WO2004013265A1

WO2004013265A1 - Lubricating oil composition

Info

Publication number: WO2004013265A1
Application number: PCT/JP2003/009884
Authority: WO
Inventors: Kazuhiro Yagishita
Original assignee: Nippon Oil Corporation
Priority date: 2002-08-05
Filing date: 2003-08-04
Publication date: 2004-02-12
Also published as: CN100500818C; JP2004067812A; JP4373650B2; EP1526170A4; CN1681910A; EP1526170A1; AU2003252378A1

Abstract

A lubricating oil composition which comprises a base oil, (A) a specific alkali metal salicylate derivative, a specific alkaline earth metal salicylate derivative and/or their (per)basic salt in an amount of 0.005 to 5 mass % in terms of the amount of the metal element (B) a phosphorus-containing wear inhibitor in an amount of 0.005 to 0.2 mass % in terms of the amount of phosphorus and (C) 0.01 to 1 mass % of an amide compound, and has a total sulfur content of 0.3 mass % or less, all the percentages being relative to the total amount of the composition. The lubricating oil composition is a low sulfur lubricating oil which is extremely excellent in wear inhibiting property and also excellent in long drain property and the like, and thus can be suitably used in particular for an internal combustion engine.

Description

Description Lubricating oil composition

[Technical field]

The present invention relates to a low-sulfur lubricating oil composition, and more particularly to a low-sulfur lubricating oil composition having excellent anti-wear properties and long drainage properties, and particularly suitable for use in internal combustion engines.

[Background technology]

Conventional lubricating oils, especially lubricating oils for internal combustion engines, have used sulfur- and phosphorus-containing additives such as zinc dialkyldithiophosphates, which are extremely excellent in antiwear and antioxidant properties, as almost essential additives. In response to recent environmental problems, the effect on exhaust gas catalysts such as three-way catalysts, oxidation catalysts, NOx storage reduction catalysts, and exhaust gas aftertreatment devices such as DPF (diesel particulate filter) installed in internal combustion engines Therefore, there is a strong demand for lubricating oils with lower sulfur, lower phosphorus and lower ash.

Until now (the disclosed low-phosphorus oils or non-phosphorus-free oils include, for example, JP-A-62-253691, JP-A-1-500912, and JP-A-6-415568. JP-A-63-304095, JP-A-63-304096, JP-A-52-704, JP-A-2-243692, JP-A-62-50 JP-A No. 1917, JP-A-62-501572, JP-A-2000-63862 and the like, and examples of the low ash oil include JP-A-8-489. No. 89, JP-A-8-253782, JP-A-9-111275, JP-A-2000-256690, etc. However, in these prior arts, When zinc dithiophosphate is reduced or not used, it is necessary to incorporate a sulfur-containing compound in order to maintain anti-wear properties. Zinc is essential. Thus, low-sulfur oil with excellent anti-wear properties, more low phosphide, no low ashing is performed lubricating oil is found near Mari far. The present inventors have found that a low-sulfur lubricating oil composition containing a phosphorus-containing compound such as quino or zinc dialkylphosphate, zinc dialkylmono'thiophosphate or triester phosphate uses zinc dithiophosphate alone. It has already been found that, while maintaining anti-wear properties, it is extremely excellent in low friction, high-temperature detergency, oxidation stability, base number maintenance, etc., and has already filed a patent application (Japanese Patent Application 2002). — 0 1 53 5 1, Japanese Patent Application 2 00 1— 3 1 594 1, Japanese Patent Application 2002— 086 145, Japanese Patent Application 2002— 086 146, Japanese Patent Application 2002-08 6 1 4 7, Japanese Patent Application 2002- No. 19910, Japanese Patent Application No. 2002-191091, Japanese Patent Application No. 2002-191092). However, when a salicylate-based detergent with a metal ratio of 5 or less, particularly a salicylate-based detergent prepared with a metal ratio of 3 or less, is used as a metal-based detergent, low friction, high-temperature detergency, and oxidation stability are obtained. Although it is possible to obtain a composition that is extremely excellent in properties and base number retention, it is possible to reduce the content of anti-wear agents containing sulfur and phosphorus, such as zinc dithiophosphate, to reduce sulfur, or contain sulfur. It has been found that the use of a non-phosphorus-containing antiwear agent may not provide sufficient anti-scuffing and cam abrasion performance of valve train wear in internal combustion engines, especially rocker arm pads.

The present invention has been made in view of the above circumstances, and provides a long drain type low sulfur lubricating oil composition containing a salicylate-based detergent, which is extremely excellent in anti-wear performance. is there.

[Disclosure of the Invention]

As a result of earnest studies, the present inventor has found that a low-sulfur lubricating oil composition containing a specific salicylate, a phosphorus-containing antiwear agent and an amide compound can solve the above-mentioned problems, and has completed the present invention. .

That is, the present invention relates to a lubricating base oil comprising, based on the total amount of the composition, (A) an alkali metal or alkaline earth metal salicylate containing at least one compound selected from the compounds represented by the following general formula (1): And 5 or 5 to 5% by mass in terms of a metal element, and (B) 0.05 to 0.2% by mass of a phosphorus-containing wear inhibitor in terms of a phosphorus element. And (C) an amide compound represented by the general formula (2) in an amount of 0.01 to 1% by mass, and the total sulfur content of the composition is 0.3% by mass or less. A lubricating oil composition characterized in that

(In the general formula (1), R ¹ is a hydrocarbon group having 1 to 40 carbon atoms, R ² is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and the hydrocarbon group is oxygen or nitrogen. M may be an alkali metal or alkaline earth metal, and n represents 1 or 2 depending on the valence of the metal.)

(In the general formula (2), R ³ represents 640 carbon atoms and R ⁴ and R ⁵ may be the same or different and each represents hydrogen or a hydrocarbon group having 1-40 carbon atoms.) 刖 B ( A) An alkali metal or alkaline earth metal salicylate in which the component is (A-1) a monoalkyl salicylate having one secondary alkyl group having 10 to 40 carbon atoms and a constituent ratio of 85 mol% or more. , And Z or a (over) basic salt thereof, wherein R ¹ in the above general formula (1) is a secondary alkyl group having 10 to 40 carbon atoms, and R ² is hydrogen. (A-2) a secondary alkyl group having 10 to 40 carbon atoms, wherein R ¹ and R ² in the general formula (1) are An alkali metal or alkaline earth metal salicylate, and Z or a (over) basic salt thereof, and (A-3) the general formula (1) R ¹ or R ² is a hydrocarbon group having 1 to less than 10 carbon atoms, the other is a secondary alkyl group having 10 to 40 carbon atoms, and the difference in carbon number between R ¹ and R ² Is preferably at least one selected from an alkali metal or alkaline earth metal salicylate and / or a (over) basic salt thereof. The secondary alkyl group having 10 to 40 carbon atoms in the component (A-1) has a carbon number of Preferably it is from 10 to less than 20 secondary alkyl groups.

The metal ratio of the component (A) is preferably -2.3 or less.

The metal ratio of the component (A) is preferably 3 or more. The component (B) is at least one selected from the group consisting of a phosphorus compound represented by the following general formula (3), a phosphorus compound represented by the following general formula (4), and a metal salt or an amine salt thereof. Preferably, it is a single compound.

(In the general formula (3), X ¹ , X ^2, and X ³ each independently represent an oxygen atom or a sulfur atom, and R ⁵ , ^16, and ¹⁷ each independently represent a hydrogen atom or a carbon atom. Represents up to 30 hydrocarbon groups.)

X

8 4 II 6 10

R— X— X— R (4)

X—R ⁹

(In the general formula (4), X ⁴ , X ⁵ , X ⁶ and X ⁷ each independently represent an oxygen atom or a sulfur atom, and R ⁸ , R ⁹ and R ^1Q each independently represent a hydrogen atom or And a hydrocarbon group having 1 to 30 carbon atoms.) The component (B) is a metal salt of a phosphorus compound in which X ¹ , X ² and X ³ in the general formula (3) are all oxygen atoms. It is preferable that at least one compound selected from the group consisting of metal salts of phosphorus compounds in which X ⁴ , X ⁵ , X ⁶ and X ⁷ in the general formula (4) are all oxygen atoms.

In the component (B), X ⁴ , X ⁵ , X ^6, and X ^{7 in} the general formula (4) are all oxygen atoms, and R ⁸ , R ^9, and R ^1Q each independently have a carbon number of 1 to It is preferably a phosphorus compound having 30 hydrocarbon groups.

The component (B), two X ^4, X ^5, X ⁶ and X ⁷ in the general formula (4) is an oxygen atom, two of R ^8, R ⁹ and R ^{1 Q} is 1 to carbon atoms With 30 hydrocarbon groups Preferably, it is a zinc salt of a phosphorus compound in which one is hydrogen. It is preferable that the content of the component (B) is 0.08% by mass or less in terms of a phosphorus element based on the total amount of the composition.

The lubricating oil composition of the present invention preferably contains at least one selected from (D) an ashless dispersant and (E) an antioxidant.

The total sulfur content of the lubricating base oil is preferably 0.05% by mass or less.

The lubricating oil composition of the present invention is preferably used for an internal combustion engine.

The lubricating oil composition of the present invention preferably has a sulfated ash content of 1.0% by mass or less.

