JPWO2012165106A1 - Lubricating oil additive and lubricating oil composition - Google Patents

Abstract

(A) a predetermined nitrogen-containing compound represented by the general formula (1), and (B) a predetermined boric acid ester compound represented by the general formula (2) and / or the general formula (3). As a lubricating oil additive containing a predetermined borate ester compound, and as a lubricating oil composition containing the lubricating oil additive and a lubricating base oil, a friction superior to that of a conventional oil-based friction modifier Provided are a lubricating oil additive and a lubricating oil composition containing an oil-based friction modifier that can exhibit a reduction effect under a wider range of friction conditions.

Description

  The present invention relates to a lubricating oil additive and a lubricating oil composition, and more particularly, a lubricating oil additive and a lubricating oil composition excellent in friction reduction performance, particularly drive system lubricating oil such as AT fluid and CVT fluid, and fuel saving for internal combustion engines. The present invention relates to a lubricating oil composition suitable as a mold lubricating oil.

  Lubricating oil is used for an internal combustion engine, an automatic transmission, a bearing, and the like in order to make the operation smooth. In particular, automatic transmission fluids such as AT fluid and belt type continuously variable transmission fluid (CVT fluid), and lubricating oils for engine combustion (engine fluids) have higher engine performance, higher output, and severe operating conditions. As a result, higher performance is required. Therefore, in order to satisfy such required performance, for example, various additives such as an antiwear agent, a metallic detergent, an ashless dispersant, and an antioxidant are blended in the engine oil. In addition, since extremely complicated friction characteristics are required in controlling the friction characteristics of the clutches of the automatic transmission, the automatic transmission oil includes an additive that increases the friction coefficient and an additive that decreases the friction coefficient. It is used in consideration of its temperature characteristics and durability. Further, in an internal combustion engine, energy loss is large in a friction portion where the lubricating oil is involved. Therefore, a friction modifier (friction modifier, hereinafter) is used to reduce friction, particularly in a fuel-saving lubricating oil that seeks to reduce fuel consumption. Are sometimes used as "FM").

  An additive generally used to lower the coefficient of friction is called FM. FM used for internal combustion engine oil can be classified into a molybdenum-based FM containing molybdenum and an oil-based agent-based FM that improves oiliness and reduces friction.

  Among these, although molybdenum type FM is excellent in the friction reduction effect in the initial stage of use, there is a limit in existing technology to maintain the friction reduction effect well for a long period of time. In addition, MoDTC (molybdenum dithiocarbamate), which is widely used in engine oil as a molybdenum-based FM, contains ash and sulfur, and MoDTP (molybdenum dithiophosphate) contains ash, sulfur, and phosphorus. Therefore, it is required to reduce the amount of molybdenum-based FM added to the exhaust gas purifying apparatus.

On the other hand, oil-based FMs such as ester-based, amine-based, and amide-based FMs can avoid the above-mentioned problems of molybdenum-based FMs, so that their importance increases from the viewpoint of environmental friendliness. ing. Further, most of the FM used for the drive system lubricating oil is the oil-based agent type FM.
Thus, improving the friction reduction performance of the oil-based agent system FM is an important issue today.

  As a technique related to such an oil-based agent system FM, for example, Patent Document 1 discloses a lubricating oil composition containing a (thio) urea compound as the oil-based agent system FM. Patent Document 2 discloses a lubricating oil composition containing a (thio) ureido compound as an oil-based agent system FM. And according to the lubricating oil composition of patent document 1 and 2, it is supposed that friction reduction performance can be improved rather than the lubricating oil composition containing the conventional oiliness agent type | system | group FM.

Japanese Patent Laid-Open No. 2005-120242 JP-A-2005-120243

  However, the lubricating oil composition containing the oil-based agent system FM described in Patent Documents 1 and 2 has a problem that the degree of the friction reducing effect can vary relatively depending on, for example, the sliding speed. The rotational speed of the internal combustion engine can vary over a wide range, for example, 600 to 8000 rpm, depending on operating conditions. Therefore, when such a lubricating oil composition containing an oil-based agent system FM is used as an engine oil or an automatic transmission oil, depending on the use conditions, the lubricating oil composition containing a molybdenum-based FM has a friction reducing effect. There was a risk of being inferior.

  Therefore, in view of the above circumstances, the present invention provides a lubricating oil additive containing an oil-based friction modifier that can exhibit a friction reducing effect superior to that of conventional oil-based friction modifiers under a wider range of friction conditions. An object is to provide a lubricating oil composition. In addition, the present invention provides a lubricating oil composition that is particularly suitable as a lubricating oil for automatic transmission oil and internal combustion engines.

In order to solve the above problems, the present invention takes the following means. That is,
The first aspect of the present invention includes (A) a nitrogen-containing compound represented by the general formula (1), and (B) a borate ester compound represented by the general formula (2) and / or the general formula ( It is a lubricating oil additive characterized by containing the boric acid ester compound represented by 3).

（一般式（１）において、Ｒ^１は炭素数１以上３０以下の炭化水素基、又は機能性を有する炭素数１以上３０以下の炭化水素基であり；Ｒ^２、Ｒ^３、及びＲ^４は、それぞれ独立に、炭素数１以上３０以下の炭化水素基、機能性を有する炭素数１以上３０以下の炭化水素基、又は水素原子であり；ｍは０又は１の整数であり、ｍが１の場合、ｎは０又は１の整数である。）

(In General Formula (1), R ¹ is a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms having functionality; R ² , R ³ , and R ⁴ are Each independently represents a hydrocarbon group having 1 to 30 carbon atoms, a functional hydrocarbon group having 1 to 30 carbon atoms, or a hydrogen atom; m is an integer of 0 or 1, and m is 1 In this case, n is an integer of 0 or 1.)

（一般式（２）において、Ｒ^５は炭素数１以上３０以下の炭化水素基、又は機能性を有する炭素数１以上３０以下の炭化水素基であり；Ｒ^６及びＲ^７は、それぞれ独立に、炭素数１以上３０以下の炭化水素基、機能性を有する炭素数１以上３０以下の炭化水素基、又は水素原子である。）

(In General Formula (2), R ⁵ is a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms having functionality; R ⁶ and R ⁷ are each independently A hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms having functionality, or a hydrogen atom.)

（一般式（３）において、Ｒ^８は炭素数１以上３０以下の炭化水素基、又は機能性を有する炭素数１以上３０以下の炭化水素基であり；Ｒ^９及びＲ^１０は、それぞれ独立に、炭素数１以上３０以下の炭化水素基、機能性を有する炭素数１以上３０以下の炭化水素基、又は水素原子である。）

(In General Formula (3), R ⁸ is a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms having functionality; R ⁹ and R ¹⁰ are each independently A hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms having functionality, or a hydrogen atom.)

  Here, in the present invention, the “functional hydrocarbon group” means a hydrocarbon group containing oxygen, nitrogen, sulfur, phosphorus, etc. in the hydrocarbon group. For example, esters, carboxylic acids, ethers And hydrocarbon groups derived from amides, amines and the like.

  1st aspect of this invention WHEREIN: It is preferable that the molar ratio of the boron conversion molar content of (B) component with respect to the molar content of (A) component is 0.05 or more and 4.0 or less.

In the present invention, the “component (A)” means the “(A) nitrogen-containing compound represented by the general formula (1)”. The “component (B)” means the above “(B) borate ester compound represented by general formula (2) and / or borate ester compound represented by general formula (3)”. The “(B) component-based molar content of component (B)” means a molar amount obtained by converting the content of the (B) component into the content of boron. That is, 1 mol of the boric acid ester compound represented by the general formula (2) corresponds to 1 mol of the boron equivalent molar content of the component (B), and 1 mol of the boric acid ester compound represented by the general formula (3) is (B Corresponds to a boron equivalent molar content of 3 moles). "Molar ratio of (B) component-based molar content to (A) component's molar content" means division ((B) component-based molar content of boron) / ((A) component's molar content amount)
Means the molar ratio calculated by. In addition, when (A) component contains a some compound, the molar content of (A) component is the sum of the molar content of all the compounds which belong to (A) component.
Moreover, when (B) component contains a some compound, the molar amount of (B) component is the sum of the boron conversion molar content of all the compounds which belong to (B) component.

