WO2004003118A1 - Lubricating oil additive, lubricating oil composition containing the same, and process for producing the same - Google Patents

Abstract

A lubricating oil additive which is obtained by imparting oil solubility to (A) a specific phosphorus compound metal salt insoluble or sparingly soluble in lubricating oils by dissolving or reacting the salt (A) in or with (B) an amine compound.

Description

 Description Lubricating oil additive, lubricating oil composition containing the same, and method for producing the same [Technical field]

 The present invention relates to a lubricating oil additive, and more particularly, to a lubricating oil additive obtained by dissolving a metal salt of a phosphorus compound that is insoluble or has low solubility in a lubricating base oil, and a lubricating oil composition comprising the same. The article and its manufacturing method.

[Background technology]

 In recent years, from the viewpoint of effective use of resources, reduction of waste oil, and cost reduction of lubricating oil users, there is a growing demand for longer drainage of lubricating oil.

 The present inventors have developed a monothiophosphate-based compound in which sulfur in the molecule is reduced in place of a sulfur-containing antiwear agent and antioxidant such as zinc dialkyldithiophosphate to enhance long drain performance of lubricating oil. A low-sulfur lubricating oil composition containing a metal salt or a metal salt of a phosphoric acid ester-based compound or a metal salt of a phosphonate ester that does not contain sulfur in the molecule maintains the anti-wear property while maintaining the base. It has been found that it has excellent long drain performance such as valency maintenance and oxidation stability, and exhibits high-temperature detergency, low friction, and the like. A patent application has already been filed for this invention (Japanese Patent Application No. 200-02-015351, Japanese Patent Application No. 2000-246946).

 These metal salts of phosphorus compounds are not only poor in handling properties but also poorly soluble in lubricating oil because zinc dialkyldithiophosphates are liquid at room temperature, whereas they are solid at room temperature. In addition, there is a problem that dissolution takes a long time, and this is a hindrance to mass-producing industrially efficient lubricating oil compositions containing these metal salts of phosphorus compounds.

An object of the present invention is to provide a technique for liquefying a metal salt of a phosphorus compound having low solubility in lubricating oil and dissolving it in the lubricating oil efficiently in a short time in view of the above circumstances. By this, a lubricating oil composition containing a metal salt of a specific phosphorus compound exhibiting extremely excellent performance such as tang drainage can be industrially efficiently produced. That is. '

[Disclosure of the Invention]

 The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that solubility in a lubricating oil can be improved by previously dissolving or reacting the phosphorus compound in an amine compound, thereby completing the present invention. Reached.

 That is, the present invention provides (A) a metal salt of a phosphorus compound represented by the general formula (1), a metal salt of a phosphorus compound represented by the general formula (2), and a metal salt of the general formula (3). And (B) an amine compound which is dissolved or reacted with at least one compound selected from the group consisting of metal salts of phosphorus compounds.

 11 1 3 13

 R-X-P-X-R

 12 _12 (1)

 X-R

(In the general formula (1), X ¹ , ² and ³ each independently represent an oxygen atom or a sulfur atom, and at least one of them is an oxygen atom, and R ¹¹ R ¹² and R ¹³ individually represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of these is a hydrogen atom.)

X ⁷

 14 4 II 6 16,

 R-X-P-X-R (2)

 15

 X-R

(In the general formula ^{(2), X 4, X} 5, X 6 and X ⁷ are each independently an oxygen atom or a sulfur atom, and at least three of these is an oxygen atom, R ^14, R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of them is a hydrogen atom.)

(一般式 （3) において X⁸、 X⁹及び X^{1 Q}は、 それぞれ個別に酸素原子又は硫 黄原子を示し、 かつこれらのうちの少なくとも 2つは酸素原子であり、 R¹⁷、 R ¹⁸及ぴ R ¹⁹は、 それぞれ個別に水素原子又は炭素数 1〜 30の炭化水素基を 示し、 かつこれらのうちの少なくとも 1つは水素原子であり、 aは 0又は 1であ る。 また、 上記一般式 （1) 〜 （3) で表されるリン化合物は、 X— R結合間に 一 (OR') _n—基があっても良く、 R' は炭素数 1〜4のアルキレン基、 nは 1〜 10の整数を示す。）

(In the general formula (3), X ⁸ , X ⁹ and X ^{1 Q} each independently represent an oxygen atom or a sulfur atom, and at least two of them are oxygen atoms, and R ¹⁷ , R ¹⁸ andぴ R ¹⁹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of them is a hydrogen atom, and a is 0 or 1. The phosphorus compounds represented by the formulas (1) to (3) may have one (OR ′) _n — group between X—R bonds, R ′ is an alkylene group having 1 to 4 carbon atoms, and n is Shows an integer of 1 to 10.)

In the lubricating oil additive of the present invention, X ¹ , X ² and X ^{3 in} the general formula (1), X ⁴ , X ⁵ , X ⁶ and X ⁷ in the general formula (2) and the general formula (1) It is preferable that all of X ⁸ , X ⁹ and X ^{1 Q} in (3) are oxygen atoms.

 The metal in the component (A) is preferably at least one metal selected from lithium, magnesium, calcium and zinc.

 The component (B) is preferably at least one amine compound selected from an amine-based antioxidant, an aliphatic amine, an ashless dispersant and a derivative thereof.

 One of the lubricating oil additives of the present invention is a lubricating oil additive obtained by dissolving the component (A) in an amine antioxidant.

 Further, one of the lubricating oil additives of the present invention is a lubricating oil additive obtained by reacting the component (A) or the lubricating oil additive with an aliphatic amine.

 One of the lubricating oil additives of the present invention is a lubricating oil additive obtained by reacting the component (A) or the lubricating oil additive with an ashless dispersant and / or a derivative thereof.

 The lubricating oil additive preferably has a reaction ratio of the aliphatic amine, the ashless dispersant or the derivative thereof to the component (A) of 0.15 or more by mass ratio.

 It is preferable that the ashless dispersant and / or a derivative thereof have a total base number of 5 mg KOH / g or more by a hydrochloric acid method.

 It is preferable that the derivative of the ashless dispersant is a boron compound derivative of the ashless dispersant.

The present invention further provides a lubricant base oil, an antioxidant, an ashless dispersant, a metal detergent, a friction modifier, an antiwear agent, a corrosion inhibitor, an antioxidant, a demulsifier, a metal, At least one selected from deactivators, defoamers, coloring agents, and viscosity index improvers And a lubricating oil additive.

 The present invention resides in a lubricating oil composition comprising the lubricating oil additive and a lubricating base oil. The present invention provides (A) a metal salt of a phosphorus compound represented by the general formula (1), a metal salt of a phosphorus compound represented by the general formula (2), and a phosphorus compound represented by the general formula (3). A method for producing a lubricating oil additive, comprising: dissolving or reacting at least one compound selected from the group consisting of metal salts of compounds with an amine compound (B).

 The present invention resides in a method for producing a lubricating oil composition, which comprises blending the lubricating oil additive into a lubricating oil. Hereinafter, the present invention will be described in detail.

 In the present invention, the component (A) includes a phosphorus compound represented by the general formula (1), a phosphorus compound represented by the general formula (2), or a phosphorus compound represented by the general formula (3). Salts obtained by reacting a metal base such as an oxide, a metal hydroxide, a metal carbonate, or a metal chloride to neutralize a part or all of the remaining acidic hydrogen can be given.

 11 1 3 13

 R-X-P-X-R

In the general formula (1), X ¹ , X ² and X ³ each independently represent an oxygen atom or a sulfur atom, and at least one of them is an oxygen atom. R ¹¹ R ¹² and R ¹³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of them is a hydrogen atom.

 X

14 4 II 6 16 _n ,

RXPXR ( ² )

 15

XR In the general formula (2), X ⁴ , X ⁵ , X ⁶ and X ⁷ each independently represent an oxygen atom or a sulfur atom, and at least three of them are oxygen atoms. R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of them is a hydrogen atom.

In the general formula (3), X ⁸ , X ⁹ and X ^{1 Q} each independently represent an oxygen atom or a sulfur atom, and at least two of them are oxygen atoms, and R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 ° carbon atoms, and at least one of these is a hydrogen atom, and a is 0 or 1.

The phosphorus compounds represented by the above general formulas (1) to (3) may or may not have one (OR ′) _n — group between the X—R bonds, and R ′ has 1 to 1 carbon atoms. 4, preferably 1 or 2 alkylene groups, and n represents an integer of 1 to 10, preferably 1 to 4. It is more preferable that there is no (〇R ′) _n — group between the X—R bonds in view of higher abrasion prevention performance or extreme pressure performance. Specific examples of the metal in the above metal base include lithium metal, lithium, sodium, potassium, cesium and other alkaline metals, calcium, magnesium, barium and other alkaline earth metals, zinc, copper, iron, lead, nickel, and the like. Examples include heavy metals such as silver, manganese, and molybdenum. Of these, alkali metals such as lithium and sodium, alkaline earth metals such as magnesium and calcium, and zinc are preferred, and zinc is most preferred.

