JP2011512432A - Grease composition used for constant velocity joints - Google Patents

Abstract

High durability, low wear, and low friction grease used for constant velocity joints used in automobile drive lines, particularly ball joints or tripod type joints and compatible with boots made of rubber or thermoplastic elastomer Composition, method of use thereof, and provision of a constant velocity joint including the grease composition.
A grease composition comprises at least one base oil, at least one calcium sulfonate soap and / or calcium sulfonate complex soap as a thickener, and at least one molybdenum-containing additive. Including.
[Selection figure] None

Description

  The present invention firstly relates to a lubricating grease used for a constant velocity joint used for a drive line of an automobile, particularly a ball joint or a tripod type joint. Furthermore, the present invention relates to a constant velocity joint including the grease composition according to the present invention.

  The operation of the components of the constant velocity joint (CVJ) is a combination of rolling, sliding and spinning. When torque is applied to the joints, they occur at the same time, causing wear on the contact surfaces of the components, as well as rolling fatigue and significant frictional forces between the surfaces. This wear results in joint failure and friction forces create Noise, Vibration, and Harshness (NVH) in the driveline. NVH is typically measured by determining the axial force produced by a plug-type CVJ. Ideally, greases used in constant velocity joints are required to reduce friction coefficient in order to reduce wear and at the same time avoid or reduce NVH by reducing friction force.

  The constant velocity joint generally has a sealing boot made of an elastomer material having a bellows shape. One end of the sealing boot is connected to the outside of the CVJ, and the other end is connected to the interconnecting shaft or output shaft of the CVJ. The boot keeps the grease inside the joint and prevents dirt and water from entering.

  Grease is required to reduce wear and friction inside the CVJ to prevent early occurrence of rolling fatigue and to be compatible with the elastomer material constituting the boot. Otherwise, premature failure of the boot due to degradation of the boot material may occur, grease leakage, and ultimately CVJ failure. The two main materials used for CVJ boots are polychloroprene rubber (CR), or thermoplastic elastomer (TPE), especially ether ester block copolymerized thermoplastic elastomer (TPC-ET).

  A typical CVJ grease includes a base oil blended with naphthenic (saturated rings) and paraffin (linear and branched saturated chain) mineral oils. Synthetic oils may also be added. The base oil described above is known to have a great influence on the deterioration (expansion and contraction) of the boot due to CR and TPE. Mineral and synthetic base oils extract plasticizers and other oil-soluble protective agents from boot materials. Paraffin mineral oils and poly-α-olefin (PAO) synthetic base oils diffuse in small quantities, especially into rubber material boots that cause shrinkage. However, naphthenic mineral oils and synthetic esters, on the other hand, diffuse into the boot material and act as a plasticizer, causing the boot material to expand. Replacement of the plasticizer or plasticizer composition, especially for naphthenic mineral oils, significantly reduces boot performance, especially at low temperatures. Then, a cold crack occurs in the boot, and eventually the CVJ is damaged. When significant swelling or softening occurs, the maximum speed that the boot can tolerate decreases due to reduced stability to speed and / or excessive radius expansion.

  In order to solve the aforementioned problems, US 6,656,890 B1 proposes a special base oil combination. It comprises 10 to 35 weight percent of one or more poly-α-olefin, 3 to 15 weight percent of one or more synthetic organic esters, and 20 to 30 weight percent of one or more naphthenic oils, The rest include one or more paraffin oils, lithium soap thickeners, sulfur-free friction modifiers (may be organic molybdenum composites), molybdenum dithiophosphates, zinc dialkyldithiophosphates, rust inhibitors, etc. Includes additional additives, antioxidants, extreme pressure additives, and adhesives. However, according to the SRV test (German, abbreviation for Schwingungen, Reibung, Verschlei β), the friction coefficient and wear of the grease composition according to US 6,656,890 B1 need to be improved.

  Accordingly, it is an object of the present invention to provide a grease composition which is firstly used in a constant velocity joint and is compatible with a boot made of rubber or a thermoplastic elastomer, and has high durability, low wear and low friction. There is to do.