The lubricating oil composition of the present invention has a sulfated ash content of 0.5% by mass or less, a total sulfur content of 0.05% by mass or less, and a phosphorus content of 0.05% by mass or less. Preferably, one or more requirements are satisfied. The present invention also provides a method for preventing wear of a valve train of an internal combustion engine, comprising using the lubricating oil composition. Hereinafter, the lubricating oil composition of the present invention will be described in detail.

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

As a mineral base oil, specifically, lubricating oil fractions obtained by depressurizing distillation of atmospheric residual oil obtained by atmospheric distillation of crude oil are subjected to solvent removal, solvent extraction, and hydrocracking. , Refined by one or more treatments such as solvent dewaxing, hydrorefining, etc., or mineral oils with wax insensitivity, base oils produced by isomerizing GTL WAX (gas to liquid wax), etc. Can be exemplified.

The sulfur content in the mineral base oil is not particularly limited as long as the total sulfur content of the composition is 0.3% by mass or less, but is 0.05 mass. / ₀ or less, more preferably 0.01% by mass or less, particularly preferably 0.05% by mass or less. By reducing the sulfur content of the mineral base oil, it has better long-drainability, and when used as a lubricating oil for internal combustion engines, it can be used in exhaust gas aftertreatment equipment. It is possible to obtain a low-sulfur lubricating oil composition capable of avoiding adverse effects as much as possible. The total aromatic content of the mineral base oil is not particularly limited, but is preferably 10% by mass or less, more preferably 6% by mass or less, still more preferably 3% by mass or less, and particularly preferably 2% by mass or less. % By mass or less. By setting the total aromatic content of the base oil to 10% by mass or less, a composition having more excellent oxidation stability can be obtained.

In addition, the above-mentioned total aromatic content means a content of aromatic fraction (aromatiicfractione) measured according to ASTM D2549. Usually, this aromatic fraction includes, in addition to alkylbenzene and alkylnaphthalene, anthracene, phenanthrene, their alkylated compounds, compounds in which four or more benzene rings are condensed, or pyridines, quinolines, phenols, naphthols And compounds having a heteroaromatic group such as a class.

Specific examples of the synthetic base oil include polyptene or a hydride thereof; 1-octene oligomer, poly- _α -olefin such as 1-decene oligomer or a hydride thereof; ditridecinoregolelate, G 2 —Diestenoles such as ethinolehexynoleate, disodecyl adipate, ditridecyl adipate, and di-ethylhexyl sebacate; neopentylglyconoleestenole, trimethylolpropanecapritolate, trimethylolonepropaneperano Polyol esters such as legonate, pentaerythritol and pentaerythritol hexanoate, and pentaerythritol peralgonate; aromatic synthetic oils such as alkyl naphthalene, alkyl benzene, and aromatic ester; And the like can be exemplified.

As the lubricating base oil in the present invention, the above-mentioned mineral base oil, the above-mentioned synthetic base oil, or an arbitrary mixture of two or more kinds selected from these can be used. Examples thereof include one or more mineral base oils, one or more synthetic base oils, and a mixed oil of one or more mineral base oils and one or more synthetic base oils.

The kinematic viscosity of the lubricating base oil used in the present invention is not particularly limited, but the kinematic viscosity at 100 ° C. is preferably 20 mm ² / s or less, more preferably 10 mm ² / s or less. It is. On the other hand, the kinematic viscosity is preferably 1 mm ² Zs or more, and more preferably 2 mm ² / s or more. If the kinematic viscosity at 100 ° C of the lubricating base oil exceeds 20 mm ² Zs, the low-temperature viscosity characteristics will deteriorate, while the kinematic viscosity will decrease. When the degree is less than 1 mm ² Z s, the formation of an oil film at a lubricating point is insufficient, so that the lubricating property is inferior and the evaporation loss of the lubricating base oil is undesirably increased. The evaporation loss of the lubricating base oil is preferably 20% by mass or less, more preferably 16% by mass or less, particularly preferably 10% by mass or less, in terms of NOACK evaporation amount. preferable. When the NOACK evaporation amount of the lubricating base oil exceeds 20% by mass, not only is the lubricating oil evaporation loss large, but also when it is used as a lubricating oil for internal combustion engines, the sulfur compound or phosphorus compound in the composition, or metal This is not desirable because there is a risk that the oil will accumulate in the exhaust gas purification device together with the lubricating base oil, which may have a negative effect on exhaust gas purification performance. Herein, the term NOACK evaporation loss and is, AS TM D 5800 which has been measured according to, under a reduced pressure of the lubricating oil sample 60 g 250 ° C, 2 Omm H 2 0 (1 9 6 P a) The amount of evaporation after holding for 1 hour at was measured.

The viscosity index of the lubricating base oil is not particularly limited, but the value is preferably 80 or more, more preferably 100 or more, so as to obtain excellent viscosity properties from low to high temperatures. Preferably it is at least 120. When the viscosity index is less than 80, the low-temperature viscosity characteristics are unfavorably deteriorated.

The component (A) in the lubricating oil composition of the present invention is an alkali metal or alkaline earth metal salicylate containing at least one compound selected from the compounds represented by the following general formula (1), and Z or (Z) It is a basic salt.

In the general formula (1), R ¹ is a hydrocarbon group having 1 to 40 carbon atoms, R ² is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, and the hydrocarbon group contains oxygen or nitrogen. M represents an alkali metal such as sodium, potassium, magnesium, norium, or calcium or an alkaline earth metal, particularly magnesium and / or magnesium. Alternatively, calcium is preferably used. N represents 1 or 2 depending on the valence of the metal M.

Examples of the hydrocarbon group having 1 to 40 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group, an alkyl-substituted cycloalkyl group, an aryl group, an alkyl-substituted aryl group, and an arylalkyl group. Specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, eptyl, octyl, noel, decyl, undecyl, dodecyl, tridecyl, Tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henycosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacososyl, Alkoxy groups having 1 to 40 carbon atoms, such as Basis

(These may be linear or branched), cycloalkyl groups having 5 to 7 carbon atoms, such as cyclopentyl group, cyclohexyl group, cycloheptyl group, methyl cyclopentyl group, dimethyl Cyclopentyl group, Methylethylcyclopentyl group, Getylcyclopentyl group, Methylcyclohexyl group, Dimethyl / Recyclohexyl group, Methynorethynolecyclohexynole group, Getinolecyclohexyl group, Methy / lecycloheptyl group, To Dimethylcyclo mouth An alkylcycloalkyl group having 6 to 10 carbon atoms such as a butyl group and a methylethylcycloheptyl group (the substitution position of the alkyl group with the cycloalkyl group is also arbitrary), a butyr group, a pentenyl group, a hexenyl group, Heptenyl, octenyl, nonenyl, decenyl, decenyl, Alkenyl groups such as a senyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group and a nonadecenyl group (these alkenyl groups may be linear or branched; Position is also arbitrary), phenyl, naphthyl and other aryl groups, trinole, xylyl, ethylphenyl, propylphenyl and butylphenyl, etc. alkyl-aryl groups having 7 to 10 carbon atoms (alkyl The group may be linear or branched, and the position of substitution on the aryl group is arbitrary.), A benzyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, etc., having 7 to 10 carbon atoms. And a reel alkyl group (these alkyl groups may be linear or branched). The hydrocarbon group is oxygen or nitrogen. Element may be contained.

In the present invention, the hydrocarbon group having 10 to 40 carbon atoms is a secondary alkyl group having 10 to 40 carbon atoms derived from a polymer or copolymer such as ethylene, propylene, or 1-butene. It is particularly preferably a secondary alkyl group having 14 to 19 carbon atoms or 20 to 26 carbon atoms. The component (A) in the present invention is one or a mixture of two or more salicylates of alkali metal or alkaline earth metal of the following (A-1) to (A-3). Is preferred.

(A-1) A monoalkyl salicylate having one secondary alkyl group having 10 to 40 carbon atoms has a constitutional ratio of 85 moles ⁰ /. The above alkali metal or alkaline earth metal salicylate, and / or a (over) basic salt thereof, wherein R ¹ in the general formula (1) is a secondary alkyl group having 10 to 40 carbon atoms. An alkali metal or alkaline earth metal salicylate having a composition ratio of the compound in which R ² is hydrogen is 40 mol% or more,

(A-2) R ^{1 or} R ² in the general formula (1) is a secondary alkyl group having 10 to 40 carbon atoms, and is a salicylate or an alkaline earth metal salicylate; (Over) basic salts,

