WO2015056783A1

WO2015056783A1 - Lubricating oil composition

Info

Publication number: WO2015056783A1
Application number: PCT/JP2014/077707
Authority: WO
Inventors: 仁小松原; 紀子菖浦; 萌奈有山
Original assignee: Ｊｘ日鉱日石エネルギー株式会社
Priority date: 2013-10-18
Filing date: 2014-10-17
Publication date: 2015-04-23
Also published as: CN105658775A; CN105658775B; JPWO2015056783A1; MX2016004798A; US20160257905A1; US20200032159A1; JP6373857B2

Abstract

Provided is a lubricating oil composition having a kinematic viscosity of 50 mm²/s at 40°C and comprising: a lubricating oil base oil including 0.5%-70% by mass of an ester-based base oil relative to the entire volume of lubricating oil base oil, and having a kinematic viscosity of 18-28 mm²/s at 40°C; and 100-1,000 ppm by mass organic molybdenum compound, relative to the entire volume of lubricating oil composition.

Description

Lubricating oil composition

The present invention relates to a lubricating oil composition.

In recent years, there has been an urgent need to save energy in automobiles, construction machinery, agricultural machinery, etc., that is, to save fuel, in response to environmental issues such as reducing carbon dioxide emissions. Engines, transmissions, final reduction gears, compression Devices such as machines and hydraulic devices are strongly required to contribute to energy saving. Therefore, the lubricating oil used in these is required to further reduce the stirring resistance and the rotational resistance as compared with the conventional one.

One way to save fuel in transmissions and final reduction gears is to reduce the viscosity of lubricating oil. For example, among automatic transmissions, automatic transmissions for automobiles and continuously variable transmissions have torque converters, wet clutches, gear bearing mechanisms, oil pumps, hydraulic control mechanisms, etc., and manual transmissions and final reduction gears are gear bearings. By reducing the viscosity of the lubricating oil used in these mechanisms, the agitation resistance and rotational resistance of torque converters, wet clutches, gear bearing mechanisms, oil pumps, etc. are reduced, and power transmission efficiency As a result, the fuel efficiency of the automobile can be improved.

However, if the base oil viscosity is lowered and a large amount of viscosity index improver is blended in order to lower the viscosity and increase the viscosity index of the lubricating oil, extreme pressure resistance and wear resistance are caused by a decrease in the oil film thickness, which is a contradiction. The seizure may be reduced, and seizure or the like may occur, causing problems in the transmission or the like. Further, when the amount of the sulfur-based extreme pressure agent and the phosphorus-sulfur-based extreme pressure agent is increased in order to improve the extreme pressure property, the oxidation stability may be remarkably deteriorated.

As a conventional lubricating oil composition, a combination of mineral oil-based and / or synthetic oil-based lubricating base oil with various additives as fuel-saving performance and sufficient durability such as gears and bearings Has been proposed (see, for example, Patent Documents 1 and 2). However, even in such a lubricating oil composition, there is room for improvement in fuel efficiency.

JP 2008-208212 A JP 2009-249498 A

The present invention has been made in view of such circumstances, and has an object to provide a lubricating oil composition having extreme pressure and wear resistance capable of reducing fuel consumption and further reducing the friction coefficient between metals. And

In order to solve the above problems, the present invention provides a lubricating oil composition shown in the following [1] to [4], a use of the composition shown in the following [5], and a production of the composition shown in the following [6]. Provide use for.

[1] A lubricating base oil containing 0.5 to 70% by mass of an ester base oil and a kinematic viscosity at 40 ° C. of 18 to 28 mm ² / s, based on the total amount of the lubricating base oil, and a lubricating oil composition A lubricating oil composition comprising 100 to 1000 ppm by mass of an organic molybdenum compound in terms of molybdenum element, based on the total amount, and having a kinematic viscosity at 40 ° C. of 50 mm ² / s or less.
[2] Further containing 2% by mass or more of a copolymer of an α-olefin and an ester monomer having a polymerizable unsaturated bond, based on the total amount of the lubricating oil composition, and the weight average of the copolymer The lubricating oil composition according to [1], having a molecular weight of 2000 to 20000.
[3] The lubricating oil composition according to [1] or [2], further containing 100 to 500 ppm by mass of a boron-containing dispersant in terms of boron element based on the total amount of the lubricating oil composition.
[4] The lubricating oil composition according to any one of [1] to [3], which is used for a hypoid gear.
[5] Use of the composition as a hypoid gear lubricant, wherein the composition contains 0.5 to 70% by mass of an ester base oil based on the total amount of the lubricant base oil, and has a kinematic viscosity at 40 ° C. Containing a lubricating base oil having an A of 18 to 28 mm ² / s and an organic molybdenum compound of 100 to 1000 ppm by mass in terms of molybdenum based on the total amount of the lubricating oil composition, and a kinematic viscosity at 40 ° C. of 50 mm Use that is ² / s or less.
[6] Use of the composition for the production of a hypoid gear lubricant, wherein the composition contains 0.5 to 70% by mass of an ester base oil based on the total amount of the lubricant base oil, and is 40 ° C. Containing a lubricating base oil having a kinematic viscosity of 18 to 28 mm ² / s and an organic molybdenum compound of 100 to 1000 mass ppm in terms of molybdenum element based on the total amount of the lubricating oil composition. Use wherein the viscosity is 50 mm ² / s or less.

