JP5738712B2 - Grease composition - Google Patents

Description

  The present invention relates to a grease composition used for a rolling bearing for automobile electrical equipment or automobile auxiliary equipment.

Due to demands for smaller and lighter automobiles and larger living spaces, there is a need for a reduction in engine room space. Along with this, electrical and auxiliary parts such as alternators and tension pulleys are also being reduced in size and weight. Further, since the engine room is hermetically sealed for quietness and the usage environment becomes high, grease that can withstand high temperatures is required.
Furthermore, as the usage environment becomes higher, the kinematic viscosity of the grease base oil becomes lower and the oil film in the lubrication part becomes thinner. In this case, the rolling elements of the bearing and the minute protrusions on the metal surface of the raceway are in contact with each other, so that the surface starting point tends to be peeled off and the lubrication life may be shortened. The oil film thickness approaches zero as much as possible when the speed of machine parts such as rolling bearings is zero. This state of zero speed is a state frequently observed in actual machine parts due to repeated start and stop and reciprocating rocking motion. As described above, there are few known grease compositions that suppress surface-origin separation when the oil film becomes thin.
As described above, a grease having both a long bearing lubrication life at high temperatures and a peeling resistance has been required for rolling bearings for automobile electrical equipment or automobile accessories.

As the grease for rolling bearings, lithium soap grease and diurea grease that are inexpensive mineral oil, lithium soap grease and diurea grease that are based on synthetic oil, and the like are used. Synthetic oil diurea grease is often used as a grease used for rolling bearings for automobile electrical equipment or automobile accessories, particularly from the viewpoint of high temperature durability.
In Patent Document 1, a base oil containing an ether-based synthetic oil in an amount exceeding 50% by mass is represented by the following general formula:
^{R 2 -NHCONH-R 1 -NHCONH-} R 3
(In the formula, R ¹ represents a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms, R ² and R ³ are the same or different groups, and are a cyclohexyl group or a cyclohexyl derivative group having 7 to 12 carbon atoms. Or an alkyl group having 8 to 20 carbon atoms.)
And the content of cyclohexyl group or derivative group thereof [{(number of cyclohexyl group or derivative group) / (number of cyclohexyl group or derivative group + number of alkyl groups)] } × 100] has been proposed that contains a gelling agent having a content of 50 to 100%.

In Patent Document 2, the following general formula:
R ₁ NHCONHR ₂ NHCONHR ₃
(In the formula, R ₁ and R ₃ have an octadecyl group as an essential component, and further include any one or both of an octyl group and a dodecyl group, R ₂ is a divalent group having 6 to 15 carbon atoms. A urea compound which represents a hydrocarbon group and is represented by a proportion of octadecyl group of 20 to 80 mol% in octadecyl group, octyl group and dodecyl group in R ₁ and R ₃ groups) As a thickener, a urea grease characterized by blending 3 to 15% by weight in a lubricating oil as a base oil has been proposed.
However, urea grease containing cyclohexylamine or alkylamine as the main component of monoamine is not preferable from the viewpoint of high temperature durability as compared with urea grease containing aromatic amine as the main component of monoamine.
In addition, as described above, since the oil film becomes thinner in a high temperature environment, the minute protrusions between the rolling elements of the bearing and the bearing ring come into contact with each other, and the surface starting point tends to peel off, which may shorten the lubrication life. . As a method for preventing this metal contact, it is a common practice to generally increase the viscosity of the lubricating oil, that is, the base oil of the grease, and increase the thickness of the oil film, but there is a concern that the torque increases as a contradiction. .

On the other hand, in Patent Document 3, without increasing the viscosity of the base oil, the grease composition using the diurea type thickener of the general formula shown below effectively prevents direct contact between both surfaces to be lubricated and is resistant to peeling. It proposes that it can improve the performance.
_{R 2 -NHCONH-R 1 -NHCONH-} R 3
(In the formula, R ₁ represents a divalent hydrocarbon group having 6 to 15 carbon atoms, and R ₂ and R ₃ are a phenyl group and / or a cyclohexyl group)
A grease having a cyclohexyl group / (cyclohexyl group + phenyl group) of R ₂ and R ₃ of 0.95 to 0.10 (molar ratio) has been proposed.
However, as described above, a urea grease containing a monoamine such as cyclohexylamine is not preferable from the viewpoint of high temperature durability.

