KR20140058531A - Lubricant composition for internal combustion engine oil - Google Patents

Abstract

조성물 전량 기준으로 인의 함유량(P질량％)과 금속계 청정제 유래의 금속 성분의 함유량(M질량％)이, 하기의 조건 A 내지 C 중 어느 하나를 만족시키는 것을 특징으로 하는 내연 기관용 윤활유 조성물이다.
A: P<0.03 및 M<0.05
B: P<0.03 및 0.05≤M≤0.12
C: 0.03≤P≤0.06 및 M<0.05
상기 내연 기관용 윤활유 조성물은 알루미늄재에 대한 내마모성을 유지하면서, 인분을 다량으로 포함하는 ZnDTP나 금속계 청정제를 대폭 저감시키는 효과를 갖는다.(B% by mass) derived from a boron-phosphide-based dispersant in a composition and a boron-phosphide-based dispersant or a boron-phosphide-based dispersant and a boron- Wherein the nitrogen content (N mass%) derived from the mid-based dispersant and the non-borohydimide-based dispersant satisfies the following formula (I)

Wherein the content of phosphorus (P mass%) and the content of metal component (M mass%) derived from the metal-based cleaner satisfy the following conditions A to C based on the total amount of the composition.
A: P < 0.03 and M < 0.05
B: P < 0.03 and 0.05 < M &
C: 0.03? P? 0.06 and M <0.05
The lubricating oil composition for an internal combustion engine has an effect of significantly reducing ZnDTP and a metal-based cleaner containing a large amount of phosphorus while maintaining abrasion resistance against an aluminum material.

Description

TECHNICAL FIELD [0001] The present invention relates to a lubricating oil composition useful as an internal combustion engine,

TECHNICAL FIELD The present invention relates to a lubricating oil composition for an internal combustion engine, and relates to a lubricating oil composition for an internal combustion engine excellent in abrasion resistance against an aluminum material even when the amount of metal derived from a phosphate or metal detergent is reduced.

BACKGROUND ART [0002] In recent years, in the automobile industry, strict regulations on exhaust gas have been introduced one after another for the purpose of reducing the environmental load, and exhaust gas post-treatment apparatuses have been developed. Exhaust gases include particulate matter (PM), hydrocarbons (HC), carbon monoxide (CO), nitrogen oxides (NO _x ) and the like which are harmful substances in addition to carbon dioxide (CO ₂ ) which is a global warming substance. The regulated value of NO _x is very strict. In order to reduce their emissions, a three-way catalyst is mounted on a gasoline vehicle and a diesel particulate filter (DPF) is mounted on the diesel vehicle. As a result, the exhaust gas is cleaned and released into the atmosphere.

In recent years, it has been reported that the engine oil poisons the active site of the three-way catalyst to lower the catalytic function, and the ash derived from the metal component is deposited on the DPF to shorten the life span. At present, the upper limit value of the phosphorus or ash content is established in the ILSAC standard or the JASO standard, which is the engine oil standard, and development of engine oil in which these amounts are reduced is under development.

 On the other hand, from the viewpoint of improving the fuel economy, the weight reduction of the engine and the mission parts due to non-ferrous is progressing. Among them, aluminum alloys, especially Al-Si alloys, are widely used. However, since additives such as zinc dithiophosphate (ZnDTP), which is the main reaction for forming a film on Fe, are used as wear resistance agents, aluminum There is a concern that the abrasion resistance of the ash decreases.

As a result, studies on a good anti-wear agent for aluminum materials have been conducted (see, for example, Patent Document 1). However, all of these wear-resistant agents do not have sufficient effect unless they are used in combination with ZnDTP containing a large amount of phosphorus, and the adverse effect on the exhaust gas post-treatment apparatus is not lost.

 Therefore, there is a desire for the emergence of a lubricating oil composition for an internal combustion engine having an excellent abrasion resistance against an aluminum material even if the content of the phosphorus is further reduced or the phosphorus is not included.

Japanese Patent Publication No. 2010-528155

An object of the present invention is to provide a lubricating oil composition for an internal combustion engine capable of significantly reducing ZnDTP and a metal detergent containing a large amount of phosphorus while maintaining abrasion resistance against an aluminum material and having excellent abrasion resistance against an aluminum material under such circumstances .

