JP4749000B2 - Grease composition - Google Patents

Description

  The present invention relates to a novel grease composition.

Lubricating grease used as a lubricant for machine parts is generally composed of a thickener, a base oil, and an additive. Most of the properties of grease are often determined by the type of thickener or the type of base oil, but various additives are added to add properties that cannot be compensated for.
In recent years, labor-saving and machine technology innovations have been promoted in the industrial world, and it has become a grease that contributes to lubrication parts in order to respond to the harsh use environment, longer machine life, smaller machine parts, and maintenance-free orientation. The required performance has been demanded higher. Accordingly, it is desired that the grease used therein is further excellent in low friction characteristics, and has heat resistance and long life characteristics. Conventional grease is greatly affected by the lubrication characteristics of the base oil itself, and there are limits to friction resistance, wear resistance, and anti-galling characteristics, and there is room for improvement. Various grease compositions in which predetermined properties are improved by adding a specific thickener or the like to the base oil have been proposed (for example, Patent Documents 1 to 3).
JP 7-34083 A JP-A-8-209176 JP 2004-204218 A

  An object of the present invention is to provide a grease composition having low friction and wear characteristics.

Means for solving the above problems are as follows.
(1) A grease composition containing at least one discotic compound and a thickener.
(2) The grease composition according to (1), wherein at least one of the discotic compounds is selected from compounds represented by the following general formula (1).

式中、Ｄはｍ個の側鎖と結合可能な環状の基を表し、Ｘは各々独立に、単結合、ＮＲ¹基（Ｒ¹は、水素原子または炭素数が１〜３０のアルキル基）、酸素原子、硫黄原子、カルボニル基、スルホニル基またはこれらの組み合わせからなる二価の連結基を表し、Ｒは各々独立に、置換もしくは無置換の、アルキル基、アルケニル基、アルキニル基、アリール基、複素環基、ハロゲン原子、ヒドロキシ基、アミノ基、メルカプト基、シアノ基、スルフィド基、カルボキシ基もしくはその塩、スルホ基もしくはその塩、ヒドロキシアミノ基、ウレイド基またはウレタン基を表す。ｍは２〜１１の整数を表す。

In the formula, D represents a cyclic group that can be bonded to m side chains, and X is each independently a single bond or an NR ¹ group (R ¹ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms). Represents a divalent linking group consisting of an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or a combination thereof, and each R is independently a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, It represents a heterocyclic group, a halogen atom, a hydroxy group, an amino group, a mercapto group, a cyano group, a sulfide group, a carboxy group or a salt thereof, a sulfo group or a salt thereof, a hydroxyamino group, a ureido group or a urethane group. m represents an integer of 2 to 11.

(3) The grease composition according to (2), wherein D is a heterocyclic residue having a 5- to 7-membered ring structure.
(4) The grease composition of (2) or (3), wherein the general formula (1) is represented by the following general formula (2).

（式中、Ｘ¹、Ｘ²およびＸ³は各々独立に、単結合、ＮＲ¹基（Ｒ¹は、水素原子または炭素数が１〜３０のアルキル基）、酸素原子、硫黄原子、カルボニル基、スルホニル基またはこれらの組み合わせからなる二価の連結基を表し、Ｒ¹¹、Ｒ¹²およびＲ¹³は各々独立に、置換もしくは無置換のアルキル基、アルケニル基、アルキニル基、アリール基、ハロゲン原子、ヒドロキシ基、アミノ基、メルカプト基、シアノ基、スルフィド基、カルボキシ基またはその塩、スルホ基またはその塩、ヒドロキヒアミノ基、ウレイド基またはウレタン基を表す。）

Wherein X ¹ , X ² and X ³ are each independently a single bond, an NR ¹ group (R ¹ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms), an oxygen atom, a sulfur atom, or a carbonyl group. Represents a divalent linking group comprising a sulfonyl group or a combination thereof, and R ¹¹ , R ¹² and R ¹³ each independently represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, halogen atom, (Represents a hydroxy group, amino group, mercapto group, cyano group, sulfide group, carboxy group or salt thereof, sulfo group or salt thereof, hydroxyamino group, ureido group or urethane group.)

(5) The grease composition of (2) or (3), wherein the general formula (1) is represented by the following general formula (3).

（式中、Ｘ²¹、Ｘ²²およびＸ²³は、各々独立に、単結合、ＮＲ¹基（Ｒ¹は、水素原子または炭素数が１〜３０のアルキル基）、酸素原子、硫黄原子、カルボニル基、スルホニル基またはこれらの組み合わせからなる二価の連結基を表し、Ｒ²¹、Ｒ²²およびＲ²³は各々独立に置換基を表す。ａ２１、ａ２２およびａ２３は各々独立して１〜５の整数を表す。）

Wherein X ²¹ , X ²² and X ²³ are each independently a single bond, NR ¹ group (R ¹ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms), oxygen atom, sulfur atom, carbonyl A divalent linking group consisting of a group, a sulfonyl group or a combination thereof, R ²¹ , R ²² and R ²³ each independently represents a substituent; Represents.)

(6) The grease composition according to any one of (1) to (5), wherein the thickener contains at least one metal soap thickener.
(7) The grease composition according to any one of (1) to (6), wherein the thickener contains at least one urea-based thickener.
(8) The grease composition according to any one of (1) to (7), wherein the thickener contains at least one inorganic thickener.
(9) The grease composition according to any one of (1) to (8), wherein the thickener contains at least one organic thickener.

