JPWO2015016259A1 - Composite ester polyamide composition, lubricant composition, lubricant and method for producing composite ester polyamide composition - Google Patents

Abstract

An object of the present invention is to provide a lubricant capable of exhibiting excellent lubrication performance and having excellent hydrolysis resistance. The present invention can be obtained by condensing a polyvalent amine containing at least two primary or secondary amino groups, a polyvalent carboxylic acid containing at least two carboxyl groups, and a monohydric alcohol having 4 or more carbon atoms. The present invention relates to a composite ester polyamide composition containing an ester polyamide. Furthermore, this invention relates to the manufacturing method of the lubricant composition containing a composite polyester composition, a lubricant, and a composite ester polyamide composition.

Description

  The present invention relates to composite ester polyamide compositions and lubricants. Specifically, the present invention relates to a composite ester polyamide composition containing a specific ester polyamide and a lubricant containing the composite ester polyamide composition.

  Lubricants generally include base oils and various additives. Base oils include mineral oils obtained from crude oils, chemically synthesized ester oils, fluorine oils, polyalphaolefin oils, and the like. Among these, ester oils are suitably used for jet aircraft, automobile engine oils, greases and the like because of their low pour point, high viscosity index, high flash point, good lubricating performance, biodegradability, and the like.

  As ester oil, monoester obtained from reaction of aliphatic monocarboxylic acid and monohydric alcohol; diester obtained from reaction of aliphatic dibasic acid and monohydric alcohol; polyhydric alcohol and aliphatic carboxylic acid; Various esters are disclosed (Patent Documents 1 to 5), such as esters obtained from the above reaction; and complex esters obtained from reaction with polyols, polybasic acids, and aliphatic monocarboxylic acids.

  Patent Documents 6 and 7 disclose ester polyamide compositions using polyvalent amines. Patent Document 6 discloses an ester polyamide composition obtained from the reaction of an aliphatic dibasic acid such as dimer acid or trimer acid, diamine and methanol. Here, the obtained ester polyamide composition is used for an optical member such as a lens. Patent Document 7 discloses an ester polyamide composition obtained from the reaction of a polyvalent amine, an aliphatic dibasic acid, and a polyhydric alcohol, and such a composition is used as a lubricant composition. ing.

JP 2002-097482 A JP 2005-154726 A JP 2005-232434 A JP 2005-213377 A JP 2005-232470 A Japanese Patent Laid-Open No. 9-12716 JP 2003-268395 A

In recent years, with the diversification and sophistication of industrial fields, lubricants are required to have high lubrication performance. For this reason, development of the polyester composition which has low friction property and was excellent in lubrication performance is calculated | required.
However, it has been clarified by the present inventors that lubricants containing polyesters and ester amide compounds described in conventional patent documents cannot sufficiently exhibit the required lubricating performance. For this reason, the further improvement was calculated | required so that sufficient lubrication performance might be exhibited.

  Moreover, since the conventional ester composition may be hydrolyzed in the lubricant, there is a problem of promoting the deterioration of the lubricant. Such a deteriorated lubricant has been a problem because it causes corrosion of metals and the like. That is, the conventional lubricant does not have excellent lubrication performance and hydrolysis resistance, and a lubricant having both of these performances is required.

  Therefore, the present inventors provide a lubricant capable of exhibiting excellent lubricating performance and having excellent hydrolysis resistance in order to solve such problems of the conventional technology. The study was advanced for the purpose.

As a result of intensive studies to solve the above problems, the present inventors have found that the lubricating performance can be improved by using a composite ester polyamide composition containing a specific ester polyamide as a lubricant. I found it. The specific ester polyamide is a condensation product of a polyvalent amine containing at least two primary or secondary amino groups, a polyvalent carboxylic acid containing at least two carboxyl groups, and a monohydric alcohol having 4 or more carbon atoms. It is ester polyamide obtained by this.
Furthermore, the present inventors have found that a composite ester polyamide composition containing such an ester polyamide can exhibit excellent hydrolysis resistance, and have completed the present invention.
Specifically, the present invention has the following configuration.

一般式（１）中、Ｒは炭素数２〜６０の脂肪族基を表し、Ｒ¹は水素原子、置換基を有してもよいアルキル基、置換基を有してもよいシクロアルキル基、置換基を有してもよいアリール基、置換基を有してもよいヘテロアリール基又は一般式（２）で表される基を表す。Ｒ²は（ｍ＋１）価以上の鎖状もしくは環状の脂肪族連結基又は芳香族連結基を表し、Ｒ³は置換基を有してもよいアルキル基、置換基を有してもよいシクロアルキル基、置換基を有してもよいアリール基、置換基を有してもよいヘテロアリール基を表す。ｎは２〜４の整数を表し、ｍは１〜３の整数を表す。

一般式（２）中、Ｒ²は（ｍ＋１）価以上の鎖状もしくは環状の脂肪族連結基又は芳香族連結基を表し、Ｒ³は置換基を有してもよいアルキル基、置換基を有してもよいシクロアルキル基、置換基を有してもよいアリール基、置換基を有してもよいヘテロアリール基を表す。ｍは１〜３の整数を表す。
［４］一般式（１）及び（２）において、ｍは１又は２の整数である［３］に記載の複合エステルポリアミド組成物。
［５］一般式（１）及び（２）において、Ｒ²の炭素数は２２〜６６である［３］又は［４］に記載の複合エステルポリアミド組成物。
［６］一般式（１）及び（２）において、Ｒ²は、ダイマー酸残基又はトリマー酸残基である［３］〜［５］のいずれかに記載の複合エステルポリアミド組成物。
［７］一般式（１）及び（２）において、Ｒ³の炭素数は６以上である［３］〜［６］のいずれかに記載の複合エステルポリアミド組成物。
［８］一般式（１）及び（２）において、Ｒ³は、オキシアルキレン構造を有する基である［３］〜［７］のいずれかに記載の複合エステルポリアミド組成物。
［９］１価アルコールは、下記一般式（３）で表される［１］〜［８］のいずれかに記載の複合エステルポリアミド組成物；

一般式（３）中、Ｒ^aは置換基を有してもよいアルキル基、置換基を有してもよいシクロアルキル基、置換基を有してもよいアルケニル基、置換基を有してもよいアリール基又は置換基を有してもよいヘテロアリール基であり、Ｘ^a1及びＸ^a2はそれぞれ独立に水素原子、ハロゲン原子又はアルキル基を表す。また、ｎａ１は２〜４の整数を表し、ｎａ２は１〜１２の整数を表す。
［１０］一般式（４）で表されるエステル成分をさらに含む［１］〜［９］のいずれかに記載の複合エステルポリアミド組成物；

