JP5019841B2 - Urea grease composition - Google Patents

Description

  The present invention relates to a grease composition that can be applied to lubricated parts of automobiles, industrial machines and the like and has excellent heat resistance and extreme pressure properties.

  In recent years, mechanical technology has been advanced more and more, and equipment has been operated under high temperature and high load conditions. Therefore, further improvement of heat resistance and extreme pressure property is desired even in the grease used in such a place. Therefore, in order to improve heat resistance and extreme pressure, various attempts have been made using organic bentonite, lithium complex, urea, calcium sulfonate complex, etc., which are thickeners for grease generally used at high temperatures. (See Patent Documents 1, 2, 3, and 4.)

Also, under high temperature and high load conditions, sliding parts that are grease-lubricated by frictional heat may be exposed to extremely high temperatures locally. It tends to harden due to evaporation, deterioration of the thickener, etc., and the original performance of the grease may not be fully exhibited. Therefore, under such severe conditions, there is a need for a grease that suppresses curing even when exposed to extremely high temperatures.

: JP 2003-321694 A : JP 2003-155491 A : JP 2004-91711 A : JP 2003-301190 A

  The present invention provides a grease composition that can be used for bearings, gears and the like used under high temperature and high load, has excellent heat resistance and extreme pressure properties, and suppresses curing even when the grease is locally exposed to high temperatures. Is.

As a result of intensive studies to achieve the above object, the present inventors have obtained a base oil composed of at least one selected from phenyl ethers, polyalphaolefins, polyol esters, and complex type polyol esters . 0.5 to 15% by mass of the polyurea compound represented by the formula (1), 3 to 30% by mass of calcium carbonate having an average particle size of 0.01 to 20 μm, and at least one selected from polytetrafluoroethylene and graphite 1 to 20% by mass of a solid lubricant and no sulfur-based extreme pressure agent or less than 3.0% by mass of a sulfur-based extreme pressure agent can significantly improve heat resistance and extreme pressure. I found it.

That is, in the present invention, a polyurea compound represented by the formula (1) is added to a base oil composed of at least one selected from phenyl ethers, poly α olefins, polyol esters, and complex polyol esters in a range of 0.5 to 0.5. 15% by mass, 3 to 30% by mass of calcium carbonate having an average particle size of 0.01 to 20 μm, and 1 to 20% by mass of at least one solid lubricant selected from polytetrafluoroethylene and graphite. There is provided a grease composition containing no extreme pressure agent or containing less than 3.0% by mass of a sulfur-based extreme pressure agent.

（式中、ｙは０〜３の整数であり、Ｒ^１及びＲ^４は炭素数１〜３０の一価の炭化水素基であり、Ｒ^２及びＲ^３は炭素数１〜３０の二価の炭化水素基である。）
また、本発明は、上記グリース組成物において、前記固体潤滑剤がポリテトラフルオロエチレンおよび黒鉛から選ばれる少なくとも１種からなり、該固体潤滑剤の含有量が５〜１８質量％であり、前記ポリウレア化合物の含有量が１〜１２質量％であるグリース組成物を提供する。

(In the formula, y is an integer of 0 to 3, R ¹ and R ⁴ are monovalent hydrocarbon groups having 1 to 30 carbon atoms, and R ² and R ³ are divalent hydrocarbons having 1 to 30 carbon atoms. It is a hydrocarbon group.)
Further, the present invention provides the grease composition, wherein the solid lubricant is at least one selected from polytetrafluoroethylene and graphite, the solid lubricant content is 5 to 18% by mass, and the polyurea A grease composition having a compound content of 1 to 12% by mass is provided.

The grease composition of the present invention is excellent in heat resistance and extreme pressure properties. Therefore, the grease composition of the present invention is extremely useful in practice.

（式中、ｙは０〜３の整数であり、Ｒ^１及びＲ^４は炭素数１〜３０の一価の炭化水素基であり、Ｒ^２及びＲ^３は炭素数１〜３０の二価の炭化水素基である。） The polyurea compound used as a grease thickener in the present invention is a polyurea compound represented by the following formula (1).

(In the formula, y is an integer of 0 to 3, R ¹ and R ⁴ are monovalent hydrocarbon groups having 1 to 30 carbon atoms, and R ² and R ³ are divalent hydrocarbons having 1 to 30 carbon atoms. It is a hydrocarbon group.)

In the formula (1), y is an integer of 0 to 3, preferably 0 or 1, and more preferably 0. R ¹ and R ⁴ are each a monovalent hydrocarbon group having 1 to 30 carbon atoms, and examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. Is mentioned. Carbon number of a hydrocarbon group is 1-30, Preferably it is 3-22, More preferably, it is 6-18. R ² and R ³ are divalent hydrocarbon groups having 1 to 30 carbon atoms, and examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. Can be mentioned. Carbon number of a hydrocarbon group is 1-30, Preferably it is 3-22, More preferably, it is 6-18.

