WO2004009746A1 - Grease composition - Google Patents

Abstract

A grease composition which comprises a lube base oil and incorporated therein (A) 2 to 30 wt.% thickener and (B) 0.1 to 10 wt.% at least one compound selected from the group consisting of phosphorus compounds represented by the following general formulae (1) and (2) and metal salts or amine salts of the compounds, the amounts being based on the whole composition. (1) [In the formula (1), X1, X2, and X3 each represents oxygen or sulfur, provided that at least two of X1, X2, and X3 are oxygen; and R1, R2, and R3 each represents hydrogen or a C1-30 hydrocarbon group.] (2) [In the formula (2), X4, X5, X6 and X7 each represents oxygen or sulfur, provided that at least three of X4, X5, X6 and X7 are oxygen; and R4, R5, and R6 each represents hydrogen or a C1-30 hydrocarbon group.]

Description

 Itoda »

Grease composition

Technical field

 [0101] The present invention relates to a grease composition.

Background art

 [0200] Grease is usually used as a lubricant for mechanical parts such as constant velocity gears, transmission gears, ball bearings, and roller bearings.

 [0093] Many of the members that make up these mechanical parts are made of metal. However, if the metal members come into contact with each other and generate friction, heat and abrasion occur in the contact portions, and as a result, grease is applied. Alternatively, the life of the mechanical component itself is shortened. Therefore, in order to reduce friction between metals, various additives such as a friction reducing agent are blended with the lubricant.

Disclosure of the invention

 However, in recent years, as the above-mentioned mechanical parts have been improved in performance and reduced in size and weight, their use conditions have become strict, and friction due to contact between metals has become more likely to occur. In such mechanical parts, a sufficient friction reducing effect may not be obtained even with the use of conventional grease to which a friction reducing agent is added.

 [0105] Also, mechanical parts filled with grease are often used at higher temperatures. Therefore, there is a strong demand for dollies that provide a high friction reducing effect even at high temperatures.

 [0106] The present invention has been made in view of the above-mentioned problems of the related art, and provides a grease composition capable of obtaining a sufficiently high friction reduction effect even at a high temperature. The purpose is to:

[0107] In order to solve the above problems, the grease composition of the present invention comprises: (A) 2 to 30% by mass of a thickening agent, based on the total amount of the composition, in a lubricating base oil; B) At least one compound selected from the group consisting of a phosphorus compound represented by the following general formula (1) or (2) and a metal salt or an amine salt thereof is compounded with 0.1 to 10% by mass. It is characterized by becoming. RXPXR

( ¹⁾

[In the formula (1), X ¹ , X ² and X ³ may be the same or different and each represent an oxygen atom or a sulfur atom, and at least two of X ¹ , X ² or X ³ are oxygen atoms. And RR ² , and R ³ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.]

X

 4 4 II 6 6

 R-X-P-X-R (2)

XR ⁵

[In the formula (2), X ⁴ , X ⁵ , X ⁶ and X ⁷ may be the same or different and each represent an oxygen atom or a sulfur atom, and at least 3 of X ⁴ , X ⁵ , X ⁶ or X ⁷ One is an oxygen atom, and R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ]

 [0008] According to the present invention, a lubricating base oil comprises (A) a thickener, (B) a phosphorus compound represented by the above general formula (1) or (2), and a metal salt or an amine salt thereof. By blending at least one compound selected from the group consisting of a predetermined amount, the friction reducing effect is sufficiently high, and the friction reducing effect is maintained at a high level even at a high temperature. Grease composition is realized. Therefore, even when mechanical parts such as constant-speed gears are made faster, smaller and lighter, or when these mechanical parts are used at high temperatures, grease is prevented by preventing heat and wear caused by friction between metals. And the life of mechanical parts can be extended sufficiently.

 [0009] The grease composition of the present invention preferably further contains an organic molybdenum compound.

 [0010] Further, in the grease composition of the present invention, it is preferable that (A) the thickening agent is lithium soap.

[001 1] In the grease composition of the present invention, (A) the thickening agent is preferably a urea thickening agent, and a urea thickening agent represented by the following general formula (3). More preferably, it is a thickener.

A-CONH-R ⁷ -NHCO-B (3)

[In the formula (3), A and B may be the same or different and each represents a group represented by one NHR ⁸ , one NR ⁹ R ^1Q or one OR ¹¹ (R ⁸ , R ⁹ , R ^1Q and R ¹¹ May be the same or different and each represents a hydrocarbon group having 6 to 20 carbon atoms), and R ⁷ represents a divalent hydrocarbon group. ]

Further, in the grease composition of the present invention, a compound represented by the general formula (1) and wherein X ¹ , X ² and X ³ are all oxygen atoms, and a compound represented by the general formula (2) Further, it is preferable that at least one of X ⁴ , X ⁵ , X ^6, and X ⁷ is selected from compounds having an oxygen atom. In this case, the component (B), Xi～X ⁷ Galle, in addition to the compounds deviation also an oxygen atom, and one X ¹ ~ X ⁷ and the remaining is a sulfur atom is an oxygen atom may include but, (B) component is preferably Xi～X ⁷ is composed of only the compound both are oxygen atoms.

BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1A and FIG. 1B are a perspective view and a top view showing a test piece used for a friction test, respectively.

BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, a preferred embodiment of the present invention will be described in detail.

 [00115] Lubricating base oils used in the grease compositions of the present invention include mineral oils and natural or synthetic oils.

