WO2011083601A1 - Lubricant composition - Google Patents

Lubricant composition Download PDF

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WO2011083601A1
WO2011083601A1 PCT/JP2010/066708 JP2010066708W WO2011083601A1 WO 2011083601 A1 WO2011083601 A1 WO 2011083601A1 JP 2010066708 W JP2010066708 W JP 2010066708W WO 2011083601 A1 WO2011083601 A1 WO 2011083601A1
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preferably
viscosity
less
lubricating
oil
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PCT/JP2010/066708
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French (fr)
Japanese (ja)
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松井 茂樹
矢口 彰
明男 武藤
麻里 長永
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Jx日鉱日石エネルギー株式会社
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C10M171/02Specified values of viscosity or viscosity index
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102Aliphatic fractions
    • C10M2203/1025Aliphatic fractions used as base material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26Overbased carboxylic acid salts
    • C10M2207/262Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/08Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
    • C10M2209/084Acrylate; Methacrylate
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28Amides; Imides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06Thio-acids; Thiocyanates; Derivatives thereof
    • C10M2219/062Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
    • C10M2219/066Thiocarbamic type compounds
    • C10M2219/068Thiocarbamate metal salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/045Metal containing thio derivatives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2220/00Specified physical or chemical properties or characteristics, i.e. function, of single compounds in lubricating compositions
    • C10N2220/02Physico-chemical properties
    • C10N2220/021Molecular weight
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2220/00Specified physical or chemical properties or characteristics, i.e. function, of single compounds in lubricating compositions
    • C10N2220/02Physico-chemical properties
    • C10N2220/022Viscosity
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2220/00Specified physical or chemical properties or characteristics, i.e. function, of single compounds in lubricating compositions
    • C10N2220/02Physico-chemical properties
    • C10N2220/033Shear stability
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2230/00Specified physical or chemical properties of lubricating compositions
    • C10N2230/06Resistance to extreme pressure; Oiliness; Abrasion resistance; Friction; Anti-wear
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2230/00Specified physical or chemical properties of lubricating compositions
    • C10N2230/52Base number (TBN)
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2230/00Specified physical or chemical properties of lubricating compositions
    • C10N2230/54Fuel economy
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2240/00Specified uses or applications of lubricating compositions
    • C10N2240/04Gear oil
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2240/00Specified uses or applications of lubricating compositions
    • C10N2240/10Internal-combustion engines
    • C10N2240/102Diesel engines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2240/00Specified uses or applications of lubricating compositions
    • C10N2240/10Internal-combustion engines
    • C10N2240/104Gasoline engines

Abstract

Disclosed is a lubricant composition containing: a lubricant base oil which has a kinematic viscosity of 1 to 20mm2/s at 100°C; a viscosity index improver (A) which has a 13C-NMR spectrum in which the ratio between the total area (M1) of a peak having a chemical shift from 36 to 38ppm and the total area (M2) of a peak having a chemical shift from 64 to 66ppm is 0.20 or more (M1/M2) in relation to the total area of all peaks; a friction modifier (B); and an overbased metal salt (C) which is obtained by over-basifying an oil-soluble metal salt with a boric acid salt of an alkali earth metal.

Description

Lubricating oil compositions

The present invention relates to a lubricating oil composition.

Conventionally, internal combustion engines and transmissions, other mechanical devices, the lubricating oil is used to smooth the operation thereof. In particular an internal combustion engine lubricating oil (engine oil) is high performance of an internal combustion engine, higher output, due to such harsh of operating conditions, high performance is required. Accordingly, To meet these performance requirements to a conventional engine oils, antiwear agents, metallic detergents, ashless dispersants, various additives such as antioxidants is blended (e.g., Patent Documents 1 to see 3.). The recent, fuel saving performance required for lubricating oil has become higher and higher, such as applying a high viscosity index base oil applications or various friction modifiers has been studied (for example, see Patent Document 4.) .

JP 2001-279287 JP JP 2002-129182 JP JP 08-302378 discloses JP 06-306384 discloses

However, not always sufficient in the conventional lubricating oil in terms of fuel economy.

For example, as a method for general fuel saving, improvement in reduction and viscosity index of the kinematic viscosity of the lubricating oil (Multigrade of by a combination of low viscosity base oil and a viscosity index improver) are known. However, such a case approach, due to the reduction of viscosity of the base oil constituting the lubricant or it reduces the lubrication performance under severe lubrication conditions (high temperature and high shear conditions), wear and seizure, fatigue the occurrence of problems such as destruction is a concern. That is, in the conventional lubricating oil, while maintaining the other practical performance such as durability, it is difficult to impart sufficient fuel savings.

Then, while maintaining the durability by preventing the above problem, in order to impart fuel economy is, HTHS viscosity at 0.99 ° C. ( "HTHS viscosity". Which is also referred to as "high-temperature high-shear viscosity") high, kinematic viscosity at while 40 ° C., it is effective to reduce the HTHS viscosity at a kinematic viscosity and 100 ° C. at 100 ° C., in the conventional lubricating oils to meet all of these requirements is very difficult. Further, only to reduce the viscosity, it is known to increase the coefficient of friction of boundary lubrication region in which the metal contact each other. To improve fuel economy, it is necessary to reduce together the friction coefficient of the boundary lubrication region.

The present invention has been made in view of such circumstances, while maintaining the HTHS viscosity at 0.99 ° C., a kinematic viscosity at 40 ° C., to sufficiently lower the HTHS viscosity at a kinematic viscosity and 100 ° C. at 100 ° C. It can be, also, an increase in the coefficient of friction of boundary lubrication region can be sufficiently suppressed, and to provide an excellent lubricating oil composition fuel economy.

In order to solve the above problems, the present invention comprises a lubricating base oil kinematic viscosity of 1 ~ 20mm 2 / s at 100 ° C., in a spectrum obtained by (A) 13 C-NMR, the total area of all peaks a viscosity index improver ratio M1 / ​​M2 of the total area M2 of the peaks between the total area M1 and chemical shift 64-66ppm of peaks between the chemical shifts 36-38ppm is 0.20 or more with respect to, (B) friction provides a modifier, a lubricating oil composition containing, overbased metal salts has been overbased with (C) an oil-soluble metal salt of an alkaline earth metal borate.

(A) above viscosity index improver is preferably a poly (meth) acrylate based viscosity index improver.

Further, the (A) viscosity index improver, PSSI of 40 or less and a ratio of weight average molecular weight and PSSI is of 1 × 10 4 or more.

Here, the term "PSSI" in the present invention, conforming to ASTM D 6022-01 (Standard Practice for Calculation of Permanent Shear Stability Index), ASTM D 6278-02 (Test Metohd for Shear Stability of Polymer Containing Fluids Using a european Diesel Injector Apparatus) was calculated based on the measured data by means permanent shear stability index of polymer (permanent shear stability index).

Further, the (B) the friction modifier is preferably an organic molybdenum compound.

Further, the (C) overbased oil-soluble metal salt overbased metal salts and overbased alkaline earth metal borate salt is obtained by overbasing an alkaline earth metal salicylate with an alkaline earth metal borate it is preferably a sex alkaline earth metal salicylates.

As described above, according to the present invention, while maintaining the HTHS viscosity at 0.99 ° C., a kinematic viscosity at 40 ° C., it is possible to sufficiently lower the HTHS viscosity at a kinematic viscosity and 100 ° C. at 100 ° C., The boundary lubrication it is possible to sufficiently suppress an increase in the friction coefficient of the region, it is possible to provide an excellent lubricating oil composition fuel economy. For example, according to the lubricating oil composition of the present invention, without using a synthetic oil or a low viscosity mineral base oil poly -α- olefin base oil and ester based base oil, the desired HTHS viscosity at 0.99 ° C. while maintaining the value, it is possible to exhibit sufficient fuel savings.

The lubricating oil composition of the present invention, a motorcycle, a four-wheel vehicles, power generation, gasoline engines, such as cogeneration, diesel engines, can also be suitably used in gas engines, etc., and further, the sulfur content 50 mass ppm not only be suitably used for these various engines that use less fuel, marine, also useful for various engines for outboard motors.