(A-3) Any ^one of R ¹ and R ² in the general formula (1) is a hydrocarbon group having 1 to 10 carbon atoms, the other is a secondary alkyl group having 10 to 40 carbon atoms, and R ¹ And an alkali metal or alkaline earth metal salicylate having a difference of 10 or more carbon atoms between R ² and R ² , and R or a (over) basic salt thereof. The (A- 1) Composition ratio of monoalkyl salicylate in component although 85 mol% or more, preferably 8 8 mole ^_0/0 or more, 1 00 mole ^_0/0 also good in terms of production cost as The composition may be comprised of 3-alkyl salicylate, 4-alkyl salicylate and 5-alkyl salicylate. In the present invention, the component (A-1) In the salicylate structure to be constituted, the composition ratio of 3-alkyl salicylate (the compound in the above general formula (1) wherein R ¹ is a secondary alkyl group having 10 to 40 carbon atoms and R ² is hydrogen) is 40 moles. %, Preferably 50 mol% or more, more preferably 60 mol% or more, and may be 100 mol%, but may be 95 mol% or less from the viewpoint of production cost. When the composition ratio of 3-alkyl salicylate is 80 mol% or less, further 60 mol% or less, particularly 55 mol% or less, particularly when the secondary alkyl group having less than 20 carbon atoms of R ¹ is described below ( If the component (C) is not used together, depending on the selection of the component (B) or the reduction of the content of the component (B), the anti-wear performance such as the rocker arm anti-scuffing performance and the anti-cam wear performance in the internal combustion engine is sufficiently exhibited. There is a possibility that the wear prevention performance is extremely improved by using the component (C) in combination, so that the constitution of the present invention is useful. In addition, as the composition ratio of 3-alkyl salicylate increases, or by making the number of carbon atoms of the secondary alkyl group 20 or more, the anti-wear performance is improved without using the component (C) in combination. The combined use of the component (C) makes it possible to further reduce the content of the component (B) (for example, 0.05% by mass or less in terms of phosphorus element). When the composition ratio of 3-alkyl salicylate is less than 40 mol%, the composition ratio of 5-salicylate is relatively high, and the oil solubility is poor. In the above component (A-2), R ¹ and R ² are a secondary alkyl group having 10 to 40 carbon atoms, and R ¹ and R ² may be different or the same, In terms of production, it is preferably a secondary alkyl group derived from the same olefin. When the component (A-1) is used alone, a composition having excellent anti-wear performance can be obtained without using the component (C). However, when the component (C) is used, the component (B) can be obtained. Is preferred because it can be further reduced (for example, 0.05 mass% or less in terms of phosphorus element). When used in combination with the component (A-1), the component ratio of the component (A-2) is 10 moles ⁰ /. As described above, it is preferable to adjust the amount to be preferably at least 20 mol%, especially at least 40 mol%, from the viewpoint of further improving the anti-wear performance. In the above component (A-3), the difference between the carbon number of R ¹ and R ² in the general formula (1) is 10 or more, and ^one of R ¹ and R ² has a carbon number of 1 to less than 10 A hydrocarbon group, preferably a hydrocarbon group having 1 to 5 carbon atoms, more preferably a methyl group, It is more preferably an alkyl group such as a tert-butyl group, particularly preferably a methyl group, and the other is a secondary alkyl group having 10 to 40 carbon atoms, preferably 10 to 30 carbon atoms. Most preferably, R ¹ is a secondary alkyl group having 10 to 40 carbon atoms and R ² is a hydrocarbon group having 1 to less than 1 ° C. The hydrocarbon group having 1 to 10 carbon atoms may contain oxygen or nitrogen, for example, a carboxyl group derived from a carboxylic acid having 1 to less than 10 carbon atoms such as a COOH group. And the like. Further, in the present invention, when the component (A-3) is used alone, a composition having excellent anti-wear performance can be obtained without using the component (C). It is preferable to use the component (B) because the component (B) can be further reduced (for example, 0.05% by mass or less in terms of a phosphorus element). Further, the (A- 1) When used in combination with components, (A- 3) composition ratio of the components is 1 0 mol% or more, preferably rather 2 0 mol% or more, particularly 3 0 mole ^_0/0 or more It is preferable to prepare it in such a way that the anti-wear performance can be further improved.

When the above components (A_l) to (A-3) are used in combination, it is preferable that the total ratio of salicylates having a substituent at least at the 3-position is 55 mol% or more. It is more preferably at least 5 mol%, particularly preferably at least 70 mol%. The component (A) of the present invention can be produced by a known method or the like, and there is no particular limitation. For example, the component (A-1) is a compound having 10 to 4 carbon atoms per mole of phenol. Alkylation using a olefin such as an ethylene polymer and carboxylation with carbon dioxide gas, or alkylation using 1 mol of the olefin per 1 mol of salicylic acid. Alkyl salicylic acid containing chilic acid as a main component is reacted with metal base such as oxide or hydroxide of alkali metal or alkaline earth metal, or alkali metal such as sodium salt or potassium salt. It can be obtained by preparing a metal salt or by replacing an alkali metal salt with an alkaline earth metal salt.

Further, the component (A-2) and the component (A-3) are known compounds disclosed in, for example, Japanese Patent Publication No. 48-33532, Japanese Patent Publication No. 50-3802, and the like. Using methods, etc. Obtainable.

Specifically, the component (A-2) is used in an amount of 1.1 to 4 mol, preferably 2 to 3 mol, and particularly preferably, instead of using 1 mol of the olefin in the method for producing the component (A-1). Can be obtained by a method using 2 to 2.5 mol.

Further, the component (A-3) is, specifically, ortho-taresol or para-cresol, or ortho-t-butylphenol or para-t-butylphenol as a starting material, preferably having 10 to 40 carbon atoms. Is a 3-methyl-15-alkylphenol or 3-alkyl-15-methylphenol selectively alkylated to the para-position or the ortho-position using an olefin such as an ethylene polymer having 10 to 30 carbon atoms, or An alkylsalicylic acid obtained by a method of carboxylating 3-t-butyl-5-alkylphenol or 3-anthalkyl-5-t-butylphenol with carbon dioxide gas or the like is used to convert an alkali metal or alkaline earth metal to an alkylsalicylic acid. Reaction with metal bases such as oxides and hydroxides, or alkali metal salts such as sodium salts and potassium salts Further, it can be obtained by, for example, replacing an alkali metal salt with an alkaline earth metal salt.

The component (A) of the present invention is obtained by adding an alkali metal or alkaline earth metal salicylate (neutral salt) obtained as described above to a further excess alkali metal or alkaline earth metal salt, alkali metal or aluminum salt. Basic salts obtained by heating lithium earth metal bases (hydroxide metals or hydroxides or oxides of alkaline earth metal) in the presence of water, carbon dioxide, boric acid or boric acid. Overbased salts obtained by reacting the above neutral salt with a base such as an alkali metal or alkaline earth metal hydroxide in the presence of an acid salt are also included.

These reactions are usually carried out in a solvent (aliphatic hydrocarbon solvent such as hexane, aromatic hydrocarbon solvent such as xylene, light lubricating oil base oil, etc.), and the metal content is 1. It is desirable to use 0 to 20% by mass, preferably 2.0 to 16% by mass.

In the present invention, the total base number of the component (A) is usually 0 to 500 mg KO HZ g, preferably 20 to 45 O mg KOH / g, and one or more selected from these. Can be used in combination of two or more. In addition, the total base number mentioned here is JISK 2501 Means the total base number by the perchloric acid method measured in accordance with 7 of “Testing Methods for Neutralization Number of Petroleum Products and Lubricating Oils”.

The component (A) of the present invention has no particular limitation on its metal ratio. Generally, one or more components having a metal ratio of 20 or less can be used. The salicylate prepared in the following, more preferably 2.3 or less, particularly 1.5 or less is particularly preferable because it is excellent in oxidation stability, high-temperature detergency, low friction, and the like. When the metal ratio is 5 or less, particularly the metal ratio is 3 or less, and the component (A-1) having one secondary alkyl group having less than 20 carbon atoms is used, the component (C) If the metal is not used, the anti-wear property may not be sufficiently exhibited as described above. Therefore, the lubricating oil composition of the present invention using the component (A-1) having a metal ratio adjusted to 5 or less is extremely useful. It is. According to the present invention, when the above-mentioned component (A-1) having a metal ratio of 2.3 or less or 3 or more, particularly a salicylate having a secondary alkyl group having a carbon number of less than 20 is used, the metal ratio is reduced. However, it is interesting that the anti-wear performance can be more excellent than when the above-mentioned (A-1) component of 2.4 to 2.9 is used.

The metal ratio here is represented by the valence of the metal element in the salicylate-based detergent X the content of the metal element (mol%) Z The content of the soap group (mol%), and the metal element is calcium, magnesium And the like. 'The soap group means a salicylic acid group and the like. In the present invention, the upper limit of the content of the component (A) is 0.4% by mass or less in terms of a metal element, and in order to reduce the sulfated ash content of the composition to 1.0% by mass or less,

It is preferable that the content of the component (A) is not more than 0.3% by mass. When used as a lubricating oil for internal combustion engines, the content of the component (A) should be 0.2% by mass or less, preferably 0.15% by mass or less, in order to minimize adverse effects on the exhaust gas aftertreatment device. More preferably, the content is most preferably 0.10% by mass or less, and a lubricating oil composition having a sulfated ash content of 0.5% by mass or less can be obtained. The lower limit of the content of the component (A) is 0.05% by mass or more, preferably 0.01% by mass or more, more preferably 0.02% by mass or more, particularly It is preferably at least 0.05 mass%. If the content of the component (A) exceeds the above upper limit, the composition has a high sulfated ash content, and when used as a lubricating oil for an internal combustion engine, it is not preferable because it may adversely affect an exhaust gas aftertreatment device. Further, the content of the component (A) is less than the lower limit. In this case, the basic performance as a metal-based detergent is not exhibited, and it becomes difficult to obtain long drain performance such as high-temperature detergency, oxidative stability, and base number retention. The term "sulfated ash" used herein refers to the value measured by the method specified in JIS K2272, 5. “Test Methods for Sulfated Ash”, and is mainly attributed to metal-containing additives. The component (B) in the present invention is a phosphorus-containing wear inhibitor, and there is no particular limitation as long as it is a wear inhibitor containing phosphorus in a molecule.

