Patent Application
20150023622
The present invention relates to a grease composition comprising a predetermined thickener and an amine antioxidant, and a rolling device in which the grease composition intervenes to a predetermined portion.
There has been known that in a rolling device such as a rolling bearing used under high load or vibratory load environment, a lubricant film intervening between a raceway surface and a rolling element is broken during use and lubricating performance declines drastically, thereby causing wear or damage on the raceway surface and the surface of the rolling element.
In order to improve seizure resistance of a grease composition, generally, there has been carried out that a grease composition comprising a high viscosity base oil having a kinematic viscosity of 100 m2/s or more at 40° C. and an extreme pressure agent is used or a used amount of the grease composition is increased. However, while these solutions improve seizure resistance, there is a problem that resistance to stirring in the rolling device is increased.
Also, Patent Document 1 discloses grease prepared using, as a thickener, a diurea compound obtained by allowing an amine mixture comprising alkylphenylamine, an alkyl group of which has 8 to 16 carbon atoms, and cyclohexylamine in a molar ratio of 1:9 to 9:1, to react with a diisocyanate compound. However, it is not considered that the amount of cyclohexylamine in the total amount of alkylphenylamine, an alkyl group of which has 8 to 16 carbon atoms, and cyclohexylamine is adjusted to 91 to 99% by mole.
Patent Document 1: JP 61-155496 A
An object of the present invention is to provide a grease composition which is excellent in seizure resistance without deteriorating resistance to stirring in the rolling device, and a rolling device in which the grease composition intervenes to a predetermined portion, by use of a grease composition comprising a base oil, a specific thickener and a specific amine antioxidant.
The grease composition of the present invention is a grease composition comprising a base oil, a thickener and an amine antioxidant, featured in that the thickener is a diurea compound obtained by allowing an amine mixture comprising alkylphenylamine, an alkyl group of which has 8 to 16 carbon atoms, and cyclohexylamine, to react with a diisocyanate compound, an amount of cyclohexylamine in the amine mixture is 91 to 99% by mole, and an amount of the amine antioxidant in the grease composition is 2.7% by mass or more.
Moreover, the grease composition of the present invention is a grease composition comprising an ashless extreme pressure additive and it is preferable that an amount of the ashless extreme pressure additive in the grease composition is 0.1 to 5.0% by mass.
Moreover, the rolling device of the present invention is a rolling device comprising: a first race member having a first raceway surface, a second race member having a second raceway surface, a plurality of rolling elements rotatably arranged between the first raceway surface and the second raceway surface, featured in that the first race member and the second race member can move relative to each other, and the rolling device comprises the grease composition intervening to rolling contact parts and/or sliding contact parts between the plurality of rolling elements and the first raceway surface and rolling contact parts and/or sliding contact parts between the plurality of rolling elements and the second raceway surface.
According to the present invention, a grease composition which is excellent especially in seizure resistance can be provided without deteriorating resistance to stirring in the rolling device, and a rolling device in which the grease composition intervenes to a predetermined portion can be also provided, by use of a grease composition comprising a predetermined thickener and an amine antioxidant.
First, a grease composition of the present invention will be explained. The grease composition of the present invention comprises a base oil, a thickener and an amine antioxidant.