  The lubricant additive according to the first aspect of the present invention includes a lubricant base oil, an ashless dispersant, an antioxidant, a friction modifier, an antiwear agent, a metallic detergent, a viscosity index improver, a corrosion inhibitor, You may further contain at least 1 sort (s) chosen from a rust preventive, a demulsifier, a metal deactivator, an antifoamer, and a coloring agent.

  According to a second aspect of the present invention, there is provided a lubricating oil composition comprising a lubricating base oil and the lubricating oil additive according to the first aspect of the present invention.

  In the present invention, an “automatic transmission” means a transmission having a function of automatically switching a gear ratio, and is generally represented by a torque converter type in which a torque converter and a multi-stage transmission are combined. The concept is not limited to an automatic transmission (AT), but also includes a continuously variable transmission (CVT: for example, a belt type, a chain type, a toroidal type, etc.) capable of changing a gear ratio continuously and continuously. .

  The lubricating oil additive according to the first aspect of the present invention contains both the component (A) and the component (B). Therefore, according to the first aspect of the present invention, a lubricating oil containing an oil-based friction modifier that can exhibit a friction reducing effect superior to that of a conventional oil-based friction modifier under a wider range of friction conditions. Additives can be provided.

  The lubricating oil composition according to the second aspect of the present invention includes the lubricating oil additive according to the first aspect of the present invention. Therefore, according to the second aspect of the present invention, the oil-based agent friction capable of exhibiting a friction reducing effect superior to the lubricating oil composition containing the conventional oil-based agent friction modifier under a wider friction condition. Lubricating oil compositions containing the modifier can be provided.

It is a graph which compares the test result of Example 1 and the test result of a comparative example. It is a graph which compares the test result of Example 3, and the test result of a comparative example. It is a graph which compares the test result of Example 2 and the test result of a comparative example. It is a graph which compares the test result of Examples 1, 4, and 5 with the test result of the comparative example 1. FIG. It is a graph which shows the test result of Example 1, 6-8.

  Hereinafter, the present invention will be described in detail.

1. Lubricating oil additive The lubricating oil additive according to the first aspect of the present invention will be described.
<(A) component>
The component (A) in the present invention is a nitrogen-containing compound represented by the general formula (1).

  In the general formula (1), m is an integer of 0 or 1, and when m is 1, n is an integer of 0 or 1. n is more preferably 0.

In the general formula (1), R ¹ is a hydrocarbon group having 1 to 30 carbon atoms or a functional hydrocarbon group having 1 to 30 carbon atoms, preferably a hydrocarbon group having 10 to 30 carbon atoms. It is a hydrocarbon group having 10 to 30 carbon atoms and having a group or functionality.

  Here, specific examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkylcycloalkyl group, an alkenyl group, an aryl group, an alkylaryl group, and an arylalkyl group.

  As the alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, Examples thereof include alkyl groups such as a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.

  As said cycloalkyl group, C5-C7 cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, can be mentioned, for example.

  Examples of the alkylcycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a diethylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylethylcyclohexyl group, a diethylcyclohexyl group, a methylcycloheptyl group, and a dimethyl group. Examples thereof include an alkylcycloalkyl group having 6 to 30 carbon atoms, such as a cycloheptyl group, a methylethylcycloheptyl group, and a diethylcycloheptyl group (the substitution position of the alkyl group with the cycloalkyl group is arbitrary).

  Examples of the alkenyl group include butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, An alkenyl group such as an octadecenyl group (the position of these double bonds is arbitrary) can be mentioned.

  As said aryl group, aryl groups, such as a phenyl group and a naphthyl group, can be mentioned, for example.

  Examples of the alkylaryl group include tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, and decylphenyl group. An alkylaryl group having 7 to 30 carbon atoms, such as an undecylphenyl group and a dodecylphenyl group (the alkyl group is preferably a straight chain. The substitution position on the aryl group is optional, but preferably the para position Can be mentioned).

  Examples of the arylalkyl group include arylalkyl groups having 7 to 30 carbon atoms such as benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, and phenylhexyl group (the alkyl group is a straight chain). The substitution position on the alkyl group is arbitrary, but the ω position (the chain end opposite to the α position is preferred).

The hydrocarbon group for R ¹ is more preferably an alkyl group or an alkenyl group. R ¹ is more preferably an alkyl group or alkenyl group having 12 to 24 carbon atoms or a functional alkyl group or alkenyl group having 12 to 24 carbon atoms, and particularly preferably an alkenyl group having 12 to 24 carbon atoms. It is. When R ¹ is an alkenyl group, the alkyl group sandwiching the double bond is preferably a straight chain. From the viewpoint of enhancing the solubility in the base oil, and when n is 1 in the general formula (1), it is preferable number of carbon atoms of R ¹ is 16 or more.

In addition, when R ¹ is an alkyl group, R ¹ is preferably linear. However, from the viewpoint of facilitating use under low temperature conditions, R ¹ is an alkyl group having a structure having a methyl group at the α-position of the N— (C═O) _n — group in the general formula (1). Is more preferable. This is because when R ¹ is an alkyl group having such a structure, the freezing point can be lowered as compared with the case where R ¹ is a completely linear alkyl group.

In General Formula (1), R ² , R ³ , and R ⁴ are each independently a hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms having functionality, or hydrogen an atom, it is preferable that at least one of R ³ and R ⁴ are hydrogen atoms, and more preferably both of R ³ and R ⁴ are hydrogen atoms. By making R ³ and / or R ⁴ a hydrogen atom, the adsorption force on the friction surface is increased, so that it is easy to enhance the friction reduction effect.

  As a preferable example of the nitrogen-containing compound represented by the general formula (1), for example, when m is 1 and n is 0, the hydrocarbon group having 1 to 30 carbon atoms or the number of carbon atoms having functionality is 1 It is a urea compound having a hydrocarbon group of 30 or less.

As a method for synthesizing such a urea compound, a known synthesis method can be used without any particular limitation.
For example, the synthesis method by reaction of an isocyanate compound and ammonia or an amine compound represented by the following general formula (4) can be mentioned.

Here, as an isocyanate compound in the said General formula (4), a well-known isocyanate compound can be especially used without a restriction | limiting. As an isocyanate compound which can be used for the reaction represented by the general formula (4), for example, R ¹ is a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon group having 1 to 30 carbon atoms having functionality. An isocyanate compound, preferably an isocyanate compound in which R ¹ is a hydrocarbon group having 10 to 30 carbon atoms or a functional hydrocarbon group having 10 to 30 carbon atoms, more preferably R ¹ has 12 to 24 carbon atoms. Examples thereof include the following alkyl groups or alkenyl groups or isocyanate compounds having a functional hydrocarbon group having 12 to 24 carbon atoms, particularly preferably an isocyanate compound having an alkenyl group having 12 to 24 carbon atoms.

  In the reaction represented by the general formula (4), a known primary or secondary amine compound or ammonia can be used as a nucleophile without particular limitation. Examples of the primary or secondary amine compound usable for the reaction represented by the general formula (4) include, for example, a hydrocarbon group having 1 to 30 carbon atoms or a hydrocarbon having 1 to 30 carbon atoms having functionality. An amine compound having a group, preferably an amine compound having a hydrocarbon group having 1 to 10 carbon atoms, more preferably an amine compound having a hydrocarbon group having 1 to 4 carbon atoms.

