WO2014148411A1

WO2014148411A1 - Composite polyester amide composition and lubricant

Info

Publication number: WO2014148411A1
Application number: PCT/JP2014/057057
Authority: WO
Inventors: 祐二寺田; 鈴木　博幸
Original assignee: 富士フイルム株式会社
Priority date: 2013-03-19
Filing date: 2014-03-17
Publication date: 2014-09-25
Also published as: JP5975914B2; JP2014181271A

Abstract

This composite polyester amide composition contains polyester amide obtained by condensing a polyhydric alcohol containing at least two hydroxyl groups, a polycarboxylic acid containing at least two carboxyl groups, and a monoamine. This composition is useful as a lubricant capable of manifesting excellent lubrication performance and hydrolysis resistance.

Description

Composite polyesteramide composition and lubricant

The present invention relates to a composite polyesteramide composition and a lubricant. Specifically, the present invention relates to a composite polyesteramide composition containing a specific polyesteramide and a lubricant containing the composite polyesteramide composition.

Lubricants generally contain base oil 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 amide compounds and describe the use of this ester amide compound as a lubricant. In Patent Document 6, a fluorine-containing alkyl ester amide compound is used as the ester amide compound, thereby obtaining a lubricant having excellent stability. Patent Document 7 proposes to use an ester amide compound having a specific structure as a solvent or a fusion aid.

JP 2002-097482 A JP 2005-154726 A JP 2005-232434 A JP 2005-213377 A JP 2005-232470 A JP 2007-070289 A Special table 2011-510046 gazette

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. Moreover, since the conventional lubricant containing polyester is hydrolyzed in the lubricant, there has been 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, a conventional lubricant containing a polyester compound does not have excellent lubrication performance and hydrolysis resistance, and a lubricant having both of these properties 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 lubricating performance can be improved by obtaining a composite polyesteramide composition containing a specific polyesteramide. The specific polyester amide is a polyester amide obtained by condensing a monoamine with a polyhydric alcohol containing at least two hydroxyl groups, a polyvalent carboxylic acid containing at least two carboxyl groups, and a monoamine.
Furthermore, the present inventors have found that a composite polyesteramide composition containing such a polyesteramide can exhibit excellent hydrolysis resistance, and have completed the present invention.
Specifically, the present invention has the following configuration.

[1] A composite polyesteramide composition comprising a polyesteramide obtained by condensing a polyamine having at least two hydroxyl groups, a polyvalent carboxylic acid having at least two carboxyl groups, and a monoamine. object.
[2] The composite polyesteramide composition according to [1], wherein the polyhydric alcohol contains three or more hydroxyl groups.
[3] The composite polyesteramide composition according to [1] or [2], wherein the polyhydric alcohol is pentaerythritol, trimethylolpropane, glycerin or dipentaerythritol.
[4] The composite polyesteramide composition according to [1], wherein at least one of the polyesteramides is represented by the following general formula (1).

(In the general formula (1), R represents an n-valent atomic group, R ¹ is an (m + 1) -valent atomic group, and represents a residue of the polyvalent carboxylic acid. R ² and R ³ each represent Independently, a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl which may have a substituent R ² and R ³ may be bonded to each other to form a cyclic structure, n represents an integer of 2 to 4, and m represents an integer of 1 to 3.)
[5] The composite polyesteramide composition according to [4], wherein in the general formula (1), n is an integer of 3 or 4.
[6] The composite polyesteramide composition according to [4] or [5], wherein in the general formula (1), m is an integer of 1 or 2.
[7] The composite polyesteramide composition as described in any one of [4] to [6], wherein in the general formula (1), R ¹ has 22 to 66 carbon atoms.
[8] The composite polyesteramide composition according to any one of [4] to [7], wherein in the general formula (1), R ¹ is a dimer acid residue or a trimer acid residue.
[9] The composite polyesteramide composition as described in any one of [4] to [8], wherein in the general formula (1), the total number of carbon atoms of R ² and R ³ is 6 or more .
[10] In any one of [4] to [9], in the general formula (1), R ² and R ³ are each independently an alkyl group which may have a substituent. A composite polyesteramide composition.
[11] In any one of [4] to [10], in the general formula (1), R is an atomic group composed of a saturated aliphatic hydrocarbon which may have a substituent. A composite polyesteramide composition.
[12] The composite polyesteramide composition according to any one of [1] to [11], wherein the viscosity at 40 ° C. is 50 to 1650 mPas.
[13] The composite polyesteramide composition according to any one of [1] to [12], an antiwear agent, a viscosity index improver, an antioxidant, a detergent, a dispersant, a flow, a curing agent, and a corrosion inhibitor. , A 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.
[14] The composite polyesteramide composition according to any one of [1] to [12], or the composition according to [13], a mineral oil, a fat compound, a polyolefin oil, a silicone oil, and a perfluoropolyether oil , An aromatic ester oil, and at least one medium selected from polyol ester lubricating oils.
[15] A lubricant comprising the composite polyesteramide composition according to any one of [1] to [12], or the composition according to [13] or [14].
[16] 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, 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 [15], which is used as a lubricant, shock absorber oil or rolling oil.
[17] A step of mixing a polyhydric alcohol containing at least two hydroxyl groups, a polyvalent carboxylic acid containing at least two carboxyl groups, and a monoamine to obtain a mixture, and a step of dehydrating and condensing the mixture. A method for producing a composite polyesteramide composition.
[18] In the step of obtaining the mixture, the equivalent ratio of mixing the polyvalent carboxylic acid with respect to the polyhydric alcohol is 1 to 3, and the equivalent ratio of mixing the monoamine is 0.5 to 3. [17] The method for producing a composite polyesteramide composition according to [17], wherein
[19] 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 advancing dehydrating condensation while azeotropically distilling water. The method for producing a composite polyesteramide composition according to [17] or [18], comprising

