JP2005008876A - Lubricant composition and method for preparation of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lubricant composition exhibiting an excellent low-friction effect on a sliding face. <P>SOLUTION: The lubricant composition comprises a molecular complex formed by an intermolecular interaction of at least one tautomerizable compounds, wherein the molecular complex comprises a compound expressed by general formula (I) which is tautomerizable and has an ester linkage (excluding a specific melamine derivative). In general formula (I), Q<SP>11</SP>is O, N or N(R<SP>13</SP>); R<SP>11</SP>-R<SP>13</SP>are each H or a substituent and at least one of which has an ester linkage and selected from a ≥4C alkyl chain, an oligo alkyleneoxy chain, a ≥2C perfluoroalkyl chain, a perfluoroalkyl ether chain and an organic polysilyl chain. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention belongs to the technical field of a lubricant composition supplied to a mechanical friction sliding portion and a method for preparing the same, and more particularly, low friction characteristics and wear resistance under extreme pressure, and sustainability of the effect. It belongs to the technical field of a lubricant composition excellent in The present invention further relates to molecular complexes useful as friction coefficient reducing agents, extreme pressure agents, and antiwear agents.

The performance required for the lubricant is that the coefficient of friction of the mechanical friction sliding portion can be lowered over a wide temperature range and a wide pressure range, and the effect is maintained as long as possible. Further, it is desired that the lubricant not only has an effect of improving the lubricity between the frictional sliding members but also can impart wear resistance to the frictional sliding member itself. The effect of reducing the coefficient of friction at the friction sliding portion and extending the life of the lubricating oil such as engine oil directly leads to an improvement in fuel consumption for mechanical driving, that is, energy saving. Extending the life of engine oil not only reduces the amount of waste oil, but also reduces the amount of CO ₂ emission, which is preferable from the viewpoint of environmental compatibility that has been attracting attention in recent years. Also, among bearing parts and gears that slide under severe friction conditions among sliding parts of industrial machinery systems, when conventional lubricants such as lubricants and greases are used, the lubrication conditions become severe. The agent may cause film breakage or seizure, and a desired low coefficient of friction may not be obtained due to wear scratches. As a result, the reliability of the device may be impaired, and particularly when the device is downsized, the frictional conditions of the sliding portion tend to become severe, which hinders the downsizing of the device. Therefore, there is a demand for an energy-saving lubricant that does not cause wear or seizure even under severe conditions, can improve the reliability of the apparatus, and can contribute to downsizing of the apparatus.

  By the way, conventionally, as the lubricant, generally, a lubricant containing a lubricant base oil as a main component and a lubricating aid such as an organic compound is used. Particularly in recent years, organic molybdenum compounds have attracted attention as lubricating aids. The organomolybdenum compound has wear resistance and extreme pressure resistance (load resistance) even when the sliding part of the machine is moving under severe friction conditions such as high temperature, high speed or low speed, high load, small size and light weight. It is attracting attention as a material that is excellent in performance such as low friction characteristics and that can effectively exhibit lubrication performance under high pressure, that is, boundary lubrication conditions, compared to fluid lubrication conditions at normal pressure. However, the organomolybdenum compound is an excellent material that exhibits an excellent lubricating effect even under severe frictional conditions. However, the lubricating oil containing it has heavy metals such as molybdenum and zinc; In addition, it contains sulfides that become sulfur oxides that adversely affect the sliding member and the environment; and phosphoric acid that eutrophies rivers and seas; From the point of view, it is clearly not preferable. Furthermore, the molybdenum oxide / molybdenum sulfide film formed on the sliding surface is gradually scraped off by friction to form a new film, and therefore suddenly if either the organic molybdenum compound or the organic zinc compound that is the source is insufficient. The effect is lost. However, when the amount of the organomolybdenum compound and the organozinc compound is increased, by-products produced as a by-product due to the removal of the coating increase in the system and adversely affect the sliding machine itself. In the system using a molybdenum compound, the actual situation is that the effect of improving the fuel consumption by extending the life of the lubricant cannot be expected so much. In this way, a material that exhibits excellent performance as a lubricant and does not contain environmentally hazardous substances or environmental pollutants such as heavy metal elements, phosphate compounds, and sulfides, and that can maintain the performance for a long period of time is still available. Not provided.

  The inventors of the present invention have made extensive studies in order to improve such drawbacks of the prior art. First, molecular complexes with specific compounds have improved environmental performance or fuel consumption by extending the life of lubricants. It has been found that it exhibits excellent lubricating performance as an excellent friction coefficient reducing agent, extreme pressure agent or antiwear agent (Patent Document 1 and Patent Document 2). Various performances are required for the lubricant, and more advanced performance has been required in recent years due to higher performance of various machines and severe use conditions.

JP 2003-64389 A JP 2003-64390 A

  The present invention has been made in view of the above-mentioned problems, and has excellent lubricant performance, particularly low frictional properties not only in a form mixed with a conventional lubricant base oil but also in a form not mixed with a lubricant base oil. It is an object of the present invention to provide a lubricant composition and a method for preparing the same. The present invention also provides a lubricant composition capable of maintaining low friction and wear resistance for a long period of time on a sliding surface, and particularly capable of maintaining low friction and wear resistance for a long period even under extreme pressure. It is an object to provide a preparation method thereof. Another object of the present invention is to provide a lubricant composition which can easily form a homogeneous thin film and can be applied to the surface of a magnetic recording medium, a micromachine, and the like, and a method for preparing the same. Furthermore, it is an object of the present invention to provide a lubricant composition that can achieve both long life and environmental compatibility by eliminating heavy metal elements, phosphate groups, and sulfides that are poor in environmental compatibility, and a method for preparing the same. And Another object of the present invention is to provide a molecular complex useful as a friction coefficient reducing agent, extreme pressure agent, or antiwear agent.

As a result of intensive studies to solve the problems of the prior art, the present inventors have found that a molecular complex comprising a compound having a specific tautomerizable partial structure has excellent lubricating performance. Based on this finding, the present invention has been completed. Furthermore, it has been found that among the molecular complexes, a complex composed of a combination of functional groups capable of forming a planar complex exhibits particularly excellent lubricating performance.
That is, in order to solve the above-mentioned problems, the lubricant composition of the present invention includes a lubricant composition containing a molecular complex formed by intermolecular interaction of one or more tautomeric compounds having an ester bond. A compound in which the molecular complex is a tautomerizable compound represented by the following general formula (I) and has an ester bond (excluding a compound represented by the following general formula (TAM)): It is characterized by including at least 1 sort of as a component.

Formula (I)

(Wherein Q ¹¹ represents an oxygen atom, a sulfur atom or N (R ¹³ ). R ^{11 to} R ¹³ each independently represents a hydrogen atom or a substituent, and at least one of them contains an ester bond, and a total carbon number of 4 or more alkyl chains, oligoalkyleneoxy chain, total carbon number of 2 or more perfluoroalkyl chains, and .R ¹¹ that represents a substituent containing at least one selected from perfluoroalkyl ether chain and organic Porishiriru chain R ¹² and R ¹¹ and R ¹³ may be bonded to each other to form a ring structure.)

General formula (TAM)

(In the formula, R ¹ , R ² and R ³ each independently represent a substituent, and x, y and z each independently represents an integer of 1 to 5)

In the lubricant composition of the present invention, the molecular complex forms a planar complex by having a combination of functional groups that express intermolecular interactions in a geometrically complementary positional relationship. Preferably it is possible.
The compound represented by the general formula (I) is a compound represented by the following general formula (II) capable of tautomerization and having an ester bond (provided that the compound represented by the general formula (TAM) Except).

Formula (II)

(Wherein Q ²¹ and Q ²² each independently represents an oxygen atom, a sulfur atom or N (R ²⁴ ). R ^{21 to} R ²⁴ each independently represents a hydrogen atom or a substituent, and at least one of them represents A substitution containing at least one selected from an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a perfluoroalkyl chain having 2 or more carbon atoms, a perfluoroalkyl ether chain and an organic polysilyl chain. R ²¹ and R ²² , R ²² and R ²³ and R ²¹ and R ²⁴ may be bonded to each other to form a ring structure.

  The compound represented by the general formula (I) is a compound that can be tautomerized and has an ester bond represented by any one of the following general formulas (III) to (XI) (provided that the general formula (TAM It is more preferred that the compound represented by

General formula (III)

(Wherein R ^{31 to} R ³³ each independently represent a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain, oligoalkyleneoxy chain, total carbon having a total carbon number of 4 or more. number 2 more perfluoroalkyl chains, represents a substituent containing at least one selected from perfluoroalkyl ether chain and organic Porishiriru chain, an oxygen atom or a sulfur atom each independently Q ³¹ and Q ³² are .R ³¹ And R ³² and R ³² and R ³³ may be bonded to each other to form a ring structure.)

Formula (IV)

(Wherein R ^{41 to} R ⁴⁴ each independently represents a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain, oligoalkyleneoxy chain, or total carbon having a total carbon number of 4 or more. Represents a substituent containing at least one selected from a perfluoroalkyl chain of 2 or more, a perfluoroalkyl ether chain, and an organic polysilyl chain, and Q ⁴¹ represents an oxygen atom or a sulfur atom R ⁴¹ and R ⁴² , R ⁴¹ And R ⁴³ and R ⁴² and R ⁴⁴ may be bonded to each other to form a ring structure.)