It will be described in detail preferred embodiments of the present invention.

The lubricating oil composition according to the present embodiment, a lubricating base oil having kinematic viscosity of 1 ~ 20mm 2 / s at 100 ° C., in a spectrum obtained by (A) 13 C-NMR, to the sum area of all peaks a viscosity index improver ratio M1 / ​​M2 of the total area M2 of the peaks between the total area M1 and chemical shift 64-66ppm peak is 0.20 or more between the chemical shift 36-38ppm, (B) a friction modifier agent, containing, and overbased metal salts and overbased with (C) an oil-soluble metal salt of an alkaline earth metal borate.

In the lubricating oil composition according to the present embodiment, a kinematic viscosity at 100 ° C. is 1 ~ 20mm 2 / s lubricating base oil (hereinafter, referred to as "lubricating base oil of the present embodiment".) Are used .

The lubricating base oil of the present embodiment, for example, a lubricating oil fraction obtained by atmospheric distillation and / or vacuum distillation of crude oil, solvent deasphalting, solvent extraction, hydrocracking, hydroisomerization , solvent dewaxing, catalytic dewaxing, hydrorefining, paraffinic mineral oil was purified alone or in combination of two or more kinds of purification processes such as sulfuric acid washing, clay treatment or the normal paraffinic base oil, among such isoparaffinic base oil, kinematic viscosity at 100 ° C. can be mentioned those of 1 ~ 20mm 2 / s.

Preferred examples of the lubricating base oil of the present embodiment, the base oil shown below (1) to (8) as a raw material, a lubricating oil fraction recovered from the feedstock and / or the feedstock, purification by predetermined purification method include a base oil obtained by recovering a lubricating oil fraction.
(1) paraffinic base crude and / or mixed base crude atmospheric distillation according distillate oil (2) paraffin-base crude and / or mixed base crude atmospheric residue distillate by vacuum distillation ( WVGO)
(3) wax obtained by a lubricating oil dewaxing process (slack wax) and / or gas-to-liquid (GTL) is synthetic wax obtained by a process such as (Fischer-Tropsch wax, GTL wax and the like)
(4) selected from the base oils (1) to (3) of one or more mixing oil and / or the mixed oil of the mild hydrocracking process oil selected (5) base oil (1) to (4) a mixture of two or more oil (6) base oil (1) to (2), (3), (4) or (5) of the deasphalted oil (DAO)
(7) mild hydrocracking process oil base oil (6) (MHC)
(8) base oil (1) to a mixture of two or more oils selected from (7).

As the predetermined purification process, hydrocracking, hydrotreating, such as hydrofinishing, due acid clay or activated clay; dewaxing such as solvent dewaxing and catalytic dewaxing; solvent refining such as furfural solvent extraction clay purification; washing sulfate, chemicals (acid or alkali) such as sodium hydroxide wash cleaning, etc. are preferable. In the present invention, may be carried out one of these purification methods alone, it may be performed in combination of two or more. Further, when combining two or more purification methods, the order is not particularly limited and can be appropriately selected.

Furthermore, as the lubricating base oil of the present embodiment, obtained by performing a predetermined process for lubricating oil fraction recovered from the base oil or the base oil selected from the base oils (1) - (8) are the following base oil (9) or (10) is particularly preferred.
(9) the base oil (1) to the lubricating oil fraction recovered from the base oil or the base oil selected from (8) by hydrogenolysis, is recovered by distillation or the like from the product or product thereof lubricating oil fraction for solvent dewaxing and catalytic dewaxing perform dewaxing process such as, or hydrocracked mineral oil obtained by distillation after the dewaxing (10) above base oil (1) - (8 the lubricating oil fraction recovered from the base oil or the base oil selected from) was hydroisomerized, the product or solvent dewaxing or catalytic dewaxing the lubricating oil fraction recovered by distillation or the like from the product perform dewaxing process such as, or hydroisomerized mineral oil obtained by distillation after you the dewaxing process.

Further, in obtaining a lubricating base oil of the above (9) or (10), at a convenient step, may further be provided solvent refining process and / or hydrofinishing treatment step as necessary.

Also, the catalyst used in the hydrocracking-hydroisomerization is not particularly limited, complex oxide having a decomposition activity (e.g., silica alumina, alumina boria, silica zirconia, and the like) or one of the composite oxide what was sintered wearing the binder as a carrier or in combination, metals (e.g., 1 or more, such as periodic table group VIa metals and group VIII metals) hydrocracking was supported with hydrogen Kano catalyst or zeolite (e.g. ZSM-5, zeolite beta, SAPO-11, etc.) carrier group VIII of the hydroisomerization catalyst supported metal having hydrogen Kano comprising at least one or more of metals including, It is preferably used. Hydrocracking catalyst and hydroisomerization catalyst may be used in combination such as by laminating or mixing.

The reaction conditions for hydrocracking, hydroisomerization is not particularly limited, hydrogen partial pressure 0.1 ~ 20 MPa, the average reaction temperature of 150 ~ 450 ℃, LHSV0.1 ~ 3.0hr-1, hydrogen / oil ratio preferably in the 50 ~ 20000scf / b.

Kinematic viscosity at 100 ° C. of the lubricating base oil of the present embodiment is required to be less 20 mm 2 / s, preferably 10 mm 2 / s or less, more preferably 7 mm 2 / s or less, more preferably 5.0 mm 2 / s or less, particularly preferably 4.5 mm 2 / s or less, and most preferably not more than 4.0 mm 2 / s. On the other hand, the kinematic viscosity at the 100 ° C. is required to be 1 mm 2 / s or more, preferably 1.5 mm 2 / s or more, more preferably 2 mm 2 / s or more, more preferably 2. 5 mm 2 / s or more, particularly preferably 3 mm 2 / s or more. The kinematic viscosity at 100 ° C. in the present invention, showing a kinematic viscosity at 100 ° C., which is measured according to ASTM D-445. When the kinematic viscosity at 100 ° C. of the lubricating base oil exceeds 20 mm 2 / s, the worse the low temperature viscosity characteristics, also there is a risk that can not be obtained sufficient fuel saving properties, the following cases 1 mm 2 / s poor lubricity oil film formation at lubricating sites is insufficient, also there is a possibility that the evaporation loss of the lubricating oil composition is increased.

In the present invention, it was collected by the lubricating oil base oil distillation kinematic viscosity in the range of below at 100 ° C. min, preferably used.
(I) less than the kinematic viscosity at 100 ° C. is 1.5 mm 2 / s or more 3.5 mm 2 / s, more preferably 2.0 ~ 3.0mm 2 / s lubricating base oils (II) a kinematic viscosity at 100 ° C. There 3.5 mm 2 / s or more 4.5mm less than 2 / s, more preferably 3.7 ~ 4.3mm 2 / s lubricating base oil (III) a kinematic viscosity at 100 ° C. is 4.5 ~ 10 mm 2 / s, more preferably 4.8 ~ 9 mm 2 / s, particularly preferably 5.5 ~ 8.0mm 2 / s lubricating base oils.

Moreover, kinematic viscosity at 40 ° C. of the lubricating base oil of the present embodiment is preferably 80 mm 2 / s or less, more preferably 50 mm 2 / s or less, more preferably 20 mm 2 / s or less, particularly preferably 18 mm 2 / s, and most preferably not more than 16 mm 2 / s. On the other hand, the 40 ° C. kinematic viscosity is preferably 6.0 mm 2 / s or more, more preferably 8.0 mm 2 / s or more, more preferably 12 mm 2 / s or more, particularly preferably 14 mm 2 / s or more, and most preferably is 15mm 2 / s or more. If the 40 ° C. kinematic viscosity of the lubricating base oil exceeds 80 mm 2 / s, the low temperature viscosity characteristics are deteriorated, and there may not be obtained sufficient fuel savings, if: 6.0 mm 2 / s it is inferior in lubricity because its insufficient oil film formation at lubricating sites, also there is a possibility that the evaporation loss of the lubricating oil composition is increased. In the present invention, aliquoted by the lubricating oil fractions kinematic viscosity in the range of below distillation or the like at 40 ° C., preferably used.
(IV) below 40 kinematic viscosity at ℃ is 6.0 mm 2 / s or more 12 mm 2 / s, more preferably 8.0 ~ 12mm 2 / s lubricating base oil (V) kinematic viscosity at 40 ℃ is 12 mm 2 / s or more 28mm less than 2 / s, more preferably 13 ~ 19 mm 2 / s of the lubricating base oil (VI) kinematic viscosity at 40 ° C. is 28 ~ 50 mm 2 / s, more preferably 29 ~ 45mm 2 / s, particularly preferably lubricating base oil of 30 ~ 40mm 2 / s.