The kinematic viscosity referred to in the present invention means the kinematic viscosity defined in ASTM D-445. The viscosity index as used in the present invention means a viscosity index measured in accordance with JIS K 2283-1993.

According to the present invention, there is provided a lubricating oil composition that has sufficient extreme pressure and wear resistance and further reduces the coefficient of friction between metals. Therefore, when applied to a manual transmission, an automatic transmission, a continuously variable transmission, or an industrial gear system for automobiles, the fuel consumption is achieved while maintaining the necessary characteristics as gear oil, particularly hypoid gear oil. Can do.

Hereinafter, preferred embodiments of the present invention will be described.

The lubricating oil composition according to this embodiment comprises (A) 0.5 to 70% by mass of an ester base oil based on the total amount of the lubricating base oil, and a kinematic viscosity at 40 ° C. is 18 to 28 mm ² / s. A lubricant base oil, and (B) 100 to 1000 ppm by mass of an organic molybdenum compound in terms of molybdenum element, based on the total amount of the lubricant composition, and a kinematic viscosity at 40 ° C. of 50 mm ² / s or less is there.

[(A) component: lubricating base oil]
The lubricating oil composition of the present embodiment comprises (A) 0.5 to 70% by mass of an ester base oil based on the total amount of the lubricating base oil, and has a kinematic viscosity at 40 ° C. of 18 to 28 mm ² / s. Contains lubricating base oil.

The alcohol constituting the ester base oil may be a monohydric alcohol or a polyhydric alcohol (polyol), and the acid constituting the ester base oil may be a monobasic acid or a polybasic acid. Moreover, if it is a base oil containing an ester bond, a complex ester compound may be used.

As the monohydric alcohol, those having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms are usually used. Such alcohols may be linear or branched, It may be saturated or unsaturated. Specific examples of the alcohol having 1 to 24 carbon atoms include methanol, ethanol, linear or branched propanol, linear or branched butanol, and linear or branched pentanol. , Linear or branched hexanol, linear or branched heptanol, linear or branched octanol, linear or branched nonanol, linear or branched decanol , Linear or branched undecanol, linear or branched dodecanol, linear or branched tridecanol, linear or branched tetradecanol, linear or branched Pentadecanol, linear or branched hexadecanol, linear or branched heptadecanol, linear or branched octadecanol, linear or branched nonadecanol , Linear or branched icosa Lumpur, linear or branched Hen'ikosanoru, linear or branched Torikosanoru, such as straight-chain or branched tetracosanol, and mixtures thereof.

As the polyhydric alcohol (polyol), those having 2 to 10 valences, preferably 2 to 6 valences are usually used. Specific examples of the divalent to 10-valent polyhydric alcohol include, for example, ethylene glycol, diethylene glycol, polyethylene glycol (ethylene glycol tri- to 15-mer), propylene glycol, dipropylene glycol, polypropylene glycol (propylene glycol 3- 15-mer), 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,2-propanediol, 2-methyl-1, Dihydric alcohols such as 3-propanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentylglycol; glycerin, polyglycerin (glycerin 2 ~ 8 mer, such as diglycerin, trig Serine, tetraglycerin, etc.), trimethylol alkanes (trimethylol ethane, trimethylol propane, trimethylol butane, etc.) and their 2- to 8-mer, pentaerythritol and their 2- to 4-mer, 1,2,4- Butanetriol, 1,3,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,4-butanetetrol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, etc. Polysaccharides such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, and the like, and mixtures thereof. It is.

As the monobasic acid, a fatty acid having 2 to 24 carbon atoms is usually used. The fatty acid may be linear or branched, and may be saturated or unsaturated. Specifically, for example, acetic acid, propionic acid, linear or branched butanoic acid, linear or branched pentanoic acid, linear or branched hexanoic acid, linear or branched Branched heptanoic acid, linear or branched octanoic acid, linear or branched nonanoic acid, linear or branched decanoic acid, linear or branched undecanoic acid, Linear or branched dodecanoic acid, linear or branched tridecanoic acid, linear or branched tetradecanoic acid, linear or branched pentadecanoic acid, linear or branched Hexadecanoic acid, linear or branched heptadecanoic acid, linear or branched octadecanoic acid, linear or branched nonadecanoic acid, linear or branched icosanoic acid, direct Linear or branched heicosanoic acid, linear or branched docosanoic acid, linear or branched tricosanoic acid, Saturated fatty acids such as linear or branched tetracosanoic acid, acrylic acid, linear or branched butenoic acid, linear or branched pentenoic acid, linear or branched hexenoic acid, Linear or branched heptenoic acid, linear or branched octenoic acid, linear or branched nonenic acid, linear or branched decenoic acid, linear or branched Undecenoic acid, linear or branched dodecenoic acid, linear or branched tridecenoic acid, linear or branched tetradecenoic acid, linear or branched pentadecenoic acid, straight Linear or branched hexadecenoic acid, linear or branched heptadecenoic acid, linear or branched octadecenoic acid, linear or branched nonadecenoic acid, linear or branched Icosenoic acid, linear or branched henicosenoic acid, linear or branched docosenoic acid, linear or branched Jo of tricosenoic acid, unsaturated fatty acids such as straight-chain or branched tetracosenoic acid, and mixtures thereof.