According to the present invention, a composite polyesteramide composition that can exhibit high lubricating performance can be obtained. Furthermore, according to the present invention, a composite polyesteramide composition having excellent hydrolysis resistance can be obtained. For this reason, the composite polyesteramide composition of the present invention does not corrode metals and is preferably used as a lubricant in 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.

(1. Composite polyesteramide composition)
The present invention relates to a composite polyesteramide composition containing a predetermined polyesteramide. The composite polyesteramide composition of the present invention includes a polyesteramide obtained by condensing a polyamine having at least two hydroxyl groups, a polyvalent carboxylic acid having at least two carboxyl groups, and a monoamine.

The polyhydric alcohol used for the condensation of the polyester amide is a compound containing at least two hydroxyl groups. The polyhydric alcohol is represented by R (OH) _n . R is an n-valent aliphatic, alicyclic or aromatic ring group, and one or more carbon atoms not adjacent to each other in R may be substituted with an oxygen atom. It is preferable that 2 to 4 hydroxyl groups are contained in one polyhydric alcohol molecule, and 3 or 4 hydroxyl groups are more preferred. That is, the polyhydric alcohol is preferably triol or tetraol.

The polyhydric alcohol used in the present invention may be any one of dihydric to tetrahydric polyhydric alcohols, or a plurality of them may be used. For example, a mixture of a divalent polyhydric alcohol and a trivalent polyhydric alcohol may be used, or a mixture of a divalent polyhydric alcohol, a trivalent polyhydric alcohol, and a tetravalent polyhydric alcohol. A mixture of a trivalent polyhydric alcohol and a tetravalent polyhydric alcohol may be used. In addition, when a divalent polyhydric alcohol is included, the content of the divalent polyhydric alcohol is preferably 40% by mass or less, and preferably 30% by mass or less with respect to the total mass of the polyhydric alcohol. Is more preferable, and it is further more preferable that it is 20 mass% or less.

R is preferably an n-valent aliphatic group containing 2 to 20, more preferably 2 to 15, more preferably 2 to 10, still more preferably 2 to 7, particularly preferably 3 to 5 carbon atoms. . However, it is not limited to this range, and depending on the application, it may be preferable that the number of carbon atoms is rather large.
Preferred examples of R include C _x H _{2X + 2-n} (x is a number from 2 to 20) or C _x H _{2X + 2-n} O _m (x is a number from 2 to 20, m satisfies m <x. And a group represented by 1 to 3 is more preferable.

Examples of the polyhydric alcohol that can be used in the present invention include the following compounds. Diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,4-dimethylolcyclohexane, neopentyl glycol; trimethylolmethane, trimethylolethane , Triols such as trimethylolpropane, trimethylolbutane, glycerol; tetraols such as trimethylolpropane, multiols such as dipentaerythritol, tripentaerythritol; xylitol, sorbitol, mannitol, erythritol, maltitol, isomalt, Sugar alcohols such as albinitol, ribitol, iditol, boremitol, and periseitol; and sugars such as glucose; and the like. Among these, neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, glycerin, pentaerythritol, dipentaerythritol, and xylitol are preferable; trimethylol propane, trimethylol butane, glycerin, pentaerythritol, and dipentayl. Erythritol and the like are more preferable; trimethylolpropane, glycerin, pentaerythritol, dipentaerythritol and the like are still more preferable; pentaerythritol and trimethylolpropane are particularly preferable. These do not need to be high-purity products, and are preferably used even in so-called industrial brands. For example, an industrial brand of pentaerythritol is said to consist of about 88% mono-, 10% di- and 1-2% tri-pentaerythritol. In the present invention, these industrial brands such as pentaerythritol are used in the present invention. Can be used as a polyhydric alcohol.