 [0016] Such a mineral oil is, for example, one obtained by a method usually used in a lubricating oil production process in the petroleum refining industry, and more specifically, a lubricating oil obtained by atmospheric distillation and reduced pressure distillation of crude oil. The oil fraction may be refined by solvent removal, solvent extraction, hydrocracking, solvent dewaxing, contact dewaxing, hydrorefining, sulfuric acid washing, clay treatment, etc.

[0017] Specific examples of the synthetic oil include poly-α-olefins such as polybutene, 11-otaten oligomer, and 1-decene oligomer, and hydrides thereof. Diestenoles, such as ridecyl glutarate, di-2-ethylhexyl adipate, disodecyl adipate, ditridecyl adipate, and di-3-ethynolehexinoresevacate; trimethylolpropane caprylate, trimethylolpropaneperargonate, pentaerythritol tonole 2 Polyol esters such as ethynolehexanoate and pentaerythritol tonoleperanolegonate; alkyl naphthalenes; alkyl benzenes, polyoxyalkylene glycols; polyphenyl ether ethers; dialkyl diphenyl ethers; silicone oils; and mixtures thereof.

 The kinematic viscosity of these lubricating base oils at 100 ° C. is preferably from 2 to 40 mm, more preferably from 3 to 2 O mm ^ Zs. In addition, the viscosity index of the base oil is preferably 90 or more, more preferably 100 or more.

 In the present invention, (A) a thickening agent, (B) a phosphorus compound represented by the general formula (1) or (2) and a metal thereof At least one compound selected from the group consisting of salts or amine salts is blended in a predetermined amount. Hereinafter, these components are sometimes referred to as component (A) and component (B).

 (A) The thickening agent is not particularly limited, but for example, a soap-based thickening agent is preferably used. By using a soap-based thickener, the effect of preventing damage to machine parts can be enhanced.

 [0211] Specific examples of the soap-based thickening agent include sodium soap, potassium soap, aluminum soap, lithium soap, and the like. Among these, water resistance and heat stability are preferred. From lithium soap is preferred. Examples of the lithium soap include lithium stearate, lithium-12-hydroxystearate, and the like.

 Preferred examples of (A) the thickener include urea-based thickeners. By using the urea-based binder, the effect of preventing mechanical parts from being damaged can be enhanced.

[0203] Examples of the urea-based penetrating agent include diurea compounds, triurea compounds, tetraurea compounds, and polyurea compounds (diurea compounds, triurea compounds). Compounds, excluding tetraurea compounds), urethane compounds such as urea 'urethane compounds and diurethane compounds, and mixtures thereof. Among these, a diurea compound, a diurea / urethane compound, a diurethane compound or a mixture thereof is preferable.

 A preferred example of the urea thickening agent is represented by the following formula (3):

A—CONH— R ⁷ — NHCO— B (3)

Can be represented by The compound represented by the general formula (3) includes a diurea compound, a diurea / urethane compound, and a diurethane compound.

In the formula (3), A and B may be the same or different and each represents a group represented by one NHR ⁸ , one NR ⁹ R ¹⁰ or one OR ¹¹ . Where R ⁸ , R ⁹ , R

^1Q and R ¹¹ may be the same or different, each represents a hydrocarbon group having 6-20 carbon atoms.

Examples of the hydrocarbon group represented by R ⁸ , R ⁹ , R ^1Q , and R ¹¹ include a linear or branched alkyl group, a linear or branched alkyl group, and cycloalkyl Groups, alkylcycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups and the like. More specifically, hexyl, heptyl, octyl, nonyl, decyl, pendecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl Hexenyl, heptenyl, octenyl, nonenyl, decenyl, pentadecenyl, dodecenyl, tetradecenyl, pentadecenyl, hexadecenyl, eicosyl or other straight-chain or branched alkyl groups; Linear or branched alkenyl group such as heptadecenyl group, octadecenyl group, nonadecenyl group, eicosenyl group; cyclohexyl group; methylcyclohexyl group; dimethylcyclohexyl group; ethylcyclohexyl group; Hexyl group, Provircyclohexyl Hexinole group, 1-methynole-1-hexinole group, butylcyclohexyl group, amylcyclohexyl group, amylmethylcyclohexyl group, hexylcyclohexinole group, heptylcyclohexinole group, Oktylsik mouth hex Alkyl, hexyl, nonylcyclohexyl, decylcyclohexyl, pendecylcyclohexyl, dodecylcyclohexyl, tridecylcyclohexyl, tetradecinolecyclohexyl, etc .; phenyl, naphthyl Alkylaryl groups such as tonoleinole, ethylphenyl, xylyl, propylphenyl, cumenyl, methylnaphthyl, ethylnaphthyl, dimethylnaphthyl, propylnaphthyl; benzyl, methylbenzyl And arylalkyl groups such as ethylbenzyl group. Of these, particularly preferred are a hexinole group, an octadecyl group and a toluyl group.

[0 0 2 7] R ⁷ in formula (3) represents a divalent hydrocarbon group. Specific examples of such a divalent hydrocarbon group include a linear or branched alkylene group, a linear or branched alkylene group, a cycloalkylene group, an arylene group, and an alkylarylene group. And arylalkylene groups. The divalent hydrocarbon group represented by R ⁷ preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms.

Preferred examples of the divalent hydrocarbon group represented by R ⁷ include an ethylene group, a 2,2-dimethyl-4-methylhexylene group, and the following formulas (4) to (13) And a group represented by the formula (5) or (7) is preferable.