  The object of the present invention described above is realized by a grease composition containing the following used in a constant velocity joint. a) at least one base oil, b) at least one calcium sulfonate soap and / or calcium sulfonate complex soap as thickener, c) at least one molybdenum-containing additive.

  Where the term weight percent is used for a component of a claimed grease composition, the term weight percent is based on the total amount of grease composition throughout the specification, unless otherwise stated.

  Preferably, the base oil composition used in the grease composition according to the present invention comprises poly-α-olefin, naphthenic oil, paraffin oil, and / or synthetic organic ester.

According to the base oil composition according to the invention, preferably the base oil composition disclosed in US 6,656,890 B1 is used, the disclosure of which is incorporated into the present invention by reference. However, the type of base oil composition may be a blend of mineral oils, a blend of synthetic oils, or a blend of mineral and synthetic oils. The base oil composition preferably has a kinematic viscosity of 32 to 250 mm ² / s at 40 ° C. and 5 to 25 mm ² / s at 100 ° C. The mineral oil is preferably selected from the group consisting of at least one naphthenic oil and / or at least one paraffinic oil. The synthetic oil that can be used in the present invention is selected from the group consisting of at least one poly-α-olefin (PAO) and / or at least one synthetic organic ester. The synthetic organic ester is preferably a dicarboxylic acid derivative having a subgenus based on aliphatic alcohols. Preferably, the aliphatic alcohol has a straight or branched carbon chain having 2 to 20 carbon atoms. Preferably, the synthetic organic ester is sebasic acid-bis (2-ethylhexylester) (“dioctyl sebacate” (DOS)), adipic acid-bis- (2-ethylhexylester) (“dioctyl adipate” (DOA)), Or selected from the group consisting of azelaic acid-bis (2-ethylhexylester) ("dioctyl azelate" (DOZ)).

When poly-α-olefin is included in the base oil composition, preferably, poly-α-olefin having a viscosity of 2 to 40 centistokes at 100 ° C is selected. Selected naphthenic oil as a base oil composition, at 40 ° C., preferably has a viscosity of 3~370mm ² / s, more preferably it has a viscosity of 20 to 150 mm ² / s. On the other hand, when paraffin oil is included in the base oil composition, the paraffin oil preferably has a viscosity of 9 to 170 mm ² / s at 40 ° C.

  In principle, at least one calcium sulfonate soap and / or calcium sulfonate complex soap used as a thickener of the grease composition according to the present invention is a reaction product of fatty acid and fatty acid, and / or fat. Group hydroxy acids and / or fatty acids. The fatty acid or hydroxy fatty acid is selected from the group consisting of 12 to 30, preferably 12 to 24, more preferably 12 to 18 carbon atoms. The aliphatic acid and / or fatty acid may be selected from the group consisting of dodecanoic acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, and / or 12-hydroxystearic acid. Aliphatic hydroxy acids and / or fatty acids are preferentially selected due to their high viscosity.

  The calcium sulfonate used in the preparation of the calcium sulfonate grease and / or the calcium sulfonate composite grease is selected from the group consisting of at least one calcium sulfonate and / or at least one overbased calcium sulfonate. The In the present invention, an overbased calcium sulfonate, particularly an overbased calcium sulfonate having a metal ratio of 6 to 35, is preferentially selected.

