CN106967479A - Lubricating oil composition and method for producing same - Google Patents

Abstract

The present invention relates to a lubricating oil composition and a method for producing the same. The lubricating oil composition of the present invention is a lubricating oil composition containing a lubricating base oil, a metal-based detergent, a molybdenum dialkyldithiocarbamate compound, and a boron-containing compound, wherein the metal-based detergent contains calcium salicylate and at least 1 selected from calcium sulfonate and a magnesium-based detergent, the lubricating oil composition optionally contains an ashless friction modifier, the content of calcium atoms is 0.12 to 0.16 mass% based on the total amount of the lubricating oil composition, the content of molybdenum atoms is 0.05 to 0.10 mass% based on the total amount of the lubricating oil composition, and a predetermined coefficient X is less than 0.050.

Description

Lubricant oil composite and its manufacture method

Technical field

The present invention relates to lubricant oil composite, for example, it is related to the lubricating oil for IC engines combination used in petrol engine Thing.

Background technology

In recent years, with the reinforcing of environmental regulations, it is desirable to which the low burn of engine for automobile is taken（Ran Charges）, therefore be gradually introducing Be equipped with direct injection mechanism and engine driven supercharging mechanism (Over Give machine Agencies) supercharged direct-injection engine.In supercharged direct-injection engine, By improving the moment of torsion under low speed rotation, output can be maintained, while reducing capacity, therefore fuel consumption can be improved.

On the other hand, in the machine oil for automobile engine, various additives have been generally mated, for example, as it is known that in order to Coefficient of friction between metal is reduced, fuel consumption is improved, coordinates molybdenum dialkyldithiocarbamacompositions.In addition, also known as ensure clear Clean property, prevent from wearing away, prevent greasy filth etc., cooperation contains calcium, the metal system cleaning agent of magnesium, various phosphorus-containing compounds, boric acid Change the ashless detergent dispersants such as dispersant.

In petrol engine, for supercharged direct-injection engine, easily occur the abnormal combustion for being referred to as low speed early combustion, because This, conventional, in order to suppress the occurrence frequency of low speed early combustion, various improvement have been carried out for machine oil.For example, in patent document 1 In, it is known that adjusting various in the way of calcium amount, magnesium amount, molybdenum amount, phosphorus amount and nitrogen quantity contained in machine oil meet particular kind of relationship formula The use level of additive.Wherein, in the concrete example of the machine oil disclosed in patent document 1, calcium amount or magnesium amount are made to be a certain amount of, together When the use level of molybdenum is suppressed to 0.01~0.04 mass %.

Prior art literature

Patent document

Patent document 1：No. WO2015/114920.

The content of the invention

But, as concrete example disclosed in patent document 1, if suppressing the use level of molybdenum, it is difficult to rub between reduction metal Wipe coefficient.

In addition, in order to suppress low speed early combustion, it is known that the calcium component in reduction machine oil is effective.But, containing dioxane In the machine oil of base molybdenum dithiocarbamate, if reduction calcium component, coefficient of friction can increase.And then, contain dialkyl disulfides For carbamic acid molybdenum, molybdenum composition in machine oil more than ormal weight, the situation that high-temperature cleaning is deteriorated is more, therefore, sometimes Coordinate substantial amounts of detergent dispersant, but detergent dispersant causes coefficient of friction to increase in most cases.

That is, it is the more than ormal weight and machine oil of calcium component reduction, it is difficult to seek to take into account high-temperature cleaning for molybdenum composition Improve the reduction with coefficient of friction.

The present invention is invention made in view of the above circumstances, and problem of the invention is to provide a kind of lubricating oil composition Thing, even if it is more than ormal weight containing molybdenum dialkyldithiocarbamacompositions, molybdenum composition and is low calcium composition, is also ensured that High-temperature cleaning, while realizing low-friction coefficient.

As a result the present inventor is had found by depth studying, for containing molybdenum dialkyldithiocarbamacompositions compound, Molybdenum composition be it is more than ormal weight and be low calcium composition lubricant oil composite, adjustment the saponification composition from calcium system cleaning agent, come The content of magnesium amount from magnesium system cleaning agent, the boron amount from boron-containing compound and Ashless friction modifiers is to meet defined pass It is formula, above-mentioned problem can be solved, so as to completes the present invention.The present invention provides following lubricant oil composite.

Lubricant oil composite, it is containing lubricant base, metal system cleaning agent, molybdenum dialkyldithiocarbamacompositions The lubricant oil composite of compound and boron-containing compound, wherein,

The metal system cleaning agent contains

Calcium salicylate and

It is at least one kind of in sulfoacid calcium and magnesium system cleaning agent,

Lubricant oil composite optionally contains Ashless friction modifiers,

In lubricant oil composite, the content of calcium atom is calculated as 0.12~0.16 mass % on the basis of lubricant oil composite total amount, together When molybdenum atom content 0.05~0.10 mass % is calculated as on the basis of lubricant oil composite total amount,

Also, the X calculated by following formula (1) is less than 0.050,

X=3.8×10^-2-2.7×10^-4×[A]-4.2×10^-1× [B]+5.4 × 10^-1×[C]-5.2×10^-3× [D]+ 7.3×10^-3×[E]・・・(1)

(in above-mentioned formula (1),

[A] is represented in the gross mass of the saponification composition from calcium salicylate, sulfoacid calcium and calcium phenoxide, the saponification from sulfoacid calcium Ratio (quality %) shared by composition,

[B] represents the content (quality %) of the magnesium atom conversion of magnesium system cleaning agent,

[C] represents the content (quality %) of the boron atom contained by lubricant oil composite,

[D] represents the content (quality %) of Ashless friction modifiers,

[E] represents the E calculated by following formula (2),

E=([A]+1) × ([B]+0.001) (2).

It should illustrate, [B]~[D] value is the value on the basis of lubricant oil composite total amount).

In addition, the present invention furthermore provides the manufacture method of following lubricant oil composite.

The manufacture method of lubricant oil composite, it is at least complexed metal system cleaning agent, dialkyl group in lubricant base Molybdenum dithiocarbamate compound and boron-containing compound and the manufacturer for obtaining the lubricant oil composite of lubricant oil composite Method,

The metal system cleaning agent contains

Calcium salicylate and

It is at least one kind of in sulfoacid calcium and magnesium system cleaning agent,

Optionally further coordinate Ashless friction modifiers in lubricant base,

In the lubricant oil composite, the content of calcium atom is calculated as 0.12~0.16 matter on the basis of lubricant oil composite total amount % is measured, while the content of molybdenum atom is calculated as 0.05~0.10 mass % on the basis of lubricant oil composite total amount,

Also, it is adjusted such that the X calculated by following formula (1) is less than 0.050,

X=3.8×10^-2-2.7×10^-4×[A]-4.2×10^-1× [B]+5.4 × 10^-1×[C]-5.2×10^-3× [D]+ 7.3×10^-3×[E]・・・(1)

(in above-mentioned formula (1),

[A] represents to come from the gross mass of saponification composition of calcium salicylate, sulfoacid calcium and calcium phenoxide, the soap from sulfoacid calcium The shared ratio (quality %) of chemical conversion point,

[B] represents the content (quality %) of the magnesium atom conversion of magnesium system cleaning agent,

[C] represents the content (quality %) of the boron atom contained by lubricant oil composite,

[D] represents the content (quality %) of Ashless friction modifiers,

[E] represents the E calculated by following formula (2),

E=([A]+1) × ([B]+0.001) (2)

It should illustrate, [B]~[D] is the value on the basis of lubricant oil composite total amount).