¾C, H ₃

又は R 〇Hで表される化合 物もしくはこれらの混合物とを、基油中、 10〜200°Cで反応させることにより 得られる。 なお、 原料化合物を表す式中の R⁷、 R⁸、 R⁹、 R¹⁰, R¹¹は、 それぞ れ式 （3) 中の R⁷、 R⁸、 R⁹、 R¹⁰、 R¹¹と同義である。 The compound represented by the formula (3) is, for example, a diisocyanate represented by OCN—R ⁷ —NCO, R ⁸ NH ₂ ,

Or by reacting a compound represented by R も し く は H or a mixture thereof in a base oil at 10 to 200 ° C. can get. Note that R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ in the formula representing the starting compound are respectively synonymous with R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ in the formula (3). It is.

 [0030] Further, (A) Benton, silica gel or the like may be used as a thickening agent.

 [0031] In the grease composition of the present invention, the mixing ratio of the component (A) is 2 to 30% by mass based on the total amount of the composition. If the compounding ratio of the thickening agent is less than 2% by mass, the effect of adding the thickening agent becomes insufficient and the grease composition cannot be sufficiently greased. For the same reason, the mixing ratio of the component (A) is preferably 5% by mass or more, more preferably 10% by mass or more based on the total amount of the composition. On the other hand, when the mixing ratio of the component (A) exceeds 30% by mass, the grease composition becomes excessively hard, so that sufficient lubrication performance cannot be obtained. For the same reason, the compounding ratio of the thickening agent is preferably 25% by mass or less, more preferably 20% by mass or less, based on the total amount of the composition.

(り [0032] The component (B) in the grease composition of the present invention is at least one kind selected from the group consisting of a phosphorus compound represented by the following general formula (1) or (2) and a metal salt or an amine salt thereof. Compound.

(R

[In the formula (1), X ¹ , X ² and X ³ may be the same or different and each represent an oxygen atom or a sulfur atom, and at least two of X ¹ , X ² or X ³ are oxygen atoms. And RR ² , and R ³ may be the same or different and each has a hydrogen atom or a carbon number of 1

Represents up to 30 hydrocarbon groups]

X

 4 4 II 6 6

 R-X-P-X-R (2)

XR ⁵

[In the formula (2), X ⁴ , X ⁵ , X ⁶ and X ⁷ may be the same or different and each represent an oxygen atom or a sulfur atom, and at least 3 of X ⁴ , X ⁵ , X ⁶ or X ⁷ One is an oxygen source And R ⁴ , R ⁵ and R ⁶ may be the same or different and each represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ]

[0303] Specific examples of the hydrocarbon group having 1 to 30 carbon atoms represented by ¹¹ to 1 ^ ⁶ include an alkyl group, a cycloalkyl group, an alkyl group, and an alkylcycloalkyl group. And aryl groups, alkylaryl groups, arylalkyl groups and the like.

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, And alkyl groups such as tridecyl group, tetradecyl group, pentadecinole group, hexadecyl group, heptadecyl group and octadecyl group (these alkyl groups may be linear or branched).

 As the cycloalkyl group, for example, a cycloalkyl group having 5 to 7 carbon atoms such as a pen mouth group, a hexyl group and a heptyl group can be exemplified. Examples of the above alkylcycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a methylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a methyloxyhexyl group, a hexyl group, and a methylsilyl group. Hexyl group, methylcycl heptyl group, dimethylcycloheptyl group, methylethylcycloheptyl group, getylcycloheptyl group, etc. The position of substitution on the kill group is also arbitrary.).

 As the alkenyl group, for example, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an otathenyl group, a nonenyl group, a decenyl group, a pentadecyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group And alkenyl groups such as pentadecenyl, hexadecenyl, heptadecenyl and octadecenyl (the alkenyl groups may be linear or branched, and the position of the double bond is arbitrary). No.

[0370] 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, Trinole, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenylenol, noninolephenyl, decylphenyl, pendecinolephenyl And an alkylaryl group having 7 to 18 carbon atoms such as a dodecylphenyl group (the alkyl group may be linear or branched, and the substitution position of the aryl group is arbitrary).

 The arylalkyl group includes, for example, a benzyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group and the like. Aryl groups (these alkyl groups may be linear or branched).

The hydrocarbon group having 1 to 30 carbon atoms represented by the above ¹ to! ^ ⁶ is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 24 carbon atoms. And more preferably an alkyl group having 3 to 18 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms.

[0400] RR ² and R ³ may be the same or different and each represent a hydrogen atom or the above-mentioned hydrocarbon group, and one to three of RR ² and R ³ are the above-mentioned hydrocarbons. Preferably, one or two are the above-mentioned hydrocarbon groups, and more preferably two are the above-mentioned hydrocarbon groups.

Further, R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom or the above-mentioned hydrocarbon group, and among R ⁴ , R ⁵ and R ⁶ , 1 to Three are preferably the above-mentioned hydrocarbon groups, more preferably one or two are the above-mentioned hydrocarbon groups, and even more preferably two are the above-mentioned hydrocarbon groups.

In the phosphorus compound represented by the general formula (1), at least two of XX ³ need to be oxygen atoms, but all of X i X ³ are oxygen atoms. Preferably, there is.

[0 0 4 3] Also, in the phosphorus compound represented by the general formula (2), but at least three of X ⁴ to X ⁷ is required to be an oxygen atom, the X ⁴ to X ⁷ All are preferably oxygen atoms. The phosphorus compound represented by the general formula (1) includes, for example, phosphorous acid and monothiophosphorous acid; the above phosphorous acid monoester having one hydrocarbon group having 1 to 30 carbon atoms. Stell, monothiophosphorous acid monoester; phosphite diester having two hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphoric acid diester; having three hydrocarbon groups having 1 to 30 carbon atoms Phosphite triesters, monothiophosphite triesters; and mixtures thereof. Of these, phosphite monoester and phosphite diester are preferred, and phosphite diester is more preferred.