The base oil is not limited particularly as far as it is a base oil to be usually used for grease, and it is possible to use one or two or more of, for example, mineral oils refined from crude oil by optional combination of treatments such as distillation under reduced pressure, solvent deasphalting, solvent extraction, hydrogenolysis, solvent dewaxing, washing with sulfuric acid, clay refining and hydrofinishing; synthetic diester oils, for example, dibutyl sebacate, di-2-ethylhexyl sebacate, dioctyl adipate, diisodecyl adipate, ditridecyl adipate, ditridecyl glutarate, methylacetyl ricinoleate, and the like; synthetic aromatic ester oils, for example, trioctyl trimellitate, tridecyl trimellitate, tetraoctyl pyromellitate, and the like; synthetic polyol ester oils, for example, trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate, and the like; synthetic ester oils, for example, complex ester oils which are oligo esters of polyhydric alcohol and a fatty acid mixture of dibasic acid and monobasic acid; synthetic polyglycol oils, for example, polyethylene glycol, polypropylene glycol, polyethylene glycol monoether, polypropylene glycol monoether, and the like; synthetic phenyl ether oils, for example, monoalkyltriphenyl ether, alkyl diphenyl ether, dialkyl diphenyl ether, pentaphenyl ether, tetraphenyl ether, monoalkyl tetraphenyl ether, dialkyl tetraphenyl ether, and the like; synthetic hydrocarbon oils, for example, poly-α-olefins such as a co-oligomer of normal paraffin, isoparaffin, polybutene, polyisobutylene, 1-deceneoligomer or 1-decene with ethylene, or hydrides thereof; synthetic silicone oils, for example, dimethyl polysiloxane, diphenyl polysiloxane, alkyl-modified polysiloxane, and the like; and further, synthetic fluorine-containing oils, for example, perfluoro polyether. In particular, alkyl diphenyl ether oil is more preferred from the viewpoint of satisfactory formation of a grease film.
The thickener to be used in the present invention is a diurea compound which is a reaction product of an amine mixture prepared by mixing specific alkylphenylamine with cyclohexylamine, in a specific mixing ratio, and a diisocyanate compound.
In the alkylphenylamine, the number of carbon atoms of its alkyl group is from 8 to 16 from the viewpoint of being environmentally friendly, easily available and good in dispersibility. The number of carbon atoms of the alkyl group is further preferably from 10 to 14 from the viewpoint of being easily available and good in dispersibility. In addition, the alkyl group may be linear or branched, and in the phenyl group, the position substituted by the alkyl group may be any of ortho-position, meta-position or para-position. Specific examples thereof are, for example, one or two or more of octylaniline, decylaniline, dodecylaniline, hexadecylaniline, isododecylaniline and the like. From the viewpoint of good dispersibility, para-dodecylaniline is more preferred.
The amount of the above-mentioned cyclohexylamine is 91% by mole or more and 99% by mole or less in the total amount (100% by mole) of specific alkylphenylamine and cyclohexylamine from the viewpoint of excellent property of forming a grease film. A more preferred amount is 93% by mole or more, further 94% by mole or more from the viewpoint of more excellent formation of a grease film, and is 98% by mole or less, further 96% by mole, also from the viewpoint of more excellent formation of a grease film.
Aromatic diisocyanates are preferred as the diisocyanate compound to be allowed to react with the amine mixture, from the viewpoint of good heat resistance of the grease, and examples thereof are, diphenylmethane-4,4′-diisocyanate, 2,4-trilenediisocyanate, 2,6-trilenediisocyanate, a mixture of 2,4-trilenediisocyanate and 2,6-trilenediisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate, and the like. In particular, from the viewpoint of availability, diphenylmethane-4,4′-diisocyanate and 2,6-trilenediisocyanate are preferred, and further, diphenylmethane-4,4′-diisocyanate is preferred from the viewpoint of good heat resistance.
The reaction of the amine mixture with the diisocyanate compound can be carried out by various methods under various conditions, and it is preferable to carry out the reaction in a base oil since a diurea compound having highly uniform dispersibility can be obtained as the thickener. For example, the reaction may be carried out by adding the base oil containing the diisocyanate compound dissolved therein to the base oil in which the specific alkylphenylamine and cyclohexylamine have been dissolved, or by adding the base oil, in which the specific alkylphenylamine and cyclohexylamine have been dissolved, to the base oil containing the diisocyanate compound dissolved therein.
The reaction temperature and time in the above-mentioned reaction are not limited particularly, and may be the same as those used in usual similar reactions. The reaction temperature is preferably from 60° C. to 170° C. from the viewpoint of solubility and volatility of the amine mixture and diisocyanate. The reaction time is preferably from 0.5 to 2.0 hours from the viewpoint of improvement of production efficiency by shortening of the production period of time and also from the viewpoint of completing the reaction of the amine mixture and diisocyanate. The reaction of an amino group of the amine mixture and an isocyanate group of the diisocyanate compound proceeds quantitatively, and a preferred ratio thereof is 1 mole of the diisocyanate compound to 2 mole of the amine mixture.