Invention effect

There is provided a kind of lubricant oil composite in the present invention, though its containing molybdenum dialkyldithiocarbamacompositions compound, molybdenum into It is divided into more than ormal weight and for low calcium composition, can also provides and can ensure that high-temperature cleaning, while low-friction coefficient can be realized.

Embodiment

Hereinafter, for the present invention, illustrated using embodiment.

The lubricant oil composite of present embodiment contains lubricant base, metal system cleaning agent, dialkyl dithio amino Formic acid molybdenum compound and boron-containing compound, optionally further contain Ashless friction modifiers, and above-mentioned metal system cleaning agent contains There is calcium salicylate and at least one kind of in sulfoacid calcium and magnesium system cleaning agent.

Also, for lubricant oil composite, the content of the calcium atom in said composition is using lubricant oil composite total amount as base Standard is calculated as 0.12~0.16 mass %, while the content of the molybdenum atom in said composition is counted on the basis of lubricant oil composite total amount For 0.05~0.10 mass %, also, the content of adjustment various additives, so that the X calculated by following formula (1) is less than 0.050。

X=3.8×10^-2-2.7×10^-4×[A]-4.2×10^-1× [B]+5.4 × 10^-1×[C]-5.2×10^-3× [D]+ 7.3×10^-3×[E]・・・(1)

(in above-mentioned formula (1),

[A] is represented in the gross mass of the saponification composition from calcium salicylate, sulfoacid calcium and calcium phenoxide, the saponification from sulfoacid calcium Ratio (quality %) shared by composition,

[B] represents the content (quality %) of the magnesium atom conversion of magnesium system cleaning agent,

[C] represents the content (quality %) of the boron atom contained by lubricant oil composite,

[D] represents the content (quality %) of Ashless friction modifiers,

[E] represents the E calculated by following formula (2),

E=([A]+1) × ([B]+0.001) (2),

It should illustrate, [B]~[D] value is the value on the basis of lubricant oil composite total amount).

In present embodiment, calcium amount and molybdenum amount in composition it is above-mentioned it is a range of in the case of, above-mentioned formula (1) value of " X " that is calculated in is the value that coefficient of friction is approximate between the metal determined by ring block method described later experiment.That is, " X " Value it is smaller, then intermetallic coefficient of friction is more likely to decrease, and is more readily obtained good fuel consumption characteristic.On the other hand, if X Value be more than 0.050, then coefficient of friction also uprise, it is difficult to improve fuel consumption.

Here, the effect of the coefficient of friction reduction of X value junior is big, therefore preferably X is less than 0.045, more preferably Less than 0.042, more preferably less than 0.040.

In addition, for X, its lower limit is not particularly limited, but from other performances required by lubricant oil composite From the viewpoint of balance etc., preferably more than 0.015, more preferably more than 0.030.

In addition, in present embodiment, if calcium atom content or molybdenum atom content outside the above range, X value It is not the value close to coefficient of friction, even if X value is less than 0.050, the value of coefficient of friction be able to not can also be reduced fully.

And then, if the above-mentioned higher limit of calcium molar ratio is more, such as in the case of being used as the machine oil of supercharged direct-injection engine, It is difficult to the occurrence frequency for suppressing low speed early combustion.If in addition, molybdenum amount is more than above-mentioned higher limit, easily occurring high-temperature cleaning and deteriorating Deng unfavorable condition.

Consider from these viewpoints, counted on the basis of lubricant oil composite total amount, calcium atom in lubricant oil composite contains Amount is preferably 0.12~0.16 mass %, more preferably more preferably 0.12~0.15 mass %, 0.12~0.14 mass %. In addition, the content of the molybdenum atom in lubricant oil composite is preferably 0.05~0.09 mass %, more preferably 0.05~0.08 Quality %.

And then, from coefficient of friction being maintained sufficiently low, while ensuring high-temperature cleaning well from the viewpoint of, with Counted on the basis of lubricant oil composite total amount, the content of contained boron atom is preferably 0.01~0.15 matter in lubricant oil composite Measure %, more preferably more preferably 0.01~0.10 mass %, 0.01~0.05 mass %.It is preferred that in lubricant oil composite Boron atom is from boron-containing compound described later (boron system detergent dispersant) entirely.

In addition, the content of calcium atom and magnesium atom in lubricant oil composite is total preferably with lubricant oil composite total amount On the basis of be calculated as below 0.3 mass %.It is below 0.3 mass % by these total contents, ash content can be reduced, therefore without load The heart blocks waste gas purification after-treatment device as diesel particulate filter device.In addition, these total contents are more preferably 0.25 Below quality %, more preferably below 0.20 mass %.

It should illustrate, total content of calcium atom and magnesium atom in composition is more than 0.12 mass %, preferably 0.13 More than quality %, more preferably more than 0.14 mass %.By improving total content, easily make lubricant oil composite described later Base number is more than 4mgKOH/g.

It should illustrate, the content of the magnesium atom in lubricant oil composite is counted on the basis of lubricant oil composite total amount is preferably Below 0.14 mass %, more preferably below 0.10 mass %, more preferably below 0.08 mass %.

It should illustrate, the whole amount of the preferably calcium atom in lubricant oil composite and magnesium atom comes from metal described later It is cleaning agent.

Hereinafter, illustrated in further detail for each composition contained by lubricant oil composite.

[lubricant base]

Lubricant base can be mineral oil or artificial oil, can also use the miscella of mineral oil and artificial oil.

It as mineral oil, for example, can enumerate, crude oil is subjected to air-distillation, obtained atmospheric residuum oil is depressurized Distillation, solvent deasphalting, solvent extraction, hydrogenative decomposition, solvent dewaxing, contact dewaxing, hydrogen are carried out by obtained lube cut Change purifying etc. in more than a kind of processing, the mineral oil purified, or, by by mineral oil system wax, utilize F- T synthesis The wax (GTL waxes) of the manufactures such as method carries out isomerization, the mineral oil manufactured therefrom etc..

On the other hand, as artificial oil, polybutene, alpha-olefin homo, copolymer (such as ethene-α-alkene can be enumerated Hydrocarbon copolymer) etc. polyolefin, the various esters such as polyol ester, dibasic acid ester, phosphate, the various ethers such as polyphenylene oxide, polyethylene glycol, Alkylbenzene, alkylnaphthalene etc..

Lubricant base can be used alone, and can also be combined two or more.

Kinematic viscosity of the lubricant base at 100 DEG C is preferably 2~15mm²/ s, more preferably 2~10mm²/ s, enters one Step is preferably 3~5mm²/s。

If kinematic viscosity of the base oil at 100 DEG C is more than above-mentioned lower limit, evaporation loss is reduced, therefore preferably. On the other hand, if the kinematic viscosity be above-mentioned higher limit below, caused by viscosity resistance power loss will not become it is excessive, because This is readily obtained fuel consumption improvement.

In addition, for lubricant base, the paraffinic components obtained by n-d-M ring analyses (being designated as %Cp sometimes) are preferably For more than 70%, preferably more than 75%, more preferably more than 80%.For lubricant base, by making paraffinic components be above-mentioned Below lower limit, easily cause oxidation stability etc. good.And then, kinematic viscosity of the lubricant base at 100 DEG C be 3~ 5mm²/ s, and %Cp is more than 80%, thus easily make it that oxidation stability is good.