Examples of the polybasic acid include dibasic acids having 2 to 16 carbon atoms and trimellitic acid. The dibasic acid having 2 to 16 carbon atoms may be linear or branched, and may be saturated or unsaturated. Specifically, for example, ethanedioic acid, propanedioic acid, linear or branched butanedioic acid, linear or branched pentanedioic acid, linear or branched hexanedioic acid, Linear or branched heptanedioic acid, linear or branched octanedioic acid, linear or branched nonanedioic acid, linear or branched decanedioic acid, linear Linear or branched undecanedioic acid, linear or branched dodecanedioic acid, linear or branched tridecanedioic acid, linear or branched tetradecanedioic acid, linear or Branched heptadecanedioic acid, linear or branched hexadecanedioic acid, linear or branched hexenedioic acid, linear or branched heptenedioic acid, linear or branched Octene diacid, linear or branched nonene diacid, linear or branched decenedioic acid, linear or branched undecenedioic acid, linear Is branched dodecenedioic acid, linear or branched tridecenedioic acid, linear or branched tetradecenedioic acid, linear or branched heptacenedioic acid, linear or branched Examples thereof include branched hexadecenedioic acid and a mixture thereof.

The combination of the alcohol and the acid forming the ester is arbitrary and is not particularly limited. Examples of the ester that can be used in the present invention include the following esters. These esters may be used alone, or 2 You may combine seeds or more.
(A) ester of monohydric alcohol and monobasic acid (b) ester of polyhydric alcohol and monobasic acid (c) ester of monohydric alcohol and polybasic acid (d) polyhydric alcohol and polybasic acid (E) Mixed ester of monohydric alcohol, mixture of polyhydric alcohol and polybasic acid (f) Mixed ester of polyhydric alcohol with monobasic acid, polybasic acid (g) Monohydric alcohol , Mixtures of polyhydric alcohols with monobasic acids and polybasic acids

Among these, (c) an ester of a monohydric alcohol and a polybasic acid is preferable because of excellent friction resistance and oxidation stability, and a dibasic acid which is an ester of a monohydric alcohol and a dibasic acid More preferably, it is an ester.

The content of the ester base oil is 0.5 to 70% by mass, preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably based on the total amount of the lubricating base oil. 3% by mass or more. Moreover, Preferably it is 60 mass% or less, More preferably, it is 55 mass% or less. When the content of the ester base oil is 0.5% by mass or more, extreme pressure properties, wear resistance, seizure resistance, and friction resistance tend to be excellent. Moreover, it exists in the tendency which is excellent in oxidation stability as ester base oil is 70 mass% or less.

The kinematic viscosity at 40 ° C. of the ester base oil is not particularly limited, but is preferably 5 mm ² / s or more, more preferably 6 mm ² / s or more, and further preferably 7 mm ² / s or more. Moreover, Preferably it is 50 mm < ² > / s or less, More preferably, it is 30 mm < ² > / s or less, More preferably, it is 20 mm < ² > / s or less. When the kinematic viscosity at 40 ° C. is 5 mm ² / s or more, or 50 mm ² / s or less, extreme pressure properties, wear resistance, and seizure resistance tend to be excellent.

The viscosity index of the ester base oil is not particularly limited, but is preferably 125 or more, more preferably 130 or more, and further preferably 135 or more. When the viscosity index is 125 or more, the low temperature fluidity tends to be excellent.

The pour point of the ester base oil is not particularly limited, but is preferably −30 ° C. or less, more preferably −50 ° C. or less, still more preferably −60 ° C. or less, and particularly preferably −70 ° C. It is as follows.

The flash point of the ester base oil is not particularly limited, but is preferably 200 ° C or higher, more preferably 250 ° C or higher, and further preferably 300 ° C or higher.

The lubricating base oil according to this embodiment may contain a base oil component other than the ester base oil as long as the ester base oil is 0.5 to 70% by mass based on the total amount of the lubricating base oil. it can. Base oil components other than the ester base oil are not particularly limited, and base oils used for ordinary lubricating oils can be used. Specifically, a mineral base oil, a synthetic base oil, or a mixture obtained by mixing two or more base oils selected from these at an arbitrary ratio can be used.