The inventor of the present invention has conducted intensive studies to develop the above-mentioned preferred lubricating oil composition for an internal combustion engine. As a result, the present inventors have found that by adjusting the nitrogen content and the boron content derived from the imide- found. The present invention has been completed based on this knowledge.

That is,

1. A boron-phosphide-based dispersant comprising a boron-phosphide-based dispersant or a boron-phosphide-based dispersant and a boron-phosphide-based dispersant, wherein the boron- (N mass%) derived from a boron hydride-based dispersant and a non-borohydimide-based dispersant satisfies the following formula (I)

Wherein the content of phosphorus (P mass%) and the content of metal component (M mass%) derived from metal detergent satisfy the following A to C based on the total amount of the composition:

A: P < 0.03 and M < 0.05

B: P < 0.03 and 0.05 &lt; M &

C: 0.03? P? 0.06 and M <0.05

(2) The boron content (B% by mass) derived from the boron hydride-based dispersant and the nitrogen content (N% by mass) derived from the boron-phosphide-based dispersant or the boron- The lubricating oil composition for an internal combustion engine as described in (1) above, which satisfies the formula (II)

3. The lubricating oil composition for an internal combustion engine as described in 1 or 2 above, further containing a sulfur-based abrasion-resistant agent, and

4. A lubricating oil composition for an internal combustion engine as described in 3 above, wherein the sulfur-based wear preventive is a disulfide compound represented by the following formula (3).

(Wherein R ¹ and R ² are each independently a hydrocarbon group of 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom or a nitrogen atom, A ¹ and A ² each independently represent a divalent Hydrocarbon group)

According to the present invention, it is possible to provide a lubricating oil composition for an internal combustion engine that is excellent in abrasion resistance against an aluminum material and can significantly reduce ZnDTP and a metal detergent containing a large amount of phosphorus while maintaining abrasion resistance against an aluminum material .

Accordingly, it is possible to provide a lubricating oil composition for an internal combustion engine that can alleviate the influence on the exhaust gas after-treatment apparatus while maintaining the abrasion resistance against the aluminum material.

The lubricating oil composition for an internal combustion engine of the present invention comprises a boron-phosphide-based dispersant or a boron-phosphide-based dispersant and a boron-phosphide-based dispersant, and contains a boron content (B% by mass) derived from a boron- (N mass%) derived from a boronimide-based dispersant or a boron-phosphide-based dispersant or a boron-phosphide-based dispersant or a boron-phosphide-based dispersant and a boron-phosphide-based dispersant.

The composition satisfying the above formula (I) can improve wear resistance.

In addition, a composition satisfying the following formula (II) can further enhance the above effects.

As described above, in the present invention, a boron hydride-based dispersant and, if necessary, a non-borohydimide-based dispersant are used.

The non-borohydimide-based dispersant is generally called an imide-based dispersant. As the non-borohydimide-based dispersant, polybutenyl succinic acid imide is preferably used. Examples of the polybutenyl succinic acid imide include compounds represented by the following formulas (1) and (2). The PIB in these formulas represents a polybutenyl group, and its number average molecular weight is usually from 800 to 3500, preferably from 900 to 2000. If the number average molecular weight is 800 or more, there is no fear that the dispersibility will deteriorate. If the number average molecular weight is 3500 or less, there is no possibility that the storage stability is lowered.

In the above formulas (1) and (2), n is usually an integer of 1 to 5, more preferably an integer of 2 to 4, so that the dispersibility is not lowered.

The production method of the polybutenyl succinic acid imide is not particularly limited, but can be produced by a known method. For example, by reacting polybutenyl succinic acid obtained by reacting polybutene and maleic anhydride at 100 to 200 ° C with polyamines such as diethylene triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine Can be obtained.

On the other hand, as the boron hydride based dispersant used in the present invention, boronated polybutenyl succinic acid imide obtained by reacting a boron compound with a non-boron hydride based dispersant exemplified by the above-mentioned formulas (1) and (2) .