  Calcium sulfonate soap used as a thickener is prepared by reaction of the aforementioned calcium sulfonate and aliphatic acid and / or fatty acid and / or hydroxy fatty acid and / or fatty acid in the presence of other chemicals Is done. Other chemicals are in particular conversion inducers, inter alia water, alcohols (for example biphenol, isobutanol, n-pentanol, or mixtures thereof or mixtures of water and alcohol), alkylene glycols, monomethyl ethers of ethylene glycol. Monomeric alkyl ethers of alkylene glycols, such as low aliphatic carboxylic acids (eg acetic acid and propionic acid), ketones, aldehydes, amines, phosphoric acids, alkyl and aromatic amines, imidazolines, alkanolamines, boronic acids (boric acid, tetracarboxylic acids) Boric acid, metaboric acid, and esters of these boronic acids), carbon dioxide, etc. (or preferably in combination with water). The calcium sulfonate complex soap used as a thickener according to the present invention comprises at least one aliphatic acid and / or fatty acid or hydroxy aliphatic acid and / or fatty acid, complexing agent (for example, one or more dicarboxylic acids). A mixture of at least one calcium sulfonate compound mixed with an acid borate or a mixture of short and / or medium chain carboxylic acids.) Is used. With the calcium sulfonate complex soap as a thickener according to the present invention, the grease composition according to the present invention functions up to a temperature of about 180 ° C. On the other hand, with a simple calcium sulfonate soap as a thickener according to the present invention, the grease composition according to the present invention functions only up to a temperature of about 120 ° C. However, a mixture of all the aforementioned soaps may be used.

The at least one molybdenum-containing additive contained in the grease composition according to the present invention preferably comprises at least one molybdenum dithiocarbamate, at least one molybdenum dithiophosphate, MoS ₂ , at least one S-Free. And selected from the group consisting of P-Free organomolybdenum compounds and / or at least one trinuclear molybdenum compound. At least one trinuclear molybdenum compound is represented by the following general formula:

Mo ₃ S _k L _n Q _z (I)

  L is an independently selected ligand having an organic group with a sufficient number of carbon atoms to impart solubility or diffusibility to the compound in the oil. The value of n is 1 to 4, and the value of k varies between 4 and 7. Q is selected from the group consisting of neutral electron donating compounds such as amines, alcohols, phosphines, and ethers. z ranges from 1 to 5 and includes non-stoichiometric values.

  All carbon atoms are present in the trinuclear molybdenum compound through all ligands, and the organic group has at least 21, preferably 25, more preferably 30, most preferably 35 carbon atoms. Have Trinuclear molybdenum compounds that can be used in the present invention are disclosed in US 6,172,013B1. This disclosure is incorporated by reference into the present invention. The trinuclear molybdenum compound is preferably 0.25 weight percent, and when the trinuclear molybdenum compound is used in CVJ, not only wear but also the friction coefficient is greatly reduced.

  The at least one molybdenum dithiophosphate (MoDTP) and / or molybdenum dithiocarbamate (MoDTC) is preferably from 0.3 weight percent, more preferably from 0.5 weight percent, most preferably from 1.0 weight percent. 3.5 weight percent, most preferably 3.0 weight percent, is included in the grease composition according to the present invention. Each value is based on the entire grease composition. However, more molybdenum-containing compounds may be used in the grease according to the invention as c) composition, preferably organic molybdenum compounds. The grease composition according to the invention comprises one or more MoDTC and / or MoDTP, in particular a mixture thereof. MoDTP according to the present invention is represented by the following general formula.

X or Y represents S or O, and each of R ¹ to R ⁴ may be the same or different, and the first (straight chain) or second (branched chain) having 6 to 30 carbon atoms ) Represents an alkyl group.

  The MoDTC according to the present invention is represented by the following general formula.

_{^{[(R 5) (R 6}} ) N-CS-S] 2 -Mo 2 O m S n ··· (III)

R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 24, preferably 3 to 18 carbon atoms. The range of m is 0-3, and the range of n is 4-1. However, m + n = 4.

  Suitably the molybdenum containing additive is selected from the group consisting of at least one molybdenum dithiocarbamate and at least one trinuclear molybdenum compound. According to a more preferred embodiment of the present invention, the grease composition is 0.2 to 5.0 weight percent, preferably 0.25 to 3 weight percent, more preferably 0.3 to 2 weight percent, More preferably, it contains 0.3 to 1.25 weight percent of a trinuclear molybdenum compound.