  More preferable specific examples of the nitrogen-containing compound represented by the general formula (1) include, for example, dodecyl urea, tridecyl urea, tetradecyl urea, pentadecyl urea, hexadecyl urea, heptadecyl urea, octadecyl urea, oleyl urea, stearyl urea. And a urea compound having at least one alkyl group or alkenyl group having 12 to 24 carbon atoms.

  Other preferable examples of the nitrogen-containing compound represented by the general formula (1) include, for example, when m is 1 and n is 1, a hydrocarbon group having 1 to 30 carbon atoms or carbon having functionality. A ureido compound having a hydrocarbon group of 1 to 30 can be exemplified.

As a method for synthesizing the ureido compound, a known synthesis method can be used without particular limitation.
For example, a synthesis method represented by the following general formula (5) by a reaction between an acid chloride and urea or a urea compound can be given.

In addition, as an acid chloride in reaction represented by the said General formula (5), a well-known acid chloride can be especially used without a restriction | limiting. The acid chloride usable in the reaction represented by general formula (5), For example, R ¹ is a hydrocarbon group having 1 to 30 carbon atoms having 1 to 30 hydrocarbon group or a functional carbon Carboxylic acid chloride, preferably R ¹ is a hydrocarbon group having 10 to 30 carbon atoms or a functional hydrocarbon group having 10 to 30 carbon atoms, more preferably R ¹ is Carboxylic acid chloride which is an alkyl group or alkenyl group having 10 to 24 carbon atoms or a hydrocarbon group having 10 to 24 carbon atoms having functionality, particularly preferably R ¹ is an alkenyl group having 12 to 24 carbon atoms. Mention may be made of certain carboxylic acid chlorides.

  Moreover, as a urea compound in reaction represented by the said General formula (5), a well-known urea compound can be especially used without a restriction | limiting. Examples of urea compounds that can be used in the reaction represented by the general formula (5) include urea, N-methylurea, N-ethylurea, N-tert-butylurea, N, N′-dimethylurea and the like. These urea compounds can be obtained, for example, by a known synthesis method such as a reaction between an isocyanate and ammonia or an amine compound.

  Other preferable examples of the nitrogen-containing compound represented by the general formula (1) include, for example, when m is 0, a hydrocarbon group having 1 to 30 carbon atoms or a functional group having 1 to 30 carbon atoms. And amide compounds having a hydrocarbon group.

  As a method for synthesizing the amide compound, a known synthesis method can be used without particular limitation.

  The content of the component (A) in the lubricating oil additive of the present invention is not particularly limited. For example, it can be set to an amount that realizes a normal or preferable content of the component (A) in the lubricating oil composition of the present invention described later.

<(B) component>
The component (B) in the present invention is a boric acid ester compound represented by the following general formula (2), a boric acid ester compound represented by the following general formula (3), or a mixture thereof.

（一般式（２）において、Ｒ^５は炭素数１以上３０以下の炭化水素基、又は機能性を有する炭素数１以上３０以下の炭化水素基であり；Ｒ^６及びＲ^７は、それぞれ独立に、炭素数１以上３０以下の炭化水素基、機能性を有する炭素数１以上３０以下の炭化水素基、又は水素原子である。）

(In General Formula (2), R ⁵ is a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms having functionality; R ⁶ and R ⁷ are each independently A hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms having functionality, or a hydrogen atom.)

（一般式（３）において、Ｒ^８は炭素数１以上３０以下の炭化水素基、又は機能性を有する炭素数１以上３０以下の炭化水素基であり；Ｒ^９及びＲ^１０は、それぞれ独立に、炭素数１以上３０以下の炭化水素基、機能性を有する炭素数１以上３０以下の炭化水素基、又は水素原子である。）

(In General Formula (3), R ⁸ is a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms having functionality; R ⁹ and R ¹⁰ are each independently A hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms having functionality, or a hydrogen atom.)

  As the component (B) in the present invention, either a borate ester compound represented by the general formula (2) or a borate ester compound represented by the general formula (3) may be used. However, the borate compound represented by the general formula (2) is more preferable. As described above, the boric acid ester compound represented by the general formula (2) and the boric acid ester compound represented by the general formula (3) may be used in combination.

  The hydrocarbon group having 1 to 30 carbon atoms in the general formula (2) and the general formula (3) is preferably an alkyl group or alkenyl group having 1 to 30 carbon atoms, and more preferably an alkyl group. . The number of carbon atoms is preferably 3 or more, more preferably 8 or more, still more preferably 12 or more, and preferably 24 or less.

The borate ester represented by the general formula (2) reacts, for example, the alcohol having a hydrocarbon group having 1 to 30 carbon atoms with orthoboric acid (H ₃ BO ₃ ) in a molar ratio of 3: 1. Can be obtained.

The boric acid ester represented by the general formula (3) is, for example, a reaction between the alcohol having a hydrocarbon group having 1 to 30 carbon atoms and orthoboric acid (H ₃ BO ₃ ) in a molar ratio of 1: 1. Can be obtained.

  The reaction conditions in the borate ester synthesis are not particularly limited. However, it is usually particularly preferable to set the reaction temperature to 100 ° C. or higher, and it becomes possible to simultaneously remove water generated as the reaction proceeds.

  Specific examples of the component (B) include, specifically, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tri-sec-butyl borate, tri-tert-butyl borate, Trihexyl borate, trioctyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, triphenyl borate, tribenzyl borate, triphenethyl borate, tritolyl borate, tri (ethylphenyl) borate, tri ( Propylphenyl) borate, tri (butylphenyl) borate, tri (nonylphenyl) borate and the like. Among these, tri-n-butyl borate, trioctyl borate, tridodecyl borate and the like are particularly preferable.

  The content of the component (B) in the lubricating oil additive of the present invention is not particularly limited. For example, it can be set to an amount that realizes a normal or preferable content of the component (B) in the lubricating oil composition of the present invention described later.

In the lubricating oil additive of the present invention and the lubricating oil composition to be described later, the molar ratio of the molar equivalent of the component (B) to the molar content of the component (A) (the molar content of the component (B) in terms of boron / (A) Component molar content is preferably 4 or less, more preferably 3.5 or less, and even more preferably 3 or less. Further, it is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.5 or more, and particularly preferably 1 or more.
As described above, “(B) component-converted molar content of component (B)” is a molar amount obtained by converting the content of component (B) to the content of boron. That is, 1 mol of the boric acid ester compound represented by the general formula (2) corresponds to 1 mol of the boron equivalent molar content of the component (B), and 1 mol of the boric acid ester compound represented by the general formula (3) is (B Corresponds to a boron equivalent molar content of 3 moles).
Even when the component (A) and / or the component (B) contains a plurality of different compounds, the preferred molar ratio between the molar content of the component (A) and the molar molar content of the component (B) is the same as above. It is. At this time, when the component (A) includes a plurality of compounds, the molar content of the component (A) is the sum of the molar contents of all the compounds belonging to the component (A). Moreover, when (B) component contains a some compound, the boron conversion molar content of (B) component is the sum of the boron conversion molar content of all the compounds which belong to (B) component.
The friction reducing effect of the lubricating oil additive and the lubricating oil composition of the present invention is further improved by making the molar ratio of the molar equivalent of boron content of the component (B) to the molar content of the component (A) within the above preferred range. It becomes possible to raise.

  In the lubricating oil additive of the present invention and the lubricating oil composition described later, at least one selected from (C) an ashless dispersant, (D) an antioxidant, and (E) an antiwear agent containing a phosphorus element. Preferably it contains seeds.