The diurea compound which is a reaction product obtained by the above-mentioned reaction is a mixture of a diurea compound (I) resulting from a reaction of both isocyanate groups of the diisocyanate compound with cyclohexylamine, a diurea compound (II) resulting from a reaction of both isocyanate groups of the diisocyanate compound with specific alkylphenylamine, and a diurea compound (III) resulting from a reaction of one isocyanate group of the diisocyanate compound with an alicyclic amine and a reaction of another isocyanate group with an aromatic amine. Here, the diurea compound (I) forms a relatively large thickener fiber, and has a property of being excellent in, such as, shear stability and adhesion to an applied part. The diurea compound (II) forms a relatively small thickener fiber, and has a property of being excellent in, such as, intervening to an applied part. In the mixture of diurea compounds in the present invention, many of diurea compounds are the diurea compound (I), since the amount of cyclohexylamine in the amine mixture used for the reaction is 91 to 99% by mole. It is assumed that by containing a small amount of the diurea compound (II) in addition to this diurea compound (I), the thickness of a grease film on the surface of a rolling element can be increased, and further this film thickness can be maintained for a long time. It is noted that the diurea compound of the present invention may be a diurea compound in which each of the above diurea compounds (I) to (III) is synthesized and mixed such that the amount of the diurea compound (I) is 82 to 99% by mole.
It is preferable that the amount of the thickener in the total amount of the base oil and the thickener is 9% by mass or more and 36% by mass or less. When the amount of the thickener is less than the lower limit, a worked penetration of the grease composition tends to be excessively high, and when the amount of the thickener is larger than the upper limit, the worked penetration of the grease composition becomes excessively low, and there is a tendency that resistance to stirring in the rolling device increases and bearing life is decreased because of seizure by lowering of flowability. A particularly preferred amount is 10% by mass or more, further 15% by mass or more, and 28% by mass or less, further 25% by mass or less, from the point that a proper worked penetration can be obtained.
The amine antioxidant in the present invention is generally an additive for providing the grease composition with antioxidant property. In the present invention, the amine oxidant is contained for providing seizure resistance in addition to antioxidant property, by being used together with a predetermined thickener.
Aromatic amine compounds are desirable as the amine antioxidant and examples thereof include diphenyl amine, alkylated diphenyl amine, phenothiazine, N-phenyl-α-naphthylamine, p,p′-diaminodiphenylmethane, aldol-α-naphthylamine, p-dodecylphenyl-1-naphthylamine. In particular, alkylated diphenyl amine is more preferred from the viewpoint of its preferable seizure resistance.
Examples of the above alkylated diphenyl amine include CAS No. 68422-68-2, 101-67-7, 68921-45-9, 68411-46-1 and the like, and among these, CAS No. 68921-45-9 is preferred from the viewpoint of satisfactory solubility into a base oil.
The amount of the above amine antioxidant in the grease composition is 2.7% by mass or more, preferably 2.9% by mass or more from the viewpoint of excellent seizure resistance (seizing load limit). Further, the preferred amount is 6% by mass or less, more preferably 5% by mass or less, since grease tends to soften.
Moreover, the grease composition of the present invention can comprise an extreme pressure additive. The extreme pressure additive is contained for improving seizure resistance by forming an extreme pressure-resistant coating film at contact parts in the rolling device.
Examples of the extreme pressure additives include ashless extreme pressure additives such as ashless dithiocarbamate (ashless DTC), sulfurized oil and fat, phosphate, ashless dithiophosphate (ashless DTP) and an S-P extreme pressure additive; and extreme pressure additives other than ashless extreme pressure additives such as antimony dithiocarbamate (SbDTC), bismuth dibutyl dithiocarbamate (BiDTC) and zinc dithiocarbamate (ZnDTC). In particular, ashless extreme pressure additives are preferable because the effect of improving extreme pressure property is high and these are environmentally friendly.