General formula (V)

(Wherein R ^{51 to} R ⁵⁴ each independently represent a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain, oligoalkyleneoxy chain, or total carbon having a total carbon number of 4 or more. Represents a substituent containing at least one selected from a perfluoroalkyl chain, a perfluoroalkyl ether chain, and an organic polysilyl chain of at least two, R ⁵¹ and R ⁵² and R ⁵¹ and R ⁵³ are bonded to each other to form a ring; A structure may be formed.)

General formula (VI)

(In the formula, R ^{61 to} R ⁶³ each independently represent a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, or a total carbon atom. Q ⁶¹ represents an oxygen atom or a sulfur atom, and R ⁶¹ and R ⁶² are bonded to each other, including a substituent containing at least one selected from a perfluoroalkyl chain, a perfluoroalkyl ether chain and an organic polysilyl chain. And a ring structure may be formed.)

（式中、Ｑ⁷¹〜Ｑ⁷³は各々独立に酸素原子または硫黄原子を表し、Ｘは−Ｃ（＝Ｒ⁷¹）−または−Ｃ（Ｒ⁷²）（Ｒ⁷³）−を表す。Ｒ⁷¹は置換基を表し、Ｒ⁷²〜Ｒ⁷⁴は各々独立に水素原子または置換基を表し、そのうち少なくとも１つは、エステル結合を含有し、且つ総炭素数４以上のアルキル鎖、オリゴアルキレンオキシ鎖、総炭素数２以上のパーフルオロアルキル鎖、パーフルオロアルキルエーテル鎖および有機ポリシリル鎖から選ばれる少なくとも１種を含む置換基を表す。Ｒ⁷²とＲ⁷³は互いに結合して、環構造を形成してもよい。） Formula (VII)

(Wherein, Q ⁷¹ to Q ⁷³ represents an oxygen atom or a sulfur atom independently, X is -C (= R ⁷¹⁾ - or ^{-C (R 72) (R 73} ) - .R 71 representing the the substituent R ^{72 to} R ⁷⁴ each independently represents a hydrogen atom or a substituent, at least one of which contains an ester bond and has an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a total carbon atom, Represents a substituent containing at least one selected from a perfluoroalkyl chain, a perfluoroalkyl ether chain, and an organic polysilyl chain of at least 2. R ⁷² and R ⁷³ may be bonded to each other to form a ring structure. .)

Formula (VIII)

(Wherein Q ^{81 to} Q ⁸³ each independently represents an oxygen atom, a sulfur atom or N (R ⁸² ). R ⁸¹ and R ⁸² each independently represents a hydrogen atom or a substituent, and at least one of them represents: Substitution containing at least one selected from an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a perfluoroalkyl chain having 2 or more carbon atoms, a perfluoroalkyl ether chain, and an organic polysilyl chain. When Q ⁸³ is N (R ⁸² ), R ⁸¹ and R ⁸² may be bonded to each other to form a ring structure.

General formula (IX)

Wherein Q ⁹¹ and Q ⁹² are each independently a single bond, N (R ⁹⁴ ) (R ⁹⁴ represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms), an oxygen atom, a sulfur atom, a carbonyl group, R ⁹¹ and R ⁹² each independently represent a hydrogen atom or a substituent, and at least one of them contains an ester bond and has a total carbon number of 4 The substituent includes at least one selected from the above alkyl chain, oligoalkyleneoxy chain, perfluoroalkyl chain having 2 or more carbon atoms in total, perfluoroalkyl ether chain, and organic polysilyl chain, and R ⁹³ represents a halogen atom, hydroxyl group Group, amino group, mercapto group, cyano group, alkylthio group, arylthio group, carboxyl group or salt thereof, sulfo group or salt thereof, hydro Represents a xyamino group, a ureido group or a urethane group.)

Formula (X)

(Wherein Q ^{101 to} Q ¹⁰³ each independently represents an oxygen atom, a sulfur atom or N (R ¹⁰³ ), R ^{101 to} R ¹⁰³ each independently represents a hydrogen atom or a substituent, and at least one of them represents: Substitution containing at least one selected from an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a perfluoroalkyl chain having 2 or more carbon atoms, a perfluoroalkyl ether chain, and an organic polysilyl chain. Represents a group.)

General formula (XI)

(Wherein Q ¹¹¹ and Q ¹¹² each independently represents an oxygen atom, a sulfur atom or N (R ¹¹⁵ ), R ^{111 to} R ¹¹⁵ each independently represents a hydrogen atom or a substituent, and at least one of them represents: Substitution containing at least one selected from an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a perfluoroalkyl chain having 2 or more carbon atoms, a perfluoroalkyl ether chain, and an organic polysilyl chain. R ¹¹¹ and R ¹¹³ , R ¹¹³ and R ¹¹⁴ , R ¹¹³ and R ¹¹⁵ , R ¹¹² and R ^114, and R ¹¹⁴ and R ¹¹⁵ may be bonded to each other to form a ring structure.

In the lubricating composition of the present invention, the molecular complex can be tautomerized and represented by the general formula (I) and has n types (n is an integer of 1 or more) of compounds A ₁ to A ₁ . a _n (where, the formula (excluding the compound represented by TAM)) preferably a molecule錯合body made.
As a preferred embodiment of the present invention, the molecular complex is a compound having an ester bond capable of tautomerization represented by the general formula (I) (provided that the compound represented by the general formula (TAM) And the above lubricant composition, which is a molecular complex containing at least one compound represented by the following general formula (XII).

General formula (XII)

(In the formula, R ¹²¹ represents a substituent, and Q ¹²¹ and Q ¹²² each independently represents an oxygen atom or a sulfur atom.)

In the lubricant composition of the present invention, the pKa of the compound which can be tautomerized by the general formula (I) and has an ester bond is preferably 2 to 12.
In the lubricant composition of the present invention, the thermal phase transition temperature pattern of the molecular complex in the differential scanning calorimetry (DSC) method is preferably different from the thermal phase transition temperature pattern of the component compound. .
The lubricant composition of the present invention includes both an embodiment containing a lubricant base oil together with the molecular complex and an embodiment not containing a lubricant base oil. In the former embodiment, it is preferable to contain 50% by mass or more of the lubricant base oil. In the latter embodiment, it is preferable to contain 50% by mass or more of the molecular complex.
In order to solve the above-mentioned problems, the method for producing a lubricant composition of the present invention is a compound that is tautomerizable and has an ester bond represented by the general formula (I) (provided that the general formula ( N) (excluding compounds represented by TAM)) (n is an integer of 1 or more), and a molecular complex comprising a compound having an n-type tautomerizable compound having an ester bond as a constituent element. It has the process to produce | generate. It is characterized by the above-mentioned. In order to solve the above-mentioned problem, the lubricant composition of the present invention is a compound that is tautomerizable and has an ester bond represented by the general formula (I) (provided that the general formula (TAM) A molecular complex comprising both compounds as constituents, and at least one compound selected from the above general formula (XII) and at least one compound capable of tautomerization It has the process to produce | generate. It is characterized by the above-mentioned.

  Further, according to the present invention, the compound represented by the general formula (I) (excluding the compound represented by the general formula (TAM)) is supplied to the sliding surface, and the general A method for reducing a friction coefficient of a sliding surface, comprising a step of forming a molecular union comprising at least a compound represented by formula (I) as a constituent; and tautomerism represented by formula (I) And a compound having an ester bond (excluding the compound represented by the general formula (TAM)) as a constituent element, and having one or more tautomers and having an ester bond A friction coefficient reducing agent, an extreme pressure agent or an antiwear agent comprising a molecular complex formed by intermolecular interaction.

  According to the present invention, a lubricant composition having excellent lubricant performance, particularly low frictional properties, and a method for preparing the same, not only in a form mixed with a conventional lubricant base oil but also in a form not mixed with a lubricant base oil Can be provided. In addition, according to the present invention, the lubricant composition can maintain low friction and wear resistance on the sliding surface for a long period of time, and particularly can maintain low friction and wear resistance for a long period even under extreme pressure. Products and methods for their preparation. In addition, according to the present invention, it is possible to provide a lubricant composition that can easily form a homogeneous thin film and can be applied to the surface of a magnetic recording medium, a micromachine, and the like, and a method for preparing the same. Furthermore, according to the present invention, by eliminating heavy metal elements, phosphate groups and sulfides which are poor in environmental compatibility, a lubricant composition capable of achieving both long life and environmental compatibility and a method for preparing the same are provided. Can do. In addition, according to the present invention, a molecular complex useful as a friction coefficient reducing agent, extreme pressure agent, or antiwear agent can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.
The present invention relates to a lubricant composition containing a molecular complex formed by an intermolecular interaction of one or more kinds of compounds capable of tautomerization and having an ester bond. In the present specification, the term tautomerism includes keto-enol tautomerism and imine-enamine tautomerism, specifically, a compound represented by the general formula (1): It refers to causing a ^{H-Q 11 -C (R 11} ) = N- type structure and ^{Q 11 = C (R 11)} -NH- mold structure conversion between the structure.
The ester bond in the present invention refers to a partial structure represented by the following general formula (a) or general formula (b). The compound used in the present invention is a compound in which at least one side chain having an ester bond is bonded to a central skeleton structure.

