JP6300684B2 - Lubricating oil composition - Google Patents

Description

  The present invention relates to a lubricating oil composition, and more particularly to a lubricating oil composition that is substantially free of a sulfur-containing metal complex and is more excellent in oxidation stability and low sludge than ever before.

Lubricating oil is used in various applications such as engine oil, drive system oil, turbine oil, hydraulic oil, and grease. In any of these uses, excellent oxidation resistance is required because of contact with peroxy radicals and peroxides, which are active species for oxidative degradation generated by heat, light, and the like. For these reasons, it is essential to add an antioxidant to the lubricating oil in order to prevent oxidative degradation.
Conventionally known as antioxidants for lubricating oils are chain terminators such as aromatic amine compounds and phenol compounds, and peroxide decomposers such as sulfur compounds and molybdenum compounds. In addition, the performance of various antioxidants varies depending on the operating temperature range, and a plurality of antioxidants are used in combination with the expectation of a synergistic effect.
Ashless antioxidants such as aromatic amine compounds and phenolic compounds have the advantage of producing less sludge, but they are self-sacrificing and cannot be used to prevent deterioration of the lubricating oil over a long period of time. was there.
On the other hand, the peroxide resolution of sulfur-containing metal complexes such as zinc dialkyldithiophosphates and molybdenum compounds is known to act catalytically and can prevent oxidative degradation over a long period of time. However, they have problems such as sludge in the process of use and damage of equipment.
The sulfur compound functions as a peroxide decomposing agent in the same manner as the sulfur-containing metal complex. However, benzyl disulfide, which is a typical sulfur-based antioxidant, has problems such as low activity compared to sulfur-containing metal complexes.

JP 2010-242085 A

  An object of the present invention is to provide a lubricating oil composition having both excellent oxidation life and low sludge properties, which cannot be achieved with a combination of a conventional sulfur-based antioxidant and a chain terminator. It is. In particular, it is suitably used as a lubricating oil for machinery that has a low operating temperature and does not lubricate the combustion chamber.

  As a result of intensive studies, the present inventors have found that a lubricating oil composition in which [A] a predetermined amount of a crosslinked sulfurized ester having a specific structure and [B] a chain terminator are blended with a lubricating oil base oil has the purpose. The present invention has been found and achieved.

（式中のＲはヒドロカルビル基を示す。ａ、ｂ、ｃ、ｄはそれぞれ個別に３以上の整数であり、ａとｂの和は８〜１４、ｃとｄの和は７〜１３である。） That is, the present invention provides a lubricating oil composition comprising [A] at least one cyclic sulfurized ester represented by the following general formula (1) or (2) and [B] a chain terminator in a lubricating base oil. The content of the cyclic sulfurized ester represented by the following general formula (1) or (2) is 10 to 400 ppm by mass as the amount of sulfur element based on the lubricating oil composition, and the sulfur-containing metal complex is substantially It is related with the lubricating oil composition characterized by not containing.

(In the formula, R represents a hydrocarbyl group. A, b, c and d are each independently an integer of 3 or more, the sum of a and b is 8 to 14, and the sum of c and d is 7 to 13. .)

The present invention also provides the above lubricating oil composition, wherein the [B] chain terminator is a hindered phenol.
Moreover, this invention is the said lubricating oil composition characterized by the sulfur content of lubricating base oil being 10 mass ppm or less.
Furthermore, the present invention is the above-described lubricating oil composition, which is used as a lubricating oil for machinery that does not lubricate the combustion chamber.

  The lubricating oil composition of the present invention is a lubricating oil composition that has both excellent oxidation life and low sludge properties, and exhibits its effect particularly when the operating temperature is low. Therefore, the operating temperature is low and the combustion chamber is lubricated. It is suitable as a lubricating oil for machinery that does not.

  Hereinafter, the present invention will be described in detail.

  Mineral oil, synthetic oil, and fats and oils are used as the lubricating base oil of the lubricating oil composition of the present invention. These may be a mixture.

  As mineral oil, for example, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, catalytic dewaxing, hydrogenation. Examples thereof include paraffinic mineral oil or naphthenic mineral oil that is refined by appropriately combining one or more purification treatments such as purification, sulfuric acid washing, and clay treatment.