The phosphorus-containing antiwear agent of the present invention includes a phosphorus compound represented by the general formula (3), a phosphorus compound represented by the general formula (4), and a metal salt or an amine salt thereof. It is preferably at least one compound selected from the group consisting of:

(

(In the general formula (3), X ¹ , X ² and X ³ each independently represent an oxygen atom or a sulfur atom, and R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a carbon atom Represents up to 30 hydrocarbon groups.)

X ⁷

8 4 II 6 10

R—X—One X—R (4)

XR ⁹

(In the general formula (4), X ⁴ , X ⁵ , ⁶ and ⁷ each independently represent an oxygen atom or a sulfur atom, and R ⁸ , ¹⁹ and ¹¹ ° each independently represent a hydrogen atom or a carbon atom. Specific examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ^{5 to} R ^{1 C)} include an alkyl group, a cycloalkyl group, and an alkenyl group. And alkyl-substituted cycloalkyl groups, aryl groups, alkyl-substituted aryl groups, and arylalkyl groups.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, Alkyl groups such as pentyl, hexyl, heptyl, octyl, noel, decyl, pendecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, etc. (These alkyl groups may be linear or branched).

Examples of the cycloalkyl group include a cycloalkyl group having 5 to 7 carbon atoms such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Examples of the alkylcycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a acetylcyclopentinole group, a methylcyclohexylole group, a dimethylcyclohexyl group, a methynoleethylcyclohexyl group, and a methylethylcyclohexyl group. Alkylcycloalkyl groups having 6 to 11 carbon atoms such as hexyl group, methylcycloheptyl group, dimethylcyclyl heptyl group, methynoleethynolecycloheptinol group, and ethynolecycloheptyl group. The substitution position is also arbitrary.).

Examples of the alkenyl group include a butenyl group, a pentenyl group, a hexenyl group, a heptyl group, an octenyl group, a nonenyl group, a decenyl group, a pentadecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, and a hexadecenyl group. And alkenyl groups such as a heptadecenyl group and an octadecyl group (the alkenyl groups may be linear or branched, and the position of the double bond is also arbitrary).

Examples of the aryl group include aryl groups such as a phenyl group and a naphthyl group. Examples of the alkylaryl group include a tolyl group, a xylinole group, an ethylphenyl group, a propynolephenyl group, a butynolepheno-nole group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, and a nonylphenyl group. A C7-C18 alkylaryl group such as an alkyl group, a decylphenyl group, an decylphenyl group, a dodecylphenyl group, etc. (The alkyl group may be linear or branched; The substitution position is also arbitrary.).

Examples of the arylalkyl group include a benzyl group, a phenylethyl group, a phenolepropyl group, a phenolebutynole group, a phenylpentinole group, and a phenylequinolene group. And an arylalkyl group having 7 to 12 carbon atoms such as a group (the alkyl group may be linear or branched).

The hydrocarbon group having 1 to 30 carbon atoms represented by R ^{5 to} R ^{1 (} is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, more preferably It is preferably an alkyl group having 3 to 18 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms.

Examples of the phosphorus compound represented by the general formula (3) include the following phosphorus compounds.

Phosphorous acid, monothiophosphorous acid, dithiophosphorous acid, trithiophosphoric acid; monophosphorous acid monoester having one hydrocarbon group having 1 to 30 carbon atoms, monothiophosphorous acid monoester, dithiophosphorous acid Acid monoester, trithiophosphite monoester; the above phosphite diester having two hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphite diester, dithiophosphite diester, trithiophosphite diester; Phosphite triesters having three hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphite triester, dithiophosphite triester, trithiophosphite triester; and mixtures thereof.

In the present invention, in order to further enhance long-drain performance such as high-temperature detergency, oxidation stability, and base number retention, two or more X i X ³ of the general formula (3) are oxygen atoms. It is particularly preferable that all of them are oxygen atoms. Examples of the phosphorus compound represented by the general formula (4) include the following phosphorus compounds.

Phosphoric acid, monothiophosphoric acid, dithiophosphoric acid, trithiophosphoric acid, tetrathiophosphoric acid; phosphoric acid monoester, monothiophosphoric acid monoester, dithiophosphoric acid monoester, trithiophosphoric acid monoester having one of the above hydrocarbon groups having 1 to 30 carbon atoms Ester, tetrathiophosphoric acid monoester; the above phosphoric diester, monothiophosphoric acid diester, dithiophosphoric acid diester, trithiophosphoric acid diester, and tetrathiophosphoric acid diester having two hydrocarbon groups each having 1 to 30 carbon atoms; Phosphoric acid triesters having three 0 hydrocarbon groups, monothiophosphoric acid triester, dithiophosphoric acid triester, trithiophosphoric acid triester, tetrathiophosphoric acid triester; and mixtures thereof. ' In the present invention, two or more of X ^{4 to} X ⁷ in the general formula (4) are oxygen atoms in order to further enhance long drain performance such as high-temperature detergency, oxidation stability, and base number retention. It is more preferable that three or more are oxygen atoms, and it is particularly preferable that all of them are oxygen atoms.

Examples of the salt of the phosphorus compound represented by the general formula (3) or (4) include a metal base such as a metal oxide, a metal hydroxide, a metal carbonate, and a metal chloride, ammonia, and a compound having 1 carbon atom. A salt obtained by reacting a nitrogen compound such as an amine compound having only 30 to 30 hydrocarbon groups or a hydroxyl group-containing hydrocarbon group in the molecule to neutralize a part or all of the remaining acidic hydrogen. Can be.

Specific examples of the metal in the metal base include alkali metals such as lithium, sodium, potassium, and cesium; alkaline earth metals such as calcium, magnesium, and barium; zinc, copper, iron, lead, nickel, silver, and the like. Examples include heavy metals such as manganese and molybdenum. Of these, alkaline earth metals such as calcium and magnesium and zinc are preferred.

The structure of the metal salt of the phosphorus compound varies depending on the valence of the metal, the number of the Η groups or SH groups of the phosphorus compound, and thus the structure is not limited at all. For example, 1 mol of zinc oxide and phosphoric acid When two moles of a diester (one Ο group) are reacted, a compound having a structure represented by the following formula is considered to be obtained as a main component, but it is considered that a polymerized molecule also exists.

For example, when 1 mol of zinc oxide is reacted with 1 mol of phosphoric acid monoester (having two OH groups), a compound having a structure represented by the following formula is considered to be obtained as a main component. It is considered that such molecules exist.

Specific examples of the nitrogen compound include ammonia, monoamine, diamine, And polyamines. More specifically, methylamine, ethylamine, propylamine, propylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pendecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, pentadecylamine, pentadecylamine, pentadecylamine , Heptadecylamine, octadecylamine, dimethylamine, getylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didindecylamine, didodecylamine, ditridecylamine Min, Ditetradecylamine, Dipentadecylamine, Dihexadecylamine, Diheptadecylamine, Di C1-C30 alkyl groups such as kutadecylamine, methylethylamine, methylpropylamine, methylbutylamine, ethylpropylamine, ethylbutylamine, and propylbutylamine, etc. Is an alkylamine having a straight or branched chain; an alkenyl group having 2 to 30 carbon atoms such as ether, propenylamine, butenylamine, octenylamine, and oleylamine (these alkenyl groups may be linear or branched); Alkenylamines which may be branched); methanolamine, ethanolamine, propanolamine, ptanolanolamine, pentanolamine, hexanolamine, heptanolamine, octanolamine, nonanolamine, methanolethanolamine. Min, Meta Alcohol groups having 1 to 30 carbon atoms, such as propanolanolamine, methanolbutanolamine, ethanolpropanolenoamine, ethanolanolbutanolamine, and propanolbutanolamine (these alcohols) An alkanolamine having a linear or branched structure); an alkylene diamine having an alkylene group having 1 to 30 carbon atoms such as methylenediamine, ethylenediamine, propylenediamine, and butylenediamine; diethylenetriamine; Polyamines such as triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine; pentadecyl getylamine, pentadecyl cetanolamine, dodecyldipropanolamine, oleyl cetanolamine, oleyl Propylene diamine, Compounds having an alkyl group or alkyl group having 8 to 20 carbon atoms in the above monoamines, diamines and polyamines such as stearyltetraethylenepentamine and N Heterocyclic compounds such as 1-hydroxyethylolimidazoline; alkylene oxide adducts of these compounds; and mixtures thereof.

Among these nitrogen compounds, aliphatic amines having an alkyl group having 10 to 20 carbon atoms or alkaryl groups such as decylamine, dodecylamine, tridecylamine, heptadecylamine, octadecylamine, oleylamine and stearylamine (these are Linear or branched) may be mentioned as a preferable example.