The viscosity index of the lubricating base oil of the present embodiment is preferably 120 or more. The viscosity index of the lubricating base oils (I) and (IV) is preferably 120-135, more preferably 120-130. The viscosity index of the lubricating base oils (II) and (V) is preferably from 120 to 160, more preferably 125-150, more preferably 135-145. The viscosity index of the lubricating base oils (III) and (VI) is preferably from 120 to 180, more preferably 125 to 160. When the viscosity index is less than the lower limit, the viscosity - temperature characteristic and heat and oxidation stability, as well as anti-evaporation deteriorates, there is a tendency that the friction coefficient is increased, also, tend to anti-wear properties is reduced It is in. Further, the viscosity index exceeds the upper limit, there is a tendency that the low-temperature viscosity characteristics are deteriorated.

Incidentally, a viscosity index in the present invention means a measured viscosity index in conformity with JIS K 2283-1993.

The density at 15 ℃ of the lubricating base oil of the present embodiment ([rho 15) will also depend on the viscosity grade of the lubricating base oil, it is less than the value of [rho represented by the following formula (A), i.e. [rho is preferably 15 ≦ [rho.
ρ = 0.0025 × kv100 + 0.816 (A)
[In this equation, kv100 represents the kinematic viscosity at 100 ° C. of the lubricating base oil (mm 2 / s). ]

In the case where a [rho 15> [rho, viscosity - temperature characteristic and heat and oxidation stability, and further tend to prevent volatilization resistance and low-temperature viscosity characteristics are deteriorated, which may worsen the fuel efficiency. Further, the efficacy of the additive may be reduced when the additive is blended into the lubricating base oil.

Specifically, density at 15 ℃ of the lubricating base oil of the present embodiment ([rho 15) is preferably 0.860 or less, more preferably 0.850 or less, more preferably 0.840 or less, particularly preferably it is 0.822 or less.

The density and the at 15 ℃ in the present invention means a measured density in compliance with 15 ℃ to JIS K 2249-1995.

Further, the pour point of the lubricating base oil of this embodiment will depend on the viscosity grade of the lubricating base oils, for example, pour point of the lubricating base oils (I) and (IV), preferably - 10 ° C. or less, more preferably -12.5 ° C. or less, more preferably -15 ° C. or less. Also, the lubricating base oils (II) and pour point (V) is preferably -10 ° C. or less, more preferably -15 ° C. or less, still more preferably not more than -17.5 ° C.. Further, the pour point of the lubricating base oils (III) and (VI), preferably -10 ° C. or less, more preferably -12.5 ° C. or less, more preferably -15 ° C. or less. If the pour point exceeds the upper limit, the low-temperature flow properties of lubricating oils employing the lubricating base oil will tend to be reduced. Incidentally, the pour point referred to in the present invention means the pour point measured in conformity with JIS K 2269-1987.

The aniline point of the lubricating base oil (AP (℃)) of the present invention will also depend on the viscosity grade of the lubricating base oil, it is greater than or equal to the value of A as represented by the following formula (B), i.e. AP ≧ it is preferable that the a.
A = 4.3 × kv100 + 100 (B)
[In this equation, kv100 represents the kinematic viscosity at 100 ° C. of the lubricating base oil (mm 2 / s). ]

In the case where the AP <A, the viscosity - temperature characteristic and heat and oxidation stability, and further tend to prevent volatilization resistance and low-temperature viscosity characteristics are deteriorated, and if the additive is blended into a lubricating base oil the efficacy of additives will tend to be lower in the.

For example, AP for the lubricating base oils (I) and (IV) is preferably 108 ° C. or higher, more preferably 110 ° C. or higher. Further, AP for the lubricating base oils (II) and (V) is preferably 113 ° C. or higher, more preferably 119 ° C. or higher. Further, AP for the lubricating base oils (III) and (VI) is preferably 125 ° C. or higher, more preferably 128 ° C. or higher. Note that the aniline point in the present invention means the aniline point measured in conformity with JIS K 2256-1985.

Iodine value of the lubricating base oil of the present embodiment is preferably 3 or less, more preferably 2 or less, more preferably 1 or less, particularly preferably 0.9 or less, and most preferably 0. 8 is less than or equal to. Although it may be less than 0.01, the relationship between the point effect is small and economics of commensurate therewith, preferably 0.001 or more, more preferably 0.01 or more, more preferably 0.03 or more, and particularly preferably 0.05 or more. By the iodine value of the lubricating base oil component with 3 or less, it is possible to drastically improve the heat and oxidation stability. Note that the iodine value referred to in the present invention, JIS K 0070 refers to "acid number of chemical products, saponification value, iodine value, hydroxyl value and unsaponifiable value" iodine value measured by the indicator titration method.

The sulfur content in the lubricating base oil of the present embodiment depends on the sulfur content of the feedstock. For example, in the case of using a raw material containing substantially no sulfur as for synthetic wax components obtained by Fischer-Tropsch reaction, it is possible to obtain a lubricating base oil containing substantially no sulfur. In the case of using a raw material containing sulfur such as a micro waxes obtained by slack wax and sperm wax process obtained in the refining process of lubricating base oil, the sulfur content of the obtained lubricating base oil is usually 100 ppm by mass greater than or equal to. In the lubricating base oil of the present embodiment, from the viewpoint of further improvement and low-sulfur thermal and oxidation stability, the content of sulfur is not more than 100 mass ppm, less than 50 ppm by mass more preferably in, it is particularly preferred further preferably 10 ppm by mass or less, more than 5 mass ppm.

The nitrogen content in the lubricating base oil of the present embodiment is preferably 7 ppm by mass or less, more preferably 5 ppm by mass or less, and more preferably not more than 3 mass ppm. If the nitrogen content exceeds 5 mass ppm, heat and oxidation stability will tend to be reduced. Incidentally, a nitrogen content in the present invention means a nitrogen content measured according to JIS K 2609-1990.

Moreover,% C p value of the lubricating base oil of the present embodiment is preferably 70 or more, preferably 80-99, more preferably 85-95, more preferably 87 ~ 94 particularly preferably from 90 to it is 94. If% C p value of the lubricating base oil is less than the above lower limit, the viscosity - temperature characteristics tend to heat and oxidation stability and frictional properties will be lowered, further, if the additive is blended into a lubricating base oil the efficacy of additives will tend to be lower in the. Further, when the% C p value of the lubricating base oil exceeds the upper limit value, the additive solubility will tend to be lower.

Moreover,% C A of the lubricating base oil of the present embodiment is preferably 2 or less, more preferably 1 or less, more preferably 0.8 or less, particularly preferably 0.5 or less. When% C A of the lubricating base oil exceeds the upper limit value, the viscosity - temperature characteristic, thermal and oxidation stability and fuel efficiency tends to decrease.

Moreover,% C N of the lubricating base oil of the present embodiment is preferably 30 or less, more preferably 4 to 25, more preferably 5-13, particularly preferably from 5 to 8. If the% C N value of the lubricating base oil exceeds the upper limit value, the viscosity - temperature characteristic, thermal and oxidation stability and frictional properties will tend to be reduced. Moreover,% C N is less than the lower limit, solubility of additives tends to be lowered.

Incidentally, say% C P in the present invention,% C A N and% C A, obtained by a method in accordance with ASTM D 3238-85, respectively (n-d-M ring analysis), the total carbon number of the paraffin carbon number It means percentage, a percentage of the total number of carbon atoms in the naphthene carbon number, and the percentage of aromatic carbon atoms in total number of carbon to. That is, the above-described% C P,% C preferred range of N and% C A are based on values determined by these methods, even lubricating base oil for example contains no naphthene, determined by the above is% C N may indicate a value greater than zero.