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

The polyvalent carboxylic acid used for the condensation of the polyester amide is a compound containing at least two carboxyl groups. 2 to 4 carboxyl groups are preferably contained in one molecule, more preferably 2 or 3, and even more preferably 2 carboxyl groups. Further, the polycarboxylic acid is particularly preferably a dimer 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.

The carboxyl group in the molecule is linked with a chain or cyclic divalent or higher valent aliphatic hydrocarbon or aromatic hydrocarbon. The number of carbon atoms of the polycarboxylic acid is preferably 4 or more, preferably 10 or more, more preferably 24 or more, further preferably 26 or more, and particularly preferably 28 or more. preferable. Further, the carbon number of the polyvalent carboxylic acid is preferably 68 or less, more preferably 62 or less, and even more 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 polyesteramide 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.

Specific examples of polyvalent carboxylic acids 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 may 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.

The monoamine that can be used in the present invention is a compound having one nitrogen atom in one molecule, and it is preferable to use a monoamine represented by NHR ² R ³ . R ² and R ³ each independently represents 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 substituent. The heteroaryl group which may have is represented. R ² and R ³ may be bonded to each other to form a cyclic structure. Among these, R ² and R ³ are each preferably an alkyl group which may have a substituent, and particularly preferably an alkyl group having a substituent.

Monoamine preferably has 6 or more carbon atoms, more preferably 7 or more, and even more preferably 8 or more. That is, it is preferable that the total number of carbon atoms of R ² and R ³ is not less than the above lower limit value. Moreover, it is preferable that carbon number of a monoamine is 30 or less, It is more preferable that it is 24 or less, It is further more preferable that it is 20 or less. By setting the carbon number of the monoamine within the above range, an increase in the viscosity of the composite polyesteramide composition can be suppressed, and the lubricating performance of the composite polyesteramide composition can be further enhanced. Moreover, the amidation reaction rate during the condensation reaction can be increased, and the acid value can be reduced.

Monoamines include hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, myristylamine, cetylamine, stearylamine, aralkylamine, behenylamine, N-methyllaurylamine, N-methylmyristylamine, N-methylcetyl Examples thereof include, but are not necessarily limited to, amine, N-methylstearylamine, N-methylaralkylamine, N-methylbehenylamine, N, N-didodecylamine, and aniline.

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

The composite polyesteramide composition of the present invention comprises mixing a polyamine having at least two hydroxyl groups, a polyvalent carboxylic acid having at least two carboxyl groups, and a monoamine as described above, and condensing the mixture. The resulting polyester amide is included. At least one polyester amide obtained by condensing the mixture is preferably represented by the following general formula (1).

Here, in the general formula (1), R represents an n-valent atomic group, R ¹ is an (m + 1) -valent atomic group, and represents a residue of a polyvalent carboxylic acid. R ² and R ³ each independently represents 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 substituent. The heteroaryl group which may have is represented. R ² and R ³ may be bonded to each other to form a cyclic structure. N represents an integer of 2 to 4, and m represents an integer of 1 to 3.

In the general formula (1), R represents an n-valent atomic group, n is 2 to 4, and n is preferably 3 or 4. That is, the polyhydric alcohol containing at least two hydroxyl groups is preferably a compound containing three or more hydroxyl groups.

The structure of the polyesteramide when R is a trivalent atomic group is represented by the general formula (2), and the structure of the polyesteramide when R is a tetravalent atomic group is represented by the general formula (3). Can do.

Here, in the general formula (2), R represents a trivalent atomic group, and R ¹ represents an (m + 1) valent atomic group, which represents a residue of a polyvalent carboxylic acid. R ² and R ³ each independently represents 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 substituent. The heteroaryl group which may have is represented. R ² and R ³ may be bonded to each other to form a cyclic structure. M represents an integer of 1 to 3.
In the general formula (3), R represents a tetravalent atomic group, and R ¹ represents an (m + 1) valent atomic group, which represents a residue of a polyvalent carboxylic acid. R ² and R ³ each independently represents 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 substituent. The heteroaryl group which may have is represented. R ² and R ³ may be bonded to each other to form a cyclic structure. M represents an integer of 1 to 3.