Japanese Patent No. 2979274 JP-A-1-268793 JP 2008-222739 A

The problem to be solved by the present invention is to provide a grease composition for rolling bearings for automobile electrical equipment or automobile auxiliary equipment, which has a long bearing lubrication life even in a high temperature environment and has excellent surface-origin type peeling resistance. is there.
Another object of the present invention is to provide a rolling bearing for automobile electrical equipment or automobile auxiliary equipment in which the grease composition is enclosed.

We have improved this by selecting appropriate thickeners, base oils and peeling additives for the issues of bearing lubrication life and surface-origin peeling resistance in high temperature environments. That is, according to the present invention, there are provided the following grease composition for automotive electrical equipment or automotive auxiliary machinery rolling bearings and automotive electrical equipment or automotive auxiliary machinery rolling bearings.
1. A grease composition for a rolling bearing for automobile electrical equipment or automobile auxiliary equipment, containing a thickener, a base oil and a peeling resistance additive,
The thickener is a diurea compound represented by the following formula (1):
The base oil contains 80% by mass or more of alkyl diphenyl ether oil based on the total mass of the base oil,
The grease composition according to claim 1, wherein the release-resistant additive is at least one selected from the group consisting of zinc oxide, sodium nitrite, sodium molybdate, sodium benzoate, sodium sebacate and calcium carbonate.

(In the formula (1), R ² is a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms.
R ¹ and R ³ are the same or different groups and represent a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or an alkyl group having 8 to 22 carbon atoms, and monovalent having 6 to 12 carbon atoms. Of the number of moles of monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms to the total number of moles of the aromatic hydrocarbon group and alkyl group having 8 to 22 carbon atoms [{(6 to 12 carbon atoms Number of monovalent aromatic hydrocarbon groups) / (number of monovalent aromatic hydrocarbon groups having 6 to 12 carbon atoms + number of alkyl groups having 8 to 22 carbon atoms)} × 100] is 80 More than mol%. )
2. In the thickener, in formula (1), R ¹ and R ³ are the same or different groups and are an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a straight chain having 8 to 12 carbon atoms. Or the grease composition of said 1 which is a compound which is a branched alkyl group.
3. Furthermore, the grease composition of the said 1 or 2 containing the organic sulfonate type | system | group rust preventive agent shown by following formula (2).
[R ⁴ —SO ₃ ] n ₁ M ₁ Formula (2)
(In the formula (2), R ⁴ represents an alkyl group, an alkenyl group, an alkyl naphthyl group, a dialkyl naphthyl group, an alkylphenyl group or a petroleum high-boiling fraction residue. The alkyl or alkenyl is linear or branched. The number of carbon atoms is 2 to 22. M ₁ represents an alkali metal, alkaline earth metal, zinc, or ammonium ion, and n ₁ represents the valence of M ₁ .
4). 4. The grease composition according to 3 above, wherein the organic sulfonate rust inhibitor is at least one selected from the group consisting of zinc salts and calcium salts.
5. 5. The grease composition according to 3 or 4 above, containing 0.5 to 2% by mass of an organic sulfonate-based rust inhibitor.
6). A rolling bearing for automobile electrical equipment or automobile auxiliary equipment in which the grease composition according to any one of 1 to 5 is enclosed.

  The grease composition of the present invention has a long bearing lubrication life even at a high temperature and has excellent peeling resistance. According to the grease composition of the present invention, an increase in torque can also be suppressed.

[Thickener]
Thickeners that can be used for grease are generally non-soaps such as metal soaps containing Li and Na, benton, silica gel, diurea compounds, and fluorine-based thickeners such as polytetrafluoroethylene. Is mentioned. However, metal soaps, benton, and silica gel do not satisfy the heat resistance, that is, the bearing lubrication life at high temperatures. Although the fluorine-based thickener is satisfactory in heat resistance, it is very expensive and lacks versatility.
In the present invention, aromatic diurea was selected from among diurea thickeners as a thickener. The thickener used in the present invention is excellent in heat resistance even at high temperatures, and therefore the grease composition of the present invention exhibits a long lubricating life. The thickener used in the present invention is represented by the following formula (1).