The component (B) includes a metal salt of a phosphorus compound wherein X ¹ , X ² and X ³ in the general formula (3) are all oxygen atoms, and X ⁴ , X ⁵ , X ⁶ and the like in the general formula (4). X ⁷ is at least one compound selected from the group consisting of metal salts of phosphorus compounds in which all are oxygen atoms, because it has excellent oxidation stability, high drainability such as high-temperature detergency, and low friction. preferable.

Also, (B) component, all X ^4, X ^5, X ⁶及Pi X ⁷ in the general formula (4) is oxygen radicals, R ^8, R ⁹及Pi R ^{1 D} are each independently carbon Phosphorus compounds, which are hydrocarbon groups of the formulas 1 to 30, are preferred because they have excellent long-drain properties such as oxidation stability and high-temperature detergency, and can further reduce friction and reduce ash.

Further, (B) component, two of X ^4, X ^5, X ⁶ and X ⁷ in the general formula (4) is an oxygen atom, two of R ^8, R ⁹ and R ^{1 Q} is C1-30 It is preferable to use a zinc salt of a phosphorus compound, one of which is hydrogen, from the viewpoint of more excellent abrasion prevention properties and enabling further reduction in phosphorus.

These are apparent from the above-mentioned series of patent applications filed by the present inventors. Among these (B) components, salts of zinc or calcium with a phosphite diester having two alkyl groups or aryl groups having 3 to 18 carbon atoms, alkyl groups or aryl groups having 3 to 18 carbon atoms, Preferably, a phosphite triester having three alkyl groups having 6 to 12 carbon atoms, a monoester of phosphoric acid having one alkyl group having 3 to 18 carbon atoms or one aryl group, and zinc or calcium A salt of zinc or calcium with a diester of phosphoric acid having two alkyl groups or aryl groups having 3 to 18 carbon atoms, or an alkyl group or aryl group having 3 to 18 carbon atoms; Preferably, it is a phosphoric acid triester having three alkyl groups having 6 to 12 carbon atoms. One or more of these components (B) can be arbitrarily compounded.

When a salt of dithiophosphoric acid diester having two alkyl groups or aryl groups having 3 to 18 carbon atoms with zinc is used, it is easy to maintain the anti-wear property of the valve train of the internal combustion engine. It is possible to reduce the content to 0.08% by mass or less, and even 0.05% by mass or less in terms of the amount of phosphorus element based on the total amount of the composition. It is most preferable to use a phosphorus-containing antiwear agent that does not contain sulfur in the molecule, since various properties such as low friction property can be further enhanced.

In the lubricating oil composition of the present invention, the content of the component (B) is 0.005% by mass or more, preferably 0.01% by mass or more, particularly preferably 0.1% by mass or more in terms of a phosphorus element based on the total amount of the composition. It is at least 02% by mass, while its content is at most 0.2% by mass, preferably at most 0.1% by mass, more preferably at most 0.08% by mass. When the content of the component (B) is less than 0.005% by mass as a phosphorus element, it is not preferable because it has no effect on the anti-wear property. On the other hand, when the content of the component (B) exceeds 0.2% by mass as a phosphorus element, it is not preferable because there is a concern that an adverse effect on an exhaust gas aftertreatment device may be caused. The component (C) in the present invention is an amide compound represented by the following general formula (2).

In the general formula (2), R ³ has 6 to 40 carbon atoms, and R ⁴ and R ⁵ may be the same or different and each represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms.

As the fatty acid in the component (C), for example, a linear fatty acid or a branched fatty acid, a saturated fatty acid or an unsaturated fatty acid may be used, and the alkyl group or the alkyl group has 6 carbon atoms. -40, preferably 9-24, and more preferably 12-20. If the fatty acid has less than 6 carbon atoms in the alkyl or alkenyl group, the solubility will be poor, and if it exceeds 40, the anti-wear properties will be reduced. Not preferred.

Specific examples of the fatty acid include heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, pendecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, and nonadecane Saturated fatty acids such as acid, icosanoic acid, henycosanoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid, pentacosanoic acid, hexacosanoic acid, heptacosanoic acid, octacosanoic acid, nonacosanoic acid, and triacontyl group. May be branched); heptenoic acid, otatenic acid, nonenoic acid, decenoic acid, pendecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenenoic acid, heptadecenoic acid, octadedecenoic acid, nonadecenenoic acid, Icosenoic acid, f Unsaturated fatty acids such as icosenoic acid, docosenoic acid, tricosenoic acid, tetracosenoic acid, pentacosenoic acid, hexacosenoic acid, heptacosenoic acid, octacosenoic acid, nonacosenic acid, and triaconthenic acid (these unsaturated fatty acids may be linear or branched. And the position of the double bond is also arbitrary).

As the fatty acid amide of the component (C), specifically, for example, the above-mentioned fatty acid or its oxychloride contains only ammonia or a hydrocarbon group having 1 to 40 carbon atoms or a hydroxyl group-containing hydrocarbon group in a molecule. And amides obtained by reacting a nitrogen compound such as an amine compound.

Specific examples of the nitrogen compound include ammonia; monomethylamine, monoethynoleamine, monopropynoleamine, monobutynoleamine, monopentylamine, monohexylamine, monoheptylamine, monooctylamine, and dimethylamido. , Methinoleethynoleamine, getinoleamine, methinolepropynoleamine, ethynolepropyramine, dipropylamine, methylbutylamine, ethylbutyramine, propylpyrubutylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, etc. Alkylamines (alkyl groups may be linear or branched); monomethanolamine, monoethanolamine, monopropanolenoamine, monoptanolenoamine, monopeamine Tano one ^ / amine, Monoeki Sanoruamin, Putanoruamin to mono, mono O click pentanol § Min, Mononona Noruamin, dimethano one Ruamin, methanol ethanol § Min, Jietano Noreamine, methanolepropanoleamine, ethanolepropanoleamine, dipropanolenoamine, methanolebutanoreamine, ethanolebutanoleamine, propanolebutanolamine, dibutanoolenoamine, dipentanooleamine, dipentanooleamine, Alkanolamines such as dihexanolamine, diheptanoamine and dioctanolamine (the alkanol groups may be linear or branched); and mixtures thereof.

Specific examples of the component (C) in the present invention include lauric acid amide, diethanolamide laurate, monopropanol amide lauric acid, amide myristic acid, diethanolamide myristic acid, and monopropanol myristic acid. Amid, palmitic acid amide, palmitic acid diethanolamide, palmitic acid monopropanolamide, stearic acid amide, stearic acid diethanolamide, stearic acid monopropanolamide, oleic acid amide, oleic acid diethanolamide, oleic acid Monopropanol amide, coconut oil fatty acid amide, coconut oil fatty acid diethanolamide, coconut oil fatty acid monopropanolamide, synthetic mixed fatty acid amide having 12 to 13 carbon atoms, synthetic mixed fatty acid having 12 to 13 carbon atoms Gietano Ruamide, synthetic mixed fatty acid monopropanol amide having 12 to 13 carbon atoms, and mixtures thereof are preferably used. Oleic acid amide and stearic acid amide are particularly preferable because of their excellent anti-wear properties. Used.

The lower limit of the content of the component (C) in the lubricating oil composition of the present invention is 0.01% by mass, preferably 0.05% by mass, based on the total amount of the composition. The upper limit of the content is 1% by mass, preferably 0.6% by mass, particularly preferably 0.4% by mass, based on the total amount of the composition. When the content of the component (C) is less than 0.01% by mass, the anti-wear property cannot be improved. On the other hand, when the content of the component (C) exceeds 1% by mass, the storage stability is improved. It is not preferable because the properties deteriorate. The lubricating oil composition of the present invention has excellent anti-wear properties by adopting the above constitution, and also has long drain properties such as low friction property, high-temperature detergency, base number maintenance property, and oxidation stability. In order to further improve the performance of the lubricating oil composition, it is preferable to include at least one selected from (D) an ashless dispersant and (II) an antioxidant. it can.

As the ashless dispersant (D), any ashless dispersant used in lubricating oils can be used.For example, a linear or branched alkyl group or alkenyl group having 40 to 400 carbon atoms may be used in the molecule. And at least one nitrogen-containing compound or a derivative thereof, or a modified product of alkenyl succinic acid imide. One or two or more selected from these can be blended.

The alkyl or alkenyl group has 40 to 400, preferably 60 to 350, carbon atoms. When the alkyl group or alkenyl group has less than 40 carbon atoms, the solubility of the compound in the lubricating base oil decreases, while when the alkyl group or alkenyl group has more than 400 carbon atoms, the lubricating oil composition has a low temperature. Each of these is not preferable because the liquidity deteriorates. This alkyl group or alkyl group may be straight-chain or branched, but is preferably, specifically, an oligomer of an olefin such as propylene, 1-butene, or isobutylene, or a copolymer of ethylene and propylene. Examples include a branched alkyl group and a branched alkenyl group derived from one.

Specific examples of the component (D) include, for example, the following compounds. One or more compounds selected from these can be used.

(D-1) Succinic imid having at least one alkyl or alkenyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof

(D-2) Benzylamine having at least one alkyl or alkyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof

(D-3) Polyamine having at least one alkyl group or alkyl group having 40 to 400 carbon atoms in the molecule, or a derivative thereof.

More specifically, examples of the above (D-1) succinic acid imide include compounds represented by the following general formulas (5) and (6).