<(C) component>
(C) As the ashless dispersant, a known ashless dispersant that can be contained in the lubricating oil composition can be used without particular limitation. Examples of compounds that can be used as component (C) include nitrogen-containing compounds having at least one linear or branched alkyl group or alkenyl group having 40 to 400 carbon atoms in the molecule and derivatives thereof, and alkenyl succinates. Examples include modified products of acid imides (for example, modified products of boric acid, modified products of sulfur compounds, acylated modified products, etc.). One or two or more compounds arbitrarily selected from these can be blended.
The alkyl group or alkenyl group has 40 or more carbon atoms, preferably 60 or more carbon atoms, and 400 or less, preferably 350 or less. When the carbon number of the alkyl group or alkenyl group is less than 40, the solubility of the compound in the lubricating base oil decreases. On the other hand, when the carbon number of the alkyl group or alkenyl group exceeds 400, the low temperature of the lubricating oil composition Since fluidity | liquidity deteriorates, it is unpreferable respectively. This alkyl group or alkenyl group may be linear or branched. Preferable examples of the alkyl group or alkenyl group include those derived from olefin oligomers such as propylene, 1-butene and isobutylene, and co-oligomers of plural types of olefins such as ethylene and propylene co-oligomers. Examples include branched alkyl groups and branched alkenyl groups.

  When the (C) component is contained in the lubricating oil additive of the present invention, the content thereof is, for example, an amount that realizes a normal or preferred content of the (C) component in the lubricating oil composition of the present invention described later. It can be.

<(D) component>
(D) As antioxidant, the well-known antioxidant which can be used for lubricating oil compositions, such as a phenolic antioxidant, an amine antioxidant, and a metal antioxidant, can be especially used without a restriction | limiting. . By adding the antioxidant, the antioxidant property of the lubricating oil composition can be further enhanced, so that the base number maintainability and the high temperature cleanability of the lubricating oil additive of the present invention and the lubricating oil composition described later can be further enhanced. .

  Examples of phenolic antioxidants include 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-bis (2,6-di-tert-butylphenol), 4,4 ′. -Bis (2-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-isopropylidenebis (2,6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6) -Nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,2'-methylenebis (4-methyl) 6-cyclohexylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2, 6-di-tert-butyl-α-dimethylamino-p-cresol, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 4,4′-thiobis (2-methyl) -6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl- 4-hydroxy-5-tert-butylbenzyl) sulfide, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide Rufide, 2,2′-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tridecyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octyl-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, octyl-3- (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate, etc. are preferred Specific examples can be given. You may use these in mixture of 2 or more types.

Examples of amine-based antioxidants include phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine, and di (alkylphenyl) amine.
You may use these in mixture of 2 or more types.
In addition, you may mix | blend combining the said phenolic antioxidant and amine type | system | group antioxidant.

  When the (D) component is contained in the lubricating oil additive of the present invention, the content thereof is, for example, an amount that realizes a normal or preferred content of the (D) component in the lubricating oil composition of the present invention described later. It can be.

<(E) component>
(E) As an antiwear agent containing phosphorus element, for example, phosphites, phosphate esters, metal salts and amine salts of phosphites, and metal salts and amine salts of phosphate esters Preferable examples can be given. Examples of phosphorus compounds that can be used as the component (E) include phosphorous acid monoesters, monothiophosphorous acid monoesters, dithiophosphorous acid monoesters, trithiophosphorous acid monoesters, phosphorous acid diesters, and monothiophosphorous acids. Acid diester, dithiophosphite diester, trithiophosphite diester, phosphoric monoester, monothiophosphoric monoester, dithiophosphoric monoester, trithiophosphoric monoester, phosphoric diester, monothiophosphoric diester, dithiophosphoric diester, trithiophosphoric diester Phosphonic acid monoester, monothiophosphonic acid monoester, dithiophosphonic acid monoester and the like.
Examples of the metal salt of the phosphorus compound that can be used as the component (E) include metal salts obtained by allowing metal bases such as metal chlorides, metal hydroxides, and metal oxides to act on these phosphorus compounds. be able to.

  The hydrocarbon group in the compound of the above component (E) may include all possible linear structures and branched structures. In addition, the position of the double bond of the alkenyl group, the position of bonding of the alkyl group to the cycloalkyl group, the position of bonding of the alkyl group to the aryl group, and the position of bonding of the aryl group to the alkyl group are arbitrary. These hydrocarbon groups may have a (poly) alkylene oxide group such as a (poly) ethylene oxide group or a (poly) propylene oxide group.

  (E) As a suitable specific example of a component, it is C1-C24, Preferably it is C4-C18, Most preferably, it is C1-C12, 1st grade, 2nd grade, or 1st grade. Mention may be made of phosphorus compounds having tertiary alkyl groups and their metal and amine salts.

  Here, the metal in a metal salt is not restrict | limited at all. Examples include alkali metals such as lithium, sodium, potassium, and cesium; alkaline earth metals such as calcium, magnesium, and barium; heavy metals such as zinc, copper, iron, lead, nickel, silver, manganese, and molybdenum. . Among these, alkaline earth metals such as calcium and magnesium and zinc are preferable, and zinc is most preferable.

  Specific examples of the amine compound in the amine salt include ammonia, monoamine, diamine, and polyamine. More specifically, an aliphatic amine having an alkyl group or an alkenyl group having 10 to 20 carbon atoms such as decylamine, dodecylamine, dimethyldodecylamine, tridecylamine, heptadecylamine, octadecylamine, oleylamine and stearylamine ( These may be linear or branched)).

  When the component (E) is contained in the lubricating oil additive of the present invention, the content is not particularly limited. For example, it can be set to an amount that realizes a normal or preferable content of the component (E) in the lubricating oil composition of the present invention described later.

2. Lubricating oil composition The lubricating oil composition according to the second aspect of the present invention will be described. The lubricating oil composition of the present invention includes at least a lubricating base oil and the above-described lubricating additive according to the first aspect of the present invention.

<Lubricant base oil>
The lubricating base oil in the lubricating oil composition of the present invention is not particularly limited, and a mineral base oil and / or a synthetic base oil used for ordinary lubricating oils can be used.

  Specifically, as the mineral base oil, the lubricating oil fraction obtained by subjecting the crude oil to atmospheric distillation obtained under reduced pressure is subjected to solvent removal, solvent extraction, hydrocracking, Method to isomerize GTL WAX (gas-to-liquid wax) produced by one or more processes such as solvent dewaxing, hydrorefining, etc., or wax isomerized mineral oil, Fischer-Tropsch process, etc. The lubricating base oil produced in (1) can be exemplified.

The total aromatic content of the mineral oil base oil is not particularly limited. However, the total amount of the base oil is 100% by mass, preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 6% by mass or less, further preferably 3% by mass or less, and particularly preferably 2% by mass. It is as follows.
The total aromatic content is most preferably 0% by mass. When the total aromatic content of the base oil exceeds 15% by mass, oxidation stability is inferior, which is not preferable.
In addition, the said total aromatic content means the aromatic fraction (aromatic fraction) content measured based on ASTMD2549. Usually, this aromatic fraction includes alkylbenzene, alkylnaphthalene, anthracene, phenanthrene, and alkylated products thereof, compounds in which four or more benzene rings are condensed, or pyridines, quinolines, phenols, naphthols, etc. Compounds having heteroaromatics and the like are included.

  Moreover, the sulfur content in the mineral oil base oil is not particularly limited. However, it is preferably 0.05% by mass or less, more preferably 0.01% by mass or less, and particularly preferably 0.001% by mass or less. By reducing the sulfur content of the mineral oil base oil, a low-sulfur lubricating oil composition that is more excellent in long drainage can be obtained.