 Further, as the phosphorus compound represented by the general formula (2), for example, phosphoric acid, monothiophosphoric acid; the above-mentioned phosphoric acid monoester having one hydrocarbon group having 1 to 30 carbon atoms, Monothiophosphoric acid monoester; phosphoric acid diester having two hydrocarbon groups having 1 to 30 carbon atoms, monothiophosphoric acid diester; phosphoric acid triester having three hydrocarbon groups having 1 to 30 carbon atoms, Monothiophosphoric acid triesters; and mixtures thereof. Of these, phosphoric acid monoesters and phosphoric acid diesters are preferred, and phosphoric acid diesters are more preferred.

 As the salt of the phosphorus compound represented by the general formula (1) or (2), a salt obtained by neutralizing a part or all of acidic hydrogen of the phosphorus compound is exemplified. Such phosphorus compound salts include only metal bases such as metal oxides, metal hydroxides, metal carbonates and metal chlorides, ammonia, hydrocarbon groups having 1 to 30 carbon atoms or hydrocarbon groups containing hydroxyl groups. Can be obtained by reacting a nitrogen compound such as an amine compound having in a molecule with a phosphorus compound.

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

The metal salt of the phosphorus compound has a different structure depending on the valency of the metal and the number of OH groups or SH groups of the phosphorus compound. Therefore, the structure is not limited at all. For example, when 1 mo 1 of zinc oxide is reacted with 2 mo 1 of phosphoric diester (having one OH group), a compound having a structure represented by the following formula (14) is obtained as a main component. It is thought that there are also polymerized molecules.

【0 0 5 0】 上記窒素化合物としては、 例えば、 アンモニア、 モノアミン、 ジァ ミン、 ポリアミンが挙げられる。 より具体的には、 メチルァミン、 ェチルァミン、 プロピルァミン、 ブチルァミン、 ペンチルァミン、 へキシルァミン、 ヘプチルァミ ン、 オタチルァミン、 ノ -ルァミン、 デシルァミン、 ゥンデシルァミン、 ドデシル ァミン、 トリデシルァミン、 テトラデシルァミン、 ペンタデシルァミン、 へキサデ シルァミン、 ヘプタデシルァミン、 ォクタデシルァミン、 ジメチルァミン、 ジェチ ルァミン、 ジプロピルァミン、 ジブチルァミン、 ジペンチルァミン、 ジへキシルァ ミン、 ジヘプチルァミン、 ジォクチルァミン、 ジノニルァミン、 ジデシルァミン、 ジゥンデシルァミン、 ジドデシルァミン、 ジトリデシルァミン、 ジテトラデシルァ ミン、 ジペンタデシルァミン、 ジへキサデシルァミン、 ジヘプタデシルァミン、 ジ ォクタデシルァミン、 メチルェチルァミン、 メチルプロピノレアミン、 メチルブチル ァミン、 ェチルプロピルァミン、 ェチルブチルァミン、 及びプロピルブチルァミン 等の炭素数 1〜 3 0のアルキル基（これらのアルキル基は直鎖状でも分枝状でもよ レ、） を有するアルキルァミン； 【0 0 5 1】 エテュルァミン、 プロぺニルァミン、 ブテニルァミン、 ォクテ二ノレ ァミン、及びォレイルァミン等の炭素数 2〜 3 0のァルケ-ル基（これらのァルケ -ル基は直鎖状でも分枝状でもよレ、） を有するアルケニルァミン；メタノールアミ ン、 エタノールァミン、 プロパノールァミン、 ブタノーノレアミン、 ペンタノールァ ミン、 へキサノールァミン、 ヘプタノールアミン、 ォクタノールァミン、 ノナノー ノレアミン、 メタノールエタノールァミン、 メタノールプロパノールァミン、 メタノ 一ルブタノールァミン、エタノールプロパノールァミン、エタノールブタノールァ ミン、 及びプロパノールブタノールアミン等の炭素数 1〜3 0のアル力ノール基For example, when 1 mo 1 of zinc oxide is reacted with a phosphoric acid monoester (two OH groups) lmo 1, a compound having a structure represented by the following formula (15) is obtained. Forces considered to be obtained as main components It is considered that there are also polymerized molecules.

[0500] Examples of the nitrogen compound include ammonia, monoamine, diamine, and polyamine. More specifically, methylamine, ethylamine, propylamine, butyramine, pentylamine, hexylamine, heptylamine, otatylamine, no-lamine, decylamine, pendecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, pentadecylamine , Heptadecylamine, octadecylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didindecylamine, dididylamine, ditricylamine , Ditetradecylamine, dipentadecylamine, dihexadecylamine, diheptadecylamine, zio C1-C30 alkyl groups such as tadecylamine, methylethylamine, methylpropynoleamine, methylbutylamine, ethylpropylamine, ethylbutylamine, and propylbutylamine (these alkyl groups are Alkylamine which may be linear or branched; [0551] Alkyl groups having 2 to 30 carbon atoms, such as etyramine, propenylamine, butenylamine, octenolamine, and oleylamine (these are not limited to linear or branched alkyl groups). Alkenylamines having the following formulas: methanolamine, ethanolamine, propanolamine, butanolanolamine, pentanolamine, hexanolamine, heptanolamine, octanolamine, nonananolamine, methanolethanolamine. Alkanol groups having 1 to 30 carbon atoms, such as methanolpropanolamine, methanolbutanolamine, ethanolpropanolamine, ethanolbutanolamine, and propanolbutanolamine.