And then, for the viscosity index (VI) of lubricant base, in order to suppress viscosity B coefficent, formula raising caused by temperature change Fuel savings, preferably more than 80, more preferably more than 90, more preferably more than 100.

It should illustrate, in lubricant oil composite, in the case of using miscella obtained by base oil of more than two kinds is combined, Kinematic viscosity, viscosity index (VI) and the %Cp of the miscella are preferably also above range.

The content of lubricant base in lubricant oil composite is counted on the basis of lubricant oil composite total amount, preferably 65~ 95 mass %, more preferably 70~95 mass %, more preferably 70~90 mass %.

[metal system cleaning agent]

The metal system cleaning agent used in present embodiment includes calcium salicylate.In present embodiment, by using calcium salicylate, Easily high-temperature cleaning is improved.

For the content of the calcium atom conversion of calcium salicylate, counted on the basis of lubricant oil composite total amount, preferably 0.08 ~0.16 mass %, more preferably 0.10~0.16 mass %, more preferably 0.10~0.14 mass %.

In addition, metal system cleaning agent is in addition to calcium salicylate, further containing sulfoacid calcium and magnesium system cleaning agent at least One.In present embodiment, as metal system cleaning agent, using sulfoacid calcium and/or magnesium system cleaning agent, thus make high-temperature cleaning Property it is good, while so that coefficient of friction is easily reduced.

It should illustrate, sulfoacid calcium and magnesium system cleaning agent can be combined both, and any one can also be used only.

As magnesium system cleaning agent, magnesium salicylate, sulfonic acid magnesium, phenol magnesium can be enumerated, sulfonic acid magnesium is preferably used.Can be independent Using a kind in them, two or more can also be mixed.The base number of magnesium system cleaning agent is not particularly limited, preferably 10~ 500mgKOH/g, more preferably 200~450mgKOH/g, more preferably 300~450mgKOH/g.

Wherein, in the case of containing sulfoacid calcium in lubricant oil composite, the content of the calcium atom of sulfoacid calcium conversion is to moisten Counted on the basis of sliding oil composition total amount, preferably 0.01~0.05 mass %, more preferably 0.01~0.04 mass %, it is further excellent Elect 0.01~0.03 mass % as.

In addition, in the case of containing magnesium system cleaning agent in lubricant oil composite, the magnesium atom conversion of magnesium system cleaning agent Content is counted on the basis of lubricant oil composite total amount, preferably 0.01~0.14 mass %, more preferably 0.01~0.10 mass %. Also, in the case of associated with sulfoacid calcium, the content of magnesium atom conversion is more preferably 0.02~0.06 mass %, not with sulphur The combination of sour calcium and in the case of being used alone, more preferably 0.04~0.08 mass %.

In addition, metal system cleaning agent can contain the metal system cleaning in addition to calcium salicylate, sulfoacid calcium, magnesium system cleaning agent Agent.As this metal system cleaning agent, the gold that can be enumerated beyond calcium phenoxide and deliming system cleaning agent and magnesium system cleaning agent Category system cleaning agent.As the metal system cleaning agent beyond deliming system cleaning agent and magnesium system cleaning agent, the cleaning of barium system can be enumerated Agent, sodium system cleaning agent, potassium system cleaning agent.

Wherein, the metal system cleaning agent preferably contained by lubricant oil composite includes cleaning selected from calcium system cleaning agent and magnesium system The metal system cleaning agent of agent.

In present embodiment, by adjust it is above-mentioned in calcium system cleaning agent contained by saponification composition amount, can adjust and rub Wipe the value of coefficient.Specifically, in the gross mass by making the saponification composition from calcium salicylate, sulfoacid calcium and calcium phenoxide, Ratio (hereinafter also referred to as " sulfonate saponification composition ") shared by saponification composition from sulfoacid calcium is improved, it is possible thereby to reduce Coefficient of friction.

Therefore, in above-mentioned formula (1), [A] for representing sulfonate saponification composition assigns the coefficient of negative, subtracted from X values Go.It should illustrate, the coefficient " -2.7 × 10 that coefficient [A] is multiplied^-4" be, by testing and its analyzing, in the profit of present embodiment The coefficient that sulfonate saponification composition is calculated for the influence of coefficient of friction is considered in sliding oil composition.

Sulfonate saponification composition (i.e., sulfoacid calcium) is easily reduced coefficient of friction, therefore preferably contains in lubricant oil composite Have, but it is also possible to do not contained in lubricant oil composite.For lubricant oil composite, even if not containing sulfonate saponification composition, By adjusting [B]~[E], it is also possible that X is in above-mentioned scope.

It should illustrate, in the case of sulfonate saponification composition, the soap from calcium salicylate, sulfoacid calcium and calcium phenoxide In the gross mass of chemical conversion point, the ratio shared by sulfonate saponification composition is preferably 10~75 mass %, more preferably 20~70 matter Measure %, more preferably 25~65 mass %.

In addition, in lubricant oil composite, magnesium system cleaning agent has the tendency of to make coefficient of friction reduction.Therefore, above-mentioned formula (1) In, [B] for representing the magnesium amount from magnesium system cleaning agent assigns the coefficient of negative, subtracted from X values.It should illustrate, coefficient The coefficient " -4.2 × 10 that [B] is multiplied^-1" it is, by testing and its analyzing, to consider in the lubricant oil composite of present embodiment The coefficient that magnesium is calculated for the influence of coefficient of friction.

And then, lubricant oil composite contains the situation of both sulfonate saponification composition (i.e., sulfoacid calcium) and magnesium system cleaning agent Under, these interaction between component, the tendency that thus there is coefficient of friction raising.The factor [E] in formula (1) represents this phase interaction With, by experiment and its analysis find that in this lubricant oil composite, the factor [E] is multiplied by 7.3 × 10^-3Correspond roughly to friction system Number is improved, in formula (1), and 7.3 × 10 are added in value " X "^-3×[E]。

As above-mentioned sulfoacid calcium or sulfonic acid magnesium, it is 300~1500, more preferably that can enumerate preferable weight-average molecular weight 400~700 alkyl aromatic compound carries out the calcium salt or magnesium salts of alkyl aryl sulfonate obtained by sulfonation.

In addition, as calcium phenoxide or phenol magnesium, alkylphenol, alkylphenol thioether, the Manny of alkylphenol can be enumerated The calcium salt or magnesium salts of uncommon reactant.

And then, as calcium salicylate or magnesium salicylate, the calcium salt or magnesium salts of alkyl salicylate can be enumerated.

As the alkyl of alkyl, preferably carbon number 4~30 contained by these each calcium system cleaning agents or magnesium system cleaning agent, The more preferably alkyl of carbon number 10~26, they can be straight chain or branched.They can be 1 grade of alkyl, 2 Level alkyl or 3 grades of alkyl.

It should illustrate, as above-mentioned each calcium system cleaning agent or magnesium system cleaning agent, can use following substantial neutral Material (neutral salt)：The Mannich of above-mentioned alkyl aryl sulfonate, alkylphenol, alkylphenol thioether, alkylphenol is anti- Answer thing, alkyl salicylate etc. directly to be reacted with oxide, the hydroxide of alkaline-earth metal (i.e., calcium or magnesium) etc., or make first Into the alkali metal salt of sodium salt, sylvite etc., then make its displacement etc. with alkali salt, thus obtain the material of substantial neutrality.

Or, can be the neutral salt that will as above obtain with excessive alkali salt, alkaline earth metal alkali water presence Material or the carbon by the neutral salt as above obtained in the presence of carbon dioxide with alkaline-earth metal obtained from lower heating Hydrochlorate or borate carry out material obtained from reacting etc..

In above-mentioned substance, if calcium system cleaning agent uses the saponification in the calcium system cleaning agent of neutral salt, calcium system cleaning agent The ratio of composition may be raised.In addition, by adjustment effect in calcium system sulfonate, calcium system phenolate, calcium system salicylate calcium Salt, calcium alkali, borate, usage amount of carbon dioxide etc., can also adjust the amount of the saponification composition contained by calcium system cleaning agent.

[molybdenum dialkyldithiocarbamacompositions compound]

In present embodiment, (" molybdenum chemical combination below, is also referred to as the molybdenum dialkyldithiocarbamacompositions compound used Thing "), specifically, it can enumerate with the compound shown in following formula (I).

[changing 1]

[in formula (I), R¹~R⁴Represent the alkyl of carbon number 4~22, R¹~R⁴Can be with identical, can also be different.X¹~X⁴Represent Sulphur atom or oxygen atom].

It is more than 4 by carbon number, the oil-soluble of molybdenum compound is good in logical formula (I).In addition, by for less than 22, Fusing point becomes than relatively low, and treatability is good, and friction reduction ability is also improved.Consider from these viewpoints, R¹~R⁴Carbon atom Number is preferably 4~18, more preferably 8~13.

R¹~R⁴Alkyl can be straight chain or side chain alkyl arbitrary form., can be with as the example of preferred alkyl Enumerate n-octyl, 2- ethylhexyls, isononyl, positive decyl, isodecyl, dodecyl, tridecyl, isotridecyl etc..

In addition, from the viewpoint of the dissolubility from base oil, storage stability and friction reduction ability, leading to formula (I) In molybdenum compound R¹And R²For identical alkyl, R³And R⁴For identical alkyl, preferably R¹And R²Alkyl and R³And R⁴ Alkyl it is different.

In addition, in logical formula (I), X¹~X⁴Represent sulphur atom or oxygen atom, X¹~X⁴Can be with identical, can also be different.It is preferred that , the ratio between sulphur atom and oxygen atom are sulphur atom/oxygen atom=1/3~3/1, more preferably 1.5/2.5~3/1.If above-mentioned In the range of, then can corrosion resistance, for lubricant base dissolubility in terms of obtain good performance.In addition, X¹~X⁴Can With all for sulphur atom or oxygen atom.

In present embodiment, the molybdenum atom preferably in lubricant oil composite is from above-mentioned molybdenum compound entirely.Therefore, it is right Above-mentioned molybdenum compound in lubricant oil composite, the content of molybdenum atom conversion is counted on the basis of lubricant oil composite total amount, excellent Elect 0.05~0.10 mass %, more preferably more preferably 0.05~0.09 mass %, 0.05~0.08 mass % as.

[boron-containing compound]

As long as the boron-containing compound detergent dispersant (boron system detergent dispersant) used in present embodiment, it is specific and Speech, can enumerate borated dispersants, alkali borate, boration epoxides, borate, borated fatty amine and Boration acid amides.Boron-containing compound can be used alone, and can also mix two or more to use.

By using these boron-containing compounds, it can make it that the high-temperature cleaning of lubricant oil composite is good.

Borated dispersants can be ashless dispersant, more specifically, for example, can enumerate, boration polyalkenyl amber Amber acid anhydrides；The not nitrogenous berated derivatives of polyalkylene succinic anhydride；Selected from including containing succinimide class, carboxylic acid amide Class, hydrocarbon monoamine, many amines of hydrocarbon, Mannich bases, phosphono amine, thio phosphono amine and phosphoramide types, thiazoles, sulfydryl Benzothiazoles (for example, such as 2,5- dimercaptos -1,3,4- thiadiazoles) and their derivative, triazole type (such as alkane Base triazole type and benzotriazole), amine, acid amides, imines, the carboxylic with more than one addition polar functional group of acid imide etc. The copolymer of acid esters (for example makes chain alkyl acrylate or methyl acrylic ester be carried out with the monomer with above-mentioned functional group Copolymerization and the product manufactured) basic nitrogen compound boric acid compound (boration basic nitrogen compound)；And their mixing Thing.

As preferred borated dispersants, boration succinimide class can be enumerated.

As boration succinimide class, alkenyl or alkyl succinic acid list acid imide can be enumerated or by alkenyl or Alkyl pyromellitic imide carries out material obtained by boration.

As alkenyl or alkyl succinic acid list acid imide, the compound shown in following logical formula (II)s can be enumerated.In addition, making For alkenyl or alkyl pyromellitic imide, the compound shown in following logical formula (III)s can be enumerated.

[changing 2]

In logical formula (II) and formula (III), R²¹、R²³And R²⁴For alkenyl or alkyl, weight average molecular weight is respectively preferably 500~ 3000, more preferably 900~3000.

If R²¹、R²³And R²⁴Weight average molecular weight be more than 500, then dissolubility that can be in lubricant base becomes Well.If in addition, less than 3000, then can expect suitably to play the effect obtained by this compound.R²³And R²⁴Can be with It is identical can also be different.

R²²、R²⁵And R²⁶The respectively alkylidene of carbon number 2~5, R²⁵And R²⁶It can be the same or different.a The integer of expression 1~10, b represents 0 or 1~10 integer.

Here, a is preferably 2~5, more preferably 2~4.If a is more than 2, it can expect to be readily obtained by boration amber The effect that amber acid imide is produced.If a is less than 5, the dissolubility for lubricant base becomes further good.

In addition, b is preferably 1~6, more preferably 2~6.If b is more than 1, it can expect suitably to play by this chemical combination The effect that thing is obtained.If b is less than 6, the dissolubility for lubricant base becomes further good.

As alkenyl, polybutylene-based, polyisobutenyl, ethylene-propylene copolymer can be enumerated, alkyl, Ke Yilie is used as Lift by they hydrogenate obtained by group.As suitable alkenyl, polybutylene-based or polyisobutenyl can be enumerated.It is polybutylene-based suitable Conjunction makes group obtained by 1- butylene and the mixture of isobutene or the isobutene polymerisation of high-purity.In addition, as suitable Alkyl typical example, can enumerate by polybutylene-based or polyisobutenyl hydrogenated obtained by group.

For boration succinimide class, for example, polyolefin is reacted with maleic anhydride, obtain alkenyl succinic anhydride, enter And polyamines and boron compound are reacted, obtain after intermediate, make the intermediate and alkenyl succinic acid anhydride reactant, carry out acid imide Change, it is hereby achieved that.Single acid imide or imidodicarbonic diamide can by change alkenyl succinic anhydride or alkyl succinic anhydride with it is many The ratio of amine is manufactured.

In addition, for boration succinimide class, the not alkenyl of boracic or alkyl amber can also be handled with boron compound The single acid imide of amber acid, alkenyl or alkyl pyromellitic imide are manufactured.

As boron compound as used herein, boric acid, borate and borate etc. can be enumerated., can be with as boric acid Enumerate orthoboric acid, metaboric acid and to boric acid (パ ラ ホ ウ acid) etc..In addition, as borate, ammonium metaborate, four can be enumerated Ammonium borates such as ammonium borate, ammonium pentaborate and eight ammonium borates etc..In addition, as borate, boric acid mono-methyl, boric acid can be enumerated Dimethyl ester, trimethylborate, boric acid mono ethyl ester, boric acid diethylester, triethyl borate, boric acid list propyl ester, boric acid dipropyl, boric acid Three propyl ester, boric acid mono-n-butylester, boric acid dibutyl ester and butyl borate etc..

As the alkali metal atom contained by alkali borate, as long as alkali metal atom, is not particularly limited, but Preferably potassium atom or sodium atom, more preferably potassium atom.

In addition, borate is comprising boron and oxygen and any electropositive compound (salt) being hydrated.It is used as borate Example, borate ion (BO can be enumerated₃ ^3-) salt, metaboric acid ion (BO₂ ^-) salt etc..It should illustrate, borate ion (BO₃ ^3-) it can for example form three borate ion (B₃O₅ ^-), tetraboric acid ion (B₄O₇ ^2-), five borate ion (B₅O₈ ^-) etc. it is various many Aggressiveness ion (polymer ion).

As specific alkali borate, for example, it can enumerate sodium tetraborate, sodium pentaborate, six Boratexes, eight boric acid Sodium, hypoboric acid sodium, potassium metaborate, three potassium borates, dipotassium tetraborate, potassium pentaborate, six potassium borates, eight potassium borates etc..In addition, alkali is golden It can also be hydrate to belong to borate.Among alkali borate, from high temperature under spatter property improve viewpoint and in base From the viewpoint of dissolubility in oil, preferably three potassium borate (KB₃O₅) and its hydrate (KB₃O₅・nH₂(n is 0.5~2.4 number to O Word)).

As boration epoxides, it can enumerate by one or more of boron compound and at least one epoxides The obtained compound of reaction product.Epoxides is that usual carbon number is 8~30, and preferably carbon number is 10~24, more It is preferred that the aliphatic epoxide that carbon number is about 12~20.As suitable aliphatic epoxide class, ten can be enumerated Dialkyl cyclic oxide, cetyl epoxides etc. and their mixture.

As the example of borate ester, can enumerate makes the suitable parent of one or more of boron compound and more than one Material obtained by the alcohol reaction of oiliness.Alcohols can use usual carbon number to be that 6~30, preferably carbon number is 8~24 Alcohols.Borate ester can also be boration phosphatide.

As borated fatty amine, can enumerate makes the amine of one or more of boron compound and carbon number 14~18 Deng the reaction of one or more of fatty amines obtained by material.Make amine and boron compound 50~300 DEG C, preferably 100~250 DEG C scope at a temperature of, with amine equivalent to the ratio between boron compound equivalent be 3：1~1：3 are reacted, it is possible thereby to manufacture boron It is acidified fatty amines.

As boration amide-type, it can enumerate by the one of straight or branched, saturation or undersaturated carbon number 8~22 Boration amide-type that the reaction product and boronic acid compounds of first aliphatic acid, urea and polyalkylene polyamine are obtained etc..

It should illustrate, be used as generation boration epoxides, borate ester, borated fatty amine, boration acid amides The concrete example of the boron compound used during class, can enumerate boron oxide, boron oxide hydrate, boron trioxide, boron trifluoride, tribromo Change boron, boron chloride, boronic acid containing (ホ ウ element acid), such as borinic acid, boric acid, tetraboric acid and metaboric acid, boron amide-type, with And the various esters of boric acid.

In boron-containing compound above, preferred boric acid dispersant, wherein preferably using boration succinimide class.Boron Acidifying succinimide class can be used alone, can also be by boration succinimide class and except boration succinimide class At least one selected from above-mentioned boron-containing compound in addition is applied in combination.

In the lubricant oil composite of present embodiment, boron-containing compound can improve high-temperature cleaning, on the other hand, boron Composition is to make the reason for coefficient of friction rises, but as long as meeting the relational expression of formula (1), it is possible to maintain fully coefficient of friction It is low.It should illustrate, find that, for boron component, the content [C] of boron atom is multiplied by 5.4 × 10 by experiment and its analysis^-1Substantially Improved corresponding to coefficient of friction, therefore, in value " X ", 5.4 × 10 are added as formula (1)^-1× [C] value.

From the viewpoint of from coefficient of friction being maintained sufficiently low, while ensuring high-temperature cleaning well, lubricating oil The content of the boron atom conversion of above-mentioned boron-containing compound in composition is counted on the basis of lubricant oil composite total amount, is preferably 0.01~0.15 mass %, more preferably 0.01~0.10 mass %, more preferably 0.01~0.05 mass %.

And then, from make coefficient of friction reduction, while ensuring high-temperature cleaning from the viewpoint of, contained by lubricant oil composite The content of boron atom relative to the molybdenum atom in lubricant oil composite content, preferably 0.1~0.8, more preferably 0.2~ 0.7, more preferably 0.3~0.6.

[Ashless friction modifiers]

Lubricant oil composite in present embodiment can contain Ashless friction modifiers, can also not contain.Lubricating oil composition Thing can further reduce coefficient of friction by containing Ashless friction modifiers.On the other hand, changed by not containing Ashless friction Enter agent, easily cause high-temperature cleaning to become good.

As Ashless friction modifiers, ester system Ashless friction modifiers, amine system Ashless friction modifiers can be enumerated.As Ashless friction modifiers, can be used alone, and two or more can also be applied in combination.

As ester system Ashless friction modifiers, the ester of aliphatic acid and aliphatic alcohol can be enumerated.It is used as aliphatic acid, Ke Yilie The aliphatic monocarboxylic acid of the alkyl with straight-chain or branched carbon number 6~30 is lifted, the carbon number of the alkyl is preferred For 8~24, more preferably 10~20.It should illustrate, alkyl said here refers to the hydrocarbon part of the carboxyl except aliphatic acid.

In addition, as aliphatic alcohol, using aliphatic polyol.Also, the ester of aliphatic acid and aliphatic alcohol can be only By partial ester obtained by a partial ester of alcohol or by full ester obtained by all alcohol esterifications, but usually using partial ester.

As above-mentioned straight-chain or the alkyl of branched carbon number 6~30, hexyl, heptyl, octyl group, nonyl can be enumerated Base, decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl, octadecane Base, nonadecyl, eicosyl, heneicosyl (ペ Application タ イ U シ Le base), docosyl, tricosyl, 20 Tetraalkyl, pentacosyl, cerul, heptacosane base, octacosyl, nonacosyl and melissyl etc. Alkyl；Hexenyl, heptenyl, octenyl, nonenyl, decene base, undecenyl, dodecenyl succinic, tridecylene base, 14 Carbene base, 15 carbene bases, hexadecene base, heptadecene base, vaccenic acid base, 19 carbene bases, eicosylene base, 20 One carbene base, two dodecenyl succinics, tricosene base, tetracosa carbon alkenyl, ppentacosene base, cerotene base, two The alkenyl of heptadecene base, two vaccenic acid bases, 29 carbene bases and melene base etc.；With two or more double bond Alkyl etc..Should illustrate, in abovementioned alkyl, alkenyl, the alkyl with two or more double bond, including can consider it is all Straight chain structure and branch structure, in addition, the position of the double bond in alkenyl and alkyl with two or more double bond is Arbitrarily.

As aliphatic acid, specifically, caproic acid can be enumerated, octanoic acid, capric acid, laurate, myristic acid, palmitic acid, hard The saturated fatty acids such as resin acid, arachidic acid, behenic acid and lignoceric acid；Myristoleic acid, palmitoleic acid, oleic acid and leukotrienes etc. Unrighted acid, preferably unrighted acid, more preferably oleic acid.