Synthetic lubricating oils include poly-α-olefins such as 1-octene oligomers and 1-decene oligomers or their hydrides, isobutene oligomers or their hydrides, paraffins, alkylbenzenes, alkylnaphthalenes, diesters (ditridecylglutarate). , Di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, etc., polyol ester (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, Pentaerythritol pelargonate), polyoxyalkylene glycol, dialkyl diphenyl ether, polyphenyl ether, and the like.
Moreover, aromatic synthetic oils such as alkylnaphthalene, alkylbenzene, and aromatic ester, or a mixture thereof can be exemplified. Among these, poly-α-olefin is preferable. As the poly-α-olefin, typically, an α-olefin oligomer or co-oligomer having 2 to 32 carbon atoms, preferably 6 to 16 carbon atoms (1-octene oligomer, decene oligomer, ethylene-propylene co-oligomer, etc.) And their hydrides.

  In the lubricating oil composition of the present invention, a mineral base oil, a synthetic base oil, or an arbitrary mixture of two or more kinds of lubricating oils selected from these can be used as the lubricating base oil. Examples thereof include one or more mineral base oils, one or more synthetic base oils, a mixed oil of one or more mineral base oils and one or more synthetic base oils, and the like.

The kinematic viscosity of the lubricating base oil is not particularly limited. However, the kinematic viscosity at 100 ° C. of the lubricating base oil is preferably 20 mm ² / s or less, and more preferably 10 mm ² / s or less. On the other hand, the kinematic viscosity at 100 ° C. is preferably 1 mm ² / s or more, and more preferably 2 mm ² / s or more. When the kinematic viscosity at 100 ° C. of the lubricating base oil exceeds 20 mm ² / s, the low-temperature viscosity characteristics deteriorate, whereas when the kinematic viscosity at 100 ° C. is less than 1 mm ² / s, Insufficient oil film formation results in poor lubricity and increases the evaporation loss of the lubricating base oil, which is not preferable.

  The amount of evaporation loss of the lubricating base oil is not particularly limited, but the NOACK evaporation amount is preferably 20% by mass or less, more preferably 16% by mass or less, and 10% by mass or less. Is particularly preferred. When the NOACK evaporation amount of the lubricating base oil exceeds 20% by mass, not only the evaporation loss of the lubricating oil is large, but also the sulfur compound, phosphorus compound, or metal component in the composition is sent to the exhaust gas purification device together with the lubricating base oil. This is not preferable because there is a risk of accumulation, which not only increases the oil consumption, but also has an adverse effect on the exhaust gas purification performance. Here, the NOACK evaporation amount is a value obtained by measuring the evaporation amount of the lubricating oil measured in accordance with ASTM D 5800.

  The viscosity index of the lubricating base oil is not particularly limited. However, from the viewpoint of obtaining excellent viscosity characteristics from low temperature to high temperature, the value of the viscosity index is preferably 80 or more, more preferably 100 or more, and particularly preferably 120 or more. There is no particular limitation on the upper limit of the viscosity index. Normal paraffin, slack wax, GTL wax, etc., or those of about 135-180 such as isoparaffin mineral oil obtained by isomerizing them, or about 150-250 such as complex ester base oil or HVI-PAO base oil Things can also be used. When the viscosity index of the lubricating base oil is less than 80, the low temperature viscosity characteristics deteriorate, which is not preferable.

<(A) component>
The content of the component (A) in the lubricating oil composition of the present invention is not particularly limited. However, on the basis of the total amount of the composition, that is, the total amount of the lubricating oil composition is 100% by mass, it is usually 0.001% by mass or more, preferably 0.01% by mass or more, particularly preferably 0.1% by mass or more. . Moreover, it is 5 mass% or less normally, Preferably it is 3 mass% or less, Most preferably, it is 1.5 mass% or less. If it is less than 0.001% by mass, the effect of reducing friction may be insufficient, and if it exceeds 5% by mass, there may be a problem in solubility as a lubricating oil composition.

<(B) component>
The content of the component (B) in the lubricating oil composition of the present invention is not particularly limited. However, on the basis of the total amount of the composition, that is, the total amount of the lubricating oil composition is 100% by mass, it is usually 0.001% by mass or more, preferably 0.01% by mass or more, particularly preferably 0.1% by mass or more. . Moreover, it is 5 mass% or less normally, Preferably it is 3 mass% or less, Most preferably, it is 1.5 mass% or less. If it is less than 0.001% by mass, the effect of reducing friction may be insufficient, and if it exceeds 5% by mass, there may be a problem in solubility as a lubricating oil composition.

  According to the lubricating oil composition of the present invention, since the component (A) and the component (B) are included together by including the lubricating oil additive of the present invention, the lubricating oil including the conventional oil-based friction modifier It is possible to provide a lubricating oil composition containing an oil-based friction modifier that can exhibit a friction reducing effect superior to that of the composition under wider friction conditions. Also, wear resistance can be improved.

In addition, the molar ratio (B) component boron conversion molar content / (A) component molar content of the (B) component boron conversion molar content with respect to the (A) component molar content in the lubricating oil composition of the present invention. ) Is preferably 4 or less, more preferably 3.5 or less, and even more preferably 3 or less, as described above. Further, it is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.5 or more, and particularly preferably 1 or more.
It is possible to further enhance the friction reducing effect of the lubricating oil composition of the present invention by setting the molar ratio of the molar equivalent of the boron component of the component (B) to the molar content of the component (A) within the preferred range. Become.

<(C), (D), and (E) component>
As described above, the lubricating oil composition of the present invention includes (C) an ashless dispersant, (D) an antioxidant, and (E) a phosphorus element in addition to the components (A) and (B). It is preferable to further contain at least one selected from an inhibitor.

  When the component (C) is contained in the lubricating oil composition of the present invention, the content is based on the total amount of the lubricating oil composition, that is, the total amount of the lubricating oil composition is 100% by mass, and usually 0.01% by mass or more. Yes, preferably 0.1% by mass or more. Moreover, it is 20 mass% or less normally, Preferably it is 10 mass% or less. When the content of the component (C) is less than 0.01% by mass, the effect of contributing to the base number maintenance in a high temperature environment may be insufficient. On the other hand, when the content exceeds 20% by mass, lubrication may occur. Since there exists a possibility that the low-temperature fluidity | liquidity of an oil composition may deteriorate significantly, each is unpreferable.

  When the component (D) is included in the lubricating oil composition of the present invention, the content is based on the total amount of the lubricating oil composition, that is, the total amount of the lubricating oil composition is 100% by mass, and is usually 5.0% by mass or less. Yes, preferably 3.0% by mass or less, more preferably 2.5% by mass or less. When the content exceeds 5.0% by mass, there is a possibility that sufficient antioxidant properties corresponding to the blending amount may not be obtained, which is not preferable. On the other hand, the content is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the total amount of the lubricating oil composition.

When the component (E) is contained in the lubricating oil composition of the present invention, the content is not particularly limited. However, it is usually 0.1% by mass or more and 5% by mass or less based on the total amount of the composition, that is, the total amount of the lubricating oil composition is 100% by mass.
However, when the lubricating oil composition of the present invention is used as a lubricating oil for internal combustion engines, from the viewpoint of reducing the burden on the exhaust gas aftertreatment device, the content of the component (E) is phosphorous based on the total amount of the composition. It is preferable to set it as 0.005 mass% or more in element conversion amount, and it is preferable to set it as 0.08 mass% or less.
When the lubricating oil composition of the present invention is used as a lubricating oil for automatic transmissions, the content of the component (E) is 0.005% by mass or more in terms of phosphorus element, based on the total amount of the composition. It is preferable to make it 0.01% by mass or more. Moreover, it is preferable to set it as 0.1 mass% or less in phosphorus element conversion amount, It is more preferable to set it as 0.05 mass% or less, It is further more preferable to set it as 0.03 mass% or less.
If the content of the component (E) is too small, the wear resistance may be insufficient, and if the content of the component (E) is too large, a seal of an exhaust gas treatment device or device (for example, an internal combustion engine or an automatic transmission). May adversely affect the material. The reason why the preferable upper limit of the phosphorus compound content differs between the internal combustion engine and the automatic transmission is that the lubricating oil for the internal combustion engine usually has a larger amount of the metallic detergent described later, and the metallic detergent. This is because the adverse effect on the sealing material is reduced by the effect of.