In the case where the grease composition comprises the extreme pressure additives, the amount thereof in the grease composition is preferably 0.1 to 5.0% by mass, more preferably 1.0 to 3.0% by mass from the viewpoint of excellent seizure resistance (seizing load limit).
In the present invention, various additives such as an antioxidant other than the above amine antioxidant, an extreme pressure additive, an antiwear additive, a dye, a color stabilizer, a viscosity improver, a structure stabilizer, a metal deactivator, a viscosity index improver and a rust-preventing additive may be added to the grease composition in proper amounts to such an extent not to impair the effect of the present invention. When these additives are contained in the grease composition, it is preferable that the total amount thereof including the above amine antioxidant and extreme pressure additives in the grease composition is 10% by mass or less.
In the present invention, the worked penetration of the grease composition is preferably 280 or more, more preferably 300 or more because channeling of the grease composition in the rolling device can be prevented and the grease composition can be sufficiently fed to the rolling contact surfaces and/or sliding contact surfaces, namely, by using a churning type grease composition, the thickness of the grease film becomes sufficient and seizure can be prevented. On the other hand, the worked penetration is preferably 400 or less from the viewpoint of preventing flow of the grease composition from the rolling contact surfaces and/or sliding contact surfaces to the outer space of the rolling device, namely, the leakage of the grease composition. In the present invention, the worked penetration is a value obtained by dropping a cone mounted on a cone penetration meter into the grease composition under environment of 25° C., measuring a depth (mm) of 5-second invasion of the cone into the grease composition, and then multiplying the measured depth by 10 in accordance with JIS K2220-7.
In the following, the rolling device of the present invention will be explained referring to the attached drawings. It should be noted that the present invention is not limited to embodiments explained below.
The rolling device of the present invention is a rolling device comprising a first race member having a first raceway surface, a second race member having a second raceway surface, a plurality of rolling elements rotatably arranged between the first raceway surface and the second raceway surface, featured in that the first race member and the second race member can move relative to each other, and the grease composition intervenes to rolling contact parts and/or sliding contact parts between the plurality of rolling elements and the first raceway surface and rolling contact parts and/or sliding contact parts between the plurality of rolling elements and the second raceway surface.
The rolling device can be a rolling bearing.
In the rolling bearing, a first raceway surface is a circular raceway surface, a second raceway surface is a circular raceway surface and the first raceway surface and the second raceway surface are rotatably arranged to each other by the rolling of the plurality of rolling elements.
The rolling bearing can be a radial bearing in which one of the first race member and the second race member is an inner ring or inner shaft, and the other is an outer ring. The radial bearing can be a radial ball bearing such as a deep groove ball bearing, an angular contact ball bearing and a self-aligning ball bearing, or a radial roller bearing such as a cylindrical roller bearing, a long cylindrical roller bearing, a needle roller bearing, a tapered roller bearing and a spherical roller bearing.
Moreover, the rolling bearing can be a thrust bearing in which one of the first race member and the second race member is a shaft washer, and the other is a housing washer. The thrust bearing can be a thrust ball bearing such as a thrust ball bearing and an angular contact thrust ball bearing, or a thrust roller bearing such as a cylindrical roller thrust bearing, a tapered roller thrust bearing, a long cylindrical roller thrust bearing, a needle roller thrust bearing and a spherical thrust roller bearing.
Further, the rolling bearing can also comprise a cage for holding all or several rolling elements of the plurality of rolling elements at intervals respectively, or a seal for demarcating a boundary line between the space where the rolling elements are provided and the outside.
The attached
The first race member 11 has a first raceway surface 11S, and the second race member 12 has a second raceway surface 12S, and the first race member 11 and the second race member 12 are arranged so that the first raceway surface 11S and the second raceway surface 12S are faced to each other. A plurality of rolling elements 13 are rotatably arranged between the first raceway surface 11S and the second raceway surface 12S at a given interval in a peripheral direction.
In the rolling bearing 10, the grease composition of the present invention intervenes to rolling contact parts and/or sliding contact parts between the first raceway surface 11S and the rolling elements 13 and/or between the second raceway surface 12S and the rolling elements 13.
The rolling device can be a linear bearing.