  According to a further preferred embodiment of the present invention, the grease composition is at least one of 0.25 to 5 weight percent, preferably 0.5 to 3 weight percent, more preferably 0.8 to 2 weight percent. Solid or liquid molybdenum dithiocarbamate. According to a further preferred embodiment of the invention, the molybdenum dithiocarbamate is selected from the group consisting of at least one solid molybdenum dithiocarbamate.

  According to a further embodiment of the invention, the grease composition comprises at least one antioxidant, at least one rust inhibitor, at least one antiwear agent, at least one wax, at least one friction modifier. And / or at least one extreme pressure agent.

  The friction modifier is a zinc compound additive, preferably 0.1 to 3.5 weight percent (preferably to 2.5 weight percent), more preferably 0.5 to 2 based on the total amount of grease. 0.0 weight percent zinc compound additive is used. The most preferred zinc compound additive is selected from the group consisting of at least one zinc dithiolate (ZnDTP) and / or zinc dithiocarbamate (ZnDTC), with ZnDTP being the most preferred. The zinc dithiolinate is preferably selected from the group of zinc dialkyldithiophosphates represented by the general formula:

^{(R 7 O) (R 8} O) SP-S-Zn-S-PS (OR 9) (OR 10) ··· (IV)

Each of R ⁷ to R ¹⁰ may be the same or different and represents the first or second alkyl group. The first alkyl group is most preferred and has 1 to 24, preferably 3 to 20, and most preferably 3 to 5 carbon atoms. In particular, when the substituents R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are a combination of first or second alkyl groups each having 3 to 8 carbon atoms, particularly excellent effects are expected.

  The zinc dithiocarbamate may suitably be selected from zinc dialkyldithiocarbamates represented by the following general formula:

R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ may be the same or different and each represents an alkyl group having 1 to 24 carbon atoms or an alkyl group having 6 to 30 carbon atoms.

  By adding at least one zinc compound additive to the grease composition according to the present invention, not only the wear of CVJ but also the friction coefficient is greatly reduced.

  The extreme pressure agent is preferably a metal-free polysulfide, or a mixture thereof, such as a sulfurized fatty acid methyl ester agent, preferably having a viscosity of 25 mm / s at 40 ° C., and 0, based on the total grease composition. 0.1 to 3 weight percent, preferably 0.3 to 2 weight percent. The total amount of inert sulfur in the extreme pressure agent at room temperature is preferably 8 to 50 weight percent (preferably ˜45 weight percent). The total amount of active sulfur as measured by ASTM D1662 is a maximum of 1 weight percent, preferably 8 weight percent at 100 ° C, preferably 20 weight percent at 140 ° C. The weight is based on the weight of the extreme pressure agent. Such an extreme pressure agent exhibits an excellent effect in reducing scuffing due to contact of CVJ internal components. When the sulfur content exceeds the above upper limit value, the rolling fatigue is started and the wear of the contact parts is promoted, which may cause deterioration of the boot material of CVJ.

  As an antioxidant, the grease composition of the present invention may comprise an amine, preferably an aromatic amine, more preferably phenyl-α-naphthylamine or di-phenylamine or derivatives thereof. Antioxidants are used to prevent degradation associated with oxidation of the grease composition. The antioxidant grease composition according to the present invention, which extends the life of the grease composition and at the same time suppresses the oxidative decomposition of the base oil composition, is contained in an amount of 0.1 to 2 percent by weight based on the entire grease composition. This extends the life of the CVJ.

  In general, the final procedure before assembling the CVJ is cleaning for removing machining waste. Therefore, it is necessary to suck up the remaining water for the grease and prevent erosion by water and water from adversely affecting the performance of the CVJ. Therefore, a rust inhibitor is required. As a rust inhibitor, the grease composition according to the present invention comprises a metal salt of oxidized wax, particularly a metal salt of petroleum acid salt prepared by a sulfonated aromatic hydrocarbon present in a small amount in lubricating oil, and / or dinonylnaphthalene. It may comprise at least one metal salt or binuclear metal salt selected from the group consisting of metal salts of alkyl aromatic acid salts such as sulfosulfonic acid, alkylbenzenesulfonic acid, or excess based alkylbenzenesulfonic acid. Examples of metal salts include sodium, potassium, calcium, magnesium, zinc, and quaternary ammonium salts, with calcium being most preferred. The calcium salt of oxidized wax also exhibits excellent effects. Particularly preferred is sodium sebacic acid as a rust inhibitor.