 The structure of the metal salt of the phosphorus compound varies depending on the valency of the metal and the number of OH groups or SH groups of the phosphorus compound, and thus the structure is not limited at all. For example, 1 mol of zinc oxide When 1 and phosphoric acid diester (one OH group) 2 mo 1 are reacted, it is thought that a compound having a structure represented by the following formula is obtained as a main component. However, if there is a polymerized molecule, Conceivable.

また、 例えば、 酸化亜鉛 1 m o 1 とリン酸モノエステル （O H基が 2つ） l m o 1 とを反応させた場合、 下記式で表わされる構造の化合物が主成分として得ら れると考えられるが、 ポリマー化した分子も存在していると考えられる。

Further, for example, when 1 mo 1 of zinc oxide is reacted with monoester of phosphoric acid (2 OH groups) lmo 1, a compound having a structure represented by the following formula is considered to be obtained as a main component. It is considered that a polymerized molecule is also present.

上記！^ ^{1 1}〜!^ ^{1 9}で表される炭素数 1〜3 0の炭化水素基としては、 具体的に は、 アルキル基、 シクロアルキル基、 アルケニル基、 アルキル置換シクロアルキ ル基、 ァリール基、 アルキル置換ァリール基、 及ぴァリールアルキル基を挙げる ことができる。

the above! Specific examples of the hydrocarbon group having 1 to 30 carbon atoms represented by ^ ¹¹ to! ^ ¹⁹ include an alkyl group, a cycloalkyl group, an alkenyl group, an alkyl-substituted cycloalkyl group, an aryl group, and an alkyl group. Examples include a substituted aryl group and an arylalkyl group.

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

 Examples of the above-mentioned 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 above alkylcycloalkyl group include a methylcyclopentyl group, a dimethynolecyclopentyl group, a methylpentyl pentinole group, a ethynolectic pentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylethylcyclohexyl group, Alkylcycloalkyl groups having 6 to 11 carbon atoms, such as acetylcyclohexyl group, methylcycloheptyl group, dimethylcyclyl heptinol group, methinoleethylcyclyl heptyl group, getylcycloheptyl group, etc. The substitution position of is also arbitrary.).

Examples of the alkenyl group include, for example, a ptenyl group, a pentenyl group, a hexenyl group, a hepturyl group, an otaturyl group, a nonenyl group, a decenyl group, a pendecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, and a hexadecenyl group. Alkenyl groups such as octadecenyl, heptadecenyl and octadecenyl The alkenyl group 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, for example, a tolyl group, an xylyl group, an ethylphenol group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, and a nonylphenyl group. C7-C18 alkylaryl group such as a benzyl group, a decylphenyl group, a decylphenyl group, a dodecylphenyl group (the alkyl group may be linear or branched, and the position of substitution with the aryl group may be Is optional).

 Examples of the above arylalkyl group include arylalkyl groups having 7 to 12 carbon atoms, such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, and phenylhexyl. May be linear or branched).

 the above ~! The hydrocarbon group having 0 to 0 carbon atoms represented by ^ is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms, and more preferably 3 to 18 carbon atoms. It is more preferably an alkyl group having 4 to 10 carbon atoms, and particularly preferably an alkyl group having 4 to 6 carbon atoms because of having high anti-wear performance and extreme pressure properties.

 Examples of the phosphorus compound represented by the general formula (1) include: phosphorous acid, monothiophosphorous acid, dithiophosphorous acid; the above-mentioned phosphorous acid monoester having one hydrocarbon group having 1 to 30 carbon atoms Phosphite monoester, dithiophosphite monoester; phosphite diester having two hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphite diester, dithiophosphite diester and the like; Mixtures can be mentioned.

In the present invention, X ^ X ³ in the general formula (1) is preferably 2 or more of them are oxygen atom, more preferably all three oxygen atoms.

Examples of the phosphorus compound represented by the general formula (2) include phosphoric acid and monothiophosphoric acid; the above-mentioned phosphoric acid monoester having one hydrocarbon group having 1 to 30 carbon atoms, and monothiophosphoric acid. Monophosphoric acid esters; phosphoric acid diesters having two hydrocarbon groups having 1 to 30 carbon atoms; monothiophosphoric acid diesters; and mixtures thereof.

In the present invention, all of X ^{4 to} X ⁷ in the general formula (2) are preferably oxygen atoms.

 As the phosphorus compound represented by the general formula (3), for example, the above-mentioned phosphonic acid having one hydrocarbon group having 1 to 30 carbon atoms, monothiophosphonic acid; the hydrocarbon group having 1 to 30 carbon atoms And monothiophosphonic acid monoesters having two of these; and mixtures thereof.

In the present invention, all of X ^{8 to} X ^{1 Q in} the general formula (3) are preferably oxygen atoms.

 Among these components (A), salts of a phosphite diester having two alkyl groups or aryl groups having 3 to 18 carbon atoms with zinc base, molybdenum base, calcium base, magnesium base, lithium base, Salts of diesters of phosphoric acid having two alkyl groups or aryl groups of 3 to 18 with zinc bases, molybdenum bases, calcium bases, magnesium bases, lithium bases, alkyl groups having 3 to 18 carbon atoms or It is preferably selected from salts of an alkyl or arylphosphonic acid monoester having two aryl groups with a zinc base, a molybdenum base, a calcium base, a magnesium base, or a lithium base.

 One or more of these components (A) can be arbitrarily compounded.

In the production of the metal salt of the phosphorus compound in the present invention, a known general production method can be used, and there is no particular limitation. Specifically, for example, in the case of a zinc salt of a phosphoric diester, a zinc base such as zinc oxide, zinc hydroxide, zinc carbonate, zinc chloride, etc. is added to 2 moles of the phosphorus compound represented by the general formula (2). ~ 2 mol, preferably 0.5-1 mol, particularly preferably 0.8-0.98 mol, preferably 0.2-2 L, preferably 0.5-1.5 L of organic solvent and water ◦ 0.5 to 1 L, preferably 0.1 to 0.5 L mixed at 40 to 100 ° C, preferably 60 to 90 ° C for 0.5 to: 10 hours The reaction is preferably carried out by heating for 1 to 6 hours. Then, the aqueous layer is removed, and the organic solvent layer is removed. After filtration, the organic solvent is removed by distillation under reduced pressure or the like. For example, in the case of a zinc salt of a phosphoric acid monoester, a zinc base such as zinc oxide, zinc hydroxide, zinc carbonate, zinc chloride or the like is used in an amount of 0.2 to 4 mol per 2 mol of the phosphorus compound represented by the general formula (2). Mol, preferably 1-2 mol, particularly preferably 1.6-1.96 mol, can be obtained using the method as described above. The organic solvent used herein is not particularly limited, but may be a generally known organic solvent such as alcohol, hexane, benzene, toluene, xylene, decalin, other compounds having an aromatic ring, or a lubricating oil. Base oil and the like can be exemplified.

 In the present invention, the neutralization ratio of the phosphorus compound with the metal salt is preferably 50% or more, more preferably 80% or more, and particularly preferably 90% or more. Compounds obtained by such a method include, for example, zinc di (2-ethylhexyl) phosphate, zinc di (2-ethylhexyl) monothiophosphate, calcium di (2-ethylhexyl) phosphate, dibutyl phosphate In the case of zinc, zinc 1,3-dimethylbutyl phosphate, etc., it is a white solid, and as it is, lubricating base oil, additives other than component (B), and lubricating oil not containing component (B) It has low solubility in the composition, and even if it is dissolved in the above-mentioned organic solvent, it may precipitate when the organic solvent is distilled off. In addition, even if such a compound is heated and mixed simultaneously with the lubricating oil composition or the lubricating base oil containing the component (B) and the component (B) and other additives, the compound is completely dissolved. It takes a long time, and if necessary, the undissolved phosphorus compound metal salt needs to be filtered, which is inefficient for industrial production.

Other methods for producing the component (A) include, for example, the method of Dorinson (ASLE Trans., 22 (2), 190 (1967)) and the method of Handley (Analyt. Chem., 35, pp991-995 (1963) ), Japanese Patent Publication No. 42-126266, Japanese Patent Publication No. 5-293357, Japanese Patent Laid-Open No. 5-222068, Japanese Patent Publication No. And the method disclosed in Japanese Patent Publication No. It is preferable that the component (A) obtained in a solid state as described above is previously mixed or dissolved in an organic solvent prior to mixing with the component (B). Further, in the above Production Examples, the component (A) obtained without distilling off the organic solvent can be used for mixing with the component (B). In addition, the component (A) The components (B) or the components (B) may be mixed in advance with the above-mentioned raw materials and reacted. The component (B) in the present invention is an amine compound, and includes various amine compounds. Preferred examples of the component (B) include amine antioxidants, aliphatic amines, ashless dispersants, and / or derivatives thereof.