Here, those in which R ¹ and R ⁴ are aliphatic hydrocarbon groups are referred to as aliphatic polyurea compounds, and those in which R ¹ and R ⁴ are alicyclic hydrocarbon groups are referred to as alicyclic polyurea compounds, and R ¹ , R ⁴ is an aromatic hydrocarbon group is called an aromatic polyurea compound.
The above thickeners can be used alone or in combination.

  The compounding quantity of the polyurea compound represented by Formula (1) is 0.5-15 mass%, The more preferable compounding quantity is 1-12 mass%, The especially preferable compounding quantity is 2-10 mass%. If the blending amount of polyurea is too small, the shear stability, which is the inherent performance of grease, tends to decrease. Moreover, in order to maintain this shear stability, if another thickener is substituted, sufficient heat resistance cannot be obtained. Therefore, in this application, it is necessary to blend the above amount of polyurea as a thickener. . If the blending amount is too large, the grease tends to become hard at high temperatures and the predetermined performance tends not to be satisfied.

The calcium carbonate used in the present invention has an average particle diameter of 0.01 to 50 μm, preferably 0.01 to 20 μm, more preferably 0.01 to 10 μm. When the average particle size is too large, the predetermined extreme pressure property tends not to be obtained. Moreover, the preferable compounding quantity of calcium carbonate is 3-30 mass%, More preferably, it is 5-25 mass%. When there is too little calcium carbonate, it exists in the tendency for heat resistance and extreme pressure property to fall. If it is too much, the effect tends to be saturated.

In the present invention, polytetrafluoroethylene (hereinafter referred to as PTFE) or graphite is used as the solid lubricant.
About PTFE, the well-known thing which is known for normal grease whose average particle diameter is 0.1-20 micrometers can be used.
Graphite is roughly classified into artificial graphite and natural graphite. Artificial graphite is produced by solidifying pitch coke with tar, pitch, etc., firing it at about 1200 ° C., and then processing it at a high temperature in a graphite furnace to grow carbon crystals. Natural graphite is graphitized over many years under natural geothermal and underground high pressure. Natural graphite is preferred as the graphite used in the present invention. Natural graphite includes scaly graphite, scaly graphite, and earthy graphite depending on the material used, but scaly graphite is preferred. Moreover, an average particle diameter of 1-15 micrometers can be used preferably. These solid lubricants can be used singly or in combination.

Here, the preferable compounding quantity of the said solid lubricant is 1-20 mass%, More preferably, it is 3-18 mass%, Most preferably, it is 5-18 mass%. If the blending amount is too small, a predetermined extreme pressure property cannot be obtained, and if the blending amount is too large, the effect tends to be saturated.
In addition, other solid lubricants usually used in grease can be used in combination as long as the predetermined performance is not impaired. Specific examples include molybdenum disulfide, tungsten disulfide, graphite fluoride, mica, MCA, boron nitride, silica, transition metal dichalcogenide incalation compounds, and the like.

The base oil used in the present invention, but as the value of the kinematic viscosity at 40 ° C., preferably in the range of 1~2000mm ² / s, more preferably in the range of ^{1~1000mm 2 / s, 10~600mm 2 /} s The range of is particularly preferable. If the kinematic viscosity is too small, the extreme pressure property tends to be low. If the kinematic viscosity is too large, the fluidity is deteriorated and the inherent performance of the grease tends to be difficult .

As the base oil, poly α-olefins (hereinafter sometimes referred PAO), polyol esters, complex type esters include phenyl ethers.
As a poly alpha olefin, the alpha olefin oligomer which is a C3-C12 alpha olefin polymer is mentioned .

Examples of the polyol esters include esters of a divalent, trivalent or tetravalent alcohol having 5 to 6 carbon atoms and a monocarboxylic acid having 3 to 18 carbon atoms, and in particular, the alcohol moiety is 1-trimethylolpropane or Those that are pentaerythritol are preferred.
Examples of the complex type esters include complex type esters composed of a divalent, trivalent or tetravalent alcohol having 5 to 6 carbon atoms, a monocarboxylic acid having 3 to 18 carbon atoms and a dicarboxylic acid having 3 to 18 carbon atoms. Particularly preferred are those in which the alcohol moiety is 1-trimethylolpropane or pentaerythritol.

Things as the full phenyl ether compounds, listed as is preferred that about 2-6 phenyl groups are bonded about 1-5 ether, the phenyl group bonded to an alkyl group having 8 to 20 carbon atoms It may be.

The above base oil, PAO, polyol esters, alone or mixed use of two or more selected from among complex-type polyol esters and phenyl ethers.