  Synthetic oils include, for example, propylene oligomer, polybutene, polyisobutylene, 1-octene oligomer, 1-decene oligomer, ethylene and propylene co-oligomer, ethylene and 1-octene co-oligomer, and ethylene and 1-decene. Poly α-olefin (PAO) such as co-oligomer or hydride thereof; isoparaffin; alkyl benzene such as monoalkylbenzene, dialkylbenzene, polyalkylbenzene; alkylnaphthalene such as monoalkylnaphthalene, dialkylnaphthalene, polyalkylnaphthalene; dioctyl adipate, dialkyl Dibasic acid esters such as 2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, ditridecyl glutarate; Tribasic acid esters such as limellitic acid; polyol esters such as trimethylolpropane caprylate, trimethylolpropane pelargonate, trimethylolpropane oleate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate; polyethylene glycol, polypropylene glycol Polyglycols such as polyoxyethyleneoxypropylene glycol, polyethylene glycol monoether, polypropylene glycol monoether, polyoxyethyleneoxypropylene glycol monoether, polyethylene glycol diether, polypropylene glycol diether, polyoxyethyleneoxypropylene glycol diether; Monoalkyldiphenyl ether, dialkyldiphenyl Ethers, monoalkyl triphenyl ethers, dialkyl triphenyl ethers, tetraphenyl ethers, monoalkyl tetraphenyl ethers, dialkyl tetraphenyl ethers, phenyl ethers such as pentaphenyl ether; silicone oils; fluoroethers such as perfluoroethers, etc. These can be used alone or in combination of two or more.

  Examples of the fat include beef tallow, lard, soybean oil, rapeseed oil, rice bran oil, coconut oil, palm oil, palm kernel oil, hydrogenated products thereof, or a mixture of two or more of these.

The sulfur content of the lubricating base oil is preferably 10 mass ppm or less, more preferably 5 mass ppm or less, and most preferably 1 mass ppm or less. Oxidation stability can be further improved by making a sulfur content into 10 mass ppm or less.
In addition, the sulfur content as used in the field of this invention means the value measured by ICP.

The total aromatic content of the lubricating base oil is not particularly limited, but is preferably 25% by mass or less, more preferably 15% by mass or less, and more preferably 5% by mass or less from the viewpoint of oxidation stability. More preferably.
The total aromatic content referred to in the present invention is the total aromatic content measured by the Petroleum Institute method JPI-5S-49-97 “Petroleum products—hydrocarbon type test method—high performance liquid chromatograph”. means.

Kinematic viscosity at 40 ° C. of the lubricating base oil is not particularly limited but is preferably 1 to 100 mm ² / s, more preferably 5~80mm ² / s, more preferably 10 to 50 mm ² / s. When the kinematic viscosity at 40 ° C. is less than 1 mm ² / s, the lubricity is lowered, and the working environment is deteriorated due to generation of mist, which is not preferable.
In addition, the kinematic viscosity at 40 ° C. in the present invention refers to a value measured by a capillary viscometer method.

The viscosity index of the lubricating base oil according to the present invention is not particularly limited, but is preferably 100 or more, more preferably 110 or more, and still more preferably 120 or more. On the other hand, it is preferably 200 or less. By setting the viscosity index to 100 or more, the viscosity-temperature characteristics, thermal / oxidation stability, and volatilization prevention properties are improved, the friction coefficient tends to decrease, and the wear prevention properties tend to be improved. Moreover, it exists in the tendency for a low temperature viscosity characteristic to improve because a viscosity index shall be 200 or less.
In addition, the viscosity index as used in the field of this invention means the viscosity index measured based on JISK2283.

  The lubricating oil composition of the present invention contains a cyclic sulfurized ester represented by the following general formula (1) or (2) or a mixture thereof as [A] component.

R in the general formula (1) or (2) represents a hydrocarbyl group.
Although carbon number of a hydrocarbyl group does not have a restriction | limiting in particular, Usually, it is 1-24, Preferably it is 1-3. Specific examples of hydrocarbyl groups include alkyl groups such as methyl, ethyl, propyl, and isopropyl groups; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups; phenyl groups, cresyl groups, and the like. Can be mentioned.
Among these, an alkyl group is preferable from the viewpoint of the adsorptivity of the lubricating surface and oxidation stability, and a methyl group and an ethyl group are particularly preferable.