In the linear bearing, the first raceway surface is a linear raceway surface and the second raceway surface is a linear raceway surface and the first race member and the second race member are linearly movable to each other by the rolling of the plurality of rolling elements.
The linear bearing can be a linear bearing in which a rolling element is a ball, or a linear bearing in which a rolling element is a roller. Also, the linear bearing can be a recirculating ball linear bearing in which a ball recirculates, or a recirculating roller linear bearing in which a roller recirculates.
The attached
The first race member 21 has a plurality of first raceway surfaces 21S and the second race member 22 has a plurality of second raceway surfaces 22S in a linear manner along the axial direction, respectively, and the first race member 21 and the second race member 22 are arranged so that the first raceway surface 21S and the second raceway surface 22S are faced to each other. A plurality of rolling elements 23 are rotatably arranged between the first raceway surface 21S and the second raceway surface 22S at a given interval or otherwise in contact to each other. Here, the second race member 22 is provided with a race groove 221 for a rolling element circulating under no load, as opposed to the second raceway surface 22S.
The cage 24 has a cylindrical shape so curved as to extend along a part of the inner peripheral surface of the second race member 22, and the both ends thereof are retained by the retaining cylinders 25. A plurality of grooves 241 with a bottom and a plurality of grooves 242 without a bottom are provided in the middle portion in contrast. The grooves 241 with a bottom form, together with a race groove 221 for a rolling element circulating under no load, a row of the rolling elements circulating under no load, while the grooves 242 without a bottom is for a row of the rolling elements circulating under load. The row of rolling elements circulating under no load and the contrasting row of rolling elements circulating under load are connected with each other at their both ends in the axial direction to form a rolling element circulating circuit. Thus, along with an axial sliding motion of the first race member 21 and the second race member 22 relative to each other, the rolling elements are circulated via the rolling element circulating circuit between the row of rolling elements circulating under no load and the row of rolling elements circulating under load.
In the linear bearing 20, the grease composition of the present invention intervenes to rolling contact parts and/or sliding contact parts between the first raceway surface 21S and the rolling elements 23 and/or between the second raceway surface 22S and the rolling elements 23.
The attached
In the moving direction of the movable element, the first race member 31 has a first raceway surface 31S (groove of rail) and the second race member 32 has a second raceway surface 32S (groove of movable element), and the first race member 31 and the second race member 32 are arranged so that the first raceway surface 31S and the second raceway surface 32S are faced to each other. A plurality of rolling elements 33 are rotatably arranged between the first raceway surface 31S and the second raceway surface 32S at a given interval or otherwise in contact to each other. Here, the second race member 32 is provided with a race groove 321 for a rolling element circulating under no load, as opposed to the second raceway surface 32S.
In the linear bearing 30, the grease composition of the present invention intervenes to rolling contact parts and/or sliding contact parts between the first raceway surface 31S and the rolling elements 33 and/or between the second raceway surface 32S and the rolling elements 33.
The rolling device can be a ball screw.
In the ball screw, a first raceway surface is a screw groove surface on the surface of a screw groove of a screw shaft and a second raceway surface is a screw groove surface on the surface of a screw groove of a nut, where the screw shaft and the nut are linearly movable to each other by the rolling of the plurality of rolling elements, namely, balls.
The attached
The first race member 41 has a first raceway surface 41S (screw groove of screw shaft) and the second race member 42 has a second raceway surface 42S (screw groove of nut) respectively in a spiral manner, and the first race member 41 and the second race member 42 are arranged (spirally engaged) so that the first raceway surface 41S and the second raceway surface 42S are faced to each other. A plurality of rolling elements 43 are rotatably arranged between the first raceway surface 41S and the second raceway surface 42S at a given interval or otherwise in contact to each other. Here, the second race member 42 is provided with a circulator tube 44.
In the ball screw 40, the grease composition of the present invention intervenes to rolling contact parts and/or sliding contact parts between the first raceway surface 41S and the rolling elements 43 and/or between the second raceway surface 42S and the rolling elements 43.
The contained amount of the grease composition of the present invention in the rolling device can be changed depending on a shape or dimension and the like of the applied part, but can be approximately the same as the conventional amount.