Examples of the boron compound include boric acid, boric acid salt and boric acid ester. Examples of the boric acid include, for example, orthoboric acid, meta boric acid, and paraboric acid. Examples of the borate salt include ammonium salts and the like, for example, ammonium metaborate, ammonium tetraborate, ammonium borate and ammonium borate such as ammonium parbate. Examples of the boric acid ester include esters of boric acid with an alkyl alcohol (preferably having 1 to 6 carbon atoms) such as monomethyl borate, dimethyl borate, trimethyl borate, monoethyl borate, diethyl borate, triethyl borate, , Dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate and tributyl borate.

Further, the mass ratio of the boron content B to the nitrogen content N in the boronated polybutenyl succinic acid imide, B / N, is preferably 0.1 to 3, more preferably 0.2 to 2.

In the lubricating oil composition for an internal combustion engine used in the present invention, the content of the boronated succinimide-based dispersant and the non-borated succinimide-based dispersant (imide-based dispersant) Is preferably 0.1 to 15 mass%, more preferably 0.5 to 10 mass%, though it is not particularly limited. When the amount is 0.1% by mass or more, good cleanliness and dispersibility are obtained. When the amount is 15% by mass or less, the effect of improving the cleanliness and dispersibility can be obtained.

The lubricating oil composition for an internal combustion engine of the present invention is further required that the content of phosphorus (P mass%) and the content of metal components (M mass%) derived from metal detergent satisfy one of A to C above. Each case of A to C will be described below.

[Case of A]

In the case of A,

P < 0.03 and M < 0.05

That is, the content of phosphorus is less than 0.03 mass% based on the total amount of the composition, and the content of the metal component derived from the metal-based detergent is less than 0.05 mass%.

If the content of phosphorus in the composition is less than 0.03 mass%, the poisoning action of the active site of the three-way catalyst is suppressed, and the catalyst life can be prolonged. Therefore, the content of phosphorus in the composition is preferably 0.01 mass% or less, more preferably 0.005 mass% or less, and particularly preferably 0.001 mass% or less.

If the metal component derived from the metal-based detergent in the composition is less than 0.05% by mass, the ash derived from the metal component is suppressed from accumulating on the DPF, and the service life thereof can be prolonged. Therefore, the content of the metal component in the composition is preferably 0.01 mass% or less, more preferably 0.005 mass% or less, particularly preferably 0.001 mass% or less.

In order to make the content of phosphorus in the composition less than 0.03 mass%, it is necessary to restrict or not blend the amount of the wear-resistant agent containing phosphorus. Therefore, the incorporation of zinc dithiophosphate (ZnDTP), which has hitherto been widely used as a very excellent antiwear agent for lubricating oil for internal combustion engines, is also restricted or prohibited.

Further, in order to make the metal component derived from the metal-based detergent in the composition less than 0.05% by mass, it is required to restrict or prohibit the mixing of the metal-based cleaner.

[Case of B]

In the case of B,

P < 0.03 and 0.05 &lt; M &

That is, the content of phosphorus is less than 0.03 mass% based on the total amount of the composition, and the content of the metal component derived from the metal-based detergent is 0.05 mass% or more and 0.12 mass% or less.

If the content of phosphorus in the composition is less than 0.03 mass%, the poisoning action of the active site of the three-way catalyst is suppressed, and the catalyst life can be prolonged. Therefore, the content of phosphorus in the composition is preferably 0.01 mass% or less, more preferably 0.005 mass% or less, and particularly preferably 0.001 mass% or less.

In order to make the content of phosphorus in the composition less than 0.03 mass%, it is necessary to restrict or not blend the amount of the wear-resistant agent containing phosphorus. Therefore, the incorporation of zinc dithiophosphate (ZnDTP), which has hitherto been widely used as a very excellent antiwear agent for lubricating oil for internal combustion engines, is also restricted or prohibited.

If the content of the metal component derived from the metallic detergent in the composition is 0.05% by mass or more, the cleanliness required as the lubricating oil for the internal combustion engine can be further increased. On the other hand, when the content of the metal component is 0.12 mass% or less, the ash derived from the metal component is suppressed from accumulating on the DPF, and the service life thereof can be prolonged. Therefore, the content of the metal component is preferably 0.05 mass% or more and 0.10 mass% or less, particularly preferably 0.05 or more and 0.08 mass% or less.