一般式（４）中、Ｒ²は（ｍ＋１）価以上の鎖状もしくは環状の脂肪族連結基又は芳香族連結基を表し、Ｒ³は置換基を有してもよいアルキル基、置換基を有してもよいシクロアルキル基、置換基を有してもよいアリール基、置換基を有してもよいヘテロアリール基を表す。ｍは１〜３の整数を表す。
［１１］４０℃における粘度が５０〜１６５０ｍＰａｓである［１］〜［１０］のいずれかに記載の複合エステルポリアミド組成物。
［１２］［１］〜［１１］のいずれかに記載の複合エステルポリアミド組成物と、摩耗防止剤、粘度指数向上剤、酸化防止剤、清浄剤、分散剤、流動、硬化剤、腐食防止剤、シール適合剤、消泡剤、錆防止剤、腐食防止剤、摩擦調整剤、及び増ちょう剤から選択される１種又は２種以上の添加剤とを含有する潤滑剤組成物。
［１３］［１］〜［１１］のいずれかに記載の複合エステルポリアミド組成物、又は［１２］に記載の潤滑剤組成物と、鉱物油、油脂化合物、ポリオレフィン油、シリコーン油、パーフルオロポリエーテル油、ジフェニルエーテル油、芳香族エステル油、脂肪族モノエステル油、脂肪族ジエステル油、及びポリオールエステル潤滑油から選択される１種又は２種以上の媒体とを少なくとも含有する潤滑剤組成物。
［１４］［１］〜［１１］のいずれかに記載の複合エステルポリアミド組成物、又は［１２］又は［１３］に記載の潤滑剤組成物を含む潤滑剤。
［１５］グリース用潤滑油、離型剤、内燃機関用エンジンオイル、金属加工用（切削用）オイル、軸受け用オイル、燃焼機関用燃料、車両エンジン油、ギヤ油、自動車用作動油、船舶・航空機用潤滑油、マシン油，タービン油、軸受用オイル、油圧作動油、圧縮機・真空ポンプ油、冷凍機油、金属加工用潤滑油剤、磁気記録媒体用潤滑剤、マイクロマシン用潤滑剤、人工骨用潤滑剤、ショックアブソーバ油又は圧延油として用いられる［１４］に記載の潤滑剤。
［１６］少なくとも２つの１級または２級アミノ基を含む多価アミンと、少なくとも２つのカルボキシル基を含む多価カルボン酸と、１価アルコールとを混合し混合物を得る工程と、混合物を脱水縮合する工程を含む複合エステルポリアミド組成物の製造方法。
［１７］混合物を得る工程は、多価アミンに対して、多価カルボン酸を混合する当量比が１〜３となり、１価アルコールを混合する当量比が０．５〜３となるように混合する工程である［１６］に記載の複合エステルポリアミド組成物の製造方法。
［１８］脱水縮合する工程は、混合物に対して１〜２５質量％の、沸点１１０〜１６０℃の炭化水素系溶剤を添加し、水を共沸させつつ、脱水縮合を進行させる工程を含む［１６］又は［１７］に記載の複合エステルポリアミド組成物の製造方法。[1] An ester obtained by condensing a polyvalent amine containing at least two primary or secondary amino groups, a polyvalent carboxylic acid containing at least two carboxyl groups, and a monohydric alcohol having 4 or more carbon atoms. A composite ester polyamide composition comprising a polyamide.
[2] The composite ester polyamide composition according to [1], wherein the polyvalent amine and the polyvalent carboxylic acid satisfy the following condition (i) or (ii):
(I) The polyvalent amine is a divalent amine containing two primary or secondary amino groups, and the polyvalent carboxylic acid is a polyvalent carboxylic acid containing three or more carboxyl groups.
(Ii) The polyvalent amine is a polyvalent amine containing three or more primary or secondary amino groups, and the polyvalent carboxylic acid is a divalent carboxylic acid containing two carboxyl groups.
[3] At least one of the ester polyamides is a composite ester polyamide composition according to [1] or [2] represented by the following general formula (1);

In General Formula (1), R represents an aliphatic group having 2 to 60 carbon atoms, R ¹ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, The aryl group which may have a substituent, the heteroaryl group which may have a substituent, or group represented by General formula (2) is represented. R ² represents a linear or cyclic aliphatic linking group or aromatic linking group having a valence of (m + 1) or more, and R ³ represents an alkyl group which may have a substituent or an cycloalkyl which may have a substituent. Represents a group, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent. n represents an integer of 2 to 4, and m represents an integer of 1 to 3.

In general formula (2), R ² represents a chain or cyclic aliphatic linking group or aromatic linking group having a valence of (m + 1) or more, and R ³ represents an alkyl group which may have a substituent, or a substituent. The cycloalkyl group which may have, the aryl group which may have a substituent, and the heteroaryl group which may have a substituent are represented. m represents an integer of 1 to 3.
[4] The composite ester polyamide composition according to [3], wherein in the general formulas (1) and (2), m is an integer of 1 or 2.
[5] The composite ester polyamide composition according to [3] or [4], wherein in general formulas (1) and (2), R ² has 22 to 66 carbon atoms.
[6] The composite ester polyamide composition according to any one of [3] to [5], wherein in general formulas (1) and (2), R ² is a dimer acid residue or a trimer acid residue.
[7] The composite ester polyamide composition according to any one of [3] to [6], wherein in general formulas (1) and (2), R ³ has 6 or more carbon atoms.
[8] The composite ester polyamide composition according to any one of [3] to [7], wherein in general formulas (1) and (2), R ³ is a group having an oxyalkylene structure.
[9] The monovalent alcohol is a composite ester polyamide composition according to any one of [1] to [8] represented by the following general formula (3);

In general formula (3), R ^a has an alkyl group which may have ^a substituent, ^a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. Or a heteroaryl group which may have a substituent, and X ^a1 and X ^a2 each independently represent a hydrogen atom, a halogen atom or an alkyl group. Na1 represents an integer of 2 to 4, and na2 represents an integer of 1 to 12.
[10] The composite ester polyamide composition according to any one of [1] to [9], further comprising an ester component represented by the general formula (4);

In general formula (4), R ² represents a chain or cyclic aliphatic linking group or aromatic linking group having a valence of (m + 1) or more, and R ³ represents an alkyl group which may have a substituent, or a substituent. The cycloalkyl group which may have, the aryl group which may have a substituent, and the heteroaryl group which may have a substituent are represented. m represents an integer of 1 to 3.
[11] The composite ester polyamide composition according to any one of [1] to [10], wherein the viscosity at 40 ° C. is 50 to 1650 mPas.
[12] The composite ester polyamide composition according to any one of [1] to [11], an antiwear agent, a viscosity index improver, an antioxidant, a detergent, a dispersant, a flow, a curing agent, and a corrosion inhibitor. And a lubricant composition containing one or more additives selected from a seal compatibilizer, an antifoaming agent, a rust inhibitor, a corrosion inhibitor, a friction modifier, and a thickener.
[13] The composite ester polyamide composition according to any one of [1] to [11], or the lubricant composition according to [12], and mineral oil, oil and fat compound, polyolefin oil, silicone oil, perfluoropoly A lubricant composition comprising at least one or two or more media selected from ether oils, diphenyl ether oils, aromatic ester oils, aliphatic monoester oils, aliphatic diester oils, and polyol ester lubricating oils.
[14] A lubricant comprising the composite ester polyamide composition according to any one of [1] to [11], or the lubricant composition according to [12] or [13].
[15] Grease lubricant, release agent, engine oil for internal combustion engine, oil for metal processing (cutting), oil for bearing, fuel for combustion engine, vehicle engine oil, gear oil, hydraulic oil for automobile, Aircraft lubricant, machine oil, turbine oil, bearing oil, hydraulic fluid, compressor / vacuum pump oil, refrigeration oil, metalworking lubricant, magnetic recording medium lubricant, micromachine lubricant, artificial bone The lubricant according to [14], which is used as a lubricant, shock absorber oil or rolling oil.
[16] A step of mixing a polyvalent amine containing at least two primary or secondary amino groups, a polyvalent carboxylic acid containing at least two carboxyl groups, and a monohydric alcohol to obtain a mixture, and dehydrating condensation of the mixture The manufacturing method of the composite ester polyamide composition including the process to do.
[17] The step of obtaining the mixture is performed such that the equivalent ratio for mixing the polyvalent carboxylic acid is 1 to 3 and the equivalent ratio for mixing the monohydric alcohol is 0.5 to 3 with respect to the polyvalent amine. The manufacturing method of the composite ester polyamide composition as described in [16] which is a process to carry out.
[18] The step of dehydrating condensation includes a step of adding 1 to 25% by mass of a hydrocarbon solvent having a boiling point of 110 to 160 ° C. with respect to the mixture, and causing dehydration condensation to proceed while azeotropically distilling water. 16] or the method for producing a composite ester polyamide composition according to [17].