(These alkanol groups may be straight-chain or branched.)

 Alkylene diamines 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, etc. Polyamines: monoamines, diamines, polyamines such as decyl ethylamine, pentadecyljetanolamine, dodecyldipropanolamine, oleyljetanolamine, oleylpropylenediamine, stearyltetraethylenepentamine, etc. A compound having an alkyl or alkenyl group having 8 to 20 carbon atoms, or a heterocyclic compound such as N-hydroxylethylolimidazoline; an alkylene oxide adduct of these compounds;

And mixtures thereof.

 Among these nitrogen compounds, an alkyl group or alkenyl having 10 to 20 carbon atoms such as decylamine, dodecylamine, tridecylamine, heptadecylamine, octadecylamine, oleylamine and stearylamine. Aliphatic amines having a group (these may be linear or branched) are preferred.

In the present invention, the component (B) is preferably a metal salt or an amine salt of the phosphorus compound represented by the above general formula (1) or (2), and more preferably a metal salt of the phosphorus compound. preferable. By using these compounds as component (B), higher friction A reduction effect tends to be obtained.

 [0555] From the viewpoint of thermal stability, a phosphorus compound represented by the general formula (2) and a salt thereof are preferable.

 [0556] As the component (B), one type may be used alone, or two or more types may be used in combination.

The mixing ratio of the component (B) is 0.1 to 10% by mass based on the total amount of the composition. / ₀ . When the blending ratio of the component (B) is less than 0.1% by mass, a sufficient friction-reducing effect cannot be obtained, and it is possible to reduce friction between metal members constituting a machine part, especially at a high temperature. Gone. For the same reason, the mixing ratio of the component (B) is preferably at least 0.3% by mass, more preferably at least 0.5% by mass, based on the total amount of the composition. Further, even if the blending ratio of the component (B) exceeds 10% by mass, no further friction reduction effect commensurate with the blending ratio is obtained. For the same reason, the blending ratio of the component (B) is preferably 7% by mass or less, more preferably 5% by mass or less, based on the total amount of the composition.

The grease composition of the present invention is obtained by blending the above components (A) and (B) with a lubricating base oil, and further comprises an organic molybdenum compound in addition to these components. You may mix.

 The organic molybdenum compound used in the present invention is, for example, a phosphoric acid or thiophosphate derivative represented by the following general formula (16), or a derivative represented by the following general formula (17) Derivatives of dithiol rubamic acid esters may be mentioned.

 X

R ~ X ~ P ~ X- Mo _b X _c (16)

 R ~~ X

Mo _b X _c (17)

In the general formulas (16) and (17), R is the same or different. Each represents a hydrocarbon group having 1 or more carbon atoms, c Xs may be the same or different, each represents an oxygen atom or a sulfur atom, and a, b, and c each represent an integer of 1 to 6. Represent.

 In the above formulas (16) and (17), examples of the hydrocarbon group represented by R include an alkyl group having 1 to 24 carbon atoms and a cycloalkyl having 5 to 7 carbon atoms. Groups, alkyl groups having 6 to 11 carbon atoms, alkyl groups having 6 to 18 carbon atoms, alkyl aryl groups having 7 to 24 carbon atoms, and aryl alkyl groups having 7 to 12 carbon atoms. 'Yes.

 As the alkyl group, specifically, a methyl group, an ethyl group, a propyl group (including all branched isomers), a butyl group (including all branched isomers),ぺ methyl group (including all branched isomers), hexyl group (including all branched isomers), heptyl group (including all branched isomers), octyl group (including all branched isomers) ), A nor group (including all branched isomers), a decyl group (including all branched isomers), a pendecyl group (including all branched isomers), a dodecyl group (including all branched isomers) To tridecyl group (including all branched isomers), tetradecyl group (including all branched isomers), pentadecyl group (including all branched isomers), Xadecyl group (including all branched isomers), heptadecyl (Including all branched isomers), octadecyl group (including all branched isomers), nonadecyl group (including all branched isomers), icosyl group (including all branched isomers) ), Henicosyl group (including all branched isomers), docosyl group (including all branched isomers), tricosyl group (including all branched isomers), tetracosyl group (including all branched isomers) Including isomers).

 [0653] Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

As the above alkylcycloalkyl group, specifically, methylcyclopentyl group (including all substituted isomers), ethylcyclopentyl group (including all substituted isomers), dimethylcyclopentyl group (Including all substituted isomers), Oral vircyclopentyl group (including all branched and substituted isomers), methylethylcyclopentyl group (including all substituted isomers), trimethylcyclopentyl group

(Including all substituted isomers), butylcyclopentyl group (including all branched and substituted isomers), methylpropylcyclopentyl group (including all branched and substituted isomers), Tylcyclopentyl group (including all substituted isomers), dimethylethylcyclopentyl group (including all substituted isomers), methylcyclohexyl group (including all substituted isomers), ethylcyclohexyl group (all Dimethylcyclohexyl group (including all substituted isomers), propylcyclohexyl group (including all branched and substituted isomers), methylethylcyclohexyl group (Including all substituted isomers), trimethylcyclohexyl group (including all substituted isomers), butylcyclohexyl group (including all (Including branched isomers and substituted isomers), methylpropyl cyclohexyl group (including all branched and substituted isomers), getylcyclohexyl group (including all substituted isomers), dimethylethyl Lecyclohexyl group (including all substituted isomers), methylcycloheptyl group (including all substituted isomers), ethyl-heptyl group (including all substituted isomers), dimethyl-cycloheptyl group (Including all substituted isomers), propylcyclyl heptyl group (including all branched and substituted isomers), methylethylcycloheptyl group (including all substituted isomers), trimethylcyclo Heptyl group (including all substituted isomers), butylcycloheptyl group (including all branched and substituted isomers), methylpropylcycloheptyl Group (including all branched isomers and substituted isomers), dimethylcycloheptyl group (including all substituted isomers), dimethylethylcycloheptyl group (including all substituted isomers), etc. No.