Above-mentioned aliphatic polyol is 2~6 yuan of alcohol, can enumerate ethylene glycol, glycerine, trimethylolpropane, pentaerythrite, D-sorbite etc., preferably glycerine.

That is, as ester system Ashless friction modifiers, the ester of preferably glycerine and above-mentioned aliphatic monocarboxylic acid.The ester can be complete Ester, but preferably partial ester, wherein, more preferably glycerine and partial ester obtained by above-mentioned unsaturated fat acid reaction.Specifically, can be with Enumerate the monoesters such as glycerine list macene acid esters, glycerine list palm acid ester, glycerin mono-fatty acid ester, the myristoleic acid of glycerine two The diester such as ester, the palm acid ester of glycerine two, diolein.

As amine system Ashless friction modifiers, aliphatic amine compound can be enumerated, as the aliphatic amine compound, is The amines of alkyl with straight-chain or branched carbon number 6~30.The alkyl of the amines preferably has carbon Atomicity 8~24, more preferably have carbon number 10~20.As the alkyl of carbon number 6~30, it can correspond to as upper State the alkyl illustrated in the alkyl of aliphatic acid.

As aliphatic amine compound, aliphatic monoamine can be illustrated or its alkylene oxide addition product, alkanolamine, aliphatic are more Amine, imidazolinium compounds etc..Specifically, lauryl amine, lauryl diethylamine, Lauryl Diethanolamine, dodecyl can be enumerated Dipropanolamine, palmitamide, stearylamine, stearyl tetren, oleyl amine, oil base trimethylene diamine, oil base diethanol amine with And aliphatic amine compound, the N of these aliphatic amine compounds, the polyoxyalkylene-N- of N- bis- such as N- hydroxyethyl oil-based imidazolines The amine alkylene oxide addition products such as alkyl (or alkenyl) (carbon number 6~28).

As Ashless friction modifiers, preferably ester system Ashless friction modifiers, wherein glycerine more preferably as described above and The ester of aliphatic acid, particularly, further preferably as the glycerin mono-fatty acid ester of glycerine and the partial ester of oleic acid, diolein.

In lubricant oil composite in present embodiment, for Ashless friction modifiers, found by experiment and its analysis, Its content [D] is multiplied by 5.2 × 10^-3Coefficient of friction raising is corresponded roughly to, therefore, in formula (1), subtract 5.2 from " X " × 10^-3× [D] value.

In the case of containing Ashless friction modifiers in lubricant oil composite, on the basis of lubricant oil composite total amount Meter, more preferably preferably 0.2~1.8 mass %, more preferably 0.2~1.7 mass %, 0.2~1.5 mass %.

[not ashless system's detergent dispersant of boracic]

In lubricant oil composite in present embodiment, as ashless system's detergent dispersant of not boracic, it can contain and be free of The succinimide class of boron.Pass through the succinimide class containing not boracic so that high-temperature cleaning is easily further improved.

As succinimide class, alkenyl or alkyl succinic acid list acid imide or alkenyl or alkyl can be enumerated Pyromellitic imide.As alkenyl or alkyl succinic acid list acid imide, the compound shown in above-mentioned logical formula (II) can be enumerated.Separately Outside, as alkenyl or alkyl pyromellitic imide, the compound shown in above-mentioned logical formula (III) can be enumerated.

The succinimide class of boracic is not counted on the basis of lubricant oil composite total amount, preferably 0.1~10 mass %, more Preferably 0.5~5 mass %, more preferably 1~4 mass %.

[other additives]

In lubricant oil composite, can further contain viscosity index improving agent, pour point depressant, abrasion performance agent, antioxidant, The additive for lubricant of defoamer etc..More than a kind in them can be used, two or more can also be applied in combination.

(viscosity index improving agent)

As viscosity index improving agent, the olefin-based copolymerization such as polymethacrylates system, ethylene-propylene copolymer can be enumerated Styrene based copolymers such as thing, styrenic-diene hydrogenated copolymer etc., wherein, preferred polymethacrylates system.It is used as poly- first Base acrylic ester, can be decentralized, the arbitrary form of non-dispersive type.

The weight average molecular weight of polymethacrylates system viscosity index improving agent is preferably 10,000~1,000,000, more preferably 10 Ten thousand~800,000, more preferably 300,000~600,000.It should illustrate, weight average molecular weight is measured by GPC, with polyphenyl second Alkene is worth as obtained by standard curve.

Viscosity index improving agent is counted on the basis of lubricating oil composition total amount, preferably 0.1~15 mass %, more preferably 0.5 ~12 mass %, more preferably 1~12 mass %.

(pour point depressant)

As pour point depressant, can for example enumerate vinyl-vinyl acetate copolymer, the condensation product of chloroalkane hydrocarbon and naphthalene, Condensation product, polymethacrylates, alkyl styrenes of chloroalkane hydrocarbon and phenol etc..

Pour point depressant preferably comprises 0.01~2 mass %, more preferably 0.05 on the basis of lubricant oil composite total amount ~1 mass %, more preferably 0.1~0.5 mass %.

(abrasion performance agent)

As abrasion performance agent, zinc dithiophosphate, trbasic zinc phosphate, zinc dithiocarbamate, disulfide class, thio carbon can be enumerated The sulfur-containing compounds such as esters of gallic acid, thiocarbamates；Phosphorous acid esters, phosphoric acid ester, phosphonic acid ester and their amine The phosphorus-containing compounds such as salt；The sulfur-bearings such as thiophosphorous acid esters, group thiophosphate, phosphonothiolic acid esters and their amine salt With phosphorus compound etc..Among them, preferred zinc dithiophosphate, as preferred concrete example, can enumerate dialkyl disulfides For trbasic zinc phosphate.

Abrasion performance agent is counted on the basis of lubricant oil composite total amount, preferably comprises 0.01~4 mass %, more preferably 0.05 ~3 mass %, more preferably 0.1~2 mass %.

(antioxidant)

Lubricant oil composite can further contain antioxidant.As antioxidant, amine system antioxidant, phenol system can be enumerated Antioxidant, sulphur system antioxidant, phosphorous antioxidant etc., among them, preferably amine system antioxidant, phenol antioxidant. These can suitably select arbitrary antioxygen from the known antioxidant used as the antioxidant of lubricating oil in the past Agent is used.

As amine system antioxidant, for example, it can enumerate the dialkyl group of diphenylamine, alkyl with carbon number 3~20 The diphenyl amine system antioxidant of diphenylamine etc.；The naphthalenes such as alpha-naphthylamine, alkyl-substituted phenyl-alpha-naphthylamine of carbon number 3~20 Amine system antioxidant.

In addition, as phenol antioxidant, such as 2,6- di-tert-butyl-4-methy phenols, the tertiary fourths of 2,6- bis- can be enumerated The monophenol system antioxidants such as base -4- ethyl -phenols, octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester；4, The biphenol systems such as 4'- methylene-bis(2,6-di-t-butyl phenol)s, 2,2' methylene bis (4- ethyl -6- tert-butyl phenols) resist Oxidant etc..

In addition, as sulphur system antioxidant, dilauryl -3,3'- thiodipropionate etc. can be enumerated, it is anti-as phosphorus system Oxidant, can enumerate phosphite ester etc..