  According to the present invention, a composite ester polyamide composition capable of exhibiting high lubricating performance can be obtained. Furthermore, according to the present invention, a composite ester polyamide composition having excellent hydrolysis resistance can be obtained. For this reason, the composite ester polyamide composition of the present invention does not corrode metals even when used for a long period of time, and is preferably used as a lubricant for various applications.

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

(Composite ester polyamide composition)
The present invention relates to a composite ester polyamide composition containing a predetermined ester polyamide. The composite ester polyamide composition of the present invention comprises a polyvalent amine containing at least two primary or secondary amino groups, a polyvalent carboxylic acid containing at least two carboxyl groups, and a monohydric alcohol having 4 or more carbon atoms. An ester polyamide obtained by condensation is included. In this invention, the composite ester polyamide composition which can exhibit high lubricating performance can be obtained by including such a specific ester polyamide. Furthermore, the composite ester polyamide composition obtained in the present invention is also characterized by having excellent hydrolysis resistance.

<Polyvalent amine>
The polyvalent amine used for the condensation of the ester polyamide is a compound containing at least two primary or secondary amino groups. It is preferable that 2-4 amino groups are contained in one molecule, and it is more preferable that 2 or 3 amino groups are contained in one molecule.

It is preferable that 2-4 amino groups are contained in one molecule of the polyvalent amine, and more preferably 2 or 3 amino groups are contained. As the polyvalent amine used in the present invention, any one of divalent to tetravalent polyvalent amines may be used, or a plurality of types may be used. For example, a mixture of a divalent amine and a trivalent amine may be used, or a mixture of a divalent amine, a trivalent amine, and a tetravalent amine may be used. A mixture of tetravalent amines may be used.
Moreover, in the molecule | numerator, either one of a primary amino group and a secondary amino group may be contained, and both may be contained.

  The amino groups in the molecule are linked by a chain or cyclic divalent or higher aliphatic hydrocarbon. The polyvalent amine preferably has 2 or more carbon atoms, more preferably 6 or more, still more preferably 7 or more, and still more preferably 8 or more. Further, the carbon number of the polyvalent amine is preferably 60 or less, more preferably 30 or less, further preferably 24 or less, and still more preferably 20 or less. By setting the carbon number of the polyvalent amine within the above range, an increase in the viscosity of the composite ester polyamide composition can be suppressed, and the lubricating performance of the composite ester polyamide composition can be further enhanced. In addition, the amidation reaction rate during the condensation reaction can be increased.

  Examples of the polyvalent amine that can be used in the present invention include ethylenediamine, hexamethylenediamine, phenylenediamine, diaminonaphthalene, diaminocyclohexane, dimeramine amine, piperazine, tris (2-aminoethylamine), adamantanediamine, and the like. .

  Specific examples of the polyvalent amine that can be used in the present invention are shown below, but the present invention is not limited thereto.

<Polyvalent carboxylic acid>
The polyvalent carboxylic acid used for the condensation of the ester polyamide is a compound containing at least two carboxyl groups. It is preferable that 2-4 carboxyl groups are contained in one molecule, and it is more preferable that 2 or 3 carboxyl groups are contained in one molecule. The polyvalent carboxylic acid is preferably dimer acid or trimer acid.
As the polyvalent carboxylic acid used in the present invention, any one of divalent to tetravalent polyvalent carboxylic acids may be used, or a plurality of types may be used. For example, a mixture of a divalent carboxylic acid and a trivalent carboxylic acid may be used, or a mixture of a divalent carboxylic acid, a trivalent carboxylic acid, and a tetravalent carboxylic acid may be used, A mixture of a trivalent carboxylic acid and a tetravalent carboxylic acid may be used.

In addition, it is preferable that the valences of the polyvalent amine and the polyvalent carboxylic acid satisfy the following condition (i) or (ii).
(I) The polyvalent amine is a divalent amine containing two primary or secondary amino groups, and the polyvalent carboxylic acid is a polyvalent carboxylic acid containing three or more carboxyl groups.
(Ii) The polyvalent amine is a polyvalent amine containing three or more primary or secondary amino groups, and the polyvalent carboxylic acid is a divalent carboxylic acid containing two carboxyl groups.
When the valences of the polyvalent amine and the polyvalent carboxylic acid satisfy the above conditions, a composite ester polyamide composition having fluidity and capable of exhibiting excellent lubricating performance can be obtained.

  The carboxyl groups in the molecule are linked by a chain or cyclic divalent or higher aliphatic hydrocarbon or aromatic hydrocarbon. One or more carbon atoms not adjacent to each other of the carbon atoms of the aliphatic hydrocarbon or aromatic hydrocarbon linking group may be substituted with oxygen atoms.

  The number of carbon atoms of the polyvalent carboxylic acid is preferably 4 or more, preferably 10 or more, more preferably 18 or more, further preferably 22 or more, and particularly preferably 26 or more. preferable. Further, the carbon number of the polyvalent carboxylic acid is preferably 70 or less, more preferably 66 or less, and further preferably 59 or less. In the present invention, the carbon number of the polyvalent carboxylic acid represents the number of carbon atoms including the carbon atom constituting the carboxyl group. Thus, the lubrication performance of the composite ester polyamide composition can be further improved by setting the carbon number of the polyvalent carboxylic acid within the above range.

  Examples of the polyvalent carboxylic acid that can be used in the present invention include terephthalic acid, phthalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and trimellitic acid. , Dimer acid, hydrogenated dimer acid, trimer acid and the like. Of these, dimer acid, hydrogenated dimer acid, and trimer acid are preferably used.

  The group connecting the carboxyl groups in the molecule is preferably an aliphatic hydrocarbon having 22 to 66 carbon atoms. Especially, as polyvalent carboxylic acid used by this invention, a dimer acid or a trimer acid can be illustrated preferably.

  Specific examples of the polyvalent carboxylic acid that can be used in the present invention are shown below, but the present invention is not limited thereto.

  In the present invention, polyhydric carboxylic acid anhydrides can be used in place of polycarboxylic acids. The polyhydric carboxylic acid anhydride is a product obtained by intramolecular or intermolecular dehydration condensation of two COOHs of the above polycarboxylic acid. The preferred form is the same as above. Examples of the anhydrides include succinic anhydride, glutaric anhydride, adipic anhydride, maleic anhydride, phthalic anhydride, nadoic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride and mixed polybasic anhydride Things are included.

<Monohydric alcohol>
The monohydric alcohol used for the condensation of the ester polyamide is a compound having one hydroxyl group in one molecule and having 4 or more carbon atoms. A monohydric alcohol is represented by R (OH). R is a monovalent aliphatic, alicyclic or aromatic ring group, and one or more carbon atoms which are not adjacent to each other in R may be substituted with an oxygen atom. R preferably has 4 or more carbon atoms, more preferably 6 or more, and even more preferably 8 or more. By setting the carbon number of the monohydric alcohol within the above range, the monohydric alcohol can be prevented from evaporating during the condensation reaction, and the condensation reaction of the ester polyamide can be efficiently advanced.

  Examples of the monohydric alcohol suitable for the present invention include butanol, pentanol, propanol, hexanol, heptanol, octanol, decanol, dodecanol, hexadecanol, octadecanol, eicosadecanol, phytosterol, isostearol, stearol. Cetol, behenol, ethylene glycol monoether, polyethylene glycol monoether and the like.

  Specific examples of the monohydric alcohol that can be used in the present invention are shown below, but the present invention is not limited thereto.