 [0665] Specific examples of the aryl group include a phenyl group and a naphthyl group.

As the alkylaryl group, specifically, a tolyl group (including all substituted isomers), a xylyl group (including all substituted isomers), an ethylphenyl group (including all substituted isomers) Propylphenyl group (all branched isomers, A) methylethylphenyl group (including all substituted isomers), a trimethylphenyl group (including all substituted isomers), a butylphenyl group (including all branched isomers, and substituted isomers). ), Methylpropylphenyl group (including all branched isomers and substituted isomers), getylphenol group (including all substituted isomers), dimethylinoethyleninophene group (including all substituted isomers) Pentyl phenyl group (including all branched and substituted isomers), hexylfunyl group (including all branched and substituted isomers), heptylphenyl group (including all branched isomers) Octylfuunyl group (including all branched and substituted isomers), nonylphenyl group (including all branched and substituted isomers) , Decyl-furyl (including all branched isomers and substituted isomers), pendecylphenyl (including all branched and substituted isomers), dodecylfunyl (including all branched isomers) , Including substituted isomers), tridecylphenyl group (including all branched isomers and substituted isomers), tetradecinolephenyl group (including all branched isomers and substituted isomers), pentadecylphenyl group (Including all branched and substituted isomers), hexadecylphenyl group (including all branched and substituted isomers), heptadecylphenyl group (including all branched and substituted isomers) Octadecylfuunyl group (including all branched isomers and substituted isomers).

 [0607] Examples of the arylalkyl group include a benzyl group, a phenyl group, a phenolic pill group (including all branched isomers), and a fuunylbutyl group (all branched isomers). And the like).

 As the compounds represented by the general formulas (16) and (17), specifically, molybdenum phosphate, molybdenum thiophosphate, molybdenum dithiophosphate, molybdenum dithiocarbamate and the like Is mentioned.

The derivative of the phosphoric acid or thiophosphate represented by the following general formula (16) and the derivative of the dithiol carbamic acid ester represented by the following general formula (17) are usually phosphoric acid. Acid esters, thiophosphoric acid esters, dithiolrubamic acid esters and inorganic molybdenum compounds (such as molybdenum trioxide, molybdic acid or its salts) as necessary It is a compound obtained by reacting with the same sulfur source.

 [0710] Since molybdenum can have various valences, the compound obtained by the above reaction is usually a mixture. Among them, the most typical compounds include compounds represented by the following formulas (18) and (19).

 In the present invention, as the organic molybdenum compound, either one of the compounds represented by the above general formulas (16) and (17) may be used alone, or both may be mixed. The compound represented by the general formula (16) is preferable from the viewpoint of thermal stability. By blending the compound represented by the general formula (16), excellent thermal stability can be obtained, particularly when the grease composition of the present invention is used as a bearing grease.

 [0722] The compounding ratio of the organic molybdenum compound is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, based on the total amount of the composition. If the blending ratio is less than 0.1% by mass, the effect of further reducing friction by the blending of the organic molybdenum compound tends not to be obtained. The mixing ratio of the organic molybdenum compound is preferably 20% by mass or less, more preferably 10% by mass or less, based on the total amount of the composition. If the compounding ratio exceeds 20% by mass, there is a tendency that no improvement in the friction reducing effect commensurate with the compounding ratio is recognized.

[073] Furthermore, in the grease composition of the present invention, a solid lubricant, an extreme pressure agent, An antioxidant, an oil agent, a rust inhibitor, a viscosity index improver, and the like can be added.

[0714] Specific examples of the solid lubricant include black), graphite fluoride, polytetrafluoroethylene, molybdenum disulfide, antimony sulfide, and alkali (earth) metal borate.

 [0757] Specific examples of the extreme pressure agent include organic compounds such as zinc dialkyldithiophosphate, zinc diaryldithiophosphate, zinc dialkyldithicarbamate, and zinc diaryldithiocarbamate. Examples thereof include sulfur compounds such as zinc compounds, dihydrocarbyl polysulfides, sulfide esters, thiazonole compounds, and thiadiazole compounds.

 As the antioxidant, specifically, phenolic compounds such as 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-p-talesol; dialle; Examples include amine compounds such as quinoresin phenylenoamine, pheninole α-naphthinoleamine, and ρ-anolequilpheninole α-naphthylamine; sulfur compounds; phenothiazine compounds.

 [077] Specific examples of the oily agent include laurylamine, myristylamine, and nodule. Amines such as lumitylamine, stearylamine, and oleylamine; lauryl alcohole, myristyl alcohol, no. Higher alcohols such as noremicinoolenorecole, stearylanorecole, and oleyl alcohol; higher fatty acids such as lauric acid, myristic acid, nonoremitic acid, stearic acid, and oleic acid; methyl laurate, myristine Fatty acid esters such as methyl oxalate, methyl palmitate, methyl stearate, and methyl oleate; amides such as laurylamide, myristylamide, palmitylamide, stearylamide, and oleylamide; oils and fats.

 [0778] Specific examples of the rust inhibitor include metal soaps; polyhydric alcohol partial esters such as sorbitan fatty acid esters; amines; phosphoric acid; phosphates and the like.