  According to the present invention, it is possible to provide a grease composition having low friction and wear characteristics.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.
The present invention relates to a grease composition containing at least one discotic compound and a thickener. In the present specification, the “discotic compound” refers to a compound having a discotic partial structure at the center thereof. The disk-shaped partial structure is a central partial structure obtained by removing the side chain portion from the molecular structure, and its morphological characteristics can be explained, for example, with respect to the hydrogen substitution product that is the original compound. Can be expressed.
First, by the following methods 1) to 5), the molecular size of the hydrogen substitution product that is the original shape of the disk-shaped partial structure is determined.
1) Construct a molecular structure as close as possible to the target molecule, preferably a planar molecular structure. In this case, as the bond distance and bond angle, it is preferable to use standard values corresponding to the orbital mixture. For example, the Chemical Society of Japan, Chemical Handbook 4th edition, Chapter II, Volume 15 (1993 published by Maruzen) You can refer to it.
2) Using the structure obtained in 1) as an initial value, the structure is optimized by a molecular orbital method or a molecular force field method. Examples of the method include Gaussian 92, MOPAC 93, CHARMm / QUANTA, and MM3. Gaussian 92 is preferable.
3) The center of gravity of the structure obtained by structure optimization is moved to the origin, and the coordinate axis is taken as the inertial principal axis (the principal axis of the inertia tensor ellipsoid).
4) Give each atom a sphere defined by the van der Waals radius and describe the shape of the molecule.
5) Measure the length in the direction of each coordinate axis on the van der Waals surface, and let them be a, b and c, respectively.
When a disk-like form is defined using a, b and c obtained by the above procedures 1) to 5), a form satisfying a ≧ b> c and a ≧ b ≧ a / 2, preferably a In this embodiment, ≧ b> c and a ≧ b ≧ 0.7a are satisfied. A form satisfying b / 2> c is also preferable.

  Further, specific examples of the discotic compound that is a hydrogen substitution product that is the original form of the discotic partial structure are described in, for example, the Chemical Society of Japan, Quarterly Chemical Review No. 22 “Liquid Crystal Chemistry”, Chapter 5, Chapter 10 Section 2 (1994 Publication Center); Destrade et al., Mol. Cryst. liq. Cryst. 71, 111 (1981); Kohne et al., Angew. Chem. 96, 70 (1984); M.M. Lehn et al. Chem. Soc. Chem. Commun. 1794 (1985); Zhang, J. et al. s. A study report by Moore et al. Am. Chem. Soc. 116, 2655 (1994); and the mother nucleus compounds and derivatives thereof. Examples include benzene derivatives, triphenylene derivatives, truxene derivatives, phthalocyanine derivatives, porphyrin derivatives, anthracene derivatives, hexaethynylbenzene derivatives, dibenzopyrene derivatives, coronene derivatives, and phenylacetylene macrocycle derivatives. Furthermore, the cyclic compounds described in the Chemical Society of Japan, “Chemical Review No. 15 New Aromatic Chemistry” (published by the University of Tokyo Press, 1977) and their electronic structures such as heteroatom substitution can be mentioned.

The discotic compound is preferably a compound having a cyclic group having a discotic partial structure and a plurality (preferably 2 to 11) side chains bonded to the cyclic group. At least one of the side chains preferably has an ester bond. In particular, at least one of the side chains preferably contains a group represented by the following general formula (4a) or general formula (4b). In the following formula, the left side (-X ⁰ ) is bonded to the D side.

In the formula, X ⁰ is a single bond, an NR ¹ group (R ¹ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms), an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or a combination thereof. Represents a linking group.
L ⁰ represents an alkylene group (preferably a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms), an NR ¹ group (R ¹ is a hydrogen atom or a carbon number of 1 to 30). An alkyl group), an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or a combination thereof. The divalent linking group may have a substituent. L ⁰ is preferably an alkylene group.
In addition, the group of the combination of X ⁰ and L ⁰ is preferably —O (C═O) -alkylene- or —O (C═O) -cycloalkylene-.
R ⁰ is located at the end of the side chain of the compound and represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

Moreover, it is more preferable that at least one of the side chains includes a group represented by the general formula (4a). Among these, it is more preferable that the side chain contains a group represented by the following general formula (4). In the following formula, the left side (-L ⁰¹ ) is bonded to the cyclic base side.

L ⁰¹ is synonymous with X ⁰ . L ⁰¹ is preferably an oxygen atom, a sulfur atom,-(C = O) O-, -NH- (C = O) O-. R ⁰¹ represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and p and q each represents an integer. R ⁰¹ preferably has 1 to 40 carbon atoms, and more preferably 1 to 20 carbon atoms. Substituents include halogen atoms, alkoxy groups (methoxy, ethoxy, methoxyethoxy, phenoxy, etc.), sulfide groups (methylthio, ethylthio, propylthio, etc.), alkylamino groups (methylamino, propylamino, etc.), acyl groups (acetyl, Propanoyl, octanoyl, benzoyl, etc.) and acyloxy groups (acetoxy, pivaloyloxy, banzoyloxy, etc.), aryl groups, heterocyclic groups, hydroxyl groups, mercapto groups, amino groups, cyano groups, nitro groups, carboxyl groups, sulfo groups, carbamoyl groups Group, sulfamoyl group, ureido group and the like. p is preferably from 1 to 20, and more preferably from 2 to 10. q is preferably 1 to 10, and more preferably 1 to 5.

  Moreover, it is also preferable that at least one of the side chains includes a group represented by the following general formula (5) or (6).

式中、Ｒ⁰¹は炭素原子数が１〜３０の置換もしくは無置換のアルキル基を表し、ｍおよびｎは各々整数を表し、一般式（４）におけるＲ⁰¹と同じ意味の基を表す。

In the formula, R ⁰¹ represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, m and n each represent an integer, and represent a group having the same meaning as R ⁰¹ in formula (4).