  The monohydric alcohol used in the present invention is preferably one represented by the following general formula (3).

Here, in the general formula (3), Ra represents an alkyl group which may have ^a substituent, ^a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. An aryl group which may have or a heteroaryl group which may have a substituent, and X ^a1 and X ^a2 each independently represent a hydrogen atom, a halogen atom or an alkyl group; Na1 represents an integer of 2 to 4, and na2 represents an integer of 1 to 12.

That the number of carbon atoms of the alkyl moiety of the alkyl group which may have a substituent represented by R ^a is preferably 3 to 17, more preferably from 4 to 13, 5 to 9 Is more preferable. The alkyl group represented by R ^a may be linear or branched. R ^a may be a cycloalkyl group.

The number of carbon atoms of the alkenyl group moiety alkenyl group which may have a substituent represented by R ^a is preferably 3 to 17, more preferably from 4 to 13, 5 to 9 Is more preferable. The alkyl group represented by R ^a may be linear, branched or cyclic.

The number of carbon atoms of the aryl moiety of the aryl group or heteroaryl group which may have a substituent represented by R ^a is preferably 6 to 17, and more preferably 6-12. Examples of the aryl group represented by ^Ra include a phenyl group and a naphthyl group, and among them, a phenyl group is particularly preferable. Examples of the heteroaryl group represented by ^Ra include imidazolyl, pyridyl, quinolyl, furyl, thienyl, benzoxazolyl, indolyl, benzimidazolyl, benzthiazolyl, carbazolyl, azepinyl Can be illustrated. The hetero atom contained in the heteroaryl group is preferably an oxygen atom, a sulfur atom, or a nitrogen atom, and more preferably an oxygen atom.

Especially, in General formula (3), it is more preferable that ^Ra is an alkyl group which may have ^a substituent. Here, the alkyl group may be a branched alkyl group. More preferably, X ^a1 and X ^a2 are each independently a hydrogen atom or an alkyl group.

  In general (3), na1 is more preferably an integer of 2 or 3, and more preferably 2. Na2 is more preferably an integer of 1 to 8, more preferably an integer of 1 to 6, and particularly preferably an integer of 1 to 3.

  The carbon number of the monohydric alcohol represented by the general formula (3) is preferably 4 or more, more preferably 6 or more, and further preferably 8 or more. By using such a monohydric alcohol, volatilization of the monohydric alcohol during the condensation reaction can be suppressed, and the condensation reaction of the ester polyamide can be advanced efficiently.

Examples of the substituent that R ^a may have include a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms (for example, methyl, ethyl, and thereafter linear or branched propyl, butyl, pentyl). Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, or tetracosyl); an alkenyl group having 2 to 35 carbon atoms (Eg, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl); a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Chloroheptyl); an aromatic ring group having 6 to 30 carbon atoms (for example, phenyl, naphthyl, biphenyl, phenanthryl, anthracenyl), a heterocyclic group (nitrogen atom, oxygen atom, and sulfur atom) Or a heterocyclic residue containing, for example, pyridyl, pyrimidyl, triazinyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, imidazolyl, oxazolyl, thiadialyl, oxadiazolyl, quinolyl, isoquinolyl); Represents a group consisting of If possible, these substituents may further have one or more substituents. Examples of the substituents include alkoxy groups, alkoxycarbonyl groups, halogen atoms, ether groups, alkylcarbonyl groups, cyano groups. Group, thioether group, sulfoxide group, sulfonyl group, amide group and the like.

(Other compounds)
In the present invention, in addition to the polyvalent amine, polyvalent carboxylic acid, and monohydric alcohol, other components may be used for the condensation reaction, and a composite ester polyamide composition containing the resulting ester polyamide is also preferably used.

(Ester polyamide)
The composite ester polyamide composition of the present invention includes an ester polyamide obtained by mixing a polyvalent amine as described above, a polyvalent carboxylic acid, and a monohydric alcohol and condensing the mixture. At least one of the ester polyamides obtained by condensing the mixture is preferably represented by the following general formula (1).

In General Formula (1), R represents an aliphatic group having 2 to 60 carbon atoms, R ¹ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, The aryl group which may have a substituent, the heteroaryl group which may have a substituent, or group represented by General formula (2) is represented. R ² represents a linear or cyclic aliphatic linking group or aromatic linking group having a valence of (m + 1) or more, and R ³ represents an alkyl group which may have a substituent or an cycloalkyl which may have a substituent. Represents a group, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent. n represents an integer of 2 to 4, and m represents an integer of 1 to 3.

In general formula (2), R ² represents a chain or cyclic aliphatic linking group or aromatic linking group having a valence of (m + 1) or more, and R ³ represents an alkyl group which may have a substituent, or a substituent. The cycloalkyl group which may have, the aryl group which may have a substituent, and the heteroaryl group which may have a substituent are represented. m represents an integer of 1 to 3.

  In the general formula (1), R represents an aliphatic group having 2 to 60 carbon atoms. The number of carbon atoms in R is preferably 6 or more, more preferably 7 or more, and still more preferably 8 or more. Further, the carbon number of R is preferably 30 or less, more preferably 24 or less, and even more preferably 20 or less.

  In general formula (1), n represents an integer of 2 to 4, and in general formulas (1) and (2), m represents an integer of 1 to 3. In general formulas (1) and (2), m is particularly preferably an integer of 1 or 2. Further, when m is 3, n is preferably 2, and when m is an integer of 1 or 2, n is preferably an integer of 3 or 4.

R ¹ is a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a heteroaryl that may have a substituent. The group represented by group or General formula (2) is represented. That is, when the polyvalent amine used in the present invention is a polyvalent amine containing a primary amino group, R ¹ represents a hydrogen atom or a group represented by the general formula (2), and the polyvalent amine used in the present invention. When the amine is a polyvalent amine containing a secondary amino group, R ¹ is an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, or an aryl that may have a substituent. It represents a heteroaryl group which may have a group or a substituent.

R ² represents a residue of a polyvalent carboxylic acid. Here, the residue of the polyvalent carboxylic acid refers to a group constituting a portion obtained by removing two carboxyl groups from the polyvalent carboxylic acid. R ² represents a chain or cyclic aliphatic linking group or aromatic linking group having an (m + 1) valence or higher, and is preferably a chain or cyclic aliphatic linking group having an (m + 1) valence or higher. One or more carbon atoms that are not adjacent to each other in the aliphatic linking group or the aromatic linking group may be substituted with an oxygen atom.

R ² preferably has 22 to 66 carbon atoms, more preferably 26 to 60 carbon atoms, and still more preferably 30 to 50 carbon atoms. R ² is preferably a dimer acid residue or a trimer acid residue. By setting R ² to the above conditions, a composite ester polyamide composition having high lubricating performance can be obtained.

R ³ represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, a substituent Represents a heteroaryl group which may have Specific examples of the group that R ³ can take include the group represented by R ^a in formula (3). In addition, the substituent of each group that R ³ may have is not particularly limited. As the substituent, the above substituents can be exemplified similarly.

R ³ may have 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more.

R ³ is preferably a group having an oxyalkylene structure. That is, R ³ is preferably a branched alkyl group or an alkyl group containing an ether bond in the chain. By using R ³ as such a substituent, the lubricating performance of the composite ester polyamide composition can be further enhanced.