General formula (a)

General formula (b)

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.
L ^o is an alkylene group, 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 group. The divalent linking group may have a substituent. L ⁰ is preferably an alkylene group.
R ⁰ represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms located at the end of the side chain of the compound. When the alkyl group and the aryl group have a substituent, the substituent includes a halogen atom, an alkoxy group (methoxy, ethoxy, methoxyethoxy, phenoxy, etc.), an alkylthio group or an arylthio group (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 Group, cyano group, nitro group, carboxyl group, sulfo group, carbamoyl group, sulfamoyl group, ureido group and the like.
Among the specific ester bonds in the present invention, a structure represented by the general formula (a) is preferable. The left side of the partial structure of the general formula (a) is bonded to the central skeleton structure side. In the lubricating composition of the present invention, particularly low friction coefficient performance and low viscosity can be realized by using the following structure having an alkyl group substituted with an ethyleneoxy group at R ⁰ .

General formula (c)

L ⁰¹ is synonymous with L ⁰ . R ⁰¹ represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. When the alkyl group and the aryl group have a substituent, the substituent is the substituent of the alkyl group represented by R ^0. Same as listed. p and q each represent an integer. 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.

  The lubricant composition of the present invention is a lubricant composition containing a molecular complex formed by an intermolecular interaction of one or more kinds of compounds capable of tautomerization and having an ester bond. The complex is composed of at least one compound (except for the compound represented by the following general formula (TAM)) that is tautomerizable and has an ester bond represented by the following general formula (I). It is characterized by including as.

Formula (I)

In the formula, Q ¹¹ represents an oxygen atom, a sulfur atom or N—R ¹³ . R ^{11 to} R ¹³ each independently represent a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, or 2 or more carbon atoms in total. This represents a substituent containing at least one selected from a perfluoroalkyl chain, a perfluoroalkyl ether chain, and an organic polysilyl chain. R ¹¹ and R ¹² , and R ¹¹ and R ¹³ may be bonded to each other to form a ring structure.

General formula (TAM)

In the formula, R ¹ , R ² and R ³ each independently represent a substituent, and x, y and z each independently represent an integer of 1 to 5.
In the general formulas (I) and (TAM), the substituents represented by R ^{11 to} R ¹³ and R ^{1 to} R ³ are each a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), Alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups, silyloxy groups, heterocyclic oxy groups , Acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino Groups, alkyl and aryl Sulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, Examples include aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, and silyl groups. Further, the substituents R ^{11 to} R ¹³ include those substituents substituted with one or more substituents selected from these substituents.

  More specifically, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl A group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted group having 5 to 30 carbon atoms). A substituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a C 5-30 bicycloalkane, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2, 2,2] octane-3-yl), and tricyclo structures having more ring structures. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted group having 3 to 30 carbon atoms) A cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), bicycloalkenyl group (Substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] octyl -2-en-4-yl)], an alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group), an aryl group (preferably having 6 carbon atoms) To 30 substituted or unsubstituted aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl),

Heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably 3 to 3 carbon atoms. 30- or 5-membered aromatic heterocyclic group such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group ( Preferably, it is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably having a carbon number) 6-30 substituted or unsubstituted aryloxy groups such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy , 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably A substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group, a substitution having 2 to 30 carbon atoms) Or an unsubstituted alkylcarbonyloxy group, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyl Oh Si group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n -Octylaminocarbonyloxy, Nn-octylcarbamoyloxy),

An alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (Preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably Is an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N- Til-anilino, diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, For example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or non-substituted having 1 to 30 carbon atoms) Substituted aminocarbonylamino such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino),

An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxy; Carbonylamino), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxy Carbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminos) Phonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms) , For example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably substituted with 1 to 30 carbon atoms) Or an unsubstituted alkylthio group such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms such as phenylthio, p-chlorophenyl) E, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio) A sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N -Acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl having 1 to 30 carbon atoms) A group, 6-30 substituted or unsubstituted arylsulfinyl groups, for example Chirusurufiniru, ethylsulfinyl, phenylsulfinyl, p- methyl phenylsulfinyl),

Alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- Methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as acetyl, pivaloyl, 2 -Chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chloropheno Cicarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxy Carbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di- n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic rings having 3 to 30 carbon atoms) An azo group, for example Phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-phthalimide), phosphino group (preferably 2-30 carbon atoms) Substituted or unsubstituted phosphino groups such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino),

A phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), a phosphinyloxy group (preferably having 2 to 2 carbon atoms) 30 substituted or unsubstituted phosphinyloxy groups, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino groups (preferably substituted or unsubstituted having 2 to 30 carbon atoms) Phosphinylamino group such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms such as trimethylsilyl, t-butyldimethyl Silyl, phenyldimethylsilyl).
Among the above substituents, those having a hydrogen atom may be removed and further substituted with one or more of the above substituents. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. More specific examples include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

However, at least one of the substituents R ^{11 to} R ¹³ contains an ester bond and has an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a perfluoroalkyl chain having 2 or more carbon atoms in total, or perfluoro It represents a substituent containing at least one selected from an alkyl ether chain and an organic polysilyl chain. The substituents R ^{11 to} R ¹³ themselves may be an alkyl group having a total carbon number of 4 or more, or an alkyl chain having a total carbon number of 4 or more may be further substituted with the exemplified substituents.

When any of R ^{11 to} R ¹³ is a group represented by the formula (a) or (b), either L ⁰ or R ⁰ is an alkyl chain or oligoalkyleneoxy chain having a total carbon number of 4 or more. And at least one selected from a perfluoroalkyl chain having 2 or more carbon atoms in total, a perfluoroalkyl ether chain, and an organic polysilyl chain. Both L ⁰ and R ⁰ may contain one kind selected from the chain. These chains are preferably included in R ⁰ .

  The alkyl chain having 4 or more carbon atoms may be linear or branched. The substituent containing an alkyl chain having 4 or more carbon atoms is preferably an n-octyl group, an n-octyloxy group, an n-octylthio group, an n-octylamino group, an n-nonyl group, or an n-nonyloxy group. N-decyl group, n-decyloxy group, n-undecyl group, n-undecyloxy group, n-dodecyl group, n-dodecyloxy group, n-dodecylthio group, n-dodecylamino group, n-pentadecyl group, Examples include n-pentadecyloxy group, n-hexadecyl group, n-hexadecyloxy group, n-hexadecylthio group, and n-hexadecylamino group. Examples of the substituent containing a branched alkyl chain having 4 or more carbon atoms include 2-ethylhexyl group, 2-ethylhexyloxy group, 2-ethylhexylthio group, 2-ethylhexylamino group, 2-hexyldecyl group, 2 -Hexyldecylthio group, 2-hexyldecylamino group, 3,7,11,15-tetramethylhexadecyl group, 3,7,11,15-tetramethylhexadecyloxy group, 3,7,11,15- Examples thereof include a tetramethylhexadecylthio group and a 3,7,11,15-tetramethylhexadecylamino group.

The alkyl part of the oligoalkyleneoxy chain may be linear or branched. Examples of the substituent containing an oligoalkyleneoxy chain include a diethyleneoxy group, a triethyleneoxy group, a tetraethyleneoxy group, a dipropyleneoxy group, and a hexyloxyethyleneoxyethyleneoxy group.
The alkyl part of the perfluoroalkyl chain having 2 or more carbon atoms may be linear or branched. Preferred examples of the substituent containing a branched perfluoroalkyl chain include a pentadecylfluoroheptyl group, a pentadecylfluoroheptylcarbonyloxy group, a heptadecylfluorooctyl group, and a pentadecylfluorooctylsulfonyl group. The alkyl part of the perfluoroalkyl ether chain may be linear or branched. Examples of the substituent containing the perfluoroalkyl ether chain include isopropylene oxide, methylene oxide, ethylene oxide and a mixed system thereof, and a substituent in which the alkyl portion of propylene oxide is substituted with fluorine.
The organic polysilyl chain is a group in which an atomic group containing a silicon atom is present in the side chain of a long chain substituent (for example, poly (p-trimethylsilylstyrene), poly (1-trimethylsilyl-1-propyne), etc.) Alternatively, it contains a silicon atom in the main chain of the long chain substituent. Preferably, the main chain of the long chain substituent contains a silicon atom. Examples of the main chain containing silicon include linear, branched, cyclic or polycyclic long-chain substituents having a repeating unit having a structure represented by the following formula (s).

Formula (S)

In the formula, R ^s1 and R ^s2 each independently represent a substituent, and R ^s1 and R ^s2 may be bonded to each other to form a ring structure. Specific examples include the substituents exemplified for the substituents R ^{11 to} R ¹³ in the general formula (I). Of these, an alkyl group is preferable. X represents an atomic group composed of an oxygen atom, a nitrogen atom, an alkylene group, a phenylene group, a silicon atom, a metal atom, or a combination thereof. X is preferably an oxygen atom or an atomic group composed of a combination of an oxygen atom and an alkylene group, and particularly preferably an oxygen atom. P represents an integer of 1 to 200, preferably 3 to 30. Specific examples of the organic polysilyl chain include polysiloxane, polysilazane, polysilmethylene, polysilphenylene, polysilane, and polymetallosiloxane.