 (B-1) Specific examples of the amine antioxidant include various aromatic amine compounds, such as alkyldiphenylamine, alkylnaphthylamine, phenyl α-naphthylamine, and alkylphenyl-amine. Amine-based antioxidants generally known for lubricating oil applications such as α-naphthylamine are preferred. These are preferably liquid at room temperature, and can be preferably used because the solubility of the component (II) is extremely high. Here, the alkyl group is an alkyl group having 1 to 30, preferably 3 to 20, and particularly preferably 4 to 10 carbon atoms, and the number of substitution is 1 to 4, preferably:! ~ 2.

 Examples of the ashless dispersant include (Β-2) succinic acid imide, (Β-3) benzylamine, (Β-4) polyamine, or Mannich reaction product of alkyl or alkenylphenol, formaldehyde and polyamine, and the like. It is preferably at least one compound selected from compound derivatives.

 In the ashless dispersant and / or derivative thereof, the total base number in the hydrochloric acid method is preferably 5 mgKOH / g or more from the viewpoint of the solubility of the component (Α) or the reactivity with the component (Α), It is more preferably at least 1 OmgKOHZg, particularly preferably at least 20 mgKOH / g. The total salt value in the hydrochloric acid method means a value measured by a method specified in 6. Potentiometric titration method (base number) of JIS K 2501.

 More specifically, examples of the above (Β-2) succinic acid imide include compounds represented by the following general formula (4) or (5).

一般式 （4) において、 R²¹は炭素数 1 2〜400、 好ましくは 6 0〜 20 0、 特に好ましくは 70〜1 50のアルキル基又はアルケニル基を示し、 aは 1 〜 5、 好ましくは 2〜 4の整数を示す。

In the general formula (4), R ²¹ represents an alkyl group or an alkenyl group having 12 to 400 carbon atoms, preferably 60 to 200, particularly preferably 70 to 150, and a represents 1 to 5, preferably 2 Indicates an integer from 4 to 4.

In the general formula (5), R ²² and R ²³ each independently represent an alkyl group or an alkenyl group having 12 to 400 carbon atoms, preferably 60 to 200, particularly preferably 70 to 150, and a polybutenyl group Is particularly preferred. b 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 (4) in which succinic anhydride is added to one end of a polyamine by imidation, and an anhydride at both ends of the polyamine. There is a so-called bis-type succinic acid imid represented by the general formula (5) to which succinic acid is added, but any of these (B_2) components and a mixture thereof can be used.

The method for producing the succinic acid imide is not particularly limited. For example, chlorinated polybutene or polyisobutene (these usually have a vinylidene structure at the end of 5 to 10 Omo 1%), or polybutene from which chlorine or fluorine has been sufficiently removed is mixed with maleic anhydride and 100 to 200 A method of reacting polybutenyl succinic acid obtained by reacting at ° C with a polyamine (for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.) can be used. In the case of producing succinic acid imide, the polybutenyl succinic acid may be reacted twice as much as the amount of the polyamine (molar ratio). The polyamine may be reacted in the same amount (molar ratio). Among these, polybutulbissuccinimide is preferable because it can impart oxidation stability, sludge dispersibility and the like to the lubricating oil composition. More specifically, examples of the benzylamine (B-3) include a compound represented by the following general formula (6).

一般式 （6) において、 R²⁴は、 炭素数 1 2〜4 00、 好ましくは 60〜 2 00、 特に好ましくは 70〜 1 50のアルキル基又はアルケニル基を示し、 cは ：!〜 5、 好ましくは 2〜 4の整数を示す。

In the general formula (6), R ²⁴ represents an alkyl group or an alkenyl group having 12 to 400 carbon atoms, preferably 60 to 200 carbon atoms, and particularly preferably 70 to 150 carbon atoms. Represents an integer of 2 to 4.

 This benzylamine is obtained, for example, by reacting a polyolefin (for example, propylene oligomer, polybutene, ethylene monoolefin copolymer, etc.) with phenol to form an alkylphenol, and then adding formaldehyde and a polyamine (for example, diethylenetriamine). , Triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.) by the Mannich reaction.

 More specifically, examples of the polyamine (B-4) include a compound represented by the following general formula (7).

R ²⁵ -NH- (CH ₂ CH ₂ NH) _d _H (7)

In the general formula (7), R ²⁵ represents an alkyl group or an alkenyl group having 12 to 400 carbon atoms, preferably 60 to 200, particularly preferably 70 to 150, and d represents:! It preferably represents an integer of 2 to 4.

 For example, polyolefins are obtained by chlorinating polyolefins (eg, propylene oligomer, polybutene, ethylene-α-olefin copolymer), and then adding ammonia-polyamines (eg, ethylenediamine, diethylenetriamine, triethylenetetramine). , Tetraethylenepentamine, pentaethylenehexamine, etc.).

As the derivative of the ashless dispersant, specifically, for example, a boron compound, an oxygen-containing organic compound, a sulfur compound, or the like, or a nitrogen compound represented by the above (Β-2) to (Β_4), or two kinds thereof are used. The remaining amino group and Ζ or imino remaining after being acted on in combination Examples include various modified compounds in which some or all of the groups are neutralized or amidated.

 Examples of the boron compound include boric acid, borates, and borate esters. Specific examples of boric acid include orthoboric acid, metaboric acid and tetraboric acid. Examples of the borate include alkali metal salts, alkaline earth metal salts, and ammonium salts of boric acid. More specifically, for example, lithium metaborate, lithium tetraborate, lithium pentaborate, perborate Lithium borate, such as lithium; sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, sodium octaborate, etc .; sodium borate; potassium metaborate, tetraborate Potassium borates such as potassium lactate, potassium pentaborate, potassium hexaborate, and potassium octaborate; calcium metaborate, calcium diborate, tricalcium tetraborate, pentacalcium tetraborate, and calcium hexaborate Calcium borate such as shim; magnesium metaborate, magnesium diborate, trimag tetraborate Siumu, tetraborate five magnesium hexaborate magnesium etc. magnesium borate; and metaborate Anmoniumu, tetraborate Anmoyuumu, pentaborate Anmoniumu, boric acid Anmoniumu such as eight borate Anmoniumu is like et be.

 Examples of the borate ester include esters of boric acid and preferably an aliphatic alcohol having 1 to 6 carbon atoms, and more specifically, for example, monomethyl borate, dimethyl borate, trimethyl borate, Monoethyl borate, getyl borate, triethyl borate, monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate, triptyl borate and the like can be mentioned.

 The succinic acid imid derivative treated with the boron compound is preferably used because it can impart heat resistance and oxidation stability to the lubricating oil composition. However, the ratio of the nitrogen equivalent to the boron equivalent (B / N equivalent) The (ratio) is not particularly limited, but is preferably 1 or less, more preferably 0.7 or less, and more preferably 0.5 or less because a complex is easily formed with the component (A). Is particularly preferred.

Specific examples of the oxygen-containing organic compound include, for example, formic acid, acetic acid, glycolic acid, propionic acid, lactic acid, butyric acid, valeric acid, cabronic acid, enanthic acid, and caprylic acid. 1-3 carbon atoms, such as acid, pelargonic acid, capric acid, pendecylic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, oleic acid, nonadecanoic acid, eicosanoic acid, etc. 0 monocarboxylic acid; polycarboxylic acid having 2 to 30 carbon atoms such as oxalic acid, phthalic acid, trimellitic acid, and pyromellitic acid or anhydrides or ester compounds; alkylene oxide having 2 to 6 carbon atoms A hydroxy (poly) oxyalkylene carbonate; By causing such an oxygen-containing organic compound to act, for example, when a part or all of the amino group or imino group in the compounds of the general formulas (4) to (7) has a structure represented by the following general formula (8) Presumed.

,---CO-R ²⁶ (8)

Wherein R ^{2 6} is a hydrogen atom, an alkyl group having 1-2 4 carbon atoms, an alkenyl group, an alkoxy group, or one O- (R ^{2 7} 0) arsenide Dorokishi (poly) Okishiaruki groups represented by _m H are shown, R ^{2 7} is an alkylene group having 1 to 4 carbon atoms, m is an integer of 1 to 5.