  The antiwear agent according to the present invention avoids contact between metals by the addition of a coating-forming mixture that protects the surface by physical absorption or chemical reaction. ZnDTP mixtures can also be used as antiwear agents. The rust inhibitor according to the present invention, preferably calcium sulfonate, is preferably used in an amount of 0.5 to 3 weight percent, based on the total grease composition.

  The grease composition of the present invention as a wax mixture contains a plurality of types of waxes. Preferably, oily waxes used in grease compositions and mixtures thereof and known as state-of-the-art technology, among montan waxes, particularly ester montan waxes, which are the reaction products of at least one montan wax acid and ester, and fine Most preferred are polyolefin waxes containing a mixture of montan and / or polyolefin wax, or mixtures thereof. The montan wax according to the present invention comprises an ester of C22-C34-fatty acid and preferably a wax alcohol having 24 to 28 carbon atoms. Esters may be included in the montan wax according to the present invention in a total of 35 to 70 weight percent. Furthermore, free fatty acid and free wax alcohol may be contained like the montan resin. Useful montan wax is supplied by Augsburg 86005 Clariant, Germany, and is sold under the name “Licowax”. Useful polyolefin waxes for the present invention are polypropylene and / or polyethylene waxes and mixtures thereof, including modified polyolefin waxes, especially co-polymers of useful comonomers such as vinyl esters and acrylic acid with ethylene. It is obtained by polymerization. The wax preferably has a viscosity of at least about 50 mPa · s at 100 ° C., more preferably at least about 100 mPa · s at 100 ° C., and most preferably at least about 200 mPa · s at 100 ° C. The viscosity is measured according to DIN 53 018. The wax used in the grease composition is in the form of powder or flakes, and is preferably added to the grease composition by stirring for a long time in a high temperature state, particularly about 80 ° C to 100 ° C.

  Conventional friction modifiers such as fatty acid amides and aliphatic phosphate amines used in the present invention have been used for many years in greases and other lubricants (see, for example, these lubricants are Klamann, Dieter- “ Lubricants ", Verlag Chemie GmbH, 1983, 1st edition, chapter 9.6). Their role is to give the lubricant a friction that is stable but not necessarily low over a wide range of operating conditions.

  According to a further embodiment of the invention, the claimed grease composition comprises 0.3 weight percent (preferably ˜1.25 weight percent) of at least one trinuclear molybdenum compound, and 0.8˜ 3 weight percent (preferably ˜2 weight percent) of at least one molybdenum dithiocarbamate.

  According to a further preferred embodiment of the invention, the claimed grease composition comprises 65 to 86.9 percent by weight of base oil composition, 16 to 20 percent by weight of at least one calcium sulfonate soap and / or Calcium sulfonate complex soap, 0.3-2 weight percent of at least one trinuclear molybdenum compound, and 0.3-3 weight percent of at least one molybdenum dithiocarbamate. The most preferred grease composition according to the present invention comprises 16-20 weight percent of at least one calcium sulfonate soap and / or calcium sulfonate complex soap, 0.3-0.7 weight percent of at least one three A nuclear molybdenum compound, 0.75 to 1.8 weight percent of at least one molybdenum dithiocarbamate, and 66.45 to 86.9 weight percent of a base oil composition. The grease composition according to the present invention may further contain other chemicals as described above.

  Moreover, this invention relates to the usage method of the grease composition which concerns on this invention in a constant velocity joint, and also the constant velocity joint containing the grease composition as described in a claim. Constant velocity joints include boots, particularly boots having at least a portion filled with a grease composition in accordance with the present invention, a first joint region assigned to the joint and a second joint region assigned to the shaft. The boot may be secured to a clamping device on the joint and / or shaft.