Examples of the metal-based detergent which gives rise to the above metal component include sulfonates, phenates, salicylates and naphthenates of alkali metals (Na, K and the like) or alkaline earth metals (Ca, Mg, Ba and the like) . Among them, Ca sulphonate, Ca phenate and Ca salicylate are preferable. Further, in these metal-based cleaning agents, the base is preferably in the range of 0 to 500 mgKOH / g, more preferably 150 to 400 mgKOH / g, and particularly preferably 200 to 350 mgKOH / g in the perchloric acid method.

The metallic detergent may be used singly or in combination of two or more.

The content of the metal-based cleaning agent may be appropriately selected so as to be the content of the metal component derived from the metal-based detergent.

[Case of C]

In the case of C,

0.03? P? 0.06 and M <0.05

That is, the content of phosphorus is 0.03 mass% or more and 0.06 mass% or less based on the total amount of the composition, and the content of the metal component derived from the metal-based detergent is less than 0.05 mass%.

If the content of phosphorus in the composition is 0.03 mass% or more, the wear resistance can be further increased. On the other hand, when the content of phosphorus is 0.06 mass% or less, the poisoning action of the active site of the three-way catalyst can be suppressed, and the catalyst life can be prolonged. In this respect, the content of phosphorus is more preferably 0.03 mass% or more and 0.05 mass% or less.

The content of phosphorus can be adjusted by the blending amount of the phosphorus-based antiwear agent. Representative phosphorus-based abrasion resistance agents include dithiophosphoric acid metals such as zinc dithiophosphate (ZnDTP) and molybdenum dithiophosphate (MoDTP), phosphoric acid or phosphorous acid esters (organic phosphoric acid esters, organic phosphoric acid esters, alkyl or aryl acid phosphates, Aryl hydrogensphosphite, and amine salts thereof), thiophosphoric acid esters, and thiophosphoric acid esters. Among them, zinc dithiophosphate, that is, zinc dihydrocarbyldithiophosphate (hydrocarbyl group preferably having 1 to 18 carbon atoms, more preferably 2 to 12 carbon atoms, alkenyl group, arylalkyl group, or alkaryl group) , And particularly preferred is zinc dialkyldithiophosphate having a secondary alkyl group having 3 to 8 carbon atoms.

On the other hand, if the content of the metal component derived from the metal-based detergent in the composition is less than 0.05% by mass, accumulation of the ash derived from the metal component in the DPF is suppressed, and the service life thereof can be prolonged. Therefore, the content of the metal component in the composition is preferably 0.01 mass% or less, more preferably 0.005 mass% or less, particularly preferably 0.001 mass% or less.

The lubricating oil composition for an internal combustion engine of the present invention preferably further contains a sulfur-based abrasion-resistant agent. As the sulfur-based abrasion-resistant agent, a sulfur-based wear-resistant agent not containing phosphorus such as sulfurized oil, sulfurized fatty acid, sulfurized ester, olefin sulfide, dihydrocarbyl polysulfide and the like is preferable. Among them, a disulfide compound represented by the following formula (3) is preferable.

(Wherein R ¹ and R ² are each independently a hydrocarbon group of 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom or a nitrogen atom, A ¹ and A ² each independently represent a divalent Hydrocarbon group)

Specific examples of the sulfur-containing compound represented by the formula (3) include bis (methoxycarbonylmethyl) disulfide, bis (ethoxycarbonylmethyl) disulfide, bis (n-propoxycarbonylmethyl) Bis (n-butoxycarbonylmethyl) disulfide, bis (n-butoxycarbonylmethyl) disulfide, bis (n-butoxycarbonylmethyl) disulfide, (Cyclopropoxycarbonylmethyl) disulfide, 1,1-bis (1-methoxycarbonylethyl) disulfide, 1,1-bis (1-methoxycarbonyl- Bis (1-methoxycarbonyl-n-butyl) disulfide, 1,1-bis (1-methoxycarbonyl- (1-methoxycarbonyl-n-dodecyl) disulfide, 2,2-bis (2-methoxycarbonyl-n-propyl) disulfide, Feed, α, α-bis (α-methoxycarbonylbenzyl) disulfide, 1,1-bis Bis (2-n-propoxycarbonylethyl) disulfide, 1,1-bis (2-ethoxycarbonylethyl) disulfide, (2-cyclopropoxycarbonylethyl) disulfide, 1,1-bis (2-methoxycarbonyl-n-propyl) disulfide, Bis (2-methoxycarbonyl-n-butyl) disulfide, 1,1-bis (2-methoxycarbonyl- (3-methoxycarbonyl-n-pentyl) disulfide, 1,1-bis (2-methoxycarbonyl-1-phenylethyl) disulfide And the like.