The content of saturated component in the lubricating base oil of the present embodiment, based on the lubricating base oils the total amount, preferably at least 90 wt%, preferably 95 wt% or more, more preferably 99 wt% or more, also, the proportion of cyclic saturated components among the saturated components is preferably not more than 40 wt%, preferably not more than 35 wt%, preferably not more than 30 wt%, more preferably 25 mass % or less, and still more preferably not more than 21 wt%. The proportion of cyclic saturated components among the saturated components is preferably 5 mass% or more, more preferably 10 mass% or more. The proportion of cyclic saturated components content of the saturated components and occupied in the saturated components satisfying the respective conditions specified above, the viscosity - it is possible to improve temperature characteristics and thermal and oxidation stability, to the lubricating base oil If the additive is compounded, the additive while sufficiently stable dissolved retained in the lubricating base oil may be a higher level expression of functions of the additives. Further, according to the present invention, it is possible to improve the frictional properties of the lubricating base oil itself, improve the friction reducing effect can be achieved and thus increased energy savings.

Note that the saturated components in the present invention, is measured by the method described in the ASTM D 2007-93.

Further, the method of separating saturated component or cyclic saturated components, the time of composition analysis of acyclic saturated components and the like can be used similar methods obtain the same result. For example, in addition to the above, ASTM
The method according to D 2425-93, the method described in ASTM D 2549-91, mention may be made of high performance liquid method chromatographic (HPLC) or a method to improve these methods.

Also, the aromatic content in the lubricating base oil of the present embodiment, based on the lubricating base oils the total amount, preferably 5 wt% or less, more preferably 4 wt% or less, more preferably 3 wt% or less, particularly preferably not more than 2 wt%, and preferably 0.1 mass% or more, more preferably 0.5 mass% or more, more preferably 1 mass% or more, particularly preferably 1.5 mass% or more. If the aromatic content exceeds the aforementioned upper limit, the viscosity - temperature characteristic, thermal and oxidation stability and frictional properties, it will tend volatile proofing property and low-temperature viscosity characteristics are deteriorated, further, the lubricating oil base oil the efficacy of additives will tend to be reduced when the additive is blended in. The lubricating base oil of the present embodiment may be those free of aromatic components, the aromatic content by the above-described lower limit, further increase the solubility of additives be able to.

Note that the aromatic content in the present invention means a value measured in conformity with ASTM D 2007-93. The aromatic content, usually, alkylbenzenes, alkylnaphthalenes, anthracene, phenanthrene and their alkylated, compounds and more benzene rings are condensed or tetracyclic, pyridines, quinolines, phenols, heteroaryl such as naphthols and aromatic compounds having an atomic include.

As the lubricating base oil of the present embodiment may be a synthetic base oil. As synthetic base oils kinematic viscosity at 100 ° C. is 1 ~ 20mm 2 / s, poly α- olefin or hydrides thereof, isobutene oligomer or hydrides thereof, isoparaffin, alkylbenzene, alkylnaphthalene, diester (ditridecyl glutarate rate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate and the like), polyol esters (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate and the like), polyoxyalkylene glycols, dialkyl ethers, polyphenyl ether and the like, among others, poly α- olefin is good Arbitrariness. The poly-α- olefins, typically having 2 to 32 carbon atoms, preferably from 6 to 16 α- olefin oligomers or co-oligomers (1-octene oligomer, decene oligomer, ethylene - propylene co-oligomers and the like) and their include hydrides it is.

Preparation of poly -α- olefin is not particularly limited, for example, a three-aluminum chloride or boron trifluoride, water, alcohols (ethanol, propanol, butanol, etc.), Friedel-Crafts comprising a complex of a carboxylic acid or ester presence of a polymerization catalyst such as a catalyst, and a method of polymerizing α- olefins.

In the lubricating oil composition according to the present embodiment, may be used a lubricating base oil according to the present embodiment alone, one lubricating base oil of the present embodiment other base oil or it may be used in combination with two or more. Note that when used in combination with the lubricating base oil and other base oils according to the present embodiment, the proportion of the lubricating base oil of this embodiment accounts for their mixed base oil is more than 30 wt% are preferred, more preferably at least 50 mass%, further preferably 70 mass% or more.

Other base oil used in combination with the lubricating base oil of the present embodiment is not particularly limited, examples of mineral base oils, for example, a kinematic viscosity at 100 ° C. is 20 mm 2 / s, greater 200 mm 2 / s or less of solvent refined mineral, hydrocracked mineral oil, hydrotreated mineral oil, and the like solvent dewaxing base oil.

As another synthetic base oils used in combination with the lubricating base oil according to the present embodiment, a kinematic viscosity at 100 ° C. is outside the range of 1 ~ 20mm 2 / s, synthetic base oils include that the It is.

(A) used in the present invention a viscosity index improver, the spectrum obtained by nuclear magnetic resonance analysis (13 C-NMR), total area of the peaks between the chemical shift 36-38ppm to the total area of all peaks (M1 ) and the ratio of the total area of ​​the peaks between the chemical shift 64-66ppm (M2), i.e. in which M1 / ​​M2 is less than 0.20.

It satisfies the above conditions (A) viscosity index improver, specifically a non-distributed or distributed ester group-containing viscosity index improver, non-dispersed or distributed poly (meth) Examples acrylate based viscosity index improver, non-dispersed or distributed olefin - (meth) acrylate copolymer viscosity index improver, a styrene - maleic acid ester copolymer viscosity index improvers and the like and mixtures thereof and the like, non-dispersive among these it is preferably a type or dispersed poly (meth) acrylate based viscosity index improver. Particularly preferably in a non-distributed or distributed polymethacrylate viscosity index improver.

M1 / M2 is preferably 0.3 or more, more preferably 0.4 or more, and particularly preferably 0.5 or more, and most preferably 0.6 or more. Moreover, M1 / ​​M2 is preferably 3.0 or less, further preferably 2.0 or less, particularly preferably 1.0 or less, and most preferably 0.8 or less. If M1 / ​​M2 is less than 0.20, not only can not be obtained fuel savings in need, there is a possibility that the low temperature viscosity characteristics are deteriorated. Moreover, M1 / ​​M2 is the case of more than 3.0, there may not be obtained fuel savings in need, there is a possibility that solubility and storage stability is degraded.

Incidentally, a nuclear magnetic resonance analysis (13 C-NMR) spectra, if it contains a diluent oil viscosity index improvers are those obtained for the diluent oil is separated by a rubber membrane dialysis polymer.

The total area of the peaks between the chemical shift 36-38ppm to the total area of all peaks (M1) in the case of viscosity index improvers, e.g. poly (meth) acrylates, as measured by 13 C-NMR, integration of the total carbon It means the ratio of the integrated intensity from a particular β branched structure poly (meth) acrylate side chains to the total intensity, the total area of ​​the peaks between the chemical shift 64-66ppm to the total area of ​​all peaks (M2) is , 13 as measured by C-NMR, it means the ratio of integrated intensity from a particular linear structure of poly (meth) acrylate side chains to the total integrated intensity of total carbon.

M1 / M2 is meant the percentage of a particular linear structure and a specific β branched structure poly (meth) acrylate side chains, another method may be used as long as equivalent results are obtained.Incidentally, 13 when the C-NMR measurement, was used as a sample in a sample 0.5g those diluted by adding deuterochloroform 3g, measurement temperature room, the resonance frequency is set to 125 MHz, assay decoupling method gated It was used.

By the above analysis,
(A) Total integrated intensity of chemical shift about 10-70Ppm (total integrated intensity attributed to total carbon of hydrocarbon), and (b) the sum (specific β branched structure of the integral intensity of the chemical shift 36-38ppm total integrated intensity due to), and (c) the sum of integrated intensity of chemical shift 64-66Ppm (total integrated intensity attributed to a specific linear structure)
Each was measured and the M1 calculates the percentage (%) of (a) 100% and the time (b). Moreover, it was M2 calculates the percentage (%) of (c) when a 100% (a).