The atoms constituting the atomic group R are preferably carbon, hydrogen, and oxygen atoms. R is preferably an aliphatic hydrocarbon atomic group that may have a substituent, or an aromatic hydrocarbon atomic group that may have a substituent. Among these, R is particularly preferably an atomic group composed of a saturated aliphatic hydrocarbon which may have a substituent. By setting R to the above configuration, a composite polyesteramide composition having excellent lubricating performance can be obtained.

In the above general formulas (1) to (3), the carbon number of R is preferably 2 or more, and more preferably 3 or more. Moreover, the carbon number of R is 20 or less, preferably 15 or less, and more preferably 10 or less.

R ¹ is an (m + 1) -valent atomic group and represents a residue of a polyvalent carboxylic acid. Here, the residue of the polyvalent carboxylic acid refers to a group constituting a part obtained by removing the carboxyl group from the polyvalent carboxylic acid. Here, m is 1 to 3. m is preferably 1 or 2, and more preferably 1.

R ¹ preferably has 2 to 66 carbon atoms. The carbon number of R ¹ may be 2 or more, preferably 4 or more, preferably 8 or more, more preferably 22 or more, further preferably 24 or more, 26 or more. Even more preferably. The carbon number of R ¹ is preferably 66 or less, more preferably 60 or less, and even more preferably 57 or less. Thus, by making the carbon number of R ¹ within the above range, the lubricating performance of the composite polyesteramide composition can be further enhanced.

R ² and R ³ each independently represents 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 substituent. The heteroaryl group which may have is represented. In addition, the substituent of each group that R ² and R ³ may have is not particularly limited. Among these, R ² and R ³ are each preferably an alkyl group which may have a substituent, and particularly preferably an alkyl group having a substituent.

The total number of carbon atoms of R ² and R ³ is preferably 6 or more, more preferably 7 or more, and even more preferably 8 or more. The total number of carbon atoms of R ² and R ³ is preferably 6 to 30, more preferably 7 to 24, and even more preferably 8 to 16.

The aryl group portion of the aryl group or heteroaryl group which may have a substituent represented by R ² and R ³ preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. . R ² and R ³ may be bonded to each other to form an aryl group. Examples of the aryl group represented by R ² and R ³ include a phenyl group and a naphthyl group, and among them, a phenyl group is particularly preferable. Examples of the heteroaryl group represented by R ² and R ³ include an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a thienyl group, a benzoxazolyl group, an indolyl group, a benzimidazolyl group, a benzthiazolyl group, and a carbazolyl group. An azepinyl group can be exemplified. 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.

Among the above-mentioned, R ² and R ³ are preferably a branched alkyl group or an alkyl group containing an ether bond in the chain. By using R ² and R ³ as such substituents, the lubricating performance of the composite polyesteramide composition can be further enhanced.

When mixing the compound of polyhydric alcohol, polycarboxylic acid and monoamine, the equivalent ratio of mixing polyhydric carboxylic acid with respect to polyhydric alcohol is 1 to 3, and monoamine with respect to polyhydric alcohol. It is preferable that the equivalent ratio of mixing is 0.5 to 3. That is, the mixing ratio is preferably polyhydric alcohol: polycarboxylic acid: monoamine = 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 terminal linking group of the side chain of the polyesteramide is preferably a carbonylamide group and end-capped, the total equivalent of the polyhydric alcohol and monoamine should be the same or larger than the equivalent of the polyvalent carboxylic acid. preferable.

The viscosity at 40 ° C. of the composite polyesteramide composition of the present invention is preferably 50 to 1650 mPas. The viscosity of the composite polyesteramide composition at 40 ° C. is preferably 50 mPas or more, more preferably 70 mPas or more, and further preferably 100 mPas or more. The viscosity of the composite polyesteramide composition at 40 ° C. 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 polyesteramide composition within the above range, the coefficient of friction of the composite polyesteramide composition can be kept low, thereby improving the lubrication 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 polyesteramide obtained in the present invention has a three-dimensional structure in which side chains are arranged radially. The polyesteramide obtained by the present invention is composed of a polyhydric alcohol capable of radially arranging a side chain, a polyvalent carboxylic acid connected to it and extending radially, and a monoamine serving as a terminal linking group of the polyvalent carboxylic acid. It is a compound. In the present invention, a polyhydric alcohol is used as a central atomic group and a side chain is provided, so that a large free volume can be ensured by the three-dimensional structure. Thereby, the outstanding lubricating performance can be exhibited. In addition, increase in viscosity and friction coefficient can be suppressed even under high pressure.
Furthermore, the lubricant of the present invention is characterized by excellent hydrolysis resistance. Such an effect is considered to be obtained by using a terminal linking group as a carbonylamide group. Thus, since the lubricant excellent in hydrolysis resistance does not corrode metals, the composite polyesteramide composition of the present invention can be applied to various materials such as metals as lubricants.