FIG. 1 shows SRV measurement results of the friction coefficients of Examples A1 to A8. FIG. 2 is a measurement result of SRV of wear in Examples A1 to A8. FIG. 3 is a measurement result by SRV of the friction coefficients of Examples B1 to B10. FIG. 4 is a measurement result by SRV of wear of Examples B1 to B10. FIG. 5 shows the results of SRV measurement of the friction coefficients of Examples C1 to C6. FIG. 6 is a measurement result of SRV of wear of Examples C1 to C6.

  Further detailed description of the present invention will be given based on the following embodiments.

In order to determine the effect of the grease composition according to the present invention on reducing the coefficient of friction as well as wear, an SRV test is performed using an Optimol Instruments SRV tester. A lower planar disc specimen made from 100Cr6 standard bearing steel of Optimol Instruments Proftechnik GmbH, (Westendstrasse 125, Munich), properly cleaned with solvent, was prepared as a grease composition as a specimen Contacted with. The SRV test is an industry standard test and in particular relates to the testing of grease for CVJ. This test consists of reciprocating an upper spherical specimen made of 100Cr6 bearing steel with a diameter of 10 mm under load on the lower planar disk specimen mentioned above. In a test to mimic a tripod type joint, a frequency of 40 Hz was applied at 80 ° C. for 60 minutes (including a running-in) under a load of 500 N. The stroke was 3.0 mm. The resulting coefficient of friction was recorded on a computer. The value recorded for each grease is the average of two measurements after two runs each. Wear is measured using a profilometer and a digital planimeter. By using a profilometer, a profile in the middle of the worn surface is obtained. The area (S) of this cross section can be measured by using a digital planimeter. The amount of wear is evaluated by V = SI, where V is the volume of wear and I is the stroke. The wear rate (Wr) is obtained from Wr = V / L [μm ³ / m], where L is the total sliding distance in the test. Regarding the familiar operation, the operation is started under the condition specified above with a load of 50 N applied for 1 minute. Thereafter, the load is increased by 50N every 30 seconds and increased to 500N.

  In addition, tests were conducted to determine the properties of rubber boots and TPE boots containing the grease composition according to Example C4 of the present invention by comparison with two commercial grease compositions A and B. Testing was based on changes in hardness (Shore D) and percentages of tension, elongation, and volume before and after thermal aging by immersion in grease at 125 ° C. for 336 hours. The above values were measured based on ISO868 (Shore D), ISO37 (change in tension / elongation), and ISO2781 (change in volume).

  Commercial greases A and B used as comparative examples are from Axel Christenson B. V. Axel CaSX51646 (Comparative Example A) obtained from Tianjin Lubricant and Grease Co., Tianjin, China. Ltd. (Jinzhi), Sinopec Corp. Super Green 2 (Comparative Example B) obtained from

  The following substances were used as the grease composition to be tested according to the present invention.

[Base oil composition (oil blend)]

Base oil used has a kinematic viscosity of about 16 mm ² / s to about 165mm ² / s, 100 ℃ at 40 ° C.. The blend of base oils is about 10 to 60 weight percent, preferably about 20 to 40 weight percent of one or more paraffin oils, about 30 to 80 weight percent, preferably about 55 to 80 weight percent of one or more. A mixture of naphthenic oil and optionally about 5 to 40 weight percent poly-α-olefin (PAO), weight based on the total amount of oil mixture. The specific oil blend used in this example is a 73 weight percent naphthenic oil SR130 manufactured at AB Nyna's Petroleum in Stockholm, Sweden, 25 weight percent obtained from Kuwait Petroleum Europort BV in Europort, The Netherlands. It consists of paraffin oil NS650 and 2 weight percent DOS.

About 20~180mm ² / s to naphthenic oils at 40 ° C., the paraffin oil about at 40 ℃ 25~400mm ² / s, the PAO is of about 6~40mm ² / s at 100 ° C. is selected.