(The poly (meth) acrylate in the present invention, general term for polyacrylate compounds and polymethacrylate compounds) poly (meth) acrylate based viscosity index improver can be used in the present embodiment, preferably, the following represented by the general formula (1) (meth) acrylate monomer (hereinafter, referred to as "monomer M-1".) is a polymer of a polymerizable monomer containing a.

Figure JPOXMLDOC01-appb-C000001
[In the general formula (1), R 1 represents hydrogen or a methyl group, R 2 represents a linear or branched hydrocarbon group having 1 to 200 carbon atoms. ]

Formula (1) in one homopolymer or poly obtained by two or more copolymerizable (meth) acrylate compound of the monomer represented is a so-called non-dispersant poly (meth) acrylates, present poly (meth) acrylate compound according to embodiment includes a monomer represented by the general formula (1), the general formula (2) and (3) one or more monomers selected from (hereinafter, respectively "monomer M-2 "and" monomer M-3 ".) may be a so-called distributed poly (meth) acrylate obtained by copolymerization.

Figure JPOXMLDOC01-appb-C000002
In General formula (2), R 3 represents a hydrogen atom or a methyl group, R 4 represents an alkylene group having 1 to 18 carbon atoms, E 1 is 1-2 nitrogen atoms, oxygen atoms 0-2 It showed an amine residue or heterocyclic residue number contains, a is 0 or 1. ]
Figure JPOXMLDOC01-appb-C000003
In General formula (3), R 5 represents a hydrogen atom or a methyl group, E 2 is one to two nitrogen atoms, an oxygen atom indicates the amine residue or heterocyclic residue containing 2 to 0. ]

The group represented by E 1 and E 2, specifically, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, anilino group, toluidino group, xylidino group, acetylamino group, benzoylamino group , morpholino group, pyrrolyl group, pyrrolino group, pyridyl group, methylpyridyl group, pyrrolidinyl group, piperidinyl group, quinonyl group, pyrrolidonyl group, Piroridono group, imidazolino group, and pyrazino group and the like.

Monomer M-2, preferred examples of the monomer M-3 is specifically dimethylaminomethyl methacrylate, diethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-methyl-5-vinylpyridine, morpholino methyl methacrylate , morpholinoethyl methacrylate, and the like N- vinylpyrrolidone and mixtures thereof can be exemplified.

There is no particular restriction on the copolymerization molar ratio of the copolymer of the monomers M-1 and a monomer M-2 ~ M-3, M-1: M-2 ~ M-3 = 99: 1 ~ 80: 20 degree, more preferably from 98: 2 to 85: 15, more preferably 95: 5 to 90:10.

The poly (meth) preparation of acrylate is arbitrary, for example, in the presence of a polymerization initiator such as benzoyl peroxide, monomer (M-1) and monomer (M-2) ~ of (M-3) the mixture can be easily obtained by radical solution polymerization.

The (A) PSSI of viscosity index improver (Permanent Shear Stability Index) is preferably 40 or less, more preferably 35 or less, more preferably 30 or less, particularly preferably 25 or less. Further, preferably 0.1 or more, more preferably 0.5 or more, even more preferably 2 or more, and particularly preferably 5 or more. PSSI is may cause cost increases less viscosity index improving effect in the case of less than 0.1, PSSI is likely to shear stability and storage stability becomes poor in case of more than 40.

(A) The weight average molecular weight of the viscosity index improver (M W) is preferably at least 100,000, more preferably 200,000 or more, even more preferably 250,000 or more, particularly preferably 300 , is 000 or more. Further, preferably 1,000,000 or less, more preferably 700,000 or less, more preferably 600,000 or less, particularly preferably 500,000 or less. If the weight average molecular weight is less than 100,000 may cause improvement effect and viscosity index improving effect of viscosity-temperature characteristic cost small increases, shear stability when the weight average molecular weight exceeds 1,000,000 solubility and the base oil, there is a possibility that the storage stability is deteriorated.

The number average molecular weight of (A) a viscosity index improver (M N) is preferably 50,000 or more, more preferably 800,000 or more, even more preferably 100,000 or more, particularly preferably 120 , is 000 or more. Further, preferably 500,000 or less, more preferably 300,000 or less, more preferably 250,000 or less, and particularly preferably 200,000 or less. If the number average molecular weight is less than 50,000 may result in improvement effect and viscosity index improving effect of viscosity-temperature characteristic cost small increases, shear stability and group when the weight average molecular weight exceeds 500,000 solubility in the oil, there is a possibility that the storage stability is deteriorated.

(A) a weight average molecular weight and PSSI ratio of the viscosity index improver (M W / PSSI) is preferably 1.0 × 10 4 or more, preferably 1.5 × 10 4 or more, more preferably 2 .0 × 10 4 or more, more preferably 2.5 × 10 4 or more, particularly preferably 3.0 × 10 4 or more. If M W / PSSI is below 1.0 × 10 4, there is a possibility that the viscosity-temperature characteristic is deteriorated i.e. deteriorates fuel efficiency.

The ratio of the weight average molecular weight to number average molecular weight of (A) a viscosity index improver (M W / M N) is preferably 0.5 or more, preferably 1.0 or more, more preferably 1.5 or more , more preferably 2.0 or more, and particularly preferably 2.1 or more.Further, it is preferred that the M W / M N is 6.0 or less, more preferably 4.0 or less, more preferably 3.5 or less, particularly preferably 3.0 or less. If the M W / M N exceeds 0.5 below and 6.0, there is a possibility that the viscosity-temperature characteristic is deteriorated i.e. deteriorates fuel efficiency.

(A) a viscosity increasing Nebahi of kinematic viscosity at 40 ° C. and 100 ° C. the index improver ΔKV40 / ΔKV100 is preferably 4.0 or less, more preferably 3.5 or less, more preferably 3.0 or less , particularly preferably 2.5 or less, most preferably 2.3 or less. Further, ΔKV40 / ΔKV100 is preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 1.5 or more, and particularly preferably 2.0 or more.
If ΔKV40 / ΔKV100 is less than 0.5, there is a possibility that the increased effect or solubility of the viscosity cost small increases, if it exceeds 4.0, the improving effect and low temperature viscosity characteristics of the viscosity-temperature characteristic there is a possibility that the inferior. Incidentally, DerutaKV40 is when adding a viscosity index improver 3.0% in SK Corp. YUBASE4, means the increase in kinematic viscosity at 40 ℃, ΔKV100 is a viscosity index improver in SK Corp. YUBASE4 3.0 % when adding means the increase in kinematic viscosity at 100 ° C..

(A) increasing the HTHS viscosity at 100 ° C. and 0.99 ° C. viscosity index improvers Nebahi ΔHTHS100 / ΔHTHS150 is preferably 2.0 or less, more preferably 1.7 or less, more preferably 1.6 or less , particularly preferably 1.55 or less. Further, ΔHTHS100 / ΔHTHS150 is preferably 0.5 or more, more preferably 1.0 or more, more preferably 1.2 or more, particularly preferably 1.4 or more.
If it is less than 0.5, there is a possibility that the increased effect or solubility of the viscosity cost small increases, if it exceeds 2.0, there is a possibility that poor improving effect and low temperature viscosity characteristics of the viscosity-temperature characteristic .
Incidentally, DerutaHTHS100 is when adding a viscosity index improver 3.0% in SK Corp. YUBASE4, means the increase of HTHS viscosity at 100 ℃, ΔHTHS150 is a viscosity index improver in SK Corp. YUBASE4 3.0 percent when added, is meant the increment of HTHS viscosity at 0.99 ° C.. Further, ΔHTHS100 / ΔHTHS150 means the increase ratio of the HTHS viscosity at increment and 0.99 ° C. of HTHS viscosity at 100 ° C.. The HTHS viscosity at 100 ° C. in the present invention, showing a high-temperature high-shear viscosity at 100 ° C. as defined in ASTM D4683. In addition, the HTHS viscosity at 0.99 ° C., shows a high-temperature high-shear viscosity at 0.99 ° C. as defined in ASTM D4683.