式中、Ｒ²⁵は置換基を表し、ａ２４は１〜５の整数を表す。

In the formula, R ²⁵ represents a substituent, and a24 represents an integer of 1 to 5.

  Moreover, it is also preferable that at least a part of the side chain is a group represented by the following general formula (7).

In the formula, L ²¹ is a single bond, an NR ¹ group (R ¹ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms), an alkylene group, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or a combination thereof. Represents a divalent linking group consisting of An oxygen atom, an oxyalkylene group, an oxycarbonyl group, an aminocarbonyl group, a carbonyloxy group, and a carbonyl group are preferable, and an oxycarbonyl group and a carbonyl group are more preferable.

Examples of the substituents R ²⁵ , R ⁷¹ and R ⁷² include halogen atoms, alkyl groups (having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms), alkenyl groups (having 2 to 40 carbon atoms, preferably 2-20), an alkynyl group (having 2 to 40 carbon atoms, preferably 2 to 20 carbon atoms), an aryl group (having 6 to 40 carbon atoms, preferably 6 to 20 carbon atoms), a heterocyclic group (carbon atoms). Cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group (having 6 to 40 carbon atoms, preferably 6 to 20), silyloxy A group (having 3 to 40 carbon atoms, preferably 3 to 20 carbon atoms), a heterooxy group (having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms), an acyloxy group (having 2 to 40 carbon atoms, preferably 2-20), carba Moyloxy group (having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms), alkoxycarbonyloxy group (having 2 to 40 carbon atoms, preferably 2 to 20 carbon atoms), aryloxycarbonyloxy group (having 7 carbon atoms) -40, preferably 7-20, amino group, acylamino group (1-40 carbon atoms, preferably 1-20 carbon atoms), aminocarbonylamino group (1-40 carbon atoms, preferably 1 ˜20), alkoxyaminocarbonylamino group (having 2 to 40 carbon atoms, preferably 2 to 20 carbon atoms), aryloxycarbonylamino group (having 7 to 40 carbon atoms, preferably 7 to 20 carbon atoms), sulfo Famoylamino group (0-40 carbon atoms, preferably 0-20), alkyl and arylsulfonylamino groups (1-40 carbon atoms, preferably 1-20), mercapto group, alkylthio group (1-40 carbon atoms, preferably 1-20), arylthio group (6-40 carbon atoms, preferably 6-20), heterocyclic thio Groups (having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms), sulfamoyl groups (having 0 to 40 carbon atoms, preferably 0 to 20 carbon atoms), sulfo groups, alkyl and arylsulfinyl groups (having 1 carbon atom) -40, preferably 1-20, alkyl and arylsulfonyl groups (1-40 carbon atoms, preferably 1-20 carbon atoms), acyl groups (1-40 carbon atoms, preferably 1-20 carbon atoms). ), Aryloxycarbonyl group (having 7 to 40 carbon atoms, preferably 7 to 20 carbon atoms), alkoxycarbonyl group (having 2 to 40 carbon atoms, preferably 2 to 20 carbon atoms), carbamoyl Groups (1-40 carbon atoms, preferably 1-20), aryl and heterocyclic azo groups (1-40 carbon atoms, preferably 1-20 carbon atoms), imide groups (4-40 carbon atoms) , Preferably 4 to 20), phosphino group (0 to 40 carbon atoms, preferably 0 to 20 carbon atoms), phosphinyl group (0 to 40 carbon atoms, preferably 0 to 20 carbon atoms), phosphini A ruoxy group (having 0 to 40 carbon atoms, preferably 0 to 20 carbon atoms), a phosphinylamino group (having 0 to 40 carbon atoms, preferably 0 to 20 carbon atoms), a silyl group (having 3 to 3 carbon atoms). 40, preferably 3-20). Furthermore, the substituents R ⁷¹ and R ⁷² also include those substituents substituted with one or more substituents selected from these substituents. As the substituent of R ⁷¹ , an alkoxy group, an alkoxycarbonyl group and an acyl group substituted with a substituent containing a linear or branched alkyl residue are preferable. a is 0 or an integer of 1 to 5, preferably 1 to 3.
R ⁷¹ preferably has 1 to 40 carbon atoms, more preferably 1 to 20 carbon atoms.

  Moreover, it is also preferable that at least one of the side chains contains a partially fluorinated carbon group or a fluorinated carbon group. The presence or absence of a double bond, a branch, a cyclic group, or an aromatic ring may be used for the fluorocarbon group. It is also preferred that at least one of the side chains is a group represented by the following general formula (8).

In the formula, L ²¹ is a single bond, an NR ¹ group (R ¹ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms), an alkylene group (preferably a linear or branched chain having 1 to 20 carbon atoms). A divalent linking group comprising an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or a combination thereof. An oxygen atom, an oxyalkylene group, an oxycarbonyl group, an aminocarbonyl group, a carbonyloxy group, and a carbonyl group are preferable, and an oxycarbonyl group and a carbonyl group are more preferable.