In order to further improve the performance of the lubricating oil composition of the present invention, known additives that can be used in the lubricating oil can be contained depending on the purpose. Examples of such additives include (F) friction modifiers other than those of the present invention, (G) anti-wear agents other than components (E), (H) metal detergents, and (I) viscosity index improvers. , (J) corrosion inhibitor, (K) rust inhibitor, (L) demulsifier, (M) metal deactivator, (N) antifoaming agent, and (O) colorant.
These additive components (F) to (O) may be contained in the lubricating oil additive according to the first aspect of the present invention.

<(F) component>
As the friction modifier other than the component (A) and the component (B), compounds known as friction modifiers for lubricating oils can be used without particular limitation. For example, an amine compound, fatty acid ester, fatty acid amide, which has at least one alkyl group or alkenyl group having 6 to 30 carbon atoms, in particular, a linear alkyl group or linear alkenyl group having 6 to 30 carbon atoms in the molecule, Oil-based friction modifiers such as fatty acids, fatty alcohols and aliphatic ethers, sulfur-containing molybdenum complexes such as molybdenum dithiocarbamate and molybdenum dithiophosphate, molybdenum-free organic molybdenum such as molybdenum amine complexes and molybdenum-succinimide complexes Molybdenum-based friction modifiers such as complexes and molybdenum disulfide can be mentioned. When the component (F) is contained in the lubricating oil composition of the present invention, the content is usually 0.1% by mass or more and 5% by mass or less, with the total amount of the lubricating oil composition being 100% by mass.

<(G) component>
Examples of the antiwear agent other than the component (E) include, for example, (mono, di, tri-thio) in addition to the phosphorus compound (not including metal) described in the section of the component (E) and the amine salt thereof. ) (Sub-) phosphoric acid triesters, (mono, di-thio) phosphonic acid diesters, phosphorous compounds such as β (mono, di) (thio) phosphorylated carboxylic acids, disulfides, sulfurized olefins, sulfurized fats and oils And sulfur-containing compounds such as dithiocarbamates. When the component (G) is contained in the lubricating oil composition of the present invention, the total amount of the lubricating oil composition is usually 100% by mass, and can be contained in the range of 0.005% by mass to 5% by mass. It is.

<(H) component>
Examples of the metal detergent include alkali metal sulfonate, alkaline earth metal sulfonate, alkali metal phenate, alkaline earth metal phenate, alkali metal salicylate, alkaline earth metal salicylate, and mixtures thereof.

  Alkali metal or alkaline earth metal sulfonate, alkali metal or alkaline earth metal phenate, and alkali metal or alkaline earth metal salicylate include alkyl aromatic sulfonic acid, alkylphenol, alkylphenol sulfide, Mannich reaction product of alkylphenol, alkyl Salicylic acid or the like is directly reacted with a metal base such as an oxide or hydroxide of an alkali metal or alkaline earth metal, or once converted to an alkali metal salt such as a sodium salt or potassium salt and then replaced with an alkaline earth metal salt (Neutral salt (normal salt) obtained by (counter cation exchange), etc., as well as these neutral salt (normal salt) and excess alkali metal salt or alkaline earth metal salt, alkali metal base or alkaline earth. Metal bases (alkali metals or A basic salt obtained by heating a hydroxide or oxide of Lucari earth metal) in the presence of water, or a neutral salt (correct salt) in the presence of carbon dioxide, boric acid or borate. An overbased salt (superbasic salt) obtained by reacting with a base such as an alkali metal or alkaline earth metal hydroxide is also included. These reactions are usually carried out in a solvent (an aliphatic hydrocarbon solvent such as hexane, an aromatic hydrocarbon solvent such as xylene, a light lubricating base oil).

  Metal-based detergents are usually commercially available in a state diluted with a solvent such as a light lubricating base oil, and are also available. In the lubricating oil composition of the present invention, generally, the metal content is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, and preferably 20% by mass or less. It is desirable to use a metallic detergent that is preferably 16% by mass or less. The base number of the metal detergent is usually 0 mgKOH / g or more, preferably 20 mgKOH / g or more, and usually 500 mgKOH / g or less, preferably 450 mgKOH / g or less. The base number referred to here is 7. JIS K2501 “Petroleum products and lubricating oils-Neutralization number test method”. Means the base number measured by the perchloric acid method according to the above.

  In the present invention, one or two or more selected from alkali metal or alkaline earth metal sulfonates, phenates, salicylates and the like can be used in combination. In the present invention, alkali metal or alkaline earth metal salicylate is particularly preferable in that it has a large friction reducing effect and is excellent in long drain properties.

  When the lubricating oil composition of the present invention contains the component (H), the content is not particularly limited. However, in the case of an internal combustion engine, it is usually 0.01% by mass or more and 5% by mass or less in terms of metal element based on the total amount of the lubricating oil composition. At this time, it is preferable to adjust the content together with other additives so that the sulfated ash content of the lubricating oil composition is 1.0% by mass or less. From such a viewpoint, the upper limit of the content of the metal-based detergent is based on the total amount of the lubricating oil composition (100% by mass) and is preferably 0.3% by mass, more preferably 0.3% by mass in terms of metal element. Is 0.2% by mass. Moreover, the lower limit is preferably 0.02% by mass, more preferably 0.05% by mass. Here, the sulfated ash is JIS K2272 5. The value measured by the method specified in “Testing method for sulfated ash” is mainly attributable to the metal-containing additive.

<(I) component>
As the viscosity index improver, specifically, a so-called non-dispersion type viscosity index improvement such as a polymer or copolymer of one or more monomers selected from various methacrylic acid esters and hydrogenated products thereof is used. A so-called dispersion type viscosity index improver obtained by copolymerizing various methacrylic acid esters containing a nitrogen compound and a non-dispersion type or dispersion type ethylene-α-olefin copolymer (in addition, propylene, 1- Butene, 1-pentene, etc.) and hydrogenated products thereof, polyisobutylene and hydrogenated products thereof, hydrogenated products of styrene-diene copolymers, styrene-maleic anhydride ester copolymers, and polyalkylstyrenes, etc. Can be mentioned.

  The molecular weight of these viscosity index improvers needs to be selected in consideration of shear stability. Specifically, the average molecular weight of the viscosity index improver is usually 5,000 or more and 1,000,000 or less in terms of weight average molecular weight in the case of dispersed and non-dispersed polymethacrylates, for example. The lubricating oil composition for applications where a strong shear force is applied, such as a lubricating oil composition for automatic transmissions, is preferably 10,000 or more, more preferably 200,000 or less, and 100,000 or less. Are more preferable, those having 50,000 or less are more preferable, and those having 30,000 or less are particularly preferable. Further, those for internal combustion engines are preferably 800,000 or less, more preferably 500,000 or less, and particularly preferably 200,000 or less. In the case of polyisobutylene or a hydride thereof mainly used for internal combustion engines, the number average molecular weight is usually 800 or more, preferably 1,000 or more, and usually 5,000 or less, preferably 4,000 or less. In the case of an ethylene-α-olefin copolymer or a hydride thereof, the number average molecular weight is usually 800 or more, preferably 3,000 or more, and usually 500,000 or less, preferably 200,000 or less. Used.

Among these viscosity index improvers, when an ethylene-α-olefin copolymer or a hydride thereof is used, a lubricating oil composition particularly excellent in shear stability can be obtained.
In the lubricating oil composition of the present invention, one or two or more compounds arbitrarily selected from the above viscosity index improvers can be contained in any amount as the component (I). When the component (I) is contained in the lubricating oil composition of the present invention, the content is usually 0.1% by mass or more and 20% by mass or less based on the lubricating oil composition.

<(J) component>
Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.