In formula (1), R ² represents a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms. Typical examples include those represented by the following structural formulas.

In formula (1), R ¹ and R ³ are the same or different groups, and represent a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or an alkyl group having 8 to 22 carbon atoms. The monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms is preferably a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. A methylphenyl group is particularly preferred. As the alkyl group having 8 to 22 carbon atoms, a linear or branched alkyl group having 8 to 12 carbon atoms is preferable. An octyl group is particularly preferred.
Ratio of moles of monovalent aromatic hydrocarbon groups having 6 to 12 carbon atoms to total moles of monovalent aromatic hydrocarbon groups having 6 to 12 carbon atoms and alkyl groups having 8 to 22 carbon atoms [{(Number of monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms) / (number of monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms + alkyl group having 8 to 22 carbon atoms] Number)} × 100] is 80 mol% or more. The ratio of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms can be adjusted by changing the charging ratio of the raw materials constituting the thickener of formula (1).
If the ratio of the number of moles of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms is less than 80%, the fluidity increases, and leakage of grease from the bearing may become a problem.
The amount of thickener can be adjusted as appropriate, but is preferably 10 to 30%, more preferably 15 to 25%, based on the total mass of the grease composition. If the amount of the thickener is too large, leakage of grease is suppressed, but heat generation of the bearing becomes large and the lubrication life cannot be satisfied. On the other hand, if the amount of the thickener is too small, heat generation of the bearing can be suppressed, but grease leakage increases, and the lubrication life cannot be satisfied as well.

[Base oil]
The base oil of this invention should just contain 80 mass% or more of alkyl diphenyl ether oil on the basis of the total mass of a base oil. The base oil of the present invention is excellent in heat resistance at high temperatures.
The alkyl group constituting the alkyldiphenyl ether may be branched or linear, but is preferably linear. 10-20 are preferable and, as for carbon number of an alkyl group, 12-14 are preferable. Alkyl diphenyl ether oil can be used alone or in combination of two or more.
The base oil that can be used in combination with the alkyldiphenyl ether oil is not particularly limited. For example, ester-based synthetic oils typified by diesters and polyol esters, poly-α-olefins, synthetic hydrocarbon oils typified by polybutene, silicone-based synthetic oils, fluorine-based synthetic oils, and the like can be used.
The base oil of the present invention is preferably a base oil having a kinematic viscosity at 40 ° C. of 30 to 300 mm ² / s, and more preferably 50 to ²⁰⁰ mm ² / s. If the kinematic viscosity at 40 ° C. is less than 30 mm ² / s, it may evaporate and heat resistance may not be preferable. When the kinematic viscosity at 40 ° C. exceeds 300 mm ² / s, the low temperature property may not be satisfied.

〔Additive〕
The release additive used in the present invention is at least one selected from the group consisting of zinc oxide, sodium nitrite, sodium molybdate, sodium benzoate, sodium sebacate and calcium carbonate.
The amount of the peeling-resistant additive can be appropriately adjusted, but is preferably 0.1 to 5% by mass with respect to the total mass of the grease composition.

The grease composition of the present invention can further contain additives usually used in rolling bearing grease compositions.
In particular, an organic sulfonate rust inhibitor is preferably included. Since the organic sulfonate rust inhibitor also functions as a dispersant, the addition effect of the organic sulfonate rust inhibitor increases the dispersion effect of the peeling additive, and exhibits a more peeling resistance effect. Therefore, it is possible to improve the peeling life even under severe lubrication conditions in which the oil film is thinned. The content in that case is preferably 0.5 to 2% by mass relative to the mass of the grease composition of the present invention.
As the organic sulfonate rust inhibitor used in the present invention, those represented by the following formula (2) are preferable.
[R ⁴ —SO ₃ ] n ₁ M ₁ Formula (2)
In the formula (2), R ⁴ represents an alkyl group, an alkenyl group, an alkyl naphthyl group, a dialkyl naphthyl group, an alkylphenyl group or a petroleum high-boiling fraction residue. The alkyl or alkenyl is linear or branched and has 2 to 22 carbon atoms. R ⁴ is preferably a dialkylnaphthyl group in which the alkyl group preferably has 6 to 18 carbon atoms, more preferably 8 to 12 carbon atoms, and particularly preferably 9 carbon atoms.
M ₁ represents an alkali metal, alkaline earth metal, zinc, or ammonium ion. Alkaline earth metals and zinc are preferred. Calcium is preferred as the alkaline earth metal.
n ₁ represents the valence of M ₁ .