  When mixing a compound of a polyvalent amine, a polyvalent carboxylic acid and a monohydric alcohol, the equivalent ratio of mixing the polyvalent carboxylic acid with respect to the polyvalent amine is 1 to 3, It is preferable that the equivalent ratio of mixing the monohydric alcohol is 0.5-3. That is, the mixing ratio is preferably polyvalent amine: polyvalent carboxylic acid: monohydric alcohol = 1: 1 to 3: 0.5 to 3. The mixing ratio is more preferably 1: 1.2 to 2.8: 0.7 to 2.8, and more preferably 1: 1.5 to 2.5: 1 to 2.5. preferable. In particular, since the side chain of the ester polyamide is preferably end-capped, the total equivalent of the polyvalent amine and the monohydric alcohol is preferably the same or larger than the equivalent of the polyvalent carboxylic acid.

  The viscosity of the composite ester polyamide composition of the present invention at 40 ° C. is preferably 50 to 1650 mPas. The viscosity of the composite ester polyamide composition at 40 ° C. is preferably 50 mPas or more, more preferably 70 mPas or more, and further preferably 100 mPas or more. Moreover, the viscosity at 40 ° C. of the composite ester polyamide composition is preferably 1650 mPas or less, more preferably 1200 mPas or less, and further preferably 1000 mPas or less. By setting the viscosity of the composite ester polyamide composition within the above range, the friction coefficient of the composite ester polyamide composition can be kept low, thereby improving the lubricating performance.

  The lubricant of the present invention has an excellent feature that the increase in the friction coefficient is small. Such an excellent effect is considered to be obtained when the ester polyamide obtained in the present invention has a three-dimensional structure in which side chains are arranged radially. The ester polyamide obtained in the present invention is composed of a polyvalent amine capable of radially arranging side chains, a polyvalent carboxylic acid connected to the polyamine and extending radially, and a monohydric alcohol serving as a terminal linking group for the polyvalent carboxylic acid. Is a compound composed of In the present invention, a large free volume can be secured by the steric structure by having a side chain with a polyvalent amine as a central atomic group. Thereby, the raise of a friction coefficient can be suppressed.

  Furthermore, the lubricant of the present invention is characterized by excellent hydrolysis resistance. Such an effect is considered to be obtained by forming a polyamine with a central atomic group and forming an amide bond between the polyamine and the polycarboxylic acid. In the present invention, the change in the molecular weight of the ester polyamide can be kept small over a long period of time by forming an amide bond with a polyamine having a central atomic group. That is, in the present invention, it is possible to obtain a composite ester polyamide composition that is prevented from being decomposed over time and having a molecular weight that is not degraded, and is less likely to deteriorate over time. Thereby, the outstanding lubricating performance can be exhibited over a long period of time. In addition, since the lubricant having excellent hydrolysis resistance does not corrode metals, it can be applied to various materials such as metals.

  In the present invention, in addition to the predetermined ester polyamide, a light component may further be included. Here, the light component refers to a component having a low molecular weight, and examples thereof include an ester component represented by the general formula (4). That is, as a light part, the ester which polyhydric carboxylic acid and monohydric alcohol reacted can be illustrated.

In general formula (4), R ² represents a chain or cyclic aliphatic linking group or aromatic linking group having a valence of (m + 1) or more, and R ³ represents an alkyl group which may have a substituent, or a substituent. The cycloalkyl group which may have, the aryl group which may have a substituent, and the heteroaryl group which may have a substituent are represented. m represents an integer of 1 to 3. Specific groups that R ² and R ³ can take are the same as the groups exemplified for R ² and R ^{3 in} the general formula (1).

  In the present invention, the viscosity of the composite ester polyamide composition can be further reduced by allowing the low viscosity liquid containing the light component as described above to coexist. Thereby, lubrication performance can be improved, and high lubrication performance can be exhibited even under extreme pressure conditions.

In the composite ester polyamide composition of the present invention, the ratio between the predetermined ester polyamide and the light component is not particularly limited. In the aspect utilized for the use of the lubricant, the content of light components is preferably 50% by mass or less, more preferably 45% by mass or less, and 40% by mass or less with respect to the predetermined ester polyamide. More preferably it is. In addition, although there is no restriction | limiting in particular about a lower limit, it is preferable that it is 15 mass% or more.
The ratio between the predetermined ester polyamide and the light component can be achieved by controlling the charging ratio of the three raw materials in the production method described later. Moreover, it can also adjust to a preferable range by isolate | separating a light part by distillation etc. and mixing with the remaining ester polyamide in arbitrary ratios.
The composition ratio between the predetermined ester polyamide and the light component containing dimer diol can be calculated by measuring gel permeation chromatography (GPC). The light component is easy to distinguish because the peak of GPC analysis appears sharply and its intensity is large.

  In the present invention, unreacted COOH in the polyvalent carboxylic acid may remain in the side chain of the ester polyamide contained in the composite ester polyamide composition, and unreacted OH in the monohydric alcohol may remain. Although it may exist, when OH and COOH remain, the hydroxyl value and the acid value increase, and depending on the use (for example, the use of a lubricant), it may not be preferable. In such a case, OH and COOH in the ester polyamide can be eliminated by separate acylation and / or esterification treatment, and the hydroxyl value and acid value can be reduced.

In order to eliminate OH in the ester polyamide, after once obtaining an ester polyamide having OH remaining in the side chain, a treatment of acylating at least a part thereof can be performed. In the acylation treatment, monobasic acid (R ¹ COOH) or monobasic acid anhydride ((R ¹ CO) ₂ O) is added to ester polyamide in which OH remains, and heated to convert the remaining OH to OCOR. ^This is a process of converting to ¹ . When the hydroxyl value is reduced by the acylation treatment, mixing with other oil-based media is preferable in terms of easy mixing.
Moreover, you may perform the process which lose | disappears COOH in ester polyamide. For example, it can be esterified by treatment with diazomethane or the like.

The ratio of unreacted OH in the ester polyamide is determined by measuring ¹³ C-NMR. In the use of the lubricant, the residual ratio of OH in the ester polyamide is preferably 0 to 40%, more preferably 0 to 35%, and further preferably 0 to 30%. In the same application, the acid value of the ester polyamide (mg number of KOH required to neutralize 1 g of the sample) is preferably 0 to 50, more preferably 0 to 40, and 0 to 30. More preferably. However, it is not limited to this range.

(Method for producing composite ester polyamide composition)
The composite ester polyamide composition of the present invention can be obtained by charging at least three raw materials of the above-described polyvalent amine, polyvalent carboxylic acid and monohydric alcohol, followed by dehydration condensation. That is, the method for producing a composite ester polyamide composition of the present invention comprises a polyvalent amine containing at least two primary or secondary amino groups, a polyvalent carboxylic acid containing at least two carboxyl groups, and a monohydric alcohol. A step of mixing to obtain a mixture and a step of dehydrating and condensing the mixture. In the production process, two raw materials (for example, a polyvalent amine and a polyvalent carboxylic acid, or a polyvalent carboxylic acid and a monohydric alcohol) may be reacted first, and then the remaining raw materials may be reacted.

  The charging ratio (mixing ratio) of the polyvalent amine, polyvalent carboxylic acid and monohydric alcohol is determined by an equivalent amount. The equivalent here means the chemical equivalent of COOH, OH or NH in the reaction. If the number of NH in one molecule of the polyvalent amine is n and the number of moles is M1, the equivalent of the polyvalent amine is defined as n × M1. Similarly, when the number of COOH in one molecule of the polycarboxylic acid is m and the number of moles is M2, the equivalent of the polyvalent carboxylic acid is defined as m × M2. Since monohydric alcohol has one OH in one molecule, M3 is defined as M3. The above ratio is a ratio of these n × M1, m × M2, and M3.