In the general formula (1) or (2), a, b, c and d are each independently an integer of 3 or more, the sum of a and b is 8 to 14, and the sum of c and d is 7 to 13. is there.
If the sum of a and b is less than 8, the solubility in the base oil is lowered. On the other hand, if it exceeds 14, the storage stability at low temperature is lowered. Further, if the sum of c and d is less than 7, the solubility in the base oil is lowered, and if it exceeds 13, the storage stability at low temperature is lowered.

  The sulfurized ester represented by the general formula (1) or (2) can be obtained as a sulfide of a fatty acid ester having at least two unsaturated bonds in the vicinity of the hydrocarbon chain. Examples of such fatty acid esters include methyl linoleate, ethyl linoleate, methyl eicosadienoate, ethyl eicosadienoate, methyl docosadienoate, and ethyl docosadienoate.

  The method for purifying the sulfurized ester represented by the general formula (1) or (2) after sulfurating the fatty acid ester as described above is not particularly limited, and any method can be used. Examples thereof include extraction by gel chromatography using silica gel.

  Specific examples of the sulfurized ester represented by the general formulas (1) and (2) include 3-nonanoic methyl ester-5-hexyl-thiolane, 3-nonanoic ethyl ester-5-hexyl-thiolane, and 3-nonanoic. Propyl ester-5-hexyl-thiolane, 3-dodecanoic methyl ester-5-propyl-thiolane, 3-dodecanoic ethyl ester-5-propyl-thiolane, 3-dodecanoic propyl ester-5-propyl-thiolane 3-hexanoic methyl ester-5-nonyl-thiolane, 3-hexanoic ethyl ester-5-nonyl-thiolane, 3-hexanoic propyl ester-5-nonyl-thiolane, 3-nonanoic methyl ester- 5-hexyl-1,2-dithiolane, 3-nonanoic eth Ester-5-hexyl-1,2-dithiolane, 3-nonanoic propyl ester-5-hexyl-1,2-dithiolane, 3-dodecanoic methyl ester-5-propyl-1,2-dithiolane, 3-dodeca Neukyl ethyl ester-5-propyl-1,2-dithiolane, 3-dodecanoic propyl ester-5-propyl-1,2-dithiolane, 3-hexanoic methyl ester-5-nonyl-1,2-dithiolane 3-hexanoic ethyl ester-5-nonyl-1,2-dithiolane, 3-hexanoic propyl ester-5-nonyl-1,2-dithiolane, and the like.

  The sulfurized esters represented by the general formulas (1) and (2) may be used alone or as a mixture. The mixing ratio in the case of mixing and using is arbitrary, but it is preferable to use it as a mixture having a mass ratio of 1: 2 to 2: 1.

  The content of the sulfurized ester represented by the general formulas (1) and (2) is 10 to 400 ppm by mass, preferably 15 to 300 ppm by mass, based on the total amount of the composition as the amount of sulfur element, and 20 to 200 mass. More preferred is ppm. If the amount is less than 10 ppm by mass, a sufficient effect cannot be obtained. If the amount exceeds 400 ppm by mass, the oxidation stability of the lubricating oil composition tends to decrease.

  The lubricating oil composition of the present invention contains a chain terminator as the [B] component.

  Specific examples of the chain terminator include hindered phenol compounds and aromatic amine compounds commonly used as antioxidants. Among these, hindered phenol is preferable.

Specific examples of the hindered phenol compound include 4,4′-methylenebis (2,6-di-tert-butylphenol) and 4,4′-bis (2,6-di-tert-butylphenol). 4,4′-bis (2-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6- tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-isopropylidenebis (2,6-di-tert-butylphenol), 2,2′-methylenebis ( 4-methyl-6-nonylphenol), 2,2′-isobutylidenebis (4,6-dimethylphenol), 2,2′-methylenebis (4-methyl) Til-6-cyclohexylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-α-dimethylamino-p-cresol, 2,6-di-tert-butyl-4 (N, N′-dimethylaminomethylphenol), 4,4′-thiobis (2-methyl) -6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3-methyl- 4-hydroxy-5-tert-butylbenzyl) sulfide, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide 2,2′-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate, tridecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ], Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and mixtures thereof.
Of these, phenolic compounds having a molecular weight of 240 or more are more preferably used because of their high decomposition temperature and their antioxidant effect even under higher temperature conditions.

  Specific examples of the aromatic amine compound include phenyl-α-naphthylamine, alkylphenyl-α-naphthylamine, dialkyldiphenylamine, N, N′-diphenyl-p-phenylenediamine, and mixtures thereof. Here, examples of the alkyl group include linear or branched alkyl groups having 1 to 20 carbon atoms.

The content of the chain terminator is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and still more preferably 0.05% by mass based on the total amount of the composition. It is 1-1 mass%.
When the content of the chain terminator is 0.01% by mass or more, sufficient antioxidant properties are obtained, and when the content is 10% by mass or less, sufficient solubility in the base oil is obtained.

  The lubricating oil composition of the present invention is characterized by containing substantially no sulfur-containing metal complex. The lubricating oil composition of the present invention realizes low sludge properties by substantially not containing a sulfur-containing metal complex.

  The sulfur-containing metal complex broadly means a general complex of an organic compound containing a sulfur atom in the structure and a metal element. Examples of the sulfur-containing metal complex include zinc dithiophosphate compounds, zinc dithiocarbamate compounds, molybdenum dithiophosphate compounds, and molybdenum dithiocarbamate compounds.

［式（３）〜（６）中、Ｒ^１〜Ｒ^１６は同一でも異なっていてもよく、それぞれ炭素数１以上２０以下の炭化水素基を表し、Ｘ^１及びＸ^２はそれぞれ酸素原子又は硫黄原子を表す。］ A zinc dithiophosphate compound, a zinc dithiocarbamate compound, a molybdenum dithiophosphate compound and a molybdenum dithiocarbamate compound are compounds represented by the following general formulas (3) to (6), respectively.

[In the formulas (3) to (6), R ^{1 to} R ¹⁶ may be the same or different and each represents a hydrocarbon group having 1 to 20 carbon atoms, and X ¹ and X ² are each an oxygen atom or sulfur. Represents an atom. ]

In the present invention, “substantially does not contain a sulfur-containing metal complex” means that it contains no sulfur-containing metal complex or contains a very small amount so that the influence can be ignored even if it is contained. Say not.
More specifically, the content of the sulfur-containing metal complex is preferably 50 mass ppm or less, more preferably 20 mass ppm or less, and most preferably 0 mass as the metal element amount based on the total amount of the composition. ppm.

According to the lubricating oil composition of the present invention, a lubricating oil composition having excellent oxidation stability and low sludge property can be obtained by the above-described configuration. However, the lubricating oil composition has the performance required for the purpose of further enhancing its performance or as a lubricating oil composition. Further, for the purpose of imparting, known lubricating oil additives can be added.
Examples of such additives include metal detergents such as calcium sulfonate; wetting agents such as diethylene glycol monoalkyl ether; film forming agents such as acrylic polymer, paraffin wax, microwax, slack wax, and polyolefin wax; fatty acid amine salts and the like. Water replacement agent; solid lubricant such as graphite, graphite fluoride, molybdenum disulfide, boron nitride, polyethylene powder; amine, alkanolamine, amide, carboxylic acid, carboxylate, sulfonate, phosphoric acid, phosphate Corrosion inhibitors such as partial esters of polyhydric alcohols; metal deactivators such as benzotriazole and thiadiazole; antifoaming agents such as methyl silicone, fluorosilicone and polyacrylate; Ashless dispersants such as Minoamido; and the like. The content when these known additives are used in combination is not particularly limited, but the amount is such that the total content of these known additives is 0.1 to 10% by mass based on the total amount of the lubricating oil composition. It is common to add.

The kinematic viscosity of the lubricating oil composition of the present invention is not particularly limited, but the kinematic viscosity at 40 ° C. is preferably 100 mm ² / s or less, and 80 mm ² / s from the viewpoint of easy supply to the lubrication site. Or less, more preferably 50 mm ² / s or less.
Meanwhile, the kinematic viscosity at 40 ° C., preferably at ^{1 mm} 2 / s or more, more preferably ^{2 mm} 2 / s or more, and still more preferably ^{3 mm} 2 / s or more.

  Since the lubricating oil composition of the present invention can achieve both excellent oxidation life and low sludge properties, it can be suitably used in a wide range of applications. In particular, when the use temperature is low, such as 120 ° C. or less, the effect is more exhibited, and therefore, it can be suitably used as a machine lubricant that does not lubricate the combustion chamber.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
The base oils and additives used in the examples and comparative examples are as follows.

[Lubricant base oil]
Base oil-1; highly refined mineral oil base oil (total aromatic content: 0.3 mass%, sulfur content: 0 mass ppm, 40 ° C. kinematic viscosity: 35 mm ² / s, viscosity index: 120)

[Sulfur-containing compounds]
([A] component);
A-1: a mixture of cyclic sulfurized esters represented by the general formulas (1) and (2) in a mass ratio of 1: 1 (R: methyl group, a = 5, b = 7, c = 4, d = 7, Sulfur content: 13% by mass)
A-2: a mixture of cyclic sulfurized esters represented by the general formulas (1) and (2) in a mass ratio of 1: 1 (R: ethyl group, a = 5, b = 7, c = 4, d = 7, Sulfur content: 12.5% by mass)
A-1 and A-2 are fractions obtained by sulfurizing methyl linoleate or ethyl linoleate to obtain a sulfurized ester, and extracting the sulfurized ester by gel chromatography using silica gel. A-1, A-2 obtained was identified by ^C 13 -NMR, FD-MS and elemental analysis.

Ｓ−２；ジベンジルジスルフィド（東京化成工業株式会社製、硫黄量：２６質量％） ([A] sulfur-containing compound other than component);
S-1: Mixture of sulfurized methyl oleate represented by the following formula (l + m = 14, n + o = 14, X = 1 to 7, sulfur content: 18% by mass)

S-2: Dibenzyl disulfide (manufactured by Tokyo Chemical Industry Co., Ltd., sulfur content: 26% by mass)

[[B] Chain terminator]
B-1: Phenolic antioxidant (di-tert-butyl-p-cresol)
B-2: Phenolic antioxidant (trade name “L135” manufactured by BASF)

(Examples 1-5 and Comparative Examples 1-5)
Table 1 shows the blending amounts and performances of various lubricating base oils and additives. The blending amount (mass%) of the base oil and the adding amount (mass%) of each additive are based on the total amount of the lubricating oil composition.
About each obtained composition, the oxidation stability and sludge prevention performance were evaluated by the ALCOA test shown below. This test is known to have a good correlation with the turbine oil oxidation stability test (abbreviated as TOST) defined in ASTM-D943.

(ALCOA test)
Collect 13 ml of test oil in a 115 ml flask and put 5 pieces of # 240 polished copper wire (1.6 mmφ × 5 cm) as a catalyst. Next, the inside of the flask is replaced with oxygen gas and quickly sealed with a mercury manometer. Thereafter, the flask is immersed in an oil bath at 115 ° C. and left for 1 hour. Read the differential pressure of the manometer at this time and record it as the test time 0h. This value was about 200 mmHg common to all the test oils used in this experiment. Thereafter, the differential pressure was measured at regular intervals, and the time when the drop in oxygen pressure reached 50 mmHg or more was taken as the oxidation life of the test oil. Moreover, the sample oil after a test was visually observed and the presence or absence of insoluble matter (sludge) was confirmed.

Claims (4)

A lubricating oil composition comprising [A] at least one cyclic sulfurized ester represented by the following general formula (1) or (2) and [B] a chain terminator in a lubricating base oil. The content of the cyclic sulfide ester represented by the formula (1) or (2) is 10 to 400 ppm by mass as the amount of sulfur element on the basis of the lubricating oil composition, and contains substantially no sulfur-containing metal complex. A characteristic lubricating oil composition.

(In the formula, R represents a hydrocarbyl group. A, b, c and d are each independently an integer of 3 or more, the sum of a and b is 8 to 14, and the sum of c and d is 7 to 13. .)   [B] The lubricating oil composition according to claim 1, wherein the chain terminator is a hindered phenol.   The lubricating oil composition according to claim 1 or 2, wherein the sulfur content of the lubricating base oil is 10 ppm by mass or less.   The lubricating oil composition according to any one of claims 1 to 3, wherein the lubricating oil composition is used as a lubricating oil for machinery that does not lubricate the combustion chamber.