In the general formula (5), R ² ° is 40 to 400 carbon atoms, preferably 60 to 35 carbon atoms. 0 represents an alkyl group or an alkyl group; and h represents an integer of 1 to 5, preferably 24.

In the general formula (6), R ²¹ and R ²² each independently represent an alkyl group or an alkenyl group having 40 to 400 carbon atoms, preferably 60 to 350 carbon atoms, and is preferably a polyptenyl group. i represents an integer of 0 to 4, preferably 1 to 3.

In addition, succinic acid imid is a so-called monotype succinic acid imid represented by general formula (5) in which succinic anhydride is added to one end of polyamine, and succinic anhydride is added to both ends of polyamine. A so-called bis-type succinic acid imid represented by the general formula (6) is included, and the composition of the present invention may contain any of them or a mixture thereof. good.

The method for producing these succinic imides is not particularly limited.For example, they are obtained by reacting a compound having an alkyl group or an alkyl group having 40 to 400 carbon atoms with maleic anhydride at 1.00 to 20 ° C. It can be obtained by reacting an alkyl or alkenyl succinic acid with a polyamine. Specific examples of the polyamine include dimethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

More specifically, examples of the above (D-2) benzylamine include compounds represented by the following general formula (7).

In the general formula (7), R ²³ represents an alkyl group or an alkenyl group having 40 to 400, preferably 60 to 350 carbon atoms, and j represents an integer of 1 to 5, preferably 2 to 4. . The method for producing this benzylamine is not limited at all. For example, a polyolefin such as a propylene oligomer, a polybutene, or an ethylene-a-olefin copolymer is reacted with a phenol to form an alkylphenol. It can be obtained by reacting formaldehyde with a polyamine such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine by a Mannich reaction.

More specifically, examples of the polyamine (D-3) include compounds represented by the following general formula (8).

^{_{R 24 - NH- (CH 2 CH}} 2 NH) k - H (8) In general formula (8), R ²⁴ is 40 to 400 carbon atoms, preferably represents a 6 0-3 50 alkyl or alkenyl group , K represents an integer of 1 to 5, preferably 2 to 4.

The method for producing the polyamine is not limited at all. For example, after chlorinating polyolefin such as propylene oligomer, polybutene, and ethylene-co-olefin copolymer, ammonia, ethylenediamine, and diethylenetriamine are added thereto. And polyethylene such as triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. As the derivatives of the nitrogen-containing compound mentioned as an example of the component (D), specifically, for example, the aforementioned nitrogen-containing compound may be a monocarboxylic acid having 1 to 30 carbon atoms (such as a fatty acid), oxalic acid, or phthalic acid. Part of residual amino and / or imino groups by the action of oxygen-containing compounds such as polycarboxylic acids having 2 to 30 carbon atoms, such as acids, trimellitic acid, and pyromellitic acid, and hydroxy (poly) alkylene carbonates. Or a compound modified with an amidated organic acid or the like by neutralizing all or amidated; the above-mentioned nitrogen-containing compound is allowed to act with boric acid to neutralize a part or all of the remaining amino group and Z or imino group. Or amidated, so-called boron-modified compound; the above-mentioned nitrogen-containing compound is treated with phosphoric acid to neutralize the remaining amino group and part or all of Z or imino group, , The so-called phosphoric acid-modified compounds; aforementioned sulfur-modified compounds obtained by a work of sulfur compounds in the nitrogen-containing compound; and modified with an organic acid such as nitrogen-containing compounds described above, boric A modified compound obtained by combining two or more types of modifications selected from elementary modification, phosphoric acid modification, and sulfur modification. Among these derivatives, boric acid-modified compounds of alkenyl succinic acid imid have excellent heat resistance, antioxidant properties and antiwear properties, and maintain the base number, high temperature cleanliness and antiwear properties in the lubricating oil composition of the present invention. It is effective to enhance the sex.

When the component (D) is contained in the lubricating oil composition of the present invention, its content is usually 0.01 to 20% by mass, preferably 0.1 to 10% by mass, based on the total amount of the lubricating oil composition. %. If the content of the component (D) is less than 0.01% by mass, the effect on high-temperature detergency is small, while if it exceeds 20% by mass, the low-temperature fluidity of the lubricating oil composition is significantly deteriorated. Therefore, each is not preferred.

(E) As the antioxidant, any phenolic antioxidant, a amine-based antioxidant, a metal-based antioxidant and the like generally used in lubricating oils can be used. Since the antioxidant of the lubricating oil composition can be further enhanced by the addition of the antioxidant, the base number retention and high-temperature detergency of the composition of the present invention can be further enhanced. Examples of phenolic antioxidants include 4,4,1-methylenebis (2,6-DG tert-butyl phenol), 4,4,1-bis (2,6-G tert-butyl phenol), 4,4,1 Bis (2-methinole 6-tert-butynolephenol), 2,2, -methylenebis (4-ethynole 6-tert-butylphenol), 2,2'-methylenebis (4-methynole 6-tert-butylinophenol), 4,4'-butylidenebis (3-methynole-6-tert-butynolephenol), 4,4,1-isopropylidenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-methylenolenate) 6-noninolephenole, 2, 2'-isobutylidenebis (4,6-dimethylphenol), 2,2, -methylenebis (4-methinole 6-hexylhexylphenol 2,6-di-tert-butyl 4-methinolephenole, 2,6-di-tert-butynole 4-eth / le-phenol, 2,4-dimethynole 6-tert-butino-lefenole, 2, 6-di-tert-hydroxydimethylamino-p-crezo-nole, 2,6-di-tert-butyl-14 (N, N, dimethinoleaminomethinolephenol), 4,4'-thiobis (2-Methynole 6-tert-butynolephenol), 4,4, -thiobis (3-methyl_6-tert-butylphenol), 2,2,2-thiobis (4-methyl-16-tert-butyl) Phenol), bis (3-methynoleic 4-hydroxy-1-5-tert-butyltinbenzinole) sulfide, bis (3,5-di-tert-butyl-4-hydroxylbenzyl) sulfide, 2,2,2 Thiodiethylenebis [3- (3,5-di-tert-butyl) -4-hydroxyphenyl) propionate], tridecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythriti Noretetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octyl-3- (3,5-di-tert-butyl-butyl-4-phenylhydroxy) pro Preferred examples include pionate, octadecyl-1- (3,5-di-tert-butyl-4-hydroxyphenylene) -propionate, 3-methynoleic 5-tert-pentynole-1-hydroxypheninole-substituted fatty acid esters, etc. It can be mentioned as. These may be used as a mixture of two or more.

Examples of the amine-based antioxidant may be, for example, phenylene Lou monument one Nafuchiruamin, Al Kirufue two routes _a one Nafuchinoreamin, the及Pi di § Honoré Kino registration phenylalanine § Min. These may be used as a mixture of two or more.

The above phenolic antioxidant and amine antioxidant may be combined and compounded.

When the component (E) is contained in the lubricating oil composition of the present invention, the content is usually 5% by mass or less, preferably 3% by mass or less, more preferably 3% by mass or less, based on the total amount of the lubricating oil composition. 2.5 mass% or less. If the content exceeds 5% by mass, it is not preferable because sufficient antioxidant properties cannot be obtained in proportion to the content. On the other hand, its content is preferably 0.00 based on the total amount of the lubricating oil composition in order to further enhance long drain performance such as high-temperature detergency, oxidative stability, and base number retention during lubricating oil deterioration. It is at least 1 mass%, preferably at least 1 mass%, particularly preferably at least 1.5 mass%.

In addition, among the components (B) of the present invention, when a compound that does not dissolve or has low solubility in lubricating oil, for example, a zinc dialkyl phosphate that is solid at room temperature is used, From the viewpoint of the solubility of the component (B) and the shortening of the production time of the lubricating oil composition, an amine compound such as the component (D), the amine antioxidant of the component (E) or a mixture thereof (B) ) In an organic solvent such as hexane, toluene and decalin at a temperature of 15 to 150 ° C, preferably 30 to 120 ° C (: particularly preferably 40 to 90 ° C). 0 minutes to 5 hours, preferably 20 minutes to 3 hours, particularly preferably 30 minutes to 1 hour, to dissolve or react, and as an oil-soluble additive obtained by distilling off the solvent by vacuum distillation or the like. It is particularly preferable to incorporate it into a lubricating oil composition (see Japanese Patent Application No. 2002-1991) The lubricating oil composition of the present invention has a Any additive commonly used in lubricating oils can be added according to the purpose. For example, metal-based detergents other than the component (A), wear inhibitors other than the component (B), friction modifiers, viscosity index improvers, corrosion inhibitors, antioxidants, demulsifiers, metal deactivators And additives such as an antifoaming agent and a coloring agent.

As the metal detergent other than the component (A), an alkali metal or alkaline earth metal sulfonate, phenate, or the like may be used.

Examples of the antiwear agent other than the component (B) include sulfur-containing compounds such as disulfides, sulfurized oils, sulfurized oils and fats, and zinc dithiol zinc rubinate. These can be contained in the composition of the present invention in the range of 0.05 to 5% by mass as long as the total sulfur content of the composition is not more than the specified amount of the present invention. It is preferred that a composition having extremely excellent abrasion resistance can be obtained without using it, and that it is not blended from the viewpoints of low sulfur content and mouth water drainage.