 These components (B-2) to (B-4) and derivatives of these compounds are considered to react with component (A) to form a complex, and are stably present in lubricating oil additives or lubricating oil compositions. It can be used particularly preferably because it can shorten the production time of the lubricating oil composition. Among these, (B-2) succinic acid imide and / or a derivative thereof is preferable, or a boron compound derivative of the components (B-2) to (B-4) is preferable, and in particular, (B-2) succinic acid A imide boron compound derivative is particularly desirable in that the lubricating oil additive or the lubricating oil composition of the present invention can further improve the heat resistance, oxidation stability, extreme pressure property and the like.

Further, other amine compounds as the component (B) include, for example, methylamine, ethynoleamine, propylamine, butynoleamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decinoleamine, pendecylamine, tridecylamine, tridecylamine, tridecylamine, dodecylamine, tridecylamine, tridecylamine, dodecylamine, tridecylamine, dodecylamine Noleamine, pentadecinoleamine, hexadeci / reamine, heptadecinoleamine, octadecinole Amin, dimethamine, getylamine, dipropionamine, dibutynoleamine, dipenty / reamine, dihexylamine, diheptylamine, dicytinoleamine, dino-lamine, didecylamine, didecylamine, diddecylamine, ditridecylamine, ditridecylamine , Dipentadecylamine, dihexadecylamine, diheptadecylamine, dioctadecylamine, methylethylamine, methinolepropylamine, methylbutynoleamine, ethylpropylamine, ethynoleptinoleamine, Propylbutynoleamine, pentylmethylamine, hexylmethylamine, heptylmethylamine, octylmethylamine, nonylmethylamine, decylmethylamine, pendecylmethylamine, dodeci Rumethylamine, tridecylmethylamine, tetradecyl / remethylamine, pentadecylmethylamine, hexadecylmethylamine, heptadecylmethylamine, octadecylmethylamine, trimethylamine, ethyldimethylamine, propyldimethylamine, Alkyl groups having 1 to 30 carbon atoms such as butyidimethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecyldimethylamine, and octadecyldimethylamine. Alkylamines which may be branched); ethenylamine, propenylamine, puturamine, otaturamine, oleylamine, octenylmethylamine, decenylmethylamine, dodecenylmethylamine, octadecenyl It has an alkenyl group having 2 to 30 carbon atoms such as tilamine, otaturdimethylamine, decenyldimethylamine, dodecenyldimethylamine, and otadecenyldimethylamine (these alkenyl groups may be linear or branched). Alkenylamine; cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexylamine, methylcyclohexylamine, and ethylcyclohexylamine; alkyl or alkenylcycloalkyl group (the alkyl or alkenyl group may be branched even if it is linear. Alicyclic amines having any of the following forms: methanolamine, ethanolamine, propanolanolamine, ptanolanolamine, pentanoleamine, hexanolamine, heptanolamine, octanolamine. , Nonano Ruamin, Dekanoruamin, dodecanol § Min, O Kuta octadecanol § Min, methanol ethanol § Min, meta no Honoré prop no Honoré amine, meta no Norev Tano one Noreamin, Etanonorepuro Alkanolamines having 1 to 30 carbon atoms such as pananolamine, ethanolbutanolamine and propanolbutanolamine (these alkanolamines may be linear or branched). Alkylene diamine having an alkylene group having 1 to 30 carbon atoms such as methylene diamine, ethylene diamine, propylene diamine, and butylene diamine; diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and the like. Polyamines; monoamines and diamines described above such as pendecyl getylamine, pendecyljetanolamine, dodecyldipropanolamine, oleyljetanolamine, oleylpropylenediamine, stearyltetraethylenepentamine and the like. , Polyamine A compound having an alkyl group or an alkenyl group having 8 to 20 carbon atoms; a heterocyclic compound such as N-hydroxylethylolimidazoline; alkylene oxide adducts of these compounds; and mixtures thereof. Can be illustrated.

 Among these amine compounds, decylamine, dodecylamine, tridecylamine, heptadecylamine, octadecylamine, oleylamine, stearylamine, decyldimethylamine, pendecylgetylamine, pendecyljetanolamine, dodecyldimethylamine, Alkyl having 8 to 20 carbon atoms, preferably 12 to 18 carbon atoms, such as tridecyldimethylamine, heptadecyldimethylamine, octadecyldimethylamine, oleyldimethylamine, and stearyldimethylamine. Preferable examples include aliphatic amines having a group or an alkenyl group (these may be linear or branched).

 When an aliphatic amine, preferably an aliphatic monoamine, is used as the component (B), it is possible to obtain a lubricating oil additive having a further excellent effect of reducing friction between metals. It is particularly preferred to use lubricating oils, since a lubricating oil additive having further excellent extreme pressure properties can be obtained.

 In the present invention, as the component (B), one or a mixture of two or more of the above-mentioned amine compounds can be used.

 Preferred embodiments of the lubricating oil additive of the present invention include the following.

① Lubricant additive made by mixing (A) component and amine antioxidant

② (A) Component or lubricating oil additive of ① and ashless dispersant and / or derivative thereof Reacted lubricating oil additive

 ③ (A) Lubricant additive obtained by reacting component (A) or lubricant additive (1) with aliphatic amine

 潤滑 Lubricating oil additive obtained by reacting component (A) with a mixture of amine antioxidant and ashless dispersant and / or its derivative

 潤滑 Lubricant additive obtained by reacting the component (A) with a mixture of an amine antioxidant and an aliphatic amine

 It is considered that the lubricating oil additive of the above (1) is in a state in which the component (A) is dissolved in an amine antioxidant. It is considered that liquefaction was caused by forming a complex with amine, ashless dispersant, and Z or its derivative.

 The lubricating oil additive of the present invention is preferably the lubricating oil additive of the above (1) to (4), and more preferably the lubricating oil additive of the above (1) or (2).

 The method for producing the lubricating oil additive of the present invention is not particularly limited as long as the component (A) is dissolved or reacted with the component (B). Preferably, the component (A) is mixed with the above-mentioned organic solvent in advance. A method of mixing and stirring with the component (B) in a dissolved state, and then, if necessary, distilling off the organic solvent. The conditions for mixing and stirring are not particularly limited, but the temperature is preferably 15 to 150 ° C, more preferably 30 to 120 ° C, and particularly preferably 40 to 90 ° C. ° C, and it is preferable to perform the reaction at a temperature equal to or lower than its boiling point from the viewpoint of safety, depending on the type of the organic solvent. The time at that time is preferably 5 minutes to 5 hours, more preferably 20 minutes to 3 hours, and particularly preferably 30 minutes to 1 hour. The distillation of the organic solvent is performed using a method such as vacuum distillation until the organic solvent is distilled off. The lubricating oil additive of the present invention thus obtained usually comprises the component (A) in an amount of 0.5 to 20% by mass, preferably 1 to 20% by mass, in terms of phosphorus element, based on the total amount of the lubricating oil additive. -10% by mass.

In preparing the lubricating oil additive of the present invention, the mixing ratio of the component (A) and the component (B) is not particularly limited, but the component (B) is added in an amount of 0.1 to 1 part by mass of the component (A). 30 parts by mass, preferably 0.15 parts by mass or more, more preferably 0.2 parts by mass or more, still more preferably 0.3 parts by mass or more, further preferably 0.5 parts by mass or more, particularly preferably 0.8 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less. By adding 0.15 parts by mass or more of the component (B), particularly an aliphatic amine ashless dispersant and Z or its derivative, to 1 part by mass of the component (A) and reacting with each other to form a lubricating oil additive. However, the additive alone dissolves in the lubricating base oil and becomes chewy. The lubricating oil additive of the present invention has a long drain performance such as a base number maintenance property and an oxidative stability while maintaining the anti-wear property of the lubricating oil composition, and exhibits high-temperature detergency, low friction property and the like. Although the basic additive is advantageously used for the purpose of the present invention, in order to further improve the performance of the obtained lubricating oil composition, the lubricating oil additive of the present invention is further added with various lubricating oil additives such as an antioxidant and an ashless At least one selected from powders, metal detergents, friction modifiers, antiwear agents, corrosion inhibitors, antioxidants, demulsifiers, metal deactivators, defoamers, colorants, and viscosity index improvers. One kind can be blended, and if necessary, a small amount may be mixed with a lubricating base oil for viscosity adjustment. In this case, the lubricating oil additive of the present invention can be provided as a package additive in which the various additives described above are arbitrarily mixed according to the required performance of the lubricating oil composition. By blending the package additive with the lubricating base oil, the method for producing the lubricating oil composition is simplified, and a lubricating oil composition which is cost-effective can be obtained. The lubricating oil composition of the present invention contains the lubricating oil additive of the present invention or a package additive in which various lubricating oil additives are blended, and a lubricating base oil (or other lubricating oil additives as necessary). And lubricating oil composition) and mixed and stirred at 15 ° C to 150 ° C, preferably 40 ° to 120 ° C (particularly preferably 60 ° to 90 ° C). It can be manufactured by the following.