Examples of the substituent R ⁸¹ include halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups, silyloxy groups, Heterooxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxyaminocarbonylamino group, aryloxycarbonylamino group, alphamoylamino group, Alkyl and arylsulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyl and arylsulfinyl groups, alkyl and arylsulfonyl groups Acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group include a silyl group. The preferred carbon number of these groups is the same as the substituents R ²⁵ , R ⁷¹ and R ⁷² . Furthermore, the substituent R ⁸¹ also includes those substituents substituted with one or more substituents selected from these substituents. At least one of the a R ^81s includes a partially fluorocarbon group and a fluorocarbon group. The presence or absence of a double bond, a branch, a cyclic group, or an aromatic ring may be used for the fluorocarbon group. As the substituent of R ⁸¹ , an alkoxy group, an alkoxycarbonyl group and an acyl group substituted with a substituent containing a linear or branched alkyl residue containing a partially fluorinated carbon group or a fluorinated carbon group are preferable. . a is 0 or an integer of 1 to 5, preferably 1 to 3.
R ⁸¹ preferably has 1 to 40 carbon atoms, more preferably 1 to 20 carbon atoms.

  The discotic compound is preferably a compound represented by the following general formula (1).

In the formula, D represents a cyclic group that can be bonded to m side chains, and X is each independently a single bond or an NR ¹ group (R ¹ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms). Represents a divalent linking group consisting of an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or a combination thereof, and each R is independently a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, It represents a heterocyclic group, a halogen atom, a hydroxy group, an amino group, a mercapto group, a cyano group, a sulfide group, a carboxy group or a salt thereof, a sulfo group or a salt thereof, a hydroxyamino group, a ureido group or a urethane group. m represents an integer of 2 to 11.

In the general formula (1), examples of the cyclic group represented by D include an aromatic group and a heterocyclic group. Examples of the aromatic ring of the aromatic group include benzene ring, indene ring, naphthalene ring, triphenylene ring, fluorene ring, phenanthrene ring, anthracene ring and pyrene ring. The aromatic group may have a substituent.
The heterocyclic group preferably has a 5-membered, 6-membered or 7-membered heterocyclic ring. A 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is most preferable. As the hetero atom constituting the heterocyclic ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable. The heterocycle is preferably an aromatic heterocycle. The aromatic heterocycle is generally an unsaturated heterocycle. An unsaturated heterocyclic ring having the most double bond is more preferable. Examples of heterocyclic rings include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline Ring, pyrazolidine ring, triazole ring, triazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring included. A triazine ring is preferred, and a 1,3,5-triazine ring is particularly preferred. The heterocycle may be condensed with another heterocycle, aliphatic ring or aromatic ring. However, monocyclic heterocycles are preferred.

In the general formula (1), X is a single bond, NR ¹ group (R ¹ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms), oxygen atom, sulfur atom, carbonyl group, sulfonyl group, or a combination thereof. Represents a divalent linking group consisting of When X is a single bond, it may be directly bonded with a nitrogen atom having a free valence such as piperidine in a heterocyclic group, and further bonded with a heteroatom without a free valence, and an oxonium salt or a sulfonium salt An onium salt may be formed like an ammonium salt. X in the general formula (1) is preferably a sulfur atom or an NR ¹ group, and R ¹ is preferably an alkyl group having 3 or less carbon atoms or a hydrogen atom.

In the general formula (1), when R is an alkyl group, the number of carbon atoms is preferably 1-30, more preferably 2-30, and even more preferably 4-30, 30 is most preferred. The alkyl group may be linear or branched. Moreover, you may have a substituent. Examples of substituents include halogen atoms, alkoxy groups (methoxy, ethoxy, methoxyethoxy, phenoxy, etc.), sulfide groups (methylthio, ethylthio, propylthio, etc.), alkylamino groups (methylamino, propylamino, etc.), acyl groups ( Acetyl, propanoyl, octanoyl, benzoyl, etc.) and acyloxy groups (acetoxy, pivaloyloxy, benzoyloxy, etc.), hydroxyl groups, mercapto groups, amino groups, carboxyl groups, sulfo groups, carbamoyl groups, sulfamoyl groups, and ureido groups.
In general formula (1), R represents an alkenyl group and the alkynyl group has the same carbon number and shape as the alkyl group, and may have the same substituent.

  In the general formula (1), when R is an aryl group, examples thereof include a phenyl group, an indenyl group, an α-naphthyl group, a β-naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, and a pyrenyl group. Group and naphthyl group are preferred. Furthermore, you may have a substituent. Examples of the substituent include, in addition to those exemplified for the substituent of the alkyl group, an alkyl group, and a substituent containing a linear or branched alkyl residue having 8 or more carbon atoms, such as an alkyl group ( Octyl, decyl, hexadecyl, 2-ethylhexyl, etc.), alkoxy groups (dodecyloxy, hexadecyloxy, etc.), sulfide groups (hexadecylthio, etc.), substituted amino groups (heptadecylamino, etc.), octylcarbamoyl groups, octanoyl groups, and decylsulfurs It is preferably substituted with a famoyl group or the like. These substituents are preferably substituted at least two, and in addition to the above substituents, they are substituted with halogen atoms, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, sulfo groups, etc. May be.

  In the general formula (1), when R is a heterocyclic group, like D, a heterocyclic group having a 5- to 7-membered ring structure is preferable, a 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is Most preferred. Specific examples of these skeletons are also included in Appendix 11 of the Iwanami Physics and Chemistry Dictionary 3rd edition (published by Iwanami Shoten). Names of major heteromonocyclic compounds page 1606 and Table 5. Names of main condensed heterocyclic compounds The compounds described on page 1607 are listed. Further, like the aryl group, these may have a substituent and are preferably substituted with a substituent containing a linear or branched alkyl residue having 8 or more carbon atoms. These substituents are preferably substituted at least two, and in addition to the above substituents, they are substituted with halogen atoms, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, sulfo groups, etc. May be.