As the friction modifier, any compound usually used as a friction modifier for lubricating oils can be used. For example, molybdenum dithiolbamate, molybdenum dithiophosphate, molybdenumamine complex, molybdenum-succinic acid A molybdenum-based friction modifier such as a meido complex or molybdenum disulfide; an alkyl group or an alkenyl group having 6 to 30 carbon atoms, particularly a linear alkyl or alkenyl group having 6 to 30 carbon atoms. Ashless friction modifiers such as amine compounds, fatty acid esters, fatty acids, aliphatic alcohols and aliphatic ethers, etc., which are present in at least one, and are usually 0.1 to 5% by mass. In the case of a sulfur-containing molybdenum complex, it can be contained within a range where the total sulfur content of the composition is not more than the prescribed amount of the present invention. The ashless friction modifiers such as the above-mentioned amine compounds and fatty acid esters are inferior to the component (C) in terms of anti-wear properties and cannot be used in place of the component (C). It may be used in combination in order to further enhance the friction reducing effect, and it is possible to obtain a lubricating oil composition having further low sulfur, phosphorus, or ash, and having low friction. The molybdenum-based friction modifier can be particularly preferably used.

As the viscosity index improver, specifically, a so-called non-dispersion type viscosity index improver such as a polymer or copolymer of one or more monomers selected from various methacrylates or a hydrogenated product thereof is used. Or a so-called dispersion type viscosity index improver obtained by copolymerizing various methacrylates containing a nitrogen compound, a non-dispersion type or dispersion type ethylene-ο-olefin copolymer (α-olefin is propylene, 1-butene , 11-pentene, etc.) or hydrides thereof, polyisobutylene or its hydrogenated products, hydrides of styrene-one-gen copolymers, styrene-mono-maleic anhydride copolymers, and polyalkylstyrenes.

The molecular weight of these viscosity index improvers must be selected in consideration of shear stability. Specifically, the number average molecular weight of the viscosity index improver is, for example, usually 5,000 to 1, 0000, 0000, preferably 100, in the case of dispersible and non-dispersible polymethacrylates. When the thing of 0,000 to 900,000 is polyisobutylene or a hydride thereof, it is usually 800 to 5,000, preferably 1,000 to 4,0,000. Is ethylene- _α -olefin copolymer or a hydride thereof, usually 800 to 500,000, preferably 3,000 to 200,000. Used.

Also, when an ethylene monoolefin copolymer or a hydride thereof is used among these viscosity index improvers, a lubricating oil composition having particularly excellent shear stability can be obtained. One or more compounds arbitrarily selected from the above viscosity index improvers can be contained in an arbitrary amount. The content of the viscosity index improver is usually 0.1 to 20% by mass based on the lubricating oil composition. Examples of the corrosion inhibitor include 'benzotriazole-based, tolyltriazole-based, thiadiazole-based, and imidazole-based compounds.

Examples of the fire retardant include petroleum sulfonate, alkylbenzene sulfonate, di-nornaphthalene sulfonate, alkenyl succinate, and polyhydric alcohol ester.

Examples of the demulsifier include polyalkylene glycol-based nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenylene ether, and polyoxyethylene alkynolenaphthyl ether.

Examples of the metal deactivator include imidazoline, pyrimidine derivatives, alkinorethiadiazole, mercaptobenzothiazonole, benzotriazonole or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4- Thiadiazolyl-1,2,5-bisdialkyldithiocarbamate, 21 (alkyldithio) benzoimidazole, and [3- (o-carboxybenzylthio) propionnitrile.

Examples of the antifoaming agent include silicone, fluorosilicole, and fluoroalkyl ether.

When these additives are contained in the lubricating oil composition of the present invention, the content is 0.005 to 5 for the corrosion inhibitor, the antioxidant, and the demulsifier, based on the total amount of the lubricating oil composition. % By mass, 0.001 to 1% by mass for a metal deactivator, and 0.005 to 1% by mass for an antifoaming agent.

The lubricating oil composition of the present invention can provide a lubricating oil composition having excellent anti-wear properties in which the total sulfur content of the composition is 0.3% by mass or less. by the selection of components及Pi various additives, the total sulfur content of 0.2% by weight of the composition or less, more preferably 0.1 mass ^_0/0 or less, more preferably 0.0 to 5% by weight of anti-wear It is also possible to obtain a low sulfur lubricating oil composition having excellent properties. Particularly, it is possible to obtain a lubricating oil composition having a sulfur content of not more than 0.01% by mass or not more than 0.05% by mass.

Further, the lubricating oil composition of the present invention comprises the component (A), the component (B) or other metals. By adjusting the content of additives contained, it is possible to reduce the sulfated ash content of the composition to 1.0% by mass or less, 0.8% by mass, more preferably 0.6% by mass or less, In particular, it can be set to 0.5% by mass or less.

The lubricating oil composition of the present invention has low sulfur and is excellent not only in anti-wear properties, but also in low friction properties, long drain properties (oxidation stability, base number maintenance properties, etc.) and high-temperature detergency. It can be preferably used as a lubricating oil for internal combustion engines such as gasoline engines for automobiles, automobiles, power generation, and marine engines, diesel engines, gas engines, etc., and is lubricating oil with low sulfur, low phosphorus and low ash. This is particularly suitable for an internal combustion engine equipped with an exhaust gas aftertreatment device. In addition, low-sulfur fuels such as gasoline, gas oil, kerosene, LPG, natural gas, or sulfur having a sulfur content of 50 mass ppm or less, more preferably 30 mass ppm or less, and particularly preferably 10 mass ppm or less are preferably used. It can be particularly preferably used as a lubricating oil for an internal combustion engine using a fuel (eg, hydrogen, dimethyl ether, alcohol, GTL (gas to liquid) fuel) which is not substantially contained, and particularly for a gasoline engine or a gas engine.

In addition, lubricating oil that requires any of the above-described performances of the present invention, lubricating oil for drive systems such as automatic or manual transmissions, grease, wet brake oil, hydraulic oil, turbine oil, compressor oil It can also be suitably used as a lubricating oil such as a bearing oil and a refrigerator oil.

[Industrial applicability]

INDUSTRIAL APPLICABILITY The lubricating oil composition of the present invention can exhibit extremely excellent performance in terms of anti-wear properties, and can achieve low sulfur, low phosphorus and low ash, low friction, long drainage It is also excellent. Therefore, in addition to lubricating oils for internal combustion engines, lubricating oils that require any of these performances, such as lubricating oils for drive systems of automatic or manual transmissions, greases, wet brake oils, hydraulic oils, It can also be suitably used as a lubricating oil such as turbine oil, compressor oil, bearing oil, and refrigerating oil.

[Best Mode for Carrying Out the Invention]

Hereinafter, the content of the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited to these examples.

(Examples 1-3, Comparative Examples 1 and 2)

As shown in Table 1, lubricating oil compositions of the present invention (Examples 1 to 3) and comparative lubricating oil compositions (Comparative Examples 1 and 2) were prepared.

The following performance evaluation test (valve-valve wear test) was performed on each of the obtained compositions. (Valve wear test)

Using a gasoline with a sulfur content of 10 ppm or less as a fuel, a valve train wear test was performed in accordance with J ASO M 328-95, and the rocker arm pad scuffing area, rocker arm wear, and cam wear after 100 hours had elapsed. It was measured. Table 1 shows the evaluation results. As is evident from the results in Table 1, monoalkyl salicylate having one secondary alkyl group having 10 to less than 20 carbon atoms as the component (A) (constituent ratio of 3-alkyl salicylate: 51 mol%: If (A-1) component) is used, it is necessary to use component (C) even if the metal ratio is 1 (Comparative Example 1) or 2.7 (Comparative Example 2). It can be seen that, although excellent in preventing the wear of the kicker arm, the anti-scruffing and cam abrasion preventive properties of the kicker arm pad are not sufficient. On the other hand, the lubricating oil composition of the present invention (Examples 1 to 3) is a low-sulfur lubricating oil composition having a total sulfur content of 0.3% by mass or less, and a total sulfur content of 0.01% by mass or less. Even when the phosphorus content is reduced to 0.08% by mass or less, the use of the component (C) results in extremely excellent wear resistance (the anti-scruffing of the rocker arm pad, the rocker arm). (Abrasion-preventing and cam-wear-preventing properties), the component (A-1) having a metal ratio of 1 was used, and the sulfated ash content of the composition was reduced to 0.5% by mass or less. In the case (Example 1), when the (Al) component having a metal ratio of 5.8 is used (Example 3), when the (A-1) component having a metal ratio of 2.7 is used (actually, It can be seen that the abrasion prevention performance was superior to that of Example 2).

In addition, in addition to the component (A-1) having a secondary alkyl group having 10 to less than 20 carbon atoms shown in the examples, the component (A-1) can be used without using the component (C). Use (A-2) a component or a component (A-3) or a compound having a secondary alkyl group having 20 to 40 carbon atoms (A-11). ) Even if the component (patent filed on the same day by the present inventors) is used, it is possible to obtain a composition excellent in anti-wear performance, and to further reduce the component (B) and reduce the phosphorus content of the composition to 0.05. Even if it is less than mass%, it has sufficient abrasion prevention properties.

