Lubricating oil composition

Abstract

The present invention provides a lubricating oil composition not containing ZnDTP but comprising: (a) a base oil; (b) molybdenum dialkyldithiocarbamate; and (c) an organic acid metal salt compound having a metal of Group 8 of a short periodic table, copper, or bismuth as a central metal.

Claims

1. A lubricating oil composition not containing ZnDTP but comprising the following components (a) to (c): (a) a base oil; (b) molybdenum dialkyldithiocarbamate; and (c) an organic acid metal salt compound which is nickel 2-ethylhexanoate, wherein a content of the molybdenum dialkyldithiocarbamate in the composition is 0.1 to 0.5 mass %, and a content of the organic acid metal salt compound in the composition is 200 to 500 ppm in terms of nickel concentration, and wherein the lubricating oil composition is free of an amine-based antioxidant.

2. The lubricating oil composition according to claim 1, wherein the base oil is synthetic oil.

3. The lubricating oil composition according to claim 1, wherein the base oil is poly alpha olefin.

4. The lubricating oil composition according to claim 1, wherein a content of the base oil is 40 mass % or more.

5. A grease composition comprising the lubricating oil composition according to claim 1, and a thickener.

6. The lubricating oil composition according to claim 1, wherein the content of the molybdenum dialkyldithiocarbamate is 0.4 mass %.

7. The lubricating oil composition according to claim 1, wherein the lubricating oil composition has a coefficient of friction measured using a ball-on-disk tester under following conditions of 0.060 or less, Friction material: steel (SUJ-2)/steel (SUJ-2, φ 8 mm ball/disk, Temperature: 60° C., Load: 10 N, Speed: 0.5 m/s, and Time: 30 min.

8. A lubricating oil composition not containing ZnDTP but comprising the following components (a) to (c): (a) a base oil; (b) molybdenum dialkyldithiocarbamate; and (c) an organic acid metal salt compound which is cobalt 2-ethylhexanoate, wherein a content of the organic acid metal salt compound in the composition is 100 to 1000 ppm in terms of cobalt concentration, and wherein the lubricating oil composition is free of an anime-based antioxidant.

9. The lubricating oil composition according to claim 8, wherein the lubricating oil composition has a coefficient of friction measured using a ball-on-disk tester under the following conditions of 0.060 or less; Friction material: steel (SUJ-2)/steel (SUJ-2, φ 8 mm ball/disk, Temperature: 60° C., Load: 10 N, Speed: 0.5 m/s, and Time: 30 min.

10. The lubricating oil composition according to claim 8, wherein the base oil is synthetic oil.

11. The lubricating oil composition according to claim 8, wherein the base oil is poly alpha olefin.

12. The lubricating oil composition according to claim 8, wherein a content of the base oil is 40 mass % or more.

13. The lubricating oil composition according to claim 8, wherein a content of the molybdenum dialkyldithiocarbamate in the composition is 0.1 to 10 mass % or more.

14. The lubricating oil composition according to claim 8, wherein a content of the molybdenum dialkyldithiocarbamate in the composition is 0.1 to 0.5 mass %.

15. The lubricating oil composition according to claim 8, wherein the content of the organic acid metal salt compound in the composition is 100 to 500 ppm in terms of cobalt concentration.

16. The lubricating oil composition according to claim 8, wherein the content of the organic acid metal salt compound in the composition is 200 to 500 ppm in terms of cobalt concentration.

17. A grease composition comprising a lubricating oil composition not containing ZnDTP but comprising the follow components (a) to (c); (a) a base oil; (b) molybdenum dialkyldithiocarbamate; and (c) an organic acid metal salt compound which is cobalt 2-ethylhexanoate, wherein a content of the organic acid metal salt compound in the composition is 100 to 1000 ppm in terms of cobalt concentration, and a thickener.

Description

DESCRIPTION OF EMBODIMENTS

(1) The base oil as the above component (a) includes, but is not limited to commonly used lubricating base oils such as mineral oils, ether-based synthetic oils, ester-based synthetic oils, and hydrocarbon-based synthetic oils or oil mixtures thereof. Among them, synthetic oils are preferable, hydrocarbon-based synthetic oils are more preferable, and poly α-olefins are particularly preferable.

(2) The kinematic viscosity of the base oil at 40° C. is not particularly limited, but is preferably 5 to 400 mm.sup.2/s, more preferably 5 to 200 mm.sup.2/s, and further preferably 5 to 70 mm.sup.2/s. The kinematic viscosity is preferably in the above ranges because MoDTC can form a film efficiently on the lubricating surface.

(3) The content of the component (a) in the composition of the present invention is generally a major amount which is an amount larger than those of the components (b) and (c), and is preferably 40% by mass or more, more preferably 40 to 99.5% by mass, and most preferably 40 to 90% by mass.