[0790] Specific examples of the viscosity index improver include polymethacrylate and polystyrene. The grease composition of the present invention is obtained, for example, by adding (A) component, (B) component, or further an organic molybdenum compound or other additives to a lubricating base oil, stirring and mixing, It can be obtained by passing through a roll mill or the like. In addition, the raw material of the component (A) is added to the lubricating base oil in advance, melted, and stirred and mixed to prepare the component (A) in the lubricating base oil. Then, the component (B) or The grease composition of the present invention can also be obtained by adding an organic molybdenum compound or other additives, stirring and mixing, and passing through a roll mill or the like.

 [0881] The grease composition of the present invention having the above-mentioned structure has a sufficiently high friction reducing effect, and the friction reducing effect is maintained at a high level at high temperatures. Therefore, it is very useful as grease for gears such as constant velocity gears and transmission gears, grease for bearings such as ball bearings and roller bearings, grease for steelmaking equipment, etc. It is particularly preferably used as grease for bearings for automobiles and railway vehicles.

 [Example]

 Hereinafter, the present invention will be described more specifically based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

 [Examples 1 to; I 2, Comparative Examples 1 to 24]

As the lubricating base oil, Examples 1 to 3, Comparative Examples 1 to 3, and Comparative Examples 13 to 15 use poly-α-olefin (kinematic viscosity at 40 ° C .: 48 mm). ² / s), Examples 4 to 12, Comparative Examples 4 to 12 and Comparative Examples 16 to 24 use mineral oil (kinematic viscosity at 40 ° C .: 100 mm s), respectively. A grease composition was prepared according to the procedure described above.

In Examples 1 to 9, Comparative Examples 1 to 9 and Comparative Examples 13 to 21, diphenylmethane 4,4′-diisocyanate (MDI) was added to a lubricating base oil and dissolved by heating. And a mixture prepared by adding heat-sensitive hexylamine or stearyl alcohol to a lubricating base oil and heating and dissolving them.MDI, heavy-mouth hexylamine and stearyl alcohol are shown in Tables 1-4. Both were mixed so as to obtain a ratio. Next, the following additives were added to the resulting gel-like substance at the mixing ratios shown in Tables 1 to 4, and the mixture was stirred and passed through a mouth mill to obtain a target grease composition. In Examples 10 to 12, Comparative Examples 10 to: I2 and Comparative Examples 22 to 24, lubricating base oil was added with lithium 12-hydroxystearate and dissolved by heating. After cooling, the following additives were blended in the blend ratios shown in Tables 2 to 4. After stirring the mixture, the mixture was passed through a roll mill to obtain a desired grease composition.

Additive

ZnP _: di (n-butyl) zinc phosphate (phosphorus content: 13.2% by mass, sulfur content: 0% by mass, zinc content: 13.0% by mass)

MoDTC: Molybdenum dioctyl dicarbamate

Mo DTP: Molybdenum Dioctyl Diphosphate

ZnDTP: Zinc dipentyl dithiophosphate.

 [0086] [Friction test]

 [0097] Using the grease compositions of Examples 1 to 12 and Comparative Examples 1 to 24, a friction test was performed in the following procedure.

FIG. 1A and FIG. 1B are a perspective view and a top view, respectively, showing a test piece used for a friction test. As shown in the figure, after filling 1 g of the grease composition into the needle holder 2 (14 mmxl 0 mmx 2.5 mm) formed in the center of the lower disk 1 (<i> 24 mm x 7.9 mm), Three needles ($ 3 mm x 13.8 mm) were accommodated in the needle holder 2, and the upper disk 4 (2 Omm x 13 mm) was placed thereon. Then, the angle theta [deg] (needle set of the straight lines perpendicular to the sliding direction of the street on the disk 4 the center O of the lower disc 1 the upper surface, a straight line 1 ₂ parallel to the longitudinal direction of the street the needle 3 the centers O These test pieces were set on an SRV friction tester so that the angle was 30 deg. In this tester, a friction test was carried out under two temperature conditions of 80 ° C and 150 ° C at a frequency of 40 Hz, an amplitude of 3 mm and a load of 1,000 N. Tables 1 to 4 show the friction coefficient 10 minutes after the start of the test. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 6 Example 7 Example 8 Example

MDI 1 1 1 1 1 1 5 5 5 Raw material ratio

 Cyclohexylamine 2 2 2 2 2 2 8 8 8

[mol]

 Thickening agent stearyl alcohol 1-----2 2 2

 12-Human 'lithium roxydisperinate---------Mixing ratio [% by mass] 15 15 15 15 15 15 8 8 8 Mineral oil [% by mass] 83 81 81 90 88 88

ΞΕ ^ Yu

 PAO [mass%] 83 81 81

 ΖπΡ [% by mass] 2 2 2 2 2 2 2 2 2 Additive MoDTC [% by mass] 2 2 2

 MoDTP [mass%] 2 2 2 t

t 80 ° C 0.055 0.045 0.040 0.055 0.045 0.040 0.055 0.045 0.040 Friction test Friction coefficient

150 ° C 0.055 0.045 0.045 0.055 0.045 0.045 0.055 0.045 0.045

Table 2

 Example 10 Example 1 1 Example 12 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example

MDI ― ― ― 1 1 1 1 1 1 Raw material ratio

 Cyclohexylamine--1 2 2 2 2 2 2

[mol]

 Thickening agent Suaryl alcohol----------

12-Human 'lithium loxocystearate Use Use Use------Mixing ratio [% by mass] 10 10 10 15 15 15 15 15 15 Mineral oil [% by mass] 88 86 86 85 83 83 Base oil