At least one of R preferably has an ester bond, more preferably an alkoxy group substituted with a substituent containing a linear or branched alkyl residue containing an ester bond. preferable. Further, it is more preferable that all of R contain an ester bond, and all of them are alkoxy groups substituted with a substituent containing a linear or branched alkyl residue containing an ester bond. Even more preferred. That is, at least one of R preferably contains a group represented by the formula (4a) or (4b), and a group represented by any one of the formulas (4) to (6). More preferably.
In addition, at least one of R—X— is preferably a group represented by the general formula (7) or (8), and all the groups represented by the general formula (7) or (8). It is also more preferable.

  Among the compounds represented by the general formula (1), compounds represented by the following general formula (2) are preferable.

In the formula, X ¹ , X ² and X ³ are each independently a single bond, an NR ¹ group (R ¹ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms), an oxygen atom, a sulfur atom, a carbonyl group, Represents a divalent linking group comprising a sulfonyl group or a combination thereof. When X ¹ , X ² , and X ³ are single bonds, they may be directly bonded with a nitrogen atom having a free valence such as piperidine as a heterocyclic group, and further bonded with a hetero atom even if there is no free valence. In addition, an onium salt may be formed such as an oxonium salt, a sulfonium salt, or an ammonium salt. X ¹ , X ² , and X ³ are each an NR ¹ group (R ¹ is an alkyl group having 1 to 30 carbon atoms or a hydrogen atom), an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or these when not a single bond A divalent linking group consisting of a combination of, for example, an oxycarbonyl group, an aminocarbonyl group, a ureylene group, an oxysulfonyl group, a sulfamoyl group and the like. A sulfur atom or an NR ¹ group is preferred, and R ¹ is preferably an alkyl group having 3 or less carbon atoms or a hydrogen atom. In this, an imino group (-NH-) is more preferable.

In the general formula (2), R ¹¹ , R ¹² and R ¹³ are each independently a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, halogen atom, hydroxy group, An amino group, a mercapto group, a cyano group, a sulfide group, a carboxy group or a salt thereof, a sulfo group or a salt thereof, a hydroxyamino group, a ureido group, or a urethane group.

The alkyl groups represented by R ¹¹ , R ¹² and R ¹³ each have 1 to 30 carbon atoms, preferably 2 to 30 carbon atoms, more preferably 4 to 30 carbon atoms, and 6 to 30 carbon atoms. Most preferred. The alkyl group may be linear or branched. Moreover, you may have a substituent. Examples of substituents include halogen atoms, alkoxy groups (methoxy, ethoxy, methoxyethoxy, phenoxy, etc.), sulfide groups (methylthio, ethylthio, propylthio, etc.), alkylamino groups (methylamino, propylamino, etc.), acyl groups ( Acetyl, propanoyl, octanoyl, benzoyl, etc.) and acyloxy groups (acetoxy, pivaloyloxy, benzoyloxy, etc.), hydroxyl groups, mercapto groups, amino groups, carboxyl groups, sulfo groups, carbamoyl groups, sulfamoyl groups and ureido groups. The carbon number and shape of R ¹¹ , R ¹² and R ¹³ as alkenyl group and alkynyl group are the same as those of the alkyl group, and may have the same substituent.

Examples of the aryl groups represented by R ¹¹ , R ¹² and R ¹³ include phenyl group, indenyl group, α-naphthyl group, β-naphthyl group, fluorenyl group, phenanthrenyl group, anthracenyl group and pyrenyl group. A phenyl group or a naphthyl group is preferred. Further, a substituent containing a linear or branched alkyl residue having 8 or more carbon atoms, such as an alkyl group (octyl, decyl, hexadecyl, 2-ethylhexyl, etc.), an alkoxy group (dodecyloxy, hexadecyloxy, 2 -Hexyldecyloxy, hexyloxyethyleneoxyethyleneoxy, etc.), sulfide groups (hexadecylthio, etc.), substituted amino groups (heptadecylamino, etc.), octylcarbamoyl groups, octanoyl groups, decylsulfamoyl groups, etc. preferable. These substituents are preferably substituted at least two, and in addition to the above substituents, they are substituted with halogen atoms, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, sulfo groups, etc. May be.

In the heterocyclic group represented by each of R ¹¹ , R ¹² and R ¹³ , a heterocyclic residue having a 5- to 7-membered ring structure is preferable, like D in the general formula (1). Is more preferable, and a 6-membered ring is most preferable. Specific examples of these skeletons are also included in Appendix 11 of the Iwanami Physics and Chemistry Dictionary 3rd edition (published by Iwanami Shoten). Names of major heteromonocyclic compounds page 1606 and Table 5. Examples include the compounds described on page 1607 of the name of the main condensed heterocyclic compound. Further, like the aryl group, these are preferably substituted with a substituent containing a linear or branched alkyl residue having 8 or more carbon atoms. These substituents are preferably substituted at least two, and in addition to the above substituents, they are substituted with halogen atoms, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, sulfo groups, etc. May be.

At least one of R ¹¹ , R ¹² and R ¹³ preferably has an ester bond, and is substituted with a substituent containing a linear or branched alkyl residue containing an ester bond. More preferably, it is an alkoxy group. Further, it is more preferred that all of R ¹¹ , R ¹² and R ¹³ contain an ester bond, and all are substituted with a substituent containing a linear or branched alkyl residue containing an ester bond. Even more preferred is an alkoxy group. That is, at least one of R ¹¹ , R ¹² and R ¹³ preferably contains a group represented by the formula (4a) or (4b), and any one of the formulas (4) to (6) It is more preferable that a group represented by
It is also preferred that at least one of R ¹¹ —X ¹ —, R ¹² —X ² — and R ¹³ —X ³ — is a group represented by the general formula (7) or (8), It is more preferable that it is group represented by General formula (7) or (8).