As mineral base oils, lubricating oil fractions obtained by subjecting crude oil to atmospheric distillation and reduced pressure distillation are subjected to solvent deburring, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid Mineral oil base oils such as paraffinic and naphthenic oils refined by combining purification treatments such as washing and clay treatment alone or in combination of two or more, base oils produced by catalytic dewaxing of normal paraffins, isoparaffins, petroleum waxes, etc. Is mentioned. These base oils may be used alone or in combination of two or more at any ratio.

Mineral oil base oils are base oils classified as Group II or Group III defined in API (American Petroleum Institute) Base Stock Categories from the viewpoint of lowering viscosity and sulfur content. Are preferred, and base oils classified in Group III are more preferred.

Synthetic base oils are produced from poly α-olefins or their hydrides, isobutene oligomers or their hydrides, isoparaffins, alkylbenzenes, alkylnaphthalenes, polyoxyalkylene glycols, dialkyldiphenyl ethers, polyphenyl ethers, and Fischer-Tropsch processes. Base oils produced by catalytic dewaxing of the wax.

The synthetic base oil is preferably a base oil produced by catalytic dewaxing of a wax produced from a poly α-olefin or a Fischer-Tropsch process. Specific examples of the poly α-olefin include oligomers or co-oligomers of 2 to 32 carbon atoms, preferably 6 to 16 carbon atoms (for example, 1-octene oligomer, 1-decene oligomer, 1-dodecene oligomer). , Ethylene-propylene co-oligomer and the like) and hydrides thereof.

There is no particular limitation on the production method of the poly α-olefin, but, for example, aluminum trichloride, boron trifluoride, or boron trifluoride and water, alcohol (for example, ethanol, propanol, or butanol), carboxylic acid, or ester ( For example, polymerization of α-olefin in the presence of a polymerization catalyst such as a Friedel-Crafts catalyst containing a complex with ethyl acetate or ethyl propionate) may be mentioned.

The kinematic viscosity of the lubricating base oil at 40 ° C. is 18 to 28 mm ² / s, preferably 20 mm ² / s or more, more preferably 22 mm ² / s or more. Moreover, Preferably it is 27 mm < ² > / s or less, More preferably, it is 26 mm < ² > / s or less. By setting the kinematic viscosity at 40 ° C. to 18 mm ² / s or more, it becomes possible to obtain a lubricating oil composition in which oil film formation is sufficient, lubricity is excellent, and evaporation loss of the base oil is small under high temperature conditions. . Further, by setting the kinematic viscosity at 40 ° C. to 28 mm ² / s or less, it is possible to obtain a lubricating oil composition having excellent low-temperature fluidity and low fluid resistance, and thus having a smaller rotational resistance.

The kinematic viscosity at 100 ° C. of the lubricating base oil is not particularly limited, but is preferably 1 mm ² / s or more, more preferably 3 mm ² / s or more, and further preferably 4 mm ² / s or more. Moreover, it is preferably 10 mm ² / s or less, more preferably 8 mm ² / s or less, and further preferably 6 mm ² / s or less. By setting the kinematic viscosity at 100 ° C. to 1 mm ² / s or more, it becomes possible to obtain a lubricating oil composition in which oil film formation is sufficient, lubricity is excellent, and evaporation loss of the base oil is small under high temperature conditions. . Moreover, it becomes possible to obtain the lubricating oil composition excellent in low-temperature fluidity | liquidity by making 100 degreeC kinematic viscosity 10 mm < ² > / s or less.

The viscosity index of the lubricating base oil is not particularly limited, but is preferably 120 or more, more preferably 125 or more, and further preferably 130 or more. By setting the viscosity index to 120 or more, it is possible to obtain a lubricating oil composition that exhibits good viscosity characteristics from low temperature to high temperature and is excellent in oxidation stability.

[(B) component: organic molybdenum compound]
The lubricating oil composition according to this embodiment contains 100 to 1000 ppm by mass of an organic molybdenum compound in terms of molybdenum element, based on the total amount of the lubricating oil composition, as a friction modifier. By combining with the component (A), the metal friction coefficient can be reduced and the fuel economy can be improved.

Examples of the organic molybdenum compound according to the present embodiment include sulfur-containing organic molybdenum compounds such as molybdenum dithiophosphate and molybdenum dithiocarbamate (MoDTC), molybdenum compounds (for example, molybdenum oxide such as molybdenum dioxide and molybdenum trioxide, and orthomolybdic acid. , Molybdate such as paramolybdic acid, (poly) sulfurized molybdate, metal salts of these molybdates, molybdate such as ammonium salt, molybdenum disulfide, molybdenum trisulfide, molybdenum pentasulfide, molybdenum sulfide such as polysulfide molybdenum , Sulfurized molybdic acid, metal salts or amine salts of sulfurized molybdic acid, molybdenum halides such as molybdenum chloride, etc.) and sulfur-containing organic compounds (eg, alkyl (thio) xanthate, thiadiazole, mercaptothiadi) Sol, thiocarbonate, tetrahydrocarbyl thiuram disulfide, bis (di (thio) hydrocarbyl dithiophosphonate) disulfide, organic (poly) sulfide, sulfide ester, etc.) or other organic compounds, molybdenum sulfide, sulfide And a complex of a sulfur-containing molybdenum compound such as molybdic acid and an alkenyl succinimide.