In the general formula (I), R ¹¹ and R ¹² and R ¹¹ and R ¹³ may be bonded to each other to form a ring structure. Examples of the ring structure that can be formed by linking R ¹¹ and R ¹² include a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyrazole ring, an oxazole ring, and a heterocyclic ring such as a thiazole ring, and their benzo-fused rings, purine rings, Heteroaromatic condensed rings such as a naphthyridine ring and a pteridine ring are exemplified. Examples of the ring structure that can be formed by linking R ¹¹ and R ¹³ include a pyrrolidine ring, a thiazolidine ring, and a piperidine ring.

  The compound represented by the general formula (I) includes a compound represented by the following general formula (II) (excluding the compound represented by the general formula (TAM)).

Formula (II)

In the formula, Q ²¹ and Q ²² each independently represent an oxygen atom, a sulfur atom or N (R ²⁴ ). R ^{21 to} R ²⁴ each independently represents a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, or 2 or more carbon atoms in total. This represents a substituent containing at least one selected from a perfluoroalkyl chain, a perfluoroalkyl ether chain, and an organic polysilyl chain. R ²¹ and R ²² , R ²² and R ^23, and R ²¹ and R ²⁴ may be bonded to each other to form a ring structure.
In the general formula (II), the substituents represented by R ^{21 to} R ²⁴ are the same as the examples of the substituents represented by R ^{11 to} R ¹³ in the general formula (I), and the preferred ranges are also the same. is there. Substituents including an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a perfluoroalkyl chain having 2 or more carbon atoms, a perfluoroalkyl ether chain, and an organic polysilyl chain are also synonymous with each of the general formula (I). The preferred range is also the same.

In the general formula (II), examples of the ring structure that can be formed by linking R ²¹ and R ²² include heterocyclic rings such as imidazole ring, triazole ring, oxadiazole ring, pyrimidine ring, triazine ring, and the like. And heteroaromatic condensed rings such as benzo-fused rings (quinazoline rings and the like), purine rings, naphthyridine rings, and pteridine rings. Examples of the ring structure that can be formed by linking R ²² and R ²³ and R ²¹ and R ²⁴ include a pyrrolidine ring, a thiazolidine ring, a piperidine ring, a pyrazole ring, an oxazole ring, and a thiazole ring.

  When the compound represented by the general formula (I) (excluding the compound represented by the general formula (TAM) has a ring structure, the planar surface that efficiently covers the sliding surface is provided. It is preferable because it can form a complex, and particularly preferably has a ring structure containing a nitrogen atom in the general formula (I). As a preferable example of the compound having a ring structure, a compound containing a tautomerizable ester bond represented by the following general formulas (III) to (XI) (however, a compound represented by the general formula (TAM) Except). Especially, the compound represented by either of the following general formula (III)-(IX) contained in the range of the compound represented by the said general formula (II) is preferable.

General formula (III)

In the formula, R ^{31 to} R ³³ each independently represent a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, or a total carbon number. It represents a substituent containing at least one selected from two or more perfluoroalkyl chains, perfluoroalkyl ether chains and organic polysilyl chains. Q ³¹ and Q ³² each independently represent an oxygen atom or a sulfur atom. R ³¹ and R ³² and R ³² and R ³³ may be bonded to each other to form a ring structure. R ^{31 to} R ³³ may include a group represented by the general formula (a) or (b), or a group itself represented by the general formula (a) or (b). Also good.

Formula (IV)

In the formula, each of R ^{41 to} R ⁴⁴ independently represents a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a total carbon number It represents a substituent containing at least one selected from two or more perfluoroalkyl chains, perfluoroalkyl ether chains and organic polysilyl chains. Q ⁴¹ represents an oxygen atom or a sulfur atom. R ⁴¹ and R ⁴² , R ⁴¹ and R ^43, and R ⁴² and R ⁴⁴ may be bonded to each other to form a ring structure. R ^{41 to} R ⁴⁴ may contain a group represented by the general formula (a) or (b), or may be a group represented by the general formula (a) or (b) itself. Good.

General formula (V)

In the formula, each of R ^{51 to} R ⁵⁴ independently represents a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, or a total carbon number. It represents a substituent containing at least one selected from two or more perfluoroalkyl chains, perfluoroalkyl ether chains and organic polysilyl chains. R ⁵¹ and R ⁵² and R ⁵¹ and R ⁵³ may be bonded to each other to form a ring structure. R ^{51 to} R ⁵⁴ may contain a group represented by the general formula (a) or (b), or may be a group represented by the general formula (a) or (b) itself. Good.

General formula (VI)

In the formula, each of R ^{61 to} R ⁶³ independently represents a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, or a total carbon number. It represents a substituent containing at least one selected from two or more perfluoroalkyl chains, perfluoroalkyl ether chains and organic polysilyl chains. Q ⁶¹ represents an oxygen atom or a sulfur atom. R ⁶¹ and R ⁶² may be bonded to each other to form a ring structure. R ^{61 to} R ⁶³ may contain a group represented by the general formula (a) or (b), or may be a group represented by the general formula (a) or (b) itself. Good.

式中、Ｑ⁷¹〜Ｑ⁷³は各々独立に酸素原子または硫黄原子を表し、Ｘは−Ｃ（＝Ｒ⁷¹）−または−Ｃ（Ｒ⁷²）（Ｒ⁷³）−を表す。Ｒ⁷¹は置換基を表し、Ｒ⁷²〜Ｒ⁷⁴は各々独立に水素原子または置換基を表し、そのうち少なくとも１つは、エステル結合を含有し、且つ総炭素数４以上のアルキル鎖、オリゴアルキレンオキシ鎖、総炭素数２以上のパーフルオロアルキル鎖、パーフルオロアルキルエーテル鎖および有機ポリシリル鎖から選ばれる少なくとも１種を含む置換基を表す。Ｒ⁷²とＲ⁷³は互いに結合して、環構造を形成してもよい。Ｒ⁷¹〜Ｒ⁷³は前記一般式（ａ）又は（ｂ）で表される基を含んでいてもよく、また前記一般式（ａ）又は（ｂ）で表される基それ自体であってもよい。 Formula (VII)

In the formula, Q ^{71 to} Q ⁷³ each independently represents an oxygen atom or a sulfur atom, and X represents —C (═R ⁷¹ ) — or —C (R ⁷² ) (R ⁷³ ) —. R ⁷¹ represents a substituent, R ^{72 to} R ⁷⁴ each independently represents a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain having 4 or more carbon atoms in total, an oligoalkyleneoxy And a substituent containing at least one selected from a chain, a perfluoroalkyl chain having 2 or more carbon atoms in total, a perfluoroalkyl ether chain, and an organic polysilyl chain. R ⁷² and R ⁷³ may be bonded to each other to form a ring structure. R ^{71 to} R ⁷³ may contain a group represented by the general formula (a) or (b), or may be a group represented by the general formula (a) or (b) itself. Good.

Formula (VIII)

In the formula, Q ^{81 to} Q ⁸³ each independently represents an oxygen atom, a sulfur atom or N (R ⁸² ). R ⁸¹ and R ⁸² each independently represents a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, or 2 or more carbon atoms. This represents a substituent containing at least one selected from a perfluoroalkyl chain, a perfluoroalkyl ether chain, and an organic polysilyl chain. When Q ⁸³ is N (R ⁸² ), R ⁸¹ and R ⁸² may be bonded to each other to form a ring structure. R ^{81 to} R ⁸³ may contain a group represented by the general formula (a) or (b), or may be a group represented by the general formula (a) or (b) itself. Good.

General formula (IX)

In the formula, Q ⁹¹ and Q ⁹² are each independently a single bond, an N (R ⁹⁴ ) group (R ⁹⁴ 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. R ⁹¹ and R ⁹² each independently represent a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, or 2 or more carbon atoms. Represents a substituent containing at least one selected from a perfluoroalkyl chain, a perfluoroalkyl ether chain and an organic polysilyl chain, and R ⁹³ represents a halogen atom, a hydroxyl group, an amino group, a mercapto group, a cyano group, an alkylthio group, an arylthio group. Represents a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a hydroxyamino group, a ureido group or a urethane group. R ^{91 to} R ⁹² may contain a group represented by the general formula (a) or (b), or may be a group represented by the general formula (a) or (b) itself. Good.

Formula (X)

In the formula, Q ^{101 to} Q ¹⁰³ each independently represents an oxygen atom, a sulfur atom or N (R ¹⁰³ ). R ^{101 to} R ¹⁰³ each independently represent a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, or 2 or more carbon atoms. This represents a substituent containing at least one selected from a perfluoroalkyl chain, a perfluoroalkyl ether chain, and an organic polysilyl chain. R ^{101 to} R ¹⁰³ may contain a group represented by the general formula (a) or (b), or may be a group represented by the general formula (a) or (b) itself. Good.