  Furthermore, the compound represented by the following general formula (3) is mentioned as a more preferable aspect of the compound represented by the said General formula (2).

In the formula, X ²¹ , X ²² and X ²³ are each independently a single bond, NR ¹ group (R ¹ is a hydrogen atom or an alkyl group having 1 to 30 carbon atoms), oxygen atom, sulfur atom, carbonyl group Represents a divalent linking group comprising a sulfonyl group or a combination thereof. When X ²¹ , X ²² , and X ²³ are single bonds, they may be directly bonded with a nitrogen atom having a free valence such as piperidine as a heterocyclic group, and further bonded with a hetero atom even if there is no free valence. In addition, an onium salt may be formed such as an oxonium salt, a sulfonium salt, or an ammonium salt. When X ²¹ , X ²² , and X ²³ are not a single bond, an NR ¹ group (R ¹ is an alkyl group having 1 to 30 carbon atoms or a hydrogen atom), an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or these It represents a divalent linking group composed of a combination, for example, an oxycarbonyl group, an aminocarbonyl group, a ureylene group, an oxysulfonyl group, a sulfamoyl group, and the like. X ²¹ , X ²² and X ²³ are preferably a sulfur atom or an NR ¹ group, and R ¹ is preferably an alkyl group having 3 or less carbon atoms or a hydrogen atom. In this, an imino group (-NH-) is more preferable.

In the formula, R ²¹ , R ²² and R ²³ each independently represents a substituent. Substituents R ²¹ , R ²² and R ²³ are a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, Silyloxy group, heterooxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxyaminocarbonylamino group, aryloxycarbonylamino group, alphamoylamino Groups, alkyl and arylsulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyl and arylsulfinyl groups, alkyl and aryls Includes sulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group It is. The preferred carbon number of these groups is the same as the substituents R ²⁵ , R ⁷¹ and R ⁷² . Furthermore, the substituents R ²¹ , R ²² and R ²³ also include those substituents substituted with one or more substituents selected from these substituents.

At least one of R ²¹ , R ²² and R ²³ preferably has an ester bond, and is substituted with a substituent containing a linear or branched alkyl residue containing an ester bond. More preferably, it is an alkoxy group. Further, it is more preferable that all of R ²¹ , R ²² and R ²³ contain an ester bond, and all are substituted with a substituent containing a linear or branched alkyl residue containing an ester bond. Even more preferred is an alkoxy group. That is, at least one of R ²¹ , R ²² and R ²³ preferably contains a group represented by the above formula (4a) or (4b), and any one of the above formulas (4) to (6) It is more preferable that a group represented by
Further, in the formula _{^{(R 21) a21 -Ph-X}} 21 -, (R 22) a22 -Ph-X 22 - and _{^{R 23) a23 -Ph-X 23}} - it is at least one of the general formula (7 ) Or (8) is also preferred, and it is more preferred that all are groups represented by the general formula (7) or (8).

  In the formula, a21, a22 and a23 each independently represents an integer of 1 to 5.

  Specific examples of the compound represented by the general formula (1) that can be used in the present invention are listed below, but the present invention is not limited to the following specific examples.

  As a method for producing the discotic compound represented by the general formula (1), for example, a method of reacting a discotic compound serving as a core of various structures with a side chain having an ester group (for example, cyanuric chloride). Nucleophilic substitution reaction, alkylation of thiocyanuric acid, coupling reaction of benzene derivative or alkylation, acylation, etherification and amidation of hydroxy-substituted benzene derivative), and side chain structure compound having ester group The method of using it to construct | assemble a cyclic structure and making it a discotic compound is mentioned. Among them, a cyclic compound having a halogen atom (for example, cyanuric chloride and pyrimidine chloride) and a compound having active hydrogen (for example, derivatives of amine, aniline, alcohol, phenol, thioalcohol, thiophenol, etc.) A method of synthesis by reaction is preferred. Among these, the reaction using cyanuric chloride is preferable.

  Examples of the organic solvent used in the reaction include halogenated hydrocarbon organic solvents such as dichloromethane, ester organic solvents such as methyl acetate or ethyl acetate, ketone organic solvents such as acetone or methyl ethyl ketone, and ether organic solvents. For example, tetrahydrofuran or dioxane, nitrile organic solvents such as acetonitrile or propionitrile, amide organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidone, 1, Examples include 3-dimethyl-3,4,5,6, -tetrahydro-2 (1H) -pyrimidinone (DMPU) or hexamethylphosphoric triamide, or a sulfoxide-based organic solvent such as dimethyl sulfoxide. If necessary, a catalyst or a base may be used. Moreover, as described in Japanese Patent Application No. 2004-080527, when cyanuric chloride and an aminophenol derivative are reacted in a mixed solvent of water and an organic solvent in the presence of a base, a high yield is obtained. Tris (hydroxyphenylamino) -1,3,5-triazines are preferred because they can be synthesized.

  In the grease composition of the present invention, the content of the discotic compound is preferably 40 to 95% by mass, more preferably 60 to 90% by mass, from the viewpoint of low friction characteristics. In the present invention, the discotic compound can be used in place of the base oil. Therefore, the grease composition of the present invention may not contain the base oil usually contained in grease.

  The grease composition of the present invention contains a thickener. The thickener used in the present invention is not particularly limited, and any of the thickeners conventionally used in general can be used. For example, soap thickeners such as Li soap and composite Li soap; urea thickeners typified by diurea; inorganic thickeners typified by organic clay and silica; and organic thickeners typified by PTFE And so on. Of these, urea-based thickeners are particularly preferable. Urea thickeners are excellent in resistance to heat generated by lubrication under high load, are cheaper than other thickeners, and are therefore highly practical.