As the organic molybdenum compound, an organic molybdenum compound that does not contain sulfur as a constituent element can be used. Specific examples of organic molybdenum compounds that do not contain sulfur as a constituent element include molybdenum-amine complexes, molybdenum-succinimide complexes, molybdenum salts of organic acids, and molybdenum salts of alcohols. Complexes, molybdenum salts of organic acids and molybdenum salts of alcohols are preferred.

In the lubricating oil composition according to the present embodiment, the content of the organomolybdenum compound is 100 to 1000 ppm by mass in terms of molybdenum element, preferably 200 ppm by mass or more, based on the total amount of the lubricating oil composition. Preferably it is 300 mass ppm or more. Or it is 900 mass ppm or less preferably, More preferably, it is 800 mass ppm or less. When the content is 100 mass ppm or more, the wear resistance and the friction resistance tend to be excellent, and when the content is 1000 mass ppm or less, the seizure resistance tends to be excellent. In addition, the molybdenum element conversion amount of the organic molybdenum compound can be obtained by, for example, ICP elemental analysis.

The lubricating oil composition according to the present embodiment includes, as a viscosity modifier, 2 wt% or more of co-polymerized α-olefin and an ester monomer having a polymerizable unsaturated bond, based on the total amount of the lubricating oil composition. A coalescence may be further contained. The copolymer preferably has a weight average molecular weight of 2000 to 20000. By further containing such a copolymer, oil film retention and extreme pressure can be further improved.

The ester monomer having a polymerizable unsaturated bond is not particularly limited as long as it is a compound having a polymerizable unsaturated bond and an ester bond, but at least one of the α carbon and β carbon of the carboxy group is ethylenically unsaturated. An α, β-ethylenically unsaturated dicarboxylic acid diester which is a diester of an unsaturated dicarboxylic acid forming a saturated bond (ie, C═C double bond) is preferred. Here, the α, β-ethylenically unsaturated dicarboxylic acid forms an ethylenically unsaturated bond with respect to both carboxy groups such as maleic acid, fumaric acid, citraconic acid, and mesaconic acid. And α, β-ethylenically unsaturated bonds are not limited to compounds present in the main chain, and only one carboxy group such as glutaconic acid has α and β carbons that are ethylenic. It is a concept that includes a compound having an unsaturated bond, and also includes a compound in which an α, β-ethylenically unsaturated bond is found in the side chain, such as itaconic acid.

The structure of the copolymer of the α-olefin and the ester monomer having a polymerizable unsaturated bond is not particularly limited as long as the weight average molecular weight is 2000 to 20000. Further, the production method is not particularly limited, and those produced by a known method can be used.

The weight average molecular weight (Mw) of the copolymer of an α-olefin and an ester monomer having a polymerizable unsaturated bond is 2000 to 20000, preferably 4000 or more, more preferably 6000 or more. Moreover, Preferably it is 15000 or less, More preferably, it is 12000 or less. By setting the weight average molecular weight to 2000 to 20000, it is possible to improve oil film retention and extreme pressure properties.
Here, the weight average molecular weight means that two columns of GHSHR-M (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation are used in series in a 150-C ALC / GPC apparatus manufactured by Waters, and tetrahydrofuran is used as a solvent. It is a weight average molecular weight in terms of standard polystyrene measured using a differential refractometer (RI) detector under conditions of a temperature of 23 ° C., a flow rate of 1 mL / min, a sample concentration of 1 mass%, and a sample injection amount of 75 μL.

In the lubricating oil composition according to the present embodiment, the copolymer content is preferably 2% by mass or more, more preferably 2.5% by mass or more, based on the total amount of the lubricating oil composition. More preferably, it is 3.5 mass% or more. By setting the content of the copolymer to 2% by mass or more, extreme pressure properties and abrasion resistance tend to be more excellent. On the other hand, the upper limit of the content is not particularly limited, but is preferably 25% by mass or less, more preferably 24% by mass or less, and further preferably 22% by mass or less. When the content of the component (D) is 25% by mass or less, sufficient extreme pressure property, abrasion resistance, seizure resistance, friction resistance and oxidation stability tend to be exhibited.

The lubricating oil composition according to this embodiment may further contain 100 to 500 mass ppm of a boron-containing dispersant in terms of boron element based on the total amount of the lubricating oil composition. Thereby, oil film retainability and extreme pressure property can be further improved.