When a sulfur- and phosphorus-containing antiwear agent such as zinc dithiophosphate is used as the component (B), the anti-wear performance is maintained as compared with a phosphorus-containing antiwear agent containing no sulfur. Abrasion-preventing properties that are even better than the above compositions can be exerted. For example, phosphorus content is reduced to 0.05% by mass or less, total sulfur content is reduced to 0.1% by mass or less, or sulfated ash content is 0%. It is considered that a composition with low ashing of 5% by mass or less and excellent in antiwear properties can be obtained.

In addition, even when the component (B) specified in the present invention, for example, a phosphoric acid triester containing no metal is used, the use of the component (C) also significantly improves the anti-wear property. It is possible to further reduce ash.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Hydrorefined mineral oil *% by mass Remaining Remaining Remaining Remaining Remaining

(A) Calcium salicylate * 2 wt% 4 1-4-Gold Jh elemental conversion wt% (0.08)--(0.08)-

(A) Calcium salicylate * 3% by mass-4 ― ― 4 Equivalent amount of metal element mass%-(0.25) One-(0.25)

(A) Calcium salicylate * mass%--2.6-equivalent to one metal element mass%-(0.25)--

(B) Phosphorus-containing antiwear agent ※ L Mass% 0.6 0.6 0.6 0.6 0.6 Phosphorus element conversion mass% (0.078) (0.078) (0.078) (0.078) (0.078)

(C) Oleic acid amide mass% 0.3 0.3 0.3-one

(D) Ashless dispersant * 6 mass% 5 5 5 5 5

(E) Antioxidant * F mass% 2 2 2 2 2 Viscosity index improver * 8 mass% 4 4 4 4 4

CO demulsifier 9 mass% 0.01 0.01 0.01 0.01 0.01

Total sulfur content mass% <0.01 <0.01 <0.01 <0.01 <0.01 Sulfated ash mass% 0.39 0.96 0.96 0.39 0.96

JASO valve train wear test

Rocker arm scuffing area% 5.8 30 1.7 77.5 74.6 Rocker arm wear jt m 2.3 1.9 1.4 5 4.7 Cam wear U rn 2.4 20.7 1.8 31.1 39.1

* Total aromatics ^. / Sulfur content 10 mass _PP m, kinematic viscosity at 100 ° C: 5.6mm2 / s, viscosity index: 125, NOACK evaporation: 8% by mass

* 2) Salicylic acid composition ratio: 3A salicylic acid 51 mol%, 4A salicylic acid 6mol%, 5A salicylic acid 35mol%, 3,5-dialkyl salicylic acid 7mol%,

5A Female droxyisophthalic acid 1 mol%, A (alkyl group): secondary C14, C16, C18, metal ratio 1, Ga content: 2.0 mass%, sulfated ash content: 6.8 mass% * 3) Salicylic acid composition ratio: 3A salicylic acid 51 mol%, 4A salicylic acid 6 mol ° /. , 5A salicylic acid 35 mol%, 3,5-dialkyl salicylic acid 7 mol%,

5A Female droxyisophthalic acid 1 mol%, A (alkyl group): secondary G14, C16, G18, metal ratio 2.7, Ca content: 6.2 mass%, sulfated ash: 21.1 mass% * Salicylic acid composition ratio: 3A salicylic acid 51 mol%, 4A salicylic acid 6 mol%, 5A salicylic acid 35 mol%, 3,5-dialkyl salicylic acid 7 mol%,

5A4 Human '13 Xyisophthalic acid 1 mol%, A (alkyl group): secondary G14, G16, G18, metal ratio 5.8, Ca content: 9.5% by mass, sulfated ash: 32.3% by mass (*) (Butyl) zinc phosphate, phosphorus content: 13.2% by mass, sulfur content: 0% by mass, zinc content: 13.0%, sulfated ash: 19.5% by mass * 6) Number average of polybutenyl succinimide and polybutenyl groups Molecular weight: 1 300

* F) octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and alkyldiphenylamine (1: 1) * 8) OCP average molecular weight: 150,000

* Polyalkylene glycol

Claims

The scope of the claims

1. In a lubricating base oil, based on the total amount of the composition, (A) an alkali metal or alkaline earth metal salicylate containing at least one compound selected from the compounds represented by the following general formula (1), and Or its (over) basic salt is 0.005 to 0.4% by mass in terms of a metal element, and (B) the phosphorus-containing wear inhibitor is 0.005 to 0.2% by mass in terms of a phosphorus element. And (C) an amide compound represented by the general formula (2) in a content of 0.01 to 1% by mass, and a total sulfur content of the composition is 0.3% by mass or less. Lubricating oil composition.

(In the general formula (2), R ³ has 640 carbon atoms, and R ⁴ and R ⁵ may be the same or different and each represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms.)

2. The component (A) is

(A-1) an alkali metal or alkaline earth metal salicylate in which the monoalkyl salicylate having one secondary alkyl group having 10 to 40 carbon atoms is 85 mol% or more, and Z or The composition of the (over) basic salt, wherein R ¹ in the general formula (1) is a secondary alkyl group having 10 to 40 carbon atoms, and R ² is hydrogen. Ratio 40 mole ^_0/0 or more in which an alkali metal or aralkyl force Li earth metal salicylate, (A- 2) secondary alkyl of R ¹ and R ² 1 0-40 carbon atoms in the general formula (1) An alkali metal or alkaline earth metal salicylate, and z or a (over) basic salt thereof, and

(A-3) In the general formula (1), one of R ¹ and R ² is a hydrocarbon group having 1 to less than 10 carbon atoms, the other is a secondary alkyl group having 10 to 40 carbon atoms, and R ¹ and R ² of the carbon atoms of the difference is 1 0 or more alkali metal or Al force Li earth metal salicylate, and / or its (over) basic salts

The lubricating oil composition according to claim 1, wherein the lubricating oil composition is one or a mixture of two or more selected from the group consisting of:

3. The secondary alkyl group having 10 to 40 carbon atoms in the component (A-1) is a secondary alkyl group having 10 to less than 20 carbon atoms. The lubricating oil composition according to the above item

4. The lubricating oil composition according to claim 1, wherein the metal ratio of the component (A) is 2.3 or less.

5. The lubricating oil composition according to claim 1, wherein the metal ratio of the component (A) is 3 or more.

6. The component (B) is at least one selected from the group consisting of a phosphorus compound represented by the general formula (3), a phosphorus compound represented by the general formula (4), and a metal salt or an amine salt thereof. 2. The lubricating oil composition according to claim 1, which is a compound of a kind.

(In the general formula (3), X ¹ , X ^2, and X ³ each independently represent an oxygen atom or a sulfur atom, and R ⁵ , ^16, and ¹⁷ each independently represent a hydrogen atom or a carbon atom. ~ 3 Shows a hydrocarbon group of 0. )

X ⁷

8 4 II 6 10

R—X—One X—R (4)

X—R ⁹

(In the general formula (4), X ⁴ , X ⁵ , X ⁶ and X ⁷ each independently represent an oxygen atom or a sulfur atom, and R ⁸ , R ⁹ and R ^{1 Q} each independently represent a hydrogen atom Or a hydrocarbon group having 1 to 30 carbon atoms.)

7. The component (B) is a metal salt of a phosphorus compound in which X ¹ , X ² and X ³ in the general formula (3) are all oxygen atoms, and X ⁴ , X ⁵ and X in the general formula (4). Jun Namerayu composition according to claim 6, wherein the ⁶ and X ⁷ is at least one compound that is selected from the group consisting of metal salts of all the phosphorus compound is an oxygen atom.

8. In the component (B), X ⁴ , X ⁵ , X ^6, and X ^{7 in} the general formula (4) are all oxygen atoms, and R ⁸ , R ^9, and R ¹¹⁵ each independently have 1 carbon atom. 7. The lubricating oil composition according to claim 6, wherein the lubricating oil composition is a phosphorus compound which is a hydrocarbon group of from 30 to 30.

9. In the component (B), two of X ⁴ , X ⁵ , X ⁶ and X ^{7 in} the general formula (4) are oxygen atoms, and two of R ⁸ , R ⁹ and R ¹⁰ have 1 carbon atoms. 7. The lubricating oil composition according to claim 6, wherein the composition is a zinc salt of a phosphorus compound having from 30 to 30 hydrocarbon groups, one of which is hydrogen.

10. The lubricating oil according to claim 1, wherein the content of the component (B) is 0.08% by mass or less in terms of a phosphorus element based on the total amount of the composition. Composition.

1 1. The lubricating oil composition according to claim 1, comprising at least one selected from the group consisting of (D) an ashless dispersant and (E) an antioxidant.

1 2. The lubricating oil composition according to claim 1, wherein the total sulfur content of the lubricating base oil is 0.05% by mass or less.

1 3. The lubricating oil composition according to claim 1, which is used for an internal combustion engine.

14. The lubricating oil composition according to claim 13, wherein the composition has a sulfated ash content of 1.0% by mass or less.

1 5. Any one or more of the following requirements: 0.5% by mass or less of sulfuric acid ash in the composition, 0.05% by mass or less of total sulfur, and 0.05% by mass or less of phosphorus. 14. The lubricating oil composition according to claim 13, which satisfies the following.

1 6. A method for preventing wear of a valve train of an internal combustion engine, comprising using the lubricating oil composition according to claim 1.