General formula (XI)

In the formula, Q ¹¹¹ and Q ¹¹² each independently represents an oxygen atom, a sulfur atom or N (R ¹¹⁵ ). R ^{111 to} R ¹¹⁵ each independently represent a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, or 2 or more carbon atoms in total. This represents a substituent containing at least one selected from a perfluoroalkyl chain, a perfluoroalkyl ether chain, and an organic polysilyl chain. R ¹¹¹ and R ¹¹³ , R ¹¹³ and R ¹¹⁴ , R ¹¹³ and R ¹¹⁵ , R ¹¹² and R ^114, and R ¹¹⁴ and R ¹¹⁵ may be bonded to each other to form a ring structure such as a spiro ring. R ^{111 to} R ¹¹⁵ may contain a group represented by the general formula (a) or (b), or may be a group itself represented by the general formula (a) or (b). Good.

Formula (III) in ^{~ (XI), R 31 ~R} 33, R 41 ~R 44, R 51 ~R 54, R 61 ~R 68, R 71 ~R 74, R 81, R 82, R 91, The substituents represented by R ⁹² , R ^{101 to} R ¹⁰³ and R ^{111 to} R ¹¹⁵ are the same as the substituents represented by R ^{11 to} R ¹³ in the aforementioned general formula (I). The same applies to the preferred range. In the formula (VII), = as R ⁷¹ is a carbon - methylene group carbon double bond is formed (= CH _2), isopropylidene group (= CMe _2), nonylidene group (= CH (n) C ₈ H ₁₇ ), benzylidene group (═CHC ₆ H ₅ ), etc .; imino group (═NH), phenylimino group (═NC ₆ H ₅ ), octylimino group (═N—) in which a carbon-nitrogen double bond is formed (N) C ₈ H ₁₇ ) and the like; an oxo group (═O) in which a carbon-oxygen double bond is formed; and a thioxo group (═S) in which a carbon-sulfur double bond is formed.

  The compounds represented by the formulas (III) to (XI) are each an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a perfluoroalkyl chain having 2 or more carbon atoms, or a perfluoroalkyl ether chain in the molecule. Or it has a substituent containing an organic polysilyl chain. About these chains, it is the same as that of the specific example of these chains in the above-mentioned general formula (I), and its preferable range is also the same.

In the above formula, R ³¹ and R ³² , R ³² and R ³³ , R ⁴¹ and R ⁴² , R ⁴¹ and R ⁴³ , R ⁴² and R ⁴⁴ , R ⁵¹ and R ⁵² , R ⁵¹ and R ⁵³ , R ⁶¹ and R ⁶² , ^R72 and ^R73 , ^R81 and ^R82 , ^R91 and ^R92 , ^R111 and ^R113 , ^R113 and ^R114 , ^R113 and ^R115 , ^R112 and ^R114, and ^R114 and ^R115 are Each may be bonded to each other to form a ring structure. Examples of the ring structure that can be formed include rings that respectively constitute the aryl group and aromatic heterocyclic group exemplified as the substituent having the cyclic structure represented by R ¹²¹ in the general formula (XII) described later. .

The compound having the tautomerism represented by the general formula (I) preferably has a pKa of 2 to 12.
The molecular complex having the compound represented by the general formula (I) as a constituent element has a combination of functional groups that express intermolecular interactions in a geometrically complementary positional relationship, It is preferable that a planar complex can be formed thereby. Here, the “combination of functional groups that express intermolecular interactions in a geometrically complementary positional relationship” generally refers to functional groups that satisfy the following requirements (1) to (5): Refers to a combination. Two interacting molecules that are constituent elements of the molecular complex are defined as a substrate σ and a receptor ρ. The high degree of molecular recognition by the receptor molecule ρ depends on a large difference between the binding free energy of the partner substrate σ and the binding free energy of other substrates with relatively small interactions, and the difference is statistically distributed. It is preferable that it is large so that it is largely deviated from the above. In order to make a large difference in the binding free energy, it is necessary to satisfy the following requirements (1) to (5).
(1) σ and ρ have three-dimensional (shape and size) complementarity (steric complementarity). That is, there are irregularities at appropriate portions of σ and ρ. Here, the unevenness refers to the complementary binding site (for example, hydrogen bond donor (convex) and hydrogen bond acceptor (concave)) as described in (2).
(2) σ and ρ have interactional complementarity. That is, on σ and ρ (preferably, so that a complementary electron and nucleus (electrostatic force, hydrogen bond, van der Waals force) distribution map can be obtained at the complementary sites where σ and ρ can bond with each other. Are properly aligned) and have complementary binding sites (electrostatic such as +/-, charge / dipole, dipole / dipole, hydrogen bond donor / hydrogen bond acceptor, etc.).
(3) A large contact area exists between ρ and σ. This can be satisfied by having a plurality of action sites described below.
(4) Multiple interaction sites exist in ρ and σ. Since non-covalent interactions are weaker than covalent bonds, multiple interaction sites are required. For example, in the case of interaction by hydrogen bonds, it is desirable that both have a hydrogen bond donor / hydrogen bond acceptor.
(5) The coupling between ρ and σ should be a strong overall binding as a whole. In theory, high stability does not necessarily mean high selectivity, but in practice it is often the case. In fact, the difference in bond free energy tends to increase as the bond becomes stronger. That is, a strong interaction is required for high binding efficiency (the proportion of σ bound is greater than the free σ). In order to recognize efficiently, that is, to achieve both high stability and high selectivity, a strong coupling is required between ρ and σ.

In addition, the “planar complex” means that when the molecular complex is adsorbed or contacted with the friction sliding surface, the frictional sliding is the smallest number according to the shape of the molecule constituting the molecular complex. It refers to a molecular complex that is arranged so as to cover the unit area of the surface. Therefore, when the molecule forming the complex is substantially rod-shaped, the inertial axis of the skeleton forming the molecule is in the same plane as the friction sliding surface, that is, parallel to the friction sliding surface, A state of precise arrangement. In addition, when the skeleton forming the molecule forming the complex has a substantially flat plate shape, the molecular plane is substantially in the same plane as the friction sliding surface, that is, parallel to the friction sliding surface and dense. Refers to the state of arrangement.
However, an alkyl group, an alkoxy group, a perfluoroalkyl group, and a polysilyl group, which are hydrophobic groups present in the general formula (I) of the present invention, are not regarded as the skeleton portion. In the present invention, “planar complex can be formed” means that the planar complex should be formed when the molecular complex is supplied to the sliding surface. It is meant to include those that do not form a planar structure before being supplied. The lubricant composition of the present invention exhibits an excellent lubricating effect when the planar complex efficiently coats the friction sliding surface. Even when the lubricant composition of the present invention is used in a mode in which it is not mixed with a lubricant base oil, it exhibits an extremely excellent lubrication effect, an effect of improving the wear resistance of the sliding surface, and further, these effects over a long period of time. Can be maintained. Moreover, the said effect can be show | played also under extreme pressure.

In the present invention, the functional group capable of tautomerization in the general formula (I) constitutes the above-mentioned “combination of functional groups that express intermolecular interaction in a geometrically complementary positional relationship”. Be the basis. The other that can constitute a tautomeric functional group in the compound represented by the general formula (I) and a “combination of functional groups that express intermolecular interaction in a geometrically complementary positional relationship” Examples of the functional group include tautomeric functional groups such as a carboxylic acid group, a thiocarboxylic acid group, a carbonamide group, a thiocarbonamide group, a carboxylic acid imide group, a thiocarboxylic acid imide group, and a ureido group.
The compound represented by the general formula (I), the (thio) carboxylic acid group, the (thio) carbonamido group, the (thio) carboxylic acid imide group and the ureido group are represented by the following formulas (XIII) to (XVI): As shown in Fig. 2, the combination strongly suggests the possibility of stabilization by intermolecular interaction complementary to the resonance structure by the electron flow described in the classical electron theory of organic chemistry. In the following formulas (XIII) and (XIV), in the general formula (I), Q ¹¹ represents N (R ¹³ ), and R ¹¹ , R ¹² and R ¹³ are omitted from the formula. did. In the following formulas (XV) and (XVI), the case where the general formula (II) represents a 2,4-bisamino group-substituted pyrimidine derivative is shown, and the substituents are omitted.

Formula (XIII)

Formula (XIV)

Formula (XV)

Formula (XVI)

In the above formula, Q ¹³¹ , Q ¹³² , Q ¹⁴¹ , Q ¹⁵¹ , Q ¹⁵² and Q ¹⁶¹ each independently represent an oxygen atom or a sulfur atom, and R ¹³¹ , R ¹⁴¹ , R ¹⁴² , R ¹⁵¹ , R ¹⁵² , R ¹⁶¹ And R ¹⁶² each independently represents a substituent, and R ¹⁴¹ and R ¹⁴² , R ¹⁵¹ and R ¹⁵² , and R ¹⁶¹ and R ¹⁶² may be bonded to each other to form a ring. The substituents represented by R ¹³¹ , R ¹⁴¹ , R ¹⁴² , R ¹⁵¹ , R ¹⁵² , R ¹⁶¹ and R ¹⁶² are the same as the substituents represented by R ^{11 to} R ¹³ in the general formula (I), The same applies to specific examples and preferred ranges. R ¹⁴¹ and R ¹⁴² , R ¹⁵¹ and R ¹⁵² , and R ¹⁶¹ and R ¹⁶² are preferably bonded to each other to form a ring. In particular, in the general formula (XVI), R ¹⁶¹ and R ¹⁶² are preferably bonded to each other to form a ring. Examples of such ring structures include benzimidazolinone, indazolinone, uracil, thiouracil, benzoxazolinone, succinimide, phthalic imide, violuric acid, barbituric acid, pyrazolone, hydantoin, rhodanine, orotic acid , Benzothiazolinone, ammelin, coumarin, maleic hydrazide, isatin, 3-indazolinone, parabanic acid, phthalazinone, urazole, alloxan, meldrum acid, uramil, caprolactone, caprolactam, thiapendione, tetrahydro-2-pyrimidinone, 2,5- Piperazinedione, 2,4-quinazolinedione, 2,4-pteridinediol, folic acid, acetylene urea, guanine, adenine, cytosine, thymine, 2,4-dioxohexahydro-1,3,5-triazine And the like.