<(K) component>
Examples of the rust inhibitor include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinic acid ester, and polyhydric alcohol ester.

<(L) component>
Examples of the demulsifier include polyalkylene glycol nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether.

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

<(N) component>
Examples of the antifoaming agent include silicone, fluorosilicol, and fluoroalkyl ether.

<(O) component>
Examples of the colorant include azo compounds.

  When these additives are contained in the lubricating oil composition of the present invention, the content thereof is (J) a corrosion inhibitor, (K) a rust inhibitor, (L) an anti-rust agent based on the total amount of the lubricating oil composition. In the case of the emulsifier, 0.005% by mass to 5% by mass, (M) in the case of the metal deactivator, 0.005% by mass to 1% by mass, and (N) in the case of the antifoaming agent, 0.0005% by mass to 1% by mass. Usually selected within the following range.

The lubricating oil composition of the present invention is a lubricating oil composition containing an oily agent-based friction modifier, and has a wider friction reducing effect than a lubricating oil composition containing a conventional oily agent-based friction modifier. Can be used under friction conditions. In addition, wear resistance can be improved. Therefore, it can be suitably used for lubricating an internal combustion engine. That is, by using the lubricating oil composition of the present invention for lubrication of an internal combustion engine, energy loss due to friction in the internal combustion engine is effectively reduced under a wider range of operating conditions, and fuel efficiency is improved. It is possible to effectively protect against wear under wider operating conditions.
Further, in an internal combustion engine, a valve mechanism is one of the mechanisms that operate under the most severe conditions regarding friction and wear, and therefore the lubricating oil composition of the present invention has the above-described enhanced friction reduction effect and wear resistance. Have. Therefore, the lubricating oil composition of the present invention can be preferably employed for lubrication of an internal combustion engine having a direct impact type or roller follower type valve operating mechanism, particularly a roller follower type valve operating mechanism.
Further, since the lubricating oil composition of the present invention contains an oil-based friction modifier that does not contain sulfur or phosphorus, exhaust gas aftertreatment can be obtained by lubricating an internal combustion engine using the lubricating oil composition of the present invention. The burden on the apparatus can be reduced. Therefore, the lubricating oil composition of the present invention can be particularly suitably employed for lubricating an internal combustion engine equipped with an exhaust gas aftertreatment device. Further, as the fuel, a low sulfur fuel, for example, gasoline, light oil or kerosene having a sulfur content of 50 mass ppm or less, more preferably 30 mass ppm or less, particularly preferably 10 mass ppm or less, or 1 mass ppm of sulfur content. Especially suitable for lubrication of internal combustion engines using the following fuels (liquefied petroleum gas (LPG), natural gas, hydrogen that does not substantially contain sulfur, dimethyl ether, alcohol, GTL fuel, etc.) Can do.

  In the boric acid ester compound, boron content can be regarded as ash. Therefore, when the lubricating oil composition of the present invention is used for lubrication of an internal combustion engine, the ash derived from the boron content is exhaust gas purification of the internal combustion engine. It may be possible to affect the device to some extent. However, on the other hand, molybdenum-based FM contains, in addition to ash derived from molybdenum, for example, sulfur content in MoDTC, and sulfur content and phosphorus content in MoDTP. Or synergistically adversely affect the exhaust gas purification device. On the other hand, the component (A) and the component (B) in the present invention contain not only a metal component such as molybdenum but also a sulfur content and a phosphorus content. Therefore, by using the lubricating oil composition of the present invention for lubricating an internal combustion engine, it becomes easier to reduce the burden on the exhaust gas purification device compared to the case where a lubricating oil composition containing molybdenum-based FM is used. .

  Further, the lubricating oil composition of the present invention can be suitably used for lubricating an automatic transmission. That is, by using the lubricating oil composition of the present invention for lubrication of an automatic transmission, the operation is effectively controlled under a wide range of operating conditions such as relaxation of a shock at the time of engagement of a clutch and prevention of shudder in slip control. It becomes possible.

  In the above description regarding the present invention, the usage mode of the lubricating oil composition of the present invention has been described by exemplifying the lubrication of an internal combustion engine and the lubrication of an automatic transmission. It is not limited. Since the lubricating oil composition of the present invention has an excellent friction reducing effect as described above, a lubricating oil that requires low friction, such as a lubricating oil for a manual transmission, grease, wet brake oil, hydraulic pressure, etc. It can also be suitably used as a lubricating oil such as hydraulic oil, turbine oil, compressor oil, bearing oil, and refrigerator oil.

  Hereinafter, based on an Example and a comparative example, it demonstrates further more concretely about this invention. However, the present invention is not limited to these examples.

<Examples 1-3, Comparative Examples 1-6>
As shown in Table 1, lubricating oil compositions of the present invention (Examples 1 to 3) and comparative lubricating oil compositions (Comparative Examples 1 to 6) were prepared.

(Example 1)
As component (A), 0.27 mass of oleyl urea (in general formula (1), m = 1, n = 0, R ¹ = oleyl group (carbon number 18), R ² = R ³ = R ⁴ = H). %, Containing 0.20% by mass (0.0094% by mass in terms of boron content) of tributyl borate (R ⁵ = R ⁶ = R ⁷ = butyl group in general formula (2)) as component (B) Then, a lubricating oil composition was prepared in which the balance was the lubricating base oil PAO2. The molar ratio (B / A) of (A) component molar content and (B) component boron conversion molar content was 1.0 (Table 1).

(Example 2)
A lubricating oil composition was prepared in the same manner as in Example 1 except that the contents of the component (A) and the component (B) were 1.1% by mass and 0.82% by mass, respectively (Table 1).

Example 3
As component (A), 0.24% by mass of oleylamide (in general formula (1), m = 0, R ¹ = oleyl group (18 carbon atoms), R ² = R ³ = R ⁴ = H), ( B) Tributyl borate (R ⁵ = R ⁶ = R ⁷ = butyl group in the general formula (2)) is contained as component 0.20% by mass (0.0094% by mass in terms of boron content), and the balance A lubricating oil composition was prepared in which is a lubricating base oil PAO2. The molar ratio (B / A) of (A) component molar content and (B) component boron conversion molar content was 1.0 (Table 1).

(Comparative Example 1)
A lubricating oil composition was prepared in the same manner as in Example 1 except that the component (B) was not contained (Table 1).

(Comparative Example 2)
A lubricating oil composition was prepared in the same manner as in Example 3 except that the component (B) was not contained (Table 1).

(Comparative Example 3)
A lubricating oil composition was prepared in the same manner as in Example 1 except that the component (A) was not contained (Table 1).

(Comparative Example 4)
A lubricating oil composition was prepared in the same manner as in Example 2 except that the component (B) was not contained (Table 1).

(Comparative Example 5)
A lubricating oil composition was prepared in the same manner as in Example 2 except that the component (A) was not contained (Table 1).

(Comparative Example 6)
It is a comparative example containing a molybdenum friction modifier instead of an oily agent friction modifier. Neither component (A) nor component (B) is contained. Instead, zinc dialkyldithiophosphate (ZnDTP) is 0.080 mass% in terms of phosphorus element content, and molybdenum dithiocarbamate (MoDTC) is 0 in terms of molybdenum content. A lubricating oil composition was prepared in the same manner as in Example 1 except that 0.05 mass% was contained (Table 1).

(Evaluation method)
Each of the prepared lubricating oil compositions was subjected to a ball-on-disk friction test. The temperature is set to 100 ° C., the load is set to 20 N, the amplitude is set to 1 mm, and after running for a fixed time at a frequency of 50 Hz, the friction coefficient is decreased while decreasing the frequency in order of 40 Hz, 30 Hz, 20 Hz, 10 Hz, 5 Hz, 3 Hz, and 2 Hz. It was measured.
For each lubricating oil composition, graphs plotted with the frequency on the horizontal axis and the friction coefficient on the vertical axis are shown in FIGS.