In addition, the grease composition of the present invention is a mixture of the base oil of each of the above components and a thickener, and various additives can be appropriately blended as necessary.
Additives include, for example, metal detergents such as alkaline earth metal phenates and alkaline earth metal salicylates; alkenyl succinimides, alkenyl succinimide boronated modified products, dispersants such as benzylamine and alkylpolyamine, zinc -Based, amine-based, and ester-based various antiwear agents; polymethacrylate-based, ethylene-propylene copolymer, styrene-isoprene copolymer, styrene-isoprene hydride, and various viscosity index improvers such as polyisobutylene Alkylphenols such as 2,6-di-tert-butyl-p-cresol, bisphenols such as 4,4′-methylenebis- (2,6-di-t-butylphenol), n-octadecyl-3- (4 '-Hydroxy-3', 5'-di-tert-butylphenol) Various antioxidants such as phenolic compounds such as lopionate, aromatic amine compounds such as naphthylamines and dialkyldiphenylamines; various rust inhibitors such as carboxylic acid partial esters of polyhydric alcohols; various corrosion inhibitors such as benzotriazole and benzimidazole And various antifoaming agents such as silicone oil. An additive can be used individually by 1 type or in combination of 2 or more types.
In addition, it is not preferable to add a large amount of overbased calcium sulfonate, calcium sulfonate complex, and sulfur-based extreme pressure agent to the grease composition of the present invention because the heat resistance and extreme pressure properties are lowered.

  Next, the present invention will be specifically described with reference to examples. In addition, this invention is not limited at all by these Examples.

(Examples 1 to 4 and Comparative Examples 1 to 11)
In Examples and Comparative Examples, grease compositions containing the following * 1 to * 21 components in the proportions (mass) shown in Tables 1 and 2 were prepared. The thickener of * 1 to * 21 is obtained by mixing the raw material of the thickener with the base oil and reacting the raw material in the base oil to obtain the thickener. As a result, * 1 to * 21 A grease composition containing these components was prepared. The grease composition was prepared by appropriately mixing the components * 1 to * 21 and milling to uniformly disperse the thickener in the grease.
Each of the obtained grease compositions was evaluated in a flammability test.

1: Aliphatic diurea: Each base oil and diphenylmethane-4,4-diisocyanate in the table were put into a heat-resistant container and heated, then octylamine was added at about 60 ° C. and reacted for about 40 minutes. Thereafter, the mixture was heated to 170 ° C. with stirring, cooled with a base oil, and milled to optimize diurea crystals, and a grease mixed and dispersed in the base oil was prepared.
(In the formula (1), y is 0, R ¹ and R ⁴ are aliphatic hydrocarbon groups having 8 carbon atoms, and R ² is an aromatic hydrocarbon group having 13 carbon atoms)

2: Alicyclic diurea: Each base oil and diphenylmethane-4,4-diisocyanate in the table are put into a heat-resistant container, heated, and then cyclohexylamine is added at about 60 ° C. and reacted for about 40 minutes. Thereafter, the mixture was heated to 110 ° C. with stirring, cooled with base oil, milled to optimize diurea crystals, and a grease mixed and dispersed in the base oil was prepared.
(In formula (1), alicyclic diurea in which y is 0, R ¹ and R ⁴ are alicyclic hydrocarbon groups having 6 carbon atoms, and R ² is an aromatic hydrocarbon group having 13 carbon atoms)

3: Aromatic diurea: Each base oil and diphenylmethane-4,4-diisocyanate in the table were put into a heat-resistant container, heated, and then paratoluidine was added at about 60 ° C. and reacted for about 40 minutes. Thereafter, the mixture was heated to 170 ° C. with stirring, cooled with a base oil, and milled to optimize diurea crystals, and a grease mixed and dispersed in the base oil was prepared.
(In the formula (1), y is 0, R ¹ and R ⁴ are aromatic hydrocarbon groups having 7 carbon atoms, and R ² is an aromatic hydrocarbon group having 13 carbon atoms)

4: Lithium-12-hydroxystearate (each base oil in the table and lithium-12-hydroxystearate (manufactured by Sakai Chemicals; trade name: S7000H) are charged into a heat-resistant container, heated, and dissolved at about 200 ° C. The base oil was cooled and milled to optimize the crystal of lithium-12-hydroxystearate, and a grease mixed and dispersed in the base oil was prepared.)

5: Lithium-hydroxystearate (each base oil in the table and lithium-hydroxystearate (manufactured by Sakai Chemicals; trade name: S7000) are put into a heat-resistant container and heated to dissolve at about 200 ° C. Then, the lithium-stearate crystals were optimized by milling and cooling, and a grease mixed and dispersed in the base oil was prepared.