The present invention will be explained below in detail by means of Examples, but is not limited to these Examples.
Measuring and testing methods are as follows.
The worked penetration is a value obtained by dropping a cone mounted on a cone penetration meter into the grease under environment of 25° C., measuring a depth (mm) of 5-second invasion of the cone into the grease, and then multiplying the measured depth by 10 in accordance with JIS K2220-7,
The seizing load limit of a test grease composition is measured with The SRV Test System available from OPTIMOL
Instruments.
A particular test method will be shown below. The test grease composition is applied on the lower test piece 53 using a template such that the thickness becomes 1 mm and the upper test piece 51 held with the upper test piece holder 52 is set on the applied test grease composition. Then, a reciprocating motion using the drive shafts 521 is started and a load application using the load bar 522 is also started. The load application using the load bar 522 is increased per step, and the load in a step before the step where the frictional force detecting device 541 detects a rapid increase of the frictional force (friction coefficient) between the lower test piece 53 and the upper test piece 51, is determined as the seizing load limit. The larger the seizing load limit is, the more excellent seizure resistance is. It is noted that the test grease composition is applied on the lower test piece 53 before the test only, and is not added after the start of the reciprocating motion.
Here, in normal quenching, quenching is carried out by soaking for 30 minutes at 820 to 850° C., oil cooling, and tempering for 1 to 2 hours at 160 to 180° C.
Load application: Starting from no load (0 N), the load is increased by 50 N per step. When the load reaches 500 N, the load is increased by 100 N per step thereafter. Here, while the load is increased, the reciprocating motion is not stopped and the load is increased taking one to two seconds. It is noted that this time of one to two seconds for increasing the load application is included in the operation time (120 seconds) under the increased load application.
Each step: 120 seconds
In Examples of the present invention, the following materials were used.
MDI: Diphenylmethane-4,4′-diisocyanate Amine
CHA: Cyclohexylamine
PDA: Para-dodecylaniline Base oil
ADE: Alkyl diphenyl ether oil
Amine antioxidant: VANLUBE SL (trade name) (alkylated diphenyl amine) available from R.T. Vanderbilt Company, Inc. Extreme pressure additive
SbDTC (antimony dithiocarbamate): VANLUBE 73 (trade name) available from R.T. Vanderbilt Company, Inc.
Ashless DTC (ashless dithiocarbamate): NA-LUBE ADTC (trade name) available from King Industries International Inc.
According to Table 1, a starting amine (CHA and/or PDA) as the thickener was mixed to ADE (base oil) being the same parts by mass as the starting amine as the thickener, and the mixture was heated to 100° C. to prepare a solution A. Separately, according to Table 1, a starting MDI as the thickener was mixed to ADE being the same parts by mass as the starting MDI as the thickener, and the mixture was heated to 140° C. to prepare a solution B. Next, the rest of ADE was heated to 100° C. and then, thereto was added the solution A and while stirring the mixture, the solution B was added thereto slowly. Thereafter, the mixture was allowed to stand at 150° C. over 60 minutes, and then cooled to room temperature, and thereto was added an amine antioxidant and an extreme pressure additive such that the amount (% by mass in grease composition) thereof was as shown in Table 1, followed by homogenization treatment with a 3-roll mill to obtain test grease. With respect to the obtained test grease, measurements of worked penetration and seizing load limit were carried out. The measurement of a seizing load limit was carried out for two samples (sample A, sample B). The results of the evaluation are shown in
From the results shown in Table 1, it is seen that in Comparative Example 1, wherein the amount of the amine antioxidant is less than 2.7% by mass, and in Comparative Examples 2 to 4, wherein the amount of CHA is 70% by mole, seizure resistance is not sufficient. On the other hand, it can be seen that in Examples 1 and 2, wherein the amount of the amine antioxidant is 2.7% by mass or more and the amount of CHA is 95% by mole, seizure resistance is improved in spite of the grease composition which has a high worked penetration and is soft.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2012-065442 | Mar 2012 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2013/058315 | 3/22/2013 | WO | 00 |