  In the present invention, the mixing ratio is preferably polyvalent amine: polyvalent carboxylic acid: monohydric alcohol = 1: 1 to 3: 0.5 to 3. The mixing ratio is more preferably 1: 1.2 to 2.8: 0.7 to 2.8, and more preferably 1: 1.5 to 2.5: 1 to 2.5. preferable. In particular, since the side chain of the ester polyamide is preferably end-capped, the total equivalent of the polyvalent amine and the monohydric alcohol is preferably the same or larger than the equivalent of the polyvalent carboxylic acid.

  The composite ester polyamide composition of the present invention can be obtained by subjecting the mixture charged as described above to a dehydration condensation reaction in the presence or absence of a catalyst.

  In the dehydration condensation, it is desirable to heat or to make an appropriate amount of a solvent azeotropic with water exist. Thereby, dehydration proceeds smoothly without coloring the product. This solvent is preferably a hydrocarbon solvent having a boiling point of 100 to 200 ° C, more preferably a hydrocarbon solvent having a boiling point of 100 to 170 ° C, and most preferably a hydrocarbon solvent having a boiling point of 110 to 160 ° C. Examples of these solvents include toluene, xylene, mesitylene and the like. If the amount to be added is too large, the liquid temperature will be in the vicinity of the solvent, and dehydration condensation will not proceed easily. On the other hand, if the amount is too small, azeotropy does not go smoothly. Therefore, the addition amount is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, particularly preferably 3 to 15% by mass with respect to the total amount of polyvalent amine, polyvalent carboxylic acid and monohydric alcohol. -12 mass% is also preferable.

  Although the reaction is accelerated by using the catalyst, it is desirable not to use it because the post-treatment of removing the catalyst is complicated and causes coloring of the product. However, when used, normal conditions and procedures are used with normal catalysts. In this regard, reference can be made to Japanese Patent Publication Nos. 2001-501989, 2001-500499, 2001-507334, and 2002-509563.

  After completion of the preparation, the reaction is performed at a liquid temperature of 120 to 250 ° C, preferably 130 to 230 ° C, more preferably 130 to 200 ° C, and particularly preferably 140 to 200 ° C. As a result, a solvent containing water is azeotroped, cooled at a cooling site such as Dean Stark, and becomes a liquid to separate water and the solvent. This water may be removed.

  As for the reaction time, since the theoretically generated water amount is calculated from the number of moles charged, it is preferable to carry out the reaction until the water amount is obtained, but it is difficult to complete the reaction completely. Even when the reaction is terminated when the theoretical water generation amount is 60 to 90%, the lubricity of the composite ester polyamide composition is good. The reaction time is 1 to 24 hours, preferably 3 to 18 hours, more preferably 5 to 18 hours, and most preferably 6 to 15 hours.

After dehydration condensation and removal of volatile matter, the remaining OH may be acylated. When acylating, a suitable amount of monobasic acid (R ¹ COOH) or monobasic acid anhydride ((R ¹ CO) ₂ O), preferably monobasic acid anhydride ((R ¹ CO) ₂ O) is added Preferably, at least a part, preferably almost all of the remaining OH can be converted to OCOR ¹ by heating at 100 ° C. or higher, more preferably 120 ° C. or higher, particularly 150 ° C. or higher. It is preferable to remove the by-product volatile matter by distillation described later. R ¹ is an alkyl group or aryl group having 1 to 10 carbon atoms, preferably an alkyl group or aryl group having 1 to 6 carbon atoms, and is a methyl group, ethyl group, butyl group, or phenyl group. Are more preferable, a methyl group or a phenyl group is preferable, and a methyl group is particularly preferable.

  Further, after dehydration condensation and removal of volatile matter, an esterification treatment may be performed in order to eliminate the remaining COOH. The esterification treatment can be performed, for example, by adding diazomethane, and at least a part, preferably almost all of COOH can be converted into a methyl ester.

  By this reaction, a composite ester polyamide composition containing a predetermined ester polyamide and a soft component containing at least the ester produced as described above is obtained. After the dehydration-condensation reaction, if desired, after acylation treatment and / or esterification treatment, the resulting composite ester polyamide composition can be used as it is for various uses, for example, as a lubricant. Various processes may be performed depending on the application.

  After completion of the reaction and the treatment after the reaction, it is preferable to perform filtration to remove dust and the like. When the composite ester polyamide becomes solid, it can be melted out or taken out as a powder by reprecipitation.

(Lubricant composition)
The present invention may relate to a lubricant composition containing at least a composite ester polyamide composition. For example, the composite ester polyamide composition of the present invention and various additives and / or media can be added to the lubricant composition.
Examples of additives include antiwear agents, viscosity index improvers, antioxidants, detergents, dispersants, flow agents, curing agents, corrosion inhibitors, seal conformers, antifoaming agents, rust inhibitors, and corrosion inhibitors. , One or more selected from friction modifiers and thickeners.
By adding such an additive, a preferable function as a lubricant such as wear suppression can be imparted. Regarding the lubricant that can be used in the present invention, the description in paragraphs [0098] to [0165] of JP2011-89106A can be referred to.

As the medium, mineral oil, oil and fat compound, polyolefin oil, silicone oil, ether oil (preferably perfluoropolyether oil, diphenyl ether oil), ester oil (preferably aromatic ester oil, aliphatic monoester oil, fat Group diester oil and polyol ester lubricating oil).
In the present invention, the “medium” means all the media generally called “fluid liquids”. However, it is not necessary to be liquid at room temperature or the temperature used, and any form of material such as solid and gel can be used in addition to liquid. There is no restriction | limiting in particular about the medium utilized in this invention, According to a use, it can select from various liquids. Regarding the medium that can be used in the present invention, the description in paragraphs [0067] to [0096] of JP-A-2011-89106 can be referred to.

(Properties of lubricant composition)
The lubricant composition of the present invention preferably has a viscosity at 40 ° C. of 1650 mPa · s or less, more preferably 1200 mPa · s or less, and even more preferably 1000 mPa · s or less. Viscosity needs to be adjusted to an appropriate viscosity depending on the usage environment.

In the lubricant composition of the present invention, the constituent elements are preferably composed only of carbon, hydrogen, oxygen and nitrogen, and more preferably composed only of carbon, hydrogen and oxygen. In addition, there are various materials that are composed only of carbon, hydrogen, and oxygen as oils used as the oily medium. By combining these, it is possible to prepare a composition whose constituent elements consist only of carbon, hydrogen, oxygen and nitrogen.
The current lubricating oil usually contains phosphorus, sulfur and heavy metals. Lubricating oil used in a two-stroke engine that also burns lubricating oil together with fuel does not include phosphorus and heavy metals in consideration of environmental impact, but sulfur is included in about half of the lubricating oil used in a four-stroke engine. Yes. In other words, with the current lubrication technology, it is inferred that the formation of a boundary lubrication film with a sulfur content is indispensable. large. Platinum and nickel are used for the exhaust gas purification catalyst, but the poisoning action of phosphorus and sulfur is a serious problem. From this point of view, the merit that the elements constituting the composition of the lubricating oil consist only of carbon, hydrogen, oxygen and nitrogen is very large. Furthermore, it consists of carbon, hydrogen and oxygen alone, which is optimal for industrial machinery other than engine oil, especially for lubricating oil for food production equipment. In the current technology, the elemental composition is taken into consideration for the environment at the expense of the friction coefficient. This is also a very preferable technique for metal cutting and machining lubricants that require a large amount of water for cooling.

(Method for preparing lubricant composition)
The lubricant composition of the present invention can be prepared by adding a complex ester polyamide composition in an oily medium or an aqueous medium, and dissolving and / or dispersing it. Dissolution and / or dispersion may be performed under heating. The addition amount of the composite ester polyamide composition is preferably 10% by mass or more with respect to the mass of the oily medium. However, it is not limited to this range, and may be outside the above range as long as the compound is an amount sufficient to exhibit a friction reducing action.