Boron-containing dispersant is a borated ashless dispersant. Examples of the ashless dispersant include a nitrogen-containing compound having at least one linear or branched alkyl group or alkenyl group having 40 to 400 carbon atoms or a derivative thereof, a modified product of alkenyl succinimide, and the like. Can be mentioned. One or more kinds arbitrarily selected from these can be blended.

The succinimide includes a so-called monotype succinimide represented by the general formula (3) in which succinic anhydride is added to one end of the polyamine, and a general formula in which succinic anhydride is added to both ends of the polyamine ( And so-called bis-type succinimide represented by 4).

In the general formula (3), R ⁹ represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably an alkyl group or alkenyl group having 60 to 350 carbon atoms, and p is 1 to 5, preferably 2 to 4. Indicates an integer.
In the general formula (4), R ¹⁰ and R ¹¹ may be the same or different and each represents an alkyl group or alkenyl group having 40 to 400 carbon atoms, preferably an alkyl group or alkenyl group having 60 to 350 carbon atoms, A polybutenyl group is preferred. q represents an integer of 0 to 4, preferably 1 to 3.

The lubricating oil composition according to this embodiment may contain one of mono-type or bis-type succinimides, or may contain both.

The production method of the succinimide is not particularly limited. For example, an alkyl succinic acid or alkenyl succinic acid obtained by reacting a compound having an alkyl group or alkenyl group having 40 to 400 carbon atoms with maleic anhydride at 100 to 200 ° C. is used as a polyamine. It can obtain by making it react. Specific examples of the polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

In the lubricating oil composition according to this embodiment, the content of the boron-containing dispersant is preferably 100 to 500 ppm by mass in terms of boron element, more preferably 150 ppm by mass, based on the total amount of the lubricating oil composition. It is above, More preferably, it is 200 mass ppm or more. More preferably, it is 450 mass ppm or less, More preferably, it is 400 mass ppm or less. When the content is 100 ppm by mass or more, extreme pressure properties, wear resistance, seizure resistance, and friction resistance tend to be excellent. Moreover, it exists in the tendency for it to be excellent with friction resistance as the content is 500 mass ppm or less. In addition, the boron element conversion amount of a boron containing dispersing agent can be calculated | required by the ICP elemental analysis method etc., for example.

The lubricating oil composition according to this embodiment may contain any additive generally used in lubricating oils depending on the purpose in order to further improve its performance. Examples of such additives include viscosity modifiers other than the above-mentioned copolymers, metal-based detergents, ashless dispersants other than boron-containing dispersants, antiwear agents (or extreme pressure agents), antioxidants, and corrosion. Examples thereof include additives such as an inhibitor, a rust inhibitor, a demulsifier, a metal deactivator, an antifoaming agent, and a friction modifier other than the component (B).

The viscosity modifier other than the copolymer is specifically a non-dispersed or dispersed ester group-containing viscosity modifier, such as a non-dispersed or dispersed poly (meth) acrylate viscosity modifier, non-dispersed. Type or dispersion type olefin- (meth) acrylate copolymer-based viscosity modifier, styrene-maleic anhydride copolymer-based viscosity modifier, and mixtures thereof. Among these, non-dispersed or dispersed poly (meta) ) An acrylate viscosity modifier is preferred. In particular, non-dispersed or dispersed polymethacrylate viscosity modifiers are preferred.

Other viscosity modifiers other than the above-mentioned copolymers include non-dispersed or dispersed ethylene-α-olefin copolymers or hydrides thereof, polyisobutylene or hydrides thereof, styrene-diene hydrogenated copolymers, Examples thereof include polyalkylstyrene.

Examples of metal detergents include sulfonate detergents, salicylate detergents, phenate detergents, and the like, including any of normal salts, basic normal salts, and overbased salts with alkali metals or alkaline earth metals. Can be blended. In use, one kind or two or more kinds arbitrarily selected from these can be blended.

As the ashless dispersant other than the boron-containing dispersant, any non-boron ashless dispersant used in lubricating oils can be used. For example, a linear or branched alkyl group or alkenyl group having 40 to 400 carbon atoms can be used. Mono- or bissuccinimide having at least one in the molecule, benzylamine having at least one alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule, an alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule Examples include polyamines having at least one, modified products of these carboxylic acids, phosphoric acids, and the like. In use, one kind or two or more kinds arbitrarily selected from these can be blended.

As the antiwear agent (or extreme pressure agent), any antiwear agent / extreme pressure agent used in lubricating oils can be used. For example, sulfur-based, phosphorus-based, sulfur-phosphorus extreme pressure agents and the like can be used. Specifically, zinc dialkyldithiophosphate (ZnDTP), phosphites, thiophosphites, dithiophosphites Acid esters, trithiophosphites, phosphate esters, thiophosphate esters, dithiophosphate esters, trithiophosphate esters, amine salts thereof, metal salts thereof, derivatives thereof, dithiocarbamate, zinc dithio Carbamate, MoDTC, disulfides, polysulfides, sulfurized olefins, sulfurized fats and oils, and the like can be given. Among these, addition of a sulfur-based extreme pressure agent is preferable, and sulfurized fats and oils are particularly preferable.