(Evaluation results)
FIG. 1 is a graph comparing the test results of Example 1 with the test results of Comparative Examples 1, 3, and 6.
As shown in FIG. 1, the lubricating oil composition of Example 1 exhibited an excellent friction reducing effect stably over the entire range of frequencies tested. In addition, it should be noted that the friction reducing effect was always superior to that of Comparative Example 6 containing a molybdenum-based friction modifier.
The friction reducing effect of the lubricating oil composition of Comparative Example 1 containing no component (B) was inferior to Example 1 over almost the entire range of frequencies tested. In addition, as a result of a large variation in the friction reduction effect depending on the frequency, the friction reduction effect in a relatively low frequency region was inferior to that of Comparative Example 6 containing a molybdenum-based friction modifier.
The friction reducing effect of the lubricating oil composition of Comparative Example 3 containing no component (A) was significantly inferior not only to Example 1 but also to Comparative Examples 1 and 6.

FIG. 2 is a graph comparing the test results of Example 3 with the test results of Comparative Examples 2, 3, and 6.
As shown in FIG. 2, the lubricating oil composition of Example 3 exhibited a stable and excellent friction reducing effect over the entire range of frequencies tested. In addition, it should be noted that the friction reducing effect was always superior to that of Comparative Example 6 containing a molybdenum-based friction modifier.
The friction reducing effect of the lubricating oil composition of Comparative Example 2 containing no component (B) was inferior to Example 3 and inferior to Comparative Example 6 in the entire range of the tested frequency range. .
The friction reducing effect of the lubricating oil composition of Comparative Example 3 containing no component (A) was significantly inferior not only to Example 3 but also to Comparative Examples 2 and 6.

FIG. 3 is a graph comparing the test results of Example 2 with the test results of Comparative Examples 4, 5, and 6.
As shown in FIG. 3, the lubricating oil composition of Example 2 exhibited a stable and excellent friction reducing effect over the entire range of frequencies tested. In addition, it should be noted that the friction reducing effect was always superior to that of Comparative Example 6 containing a molybdenum-based friction modifier.
The friction reducing effect of the lubricating oil composition of Comparative Example 4 containing no component (B) was inferior to that of Example 2 in most of the tested frequency range. In addition, as a result of the friction reduction effect varying depending on the frequency, the friction reduction effect in a relatively low frequency region was inferior to that of Comparative Example 6 containing a molybdenum friction modifier.
The friction reducing effect of the lubricating oil composition of Comparative Example 5 containing no component (A) was significantly inferior not only to Example 2 but also to Comparative Examples 4 and 6.

  From the above test results, according to the lubricating oil composition of the present invention, it is possible to exhibit a friction reducing effect superior to a lubricating oil composition containing a conventional oil-based friction modifier under a wider friction condition. It has been shown that lubricating oil compositions can be provided that contain an agent based friction modifier.

<Examples 1, 4, and 5 and Comparative Example 1>
In addition to the lubricating oil compositions of Example 1 and Comparative Example 1, two types of lubricating oil compositions of the present invention (Examples 4 and 5) were prepared as shown in Table 2.

Example 4
(B) The component is trioctyl borate (in formula (2), R ⁵ = R ⁶ = R ⁷ = octyl group.
A lubricating oil composition was prepared in the same manner as in Example 1 except for (Table 2). In addition, content of (B) component was 0.0094 mass% same as Example 1 in conversion of boron content.

(Example 5)
A lubricating oil composition was prepared in the same manner as in Example 1 except that the component (B) was trioctadecyl borate (R ⁵ = R ⁶ = R ⁷ = octadecyl group in the general formula (2)) (Table 2). ). In addition, content of (B) component was 0.0094 mass% same as Example 1 in conversion of boron content.

(Evaluation method)
A ball-on-disk friction test was performed as described above. The results are shown in FIG.

(Evaluation results)
FIG. 4 is a graph comparing the test results of Examples 1, 4, and 5 with the test results of Comparative Example 1.
As shown in FIG. 4, even when the compound of the component (B) was changed as in Examples 4 and 5, the same excellent friction reducing effect as that of Example 1 was exhibited.

<Example 1, 6-8>
In addition to the lubricating oil composition of Example 1, three types of lubricating oil compositions of the present invention (Examples 6 to 8) were prepared as shown in Table 3.

(Example 6)
Except for changing the content of the component (B) so that the molar ratio (B / A) between the molar content of the component (A) and the boron equivalent molar content of the component (B) is 0.5. A lubricating oil composition was prepared in the same manner as in Example 1 (Table 3).

(Example 7)
Except for changing the content of the component (B) so that the molar ratio (B / A) between the molar content of the component (A) and the boron equivalent molar content of the component (B) is 2.0. A lubricating oil composition was prepared in the same manner as in Example 1 (Table 3).

(Example 8)
Except for changing the content of the component (B) so that the molar ratio (B / A) between the molar content of the component (A) and the boron-converted molar content of the component (B) is 4.0. A lubricating oil composition was prepared in the same manner as in Example 1 (Table 3).

(Evaluation method)
A ball-on-disk friction test was performed as described above. The results are shown in FIG.

(Evaluation results)
FIG. 5 is a graph showing the test results of Examples 1 and 6-8.
As shown in FIG. 5, the lubricating oil compositions of Examples 1, 6, and 7 in which the molar ratio (B / A) of the component content (A) and the component content (B) is within a preferable range, Stable and excellent friction reduction effect was exhibited over the entire range of tested frequencies.
In addition, the lubricating oil composition of Example 8 exhibited an excellent friction reducing effect in a relatively low frequency range.

  From the above test results, the lubricating oil composition of the present invention is good even if the molar ratio (B / A) of the molar content of the component (A) and the molar molar content of the component (B) is changed. It was shown that the friction reducing effect can be exhibited.

  While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. However, the present invention can be changed as appropriate without departing from the spirit or concept of the invention that can be read from the claims and the entire specification. Lubricating oil additives and lubricating oil compositions with such changes are also included in the present invention. It should be understood as encompassed within the technical scope.

  The lubricating oil additive and lubricating oil composition of the present invention can be suitably used for lubricating various machines, and in particular, can be suitably used for lubricating internal combustion engines and automatic transmissions.

Claims (4)

(A) the nitrogen-containing compound represented by the general formula (1), and
(B) A lubricating oil additive comprising a borate ester compound represented by the general formula (2) and / or a borate ester compound represented by the general formula (3).

(In General Formula (1), R ¹ is a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms having functionality; R ² , R ³ , and R ⁴ are Each independently represents a hydrocarbon group having 1 to 30 carbon atoms, a functional hydrocarbon group having 1 to 30 carbon atoms, or a hydrogen atom; m is an integer of 0 or 1, and m is 1 In this case, n is an integer of 0 or 1.)

(In General Formula (2), R ⁵ is a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms having functionality; R ⁶ and R ⁷ are each independently A hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms having functionality, or a hydrogen atom.)

(In General Formula (3), R ⁸ is a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms having functionality; R ⁹ and R ¹⁰ are each independently A hydrocarbon group having 1 to 30 carbon atoms, a hydrocarbon group having 1 to 30 carbon atoms having functionality, or a hydrogen atom.) Lubrication according to claim 1, characterized in that the molar ratio of the molar molar content of the component (B) to the molar content of the component (A) is 0.05 or more and 4.0 or less. Oil additive. Lubricant base oil, ashless dispersant, antioxidant, friction modifier, antiwear agent, metallic detergent, viscosity index improver, corrosion inhibitor, rust inhibitor, demulsifier, metal deactivator, defoamer The lubricating oil additive according to claim 1 or 2, further comprising at least one selected from an agent and a colorant. A lubricating oil composition comprising a lubricating base oil and the lubricating oil additive according to any one of claims 1 to 3.

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