(Use of lubricant composition)
The lubricant composition of the present invention is useful as a lubricant. That is, the present invention also relates to a lubricant including the above-described composite ester polyamide composition or a lubricant including the above-described lubricant composition.
The lubricant of the present invention is supplied, for example, between two sliding surfaces, and can be used to reduce friction. The composition of the present invention can form a film on the sliding surface. As for the material of the sliding surface, in steel, specifically, carbon steel for machine structure, alloy steel for structural machinery such as nickel chrome steel, nickel chrome molybdenum steel, chrome steel, chrome molybdenum steel, aluminum chrome molybdenum steel, Examples include stainless steel and multi-aged steel.

As the material of the sliding surface, various metals other than steel, or inorganic or organic materials other than metals are widely used. Examples of inorganic or organic materials other than metals include various plastics, ceramics, carbon, etc., and mixtures thereof. More specifically, examples of the metal material other than steel include cast iron, copper / copper-lead / aluminum alloy, castings thereof, and white metal.
In addition, about the material of a sliding surface, description of Paragraph [0168]-[0175] of Unexamined-Japanese-Patent No. 2011-89106 can be referred.

  The lubricant of the present invention can be used for various applications. For example, lubricating oil for grease, release agent, engine oil for internal combustion engine, oil for metal processing (cutting), oil for bearing, fuel for combustion engine, vehicle engine oil, gear oil, hydraulic oil for automobile, ship / aircraft Lubricant, machine oil, turbine oil, bearing oil, hydraulic fluid, compressor / vacuum pump oil, refrigerator oil, metalworking lubricant, magnetic recording medium lubricant, micromachine lubricant, artificial bone lubricant It can be used as an agent, shock absorber oil or rolling oil. It is also used for air conditioners and refrigerators with reciprocating and rotary hermetic compressors, automotive air conditioners and dehumidifiers, freezers, refrigerated warehouses, vending machines, showcases, chemical plant and other cooling devices. .

As a lubricant for metal processing that does not contain chlorine compounds, for example, when hot rolling metal materials such as steel materials and Al alloys, or when performing processing such as cutting, cold rolling oil of aluminum, cutting oil, As metal processing oil such as grinding oil, drawing oil, press processing oil and plastic processing oil of metal, especially as a deterrent for wear, breakage and surface roughness during high speed and high load processing, as well as broaching and gun drilling It is also useful as a metal working oil composition that can be applied to low speed and heavy cutting.
Further, it can be used for various grease lubricants, magnetic recording medium lubricants, micromachine lubricants, artificial bone lubricants, and the like. In addition, since the elemental composition of the composition can be a carbohydrate, for example, polyoxyethylene ether widely used in cake mix, salad dressing, shortening oil, chocolate, etc. as an emulsifying, dispersing or solubilizing agent is used. By using the composition of the sorbitan fatty acid ester containing edible oil as the base oil as the lubricating oil, a high-performance lubricating oil that is completely harmless to the human body can be used for lubrication of food production line manufacturing equipment and medical equipment members.
Furthermore, the composition of the present invention can be used as cutting oil or rolling oil by emulsifying and dispersing it in an aqueous system or by dispersing it in a polar solvent or a resin medium.

Moreover, the lubricant composition of the present invention can be used for various applications as a release agent. For example, polycarbonate resin, flame retardant polycarbonate resin, crystalline polyester resin which is the main component of image forming toner used in electrophotographic apparatus and electrostatic recording apparatus, various molding thermoplastic resin compositions and semiconductor encapsulating Used as a mold release agent for epoxy resin compositions. One embodiment of the release agent is an embodiment containing 0.01 to 10 parts by mass (preferably 0.1 to 5 parts by mass) of the composite ester polyamide composition with respect to 100 parts by mass of a resin such as a polycarbonate resin.
Moreover, it can also be used as an antifouling agent that promotes the removal of dirt attached to the fiber product and prevents the fiber product from being soiled by being kneaded or applied in advance to a textile product such as clothing.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

(Examples 1 to 24)
<Synthesis of ester polyamide>
(Synthesis Example 1)
Dean-Stark dehydrator for 7 parts by mass of hexamethylenediamine (PA-5), 67 parts by mass of dimer acid (CA-26: trade name Tsunodim 395) and 26 parts by mass of 2- (2-ethylhexyloxy) ethanol (MA-1) Was charged into a reaction vessel with. The mixture was stirred at a liquid temperature of 160 to 200 ° C. for 12 hours. Water was generated during stirring and 4 parts by weight of water was removed. The mixture was allowed to cool to room temperature, and 96 parts by mass of a composite ester polyamide composition PEA-1 was obtained as a yellow transparent liquid.

(Synthesis Example 2)
6 parts by mass of tris (2-aminoethylamine) (PA-21), 69 parts by mass of dimer acid (CA-26: trade name Tsunodim 395), 25 parts by mass of 2- (2-ethylhexyloxy) ethanol (MA-1) A reaction vessel equipped with a Dean-Stark dehydrator was charged. The mixture was stirred at a liquid temperature of 160 to 200 ° C. for 12 hours. Water was generated during stirring and 4 parts by weight of water was removed. The mixture was allowed to cool to room temperature, and 96 parts by mass of a composite ester polyamide composition PEA-2 was obtained as a yellow transparent liquid.

  The compounds shown in Table 1 were reacted, and composite ester polyamide compositions PEA-3 to PEA-24 were synthesized in the same manner as described above.

<Polyvalent amine>
The polyvalent amines used in the examples of the present invention are as follows.

<Polyvalent carboxylic acid>
The polyvalent carboxylic acids used in the examples of the present invention are as follows.

<Monohydric alcohol>
The monohydric alcohol used in the examples of the present invention is as follows.

<Preparation of lubricant>
The obtained composite ester polyamide composition and mineral oil (100 neutral oil, viscosity 4.4 mm / s ^{2 at} 100 ° C.) were mixed at a mass ratio of 25/75, and calcium sulfonate 2.0 as a metallic detergent. A lubricant containing% by weight was prepared. The friction coefficient of the lubricant was measured by the following method.

<Evaluation>
Test Example 1: Evaluation as Lubricating Oil for Internal Combustion Engine The composite ester polyamide composition PEA-1 of the present invention and mineral oil (100 neutral oil, viscosity 4.4 mm / s ^{2 at} 100 ° C.) in a mass ratio of 25 / A lubricant L1 containing 2.0% by mass of calcium sulfonate as a metallic detergent was prepared, and the coefficient of friction was measured. Further, lubricants L2 to L24 were prepared in the same manner as in Example 1 except that the compositions PEA2 to 24 were used instead of the composition PEA-1 of the present invention, and the friction coefficients were measured. Evaluation was made according to the following evaluation criteria as an index for evaluating the coefficient of friction. The evaluation results are shown in Table 1 below. The friction coefficient was determined using a vibration type friction and wear tester (manufactured by Optimol Instruments Prutechnik GmbH, trade name: SRV 4), with a vibration frequency of 100 Hz, an amplitude of 2.0 mm, a load of 30 N, a temperature of 65 ° C., and a test time of 30 minutes. Measured in In addition, the evaluation is C grade or higher.
Rank A: Friction coefficient <0.05
B rank: 0.05 ≦ coefficient of friction <0.06
C rank: 0.06 ≦ friction coefficient <0.07
D rank: friction coefficient ≧ 0.07

Test Example 2: Evaluation of Hydrolytic Stability The hydrolytic stability of the composite ester polyamide compositions PEA-1 to 24 of the present invention and the comparative compound was ranked according to the following evaluation criteria according to ASTM D2619. The test conditions and evaluation items are as follows. In addition, the evaluation is C grade or higher.