Examples of the antioxidant include ashless antioxidants such as phenols and amines, and metal antioxidants such as copper and molybdenum. Specifically, for example, phenol-based ashless antioxidants include 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert- Examples of amine-based ashless antioxidants include phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine, and dialkyldiphenylamine.

Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.

Examples of the rust preventive include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.

Examples of the demulsifier include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether.

Examples of the metal deactivator include imidazoline, pyrimidine derivatives, alkylthiadiazole, mercaptobenzothiazole, benzotriazole or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolyl-2,5-bis. Examples thereof include dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole, β- (o-carboxybenzylthio) propiononitrile.

Examples of the antifoaming agent include silicone oil having a kinematic viscosity at 25 ° C. of 1,000 to 100,000 mm ² / s, alkenyl succinic acid derivative, ester of polyhydroxy aliphatic alcohol and long chain fatty acid, methyl salicylate and o- Examples thereof include esters with hydroxybenzyl alcohol.

Examples of the friction modifier other than the component (B) include ashless friction modifiers, and any compound usually used as an ashless friction modifier for lubricating oils can be used. Having at least one hydrocarbon group, preferably an alkyl group or an alkenyl group, particularly a straight-chain alkyl group or straight-chain alkenyl group having 6 to 30 carbon atoms in the molecule, amine-based, imide-based, fatty acid ester-based, fatty acid amide Ashless friction modifiers such as those based on fatty acids, fatty alcohols, aliphatic alcohols, and aliphatic ethers.

When these additives are contained in the lubricating oil composition according to this embodiment, the content of each additive is preferably 0.01 to 20% by mass based on the total amount of the lubricating oil composition.

The kinematic viscosity at 40 ° C. of the lubricating oil composition according to this embodiment is 50 mm ² / s or less, preferably 48 mm ² / s or less, more preferably 45 mm ² / s or less. By setting the kinematic viscosity at 40 ° C. to 50 mm ² / s or less, the necessary low-temperature fluidity and sufficient fuel saving performance tend to be obtained. Further, the lower limit value of the kinematic viscosity at 40 ° C. of the lubricating oil composition according to the present embodiment is not particularly limited, but is preferably 20 mm ² / s or more, more preferably 30 mm ² / s or more, and still more preferably. Is 35 mm ² / s or more. By setting the kinematic viscosity at 40 ° C. to 20 mm ² / s or more, it tends to be more excellent in oil film retention and evaporability at the lubrication site.

The lubricating oil composition according to the present embodiment has sufficient extreme pressure and wear resistance capable of reducing fuel consumption, and further can reduce the coefficient of friction between metals. It can be suitably used as gear oil for a transmission, continuously variable transmission or industrial gear system, particularly as a hypoid gear oil for driving systems of automobiles and railway vehicles.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.

(Examples 1 to 18 and Comparative Examples 1 to 4)
As shown in Tables 1 and 2, lubricating oil compositions of Examples 1 to 18 and Comparative Examples 1 to 4 were prepared, respectively. The resulting lubricating oil composition was measured for extreme pressure properties, abrasion resistance, seizure resistance, friction resistance and oxidation stability, and the results are also shown in Tables 1 and 2.

Details of each component shown in Table 1 and Table 2 are as follows.
Base oil A-1: Poly α-olefin [Group IV, kinematic viscosity at 40 ° C .: 19 mm ² / s, kinematic viscosity at 100 ° C .: 4.1 mm ² / s, viscosity index: 126, pour point: −66 ° C., flash point : 220 ° C]
Base oil A-2: Poly α-olefin [Group IV, kinematic viscosity at 40 ° C .: 30.3 mm ² / s, kinematic viscosity at 100 ° C .: 5.9 mm ² / s, viscosity index: 142, pour point: <−54 ° C. Flash point: 246 ° C]
Base oil A-3: poly α-olefin [Group IV, kinematic viscosity at 40 ° C .: 48 mm ² / s, kinematic viscosity at 100 ° C .: 8.0 mm ² / s, viscosity index: 139, pour point: −48 ° C., flash point : 260 ° C]
Base oil A-4: Poly α-olefin [Group IV, kinematic viscosity at 40 ° C .: 396 mm ² / s, kinematic viscosity at 100 ° C .: 39 mm ² / s, viscosity index: 147, pour point: −36 ° C., flash point: 281 ° C]
Base oil A-5: hydrorefined mineral oil [Group III, kinematic viscosity at 40 ° C .: 33.97 mm ² / s, kinematic viscosity at 100 ° C .: 6.208 mm ² / s, viscosity index: 133, sulfur content: less than 10 ppm by mass ,% C _P : 80.6,% C _N : 19.4,% C _A : 0]
Base oil B-1: dibasic acid ester [Group V, azelaic acid + 2 ethylhexanol, 40 ° C. kinematic viscosity: 10.3 mm ² / s, 100 ° C. kinematic viscosity: 2.9 mm ² / s, viscosity index: 138, flow Point: -72 ° C, flash point: 220 ° C]
Organic molybdenum compound F-1: Molybdenum dithiocarbamate (MoDTC) [Molybdenum element conversion: 10% by mass]
Boron-containing dispersant G-1: Boronated succinimide [in terms of boron element: 2.0% by mass, nitrogen in terms of element: 2.3% by mass, weight average molecular weight: 1000]
Non-boron dispersant H-1: Succinimide [nitrogen element conversion: 2.3 mass%, weight average molecular weight: 1000]
Performance additive C-1: Additive package containing phosphorus-based antiwear agent, sulfur-based extreme pressure agent, metal deactivator, friction modifier, antifoaming agent, etc. [phosphorus element conversion: 1.40% by mass, sulfur Element conversion: 22.9% by mass]
Viscosity modifier J-1: Copolymer of α-olefin and α, β-ethylenically unsaturated dicarboxylic acid diester [weight average molecular weight: 10,000]
Viscosity modifier J-2: Copolymer of α-olefin and α, β-ethylenically unsaturated dicarboxylic acid diester [weight average molecular weight: 7000]
Viscosity modifier J-3: oligomer of ethylene and α-olefin [number average molecular weight: 3700]