  The urea-based thickener may be any of a diurea compound and a polyurea compound. Diurea compounds include, for example, phenylene diisocyanate, diphenyl diisocyanate, phenyl diisocyanate, diphenylmethane diisocyanate, octadecane diisocyanate, decane diisocyanate, hexane diisocyanate and the like, octylamine, dodecylamine, hexadecylamine, otatadecylamine, oleylamine, aniline , P-toluidine, cyclohexylamine and other monoamines. The polyurea compound can be obtained, for example, by reacting the same diisocyanate as exemplified above with a diamine such as ethylenediamine, propanediamine, butanediamine, hexanediamine, octanediamine, phenylenediamine, tolylenediamine, xylenediamine and the like. The urea thickener is preferably selected from diurea compounds, selected from diurea compounds obtained by reaction of aliphatic amines such as octylamine and stearylamine, cyclohexylamine or mixtures thereof with diisocyanate compounds. More preferably. Further, a thickener which is a mixture of a urea compound represented by the general formula (1) and a diurea compound represented by the general formula (2) described in JP-A-11-241084; JP-A-7-34083 Aromatic diurea compounds described in the publication can also be used.

  The range of the preferred content of the thickener in the grease composition of the present invention varies depending on the type of thickener. In the grease composition of the present invention, for example, the content of the soap-based thickener is usually preferably 1 to 30% by mass, and more preferably 10 to 25% by mass. The content of the urea-based thickener is usually preferably from 0.1 to 30% by mass, and more preferably from 1 to 25% by mass.

  The grease composition of the present invention may contain other additives such as a rust inhibitor and an antioxidant in addition to the thickener, as long as preferable characteristics are not impaired. For example, metal soaps composed of metal salts other than lithium, other thickeners such as benton and silica gel; antioxidants such as amines, phenols, sulfurs, zinc dithiophosphates; chlorines, sulfurs, phosphoruss, Extreme pressure agents such as zinc dithiophosphate and organic molybdenum; oily agents such as fatty acids and vegetable oils; rust preventive agents such as petroleum sulfonates, dinonylnaphthalene sulfonates and sorbitan esters; metal deactivators such as benzotriazole and sodium nitrite; Viscosity index improvers such as polymethacrylate, polyisobutylene and polystyrene can be added singly or in combination of two or more. Moreover, you may add a montan wax, as described in Unexamined-Japanese-Patent No. 2002-371290.

  The grease composition of the present invention can be mixed with one or more ordinary lubricant base oils as necessary within a range not impairing the effects of the present invention. The base oil is not particularly limited, and any of base oils conventionally used for lubricants or greases can be used. As the base oil, mineral oil, synthetic oil, or a mixed oil thereof can be used. Mineral oil can be obtained, for example, by treating a lubricating oil raw material derived from paraffinic, intermediate group or naphthenic crude oil by atmospheric pressure or vacuum distillation with an aromatic extraction solvent such as phenol, furfural or N-methylpyrrolidone. Hydrorefined oil obtained by contact with hydrogen under hydrotreating conditions in the presence of hydrotreating catalysts such as solvent refined raffinate, lubricating oil feedstock silica-alumina-supported cobalt and molypden, hydrocracking Hydrocracked oil obtained by contacting with hydrogen under severe cracking reaction conditions in the presence of a catalyst, isomerized oil obtained by contacting wax with hydrogen under isomerization conditions in the presence of an isomerizing catalyst, Or a lubricating oil fraction obtained by combining a solvent refining process, a hydrotreating process, a hydrocracking process, an isomerization process, etc. That. In particular, a high viscosity index mineral oil obtained by a hydrocracking process or an isomerization process can be mentioned as a suitable one. In any of the production methods, steps such as a dewaxing step, a hydrofinishing step, and a white clay treatment step can be arbitrarily employed by a conventional method. Specific examples of the mineral oil include light neutral oil, medium neutral oil, heavy neutral oil, bright stock, and the like, and the base oil can be adjusted by appropriately mixing so as to satisfy the required properties. Examples of the synthetic oil include poly α-olefin, α-olefin oligomer, polybutene, alkylbenzene, polyol ester, dibasic acid ester, polyoxyalkylene glycol, polyoxyalkylene glycol ether, and silicone oil. These base oils can be used alone or in combination of two or more kinds, and mineral oil and synthetic oil may be used in combination.

  The grease composition of the present invention can be used as a lubricating grease used for various internal combustion engines, machine tools such as machine tools, and sliding parts of parts.

The present invention will be described more specifically with reference to the following examples. The materials, reagents, ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following examples.
[Synthesis Example: Synthesis Example of N-28]
N-28 was synthesized according to the following synthesis scheme.

(Synthesis of Compound (N-28-A))
To a 1 L reaction vessel equipped with a stirrer and a reflux condenser, 130 mL of toluene, 345 g (1.3 mol) of 11-bromoundecanoic acid and 0.1 mL of N, N-dimethylformamide were added. To this solution, 114 mL (1.58 mol) of thionyl chloride was added dropwise over 30 minutes. After dropping, the mixture was stirred for 2 hours while controlling at 60 ° C. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 373 g of the compound (N-28-A) (yield: 99%).