By the above formulas (XIII) to (XVI), specific examples satisfying the above-mentioned complementary requirements (1) to (5) for complex formation were shown. The stereocomplementarity of (1) will be described using (XV) as an example. Both the 2,4-diaminotriazine structure (referred to as σ) and the acid imide (referred to as ρ) have irregularities. At σ, the convexity is an amino group and the nitrogen of the triazine ring is concave. On the other hand, in ρ, the carbonyl group is concave and the central amino group is convex. σ has a structure arranged in the order of convex and concave, and ρ has a structure arranged in the order of concave and convex. As a result, σ and ρ can be hydrogen-bonded reasonably at the same distance at three locations, realizing strong intermolecular bonds.
The interaction complementarity of (2) is described as a concerted electron flow in the formulas (XIII) to (XVI), but the starting point of → in the formula (XIII) is the arrival point of δ ⁻ and →. Is expressed as the following formula (XVIII) where δ ^{+ is represented} as δ ⁺ , and it can be explained by electrostatic transfer of electrons.

Formula (XVIII)

Again, a series of electron flows represented by the formulas (XIII) to (XVI) will be described. It is energetically advantageous that the electron flow flows two-dimensionally (planarly) rather than three-dimensionally. ,preferable. From this point, in Formulas (XIV) to (XVI), R and R ′ are preferably bonded to each other to form a ring, preferably conjugated, and preferably an aromatic ring. . R in formula (XIII) is also preferably a ring structure group, and is preferably an aromatic ring group (including both an aryl group and an aromatic heterocyclic group).
The formula (XV) will be described. The 2,4-diaminotriazine structure (A) and the acid imide structure (B) are hydrogen-bonded at three positions. In (A), the amino group is convex and the triazine ring is Nitrogen atoms in are concave.

As a preferred embodiment of the molecular complex, a compound containing n types (n is an integer of 1 or more) of ester bonds represented by the general formula (I) (wherein the general formula (TAM) ) excluding the compound represented by) molecules錯合body consisting of a ₁ to a _n and the like. In addition, as a preferable embodiment of the molecular complex, a combination of the tautomerizable compound represented by the general formula (I) and a compound containing a tautomerizable ester bond such as (thio) carboxylic acid A combination of a compound containing a tautomerizable ester bond represented by the general formula (I) and a (thio) carboxylic acid represented by the following general formula (XII): Particularly preferred. The (thio) carboxylic acid represented by the following general formula (XII), together with the compound represented by the above general formula (I), forms a molecular complex by interaction satisfying the requirements of the above (1) to (5). It is a compound that can be formed.

General formula (XII)

In the formula, R ¹²¹ represents a substituent, and Q ¹²¹ and Q ¹²² each independently represents an oxygen atom or a sulfur atom. The substituent represented by R ¹²¹ is the same as the substituent represented by each of R ^{11 to} R ^{13 in} the general formula (I), and the specific examples and preferred ranges thereof are also the same. The compound represented by the formula (XII) includes an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a perfluoroalkyl chain having 2 or more carbon atoms, a perfluoroalkyl ether chain, and an organic polysilyl chain in the molecule. It preferably has a substituent containing at least one selected. Specific examples of these chains are the same as the specific examples of these chains in the aforementioned general formula (I), and preferred ranges are also the same.

In the general formula (XII), the substituent represented by R ¹²¹ is preferably a substituent having a cyclic structure. As the substituent having the cyclic structure, an aryl group and an aromatic heterocyclic group are preferable. Examples of the aryl group 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. Of these, a phenyl group and a naphthyl group are preferable.
These aryl groups include a substituent containing at least one selected from an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a perfluoroalkyl chain having 2 or more carbon atoms, a perfluoroalkyl ether chain, and an organic polysilyl chain. Is preferably substituted, and more preferably 2 or more. Specific examples of the substituent containing these chains are the same as described above. In particular, the aryl group is a substituent containing a linear or branched alkyl chain having 8 or more carbon atoms, such as an alkyl group (octyl, decyl, hexadecyl, 2-ethylhexyl, etc.), an alkoxy group (dodecyloxy). , Hexadecyloxy etc.), alkylthio group or arylthio group (hexadecylthio etc.), substituted amino group (heptadecylamino etc.), octylcarbamoyl group, octanoyl group or decylsulfamoyl group. More preferably, the aryl group is substituted with two or more substituents containing a linear or branched alkyl chain having 8 or more carbon atoms. The aryl group may be substituted with a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group or the like in addition to the above-described substituent.
The aromatic heterocyclic group is preferably a 5- to 7-membered heterocyclic group, more preferably a 5-membered or 6-membered ring, and most preferably a 6-membered ring. Specific examples of these skeletons are given 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. Name of main condensed heterocyclic compound The heterocyclic ring described on page 1607 is mentioned. The aromatic heterocyclic group includes an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a perfluoroalkyl chain having 2 or more carbon atoms, a perfluoroalkyl ether chain, and an organic polysilyl group. It is preferably substituted with a substituent containing at least one selected from chains, more preferably 2 or more. Specific examples of the substituent containing these chains are the same as described above. In addition to these substituents, the aromatic heterocyclic group may be substituted with a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, or the like.

The compound capable of forming a complex with the compound represented by the general formula (I) may be a low molecular compound or a high molecular compound. The molecular complex may be a molecular complex of the compound represented by the general formula (I) and two or more kinds of compounds.
Of the compounds represented by the general formula (I), the general formulas (III) to (XI) are preferable in that a wider plane can be formed by combining the same structure molecules or different molecules. Further, among them, the barbituric acid derivative represented by the general formula (VII) is more preferable in that it forms a better complex. In addition, the isocyanuric acid derivative represented by the general formula (VIII) can form a planar complex at two or three positions in the molecule, and is expected to form a supramolecular planar complex. Moreover, also when using in combination with the compound represented by general formula (XII), the compound represented by general formula (VII) and (VIII) is preferable. However, even in the general formula (II), a compound having a planar skeleton in the vicinity of a site capable of tautomerization forms a good planar complex with (XI) from another cyclic planar molecule (III). There is expected. Therefore, the structure of the specific general formula cannot be limited to the structure of the specific general formula that is most preferable, and the structure according to (1) to (5) described above is appropriately incorporated into the molecular structure. The preference is determined.

  From the requirements for complex formation described so far, it is clear that planar bond formation and molecules with planar or ring structure substituents are preferred, but this factor is described not only for complex formation but also below. Thus, it is also preferable for efficiently covering the friction sliding surface, that is, the interaction with the friction sliding surface. The frictional sliding surface is generally composed of an inorganic material, that is, a metal, or a metal oxide thin film or ceramic formed by oxidation of the material, but is stronger than the van der Waals force, which is a general interaction between organic materials, and has a polar static surface. Electrical interaction is dominant. Considering the organic compound that forms a strong interaction with such a surface in light of the above requirements (1) to (5) (when considering the sliding surface as σ and the organic compound covering this as ρ) , (1) has an advantageous planar structure, and (2) has a site in the molecule that exhibits a polar electrostatic interaction stronger than the van der Waals force. The polar bond of the complex formed by the bond is preferable for the polar sliding surface. Further, regarding (3), a planar structure is preferable. Regarding (4), when the complex is an aryl melamine, the complementary atomic group is equivalent from several directions, and the complex is not only between two molecules but also between multiple molecules. It is clear that there is a possibility of forming a coalescence, which is very advantageous, and therefore also with respect to (5) that the inventive complex is suitable for a strong interaction with the sliding surface. It is presumed that such a factor can provide extremely high wear resistance even under extreme pressure while being covered only with the molecular complex.

  When the molecular complex has a nonpolar or hydrophobic group, it is possible to further prevent the sliding surfaces from contacting each other and to relieve the stress. Examples of the nonpolar or hydrophobic group include a long chain alkyl group, a perfluoroalkyl group, an oligoalkoxy group, a perfluoroalkyl ether group, and an organic polysiloxane group. Since these hydrophobic groups are nonpolar, they are oriented so as to repel the polar sliding surface for energy stabilization. By introducing the compound represented by the general formula (I) constituting the molecular complex (and other constituent compounds) at an appropriate position, for example, as shown in FIG. The lubricant can be oriented. On the sliding surface, the lubricant having the orientation shown in FIG. 1 is presumed to exhibit a very low coefficient of friction.

  Substances that exhibit strong interaction between molecules generally have high crystallinity, high melting point, poor solubility, difficult dispersibility, and poor handleability. However, by introducing a hydrophobic group, The solubility and dispersibility of the complex in the lubricant base oil can be improved, and it can be made difficult to crystallize, so that the handleability is improved. Furthermore, even when it is not mixed with the lubricant base oil, it is excellent in thin film formation on the sliding surface, and in particular, it can maintain a low viscosity at a low temperature, which is a great advantage as a lubricant.