6: Complex lithium soap (each base oil and 12-hydroxystearate in the table are put into a heat-resistant container and heated. Next, an aqueous lithium hydroxide solution is added at about 80 ° C., and lithium-12 is added by saponification reaction. -Generate hydroxy stearate, add lithium hydroxide and azelaic acid at about 90 ° C and react for about 2 hours to form lithium complex soap, then heat and semi-melt, then quench. The lithium complex soap crystals were optimized by carrying out the process, and the resulting lithium-12-hydroxystearate / azelaic acid complex lithium soap uniformly mixed and dispersed in the base oil)

7: Calcium sulfonate complex (Pour base oil into a heat-resistant container, add calcium sulfonate with a base number of 400 and methanol, stir well, then heat to around 80-90 ° C to volatilize and remove methanol, Next, boric acid, acetic acid, behenic acid and stearic acid and an aqueous calcium hydroxide solution were added to the mixture and heated to about 150 ° C. with vigorous stirring. After holding for about 30 minutes and cooling, the calcium complex obtained by optimizing the crystals of the calcium sulfonate complex The components of the resulting composition are as follows.

(Base oil component) 60% by mass
(Calcium sulfonate complex component)
Calcium sulfonate + calcium carbonate 36.0% by mass
Calcium behenate 0.8% by mass
Calcium distearate 0.6% by mass
Calcium borate 0.7% by mass
Calcium acetate 1.9% by mass

* 8: Mineral oil (hydrorefined mineral oil at 40 ° C. kinematic viscosity: 100 mm ² / s)
* 9: PAO (alpha olefin polymer having 10 carbon atoms, kinematic viscosity at 40 ° C .: polyalphaolefin having 60 mm ² / s)
* 10: Polyol ester (tetraester of pentaerythritol and C8-10 monocarboxylic acid, kinematic viscosity at 40 ° C .: 30 mm2 / s)
* 11: Complex ester (complex ester of pentaerythritol, monocarboxylic acid having 8 to 10 carbon atoms, and dicarboxylic acid having 6 carbon atoms, viscosity at 40 ° C .: 105 mm ² / s)
* 12: Alkylated diphenyl ether (trade name “MORESCO HIGH LUB LB-100”, manufactured by Matsumura Oil Co., Ltd., 40 ° C. viscosity: 100 mm ² / s)

* 13: Calcium carbonate A (calcium carbonate with an average particle size of 0.15 μm)
* 14: Calcium carbonate B (calcium carbonate with an average particle size of 2.0 μm)
15: PTFE (PTFE having an average particle size of 0.5 μm)
16: Graphite (scale-like graphite having an average particle diameter of 5 μm)
17: Molybdenum disulfide (molybdenum disulfide having an average particle diameter of 2 μm)
* 18: Basic Ca sulfonate (trade name “NASUL 729” KING
INDUSTRIES)
* 19: Sulfur-phosphorus additive (trade name “Angra Mall 99” manufactured by Nippon Lubrizol)
* 20: Sulfur-based extreme pressure agent, sulfurized lard (sulfur content: 30% by mass)
* 21: Antioxidant (diphenylamine)

(Measuring method)
Heat Resistance Test Grease was applied to the steel sheet with a thin film having a thickness of 2 mm, heated in a thermostatic bath at 280 ° C. for 3 hours, and allowed to reach room temperature, and the immiscible penetration before and after the test was measured. Evaluation was performed according to the following criteria.
A: The difference in the immiscible consistency before and after the test is in the range of −20 to less than 20. ○: The difference in the immiscible consistency before and after the test is in the range of −60 to less than 60 (excluding the range of ◎).
×: The difference immiscible penetration before and after the test is - 60 or less than 60 or more ranges

Extreme pressure test A shell four-ball test (according to ASTM D2596) was performed. Evaluation was performed by the fusion load (unit: N).

Claims (2)

0.5-15% by mass of the polyurea compound represented by the formula (1) is added to a base oil composed of at least one selected from phenyl ethers, poly-alpha olefins, polyol esters and complex-type polyol esters , average particle size 3 to 30 wt% calcium carbonate having a diameter 0.01 to 20 .mu.m, and at least one solid lubricant selected from polytetrafluoroethylene and graphite containing 1 to 20 mass%, not containing sulfur-based extreme pressure agent Or a sulfur composition containing less than 3.0% by mass of a sulfur-based extreme pressure agent.

(In the formula, y is an integer of 0 to 3, R ¹ and R ⁴ are monovalent hydrocarbon groups having 1 to 30 carbon atoms, and R ² and R ³ are divalent hydrocarbons having 1 to 30 carbon atoms. It is a hydrocarbon group.) The solid lubricant comprises at least one selected from polytetrafluoroethylene and graphite, the solid lubricant content is 5 to 18% by mass, and the polyurea compound content is 1 to 12% by mass. The grease composition according to claim 1, wherein: