Patent Application
20100035779
The present invention relates to a grease and, more specifically, to a grease which excels in both low-temperature performance and high-temperature performance, which has low oil separation tendency even under high centrifugal force and which is particularly suited for use in a rotational transmission device having a built-in one-way clutch.
Greases which permit easier handling as compared with lubricating oils are widely used for lubricating various lubrication sites of automobiles and various industrial machines.
There are a number of kinds of greases. For example, JIS (Table 1 of JIS K2220) refers to greases for use in various applications and specifies properties and performance required in respective applications. For example, “grease class 3 for ball or roller bearing” is defined as being applicable over a wide-temperature range, excellent in low-temperature performance and in heat resistance and usable for ball or roller bearings in a temperature range of −30 to 130° C..
In recent years, mechanical parts of automobiles and various other industrial machines have been designed to be operable in a wider temperature range and under more severe lubrication conditions than before. Additionally, as a result of development of new types of machines and mechanical parts, not only operability in a wider temperature range and under more severe lubrication conditions but also performance specific to such machines is now often required.
For example, in recent years, for the transmission of a driving force in a specific direction only, a rotational transmission device with a built-in one-way clutch has been used in automobile auxiliaries such as an alternator, auxiliary driving device and engine crankshaft, for example. The rotational transmission device with a built-in one-way clutch is a device which includes an inner-diameter-side member; a cylindrical, outer-diameter-side member concentrically located around the inner-diameter-side member; ball or roller bearings located between the outer surface of the inner-diameter-side member and the inner surface of the outer-diameter-side member for supporting the inner-diameter-side member and the outer-diameter-side member while permitting relative rotation therebetween; and a one-way clutch adapted for transmitting only such a rotational force that rotates one of the outer-diameter-side member and the inner-diameter-side member relative to the other in a specified direction.
Such an alternator and the like now progress in performance and output and are also used in a wide area including cold climate areas. As a consequence, the conditions under which the rotational transmission device with a built-in one-way clutch is used become severe. Namely, the rotational transmission device is required to operate at a higher revolution speed and a higher load and to achieve a desired performance under an extremely low temperature so as to withstand use in cold climate areas. In this circumstance, a grease used in such a rotational transmission device with a built-in one-way clutch operated under severe conditions is desired to produce a high performance and to satisfy the following characteristics: (i) The grease must provide satisfactory clutch engagement property (intermeshing ability) at low temperatures. When an engine is started in an extremely cold area in winter, satisfactory clutch engagement property (intermeshing ability) is demanded in order to achieve smooth operation.
It is known that the grease performance at low temperatures may be improved by using a low viscosity base oil. A grease using a low viscosity base oil, however, cannot achieve a good performance at high temperatures, because the base oil is apt to vaporize and to cause oil separation. When, on the other hand, a high viscosity base oil is used, the grease performance at low temperatures is deteriorated though the grease performance at high temperatures is improved.
Namely, the good clutch engagement property as described in (i) above and the long life of bearings in a test at high temperatures as described in (ii) above are generally opposing properties. Thus, when one of the two properties is improved, the other property is deteriorated. It is, therefore, difficult to improve both properties at the same time. Also, to reduce oil separation under a high centrifugal force as described in (iii) above and to improve performance at low temperatures as described in (i) above are also opposing properties.
As conventional greases for use in such a rotational transmission device with a built-in one-way clutch, there are disclosed a grease in which an ether-based base oil such as an alkyl diphenyl ether is used (see, for example, Patent Documents 1 and 2), a grease in which a polyol ester having a kinematic viscosity at 40° C. of 20 mm2/s or less is used (see, for example, Patent Document 3), a grease in which a thickener composed of a diurea compound and a mineral oil, a poly-α-olefin oil or a polyol ester oil is used (see, for example, Patent Document 4), and a grease in which a urea thickener is compounded into an ester-based or synthetic oil-based base oil having a pressure viscosity coefficient of 12 Pa−1 or more (see, for example, Patent Document 5).
The grease using an alkyl diphenyl ether is not satisfactory with respect to low temperature properties, i.e. clutch engagement property at low temperatures. The grease using a base oil containing a polyol ester is unsatisfactory with respect to high temperature property, i.e. the results of a bearing life test at high temperatures are unsatisfactory. Thus, the above two greases cannot satisfy the low temperature performance and high temperature performance at the same time. The other greases using a mineral oil or a poly-α-olefin oil have similar problems. Accordingly, there is a room for further improving the grease.
[Patent Document 1] Japanese Unexamined Patent Application Publication No. 2006-162032
[Patent Document 2] Japanese Unexamined Patent Application Publication No. H11-82688
[Patent Document 3] Japanese Unexamined Patent Application Publication No. 2006-161827
[Patent Document 4] Japanese Unexamined Patent Application Publication No. 2006-132619
[Patent Document 5] Japanese Unexamined Patent Application Publication No. 2000-234638
Under the above-mentioned circumstance, the present invention has as its object the provision of a grease which excels in both low-temperature performance and high-temperature performance, which has reduced oil separation even under high centrifugal force (acceleration) and which, when used in a rotational transmission device having a built-in one-way clutch, can provide satisfactory clutch engagement property (intermeshing ability) at low temperatures and a prolonged bearing life at high temperatures and is less apt to cause oil separation under high centrifugal force.
The present inventors have made an earnest study with a view toward developing a lubricant having the above desirable properties and, as a result, have found that the above problems can be solved by using a grease containing as a base oil a diester of a dicarboxylic acid having a total carbon number in a specific range. The present invention has been completed based on the above finding.
That is, the present invention provides the following greases:
R1OOC—(R2)n—COOR3 (I)
wherein R1 and R3 each independently represent a C4 to C20 monovalent aliphatic hydrocarbon group, R2 represents a C1 to C20 divalent hydrocarbon group and n is 0 or 1.
R4—NHCONH—R5—NHCONH—R6 (V)
wherein R4 and R6 each independently represent a C6 to C14 monovalent chain hydrocarbon group, a C6 to C12 monovalent alicyclic hydrocarbon group or a C6 to C12 monovalent aromatic hydrocarbon group, and R5 represents a C6 to C15 divalent aromatic hydrocarbon group.
[(X+Y)/(X+Y+Z)]×100≧90 (a)
X/Y=50/50 to 0/100 (b)
wherein X is a content (mole %) of the chain hydrocarbon groups, Y is a content (mole %) of the alicyclic hydrocarbon groups and Z is a content (mole %) of the aromatic hydrocarbon groups in the groups R4 and R6.
According to the present invention, there can be provided a grease which excels in both low-temperature performance and high-temperature performance, which has low oil separation tendency even under high centrifugal force (acceleration) and which, when used in a rotational transmission device having a built-in one-way clutch, can provide satisfactory clutch engagement property (intermeshing ability) at low temperatures and a prolonged bearing life at high temperatures and is less apt to cause oil separation under high centrifugal force.
A grease of the present invention is characterized by using a base oil containing at least 50% by mass of a diester compound which has a total carbon number of 28 to 40 and which is represented by the general formula (I):
R1OOC—(R2)n—COOR3 (I)
wherein R1 and R3each independently represent a C4 to C20 monovalent aliphatic hydrocarbon group, R2 represents a C1 to C20 divalent hydrocarbon group and n is 0 or 1.
As the C1 to C20 divalent hydrocarbon group represented by R2 in the above general formula (I), there may be mentioned a straight chained or branched C1 to C20 alkylene group, a straight chained or branched C2 to C20 alkenylene group, a divalent C5 to C20 alicyclic structure-containing group, and a divalent C6 to C20 aromatic ring structure-containing group.
A dicarboxylic acid from which the above diester compound is derived may be represented by the following general formula (II):
HOOC—(R2)n—COOH (II)
wherein R2 and n are as defined above. When n is 0, the dicarboxylic acid is oxalic acid. As the dicarboxylic acid in which n is 1, there may be mentioned the following compounds.
Examples of the dicarboxylic acid of the above formula in which R2 represents a straight chained or branched C1 to C20 alkylene group include malonic acid, succinic acid, 2-methylsuccinic acid, glutaric acid, adipic acid, various heptanedioic acids such as pimelic acid, various octanedioic acids such as suberic acid, various nonanedioic acids such as azelaic acid, various decanedioic acids such as sebacic acid, various undecanedioic acids, various dodecanedioic acids, various tridecanedioic acid, various tetradecanedioic acids, various pentadecanedioic acids, various hexadecanedioic acids, various heptadecanedioic acids, various octadecanedioic acids, various eicosanedioic acids and various docosanedioic acids.
Examples of the dicarboxylic acid of the above formula in which R2 represents a straight chained or branched C2 to C20 alkenylene group include maleic acid, fumaric acid, itaconic acid, citraconic acid (cis-methylbutenedioic acid), mesaconic acid (trans-methylbutenedioic acid), various hexenedioic acid, various octenedioic acid, various decenedioic acid, various dodecenedioic acid, various tetradecenedioic acids, various hexadecenedioic acids, various octadecenedioic acid, various eicosenedioic acids and various docosenedioic acids.
Examples of the dicarboxylic acid of the above formula in which R2 represents a divalent C5 to C20 alicyclic structure-containing group include various cyclopentane dicarboxylic acids, various cyclopentene dicarboxylic acids, various cyclohexane dicarboxylic acids, various cyclohexene dicarboxylic acids, various tetralin dicarboxylic acids and various decalin dicarboxylic acids. These alicyclic structure-containing dicarboxylic acids may contain a suitable substituent or substituents such as alkyl groups on their rings.
Examples of the dicarboxylic acid of the above formula in which R2 represents a divalent C6 to C20 aromatic structure-containing group include phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid. These aromatic ring structure-containing dicarboxylic acids may contain a suitable substituent or substituents such as alkyl groups on their rings.
In the present invention, it is preferred that n be 1 and R2 be a divalent C3 to C15 hydrocarbon group in the above general formulas (I) and (II).
As the monovalent C4 to C20 aliphatic hydrocarbon group represented by R1 and R3 in the above general formula (I), there may be mentioned a straight chained or branched alkyl group, a straight chained or branched alkenyl group or an alicyclic structure-containing group. The carbon number of the monovalent aliphatic hydrocarbon group is determined in view of the carbon number of the group R2 so that a total carbon number of the diester compound falls within a range of 28 to 40.
When n is 1 and R2 is a divalent C3 to C15 hydrocarbon group as described above, it is preferred, for reasons of easiness of production, that R1 and R3 be the same with each other and each represent a monovalent C6 to C17 aliphatic hydrocarbon group and that a total carbon number of the diester compound be within a range of 28 to 40. It is more preferred that R1 and R3 be the same with each other and each represent a monovalent C6 to C14 aliphatic hydrocarbon group and that a total carbon number of the diester compound be within a range of 28 to 34. It is still more preferred that R1 and R3 be the same with each other and each represent a monovalent C7 to C14 aliphatic hydrocarbon group and that a total carbon number of the diester compound be within a range of 30 to 34. In this case it is particularly preferred that a total carbon number of the diester compound be 30.
Alcohols from which the above diester compound is derived are represented by the following general formulas (III) and (IV):
R1—OH (III)
R3—OH (IV)
wherein R1 and R3 are as defined above. As the alcohols of the above formulas in which R1 and R3 are each a straight chained or branched alkyl group, there may be mentioned various butyl alcohols, various pentyl alcohols, various hexyl alcohols, various octyl alcohols, various nonyl alcohols, various decyl alcohols, various dodecyl alcohols, various tetradecyl alcohols and various hexadecyl alcohols.
As the alcohols of the above formulas in which R1 and R3 are each a straight chained or branched alkenyl group, there may be mentioned various butenyl alcohols, various hexenyl alcohols, various octenyl alcohols, various decenyl alcohols, various dodecenyl alcohols, various tetradecenyl alcohols and various hexadecenyl alcohols.
As the alcohols of the above formulas in which R1 and R3 are each an alicyclic structure-containing group, there may be mentioned cyclopentyl alcohol, cyclopentanemethanol, cyclopentenyl alcohol, cyclopentenemethanol, cyclohexyl alcohol, cyclohexanemethanol, cyclohexenyl alcohol and cyclohexenemethanol. These alicyclic structure-containing alcohols may contain a suitable substituent or substituents such as alkyl groups on their rings.
In the present invention, it is preferred that R1 and R3 be a branched, monovalent aliphatic hydrocarbon group. In this case, alicyclic structure-containing groups are intended to be comprised by the branched groups.
As the branched, monovalent aliphatic hydrocarbon group, a branched alkyl group is preferred. Specific examples of the branched alkyl group include an isopentyl group, a tert-pentyl group, an isohexyl group, an isooctyl group, a 2-ethylhexyl group, a 2-propylheptyl group, a 2-butyloctyl group, a 3,5,5-trimethylhexyl group, an isononyl group, a 3,7-dimethyloctyl group, a 2-pentylnonyl group and a 2-hexyldecyl group.
Among alcohols represented by the above general formulas (III) and (IV), a branched alcohol may be produced, for example, by Guerbet reaction in which a primary alcohol is subjected to bimolecular condensation at a high temperature and a high pressure, by an oxo synthesis method or by dimerization or oligomerization of an α-olefin.
Specific examples of the diester compound represented by the above general formula (I) include di-2-butyloctyl adipate, diisotridecyl adipate, di-2-pentylnonyl adipate; diisodecyl pimelate, di-2-butyloctyl pimelate; diisodecyl suberate, di-2-propylheptyl suberate, di-3,7-dimethyloctyl suberate, di-2-butyloctyl suberate; diisodecyl azelate, di-2-propylheptyl azelate, di-3,7-dimethyloctyl azelate, di-2-butyloctyl azelate; diisononyl sebacate, di-3,5,5-trimethylhexyl sebacate, diisodecyl sebacate, di-2-propylheptyl sebacate, di-3,7-dimethyloctyl sebacate, di-2-butyloctyl sebacate; di-2-ethylhexyl dodecanedioate, diisooctyl dodecanedioate, diisononyl dodecanedioate, di-3,5,5-trimethylhexyl dodecanedioate, diisodecyl dodecanedioate, di-3,7-dimethyloctyl dodecanedioate; diisooctyl tetradecanedioate, di-2-ethylhexyl tetradecanedioate, diisononyl tetradecanedioate, di-3,5,5-trimethylhexyl tetradecanedioate, diisodecyl tetradecanedioate, di-3,7-dimethyloctyl tetradecanedioate; diisodecyl cyclohexane-1,2-dicarboxylate, di-2-propylheptyl cyclohexane-1,2-dicarboxylate, di-3,7-dimethyloctyl cyclohexane-1,2-dicarboxylate, di-2-butyloctyl cyclohexane-1,2-dicarboxylate; various dialkyl esters obtainable by replacing the cyclohexane-1,2-dicarboxylic acid moiety of the above-described dialkyl cyclohexane-1,2-dicarboxylates by a cyclohexane-1,3-dicarboxylic acid moiety or a cyclohexane-1,4-dicarboxylic acid moiety; diisodecyl phthalate, di-2-propylheptyl phthalate, di-3,7-dimethyloctyl phthalate, di-2-butyloctyl phthalate; and various dialkyl esters obtainable by replacing the phthalic acid moiety of the above-described dialkyl phthalates by an isophthalic acid moiety or a terephthalic acid moiety.
There is no specific restriction on a method for preparing the diester compounds represented by the above general formula (I). The desired diester compound may be obtained by subjecting the above-described dicarboxylic acids and alcohols to esterification by any conventionally known method.
The above-described diester compounds may be used singly or in combination of two or more thereof. It is essential that the diester compound should be contained in the base oil in an amount of 50% by mass or more. When the content of the diester compound in the base oil is 50% by mass or more, it is possible to obtain a grease which satisfies properties required for use in various applications, especially a grease for use in a rotational transmission device having a built-in one-way clutch. The content is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more.
The grease of the present invention may contain other base oil, if desired, in an amount of 50% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, as long as the effect of the present invention is not adversely affected.
As the “other base oil,” there may be mentioned, for example, alicyclic hydrocarbon compounds, mineral oils and various synthetic oils.
Examples of the alicyclic hydrocarbon compounds include alkane derivatives having two or more cyclohexane rings, such as 2,4-dicylohexyl-2-methylpentane and 2,4-dicyclohexylpentane; alkane derivatives having one or more decalin rings and one or more cyclohexyl rings, such as 1-cyclohexyl-1-decalylethane; and alicyclic compounds having two or more bicyclo[2.2.1]heptane rings, bicyclo[3.2.1]octane rings, bicyclo[2.2.2]octane rings and/or bicyclo[3.2.0]octane rings, such as endo-2-methyl-exo-3-methyl-exo-2-[(exo-3-methylbicyclo[2.2.1]hepto-exo-2-yl)methyl]-bicyclo[2.2.1]heptane.
Examples of the mineral oil include paraffinic mineral oils and naphthenic mineral oil. Examples of the synthetic oils include poly-α-olefins such as 1-decene oligomers, polybutenes, alkyl benzenes, alkyl naphthalenes and polyalkylene glycols.
In the present invention, the base oil may contain a viscosity increasing agent. The viscosity increasing agent is used, if necessary, to increase the viscosity of the base oil and to adjust the kinematic viscosity thereof to a proper value.
Specific examples of the viscosity increasing agent include polybutene, polyisoprene, polymethacrylate (PMA), an olefin copolymer (OCP), polyalkylstyrene (PAS) and a styrene-diene copolymer (SCP). It is particularly preferable to use at least one selected from polybutene, polyisobutyrene, a styrene-isoprene copolymer, an ethylene-α-olefin copolymer (all of which have a number average molecular weight of 800 to 10,000, more preferably 1,000 to 5,000) and polymethacrylate which has a weight average molecular weight of 10,000 to 1,000,000, preferably 100,000 to 800,000. The compounding amount of the viscosity increasing agent is generally about 0.01 to 20% by mass, in terms of the amount of resin, based on the weight of the composition. The compounding amount is suitably selected so that the viscosity of an oil component of the grease (which will be described hereinbelow) has a desired viscosity value.
It is preferred that a kinematic viscosity at 40° C. of an oil component of the grease be adjusted. The term “oil component” as used herein is intended to refer to a component remaining after removing a thickener from the grease. More specifically, the oil component is a mixture of the above-described base oil, the above-described viscosity increasing agent and various additives which will be described hereinafter. Namely, when neither the viscosity increasing agent nor additives are compounded, the oil component is the base oil only. When the base oil and viscosity increasing agent are used without compounding additives, then a mixture of the base oil and viscosity increasing agent is the oil component. When the base oil is used together with the viscosity increasing agent and additives, a mixture of them is the oil component.
The oil component may be obtained as a separated matter by centrifuging the grease.
It is preferred that the oil component of the grease of the present invention have a kinematic viscosity at 40° C. of 15 to 150 mm2/s, more preferably 20 to 90 mm2/s, still more preferably 30 to 60 mm2/s. When the kinematic viscosity at 40° C. of the oil component is 15 mm2/s or more, oil separation of the grease may be suppressed. When the kinematic viscosity at 40° C. of the oil component is 150 mm2/s or less, the properties of the grease at low temperatures may be maintained in good conditions.
The grease of the present invention may be obtained by compounding a thickener into a base oil containing at least 50% by mass of a diester compound having a total carbon number of 28 to 40 and represented by the above general formula (I).
The thickener used in the present invention is not specifically restricted. Either a soap thickener or a non-soap thickener may be used. Preferably used is a thickener which can provide a grease having a dropping point of 230° C. or higher. When the grease has a dropping point of 230° C. or higher, a possibility of causing problems in relation to lubrication such as softening at high temperatures and resulting leakage or seizing may be suppressed.
As the soap thickener, there may be mentioned a metal soap obtained by saponifying a carboxylic acid or its ester with a metal hydroxide such as an alkali metal hydroxide or an alkaline earth metal hydroxide.
Examples of the metal include sodium, calcium, lithium and aluminum. Examples of the carboxylic acid include crude fatty acids obtained by hydrolyzing fats and oils, followed by removal of glycerin, monocarboxylic acids such as stearic acid, monohydroxycarboxylic acids such as 12-hydroxystearic acid, dibasic carboxylic acids such as azelaic acid, and aromatic carboxylic acids such as terephthalic acid, salicylic acid and benzoic acid. These soap thickeners may be used singly or in combination of two or more thereof.
Preferred example of the soap thickener is a lithium 12-hydroxystearate. When compounding a soap thickener into a base oil, it is possible to add a carboxylic acid and the above-mentioned metal hydroxide into the base oil to perform saponification thereof in the base oil.
As another type of the soap thickener, there may be mentioned various complex soaps. Examples of the complex soap include a lithium complex soap, an aluminum complex soap and a calcium complex soap.
The lithium complex soap, which is a lithium-based complex soap, may be obtained by reacting a fatty acid, such as stearic acid, oleic acid or palmitic acid, and/or a C12 to C24 hydroxy fatty acid having at least one hydroxyl group with a lithium compound, such as lithium hydroxide, together with an aromatic carboxylic acid and/or C2 to C12 (more preferably C4 to C9) aliphatic dicarboxylic acid. Such a lithium complex soap is a more preferable thickener because of its superior heat resistance as compared with a lithium soap.
The C12 to C24 hydroxy fatty acid is not specifically limited and may be, for example, 12-hydroxystearic acid, 12-hydroxylauric acid or 16-hydroxypalmitic acid. Among these, 12-hydroxystearic acid is particularly preferred.
As the aromatic carboxylic acid, there may be, for example, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimelitic acid, pyromelitic acid, salicylic acid and p-hydroxybenzoic acid.
The C2 to C12 aliphatic dicarboxylic acid is not specifically limited and may be, for example, azelaic acid, sebacic acid, oxalic acid, malonic acid, succinic acid, adipic acid, pimelic acid, suberic acid, undecanedioic acid and dodecanedioic acid. Above all, azelaic acid is preferred.
It is preferred that the aromatic carboxylic acid and/or C2 to C12 aliphatic dicarboxylic acid be present in an amount of 20 to 90% by mass based on a total mass of the fatty acid and/or C12 to C24 hydroxy fatty acid having at least one hydroxyl group and the aromatic carboxylic acid and/or C2 to C12 aliphatic dicarboxylic acid. When the amount is within the range of 20 to 90% by mass, a thickener having good thermal stability may be obtained and a grease having a long service life at high temperatures may be advantageously obtained.
As a non-soap thickener, a urea compound or bentonite treated with an organic compound may be used.
As the urea compound used as the thickener, there may be used any urea compound which has been hitherto utilized as a urea thickener. Examples of the urea compound include a diurea compound, a triurea compound, a tetraurea compound and a urea-urethane compound.
Because the urea compound has excellent heat resistance and water resistance and is particularly excellent in stability at high temperatures, it is suitably used in a high temperature environment.
Of the above-described various thickeners, lithium soap thickeners, preferably lithium complex soaps, and urea thickeners are suitably used in the present invention. Because of excellent performance, the urea thickeners are particularly preferred. Of the urea thickeners, diurea compounds are particularly preferred.
As the diurea compound, there may be mentioned, for example, a compound represented by the following general formula (V):
R4NHCONHR5NHCONHR6 (V)
wherein R4 and R6 each independently represent a monovalent C6 to C24 chained hydrocarbon group, a monovalent C6 to C12 alicyclic hydrocarbon group or a monovalent C6 to C12 aromatic hydrocarbon group and R5 represents a divalent C6 to C15 aromatic hydrocarbon group.
As the divalent C6 to C15 aromatic hydrocarbon group represented by R5 of the above general formula (V), there may be mentioned a phenylene group, a diphenylmethane group and a tolylene group.
The monovalent C6 to C24 chain hydrocarbon group represented by R4 and R6 of the above general formula (V) maybe a straight chained or branched, saturated or unsaturated hydrocarbon group. Thus, as the monovalent C6 to C24 chain hydrocarbon group, there may be mentioned straight chained and branched chained hydrocarbon groups such as various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, various octadecenyl groups, various nonadecyl groups, various eicodecyl groups. Of these hydrocarbons, C13 to C20 straight chained or branched, saturated or unsaturated hydrocarbon groups are preferred. Particularly preferred are C16 to C18 chain hydrocarbon groups such as various hexadecyl groups, various heptadecyl groups, various octadecyl groups and various octadecenyl groups.
The monovalent C6 to C12 alicyclic hydrocarbon group represented by R4 and R6 of the above general formula (V) may be a cyclohexyl group or a C7 to C12 alkyl-substituted cyclohexyl group. Thus, the monovalent C6 to C12 alicyclic hydrocarbon group may be, for example, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, an ethylcyclohexyl group, a diethylcyclohexyl group, a propylcyclohexyl group, an isopropylcyclohexyl group, a 1-methylpropylcyclohexyl group, a butylcyclohexyl group, an amylcyclohexyl group, an amylmethylcylohexyl group or a hexylcyclohexyl group. Above all, a cyclohexyl group, a methylcyclohexyl group and an ethylcyclohexyl group are preferred for reasons of easiness of production.
The monovalent C6 to C12 aromatic hydrocarbon group represented by R4 and R6 of the above general formula (V) may be, for example, a phenyl group, a toluyl group, a benzyl group, an ethylphenyl group, a methylbenzyl group, a xylyl group, a propylphenyl group, a cumenyl group, an ethylbenzyl group, a methylphenethyl group, a butylphenyl group, a propylbenzyl group, an ethylphenethyl group, a pentylphenyl group, a butylbenzyl group, a propylphenethyl group, a hexylphenyl group, a pentylbenzyl group, a butylphenethyl group, a heptylphenyl group, a hexylbenzyl group, a pentylphenethyl group, an octylphenyl group, a butylbenzyl group, a hexylphenethyl group, a nonylphenyl group or an octylbenzyl group.
In the present invention, the proportion of the hydrocarbon groups of R4 and R6 that constitute the terminal groups of the diurea compound, namely the composition of the raw material amines (or mixed amines) from which the R4 and R6 are derived, is not specifically limited. However, it is preferred that chain hydrocarbon groups or alicyclic hydrocarbon groups be the main components of the whole hydrocarbon groups. For example, it is preferred that the groups R4 and R6 satisfy the following formulas (a) and (b):
[(X+Y)/(X+Y+Z)]×100≧90 (a)
X/Y=50/50 to 0/100 (b)
wherein X is a content (mole %) of the chain hydrocarbon groups, Y is a content (mole %) of the alicyclic hydrocarbon groups and Z is a content (mole %) of the aromatic hydrocarbon groups in the groups R4 and R6.
When the above conditions (a) and (b) are met, tendency of oil separation, particularly oil separation under high centrifugal (acceleration) conditions may be suppressed.
The value of [(X+Y)/(X+Y+Z)]×100 in the formula (a) is more preferably 95 or more, particularly preferably 98 or more. The value of X/Y in the formula (b) is more preferably 30/70 to 5/95, particularly preferably 25/75 to 15/85.
The diurea compound may be generally obtained by reaction of a diisocyanate with a monoamine. The diisocyanate may be, for example, diphenylene diisocyanate, diphenylmethane diisocyanate, or tolylene diisocyanate. For reasons of harmlessness, diphenylmethane diisocyanate is preferred. The monoamine may be an amine corresponding to the chain hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group of R4 and R6 of the above general formula (V) and may be, for example, hexadecylamine, heptadecylamine, octadecylamine, octadecenylamine or the like chain hydrocarbon amine, cyclohexylamine or the like alicyclic hydrocarbon amine, octylphenylamine or the like aromatic hydrocarbon amine, or a mixture of these amines.
The compounding amount of the above-described thickener in the grease is not specifically restricted as long as the intended grease characteristics may be obtained but is preferably 10 to 30% by mass, more preferably 10 to 20% by mass, based on the grease.
The thickener used in the grease of the present invention serves to impart a desired penetration thereto. When the amount of the thickener is excessively small, a desired penetration is not obtainable. When the compounding amount is excessively large, the lubricity of the grease is reduced.
The grease according to the present invention may optionally contain a known additive or additives such as a lubricity improver, a detergent-dispersant, an antioxidant, an anti-corrosive agent, a rust preventing agent and an antifoaming agent as long as the object of the present invention is not adversely affected.
As the lubricity improver, there maybe mentioned, for example, sulfur compounds (sulfurized fats and oils, sulfurized olefins, polysulfides, sulfurized mineral oils, thiophosphates such as triphenylphosphorothioate, thiocarbamic acids, thioterpenes, dialkylthiodipiropionates), phosphoric acid esters and phosphorous acid esters (tricresyl phosphate, triphenyl phosphite, etc.). As the detergent-dispersant, there may be mentioned, for example, succinimide and boron-containing succinimide.
As the antioxidant, there may be used an amine type antioxidant, a phenol type antioxidant or a sulfur type antioxidant. Among these, an amine type antioxidant is preferred. Examples of the amine type antioxidant include monoalkyldiphenylamine-based compounds such as monooctyldiphenylamine and monononyldiphenylamine; dialkyldiphenylamine-based compounds such as 4,4′-dibutyldiphenylamine, 4,4′-dipentyldiphenylamine, 4,4′-dihexyldiphenylamine, 4,4′-diheptyldiphenylamine, 4,4′-dioctyldiphenylamine and 4,4′-dinonyldiphenylamine; polyalkyldiphenylamine-based compounds such as tetradibutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, tetranonyldiphenylamine; and naphthylamine-based compounds such as α-naphthylamine, phenyl-α-naphthylamine, butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexylphenyl-α-naphthylamine, heptylphenyl-α-naphthylamine, octylphenyl-α-naphthylamine and nonylphenyl-α-naphthylamine.
As the anti-corrosive agent, there may be mentioned, for example, benzotriazole type and thiazole type corrosion inhibitors. As the rust preventing agent, there may be mentioned, for example, metal sulfonate type and succinic ester type rust preventing agents. As the antifoaming agent, there may be mentioned, for example, silicone type and fluorinated silicone type antifoaming agents.
The compounding amount of the additives may be adequately determined according to the objects of their use. In general, a total amount of these additives is 30% by mass or less based on the lubricant.
A method for preparing the grease according to the present invention is not specifically limited. Generally, the following method may be used.
First, a base oil is added with a predetermined proportion of a thickener and, if desired, with a viscosity increasing agent. The mixture is heated to a predetermined temperature to obtain a homogeneous mixture.
This is then cooled. When a predetermined temperature is reached, various additives, if desired, are added in predetermined amounts, thereby obtaining a grease of the present invention.
The grease according to the present invention excels in both low-temperature performance and high-temperature performance, has reduced oil separation even under high centrifugal force (acceleration) and is suited for use in rotational transmission devices such as gears, belts, chains, traction drive transmissions, feed screws, clutches, telescopic shafts and bearings. In particular, the grease is useful for use in various bearings and pulleys for direct-acting devices and electrical accessories of automobiles. Especially, when the grease is used in a rotational transmission device having a built-in one-way clutch, the grease can provide satisfactory clutch engagement property (intermeshing ability) at low temperatures and a prolonged bearing life at high temperatures and is less apt to cause oil separation under high centrifugal force.
The present invention will be next described in more detail by way of examples. It should be noted that the present invention is not limited to these examples in any way.
The various properties were determined by the following methods.
The kinematic viscosity was measured in accordance with JIS K2283.
The consistency was measured in accordance with JIS K2220.7.5.
A grease was charged in a clutch pulley unit (real unit) disclosed in FIG. 1 of Japanese Unexamined Patent Application Publication No. 2006-64136. An outer wheel was rotated in an interlocking state between the outer wheel and an inner wheel. The angular acceleration (limit angular speed: rad/sec2) of the outer wheel beyond which the inner wheel failed to follow was measured. The higher the value, the better is the clutch engagement property (intermeshing ability).
In 6305VV bearings (manufactured by NSK Ltd) were charged 3.4 g of a grease. The bearings were then continuously operated at 160° C., 10,000 rpm, a thrust load of 98 N and a radial load of 98 N to measure the time (bearing life time) at which the bearings are seized as a result of deterioration of the grease.
In the above experiment, a plurality (five) of bearings were tested. The measured values were Weibull-plotted, from which the life at accumulated probability of 50% (L50 life) was determined. The L50 life represents the bearing life.
An ultracentrifuge “HIMAC CP70G” manufactured by Hitachi Koki Co., Ltd. was used. Grease was filled in a vessel and centrifuged at centrifugal acceleration of 1.8×105 m2/s (20,000 G) at 50° C. for 5 hours. A weight ratio of an oil component separated from the grease was determined as an amount of oil separation.
The base oils used were as follows:
Diisodecyl sebacate obtained by esterification of sebacic acid with 3,7-dimethyloctyl alcohol (isodecyl alcohol) in the conventional manner was used. The diisodecyl sebacate has a total carbon number of 30, a kinematic viscosity of 20 mm2/s at 40° C., a flash point of 262° C. and a density of 0.913 g/cm3.
An alkylbenzene having a kinematic viscosity of 56 mm2/s at 40° C., a flash point of 192° C. and a density of 0.895 g/cm3 was used.
Diisononyl phthalate obtained by esterification of phthalic anhydride with 3,5,5-trimethylhexyl alcohol (isononyl alcohol) in the conventional manner was used. The diisononyl phthalate has a total carbon number of 26, a kinematic viscosity of 28 mm2/s at 40° C., a flash point of 236° C. and a density of 0.978 g/cm3.
Diester of neopentyl glycol with 3,5,5-trimethylhexyl alcohol having a kinematic viscosity of 13 mm2/s at 40° C., a flash point of 200° C. and a density of 0.913 g/cm3 was used.
A grease having the compounding composition shown in Table 1 was prepared using the base oil 1 and urea thickener 1 by the following method.
Diphenylmethane-4,4′-diisocyanate in the whole amount to be used was dissolved with heating in two thirds of the total amount to be used of the base oil 1 (including a viscosity increasing agent (polymethacrylate) having a weight average molecular weight of 450,000). In the remainder of the base oil-1, mixed amines (a mixture of n-octadecylamine and cyclohexylamine with 20:80 molar ratio) in an amount of two times the mole of the diphenylmethane-4,4′-diisocyanate were dissolved with heating.
The base oil 1 containing the diphenylmethane-4,4′-diisocyanate was charged in a grease production vessel and vigorously stirred at 50 to 60° C., to which the base oil 1 containing the mixed amines was gradually added with heating. After a temperature of 160° C. was reached, the grease was further maintained at that temperature for one hour. The compounding amount of the urea thickener was 17% by mass based on a total amount of the grease.
The resulting mixture was cooled to 80° C. at a rate of 50° C./h and blended with an antioxidant, a lubricity improver and a rust preventing agent. The resulting mixture was allowed to spontaneously cool to room temperature and then subjected to a finish treatment using a three-roll device to obtain a grease.
The thus obtained grease was measured for the worked penetration and subjected to the engagement property test (at −30° C., −20° C., 0° C. and 80° C.), the bearing life test at high temperatures and the oil separation test under high centrifugal force. The results are summarized in Table 1.
Greases were prepared in the same manner as that in Example 1 except that neither the viscosity increasing agent nor the lubricity improver was used and that the compounding amount of the urea thickener was changed as shown in Table 1. Each of the thus obtained greases was measured for the worked penetration and subjected to the engagement property test (at −30° C., −20° C., 0° C. and 80° C.), the bearing life test at high temperatures and the oil separation test under high centrifugal force. The results are summarized in Table 1.