The content of the sulfur-based wear preventive agent is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, based on the total amount of the composition. When the blending amount is 0.05 mass% or more, sufficient abrasion resistance is obtained, and when it is 5 mass% or less, there is no possibility of corrosion.

The lubricating oil composition of the present invention may be blended with an additive used in a lubricating oil composition such as conventionally known lubricating oil for an internal combustion engine as long as it does not impair the conditions such as the above-mentioned ingredients, metal components and the like required by the present invention. For example, other friction modifiers, viscosity index improvers, pour point depressants, antioxidants, rust inhibitors and the like can be mentioned.

Examples of the other friction modifiers include an ashless friction modifiers such as fatty acid esters, aliphatic amines, and higher alcohols.

As the viscosity index improver, a so-called non-dispersion type viscosity index improver such as a copolymer based on various methacrylic acid esters or any combination thereof, a hydrogenation product thereof and the like, and a so- Type viscosity index improver, and the like.

Examples of the non-dispersed or dispersed ethylene -? - olefin copolymer (propylene, 1-butene, 1-pentene and the like as the? -Olefin) and its hydride, polyisobutylene and its hydrogenated product, Diene hydrogenated copolymers, styrene-maleic anhydride ester copolymers, and polyalkylstyrenes. The molecular weight (number average molecular weight) of these viscosity index improvers is, for example, 5000 to 1000000, preferably 100000 to 800000 for dispersed and non-dispersed polymethacrylates, 800 to 800000 for polyisobutylene or its hydride, 5000, and in the case of the ethylene -? - olefin copolymer and the hydride thereof, it is 800 to 300000, preferably 10000 to 200000.

Examples of the antioxidant include phenol-based antioxidants and amine-based antioxidants. As the phenol-based antioxidant, for example, 4,4'-methylenebis (2,6-di-t-butylphenol); 4,4'-bis (2,6-di-t-butylphenol); 4,4'-bis (2-methyl-6-t-butylphenol); 2,2'-methylenebis (4-ethyl-6-t-butylphenol); 2,2'-methylenebis (4-methyl-6-t-butylphenol); 4,4'-butylidenebis (3-methyl-6-t-butylphenol); 4,4'-isopropylidenebis (2,6-di-t-butylphenol); 2,2'-methylenebis (4-methyl-6-nonylphenol); 2,2'-isobutylidenebis (4,6-dimethylphenol); 2,2'-methylenebis (4-methyl-6-cyclohexylphenol); 2,6-di-t-butyl-4-methylphenol; 2,6-di-t-butyl-4-ethylphenol; 2,4-dimethyl-6-t-butylphenol; 2,6-di-t-amyl-p-cresol; Di-t-butyl-4- (N-N'-dimethylaminomethylphenol); 4,4'-thiobis (2-methyl-6-t-butylphenol); 4,4'-thiobis (3-methyl-6-t-butylphenol); 2,2'-thiobis (4-methyl-6-t-butylphenol); Bis (3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide; Bis (3,5-di-t-butyl 4-hydroxybenzyl) sulfide; n-octadecyl 3- (4-hydroxy-3,5-di-t-butylphenyl) propionate; 2,2'-thio [diethylbis-3- (3,5-di-t-butyl 4-hydroxyphenyl) propionate]. Of these, phenol-based ones and bisphenol-based ones containing an ester group are particularly suitable.