When the lubricating oil additive of the present invention is added to a lubricating base oil or a lubricating oil composition, there is no particular limitation on the amount of addition, but the preferred lower limit is expressed in terms of phosphorus element based on the total amount of the composition. The value is 0.005% by weight, more preferably 0.01% by weight, particularly preferably 0.02% by weight, while the preferred upper limit is 0.4% by weight, more preferably 0.2 mass. / ₀ , particularly preferably 0.1% by mass. Hereinafter, the lubricating base oil constituting the lubricating oil composition of the present invention and the above-mentioned additives that can be used as necessary other than the lubricating oil additive of the present invention will be described. The lubricating base oil is not particularly limited, and mineral base oils and synthetic base oils 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 base oils produced by a method of isomerizing wax-catalyzed mineral oil or GTL WAX (gas to liquid wax). Can be illustrated.

 The total aromatic content of the mineral base oil is not particularly limited, but is preferably 15% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 2% by mass or less. If the total aromatic content of the base oil exceeds 15% by mass, the oxidation stability is poor, which is not preferable.

 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, pyridines, quinolines, phenols, Compounds having heteroaromatics such as naphthols are included.

 The sulfur content in the mineral oil base oil is not particularly limited, but is preferably 0.01% by mass or less, more preferably 0.005% by mass or less, and 0.001% by mass. It is particularly preferred that: By reducing the sulfur content of the mineral base oil, a lubricating oil composition having more excellent long drain properties can be obtained.

Specific examples of the synthetic base oil include polybutene or a hydride thereof; poly- _a -olefin such as 1-octene oligomer and 1-decene oligomer or a hydride thereof; ditridecinoregolelate, G2-ethyl Diesters such as hexyl adipate, disodecyl adipate, ditridecyl adipate, and di-2-ethylhexyl sebacate; trimethylolpropane caprylate, trimethylol propyl nonoperanolegonate, and pentaerythritol tonole 1-2-ethyl Polyphenols such as hexanoate and pentaerythritol perargonate; triesters of neopentynole glycol; alkyl naphthalenes, alkyl benzenes and fragrances Examples thereof include aromatic synthetic oils such as aromatic esters and mixtures thereof. In the present invention, the mineral base oil, the synthetic base oil, or an arbitrary mixture of two or more lubricating oils 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 is not particularly limited, but the kinematic viscosity at 100 ° C. is preferably 20 m Hi ² / s or less, more preferably 10 mm ² / s or less. On the other hand, the kinematic viscosity is preferably at least 1 mm ² Zs, more preferably at least 2 mm ² / s. If the kinematic viscosity of the lubricating base oil at 100 ° C exceeds 20 mm ² / s, the low-temperature viscosity characteristics deteriorate, while if the kinematic viscosity is less than 1 mm ² Z s, Insufficient oil film formation leads to poor lubricity and large loss of evaporation of the lubricating base oil, which is not preferred.

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 the lubricating base oil evaporation loss is large, but also when the lubricating base oil is used as a lubricating oil for internal combustion engines, the sulfur compounds and phosphorus compounds in the composition Alternatively, there is a possibility that the metal component may be deposited on the exhaust gas purification device together with the lubricating base oil, which is not preferable because there is a concern that the exhaust gas purification performance may be adversely affected. The NOACK evaporation here means 250 g of lubricating oil sample according to ASTM D5800. C, is 20 mmH ₂ 0 that the amount of evaporation was kept 1 hour under reduced pressure of (1 9 6 P a) 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, and still more preferably, so as to obtain excellent viscosity characteristics from low to high temperatures. Is 1 20 or more. When the viscosity index is less than 80, the low-temperature viscosity characteristics deteriorate, which is not preferable.

As the antioxidant, in addition to the amine-based antioxidant in the above-mentioned component (B), any phenol-based antioxidant, metal-based antioxidant, and other compounds generally used in lubricating oils can be used. It is. By adding the antioxidant, it is possible to further enhance the long drain performance of the lubricating oil composition. Examples of phenolic antioxidants include 4,4, -methylenebis (2,6-di-tert-butynolephenone), 4,4'-bis (2,6-di-tert-butylphenol), 4,4 1,2-bis (2-methyl-1-6-tert-butylphenol), 2,2,1-methylenebis (4-ethynole 6-tert-butynolephene), 2,2, -methylenebis (4-methyl-1-6-tert-butylphenol) ), 4,4'butylidenebis (3-methyl-6-tert-butylphenol), 4,4,1-isopropylidenebis (2,6-di-tert-butylphenol), 2,2,1-methylenebis (4_ Methyl-6-noelphenol, 2,2,1-isobutylidenebis (4,6-dimethylphenol), 2,2, -methylenbis (4-methylenole 6-hexylhexenophenol), 2,6-zy te rt Butinole 4—Methinolephenore, 2,6-Ditert-butinole 4-Echinolephenore, 2,4-Dimethinole 6—tert_Ptinolephenore, 2,6-Di-tert-α— Dimethylamino-p-creso-ole, 2,6-di-tert-butyl-4 (N, N, 1-dimethylaminomethylphenol), 4,4,1-thiobis

(2-methinole 6-tert-butynolepheno / re), 4,4,1-thiobis (3-methyl-6-tert-butylbutylphenol), 2,2'-thiobis (4-methyl-16-tert-butylphenol), Bis (3-methyl_4-hydroxy-5-tert-butylin-benzinole) snorefied, bis (3,5-di-tert-butylin-1-4-hydroxoxybenz / le) s / sulfide, 2,2'-thio Diethylenebis [3- (3,5-di-tert-butyl) 4-hydroxyphenyl) propionate], tridecinole-3- (3,5-di-tert-butynole 4-hydroxypheninole) propionate, pentaerythrityl Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octyl-3-(3,5-di-tert-butyl-4-hydroxy-4-) ) Propionate, octadecyl / re 3_ (3,5-di-tert-butyl-14-hydroxyphenyl) propionate, 3-methyl-5-tert-butyl-4-hydroxypropyl-substituted fatty acid esters and the like are preferred examples. Can be mentioned. These may be used as a mixture of two or more.

Examples of the ashless dispersant include the ashless dispersant in the above component (B). This can be preferably used to further improve sludge dispersibility, high temperature cleanability, and oxidation stability.

 Examples of the metal-based detergent include alkali metal or alkaline earth metal sulfonates, salicylates, phenates, and phosphonates, and have a neutral, basic, or overbased total base number of 0 to 50 O mg. A known KO HZ g can be used. Examples of the alkali metal include sodium and potassium, and examples of the alkaline earth metal include calcium and magnesium. Calcium and magnesium are preferred, and calcium is particularly preferred. The metal ratio of these metal-based detergents is usually from 1 to 20% by mass, and is not particularly limited. Therefore, an alkali metal or alkaline earth metal salicylate having a metal ratio adjusted to 2.3 or less, an alkali metal or alkaline earth metal salicylate having a metal ratio of 1.5 or less, and a metal ratio of 1 to 20 are used. It is preferred to use a mixture of alkali metal or alkaline earth metal sulfonates. Here, the metal ratio is represented by the valence of the metal element in the metal-based detergent X the content of the metal element (mo 1%) / the content of the soap group (mo 1%), and the metal element is calcium. , Magnesium and the like, a soap group means a sulfonic acid group, a salicylic acid group and the like.

 Examples of the friction modifier include molybdenum dithiol molybdate, molybdenum dithiophosphate, molybdenum disulfide, long-chain aliphatic amine, long-chain fatty acid, long-chain fatty acid ester, long-chain fatty acid amide, and long-chain fatty alcohol. Is mentioned.

 The anti-wear agents other than the component (A) include phosphoric acid, phosphoric monoester, phosphoric diester, phosphoric triester, phosphorous acid, phosphorous monoester, phosphorous diester, phosphorous triester, And their amine salts, zinc dithiophosphate, zinc dithiophosphate, disulfides, sulfurized olefins, sulfurized fats and oils, etc., which can be used, but those containing no sulfur are particularly preferred. . Examples of the corrosion inhibitor include benzotriazole, tolyltriazole, thiadiazole, and imidazole compounds.

Examples of the protective agent include petroleum sulfonate, alkylbenzene sulfonate, dinonylnaphthalene sulfonate, alkenyl succinate, and polyvalent Alcohol esters and the like.

 Examples of the demulsifier include polyalkylene dalicol-based nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene alkyl naphthyl ether.

 Examples of the metal deactivator include imidazoline, pyrimidine derivatives, alkylthiadiazole, mercaptobenzothiazole, benzotriazole or derivatives thereof, 1,3,4-thiadiazole polysulfide, 1,3,4-thiadiazolylol 2 , 5 -bisdialkyldithiocarbamate, 2- (alkyldithio) benzimidazonole, and / 3- (o-potoxybenzinorethio) propionnitrile. Note that thiazoles and thiadiazoles can be used together with the composition of the present invention as an additive having antiwear properties.