(4) MoDTC as the component (b) is preferably molybdenum dialkyldithiocarbamate represented by following formula (1)
(R.sub.1R.sub.2N—CS—S).sub.2—Mo.sub.2O.sub.mS.sub.n  (1),
where R.sub.1 and R.sub.2 independently represent an alkyl group having 1 to 24 carbon atoms and preferably 2 to 18 carbon atoms, m is 0 to 3, n is 4 to 1, and m+n=4.

(5) The content of MoDTC described above in the composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.1 to 0.5% by mass. These ranges are preferable because it is possible to exhibit a friction reduction effect at an economically rational concentration.

(6) The organic acid metal salt compound, which is the component (c) having a metal of Group 8 of the short periodic table, copper, or bismuth as a central metal, is preferably a compound whose oxidation potential of the central metal (a potential at which, when a valence of the central metal in the organic acid metal salt compound is X, the metal emits electrons from a zero-valent state to change to an X-valent metal cation) is +0.5 V (vs SHE) or less.

(7) The central metal constituting the organic acid metal salt compound is preferably a metal of Group 8 of the short periodic table. The metal of Group 8 is particularly preferably iron (oxidation potential: +0.440 V (vs SHE)), cobalt (oxidation potential: +0.277 V (vs SHE), and nickel (oxidation potential: +0.250 V (vs SHE)). Further, nickel is particularly preferable. Note that the oxidation potentials described herein are values described in Sakichi Goto, edited by the Chemical Society of Japan, “Kinzoku no Kagaku,” p 18-21, Dainippon Tosho Publishing Co., Ltd. (1971) or edited by Electrochemical Society of Japan, “Denki Kagaku Binran.” Sixth Edition. p 92-95. Maruzen Publishing Co., Ltd. (2013).

(8) The organic acid constituting the organic acid metal salt compound can be represented by the following formula (2), and can include aliphatic carboxylic acids, alicyclic carboxylic acids, and aromatic carboxylic acids. In addition, any of monocarboxylic acids, dicarboxylic acids, other polycarboxylic acids, and the like may be used, and saturated or unsaturated carboxylic acids are also used.
R.sub.3(COOH).sub.p  (2)
where R.sub.3 is a saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, or an alicyclic hydrocarbon group or an aromatic hydrocarbon group substituted with at least one chained saturated or unsaturated hydrocarbon group, the alicyclic hydrocarbon group or the aromatic hydrocarbon group having 1 to 30 carbon atoms in total. A saturated or unsaturated aliphatic hydrocarbon group having 1 to 30 carbon atoms is preferable. A linear or branched alkyl group having 1 to 30 carbon atoms is preferable. A branched alkyl group having 1 to 18 carbon atoms is more preferable. A branched alkyl group having 1 to 10 carbon atoms is more preferable. The value p is an integer of 1 to 4, and p is particularly preferably 1.

(9) Specific examples of the component (c) of the present invention include cobalt salts, nickel salts, copper salts, and bismuth salts of the above-described carboxylic acids, and the like. Among them, cobalt 2-ethylhexanoate, nickel 2-ethylhexanoate, copper neodecanoate, and bismuth 2-ethylhexanoate are preferable. Cobalt 2-ethylhexanoate and nickel 2-ethylhexanoate are particularly preferable.

(10) The content of the component (c) in the composition of the present invention is preferably 50 to 5000 ppm, more preferably 50 to 3000 ppm, further preferably 100 to 1000 ppm, and particularly preferably 200 to 500 ppm in terms of central metal element concentration. These ranges make it possible to exhibit a friction reduction effect without inhibiting the reaction on the lubricating surface of MoDTC. In particular, the content is preferably 200 to 500 ppm in the case where the central metal is an element of Group 8, the content is preferably 100 to 250 ppm in the case of copper, and the content is preferably 100 to 250 ppm in the case of bismuth. The concentration of the component (c) in terms of central metal element is preferably lower than the concentration of the component (b) in terms of molybdenum, and when the concentration of the component (c) in terms of central metal element is set to 1, the concentration of the component (b) in terms of molybdenum is 0.1 to 10 and preferably 0.2 to 5. The content of the component (c) and the component (b) is preferably in those ranges because it is possible to exhibit a friction reduction effect without inhibiting the reaction on the lubricating surface of MoDTC.

(11) The lubricating oil composition of the present invention does not contain ZnDTP, and this means that it does not contain such an amount of ZnDTP that causes loss of catalytic activity.