  The organic sulfonate rust inhibitor is preferably at least one selected from the group consisting of zinc salts and calcium salts. The organic sulfonate rust inhibitor is particularly preferably dinonyl naphthalene sulfonate zinc salt and / or dinonyl naphthalene sulfonate calcium salt.

It is also preferable to contain an antioxidant typified by amines and phenols. In particular, in a high temperature environment, the grease is oxidized and deteriorated. Therefore, it is desirable to use an antioxidant in combination rather than using an amine or a phenol alone. When these antioxidants are included, the total amount is preferably 0.5 to 6% by mass relative to the mass of the grease composition of the present invention.
Other additives include antioxidants such as quinoline, rust inhibitors other than the organic sulfonate rust inhibitors such as amines and carboxylates, inorganic passivating agents, and metal corrosion prevention typified by benzotriazole. Agent, fatty acid, fatty acid ester, oil-based agent typified by phosphate ester, anti-wear agent and extreme pressure agent typified by phosphorus-based, sulfur-based, organometallic-based, metal oxide salt, solid typified by molybdenum disulfide Examples include lubricants. The content of these optional additives is usually 0.5 to 5% by mass with respect to the mass of the grease composition of the present invention.

[Mixing consistency]
The penetration of the grease composition of the present invention is preferably 200 to 300, more preferably 220 to 280. If the blending degree exceeds 300, leakage due to high-speed rotation increases, and the lubrication life may not be satisfied. On the other hand, if the blending degree is less than 200, the fluidity of the grease is deteriorated and the lubricating life may not be satisfied.

〔bearing〕
The bearing enclosing the grease composition of the present invention is a rolling bearing for automobile electrical equipment or automobile auxiliary equipment. Examples of automobile electrical equipment / auxiliaries include an alternator, an electromagnetic clutch for a car air conditioner, an intermediate pulley, an idler pulley, and a tension pulley.

Preparation of test grease Isocyanate (diphenylmethane diisocyanate, tolylene diisocyanate) and monoamine (p-toluidine, cyclohexylamine, octylamine) were charged in the molar ratios shown in Tables 1 and 2, and these were reacted in the base oil. After heating and cooling, a base grease was obtained.
Base oil and various additives were added to the base grease, and after kneading with a three-roll mill, grease compositions of Examples 1 to 11 and Comparative Examples 1 to 8 were obtained so that the penetration was 250. The content of the antioxidant was 3% by mass based on the total mass of the grease composition. In the table, the values of the anti-peeling additive and the rust inhibitor mean mass% when the total grease is 100. The blending penetration is JIS K2220. Measured according to

The base oils and additives used to make the grease are as follows:
<Base oil>
○ Alkyl diphenyl ether oil / C12-C14 alkyl diphenyl ether oil: Kinematic viscosity at 40 ° C = 97 mm ² / s
○ Polyol ester oil and dipentaerythritol ester oil: Kinematic viscosity at 40 ° C = 76.9mm ² / s
○ Synthetic hydrocarbon oil / poly α-olefin oil: Kinematic viscosity at 40 ℃ = 68.0mm ² / s
<Release resistance additive>
○ Zinc oxide ○ Sodium nitrite ○ Sodium molybdate ○ Sodium benzoate ○ Sodium sebacate ○ Calcium carbonate <rust inhibitor>
○ Zinc sulfonate / dinonylnaphthalenesulfonic acid Zn salt ○ Calcium sulfonate / dinonylnaphthalenesulfonic acid Ca salt <Antioxidant>
Amine antioxidant (alkyldiphenylamine)
Phenolic antioxidants (hindered phenols)