<Test conditions>
Mixing ratio 75 g of sample, 25 g of water, test temperature 93 ° C., test time 48 hr, catalyst material copper <evaluation item> acid value before test, acid value after test <evaluation criteria>
Rank A: acid value after test (mgKOH / g) / acid value before test (mgKOH / g) <= 1.2
B rank: 1.2 <acid value after test (mgKOH / g) / acid value before test (mgKOH / g) <= 1.5
C rank: 1.5 <acid value after test (mgKOH / g) / acid value before test (mgKOH / g) <= 5
D rank: 5.0 <acid value after test (mgKOH / g) / acid value before test (mgKOH / g)

(Comparative Example 1)
Lubricant in the same manner as in Example 1 except that the reaction product (PEA-25) described in Example of JP-A-9-12716 was used instead of the composite ester polyamide composition (PEA-1) of the present invention. L25 was prepared and evaluated in the same manner. The results are shown in Table 1.

As can be seen from Table 1, it can be understood that the friction coefficient of the samples of Examples 1 to 24 is lower than that of the sample of the comparative example. Therefore, the lubricant of the present invention can be suitably used as an automotive lubricating oil such as an internal combustion engine such as an automobile engine, a gear oil, an automatic transmission fluid, and a shock absorber oil.
Moreover, it turns out that all the composite ester polyamide compositions of this invention are stable to hydrolysis and have the characteristic which does not change easily.

  According to the present invention, a composite ester polyamide composition capable of exhibiting high lubricating performance can be obtained. Furthermore, according to the present invention, a composite ester polyamide composition having excellent hydrolysis resistance can be obtained. For this reason, the composite ester polyamide composition of the present invention does not corrode metals, is preferably used as a lubricant in various applications, and has high industrial applicability.

Claims (18)

  Includes an ester polyamide obtained by condensing a polyvalent amine containing at least two primary or secondary amino groups, a polyvalent carboxylic acid containing at least two carboxyl groups, and a monohydric alcohol having 4 or more carbon atoms The composite ester polyamide composition characterized by the above-mentioned. The composite ester polyamide composition according to claim 1, wherein the polyvalent amine and the polyvalent carboxylic acid satisfy the following condition (i) or (ii):
(I) The polyvalent amine is a divalent amine containing two primary or secondary amino groups, and the polyvalent carboxylic acid is a polyvalent carboxylic acid containing three or more carboxyl groups.
(Ii) The polyvalent amine is a polyvalent amine containing three or more primary or secondary amino groups, and the polyvalent carboxylic acid is a divalent carboxylic acid containing two carboxyl groups. The composite ester polyamide composition according to claim 1 or 2, wherein at least one of the ester polyamides is represented by the following general formula (1):

In General Formula (1), R represents an aliphatic group having 2 to 60 carbon atoms, R ¹ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, The aryl group which may have a substituent, the heteroaryl group which may have a substituent, or group represented by General formula (2) is represented. R ² represents a linear or cyclic aliphatic linking group or aromatic linking group having a valence of (m + 1) or more, and R ³ represents an alkyl group which may have a substituent or an cycloalkyl which may have a substituent. Represents a group, an aryl group which may have a substituent, and a heteroaryl group which may have a substituent. n represents an integer of 2 to 4, and m represents an integer of 1 to 3.

In general formula (2), R ² represents a chain or cyclic aliphatic linking group or aromatic linking group having a valence of (m + 1) or more, and R ³ represents an alkyl group which may have a substituent, or a substituent. The cycloalkyl group which may have, the aryl group which may have a substituent, and the heteroaryl group which may have a substituent are represented. m represents an integer of 1 to 3.   The composite ester polyamide composition according to claim 3, wherein m is an integer of 1 or 2 in the general formulas (1) and (2). The composite ester polyamide composition according to claim 3 or 4, wherein, in the general formulas (1) and (2), R ² has 22 to 66 carbon atoms. In the general formula (1) and (2), R ² is, complex esters polyamide composition according to any one of claims 3 to 5 is a dimer acid residues or trimer acid residue. In the general formula (1) and (2), the number of carbon atoms in R ³ are complex esters polyamide composition according to any one of claims 3 to 6 is 6 or more. In the general formula (1) and (2), R ³ is, complex ester polyamide composition according to any one of claims 3 to 7 is a group having an oxyalkylene structure. The said monohydric alcohol is a composite ester polyamide composition of any one of Claims 1-8 represented by following General formula (3);

In general formula (3), R ^a has an alkyl group which may have ^a substituent, ^a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. Or a heteroaryl group which may have a substituent, and X ^a1 and X ^a2 each independently represent a hydrogen atom, a halogen atom or an alkyl group. Na1 represents an integer of 2 to 4, and na2 represents an integer of 1 to 12. The composite ester polyamide composition according to any one of claims 1 to 9, further comprising an ester component represented by the general formula (4);

In general formula (4), R ² represents a chain or cyclic aliphatic linking group or aromatic linking group having a valence of (m + 1) or more, and R ³ represents an alkyl group which may have a substituent, or a substituent. The cycloalkyl group which may have, the aryl group which may have a substituent, and the heteroaryl group which may have a substituent are represented. m represents an integer of 1 to 3.   The composite ester polyamide composition according to any one of claims 1 to 10, wherein the viscosity at 40 ° C is 50 to 1650 mPas.   The composite ester polyamide composition according to any one of claims 1 to 11, an antiwear agent, a viscosity index improver, an antioxidant, a detergent, a dispersant, a flow, a curing agent, a corrosion inhibitor, and seal compatibility. Lubricant composition containing one or more additives selected from agents, antifoaming agents, rust inhibitors, corrosion inhibitors, friction modifiers, and thickeners.   The composite ester polyamide composition according to any one of claims 1 to 11, or the lubricant composition according to claim 12, a mineral oil, an oil and fat compound, a polyolefin oil, a silicone oil, a perfluoropolyether oil, A lubricant composition containing at least one or two or more media selected from diphenyl ether oil, aromatic ester oil, aliphatic monoester oil, aliphatic diester oil, and polyol ester lubricating oil.   A lubricant comprising the composite ester polyamide composition according to any one of claims 1 to 11, or the lubricant composition according to claim 12 or 13.   Grease lubricants, mold release agents, engine oils for internal combustion engines, metal processing (cutting) oils, bearing oils, combustion engine fuels, vehicle engine oils, gear oils, automotive hydraulic oils, marine and aircraft lubricants Oil, machine oil, turbine oil, bearing oil, hydraulic oil, compressor / vacuum pump oil, refrigerator oil, metalworking lubricant, magnetic recording medium lubricant, micromachine lubricant, artificial bone lubricant, The lubricant according to claim 14, which is used as a shock absorber oil or a rolling oil.   A step of mixing a polyvalent amine containing at least two primary or secondary amino groups, a polyvalent carboxylic acid containing at least two carboxyl groups, and a monohydric alcohol to obtain a mixture; and a step of dehydrating and condensing the mixture. A method for producing a composite ester polyamide composition comprising:   In the step of obtaining the mixture, the equivalent ratio of mixing the polyvalent carboxylic acid with respect to the polyvalent amine is 1 to 3, and the equivalent ratio of mixing the monohydric alcohol is 0.5 to 3. The method for producing a composite ester polyamide composition according to claim 16, which is a step of mixing.   The dehydrating and condensing step includes a step of adding 1 to 25% by mass of a hydrocarbon solvent having a boiling point of 110 to 160 ° C. with respect to the mixture, and causing dehydration condensation to proceed while azeotropically distilling water. A method for producing a composite ester polyamide composition according to 16 or 17.