In the present invention, in addition to the predetermined polyester amide, a light component may be further included. Here, the light component refers to a component having a low molecular weight, and refers to an acid amide obtained by reacting all carboxyl groups of a polyvalent carboxylic acid with a monoamine and a compound having a smaller molecular weight. The viscosity of the composite polyesteramide composition can be further reduced by allowing a liquid having a lower viscosity, such as a light component, to coexist. Thereby, higher lubrication performance can be exhibited.

In the composite polyesteramide composition of the present invention, the ratio between the predetermined polyesteramide and the light component is not particularly limited. In the aspect utilized for the use of the lubricant, the light content 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 polyesteramide. 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 polyesteramide 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 polyesteramide in arbitrary ratios.
In addition, the composition ratio of a predetermined polyesteramide and a light component containing a polyvalent carboxylic acid 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 OH in the dimer diol may remain in the side chain of the polyesteramide contained in the composite polyesteramide composition, and unreacted COOH in the polyvalent carboxylic acid exists. However, if OH and COOH remain, the hydroxyl value and the acid value increase, which may be undesirable depending on the application (for example, the use of a lubricant). In such a case, OH and COOH in the polyester amide can be eliminated by a separate acylation and / or esterification treatment to reduce the hydroxyl value and the acid value.

In order to eliminate OH in the polyester amide, after once obtaining a polyester amide 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 polyester amide in which OH remains, and heated to convert the remaining OH to OCOR ¹ It is a process to convert to. 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 polyesteramide. For example, it can be esterified by treatment with diazomethane or the like.

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

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

The charge ratio (mixing ratio) of the polyhydric alcohol, polycarboxylic acid and monoamine is determined by the equivalent amount. The equivalent here means the chemical equivalent of COOH, OH or NH in the reaction. When the number of OH in one molecule of the polyhydric alcohol is n and the number of moles is M1, the equivalent of the polyhydric alcohol is defined as n × M1. Similarly, when the number of COOH in the polyvalent carboxylic acid molecule is m and the number of moles is M2, the equivalent of the polyvalent carboxylic acid is defined as m × M2. Since monoamine has one NH in one molecule, M3 is defined as M3. The above ratio is a ratio of these n × M1, 2 × M2, and M3.

In the present invention, the mixing ratio is preferably polyhydric alcohol: polycarboxylic acid: monoamine = 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 terminal linking group of the side chain of the polyesteramide is preferably a carbonylamide group and end-capped, the total equivalent of the polyhydric alcohol and monoamine should be the same or larger than the equivalent of the polyvalent carboxylic acid. preferable.

The composite polyesteramide 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.

During the dehydration condensation, it is desirable to heat or make an appropriate amount of a solvent azeotropic with water present. 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, based on the total amount of polyhydric alcohol, polyvalent carboxylic acid and monoamine. Mass% is also preferred.

Although the reaction is accelerated by using a 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. Regarding this, reference can be made to the references in JP-T 2001-501989, JP-A 2001-500509, JP-A 2001-507334, and JP-A 2002-509563.

After completion of the preparation, the reaction is carried out at a liquid temperature of 120 to 250 ° C., preferably 130 to 230 ° C., more preferably 130 to 200 ° C., 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 polyesteramide 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 a methyl group, an ethyl group, a butyl group, or a 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 polyesteramide composition containing a predetermined polyesteramide 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 obtained composite polyesteramide 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 polyesteramide becomes a solid, it can be melted and taken out or taken out as a powder by reprecipitation.

(3. Composition)
The present invention may relate to a composition containing at least a composite polyesteramide composition. For example, the composite polyesteramide composition of the present invention and various additives and / or media can be added to the 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, reference can be made to the descriptions in paragraphs [0098] to [0165] of JP2011-89106A.

Examples of the medium include one or more selected from mineral oils, fat compounds, polyolefin oils, silicone oils, perfluoropolyether oils, aromatic ester oils, and polyol ester lubricating oils.
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 JP2011-89106A can be referred to.