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

 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-α-olefin copolymer (α-olefin is propylene, Or a hydrogenated product thereof, polyisobutylene or a hydrogenated product thereof, a hydrogenated product of a styrene-one-gen copolymer, a styrene-monomaleic anhydride copolymer, and a polyalkylstyrene.

The molecular weight of these viscosity index improvers must be selected in consideration of shear stability. More specifically, the number average molecular weight of the viscosity index improver is usually from 5,000 to 1,000, preferably 100, in the case of dispersible and non-dispersible polymethacrylates. , 000 to 900, 000, when polyisobutylene or a hydride thereof is used, it is usually 800 to 5,000, preferably 1, 000 to 4,000. When the product is an ethylene monoolefin copolymer or a hydride thereof, it is usually from 800 to 500,000, preferably from 3,000 to 200,000. Use Can be

 When an ethylene-α-olefin 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.

 When these additives are included in the lubricating oil composition (for example, when these additives are used as package additives), the content is determined based on the total amount of the lubricating oil composition to prevent oxidation. 0.05 to 5% by mass for each of the antiwear agent, friction modifier, corrosion inhibitor, antioxidant, and demulsifier other than the component (II), 0 for ashless dispersant and metal detergent. 0.1 to 10% by mass, 0.05 to 1% by mass for the metal deactivator, 0.005 to 1% by mass for the defoamer, 0.1 to 2 for the viscosity index improver. It is usually selected from the range of 0% by mass.

 In the present invention, the sulfur content is reduced to 0.3% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less by reducing or not using the additive containing sulfur. Alternatively, a lubricating oil composition containing substantially no sulfur can be obtained.

 The lubricating oil additive or lubricating oil composition of the present invention can be preferably used as a lubricating oil additive for internal combustion engines such as gasoline engines, motorcycle engines, diesel engines, and gas engines for motorcycles, automobiles, power generation, and ships. But low sulfur fuels, such as sulfur

50 mass 111 or less, more preferably 30 mass ppm or less, particularly preferably 10 mass ppm or less gasoline, gas oil, or kerosene, or fuel with a sulfur content of 1 mass ppm or less (LPG, natural gas, sulfur Hydrogen, dimethyl ether, alcohol, GTL (gas to liquid), etc., which are not contained in gas, can be particularly preferably used as a lubricating oil additive for internal combustion engines, especially a lubricating oil additive for gas engines. Further, the lubricant additive of the present invention can improve the long drain property while maintaining the anti-wear property. Therefore, the lubricant additive for a drive system such as an automatic or manual transmission which requires such performance is used. It can be suitably used as a lubricating oil additive such as lubricating oil, wet brake, hydraulic oil, turbine oil, compressor oil, bearing oil, and refrigeration 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. However, the present invention is not limited to these Examples.

(Example:! ~ 1 3)

 Lubricating oil additives A to M of the present invention (Examples 13) were prepared according to the following formulation.

 (1) Preparation of metal salt of phosphorus compound

b) ジブチルリン酸の代わりにモノ及ぴジ （1, 3—ジメチル） プチルリン酸 混合物を用いた以外は前記 a) と同様の操作を行い、 モノ及ぴジ （1， 3.—ジメ チル） ブチルリン酸亜鉛混合物 （白色固体： リン含有量 1 3. 8質量％、 亜鉛含 有量： 1 8. 7質量％) を得た。 得られた化合物は下記構造を有する化合物の混 合物が主成分であると推定される。 a) 0.196 mol of zinc oxide and 0.4 mol of dibutyl phosphoric acid were mixed with 200 ml of hexane and 40 ml of water, and the mixture was heated and stirred at 80 ° C. for 4 hours. After removing the aqueous layer of the obtained mixture and filtering the hexane layer, hexane of the filtrate was distilled off under reduced pressure to give a white solid (zinc dibutyl phosphate: phosphorus content: 13.2% by mass, zinc) Content: 13% by mass). The obtained compound is presumed to be mainly composed of a compound having the following structure.

b) Perform the same operation as in a) except that a mixture of mono- and di- (1,3-dimethyl) butylphosphoric acid was used instead of dibutyl phosphoric acid to obtain mono- and di- (1,3-dimethyl) butyl phosphoric acid. A zinc acid mixture (white solid: phosphorus content 13.8% by mass, zinc content: 18.7% by mass) was obtained. The obtained compound is assumed to be mainly composed of a mixture of compounds having the following structures.

c) 酸化亜鉛の代わりに水酸化カルシウムを用い、 ジブチルリン酸の代わりに ジ（2—ェチルへキシル） リン酸を用いた以外は a) と同様の操作を行い、 ジ（2 ーェチルへキシル) リン酸カルシウム （白色固体： リン含有量 9. 1質量％、 力 ルシゥム含有量： 5. 8質量％) を得た。

c) Perform the same operation as a) except that calcium hydroxide was used instead of zinc oxide and di (2-ethylhexyl) phosphoric acid was used instead of dibutyl phosphoric acid. -Ethylhexyl) calcium phosphate (white solid: phosphorus content: 9.1% by mass, potassium content: 5.8% by mass) was obtained.

 d) The same operation as in a) was performed except that di (2-ethylhexyl) phosphoric acid was used instead of dibutyl phosphoric acid, and zinc di (2-ethylhexyl) phosphate (white solid: phosphorus content 8 .8% by mass, zinc content: 9.1% by mass).

 Further, the same operation as described above was carried out by appropriately changing the starting materials to obtain the following compounds having a neutralization ratio of 95 to 98%. These were all solids at room temperature.

 e) Mono- and di- (n-butyl) zinc phosphate mixtures

 f) Mono and di (2-ethylhexyl) zinc phosphate mixture

 g) Mono- and di- (n-octyl) zinc phosphate mixture

 h) Mono and di (isodecyl) zinc phosphate mixtures

 i) Mono- and di- (n-dodecyl) zinc phosphate mixture

 j) Mono and di (isotridecyl) zinc phosphate mixture

 k) Mono and di (oleyl) zinc phosphate mixtures

 1) Mono and di (stearyl) zinc phosphate mixture

 m) Mono- and di- (2-ethylhexyl) calcium phosphate mixture

 n) di (2-ethylhexyl) magnesium phosphate

 o) Mono- and di (2-ethylhexyl) magnesium phosphate mixture

 p) di (2-ethylhexyl) lithium phosphate

 q) Zinc salt of 2- (ethylhexyl) phosphonate mono (2-ethylhexyl) ester

 (2) Preparation of mixed additives A to D with amine antioxidant (Examples 1 to 4)

A) After dissolving 500 g of the white solid obtained in the above (1) a) in 1 kg of hexane, 50 Og of alkyldiphenylamine (alkyl group: butyl and octyl groups) was added, and the mixture was added at 40 ° C. After stirring and mixing for 30 minutes under reduced pressure, hexane was distilled off under reduced pressure to obtain viscous additive A (phosphorus content: 6.6% by mass) which was fluid at room temperature.

B) The same operation as in A) was performed except that the white solid obtained in (1) b) above was used, and a viscous additive B (phosphorus content: 6.9 % By mass). C) The same operation as in A) was performed except that the white solid obtained in (1) c) above was used, and a viscous additive C (phosphorus content: 4.55 % By mass).

 D) The same operation as in A) was performed except that the white solid obtained in (1) d) above was used, and a viscous additive D (phosphorus content: 4.4) which was fluid at normal temperature. % By mass).

 (3) Preparation of mixed additives E to H with ashless dispersant (Examples 5 to 8)

 E) After dissolving 200 g of the white solid obtained in the above (1) a) in 1 kg of hexane, a commercially available polypturyl succinic acid ashless dispersant SB (polybutyl group molecular weight: 1300, Nitrogen content: 1.3 mass%, boron content: 0.5 mass%, total base number (hydrochloric acid method): 24 mg KOH / g) 800 g was added, and the mixture was heated and stirred at 40 ° C for 30 minutes. Hexane was distilled off under reduced pressure to obtain a viscous additive E (phosphorus content: 2.64% by mass) which was fluid at room temperature.

 F) The same operation as in E) was performed except that the white solid obtained in (1) b) was used, and a viscous additive F (phosphorus content: 2.76 % By mass).

 G) The same operation as in E) was performed except that the white solid obtained in (1) c) was used, and a viscous additive G (phosphorus content: 1.8 2% by mass).

 H) The same operation as in E) was performed except that the white solid obtained in (1) d) was used, and a viscous additive H (phosphorus content: 1.76) which was fluid at room temperature. % By mass).