These antioxidants can individually contain, or be combined a variety of and contain, it is usually preferred to combine two or more Use, more preferably combine amine system antioxidant and phenol antioxidant.

The content of antioxidant is counted on the basis of total composition, preferably 0.01~10 mass %, preferably 0.1~5 matter Measure %, more preferably 0.5~3 mass %.

(defoamer)

In addition, as defoamer, such as can enumerate silicone oil and fluoro silicone oil.The content of defoamer is with silicone conversion amount Meter, more preferably preferably 0.1~30 mass ppm, more preferably 0.5~15 mass ppm, 1~10 mass ppm.

In present embodiment, as described above, lubricant oil composite can contain lubricant base, metal system cleaning agent, two Alkyl molybdenum dithiocarbamate compound and boron-containing compound, but from practicality for, preferably comprise lubricant base, metal It is cleaning agent, molybdenum dialkyldithiocarbamacompositions compound, not boron-containing compound, the succinimide class of boracic and selected from upper State it is at least one kind of in other additives enumerated, or, contain lubricant base, metal system cleaning agent, dialkyl dithio ammonia Base formic acid molybdenum compound, boron-containing compound, the succinimide class of boracic, Ashless friction modifiers and do not enumerated selected from above-mentioned It is at least one kind of in other additives.

<The physical property of lubricant oil composite>

The preferred base number of lubricant oil composite of present embodiment is 4~more than 10mgKOH/g.By the alkali for making lubricant oil composite It is worth for more than 4mgKOH/g, the generation of the deposit of engine interior when can suppress high temperature operation prevents the accumulation of greasy filth, Engine interior is set to keep cleaning.Furthermore it is possible to neutralize the reasons such as the deterioration of engine oil and cause the acidic materials of generation, prevent Only retrial is worn away.In addition, by making base number be below 10mgKOH/g, easily make it that calcium atom, magnesium in lubricant oil composite are former The content reduction of son.

From the viewpoint of more than, the base number of lubricant oil composite is more preferably 5~10mgKOH/g, more preferably 6 ~10mgKOH/g.

Kinematic viscosity of the lubricant oil composite of present embodiment preferably at 100 DEG C is less than 12.5mm²/ s, while High-temperature high shear viscosity (HTHS viscosity) at 150 DEG C is less than 3.5mPa s.Pass through this range of viscosities, it can be ensured that supercharging is straight Lubricity in fuel-injection engine etc..

In addition, the kinematic viscosity at 100 DEG C of lubricant oil composite is more preferably 6.1~12.5mm²/ s, further preferably For 6.1~9.3mm²/s.And then, the HTHS viscosity at 150 DEG C is more preferably 1.7~3.2mPa s, more preferably 2.0 ~2.9mPa s.

[manufacture method of lubricant oil composite]

The manufacture method for the lubricant oil composite that an embodiment of the invention is related to makes at least to coordinate in lubricant base Metal system cleaning agent, molybdenum dialkyldithiocarbamacompositions compound and boron-containing compound and obtain lubricant oil composite Method, is adjusted so that the content of calcium atom, the content of molybdenum atom and the X that is calculated by formula (1) are in above-mentioned regulation model Enclose.In this manufacture method, Ashless friction modifiers can be coordinated in lubricant base, can also be mismatched.And then, it can coordinate Not the succinimide class of boracic, other additive.Details and use level of these each compositions etc. and above-mentioned each composition Details and each composition content it is identical, omit the description.

In addition, as described above, X values are the close values of value with testing coefficient of friction between the metal determined with ring block method.Cause This, if using formula (1), even if unactual manufacture lubricant oil composite, can also in advance be measured according to the formula of lubricant oil composite The coefficient of friction of the lubricant oil composite arrived.Accordingly it is also possible to X values be calculated in advance by formula (1), with X value in above-mentioned rule The mode for determining scope determines the formula of lubricant oil composite, then manufactures lubricant oil composite.

[purposes of lubricant oil composite]

Above-mentioned lubricant oil composite can be used for the lubricating oil of various uses, be preferred for the lubrication in internal combustion engine, wherein more excellent From petrol engine purposes is made, it is particularly suitable for being equipped with the supercharged direct-injection engine of direct-injection mechanism and booster body.Pass through Above-mentioned lubricant oil composite is used for this purposes, low speed early combustion can be prevented, at the same can play excellent spatter property and Fuel savings energy.

[friction of internal combustion engine reduces method]

In addition, it is to add above-mentioned in internal combustion engine that the friction for the internal combustion engine that an embodiment of the invention is related to, which reduces method, Lubricant oil composite, reduce internal combustion engine sliding surface produce friction.Above-mentioned sliding surface is preferably metal covering-metal covering.

Method is reduced by the friction of the internal combustion engine of present embodiment, makes calcium atom and molybdenum in lubricant oil composite former Son is a certain amount of, while the X calculated by formula (1) is adjusted into above-mentioned prescribed limit, it may thereby be ensured that excellent cleaning Property, while making friction minimizing effect good, realize excellent fuel savings.In addition, the situation that internal combustion engine is petrol engine is Suitably, particularly in the case of supercharged direct-injection engine, it is also possible to prevent low speed early combustion.

Embodiment

Then, the present invention is illustrated by embodiment in further detail, but the present invention is not by any restriction of these examples.

The assay method of various characters in this specification, evaluation method are as described below.

(1) kinematic viscosity

According to JIS K2283：2000, the value determined using glass system capillary viscosimeter.

(2) viscosity index (VI)

According to JIS K 2283：2000, the value of measure.

HTHS viscosity in (3) 150 DEG C

By ASTM D4683 method, using TBS viscosimeters (Tapered Bearing Simulator Viscometer), In shear rate 10⁶sec^-1, rotating speed (motor) 3000rpm, 3 μm of rotor/stator interval, determine under conditions of 150 DEG C of oil temperature The value arrived.

(4) paraffinic components (%Cp) that ring analysis is obtained

The ratio (percentage) of paraffinic components calculated with ring analysis n-d-M methods is shown, determined according to ASTM D-3238 The value arrived.

(5) saponification composition

For calcium system cleaning agent, rubber membrane dialysis is carried out, after the rubber membrane residual component HCl treatment after dialysis, will be utilized The composition that diethyl ether is obtained by extraction is quantified as saponification composition.

(6) calcium atom, magnesium atom, phosphorus atoms, molybdenum atom, the assay method of the content of boron atom

It is measured according to JPI-5S-38-92.

(7) base number

The base number of lubricant oil composite is according to JIS K2501：2003 perchlorate method is measured.In addition, metal system is cleaned The base number of agent is according to JIS K2501：2003 perchlorate method determines obtained value.

(8) coefficient of friction (LFW-1 experiments)

Use coefficient of friction between ring block method testing machine (LFW-1) measure metal.Specific experimental condition is as described below.

Test tool：

Ring：S-10 standard materials

Block：SUJ-2

Experimental condition：

Oil temperature：80℃

Loading：30kgf

Rotating speed：160rpm.

(9) heat pipe experiment

Carried out based on JPI-5S-55-99.Specifically, lubrication is made in the internal diameter 2mm glass of 280 DEG C of temperature is held in Fluid composition with 0.3ml/ hours, air was continued to flow through 16 hours with 10ml/ minutes.By the paint adhered in glass tube and colorimetric Card compares, and transparent situation is evaluated as into 10 points, and black situation is evaluated as into 0 point.Scoring is higher, and expression spatter property is higher.