  Whether or not the compound represented by the general formula (I) forms a molecular complex, for example, when a crystal is obtained, the presence or absence of complex formation is determined by analyzing the crystal. Can do. Further, even when crystals are not obtained, solvation due to complex formation of the compound (ρ) represented by the general formula (I) and the compound (σ) having a functional group capable of interacting with ρ is also possible. If the intermolecular force (bond free energy) included and the bond free energy by solvation of each of ρ and σ are approximately the same or the latter is larger, it can be presumed that a complex is formed. Also, the thermal phase transition temperature pattern of each of ρ and σ is compared with the thermal phase transition temperature pattern after mixing ρ and σ in a stoichiometric integer ratio, and the thermal phase transition temperature of each of ρ and σ is compared. The presence or absence of complex formation can be determined by confirming that the thermal properties unique to the complex are clearly different from the pattern. When ρ and σ are in a simple mixed state where they do not interact, the transition temperature peak only shifts according to the mixing ratio, such as the freezing point depression, but in most cases the complex is formed. A thermal transition peak occurs in a new temperature range. Furthermore, the presence or absence of complex formation can be determined by comparing the complex and the FT-IR spectra of ρ and σ, respectively, and confirming the shift of the vibration absorption spectrum of the functional group that interacts.

  Specific examples of the compound represented by the general formula (I) are shown below, but the present invention is not limited to the following specific examples.

General formula (V)

General formula (V)

Formula (VII)

Formula (VII)

Formula (VIII)

Formula (VIII)

Formula (VIII)

Formula (VIII)

Formula (VIII)

Formula (VIII)

Formula (IX)

Formula (IX)

  Specific examples of the compound represented by the general formula (XII) are shown below, but the present invention is not limited to the following specific examples.

Formula (XII)

Formula (XII)

Formula (XII)

Formula (XII)

  In the following Tables 1 to 4, specific examples of molecular complexes composed of the compounds represented by the general formula (I), which are combinations satisfying the requirements (1) to (5) described above, are listed. . In the table, specific examples (L) of the molecular complex are represented using symbols of specific compound examples of the general formula (I) and the general formula (XII). The molecular complex (L) was prepared at 1/1 (mol / mol).

  The compound represented by the general formula (I) and the compound capable of forming a complex with the compound can be synthesized by combining conventionally known production methods.

The molecular complex used in the lubricant composition of the present invention can be used alone as a lubricant. In addition, the molecular complex can be used in a form mixed with a lubricant base oil as a lubricating aid.
The lubricant base oil is not particularly limited, and any lubricant base oil that is generally used as a lubricant base oil can be used, and examples thereof include mineral oil, synthetic oil, and mixed oils thereof. For example, a solvent refined raffinate obtained by treating a lubricating oil raw material derived by atmospheric or vacuum distillation of paraffinic, intermediate group or naphthenic crude oil with an aromatic extraction solvent such as phenol, furfural, N-methylpyrrolidone; Hydrotreating oil obtained by contacting hydrogen under hydrotreating conditions in the presence of a hydrotreating catalyst such as cobalt or molybdenum using silica-alumina as a carrier for the lube oil; hydrogenating the lube oil Isomerized oil obtained by contacting with hydrogen under isomerization conditions under severe cracking reaction conditions in the presence of cracking catalyst; solvent refining process and hydrotreating process, or hydrocracking process and isomerism A lubricating oil fraction obtained by combining a crystallization step and the like. Particularly preferred are high viscosity index mineral oils obtained by hydrocracking and isomerization processes. In any of the production methods, steps such as a dewaxing step, a hydrofinishing step, and a white clay treatment step can be arbitrarily added. The mineral oil can be classified into light neutral oil, medium neutral oil, heavy neutral oil, bright stock, and the like, and can be appropriately mixed according to required performance.

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 mineral oils and synthetic oils can be used alone or in combination of two or more kinds, and mineral oil and synthetic oil may be used in combination. Such lubricating base oils are usually at a temperature 100 ° C., it has a kinematic viscosity of 2 to 20 mm ² / s, preferably has a kinematic viscosity of 3 to 15 mm ² / s. A mixed base oil having an optimal kinematic viscosity can be appropriately selected so as to be suitable for the lubrication conditions of the mechanical friction sliding portion in which the lubricant composition of the present invention is used.

  In an embodiment in which the lubricant composition of the present invention is a mixture of the molecular complex and the lubricant base oil, a preferable blending amount of the molecular complex is 0.01 based on the total mass of the lubricant base oil. More preferably, it is 0.01-10 mass%, Most preferably, it is 0.05-5 mass%. The content of the lubricant base oil is preferably 50% by mass or more. In an embodiment not containing a lubricant base oil, the molecular complex is preferably contained in an amount of 50% by mass or more, more preferably 80% by mass or more, and most preferably 90% by mass or more.

  The lubricant composition of the present invention contains the molecular complex as a main component, but does not impair the effects of the present invention as necessary in order to ensure practical performance adapted to various applications. Within the scope, various additives used in conventional lubricants such as bearing oils, gear oils, power transmission oils, specifically antiwear agents, extreme pressure agents, antioxidants, viscosity index improvers , Cleaning dispersants, metal deactivators, corrosion inhibitors, rust inhibitors, antifoaming agents, and the like can also be added.

The lubricant composition of the present invention includes n types of compounds containing a tautomerizable ester bond represented by the general formula (I) (excluding the compound represented by the general formula (TAM)). (N is an integer of 1 or more) and can be produced through a step of generating a molecular complex having the compound containing the n types of tautomerizable ester bonds as a constituent element. For example, in a lubricant composition mixed with a lubricant base oil, a compound containing n types (n is an integer of 1 or more) of tautomerizable ester bonds represented by the general formula (I) is used. By adding to a lubricant base oil, a molecular complex can be produced and produced in the lubricant base oil. Moreover, after producing | generating a molecular complex beforehand, it can also add to lubricant base oil. In an embodiment that does not include a lubricant base oil, a molecular complex is produced by producing a mixture of two or more compounds containing an ester bond capable of tautomerization represented by the general formula (I). Can do.
Further, it contains a molecular complex of (thio) carboxylic acid and a tautomerizable compound represented by the general formula (I) (excluding the compound represented by the general formula (TAM)). The lubricant composition according to the aspect includes at least one compound having a tautomerizable ester bond represented by the general formula (I) (excluding the compound represented by the general formula (TAM)). And at least one tautomerizable compound represented by the above general formula (XII) is added to produce a molecular complex having both compounds as constituent elements. . In the aspect of mixing with the lubricant base oil, the (thio) carboxylic acid and the compound represented by the general formula (I) are mixed in advance to form a molecular complex containing both compounds, and then the lubricant. It may be added to the base oil or individually added to the lubricant base oil, and after the addition, a molecular complex containing both compounds may be formed in the lubricant base oil.

  The lubricant composition of the present invention has an effect of reducing the friction coefficient of the sliding surface and improving the wear resistance of the sliding surface by being supplied to the sliding surface that is in contact and relatively moves. . Furthermore, it has an excellent effect of maintaining this effect for a long time. When using lubricants such as conventional lubricants and greases, even if it is supplied to sliding surfaces that move under severe friction conditions that cause oil film breakage, seizure is reduced and wear resistance is improved. Can be maintained at a low coefficient of friction. For example, it can be suitably used as an energy-saving lubricant in bearings and gears that move under severe friction conditions. Furthermore, it is possible to improve the reliability of the sliding part device and contribute to the miniaturization of the sliding part device. The lubricant composition of the present invention has characteristics such as a low coefficient of friction and excellent resistance to friction and extreme pressure under severe lubrication conditions. The lubricant composition of the present invention can be sufficiently viscous even at −40 ° C. by being appropriately mixed with various tautomeric compounds and can be used even at low temperatures. And can.

  The present invention will be described more specifically with reference to the following examples. The materials, reagents, amounts and ratios of substances, operations, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples.

Lubricants of Examples 1 to 8 were prepared using L-14, L-70, L-77, L-116 and a lubricant base oil as the molecular complex of the present invention. Further, the lubricants of Comparative Examples 1 to 8 were prepared using the comparative compounds M-1 and M-2 shown below and a lubricant base oil, and using only a normal lubricant base oil. Each of the prepared lubricants was subjected to a friction test using a reciprocating friction tester (SRV friction wear tester) under the following conditions to evaluate the friction coefficient.
[Test conditions]
The test conditions were cylinder-on-plate conditions.
Test piece (friction material): SUJ-2
Plate: φ24 × 6.9mm
Cylinder: φ11 × 15mm
Temperature: 90 ° C
Load: 400N
Amplitude: 1.5 mm
Frequency: 50Hz
Test time: 5 minutes from the start of test Table 5 shows the results of Examples 1 to 8 and Table 6 shows the results of Comparative Examples 1 to 8, respectively.

Comparative compound (M-1)

Comparative compound (M-2)

It is a schematic diagram which shows one example of orientation of the lubricant composition of this invention.