[Calcium sulfonate soap]

  The calcium sulfonate soap according to an embodiment of the present invention is an excess-based calcium sulfonate soap, an excess-based sulfone having a metal ratio of 6 to 35 mixed with 12-hydroxystearic acid in a solvent of neutral oil. It is obtained by the reaction of calcium acid, calcium carboxylate, isopropyl alcohol, and phosphoric acid. A method capable of producing the calcium sulfonate soap used is disclosed in US 5,126,062.

[Trinuclear molybdenum compound (TNMoS)]

  The trinuclear molybdenum compound used in the grease composition according to the present invention is a sulfur-containing trinuclear molybdenum compound and is manufactured by Infineum International Ltd., UK. And is available under the trade name C9455B. Its structure is defined by US 6,172,013B1.

[More molybdenum compounds]

  Chemical formula: 2-Ethylhexy polybdenum dithiophosphate, which is dilute molybdenum dithiophosphate (MoDTP) sold by Asahi Denka Kogyo Co., Ltd. in Japan under the name Sakuraurabe 300 (S-300), is used. Furthermore, manufactured by Asahi Denka Kogyo Co., Ltd. in Japan and sold under the name Sakurarabe 600 (S-600), or R. T.A. Solid molybdenum molybdenum dithiocarbamate (MoDTC solid) manufactured by Vanderbilt Company and sold under the trade name of Polyvan A is used.

Furthermore, S-Free and P-Free organic molybdenum additives sold under the trade name S-701 from Asahi Denka Kogyo Co., Ltd. in Japan, and manufactured by Asahi Denka Kogyo Co., Ltd. in Japan, 200) and molybdenum dithiocarbamate sold under the trade name. This is a molybdenum amine complex represented by a general chemical formula of R ₂ N—Mo _X O _Y H as in the case of ordinary MoS ₂ .

[Additional additives]

  Zinc compound additives as friction modifiers, ie, UK1 Oxford Infineum International Ltd. Zinc diocylic acid ZnDTP sold under the trade name C9425 is used. This is zinc diotinoic acid having a first and / or second alkyl group, diluted with mineral oil. The alkyl group has in particular 3 to 8, preferably 4 to 5 carbon atoms.

  First, the effectiveness of the grease composition according to the present invention was tested by measuring the friction coefficient and wear of the six types of grease shown in Table 1.

The measurement results by SRV of the wear and friction coefficient of Examples A1 to A8 are shown in FIGS. Simple addition of MoS ₂ resulted in the lowest coefficient of friction but the greatest wear. On the other hand, the wear of A3 was very small with respect to the increase of the friction coefficient, as compared with A1 of the grease composition which is composed only of the base oil and calcium sulfonate soap and does not depend on the present invention. In addition, A2 and A5 also showed good results with respect to wear.

  In further additional tests, the amount of MoDTC solid as well as TNMoS was changed. Ten grease compositions were made according to Table 2.

  In Examples B1 to B3, the amount of TNMoS is changed. On the other hand, in Examples B4 to B7, the amount of MoDTC solid is changed. In Examples B8 to B10, MoDTC solids having different amounts were mixed with 0.5 weight percent of TNSMoS. The measurement result by SRV of wear and a friction coefficient is shown in FIG.3 and FIG.4.

  Example B3 showed the lowest coefficient of friction, but the wear was an intermediate value among the results obtained. A low coefficient of friction was measured in Examples B9 to B10. Among them, B9 showed one of the lowest friction coefficients. This test result shows that a combination of different molybdenum-containing compounds is particularly desirable, and that the range of molybdenum compounds used is very sensitive to friction coefficient and wear measurements.

  In the third test, the effect of adding 0.5 weight percent of different molybdenum-containing compounds and ZnDTP to 1.5 weight percent of MoDTC solid was evaluated. The tested grease compositions C1-C6 are defined in Table 3.

  The measurement result by SRV of wear and a friction coefficient is shown in FIG.5 and FIG.6. One is derived from C4, most preferably having a solid weight MoDTC solid of 1.5 weight percent and a trinuclear molybdenum compound amount of 0.5 weight percent. This is because the wear and the coefficient of friction are not less than those of other compositions.