Examples of the amine-based antioxidant include mono-octyldiphenylamine; Monoalkyldiphenylamine-based 4,4'-dibutyldiphenylamine such as monononyldiphenylamine; 4,4'-dipentyldiphenylamine; 4,4'-dioctyldiphenylamine; 4,4'-diheptyldiphenylamine; 4,4'-dioctyldiphenylamine; Dialkyldiphenylamine-based, tetrabutyldiphenylamine such as 4,4'-dinonyldiphenylamine; Tetrahexyldiphenylamine; Tetraoctyldiphenylamine; Naphthylamine-based ones such as tetramononyldiphenylamine and tetranonyldiphenylamine, and specific examples include? -Naphthylamine; Phenyl-a-naphthylamine; Butylphenyl -? - naphthylamine; Pentylphenyl -? - naphthylamine; Hexylphenyl -? - naphthylamine; Heptylphenyl -? - naphthylamine; Octylphenyl -? - naphthylamine; Naphthylamine and nonylphenyl-a-naphthylamine, and the like. Of these, dialkyldiphenylamine-based and naphthylamine-based ones are suitable.

These antioxidants may be used alone or in combination of two or more. Particularly, it is preferable to use one or more phenol antioxidants and at least one amine antioxidant in combination.

Examples of the rust inhibitor include alkyl benzene sulfonates, dinonyl naphthalene sulfonates, alkenyl succinic acid esters, and polyhydric alcohol esters.

The mixing ratio of the above-mentioned other additives may be suitably selected within a range usually used.

The lubricating oil composition of the present invention contains the various additives described above in a lubricating oil base oil (simply referred to as &quot; base oil &quot;) to obtain a lubricating oil composition having desired performance.

The base oil used in the present invention is not particularly limited and may be appropriately selected from conventionally known mineral base oils (which may be simply referred to as "mineral oil") and synthetic base oils (which may be simply referred to as "synthetic oil" Can be used.

The mineral oil may be, for example, a distillate obtained by atmospheric distillation of paraffin-derived crude oil, intermediate-machine crude oil or naphthene-derived crude oil, or distillation residue of atmospheric distillation by distillation under reduced pressure, For example, solvent refined oil, hydrogenated refined oil, hydrocracked oil, dewaxed oil, and white clay treated oil. Furthermore, the isomerization induction of waxes (slack waxes) can be used.

On the other hand, examples of the synthetic oil include poly-alpha -olefin, alpha-olefin oligomer having 8 to 14 carbon atoms, polybutene, polyol ester, alkylbenzene and the like.

In the present invention, as the base oil, one or more of the above-mentioned mineral oils may be used. The above synthetic oils may be used singly or in combination of two or more. Further, at least one mineral oil and at least one synthetic oil may be used in combination.

The content of the base oil in the composition is preferably 70% by mass or more, and more preferably 80% by mass or more.

As the base oil, the kinematic viscosity at 100 캜 is preferably 1.5 to 50 mm 2 / s, more preferably 3 to 30 mm 2 / s, and particularly preferably 3 to 15 mm 2 / s. When the kinematic viscosity at 100 DEG C is 1.5 mm &lt; 2 &gt; / s or more, the evaporation loss is small. When the kinematic viscosity is 50 mm / s or less, the power loss due to viscous resistance is suppressed.

The base oil preferably has a viscosity index of 80 or more, more preferably 90 or more, particularly 100 or more. When the viscosity index is 80 or more, viscosity change with temperature of the base oil is small and stable lubrication performance is exhibited.

As the base oil, it is preferable that the sulfur measured in accordance with JIS K 2541 is 50 mass ppm or less. When the sulfur content is 50 mass ppm or less, the wear resistance of the low friction sliding material is improved. The more preferable sulfur content is 30 mass ppm or less, furthermore 20 mass ppm or less.

Further, as the base oil, the% C _A by a ring analysis is used to not more than 3.0, preferably in terms of stability. Here,% C _A by ring analysis represents the ratio (percentage) of aromatic fractions calculated by ring analysis ndM method. When% C _A is 3.0 or less, it shows good oxidation stability. The more preferable% C _A is not more than 1.0, and further not more than 0.5.

[Example]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is by no means limited by these examples.