Claims (11)

A lubricant composition comprising a molecular complex formed by intermolecular interaction of one or more tautomeric compounds, wherein the molecular complex is tautomeric and has an ester bond A lubricant composition comprising as a constituent element a compound represented by the general formula (I) (excluding a compound represented by the following general formula (TAM)).
Formula (I)

(Wherein Q ¹¹ represents an oxygen atom, a sulfur atom or N (R ¹³ ). R ^{11 to} R ¹³ each independently represents a hydrogen atom or a substituent, and at least one of them contains an ester bond, and a total carbon number of 4 or more alkyl chains, oligoalkyleneoxy chain, total carbon number of 2 or more perfluoroalkyl chains, and .R ¹¹ that represents a substituent containing at least one selected from perfluoroalkyl ether chain and organic Porishiriru chain R ¹² and R ¹¹ and R ¹³ may be bonded to each other to form a ring structure.)
General formula (TAM)

(In the formula, R ¹ , R ² and R ³ each independently represent a substituent, and x, y and z each independently represents an integer of 1 to 5) The molecular complex is characterized in that a planar complex can be formed by having a combination of functional groups whose constituent elements exhibit intermolecular interactions in a geometrically complementary positional relationship. Item 2. The lubricant composition according to Item 1. The compound represented by the general formula (I) is a tautomerizable compound represented by the following general formula (II) and has an ester bond (provided that the compound represented by the general formula (TAM) The lubricant composition according to claim 1 or 2, wherein
Formula (II)

(Wherein Q ²¹ and Q ²² each independently represents an oxygen atom, a sulfur atom or N (R ²⁴ ). R ^{21 to} R ²⁴ each independently represents a hydrogen atom or a substituent, and at least one of them represents A substitution containing at least one selected from an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a perfluoroalkyl chain having 2 or more carbon atoms, a perfluoroalkyl ether chain and an organic polysilyl chain. R ²¹ and R ²² , R ²² and R ²³ and R ²¹ and R ²⁴ may be bonded to each other to form a ring structure. The compound represented by the general formula (I) can be tautomerized and has an ester bond represented by any one of the following general formulas (III) to (XI) (provided that the general formula (TAM The lubricant composition according to any one of claims 1 to 3, wherein the compound represented by (1) is excluded).
General formula (III)

(Wherein R ^{31 to} R ³³ each independently represent a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain, oligoalkyleneoxy chain, total carbon having a total carbon number of 4 or more. number 2 more perfluoroalkyl chains, represents a substituent containing at least one selected from perfluoroalkyl ether chain and organic Porishiriru chain, an oxygen atom or a sulfur atom each independently Q ³¹ and Q ³² are .R ³¹ And R ³² and R ³² and R ³³ may be bonded to each other to form a ring structure.)
Formula (IV)

(Wherein R ^{41 to} R ⁴⁴ each independently represents a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain, oligoalkyleneoxy chain, or total carbon having a total carbon number of 4 or more. Represents a substituent containing at least one selected from a perfluoroalkyl chain of 2 or more, a perfluoroalkyl ether chain, and an organic polysilyl chain, and Q ⁴¹ represents an oxygen atom or a sulfur atom R ⁴¹ and R ⁴² , R ⁴¹ And R ⁴³ and R ⁴² and R ⁴⁴ may be bonded to each other to form a ring structure.)
General formula (V)

(Wherein R ^{51 to} R ⁵⁴ each independently represent a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain, oligoalkyleneoxy chain, or total carbon having a total carbon number of 4 or more. Represents a substituent containing at least one selected from a perfluoroalkyl chain, a perfluoroalkyl ether chain, and an organic polysilyl chain of at least two, R ⁵¹ and R ⁵² and R ⁵¹ and R ⁵³ are bonded to each other to form a ring; A structure may be formed.)
General formula (VI)

(In the formula, R ^{61 to} R ⁶³ each independently represent a hydrogen atom or a substituent, and at least one of them contains an ester bond and has an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, or a total carbon atom. Q ⁶¹ represents an oxygen atom or a sulfur atom, and R ⁶¹ and R ⁶² are bonded to each other, including a substituent containing at least one selected from a perfluoroalkyl chain, a perfluoroalkyl ether chain and an organic polysilyl chain. And a ring structure may be formed.)
Formula (VII)

(Wherein, Q ⁷¹ to Q ⁷³ represents an oxygen atom or a sulfur atom independently, X is -C (= R ⁷¹⁾ - or ^{-C (R 72) (R 73} ) - .R 71 representing the the substituent R ^{72 to} R ⁷⁴ each independently represents a hydrogen atom or a substituent, at least one of which contains an ester bond and has an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a total carbon atom, Represents a substituent containing at least one selected from a perfluoroalkyl chain, a perfluoroalkyl ether chain, and an organic polysilyl chain of at least 2. R ⁷² and R ⁷³ may be bonded to each other to form a ring structure. .)
Formula (VIII)

(Wherein Q ^{81 to} Q ⁸³ each independently represents an oxygen atom, a sulfur atom or N (R ⁸² ). R ⁸¹ and R ⁸² each independently represents a hydrogen atom or a substituent, and at least one of them represents: Substitution containing at least one selected from an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a perfluoroalkyl chain having 2 or more carbon atoms, a perfluoroalkyl ether chain, and an organic polysilyl chain. When Q ⁸³ is N (R ⁸² ), R ⁸¹ and R ⁸² may be bonded to each other to form a ring structure.
General formula (IX)

Wherein Q ⁹¹ and Q ⁹² are each independently a single bond, N (R ⁹⁴ ) (R ⁹⁴ represents a hydrogen atom or an alkyl group having 1 to 30 carbon atoms), an oxygen atom, a sulfur atom, a carbonyl group, R ⁹¹ and R ⁹² each independently represent a hydrogen atom or a substituent, and at least one of them contains an ester bond and has a total carbon number of 4 The substituent includes at least one selected from the above alkyl chain, oligoalkyleneoxy chain, perfluoroalkyl chain having 2 or more carbon atoms in total, perfluoroalkyl ether chain, and organic polysilyl chain, and R ⁹³ represents a halogen atom, hydroxyl group Group, amino group, mercapto group, cyano group, alkylthio group, arylthio group, carboxyl group or salt thereof, sulfo group or salt thereof, hydro Represents a xyamino group, a ureido group or a urethane group.)
Formula (X)

(Wherein Q ^{101 to} Q ¹⁰³ each independently represents an oxygen atom, a sulfur atom or N (R ¹⁰³ ), R ^{101 to} R ¹⁰³ each independently represents a hydrogen atom or a substituent, and at least one of them represents: Substitution containing at least one selected from an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a perfluoroalkyl chain having 2 or more carbon atoms, a perfluoroalkyl ether chain, and an organic polysilyl chain. Represents a group.)
General formula (XI)

(Wherein Q ¹¹¹ and Q ¹¹² each independently represents an oxygen atom, a sulfur atom or N (R ¹¹⁵ ), R ^{111 to} R ¹¹⁵ each independently represents a hydrogen atom or a substituent, and at least one of them represents: Substitution containing at least one selected from an alkyl chain having 4 or more carbon atoms, an oligoalkyleneoxy chain, a perfluoroalkyl chain having 2 or more carbon atoms, a perfluoroalkyl ether chain, and an organic polysilyl chain. R ¹¹¹ and R ¹¹³ , R ¹¹³ and R ¹¹⁴ , R ¹¹³ and R ¹¹⁵ , R ¹¹² and R ^114, and R ¹¹⁴ and R ¹¹⁵ may be bonded to each other to form a ring structure. The molecular錯合body, the represented tautomerism possible by the general formula (I), and Compound A ₁ to A _n (where n-type having an ester bond (n is an integer of 1 or more), the general formula The lubricant composition according to any one of claims 1 to 4, which is a molecular complex comprising (excluding a compound represented by (TAM)). The molecular complex is a tautomerizable compound represented by the general formula (I) and has an ester bond (excluding the compound represented by the general formula (TAM)), and the following general formula The lubricant composition according to any one of claims 1 to 4, comprising at least one compound represented by (XII) capable of tautomerization.
General formula (XII)

(In the formula, R ¹²¹ represents a substituent, and Q ¹²¹ and Q ¹²² each independently represents an oxygen atom or a sulfur atom.) The lubricant composition according to any one of claims 1 to 6, wherein the tKa of the compound represented by the general formula (I) and having an ester bond has a pKa of 2 to 12. The thermal phase transition temperature pattern in the differential scanning calorimetry (DSC) method of the molecular complex is different from the thermal phase transition temperature pattern of the component compound. Lubricant composition. Furthermore, lubricant composition of any one of Claims 1-7 containing 50 mass% or more of lubricant base oils. 2. n types (n is 1) of compounds (excluding the compound represented by the general formula (TAM)) capable of tautomerization represented by the general formula (I) in claim 1 and having an ester bond. A method for preparing a lubricant composition, comprising the step of generating a molecular complex comprising a compound having an n-type tautomerism and having an ester bond as a constituent element. At least one of the tautomerizable compounds represented by the general formula (I) in claim 1 and having an ester bond (excluding the compounds represented by the general formula (TAM) in claim 1) A step of adding a seed and at least one tautomeric compound represented by the general formula (XII) in claim 6 to form a molecular complex having both compounds as constituents. Preparation method of the agent composition.

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