  Finally, combinations of three molybdenum compound additives or two molybdenum compound additives and ZnDTP were tested according to Table 4. The amount of MoDTC solid has not changed.

  As shown in FIGS. 7 and 8, in Examples D1 to D5, the lowest friction coefficient was obtained from D5. On the other hand, the wear of D2 and D4 was very low. However, because of the lowest coefficient of friction, a grease composition of D5 that is very similar to D4 is considered advantageous.

Finally, the characteristics of boots with different greases were measured. The grease composition of Example C4 was compared with commercially available greases A and B for comparison. The results are shown in Table 5.

  According to Table 5, good results for changes in tension and elongation were measured in combination with TPE boots. According to the endurance test of Example C4, the life of the constant velocity joint can be doubled compared to the one with a boot using commercially available greases such as A and B.

  In summary, the grease composition according to the present invention is advantageous in terms of coefficient of friction and wear, and shows a significant effect on the coefficient of friction and wear. That leads to good extreme pressure performance. In particular, a combination of two or three different molybdenum-containing compounds, up to a total of 3.5 weight percent, is preferred, especially molybdenum dithiocarbamate as well as trinuclear molybdenum compounds, which are individual. Is preferred. A combination of the two is most preferable.

Claims (14)

a) at least one base oil;
b) at least one calcium sulfonate soap and / or calcium sulfonate complex soap as thickener;
c) A grease composition for use in constant velocity joints, comprising at least one molybdenum-containing additive.   The grease composition of claim 1 comprising 12 to 20 weight percent of at least one calcium sulfonate soap and / or calcium sulfonate complex soap. At least one molybdenum-containing additive, at least one molybdenum dithiocarbamate, at least one molybdenum dithiophosphate, MoS _2, organic molybdenum compound of at least one S-the Free and P-the Free, and / or at least 1 The grease composition according to claim 1 or 2, selected from the group consisting of a species of trinuclear molybdenum compound.   The grease composition according to any one of claims 1 to 3, wherein the molybdenum-containing additive is selected from the group consisting of at least one molybdenum dithiocarbamate and at least one trinuclear molybdenum compound.   The grease composition according to any one of claims 1 to 4, comprising 0.2 to 5 percent by weight of at least one trinuclear molybdenum compound.   6. A grease composition according to any preceding claim comprising from 0.25 to 5 weight percent of at least one molybdenum dithiocarbamate.   The grease composition according to any one of claims 3 to 6, wherein the molybdenum dithiocarbamate is selected from the group consisting of at least one solid molybdenum dithiocarbamate.   8. The method according to claim 1, comprising from 0.3 weight percent to 2.0 weight percent of at least one trinuclear molybdenum compound and from 0.5 weight percent to 3 weight percent of at least one molybdenum dithiocarbamate. The grease composition as described.   The grease composition according to any one of claims 4 to 8, further comprising at least one molybdenum dithiophosphate.   The grease composition according to any one of claims 1 to 9, wherein the base oil composition comprises poly-α-olefin, naphthenic oil, paraffin oil, and / or a synthetic organic ester.   At least one antioxidant, at least one rust inhibitor, at least one antiwear agent, at least one wax, at least one friction modifier, and / or at least one extreme pressure agent; The grease composition according to any one of claims 1 to 10, further comprising:   65 weight percent to 86.9 weight percent base oil composition, 16 weight percent to 20 weight percent at least one calcium sulfonate soap and / or calcium sulfonate complex soap, 0.3 weight percent to 2.0 weight percent 12. A grease composition according to any one of the preceding claims comprising at least one trinuclear molybdenum compound, and 0.5 to 3 weight percent of at least one molybdenum dithiocarbamate.   The method for using a grease composition according to any one of claims 1 to 12, comprising the step of using the grease composition for a constant velocity joint.   A constant velocity joint comprising the grease composition according to claim 1.

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