioxidants. Can be mentioned. By adding an antioxidant, the oxidation stability of the lubricating oil composition can be further enhanced.
• the metal detergent examples include those containing a compound selected from sulfonates such as calcium, magnesium and barium, phenates, salicylates, and carboxylates, such as overbased salts, basic salts, and neutral salts. Those having different base numbers can be arbitrarily selected and used.
• the metal detergent is usually blended in the lubricating oil composition at a metal amount of 0.01 to 1% by mass.
• friction modifier examples include organic molybdenum compounds, fatty acids, fatty acid esters, fats and oils, alcohols, amines, amides, and the like.
• the friction modifier is usually blended in the lubricating oil composition at 0.01 to 5% by mass.
• the corrosion inhibitor examples include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.
• the antioxidant is usually blended at 0.1 to 5% by mass in the lubricating oil composition.
• rust preventive examples include petroleum sulfonate, alkyl sulfonate, fatty acid, fatty acid soap, fatty acid amine, alkyl polyoxyalkylene, alkenyl succinic acid ester, and polyhydric alcohol fatty acid ester.
• the rust preventive is usually blended in the lubricating oil composition at 0.01 to 5% by mass.
• the demulsifier examples include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether.
• the demulsifier is usually blended in the lubricating oil composition at 0.01 to 5% by mass.
• metal deactivator examples include pyrroles, imidazoles, pyrazoles, pyrazines, pyrimidines, pyridazines, triazines, triazoles, thiazoles, thiadiazoles and the like.
• the metal deactivator is usually blended in the lubricating oil composition at 0.01 to 3% by mass.
• antifoaming agent examples include dimethylpolysiloxanes and their fluorinated derivatives, polyacrylates and their fluorinated derivatives, and perfluoropolyethers.
• the antifoaming agent is usually blended in the lubricating oil composition at 0.001 to 1% by mass.
• pour point depressant for example, a polymethacrylate polymer compatible with the lubricating base oil to be used can be used.
• the pour point depressant is usually blended in the lubricating oil composition at 0.01 to 3% by mass.
• Kinematic viscosity at 40 ° C. of the lubricating oil composition of the present invention is preferably 20 ⁇ 120mm 2 / s, more preferably 40 ⁇ 100mm 2 / s. More preferably, it is 50 to 80 mm 2 / s.
• the kinematic viscosity at 100 ° C. of the lubricating oil composition of the present invention is preferably 3 to 40 mm 2 / s, more preferably 4 to 20 mm 2 / s, still more preferably 5 to 15 mm 2 / s, and particularly preferably 8 to 15 mm 2. / S.
• KV40 means the kinematic viscosity at 40 ° C.
• KV100 means the kinematic viscosity at 100 ° C.
• VI means the viscosity index.
• KV100 4 mm 2 / s
• Synthetic base oil 1 Fischer-Tropsch derived base oil
• KV100 8 mm 2 / s
• Synthetic base oil 2 ethylene- ⁇ -olefin base oil
• KV100 40 mm 2 / s
• Sulfur-based extreme pressure agent The amount of active sulfur in the following is a value measured by a method based on ASTM D1662, The amount of active sulfur in the sulfur-based extreme pressure agent.
• Phosphorus extreme pressure agent / Phosphorus extreme pressure agent 1 Acid phosphate ester amine salt (C8-C18 alkyl)
• Phosphorus extreme pressure agent 2 acidic thiophosphate ester amine salt (C8 to C18 alkyl)
• the lubricating oil composition of the present invention is excellent in wear prevention, scoring prevention and oxidation stability.
• Comparative Example 1 with a low content of sulfur-based extreme pressure agent has insufficient scoring prevention properties
• Comparative Example 2 with a too high content of sulfur-based extreme pressure agent has poor oxidation stability.
• Comparative Example 3 using a sulfur-based extreme pressure agent having a high amount of active sulfur the wear resistance is not sufficient.
• the lubricating oil composition of the present invention can suppress the occurrence of wear on bearings and scoring on gear tooth surfaces even when the viscosity is lowered.
• the lubricating oil composition of the present invention can be suitably used as an automotive lubricating oil, and is particularly suitable as a transmission gear oil and a differential gear oil.

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• 2016
  • 2016-01-27 JP JP2016013271A patent/JP2017132875A/ja active Pending
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  • 2017-01-26 WO PCT/JP2017/002825 patent/WO2017131121A1/ja active Application Filing
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