The content of (A) a viscosity index improver in the lubricating oil composition according to the present embodiment is preferably a total amount of the lubricating oil composition reference is 0.01 to 50 mass%, more preferably from 0.5 to 40 wt%, more preferably 1 to 30 mass%, particularly preferably 3 to 20% by weight, most preferably 5 to 10 mass%. If the content of (A) a viscosity index improver is less than 0.1 wt%, since the effect of reducing the viscosity index improving effect or product viscosity is reduced, there may not model improves fuel economy. If it exceeds 50 wt%, the product cost is significantly increased, since the need to reduce the viscosity of the base oil coming out, lowering the lubricating performance in harsh lubrication conditions (high temperature and high shear conditions), wear and seizure, there is a concern that the cause of problems such as fatigue fracture.

In the lubricating oil composition according to the present embodiment, as a viscosity index improver, in addition to the above component (A), can be used other viscosity index improvers. As an example, non-dispersed or distributed ethylene -α- olefin copolymer or its hydrogenation product, polyisobutylene or its hydride, styrene - can be exemplified diene hydrogenated copolymers and polyalkyl styrene.

The lubricating oil composition according to the present embodiment comprises (B) a friction modifier. Thus, as compared with the case where the present constitution is not provided, it is possible to increase the fuel efficiency performance. The (B) a friction modifier, one or more friction modifiers selected from organic molybdenum compounds and ashless friction modifiers and the like.

The organic molybdenum compound used in the present embodiment, molybdenum dithiophosphate, organic molybdenum compounds containing sulfur such as molybdenum dithiocarbamate (MoDTC), molybdenum compounds (such as molybdenum dioxide, molybdenum oxide such as molybdenum trioxide, ortho molybdate , para molybdate, (poly) molybdic acid, such as molybdenum sulfide acid, metal salts of these molybdic acid, molybdate and ammonium salts, molybdenum disulfide, molybdenum trisulfide, pentasulfide molybdenum, molybdenum sulfide and poly molybdenum sulfide , sulfurized molybdic acid, metal salts or amine salts of sulfurized molybdenum acid, and halogenated molybdenum) molybdenum chloride, sulfur-containing organic compounds (e.g., alkyl (thio) xanthates, thiadiazole, Merukaputochiaji Tetrazole, thiocarbonates, tetra hydrocarbyl disulfide, bis (di (thio) hydrocarbyl dithiophosphates phosphonate) disulfide, organic (poly) sulfide, complexes of the sulfide ester), or other organic compounds, or the sulfide molybdenum may be mentioned complexes of the sulfur-containing molybdenum compound with an alkenyl succinimide such as sulfurized molybdic acid.

The organic molybdenum compound may be an organic molybdenum compound containing no sulfur as a constituent element. The organic molybdenum compounds containing no sulfur as a constituent element, specifically, molybdenum - amine complexes, molybdenum - imido complexes succinic acid, molybdenum salts of organic acids, such as molybdenum salts of alcohols. Among them, molybdenum - amine complexes, molybdenum salts of molybdenum salts and alcohol organic acid.

In the lubricating oil composition according to the present embodiment, when an organic molybdenum compound, although its not content particularly limited, based on the total amount of the lubricating oil composition, of molybdenum terms of element, preferably 0.001 mass% or more, more preferably 0.005 mass% or more, more preferably 0.01 mass% or more, and particularly preferably 0.03 mass% or more, also preferably 0.2 mass% or less, more preferably 0.1 % or less, more preferably 0.08 wt% or less, particularly preferably not more than 0.06 mass%. If the content is less than 0.001 mass%, the thermal and oxidation stability of the lubricating oil composition will be insufficient, in particular, it tends to be impossible to maintain excellent detergency for a long period of time. On the other hand, if the content exceeds 0.2 mass%, not to obtain the effect commensurate with the amount and the storage stability of the lubricating oil composition will tend to be reduced.

As the ashless friction modifier, may be used any compound usually used as a friction modifier for lubricating oils, for example, oxygen atoms in the molecule, a nitrogen atom, one selected from a sulfur atom or 2 containing species or more hetero element include compounds having 6 to 50 carbon atoms. More specifically, the alkyl or alkenyl group having 6 to 30 carbon atoms, especially straight-chain alkyl group having 6 to 30 carbon atoms, straight-chain alkenyl groups, branched alkyl groups, at least one have a branched alkenyl group in a molecule , amine compounds, fatty acid esters, fatty amides, fatty acids, fatty alcohols, aliphatic ethers, urea compounds, ashless friction modifiers such as hydrazide compounds.

The content of the ashless friction modifier in the lubricating oil composition according to the present embodiment, based on the total amount of the lubricating oil composition, preferably from 0.01% by mass or more, more preferably 0.1 mass% or more, more preferably is at least 0.3 wt%, and preferably 3 wt% or less, more preferably 2 wt% or less, still more preferably not more than 1 wt%. When the content of the ashless friction modifier is less than 0.01 wt%, there is a tendency that the friction reducing effect by the addition is insufficient, and when it exceeds 3 wt%, effects such as anti-wear additive there tends to solubility inhibited easily, or additives is deteriorated.

In the present embodiment, as the (B) the friction modifier is preferably a molybdenum-based friction modifier, more preferably an organic molybdenum compound containing sulfur, more preferably molybdenum dithiocarbamate.

In the lubricating oil composition according to the present embodiment, (C) an oil-soluble metal salt the overbased metal salt obtained by overbasing an alkaline earth metal borate (hereinafter, "(C) first overbased that metal salt ".) containing. Thus, as compared with the case where the present constitution is not provided, it is possible to increase the fuel efficiency performance.

Used in this embodiment (C) first overbased metal salts, alkaline earth metal sulfonate oil-soluble, alkaline earth metal salicylate, alkaline-earth metal phenate, an oil-soluble metal salts, such as alkali earth metal phosphonates If it can be obtained by alkaline earth metal hydroxide or oxide, and boric acid or boric anhydride reaction. Examples of the alkaline earth metals, magnesium, calcium, and barium, calcium is preferred. As the oil-soluble metal salt is preferably used an alkaline earth metal salicylate.

(C) base number of the first overbased metal salt is preferably at 50 mg KOH / g or more, more preferably 100 mg KOH / g or more, still more preferably 150 mgKOH / g or more, 200 or more it is particularly preferred is. Also, preferably at most 500 mgKOH / g, more preferably at most 400 mg KOH / g, even more preferably at most 300 mgKOH / g. Base number referred to in the present invention is a value measured by JIS K 2501 5.2.3.

The particle size of (C) a first overbased metal salt is preferably 0.1μm or less, more preferably 0.05μm or less.

(C) preparation of a first overbased metal salt is optional, for example, the oil-soluble metal salts, alkaline earth metal hydroxide or oxide, and boric acid or boric acid anhydride, water, methanol , ethanol, propanol, alcohol and benzene, such as butanol, toluene, allowed to react for 2 to 8 hours at 20 ~ 200 ° C. in the presence of a diluent such as xylene, water and optionally followed by heating to 100 ~ 200 ° C. obtained by removing the alcohol and diluting solvent Te. These detailed reaction conditions, the raw material is appropriately selected depending on the amounts of reactants. The details of the preparation, for example, JP 60-116688 discloses, this is described in JP-A-61-204298. The particle size of the overbased metal salts of oil-soluble metal salts prepared by the above method overbased alkaline earth metal borate typically 0.1μm or less, because the total base number is usually 100 mg KOH / g or more it can be preferably used in the lubricating oil composition according to the present embodiment.

The content of overbased metal salts in the lubricating oil composition (C) first according to the present embodiment, the lubricating oil based on the total amount of the composition, preferably from 0.01 to 30 mass%, more preferably 0.05 ~ is 5% by mass. If the content is less than 0.01% by mass, there is a possibility that fuel saving effect is not only lasts a short time, and when exceeding 30% by mass, may not be obtained effect commensurate with the amount There is not preferable.