(12) In the lubricating oil composition of the present invention, when necessary, it is possible to appropriately select and further blend a viscosity index improver, an ashless dispersant, an antioxidant, an extreme pressure agent, an anti-wear agent, a metal deactivator, a pour point depressant, an anti-corrosion agent, other friction modifier, or the like. If the lubricating oil composition of the present invention contains optional additives, they are usually used at a proportion of 25% by weight or less in total of MoDTC and these additives excluding the viscosity index improver.

(13) Viscosity index improvers usable include, for example, those of polymethacrylate type, polyisobutylene type, ethylene-propylene copolymer type, styrene-butadiene hydrogenated copolymer type, and the like, and these are usually used at a proportion of 3% by weight to 30% by weight.

(14) Ashless dispersants include, for example, those of polybutenyl succinimide type, polybutenyl succinic acid amide type, benzylamine type, and succinic acid ester type, and these are usually used at a proportion of 0.05% by weight to 7% by weight.

(15) Antioxidants can include, for example, amine-based antioxidants such as alkylated diphenylamines, phenyl-α-naphthylamine, and alkylated phenyl-α-naphthylamines, phenolic antioxidants such as 2,6-di-t-butylphenol and 4,4′-methylenebis-(2,6-di-t-butylphenol), and the like, and these are usually used at a proportion of 0.05% by weight to 5% by weight.

(16) Extreme pressure agents include, for example, dibenzyl sulfide, dibutyl disulfide, and the like, and these are usually used at a proportion of 0.05% by weight to 3% by weight.

(17) Metal deactivators include, for example, benzotriazole, benzotriazole derivatives, thiadiazoles, and the like, and these are usually used at a proportion of 0.01% by weight to 3% by weight.

(18) Pour point depressants include, for example, ethylene-vinyl acetate copolymers, condensates of chlorinated paraffin and naphthalene, condensates of chlorinated paraffin and phenol, polymethactylates, polyalkylstyrenes, and the like, and these are usually used at a proportion of 0.1% by weight to 10% by weight.

(19) Anti-wear agents include, for example, phosphoric acid esters, acidic phosphoric acid esters, phosphorous acid esters, acidic phosphorous acid esters, zinc dialkyl dithiophosphates, sulfur compounds, and the like, and these are usually used at a proportion of 0.01% by weight to 5% by weight.

(20) As other additives, any additives can be selected and used as long as they do not inhibit the action of MoDTC and the organic acid salt metal compound of the present invention.

(21) The lubricating oil composition of the present invention is preferably used by being added to an engine oil. The lubricating oil composition of the present invention can also be applied as it is, or a thickener can be added to form a grease composition. When the lubricating oil composition of the present invention is applied as it is, a coating is formed on a resin surface or a metal surface of a bearing or the like. Thickeners which can be used to form a grease composition include metal soaps such as Li soap, and diurea compounds such as aliphatic diurea, alicyclic diurea, aromatic diurea, or mixtures thereof. Those skilled in the art can appropriately determine the penetration of a grease composition (60-stroke worked penetration measured by JIS K2220 7.) and the proportion of the thickener according to the application site of the grease.

EXAMPLES

(22) Next, the present invention is further specifically described with reference to Examples and Comparative Examples. The conditions and method of measuring the coefficient of friction of the base oils, MoDTC, organometallic compounds, and lubricating oil compositions used in Examples and Comparative Examples are as follows.

(23) [Lubricating Base Oil]

(24) α-olefin oligomer (kinematic viscosity (@ 40° C.) 48.5 mm.sup.2/s) (hereinafter abbreviated as “PAO”)

(25) [MoDTC]

(26) MoDTC: molybdenum dialkyldithiocarbamate (the structure is as in the formula (1))

(27) [Organic Acid Salt Compound]

(28) Ni-OCTOATE (salt whose central metal is Ni and organic acid is 2-ethylhexanoic acid)

(29) Co-OCTOATE (salt whose central metal is Co and organic acid is 2-ethylhexanoic acid)

(30) Cu neodecanoate (salt whose central metal is Cu and organic acid is neodecanoic acid)

(31) Bi-OCTOATE (salt whose central metal is Bi and organic acid is 2-ethylhexanoic acid)

(32) Zn-OCTOATE (salt whose central metal is Zn and organic acid is 2-ethylhexanoic acid)

(33) Mn-OCTOATE (salt whose central metal is Mn and organic acid is 2-ethylhexanoic acid)

(34) Zr-OCTOATE (salt whose central metal is Zr and organic acid is 2-ethylhexanoic acid)

(35) Note that each of the MoDTC concentrations (% by weight) in the tables is 200 ppm in terms of Mo concentration.

(36) [Method of Measuring Coefficient of Friction]

(37) The coefficient of friction was measured under the following conditions using a ball-on-disk tester.

(38) Friction material: steel (SUJ-2)/steel (SUJ-2), φ 8 mm ball/disk

(39) Temperature: 60° C. and 80° C.