Greases having the compositions shown in Table 1 were prepared in the manner described in Example 1 using the base oil or a combination of the base oil with the viscosity increasing agent, and the urea thickener as shown in Table 1. Each of the thus obtained greases was measured for the worked penetration and subjected to the engagement property test (at −30° C., −20° C., 0° C. and 80° C.), the bearing life test at high temperatures and the oil separation test under high centrifugal force. The results are summarized in Table 1.
Each of commercial products A, B and C was measured for the worked penetration and subjected to the engagement property test (at −30° C., −20° C., 0° C. and 80° C.), the bearing life test at high temperatures and the oil separation under high centrifugal force. The results are summarized in Table 1.
The commercial product A is a commercially available urea-based grease containing an alkyl-substituted diphenyl ether as a base oil, the commercial product B is a commercially available urea-based grease containing a pentaerythritol ester as a base oil, and the commercial product C is a commercially available urea-based grease containing a poly-α-olefin as a base oil.
1) Viscosity increasing agent: polymethacrylate having a weight average molecular weight of 450,000
2) Urea thickener 1: product obtained by reacting diphenylmethane-4,4′-diisocyanate with a two-fold molar amount of mixed amines (a mixture of n-octadecylamine and cyclohexylamine), [(X + Y)/(X + Y + Z)] × 100 = 100, X/Y = 20/80
3) Antioxidant: a mixture of octylphenyl-1-naphthylamine (2 parts by weight), p,p′-dioctyldiphenylamine (2 parts by weight) and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (1 part by weight)
4) Lubricity improver: triphenylphosphorothioate
5) Rust preventing agent: zinc stearate
Greases having the compositions shown in Table 2 were prepared in the same manner as that in Example 1 using the base oil, the viscosity increasing agent and the urea thickener as shown in Table 2. The urea thickeners 2 used in these examples were prepared while changing mixing ratios of mixed amines (mixture of n-octadecylamine and cyclohexylamine) which were raw materials for preparing the urea thickener.
Each of the thus obtained greases was measured for the worked penetration and subjected to the oil separation test under high centrifugal force. The results are summarized in Table 2.
6) Urea thickener 2: product obtained by reacting diphenylmethane-4,4′-diisocyanate with a two-fold molar amount of mixed amines (a mixture of n-octadecylamine and cyclohexylamine), [(X + Y)/(X + Y + Z)] × 100 = 100, X/Y = 0/100 to 80/20
1) to 5) are the same as those in Table 1
Greases having the compositions shown in Table 3 were prepared in the same manner as that in Example 1 using the base oil, the viscosity increasing agent and the urea thickener as shown in Table 3. The urea thickeners used in these examples were prepared using different chain hydrocarbon amines in the raw material mixed amines.
Each of the thus obtained greases was measured for the worked penetration and subjected to the oil separation test under high centrifugal force. The results are summarized in Table 3.
7)Urea thickener 3: product obtained by reacting diphenylmethane-4,4′-diisocyanate with a two-fold molar amount of mixed amines (a mixture of the chain hydrocarbon amine shown and cyclohexylamine), [(X + Y)/(X + Y + Z)] × 100 = 100, X/Y = 20/80
1) to 5)are the same as those in Table 1
From the results shown in Table 1, it is appreciated that the greases of the present invention (Examples 1 to 3) are excellent in engagement property throughout the temperature range of −30 to 80° C., particularly at low temperatures and have good bearing life at high temperatures and reduced oil separation under high centrifugal force. In contrast, the grease of Comparative Example in which an alkylbenzene is used as a base oil, the grease of Comparative Example 2 in which a diester having a total carbon number of 26 is used and greases of Comparative Examples 4 to 6 which are commercial products, are all unsatisfactory with respect to the engagement property at low temperature (−30° C.). The grease of Comparative Example 3 in which a neopentyl ester is used as a base oil is problematic with respect to its performance at high temperature and has short bearing life at high temperatures, though the engagement property thereof is good.
From the results shown in Table 2, it is also understood that the greases of the present invention (Examples 9 to 12) show oil separation at high centrifugal force of 20% by mass or less and that the greases having X/Y values of 8/92 and 20/80 (Examples 5 and 6) are excellent in this respect.
Additionally, from the results shown in Table 3, it is appreciated that oil separation is further reduced when the chain hydrocarbon (alkyl) amine used in the raw material mixed amines has a carbon number of 12 (Example 10), a carbon number of 14 (Example 11) and a carbon number of 18 (Example 12) and that the greases of Example 11 (carbon number: 14) and of Example 12 (carbon number: 18) are excellent in this respect.
The grease according to the present invention is excellent in both low-temperature performance and high-temperature performance and has low oil separation tendency even under high centrifugal force (acceleration) and may be used in various applications. In particular, when the grease is used in a rotational transmission device having a built-in one-way clutch, the grease can provide satisfactory clutch engagement property (intermeshing ability) at low temperatures and a prolonged bearing life at high temperatures and is less apt to cause oil separation under high centrifugal force. Therefore, the grease may be suitably used in various rotational transmission devices having a built-in one-way clutch.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2006-275436 | Oct 2006 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP07/69601 | 10/5/2007 | WO | 00 | 4/6/2009 |