 PAO [mass%] 85 83 83

 ZnP [mass%] 2 2 2

 Additive MoDTC [mass%] 2 2 2

 MoDTP [% by mass] 2 2 2

 80 ° C 0.055 0.045 0.040 0.180 0.050 0.055 0.190 0.050 0.055 Friction test Friction coefficient

150 ° C 0.055 0.045 0.045 0.230 0.120 0.160 0.230 0.120 0.160

Table 3

 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 1 1 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 1

MDI 5 5 5----1 1 1 Raw material ratio

 Cyclohexylamine 8 8 8---2 2 2

[mol]

 Stearyl alcohol 2 2 2------

Lithium 12-hydroxystearate mono--use use use---blending ratio [mass%] 8 8 8 10 10 10 15 15 15 mineral oil [mass%] 92 90 90 90 88 88

 Motoda

 PAO [mass%] 83 81 81

ZnP [% by mass]

 MoDTC [mass%] 2 2 2

 Additive

 MoDTP [% by mass] 2 2 2

ZnDTP [mass%] 2 2 2

 80 ° C 0.185 0.050 0.055 0.180 0.055 0.055 0.050 0.045 0.040 Friction test Friction coefficient

150. C 0.235 0.130 0.165 0.225 0.125 0.230 0.195 0.090 0.130

Table 4

 Comparative Example 1 6 Comparative Example 1 7 Comparative Example 1 8 Comparative Example 1 9 Comparative Example 20 Comparative Example 21 Comparative Example 22 Comparative Example 23 Comparative Example 2

MDI 1 1 1 5 5 5 1 1 1 Raw material ratio

 Cyclohexylamine 2 2 2 8 8 8 _ _ [mol]

 Thickening agent Suaryl alcohol 1 1 1 2 2 2 ― ― 1

12 - Human 'Rokishisu亍Arin lithium - - - - - - used used used proportion [weight _^0/0] 15 1 5 15 8 8 8 10 10 10 Mineral oil [% by weight] 83 81 81 90 88 88 88 86 86 Base oil

 PAO [% by mass]

 ZnP [% by mass]

 MoDTC [mass%] 2 2 2

 Additive

 MoDTP [mass%] 2 2 2 to ZnDTP [mass? 4] 2 2 2 2 2 2 2 2 2

 80 ° C 0.050 0.045 0.040 0.050 0.045 0.040 0.050 0.045 0.040 Friction test Friction coefficient

150 ° C 0.190 0.085 0.130 0.185 0.090 0.1 35 0.190 0.085 0.1 35

[0809] As shown in Tables 1 and 2, when the grease compositions of Examples 1 to 12 were used, the grease compositions of Examples 1 to 12 could sufficiently be used under both 80 ° C and 150 ° C temperature conditions. It exhibited a low coefficient of friction and a high level of friction reduction effect. Further, when the grease compositions of Examples 2, 3, 5, 6, 8, 9, 11, and 12 in which an organic molybdenum compound was further combined were used, the friction reducing effect could be further enhanced. .

 On the other hand, when the grease compositions of Comparative Examples 1 to 24 were used, the coefficient of friction at 150 ° C. was low, and the friction characteristics at high temperatures were insufficient. Was. Industrial applicability

 [099] As described above, according to the present invention, a grease composition having a sufficiently high friction reducing effect and maintaining the friction reducing effect at a high level at high temperatures is realized. Therefore, even when mechanical parts such as constant-speed gears are made faster, smaller and lighter, or when these mechanical parts are used at high temperatures, grease is prevented by preventing heat and wear caused by friction between metals. And the life of mechanical parts can be sufficiently extended.

Claims

Guo Qing's example  1. In lubricating base oil, based on the total amount of the composition,  (A) 2-30 mass% thickening agent,  (B) at least one compound selected from the group consisting of phosphorus compounds represented by the following general formula (1) or (2) and metal salts or amine salts thereof in an amount of 0.1 to 10% by mass; A grease composition comprising RXPXR ³  I 2-> (1)  X-R [In the formula (1), X ¹ , X ² and X ³ may be the same or different and each represent an oxygen atom or a sulfur atom, and at least two of X ¹ , X ^{2 and} X ³ are oxygen atoms. , R \ R ² , and R ³ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. X  4 4 II 6 6  R-X-P-X-R (2) XR ⁵ [In the formula (2), X ⁴ , X ⁵ , X ⁶ and X ⁷ may be the same or different and each represent an oxygen atom or a sulfur atom, and at least 3 of X ⁴ , X ⁵ , X ⁶ or X ⁷ One is an oxygen atom, and R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. ]  2. The grease composition according to claim 1, further comprising an organic molybdenum compound.  3. The grease composition according to claim 1, wherein the thickener is lithium soap.  4. The grease composition according to claim 1, wherein the thickener is a urea thickener. 5. The thickening agent is an urea-based penetrating agent represented by the following general formula (3). The grease composition according to claim 1, wherein A— CONH— R ⁷ — NHCO— B (3) [In the formula (3), A and B may be the same or different, and each represents a group represented by one NHR ⁸ , one NR ⁹ R ^{1 C)} or one OR ¹¹ (R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may be the same or different and each represents a hydrocarbon group having 6 to 20 carbon atoms), and R ⁷ represents a divalent hydrocarbon group. ] 6. A compound represented by the general formula (1), wherein X ¹ , X ² and X ³ are all oxygen atoms, and X ⁴ , X ⁵ , X ⁶ and X ⁷ represented by the general formula (2) and 2. The grease composition according to claim 1, wherein the grease composition contains at least one compound selected from the group consisting of oxygen atoms.