The composition and performance of a lubricating oil composition for an internal combustion engine (hereinafter sometimes simply referred to as &quot; lubricating oil composition &quot;) were measured by the following methods.

&Lt; Composition of lubricating oil composition >

1. Quantification of boron, phosphorus and calcium

Measured according to ASTM D5185.

2. Determination of nitrogen

And measured according to JIS K2609.

3. Sulfur

Measured according to JIS K2541.

&Lt; Performance of lubricating oil composition >

3. Evaluation of wear resistance

Using a SRV friction tester (reciprocating friction tester), a friction test was performed between the cylinder and the disk under the following test conditions to measure the abrasion loss diameter generated in the cylinder.

Exam conditions

Test piece: cylinder (standard material; SUJ2), disk (Si containing aluminum: AA (American Aluminum Association) standard "A390"

Test temperature: 130 ° C

· Load: 200N

· Amplitude: 3.0mm

· Frequency: 20Hz

· Test time: 1 hour

Example  A1 to A10 and Comparative Example  A1 to A8

A lubricating oil composition having the compositions shown in Tables 1 and 2 was prepared and its abrasion resistance was measured. The results are shown in Tables 1 and 2.

The components used in the production of the lubricating oil composition are as follows.

(1) base oil 1: hydrogenated refined mineral oil (100N), kinematic viscosity at 40 占 폚 21.0 mm2 / s, kinematic viscosity at 4.5 占 퐉 / s at 100 占 폚, viscosity index of 127,

(Perchloric acid method) 30.6 mg KOH / g, a nitrogen content 1.8% by mass, a boron content 2.1% by mass, and a boron content of 1%

(3) Boron hydride 2: polybutenyl succinic acid bisimide boron: number average molecular weight of polybutenyl group: 950, base (perchloric acid method) 25 mgKOH / g, nitrogen content 1.2 mass%, boron content 1.3 mass%

(4) Non-boron hydride 1: polybutenyl succinic acid monoimide: polybutenyl group having a number average molecular weight of 950, a base (perchloric acid method) of 44 mg KOH / g, a nitrogen content of 2.1%

(5) Non-boron hydride 2: polybutenyl succinic acid bisimide: polybutenyl group having a number average molecular weight of 1300, a base (perchloric acid method) of 11.9 mg KOH / g, a nitrogen content of 1.0%

(6) Sulfur type abrasion resistance agent: bis (n-octoxycarbonylmethyl) disulfide, sulfur content 158 mass ppm

(7) Metal cleaner: Ca salicylate, base (perchloric acid method) 270 mg KOH / g

(8) Permanent anti-wear agent: zinc dithioalkyl dithiophosphate: 9.0% by mass of Zn, 8.0% by mass of phosphorus, 17.1% by mass of sulfur, A mixture of a secondary butyl group and a secondary hexyl group

(9) Other additives: Mixtures of antioxidants (phenolic antioxidants and amine antioxidants), metal deactivators (alkylbenzotriazoles) and antifoaming agents (silicone).

The following can be seen from Tables 1 and 2.

(1) The lubricating oil composition of the present invention satisfying the formula (I) is excellent in abrasion resistance against an aluminum material (Examples A1 to A10). In particular, the abrasion resistance of the lubricating oil compositions of Examples A4 to A8 satisfying the formula (II) is superior to the aluminum material.

On the other hand, the lubricating oil composition that does not satisfy the formula (I) has a lower abrasion resistance to aluminum materials than the inventive examples A1 to A10 (Comparative Examples A1 to A8).

(2) Since the lubricating oil composition of the present invention (Examples A1 to A10) is excellent in abrasion resistance even without containing P component, and the P content and the metal component derived from the metal detergent are both extremely small, The effect of preventing poisoning of the DPF and the effect of suppressing the deterioration of the life of the DPF are excellent.

Example  B1 to B9 and Comparative Example  B1 to B7

Lubricating oil compositions having the compositions shown in Tables 3 and 4 were prepared and their abrasion resistance was measured. The results are shown in Tables 3 and 4.

The components used in the production of the lubricating oil composition and the measuring method of the composition and performance are the same as those in Examples A1 to A10 and Comparative Examples A1 to A8.