In the lubricating oil composition according to the present embodiment, (C) in addition to the first overbased metal salts, overbased metal overbased with (E) an oil-soluble metal salt of alkaline earth metal carbonate salts be used in combination (hereinafter, referred to as "(E) a second overbased metal salt".) it is more preferred. (E) The second overbased metal salts, overbased alkaline earth metal sulfonates, alkaline earth metal an alkaline earth metal phenate obtained by overbasing an alkaline earth metal sulfonate in an alkaline earth metal carbonate overbased alkaline earth metal phenate and overbased carbonate salt, overbased alkaline earth metal salicylate, etc. and alkaline earth metal salicylates and overbased alkaline earth metal carbonate can be exemplified. Examples of the alkaline earth metals, magnesium, calcium, and barium, calcium is preferred. Among these, it is particularly preferable to use an overbased calcium salicylate obtained by overbasing an alkaline earth metal carbonates and alkaline earth metal salicylates.

When used in lubricating oil compositions according to the present embodiment and (C) first and overbased metal salt (E) a second overbased metal salts, (E) a second overbased metal salts base number of, is preferably 50 mg KOH / g or more, more preferably 100 mg KOH / g or more, more preferably 150 mgKOH / g or more, particularly preferably 200 mg KOH / g or more. Also, preferably at most 500 mgKOH / g, more preferably at most 400 mg KOH / g, even more preferably at most 300 mgKOH / g.

The lubricating oil composition according to the present embodiment can further to improve its performance, contain optional additives that are commonly used in lubricating oil in accordance with the purpose. Such additives include, for example, the first and second overbased metal salts other than metal-based detergents, ashless dispersants, anti-wear agent (or extreme pressure), antioxidants, corrosion inhibitors , mention may be made of rust inhibitors, demulsifiers, metal deactivators, additives such as antifoaming agents.

Examples of the first and second overbased metal salts other than metal-based detergents, alkali metal / alkaline earth metal sulfonates, alkali metal / alkaline earth metal phenates, and the like alkali metal / alkaline earth metal salicylate normal salts or basic salts. Sodium as the alkali metal, potassium, magnesium as the alkaline earth metals, calcium, and barium, magnesium or calcium are preferable, especially calcium is more preferable.

The ashless dispersants, lubricants any ashless dispersants can be used for use in, for example, mono- or having at least one straight-chain or branched alkyl or alkenyl group having 40 to 400 carbon atoms in the molecule bissuccinimide, polyamines having at least one alkyl or alkenyl group of benzylamine or carbon atoms 40-400, having at least one alkyl or alkenyl group having 40 to 400 carbon atoms in the molecule in the molecule, or these, boron compounds, carboxylic acids, modified Hinto with phosphoric acid and the like. In use may contain a single type or two or more selected arbitrarily from these.

The anti-wear agent (or extreme pressure agents), any anti-wear agents, extreme pressure agents for use in lubricating oils can be used. For example, sulfur-based, phosphorus-based, sulfur - phosphorus extreme pressure agent or the like can be used, and specific examples include a zinc dialkyldithiophosphate (ZnDTP), phosphites, thiophosphite esters, dithiophosphoric phosphorous acid esters, trithiophosphoric phosphites, phosphoric acid esters, thiophosphoric acid esters, dithiophosphoric acid esters, trithiophosphoric acid esters, amine salts of these, these metal salts, derivatives thereof, dithiocarbamates, zinc dithiocarbamate carbamate, MoDTC, disulfides, polysulfides, sulfurized olefins, and the like sulfurized fats and oils. Preferably the addition of the sulfur-based extreme pressure agents among these, especially sulfurized fats and oils are preferred.

As the antioxidant, phenol-based ashless antioxidants amine such as copper, metal antioxidants molybdenum or the like. Specifically, for example, as a phenol-based ashless antioxidant, 4,4'-methylenebis (2,6-di -tert- butylphenol), 4,4'-bis (2,6-di -tert- butylphenol). Examples of amine-based ashless antioxidant, phenyl -α- naphthylamine, alkylphenyl -α- naphthylamine, dialkyldiphenylamines, and the like.

Examples of corrosion inhibitors include benzotriazole, tolyltriazole-based, thiadiazole, or imidazole-based compounds.

Examples of the rust inhibitor include petroleum sulfonates, alkylbenzene sulfonates, dinonyl naphthalene sulfonates, alkenyl succinic acid ester or polyhydric alcohol esters, etc., it can be mentioned.

The demulsifier, for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ether or a polyalkylene glycol-based non-ionic surfactants such as polyoxyethylene alkyl naphthyl ether and the like, can be mentioned.

Examples of the metal deactivators include imidazolines, pyrimidine derivatives, alkyl thiadiazole, mercapto benzothiazole, benzotriazole or derivatives thereof, 1,3,4-thiadiazole polysulfides, 1,3,4-thiadiazolyl-2,5-bis dialkyldithiocarbamate, 2- (alkyldithio) benzimidazole or beta-(o-carboxybenzyl thio) propionitrile, and the like.

As the defoaming agent, for example, silicone oil kinematic viscosity at 25 ° C. is from 1000 to 100,000 mm 2 / s, alkenylsuccinic acid derivatives, esters of polyhydroxy aliphatic alcohols and long chain fatty acids, methyl salicylate o- hydroxybenzyl alcohol and the like.

The if to be contained in the lubricating oil composition according to the present embodiment these additives, the content of each of the lubricating oil composition the total amount, preferably 0.01 to 10 mass%.

Kinematic viscosity at 100 ° C. of the lubricating oil composition according to the present embodiment, 4 is preferably ~ 12 mm 2 / s, preferably not more than 9 mm 2 / s, more preferably 8 mm 2 / s or less, more preferably 7 .8mm 2 / s or less, particularly preferably not more than 7.6 mm 2 / s. The kinematic viscosity at 100 ° C. of the lubricating oil composition according to the present embodiment is preferably 5 mm 2 / s or more, more preferably 6 mm 2 / s or higher, more preferably 6.5 mm 2 / s or more, particularly preferably is 7mm 2 / s or more. The kinematic viscosity at 100 ° C. in the present invention, showing a kinematic viscosity at 100 ° C., which is measured according to ASTM D-445. If the kinematic viscosity at 100 ° C. of less than 4 mm 2 / s, there is insufficient lubricity may, possibly low-temperature viscosity and sufficient fuel saving performance may not be obtained necessary in the case of more than 12 mm 2 / s is there.

Kinematic viscosity at 40 ° C. of the lubricating oil composition according to the present embodiment is preferably 4 ~ 50mm 2 / s, preferably 40 mm 2 / s or less, more preferably 35 mm 2 / s or less, particularly preferably 32mm 2 / s or less, and most preferably not more than 30 mm 2 / s. Moreover, kinematic viscosity at 40 ° C. of the lubricating oil composition according to the present embodiment is preferably 10 mm 2 / s or more, more preferably 20 mm 2 / s or higher, more preferably 25 mm 2 / s or more, particularly preferably 27 mm 2 / s or more. The kinematic viscosity at 40 ° C. in the present invention, showing a kinematic viscosity at 40 ° C. which is measured according to ASTM D-445. If it is less than the dynamic viscosity of 4 mm 2 / s at 40 ° C., there is insufficient lubricity may, possibly low-temperature viscosity and sufficient fuel saving performance may not be obtained necessary in the case of more than 50 mm 2 / s is there.

The viscosity index of the lubricating oil composition according to the present embodiment is preferably in the range from 140 to 400, preferably 190 or more, more preferably 200 or more, more preferably 210 or more, and particularly preferably 220 or more. In the case the viscosity index of the lubricating oil composition according to the present embodiment is less than 140, while maintaining the HTHS viscosity of 0.99 ° C., it may become difficult to improve fuel economy, further -35 ° C. it may become difficult to reduce the low temperature viscosity. Further, if the viscosity index of the lubricating oil composition according to the present embodiment is 400 or more, there is a possibility that evaporation is deteriorated, a problem due to lack of compatibility with more solubility and sealing material additives there is likely to occur.

HTHS viscosity at 100 ° C. of the lubricating oil composition according to the present embodiment is preferably from 5.5 mPa · s, more preferably 5.0 mPa · s or less, more preferably not more than 4.8 mPa · s, in particular preferably less than or equal to 4.7mPa · s. Further, preferably 3.0 mPa · s or more, more preferably 3.5 mPa · s or more, particularly preferably 4.0 mPa · s or more, and most preferably 4.2 mPa · s or more. The HTHS viscosity at 100 ° C. in the present invention, showing a high-temperature high-shear viscosity at 100 ° C. as defined in ASTM D4683. If HTHS viscosity at 100 ° C. of less than 3.0 mPa · s, there is insufficient lubricity may, low temperature viscosity and sufficient fuel efficiency performance is not obtained the required if more than 5.5 mPa · s I fear there is.