(40) Load: 10 N

(41) Speed: 0.5 m/s

(42) Time: 30 min

(43) The average value during the last 5 minutes of the 30 minute measurement was used as the measured value of the coefficient of friction.

Comparative Example 1 and Examples

(44) Comparative Example 1 used PAO as a lubricating base oil, which was blended with 0.4% by weight of MoDTC. In Examples, organic acid metal salt compounds were further blended at the proportions presented in Table 1.

(45) The coefficients of friction of the resulting lubricating oil compositions were measured. Comparative Example 1 exhibited a good coefficient of friction at 80° C., and exhibited a higher value at 60° C. than the coefficient of friction at 80° C. Therefore, it is considered that, in the case of MoDTC alone, a friction reduction effect is exhibited around 80° C. On the other hand, at 80° C. and 60° C., Examples exhibited coefficients of friction similar to the coefficient of friction of Comparative Example 1 at 80° C. From the above, it has been found that, in combination with an organic acid metal salt compound, it is possible to obtain a friction reduction effect even at a lower temperature than the case where MoDTC alone is added to the base oil.

Comparative Examples 2 to 7

(46) PAO was used as a lubricating base oil, which was blended with 0.4% by weight of MoDTC and further with organic acid metal salt compounds in the proportions presented in Table 2.

(47) The coefficients of friction of the resulting lubricating oil compositions were measured. In each case, the coefficient of friction at 60° C. was higher than the coefficient of friction at 80° C. Therefore, it is considered that, as in Comparative Example 1, the lubricating oil compositions of Comparative Examples 2 to 7 exhibit a friction reduction effect around 80° C.

(48) For the metal elements of the organic acid metal salts used in Examples and Comparative Examples 2 to 7, the oxidation potentials (Sakichi Goto, edited by the Chemical Society of Japan, “Kinzoku no Kagaku,” p 18-21, Dainippon Tosho Publishing Co., Ltd. (1971)) and the coefficients of friction of the corresponding metal cations were compared. Then, the lower the oxidation potential, the lower the coefficient of friction at low temperature when combined with MoDTC. From the experimental results of the present inventors, the threshold of the oxidation potential of the metal cation exhibiting the above effect is estimated to be between +0.763 V of Zn-OCTOATE (salt of Zn.sup.2+) and +0.277 V of Co-OCTOATE (salt of Co.sup.2+).

(49) TABLE-US-00001 TABLE 1 Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 PAO Balance Balance Balance Balance Balance Balance Balance MoDTC % by Weight 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Organic Acid Metal Salt Compound Metal Content (ppm) Ni-OCTOATE 500 200 Co-OCTOATE 500 200 Cu Neodecanoate 200 Bi-OCTOATE 200 Oxidation Potential of Organic Acid — +0.250 +0.250 +0.277 +0.277 −0.340 −0.317 Metal Salt Compound (V vs. SHE) Metal Content Ratio — 2.5 1.0 2.5 1.0 1.0 1.0 Mo [ppm]/(Metal Content of Organic Acid Metal Salt) [ppm] Coefficient of 60° C. Δ ◯ ◯ ◯ ◯ ◯ ◯ Friction 80° C. ◯ ◯ ◯ ◯ ◯ ◯ ◯

(50) The coefficient of friction in the table: ◯ means 0.060 or less. Δ means 0.061 to 0.100, and x means 0.101 or more.

(51) The values of the oxidation potentials of the organic acid metal salt compounds were taken from the above-described “Kinzoku no Kagaku” or “Denki Kagaku Binran.”

(52) TABLE-US-00002 TABLE 2 Comp. Comp. Comp. Comp. Comp. Comp. Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 PAO Balance Balance Balance Balance Balance Balance MoDTC % by Weight 0.4 0.4 0.4 0.4 0.4 0.4 Organic Acid Metal Salt Compound Metal Content (ppm) Zn-OCTOATE 500 200 Mn-OCTOATE 500 200 Zr-OCTOATE 500 200 Organic Acid Metal Oxidation Potential of +0.763 +0.763 +1.18 +1.18 +1.58 +1.58 Organic Acid Metal Salt Compound (V vs. SHE) Metal Content Ratio Mo [ppm]/(Metal Content of Organic Acid Metal 2.5 1.0 2.5 1.0 2.5 1.0 Salt) [ppm] Coefficient of 60° C. Δ Δ X Δ X Δ Friction 80° C. ◯ ◯ ◯ ◯ Δ ◯

(53) The coefficient of friction in the table: ◯ means 0.060 or less. Δ means 0.061 to 0.100, and x means 0.101 or more.

(54) The values of the oxidation potentials of the organic acid metal salt compounds were taken from the above-described “Kinzoku no Kagaku” or “Denki Kagaku Binran.”