The molybdenum element equivalent amount in the organic molybdenum compound, the boron element equivalent amount in the boron-containing dispersant, the phosphorus element equivalent amount and the sulfur element equivalent amount in the performance additive were determined by ICP elemental analysis.

(1) Extreme pressure test In accordance with ASTM D 2596, a maximum non-seizure load (LNSL) at 1800 revolutions of each lubricating oil composition was measured using a high-speed four-ball tester. In this test, the larger the maximum non-seizure load, the better the extreme pressure property.
(2) Abrasion resistance test A four-ball test (ASTM D4172) was conducted under the following conditions, and the wear scar diameter (mm) was measured to evaluate the abrasion resistance. In this test, the smaller the wear scar diameter, the better the wear resistance.
Load: 800N
Rotation speed: 1800rpm
Temperature: 80 ° C
Test time: 30 minutes (3) Seizure resistance test Using a Falex tester described in ASTM D3233, seizure load was measured and seizure resistance was evaluated. This seizure resistance indicates the extreme pressure between steels. Test conditions are shown below. In this test, the larger the seizure load, the better the seizure resistance.
Temperature: 110 ° C
Rotation speed: 290rpm
(4) Friction resistance test Using a block-on-ring tester (LFW-1) described in ASTM D2174, the friction coefficient was measured under the following test conditions. Moreover, in this test, the friction coefficient was calculated | required about both the new oil of a lubricating oil composition, and the deteriorated oil which performed the oxidation stability test mentioned later at 135 degreeC for 48 hours. In this test, the smaller the friction coefficient, the better the friction resistance.
Ring: Falex S-10 Test Ring (SAE4620 Steel)
Block: Falex H-60 Test Block (SAE01 Steel)
Oil temperature: 90 ° C
Load: 222-3113N
Sliding speed: 0.5m / s
(5) Oxidation stability test JIS K 2514 The acid value increase was measured under the following conditions in accordance with (Oxidation stability test method for lubricating oil for internal combustion engines). In this test, the smaller the acid value increase, the better the oxidation stability.
Temperature: 135 ° C
Test time: 96 hours

As is clear from Tables 1 and 2, the lubricating oil compositions of Examples 1 to 18 were compared with the lubricating oil compositions of Comparative Examples 1 to 4 in terms of extreme pressure, abrasion resistance, seizure resistance, It was found that the friction resistance and oxidation stability were excellent, and the coefficient of friction between metals was small.

Claims

A lubricating base oil containing 0.5 to 70% by mass of an ester base oil and a kinematic viscosity at 40 ° C. of 18 to 28 mm 2 / s, based on the total amount of the lubricating base oil;
Based on the total amount of the lubricating oil composition, 100 to 1000 ppm by mass of an organic molybdenum compound in terms of molybdenum element;
And a kinematic viscosity at 40 ° C. of 50 mm 2 / s or less.
Further containing 2% by mass or more of a copolymer of an α-olefin and an ester monomer having a polymerizable unsaturated bond, based on the total amount of the lubricating oil composition, and the weight average molecular weight of the copolymer is 2000 The lubricating oil composition of claim 1, wherein the lubricating oil composition is ˜20,000.
The lubricating oil composition according to claim 1 or 2, further comprising 100 to 500 ppm by mass of a boron-containing dispersant in terms of boron element based on the total amount of the lubricating oil composition.
The lubricating oil composition according to any one of claims 1 to 3, which is used for a hypoid gear.