The following can be seen from Tables 3 and 4.

(1) The lubricating oil composition of the present invention satisfying the formula (I) is excellent in abrasion resistance against an aluminum material (Examples B1 to B9). In particular, the abrasion resistance of the lubricating oil compositions of Examples B5 to B8 satisfying the formula (II) is superior to the aluminum material.

On the contrary, all of the lubricating oil compositions that do not satisfy the formula (I) are inferior in abrasion resistance to aluminum materials (Comparative Examples B1 to B7).

(2) The lubricating oil composition of the present invention (Examples B1 to B9) is excellent in the anti-poisoning effect of the three-way catalyst because the abrasion resistance is good and the content of the P content is very small even if P content is hardly contained. Also, since the content of the metal component originating from the metal detergent is 0.05% by mass or more and the metal detergent is contained, the cleanliness is very good. On the other hand, since the content of the metal component originating in the metal detergent is 0.12% by mass or less, The effect is also good.

Example C1  To C10  And Comparative Example C1  To C8

Lubricating oil compositions for internal combustion engines having the compositions shown in Tables 5 and 6 were prepared and their abrasion resistance was measured. The results are shown in Tables 5 and 6.

The components used in the production of the lubricating oil composition and the measuring method of the composition and performance are the same as those in Examples A1 to A10 and Comparative Examples A1 to A8.

The following can be seen from Tables 5 and 6.

(1) The lubricating oil composition of the present invention satisfying the formula (I) is excellent in abrasion resistance against an aluminum material (Examples C1 to C10). In particular, the abrasion resistance of the lubricating oil compositions of Examples C5 to C8 satisfying the formula (II) is superior to the aluminum material.

On the other hand, all of the lubricating oil compositions that do not satisfy the formula (I) are inferior in abrasion resistance to aluminum materials (Comparative Examples C1 to C8).

(2) The lubricating oil compositions (Examples C1 to C10) of the present invention are further excellent in abrasion resistance because the P content is 0.03 mass% or more. Further, since the P content is 0.06 mass% or less, the effect of preventing the poisoning of the three-way catalyst is good. In addition, since the content of the metal powder is less than 0.05 mass%, the effect of suppressing the reduction of the lifetime of the DPF is also excellent.

[Industrial applicability]

The lubricating oil composition for an internal combustion engine of the present invention is excellent in abrasion resistance against an aluminum material and provides a lubricating oil composition for an internal combustion engine capable of significantly reducing ZnDTP and a metal detergent containing a large amount of phosphorus while maintaining abrasion resistance against an aluminum material .

Therefore, the present invention can be effectively utilized as a lubricating oil composition for an internal combustion engine capable of reducing the influence of an internal combustion engine using an aluminum material on an exhaust gas after-treatment apparatus.

Claims (4)

(B% by mass) derived from a boron-phosphide-based dispersant in a composition and a boron-phosphide-based dispersant or a boron-phosphide-based dispersant and a boron- Wherein the nitrogen content (N mass%) derived from the mid-based dispersant and the non-borohydimide-based dispersant satisfies the following formula (I)

Wherein the content of phosphorus (P mass%) and the content of metal component (M mass%) derived from metal detergent satisfy the following A to C based on the total amount of the composition.
A: P < 0.03 and M < 0.05
B: P < 0.03 and 0.05 < M &
C: 0.03? P? 0.06 and M <0.05 The method according to claim 1, wherein a boron content (B% by mass) derived from a boron phosphide-based dispersant and a nitrogen content (N% by mass) derived from a boronizedimide-based dispersant or a boronizedimide- (II) &lt; / RTI &gt; of the lubricating oil composition.

3. The lubricating oil composition according to claim 1 or 2, further comprising a sulfur-based abrasion-resistant agent. 4. The lubricating oil composition for an internal combustion engine according to claim 3, wherein the sulfur-based wear preventive is a disulfide compound represented by the following formula (3).

(Wherein R ¹ and R ² are each independently a hydrocarbon group having 1 to 30 carbon atoms which may contain an oxygen atom, a sulfur atom or a nitrogen atom, A ¹ and A ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms Lt; / RTI &gt; hydrocarbon group)