[embodiment 1~9, comparative example 1~3]

Formula according to table 1, prepares each embodiment, the lubricant oil composite of comparative example.For obtained lubricating oil composition Thing, determines each character and the content of each atom in lubricant oil composite.In addition, determining friction system by LFW-1 experiments Number, while implementing heat pipe experiment.These results are shown in table 1.

It should illustrate, the use level of viscosity index improving agent be adjusted, so that the lubricant oil composite of embodiment and comparative example HTHS viscosity at 150 DEG C is 2.3mPa s.

[table 1]

It should illustrate, that Details as Follows is described for each composition in table 1.

Lubricant base：Kinematic viscosity (100 DEG C) 4.0mm²/ s, viscosity index (VI) 130, %Cp：87 mass % mineral oil

Calcium system cleaning agent 1：Calcium salicylate

Calcium system cleaning agent 2：Sulfoacid calcium

Magnesium system cleaning agent：Sulfonic acid magnesium, base number：410mgKOH/g

Friction improver：Molybdenum dialkyldithiocarbamacompositions compound

Ashless system's friction improver：Glycerin mono-fatty acid ester

Viscosity index improving agent：The polymethacrylates of weight average molecular weight 300,000

Pour point depressant：The polymethacrylates of weight average molecular weight 50,000

Additive is set with A：Boron system detergent dispersant, the not alkenyl succinimide of boracic, zinc dialkyl dithiophosphate, phenol system The mixture of antioxidant and amine system antioxidant

Additive is set with B：In additive suit A, the amount of increase boron system detergent dispersant

Additive is set with C：The not alkenyl succinimide of boracic, zinc dialkyl dithiophosphate, phenol antioxidant and amine It is the mixture of antioxidant.

As shown in Table 1, in embodiment 1~9, metal system cleaning agent, dialkyl group are contained in lubricant oil composite Calcium atom amount and molybdenum atom amount in molybdenum dithiocarbamate compound and boron-containing compound and composition are regulation Scope, while X values be less than 0.050, it is possible thereby to spatter property be maintained, while making the value of coefficient of friction reduces.

On the other hand, in comparative example 1,2, metal system cleaning agent, dialkyl dithio amino are contained in lubricant oil composite Calcium atom amount and molybdenum atom amount in formic acid molybdenum compound and boron-containing compound and composition are defined scope but X It is worth for more than 0.050, therefore coefficient of friction becomes big, it is impossible to the lubricant oil composite with good fuel savings is provided.

In addition, as shown in comparative example 3, even if X value is less than 0.050, if but not containing boron-containing compound, heat pipe experiment Scoring step-down, it is impossible to obtain enough spatter properties.

Claims (11)

1. lubricant oil composite, it is containing lubricant base, metal system cleaning agent, molybdenum dialkyldithiocarbamacompositions chemical combination The lubricant oil composite of thing and boron-containing compound, wherein,

The metal system cleaning agent contains calcium salicylate and at least one kind of in sulfoacid calcium and magnesium system cleaning agent,

The lubricant oil composite optionally contains Ashless friction modifiers,

In the lubricant oil composite, the content of calcium atom is calculated as 0.12~0.16 matter on the basis of lubricant oil composite total amount % is measured, while the content of molybdenum atom is calculated as 0.05~0.10 mass % on the basis of lubricant oil composite total amount,

Also, the X calculated by following formula (1) is less than 0.050,

X=3.8 × 10^-2-2.7×10^-4×[A]-4.2×10^-1× [B]+5.4 × 10^-1×[C]-5.2×10^-3× [D]+ 7.3×10^-3×[E]・・・(1)

In above-mentioned formula (1),

[A] is represented in the gross mass of the saponification composition from calcium salicylate, sulfoacid calcium and calcium phenoxide, the saponification from sulfoacid calcium Ratio (quality %) shared by composition,

[B] represents the content (quality %) of the magnesium atom conversion of magnesium system cleaning agent,

[C] represents the content (quality %) of boron atom contained in lubricant oil composite,

[D] represents the content (quality %) of Ashless friction modifiers

[E] represents the E calculated by following formula (2)

E=([A]+1) × ([B]+0.001) (2)

It should illustrate, [B]~[D] value is the value on the basis of lubricant oil composite total amount.

2. the lubricant oil composite described in claim 1, wherein, in lubricant oil composite, the content of calcium atom and magnesium atom The total of content is calculated as on the basis of lubricant oil composite total amount below 0.3 mass %.

3. the lubricant oil composite described in claim 1 or 2, wherein, kinematic viscosity of the lubricant base at 100 DEG C is 3~5mm²The %Cp that/s, n-d-M ring analysis are obtained is more than 80%.

4. the lubricant oil composite described in any one of claims 1 to 3, wherein, the boron-containing compound is selected from boration point At least 1 in powder, alkali borate, boration epoxides, borate, borated fatty amine and boration acid amides Kind.

5. the lubricant oil composite described in any one of Claims 1 to 4, it further contains the succinimide class of not boracic.

6. the lubricant oil composite described in any one of Claims 1 to 5, wherein, the Ashless friction modifiers are selected from ester system It is at least one kind of in Ashless friction modifiers and amine system Ashless friction modifiers.

7. the lubricant oil composite described in any one of claim 1~6, wherein, further containing selected from viscosity index improving agent, More than a kind of additive for lubricant in pour point depressant, abrasion performance agent, antioxidant and defoamer.

8. the lubricant oil composite described in any one of claim 1~7, wherein, the kinematic viscosity at 100 DEG C is less than 12.5mm²/ High-temperature high shear viscosity (HTHS viscosity) at s, and 150 DEG C is less than 3.5mPa s.

9. the lubricant oil composite described in any one of claim 1~8, its base number is 4~10mgKOH/g.

10. the lubricant oil composite described in any one of claim 1~9, it is used for internal combustion engine.

11. the manufacture method of lubricant oil composite, it is at least complexed metal system cleaning agent, dialkyl group two in lubricant base Thiocarbamic acid molybdenum compound and boron-containing compound and the manufacturer for obtaining the lubricant oil composite of lubricant oil composite Method,

The metal system cleaning agent contains calcium salicylate and at least one kind of in sulfoacid calcium and magnesium system cleaning agent,

Optionally further coordinate Ashless friction modifiers in lubricant base,

In the lubricant oil composite, the content of calcium atom is calculated as 0.12~0.16 matter on the basis of lubricant oil composite total amount % is measured, while the content of molybdenum atom is calculated as 0.05~0.10 mass % on the basis of lubricant oil composite total amount,

Also, it is adjusted such that the X calculated by following formula (1) is less than 0.050,

X=3.8 × 10^-2-2.7×10^-4×[A]-4.2×10^-1× [B]+5.4 × 10^-1×[C]-5.2×10^-3× [D]+ 7.3×10^-3×[E]・・・(1)

In above-mentioned formula (1),

[A] is represented in the gross mass of the saponification composition from calcium salicylate, sulfoacid calcium and calcium phenoxide, the saponification from sulfoacid calcium Ratio (quality %) shared by composition,

[B] represents the content (quality %) of the magnesium atom conversion of magnesium system cleaning agent,

[C] represents the content (quality %) of boron atom contained in lubricant oil composite,

[D] represents the content (quality %) of Ashless friction modifiers

[E] represents the E calculated by following formula (2)

E=([A]+1) × ([B]+0.001) (2)

It should illustrate, [B]~[D] is the value on the basis of lubricant oil composite total amount.