<Test method>
(1) Bearing lubrication life test (according to ASTM D3336)
This test is an inner ring rotation test for evaluating the bearing lubrication life at high temperatures. The rolling bearing was operated under the following conditions, and the time until the motor generated an overcurrent (4 amps) or the bearing temperature increased by + 15 ° C. was defined as the lubrication life.
Bearing type: 6204 Metal seal Test temperature: 180 ℃
Rotation speed: 10000rpm
Test load: Axial load 66.7N Radial load 66.7N

Evaluation
More than 400 hours ... ○ (pass)
Less than 400 hours ... x (failed)

(2) Outline of rolling 4-ball test test method Prepare three steel balls for bearings with a diameter of 15 mm and place them in a cylindrical container with an inner diameter of 40 mm and a height of 14 mm, and fill the test grease with about 20 g. When one φ5 / 8 inch bearing steel ball is brought into contact with the three steel balls and rotated at a predetermined rotational speed, the lower three steel balls revolve while rotating. This is continuously rotated until peeling occurs on the steel ball surface.
* Peeling occurs between the spheres with the highest surface pressure.
* The service life is the number of times the upper steel ball contacts the lower steel ball when peeling occurs.

Test conditions Test steel balls: φ5 / 8in bearing steel balls (rotating balls), φ15mm bearing steel balls (driven balls)
Test load: 400kgf (6.5GPa)
Rotation speed: 1500rpm
Number of test repetitions: 5 (Average life: average of n = 5)

Evaluation
20 × 10 ⁶ times or more… ○ (pass)
20 x 10 Less than ⁶ times ... x (failed)

Comprehensive evaluation Bearing lubrication life test, rolling four-ball test both pass ... ○ (pass)
Bearing lubrication life test, rolling four-ball test test Either one of them failed ... × (failed)

The grease compositions of Examples 1 to 11 in which the thickener is an aromatic diurea (consisting of diphenylmethane diisocyanate and p-toluidine), the base oil contains an alkyl diphenyl ether oil, and contains the prescribed additives, All rolling four-ball tests pass.
On the other hand, the grease compositions of Comparative Examples 1 to 8 that do not contain any of them fail either the bearing lubrication life or the rolling four-ball test.

Claims (4)

A grease composition for a rolling bearing for automobile electrical equipment or automobile auxiliary equipment, containing a thickener, a base oil and a peeling resistance additive,
The thickener is a diurea compound represented by the following formula (1):
The base oil contains 80% by mass or more of alkyl diphenyl ether oil based on the total mass of the base oil,
The release-resistant additive is at least one selected from the group consisting of zinc oxide, sodium molybdate, sodium benzoate and calcium carbonate ,

(In the formula (1), R ² is a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms.
R ¹ and R ³ are the same or different groups and represent a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms or an alkyl group having 8 to 22 carbon atoms, and monovalent having 6 to 12 carbon atoms. Of the number of moles of monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms to the total number of moles of the aromatic hydrocarbon group and alkyl group having 8 to 22 carbon atoms [{(6 to 12 carbon atoms Number of monovalent aromatic hydrocarbon groups) / (number of monovalent aromatic hydrocarbon groups having 6 to 12 carbon atoms + number of alkyl groups having 8 to 22 carbon atoms)} × 100] is 80 More than mol%. )
Furthermore, the said grease composition characterized by including at least 1 type of the organic sulfonate type | system | group antirust agent shown by following formula (2) .
[R ⁴ —SO ₃ ] n ₁ M ₁ Formula (2 )
(In the formula (2), R ⁴ represents an alkyl group, an alkenyl group, an alkyl naphthyl group, a dialkyl naphthyl group, an alkylphenyl group or a petroleum high-boiling fraction residue. The alkyl or alkenyl is linear or branched. The carbon number is 2 to 22. M ₁ represents calcium or zinc, and n ₁ represents the valence of M ₁ . In the thickener, in formula (1), R ¹ and R ³ are the same or different groups and are an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a straight chain having 8 to 12 carbon atoms. Or the grease composition of Claim 1 which is a compound which is a branched alkyl group. The grease composition according to claim 1 or 2 , comprising 0.5 to 2% by mass of an organic sulfonate rust inhibitor. A rolling bearing for automobile electrical equipment or automobile auxiliary equipment in which the grease composition according to any one of claims 1 to 3 is enclosed.