The metal salts of the various phosphorus compounds shown in the above (1) e) to q) were subjected to the same operation as above using commercially available imidized dispersant SB of succinic acid as a result of flowability at room temperature. A sticky additive (e _SB ~ (! _SB )) was obtained.

 (4) Preparation of Additives I to M with Amine Antioxidant and Ashless Dispersant (Examples 9 to 13)

I) 400 g of the additive A obtained in the above (2) A), 600 g of the commercially available polybuturic succinic acid imide-based ashless dispersant SB were added, and the mixture was heated and stirred at 80 ° C. for 1 hour. There was obtained an additive I (phosphorus content: 2.64% by mass) which was fluid at room temperature.

 J) To 400 g of the additive B obtained in the above (2) B), 600 g of the above-mentioned commercially available polyptenyl succinic acid imide-based ashless dispersant SB was added, and the mixture was heated and stirred at 80 ° C for 1 hour. Additive J (phosphorus content: 2.76% by mass) was obtained.

 K) To 400 g of the additive C obtained in the above (2) C), 600 g of the above-mentioned commercially available polyptenyl succinic acid imide-based ashless dispersant SB was added, and the mixture was heated and stirred at 80 ° C for 1 hour, and at room temperature. A fluid additive K (phosphorus content: 1.82% by mass) was obtained.

 L) To 400 g of the additive D obtained in the above (2) D), 600 g of the commercially available polypulmic acid succinic acid-based ashless dispersant SB was added, and the mixture was heated and stirred at 80 ° C for 1 hour, and at room temperature. A fluid additive L '(phosphorus content: 1.76% by mass) was obtained.

 M) 100 g of the additive A obtained in the above (2) A), 400 g of the commercially available polybutulco succinic acid ashless dispersant SB, a calcium salicylate detergent (potassium content: 6. 400 g of 2% by mass, metal ratio: 2.7) and 100 g of octyl-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate are added, and the mixture is heated and stirred at 80 ° C. for 1 hour, and then room temperature. As a result, a fluid additive M (phosphorus content: 0.66% by mass, calcium content: 2.5% by mass) was obtained.

 (5) Preparation of Additives N to U with Aliphatic Amine Compound, Aliphatic Amine Compound and Amine Antioxidant (Examples 14 to 21)

 N) After dissolving 50 g of zinc dibutyl phosphate obtained in the above (1) a) in 100 g of hexane, add 50 g of oleylamine, stir and mix at 40 ° C. for 30 minutes, and perform low pressure distillation. The xan was distilled off to obtain a transparent liquid additive N (phosphorus content: 6.6% by mass) at room temperature.

 O) The same operation as in N) was performed, except that 50 g of dodecylamine was used instead of oleylamine, to obtain a transparent liquid additive O (phosphorus content: 6.6% by mass) at room temperature.

 P) The same operation as in the above N) was carried out except that 50 g of dodecyldimethylamine was used instead of oleylamine, to obtain an additive P (phosphorus content: 6.6% by mass) which was a transparent liquid at ordinary temperature. .

Q) Instead of oleylamine, 10 g of oleylamine and alkyldiphenylamine (Alkyl group: butyl group and octyl group) The same operation as in N) above was performed except that 40 g of the mixture was used, and the transparent liquid additive Q (phosphorus content: 6.6 at room temperature) was used. Mass%).

 R) The same operation as in N) above was performed except that a mixture of 10 g of dodecylamine and 40 g of alkyldiphenylamine (alkyl group: butyl and octyl groups) was used instead of oleylamine. As a result, a transparent liquid additive R (phosphorus content: 6.6% by mass) was obtained.

 S) The same operation as in N) was performed except that 50 g of the mono- and di (1,3-dimethylbutyl) zinc phosphates obtained in (1) b) were used. S (phosphorus content: 6.9% by mass) was obtained.

 T) 50 g of zinc di (2-ethylhexyl) phosphate obtained in the above (1) d), 25 g of dodecyldimethylamine, and 25 g of alkyldiphenylamine (alkyl group: butyl group and octyl group) The same operation as in the above N) was performed except for using, to obtain a transparent liquid additive T (phosphorus content: 4.4% by mass) at room temperature.

 U) The same operation as in the above N) was performed except that 50 g of di (2-ethylhexyl) magnesium phosphate shown in the above (1) n) was used to obtain a transparent liquid additive U at room temperature.

 In addition, a storage stability test was performed on the obtained lubricating oil additives A to U (Examples 1 to 21) of the present invention, but no precipitation or clouding was observed.

(Examples 22 to 57, and Comparative Examples 1 to 12)

 Using the lubricating oil additives A to M of the present invention obtained above (Examples 1 to 13), lubricating oil compositions of the present invention (Examples 22 to 57) were prepared according to the compositions shown in Tables 1 to 3. . At the time of preparation, solubility tests of additives were performed. In the solubility test, each component containing the additive was collected in a mixing container at room temperature, mixed with heating and stirring at 80 ° C, and the dissolution state of the additive (presence or absence of insoluble components) was checked visually at predetermined intervals. It was done by observation.

Further, for comparison, lubricating oil compositions (Comparative Examples 1 to 12) were prepared according to the compositions shown in Table 4 by a conventional method. Then, a solubility test was performed in the same manner as described above, and evaluation was performed in the same manner. Tables 1 to 4 show these evaluation results. ω

ο

2) Total aromatic content 1.2 mass ¹¹ , sulfur content 10 mass _PP m, kinematic viscosity at 100 ° C: 5.6 mm ² / s, viscosity index: 125

3) Triester of neopentyl glycol 100 ° C kinematic viscosity: 4.3mm ² / s Viscosity index: U3

 4) Additive A produced according to Production Example A) (phosphorus content: 6.6% by mass)

 5) Additive B produced according to Production Example B) (phosphorus content: 6.9% by mass)

 6) Additive C produced according to Production Example C) (phosphorus content: 4.55% by mass)

 7) Additive D produced according to Production Example D) (phosphorus content: 4.4% by mass)

 8) Polybutenyl succinimide, number average molecular weight of polybutenyl group: 1300 Nitrogen content: 1.6% by mass, boron content: 0% by mass

9) Ca content: 2.3 mass%, metal ratio: 1

 10) Ca content: 12% by mass, metal ratio: 10

 1D OCP average molecular weight: 150,000

12) Polyalkylene glycol

Table 2

C

1) Total aromatic content: 5.5 mass%, sulfur content: 1300 mass ppm 100 kinematic viscosity: 5.45 mm ² , viscosity index: 125

2) Total aromatic content: 1.2 mass%, sulfur content: 10 mass _PP m 100 ° C kinematic viscosity: 5.6 mm ² , viscosity index: 125

3) Triester of neopentyl glycol 100 ° C kinematic viscosity: 4.3 mm ² / s Viscosity index: 143

 4) Additive E produced according to Production Example E) (phosphorus content: 2.64% by mass)

 5) Additive F produced according to Production Example F) (phosphorus content: 2J6 mass <%)

 6) Additive G produced according to Production Example G) (phosphorus content: 1.82% by mass)

 7) Additive H produced according to Production Example H) (phosphorus content: 1 J6% by mass)

 8) Polyvinyl succinimide, number average molecular weight of polybutenyl group: 1300 Nitrogen content: 1.6 mass. Boron content: 0% by mass

 9) Ga content: 4.15 mass%, metal ratio: 1.8 10) Ga content: 4.8 mass%, metal ratio: 2.1 11 1) Ca content: 8.12 mass%, metal ratio: 4.3

1 2) Alkyl diph: L-nilamine (alkyl group: butyl group, octyl group) 13) OCP average molecular weight: 150,000 14) polyalkylene glycol

Table 3

CO

t

 1) Total aromatic content: 5.5 mass%, sulfur content: 1300 mass ppm 100 ° C kinematic viscosity: 5.45 mm2 / s, viscosity index: 125

 2) Total aromatic content: 1.2 mass "½, sulfur content: 10 mass ppm, kinematic viscosity at 100 ° C 5.6 mm2 / s, viscosity index: 125

 3) Triester of neopentyl glycol 100 ° C kinematic viscosity: 4.3mm2 / s Viscosity index: 143

 4) Additive I produced according to Production Example I) (phosphorus content: 2.64% by mass)

 5) Additive J produced according to Production Example J) (phosphorus content: 2.76% by mass)

 6) Additive K produced according to Production Example K) (phosphorus content: 1.82% by mass)

 7) Additive L produced according to Production Example L) (phosphorus content: 1.76% by mass)

 8) Production example Additive produced by Μ) リ ン (phosphorus content: 0.66% by mass, Ca content: 2.5% by mass)

9) Polyvinyl succinimide, number average molecular weight of polybutenyl group: 1300 Nitrogen content: 1.6% by mass, boron content: 0% by mass. / ₀