HTHS viscosity at 0.99 ° C. of the lubricating oil composition according to the present embodiment is preferably from 3.5 mPa · s, more preferably 3.0 mPa · s or less, more preferably not more than 2.8 mPa · s, in particular preferably less than or equal to 2.7mPa · s. Further, preferably 2.0 mPa · s or more, more preferably 2.3 mPa · s or more, more preferably 2.4 mPa · s or more, particularly preferably 2.5 mPa · s or more, and most preferably 2.6 mPa · s or more it is. The HTHS viscosity at 0.99 ° C. in the present invention, showing a high-temperature high-shear viscosity at 0.99 ° C. as defined in ASTM D4683. If HTHS viscosity at 0.99 ° C. of less than 2.0 mPa · s, there is insufficient lubricity may, low temperature viscosity and sufficient fuel efficiency performance is not obtained the required if more than 3.5 mPa · s I fear there is.

Further, (HTHS viscosity at HTHS viscosity / 100 ° C. at 0.99 ° C.) ratio of the HTHS viscosity at HTHS viscosity and 100 ° C. at 0.99 ° C. of the lubricating oil composition according to the present embodiment is preferably 0.50 or more , more preferably 0.52 or more, more preferably 0.54, particularly preferably 0.55 or more, and most preferably 0.56 or more. When the ratio is less than 0.50, there may not low-temperature viscosity and sufficient fuel efficiency performance obtained required.

The lubricating oil composition according to the present embodiment is excellent in fuel economy and lubricity, without using a synthetic oil or a low viscosity mineral base oil poly -α- olefin base oil and ester based base oil, 150 while maintaining the HTHS viscosity ° C. at a constant level, it is effective for improving fuel efficiency, in which significantly reduce the HTHS viscosity of kinematic viscosity and 100 ° C. at 40 ° C. and 100 ° C. of the lubricating oil. Such excellent lubricating oil composition according to the present embodiment having the characteristics, fuel saving gasoline engine oil, can be suitably used as a fuel-saving engine oil, such as fuel saving diesel engine oil.

Hereinafter, a more detailed explanation of the present invention based on examples and comparative examples, the present invention is not intended to be limited to the following Examples.

[Examples 1-5, Comparative Examples 1-3]
In Examples 1-5 and Comparative Examples 1-3, respectively by using the base oils and additives shown below to prepare a lubricating oil composition having the composition shown in Table 2. Properties of base oil O-1, O-2, O-3 shown in Table 1.
(Base oil)
O-1 (base oil 1): n-paraffin-containing oil hydrocracking / hydroisomerisation mineral oils O-2 (base oil 2): ​​n-paraffin-containing oil hydrocracking / hydroisomerisation mineral oils O-3 (base oil 3): hydrocracking mineral oil (additives)
A-1: polymethacrylate (M1 = 1.45, M2 = 3.99, M1 / ​​M2 = 0.48, ΔKV40 / ΔKV100 = 1.9, ΔHTHS100 / ΔHTHS150 = 1.48, MW = 400,000, PSSI = 12, Mw / Mn = 3.1, Mw / PSSI = 33,333)
A-2: polymethacrylate (M1 = 0.60, M2 = 0.95, M1 / ​​M2 = 0.64, ΔKV40 / ΔKV100 = 2.2, ΔHTHS100 / ΔHTHS150 = 1.51, MW = 400,000, PSSI = 20, Mw / Mn = 2.2, Mw / PSSI = 20,000)
a-1: Distributed polymethacrylate (M1 = 0.46, M2 = 3.52, M1 / ​​M2 = 0.13, ΔKV40 / ΔKV100 = 3.3, ΔHTHS100 / ΔHTHS150 = 1.79, MW = 300,000 , PSSI = 40, Mw / Mn = 4.0, Mw / PSSI = 7500)
B-1: MoDTC (Mo content of 10 mass%)
C-1: Calcium salicylate of calcium overbased borate was overbased with calcium borate salicylate (base number 190 mg KOH / g, Ca content 6.8 wt%, B content of 2.7 mass%)
c-1: overbased calcium salicylate (base number 170 mg KOH / g, Ca content 6.3%)
d-1: succinimide dispersant (Mw13000)
e-1: ZnDTP (sec- type, P content 6.2 wt%)
f-1: Others additives (antioxidants, antiwear agents, pour point depressants, antifoaming agents, etc.).

Figure JPOXMLDOC01-appb-T000004

[Evaluation of the lubricating oil composition]
For each of the lubricant compositions of Examples 1-5 and Comparative Examples 1-3, the kinematic viscosity at 40 ° C. or 100 ° C., was measured HTHS viscosity at viscosity index, 100 ° C. or 0.99 ° C.. The measurement of fuel economy was measured engine friction. Each physical property value, the measurement of fuel economy was carried out by the following evaluation methods. The results obtained are shown in Table 2.
(1) Kinematic Viscosity: ASTM D-445
(2) Viscosity index: JIS K 2283-1993
(3) HTHS viscosity: ASTM D-4683
(4) Engine friction test: using a 2L engine, oil temperature 60 ° C. ~ 100 ° C., an average value of friction at each measurement point of the rotation number 500 ~ 1500 rpm, friction when the reference oil Comparative Example 1 It was calculated the rate of improvement.

Figure JPOXMLDOC01-appb-T000005

As shown in Table 2, using a polymethacrylate having a specific structure, and lubricating oil compositions of an oil-soluble metal salt [the addition of overbased metal salts and overbased alkaline earth metal borate Examples 1-5 things, indicates that the motoring friction improvement rate (reduction rate of friction) is large, and excellent fuel economy. In contrast, the lubricating oil composition of Comparative Example 1 containing no overbased metal salts of oil-soluble metal salts and overbased alkaline earth metal borate is intended HTHS viscosity comparable at 0.99 ° C. Despite the motoring friction is large (improvement rate is small). Also not contain an overbased metal salt oil-soluble metal salts and overbased alkaline earth metal borate, and lubricating oil compositions also motoring friction of Comparative Example 2 containing no present predetermined polymethacrylate It is large (improvement rate is small). The lubricating oil composition of Comparative Example 3 containing no friction modifiers also motoring friction is large (improvement rate is small). The lubricating oil composition of the present invention, without using a synthetic oil or a low viscosity mineral base oil poly -α- olefin base oil and ester based base oil, while maintaining the high-temperature high-shear viscosity at 0.99 ° C., in addition to being able to reduce the 100 ° C. HTHS viscosity, by adding a friction modifier and a particular metal-based detergent, it can be seen that significantly better fuel economy.

Claims (5)

  1. A lubricating base oil kinematic viscosity of 1 ~ 20mm 2 / s at 100 ° C.,
    In the spectrum obtained by the 13 C-NMR, the ratio M1 / M2 of the total area M2 of the peaks between the total area M1 and chemical shift 64-66ppm of peaks between the chemical shifts 36-38ppm to the total area of all peaks 0 a viscosity index improver is .20 or higher,
    And friction modifiers,
    And overbased metal salts of oil-soluble metal salts and overbased alkaline earth metal borate,
    The lubricating oil composition characterized by containing a.
  2. Wherein the viscosity index improver is a poly (meth) acrylate based viscosity index improver, the lubricating oil composition of claim 1.
  3. The viscosity index improver, PSSI of 40 or less, and wherein the at ratio of the weight average molecular weight and PSSI is of 1 × 10 4 or more, the lubricating oil composition according to claim 1 or 2.
  4. It said friction modifier is characterized in that an organic molybdenum compound, a lubricating oil composition according to any one of claims 1 to 3.
  5. Overbased metal salt of the oil-soluble metal salts and overbased alkaline earth metal borate, characterized in that an alkaline earth metal borate is a overbased alkaline earth metal salicylate the lubricating oil composition according to any one of claims 1-4.
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