(Synthesis of Compound (N-28-B))
1 L of acetonitrile, 272 g (1.3 mol) of diethylene glycol monohexyl ether, and 199 g (1.43 mol) of triethylamine were added to a 3 L reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, and stirred to obtain a solution. The solution was cooled to 16 ° C., and 369 g (1.3 mol) of the obtained (N-28-A) was added dropwise over 1 hour while stirring the solution. After completion of dropping, the mixture was stirred at room temperature for 1.5 hours. After extraction with ethyl acetate and washing of the organic layer with water, the organic layer was separated and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 590 g of compound (N-28-B).

(Synthesis of Compound (N-28-C))
In a 3 L reaction vessel equipped with a stirrer, reflux condenser and thermometer, 70 g (0.45 mol) of 4-nitrocatechol, 481 g (1.1 mol) of (N-28-B) obtained and N, N- 350 mL of dimethylformamide was added and stirred to obtain a solution. To this was added 152 g (1.1 mol) of potassium carbonate, and the mixture was heated to 98 ° C. and stirred for 2 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate, and the organic layer was washed with water. The organic layer was separated and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 455 g of the compound (N-28-C).

(Synthesis of Compound (N-28-D))
To a 3 L reaction vessel equipped with a stirrer, reflux condenser and thermometer, 150 g (2.7 mol) of reduced iron, 600 mL of isopropyl alcohol, 120 mL of water and 15 g of ammonium chloride were added, and the mixture was heated to 90 ° C. with stirring and refluxed. . Into this, the obtained compound (N-28-C) was added dropwise, and the stirring was continued for 2 hours. After completion of the reaction, the mixture was filtered through Celite while being heated and washed with ethyl acetate. The filtrate was extracted with ethyl acetate and washed with water, and then the organic layer was separated and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 425 g of a crude product. Purification by silica gel column fractionation gave 237 g (91%) of compound (N-28-D).

(Synthesis of Compound N-28)
To a 3 L glass kettle equipped with a stirrer, a reflux condenser and a thermometer, 500 mL of N, N-dimethylformamide was poured, and 220 g (0.26 mol) of the obtained compound (N-28-D) was added. Next, 15 g (0.08 mol) of cyanuric chloride was added over 30 minutes. And 40 g (0.3 mol) of potassium carbonate was added, and the mixture was heated and stirred at 98 ° C. for 2 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate, and the organic layer was washed with water. The organic layer was separated and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 232 g of a crude product. Purification was performed by silica gel column separation to obtain 166 g (yield 80%) of compound (N-28).
The NMR data of the synthesized compound is shown below.
¹ H NMR (300 MHz CDCl ₃ ): δ 7.15-6.80 (m, 9H), 4.25 (t, 12H), 3.95 (t, 12H), 3.70 (t, 12H), 3 .65 (t, 12H), 3.60 (m, 12H), 3.45 (t, 12H), 2.30 (t, 12H), 1.80-1.30 (m, 144H),. 85 (t, 18H).

[Example: Performance evaluation of grease composition]
Exemplified compounds N-28, N-34 and S-25 were used to prepare greases (Examples 1 to 5) having the compositions shown in Table 1 below, respectively. Further, greases (comparative examples 1 to 4) having compositions shown in Table 2 below were prepared using various lubricant base oils.
A friction test was performed to measure the friction coefficient and the wear scar depth. In addition, the friction coefficient in an Example was measured using the reciprocating type friction tester (SRV friction wear tester), and the friction test was done on the following test conditions. The results of Examples 1 to 5 are shown in Table 1, and similarly, the results of Comparative Examples 1 to 4 are shown in Table 2.
(Test conditions)
The test conditions were ball-on-plate conditions.
Test piece (friction material): SUJ-2
Plate: φ24 × 6.9mm
Ball: φ10mm
Temperature: 150 ° C
Load: 200N
Amplitude: 1.0 mm
Frequency: 50Hz
Test time: measured 30 minutes after the start of the test.

  ADVANTAGE OF THE INVENTION According to this invention, the grease composition which can be used as lubrication grease used for various internal combustion engines and machine tools, such as a machine tool, a sliding part of components, etc. can be provided.

Claims (6)

A grease composition containing at least one discotic compound represented by the following general formula (3) and a diurea thickener.

(Wherein, X ^21, X ²² and X ²³ are each independently, N R ¹ group (R ¹ is hydrogen atom or an alkyl group of carbon number 1 to 30), or a sulfur atom, R ²¹ , R ²² and R ²³ each independently represents a substituent represented by any of the following formulas (4a), (4b) and (4): a21, a22 and a23 each independently represents an integer of 1 to 5 Represents.)

(In the formula (4a) and (4b), X ⁰ is a single bond, oxygen radicals, or -OCO- and represents; L ⁰ is the carbon number 1 to 20, linear, branched, or cyclic It represents an alkylene group; R ⁰ is located in the end of the side chain compound, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group; L ⁰¹ represents an oxygen atom, a sulfur atom, - (C = O ) O— or —NH— (C═O) O—; R ⁰¹ represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, p represents an integer of 1 to 20, q Represents an integer of 1 to 10.) The grease composition according to claim 1, wherein the diurea thickener is selected from diurea compounds obtained by reacting an aliphatic amine, cyclohexylamine or a mixture thereof with a diisocyanate compound. The grease composition according to claim 1 or 2, comprising 0.1 to 30% by mass of the thickener. The grease composition according to any one of claims 1 to 3, wherein in the general formula (3), X ²¹ , X ²² and X ²³ are each NH or a sulfur atom. In the said General formula (3), a21, a22, and a23 are respectively independently 1 or 2, The grease composition of any one of Claims 1-4. The grease composition according to any one of claims 1 to 5, wherein X ⁰ in the formulas (4a) and (4b) and L ⁰¹ in the formula (4) are oxygen atoms.