10) Ga content: 6.2% by mass, metal ratio: 2.7 1 1) octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate 12) OCP average molecular weight: 150,000 13) polyalkylene glycol system

Table 4

 1) Total aromatic content: 5.5 mass%, sulfur content: 1300 mass ppm 100 ° C kinematic viscosity: 5.45 mm2 / s, viscosity index: 125

2) total aromatic content: 1.2 mass%, sulfur content: 10 mass _P pm 100 ° C kinematic viscosity: 5.6mm2 / s, viscosity index: 125

 3) Triester of neopentyl glycol 100 ° C kinematic viscosity: 4.3mm2 / s Viscosity index: 143

 4) Alkyl group: butyl group, phosphorus content: 13.2 mass << ½, zinc content: 13 mass%, sulfur content: 0 mass%

 5) Alkyl group: 1,3 dimethylbutyl group, phosphorus content: 13.8 mass%, zinc content: 18.7 mass%

 6) Alkyl group: 2-ethylhexyl group, phosphorus content: 9.1% by mass, calcium content: 5.8% by mass

 7) Alkyl group: 2-ethylhexyl group, phosphorus content: 8.8% by mass, zinc content: 9.1% by mass

 8) Polybutenyl succinimide, number average molecular weight of polybutenyl group: 1300 Nitrogen content: 1.6% by mass, boron content: 0% by mass

9) Ga content: 6.2% by mass, metal ratio: 2.7

 10) Alkyl diphenylamine (alkyl group: butyl group and octyl group)

 1D OCP average molecular weight; 150,000

12) Polyalkylene glycol

As shown in Tables 1 to 3, it can be seen that the lubricating oil composition containing the lubricating oil additive of the present invention disappeared after 16 hours and completely dissolved. Further, as shown in Examples 34 to 57 of Tables 2 and 3, the lubricating oil composition containing the lubricating oil additive of the present invention obtained by using the ashless dispersant as the component (B) is: After 2 hours, the insoluble matter had disappeared, indicating that it was completely dissolved in a short time. It has been confirmed that the lubricating oil composition thus obtained has no problem in storage stability. It has been confirmed that zinc dialkyl monothiophosphate (Note 7 in Table 4) can be oil-solubilized by the same method, and that a lubricating oil composition can be manufactured in a short time.

Further, the additives e _SB to (! _SB obtained in the above (3) and the additives N to U obtained in the above (5) are used in the lubrication described in the notes 1) to 3) in Tables 1 to 4. As a result of dissolution in the oil base oil, the insoluble matter disappeared within 2 hours and completely dissolved.

 On the other hand, as shown in Table 4, when the metal salt of the phosphorus compound was heated and stirred at the same time as the lubricating base oil and other additives (Comparative Examples 1 to 12), insolubles were present even after 16 hours. However, it could not be completely dissolved. It takes more time for complete dissolution.

 In Examples 5 to 13 (additives E to M of the present invention), polybutenyl succinic acid unmodified boric acid was used instead of the commercially available polyptenyl succinic acid ashless dispersant SB. Ashless dispersant SA (molecular weight of polybutenyl group: 1300, nitrogen content: 1.6% by mass, boron content: 0% by mass, total base number (hydrochloric acid method): 24 mg KOH / g) Similar results were obtained with the lubricating oil composition in which the obtained lubricating oil additive of the present invention was similarly blended.

Further, the lubricating oil composition of the present invention has the same anti-wear properties as compared with the case where zinc dialkyldithiophosphate is used, and has a long drain property such as oxidation stability and base number maintenance property, and has a high temperature. Cleanliness, low friction, copper corrosion, etc. can be significantly improved, and the sulfur content is 0.3% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, particularly substantially A low-sulfur lubricating oil composition containing no sulfur can be obtained, and the above-described various characteristics can be obtained in an internal combustion engine using gasoline having a sulfur content of 10 mass ppm or less and natural gas having a sulfur content of 1 mass ppm or less. About performance Have also confirmed.

[Industrial applicability]

 The lubricating oil additive of the present invention makes it possible to completely dissolve a metal salt of a phosphorus compound that is insoluble or has low solubility in a lubricating oil in a short period of time in a lubricating oil. When a lubricating oil composition is prepared using an ashless dispersant or an additive obtained by pre-dissolving or reacting with a salt of an aliphatic amine as an amine compound, the lubricating oil composition can be manufactured in a time as short as a normal lubricating oil composition. It is possible to do. Therefore, the present invention can provide a lubricating oil additive which is extremely useful for industrially mass-producing a lubricating oil composition having the above-described excellent performance, and a method for producing the same.

Claims

The scope of the claims 1. (A) a metal salt of a phosphorus compound represented by the general formula (1), a metal salt of a phosphorus compound represented by the general formula (2), and a metal salt of a phosphorus compound represented by the general formula (3) A lubricating oil additive obtained by dissolving or reacting at least one compound selected from the group consisting of (B) an amine compound.  11 1 3 13  R-X-P-X-R ^ ⁽¹⁾ (In the general formula (1), X ¹ , ² and ³ each independently represent an oxygen atom or a sulfur atom, and at least one of them is an oxygen atom; R ¹¹ R ¹² and R ¹³ Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of these is a hydrogen atom.) X ⁷  14 4 II 6 16 RXPXR ( ² )  15  X-R (In the general formula ^{(2), X 4, X} 5, X 6 and X ⁷ are each independently an oxygen atom or a sulfur atom, and at least three of these is an oxygen atom, R ^14, R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of them is a hydrogen atom.)

(Formula (X ⁸ in 3), X ⁹及Pi X ^{1 C)} are each independently an oxygen atom or a sulfur atom, and at least two of these is an oxygen atom, R ^17, R ¹⁸ and R ¹⁹ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of them is a hydrogen atom, and a is 0 or 1. You. Further, the phosphorus compounds represented by the above general formulas (1) to (3) may have a-(OR ') n- group between the X-R bonds, and R, is an alkylene having 1 to 4 carbon atoms. A group, n represents an integer of 1 to 10; ) 2. X ¹ , X ² and X ^{3 in} the general formula (1), X ⁴ , X ⁵ , X ⁶ and X ^{7 in} the general formula (2) and X ⁸ , X ⁹ and X ^{7 in} the general formula (3) The lubricating oil additive according to claim ¹ , wherein all of X ^{1 G} are oxygen atoms. 3. The lubricating oil additive according to claim 1, wherein the metal in component (A) is at least one metal selected from lithium, magnesium, calcium, and zinc. 4. The lubricating oil according to claim 1, wherein the component (B) is at least one amine compound selected from an amine antioxidant, an aliphatic amine, an ashless dispersant, and a derivative thereof. Additive. 5. A lubricating oil additive obtained by dissolving the component (A) in an amine antioxidant. 6. A lubricating oil additive obtained by reacting the component (A) or the lubricating oil additive according to claim 5 with an aliphatic amine. 7. The component (A), characterized in that the lubricating oil additive according to claim 5 or the lubricating oil additive according to claim 6 is reacted with an ashless dispersant and / or a derivative thereof. And lubricating oil additives. 8. The claim 6 or 7, wherein the reaction ratio of the aliphatic amine, the ashless dispersant and / or the derivative thereof to the component (A) is 0.15 or more by mass ratio. Lubricating oil additives. 9. Claims 4, 7, or 8 wherein the ashless dispersant and / or a derivative thereof has a total base number by a hydrochloric acid method of 5 mg KOH / g or more. A lubricating oil additive as described. 10. The ashless dispersant and Z or a derivative thereof are boron compound derivatives of the ashless dispersant, wherein the ashless dispersant and Z or a derivative thereof are boron compound derivatives of the ashless dispersant. Lubricating oil additives. 11. The lubricating oil additive according to claim 4, 6, or 8, wherein the aliphatic amine is a tertiary amine. 12. The lubricant additive according to any one of claims 1 to 11, further comprising a lubricant base oil, an antioxidant, an ashless dispersant, a metal-based detergent, and a friction modifier. , Abrasion inhibitor, corrosion inhibitor, antioxidant, demulsifier, metal deactivator, defoamer, coloring agent, and viscosity index improver. Lubricating oil additives. 13. A lubricating oil composition comprising the lubricating oil additive according to any one of claims 1 to 12 in a lubricating base oil. 14. (A) Metal salt of phosphorus compound represented by general formula (1), metal salt of phosphorus compound represented by general formula (2), and metal of phosphorus compound represented by general formula (3) A method for producing a lubricating oil additive, comprising dissolving or reacting at least one compound selected from the group consisting of salts with an amine compound (B). 15. A method for producing a lubricating oil composition, comprising adding the lubricating oil additive according to any one of claims 1 to 12 to a lubricating oil.