(3-2. Properties of the composition of the present invention)
The composition of the present invention preferably has a viscosity at 40 ° C. of 1650 mPa · s or less, more preferably 1000 mPa · s or less, and even more preferably 500 mPa · s or less. A smaller viscosity contributes to lower fuel consumption and is preferable, but it varies greatly depending on the viscosity of the base oil used, the structure of the compound of the present invention, the amount added, and the coexisting additive, and an appropriate viscosity is required depending on the use environment. It is necessary to match. However, since the present invention does not require the suppression of the base oil viscosity reduction under high temperature and extreme pressure conditions with the viscosity index improver in the current technology, the viscosity increase at low temperature due to the addition of the viscosity index improver. One of the features is that the effect of the low-viscosity base oil directly contributes to fuel consumption.

In the 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. However, since it contains elemental sulfur, the load on the catalyst for exhaust gas purification is extremely high. 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.

(4. Method for preparing the composition of the present invention)
The composition of the present invention can be prepared by adding the complex polyesteramide 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 amount of the composite polyesteramide composition added is preferably 10% by mass or more based on 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.

(5. Use of the composition of the present invention)
The composition of the present invention is useful as a lubricant. That is, the present invention also relates to a lubricant containing the above-described composite polyesteramide composition or the above-described 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.
For the material of the sliding surface, reference can be made to the descriptions in paragraphs [0168] to [0175] of JP2011-89106A.

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 cooling devices .

As a lubricant for metal processing that does not contain chlorine-based 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, grinding oil, drawing oil, metal working oil such as press working oil and metal plastic working oil, especially as a deterrent to wear, breakage and surface roughness during high speed and high load processing, broaching, gun drilling It is also useful as a metalworking oil composition that can be applied to low speed and heavy cutting. In particular, since the lubricant of the present invention is excellent in hydrolysis resistance, it is preferably used because it does not corrode metals even when used as such a lubricant for metal processing.
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 composition of this invention can be utilized for various uses also as a mold 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 polyesteramide 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 detachment of dirt adhering 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.

Hereinafter, 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 21)
<Polyhydric alcohol>
The polyhydric alcohols 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.

<Monoamine>
The monoamines used in the examples of the present invention are as follows.

<Synthesis of polyester amide>
The polyhydric alcohol described in Table 1, the polyvalent carboxylic acid, and the monoamine were charged into a reaction vessel equipped with a Dean-Stark dehydrator so as to have the mass parts described in Table 1. Thereafter, the mixture was stirred at a liquid temperature of 160 to 200 ° C. for 12 hours. Water was generated during stirring and 17 g of water was removed. The mixture was allowed to cool to room temperature to obtain a polyesteramide composition (PEE 1 to 81) as a yellow transparent liquid.

<Preparation of composite polyesteramide composition>
Each polyesteramide composition (PEE 1 to 87) obtained in Examples 1 to 21 and mineral oil (100 neutral oil, viscosity of 4.4 mm / s ^{2 at} 100 ° C.) were mixed at a mass ratio of 25/75. Then, a lubricant containing 2.0% by mass of calcium sulfonate as a metal detergent was prepared. The friction coefficient of the lubricant was measured by the following method.

<Evaluation>
The friction coefficient was measured at 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 using a vibration type frictional wear tester (manufactured by Optimol Instruments Prutechnik GmbH, trade name: SRV 4). did. The evaluation results are shown in Table 1 below.
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

Hydrolysis resistance, evaluated according to ASTM D2619. The test temperature was 93 ° C., the test time was 48 hours, and copper was used as the catalyst. The acid value of each sample before and after the test was measured, and the ratio (Q / P) of the acid value P (mgKOH / g) before the test and the acid value Q (mgKOH / g) after the test was calculated. The evaluation results are shown in Table 1 below.
Rank A: Q / P <= 1.2
B rank: 1.2 <Q / P <= 1.5
C rank: 1.5 <Q / P <= 5
D rank: 5.0 <Q / P

(Comparative Example 1)
Instead of the polyesteramide composition of Example 1, in Comparative Example 1, ester dimethylamide (CC-1) described in Examples of Special Table 2011-510046 was used. The ester dimethylamide described in the examples of JP2011-510046 was obtained from methanol, succinic anhydride and dimethylamine according to the method described in the examples of JP2011-510046.
Except having used said compound, it carried out similarly to Example 1, and prepared the composite polyesteramide composition, respectively, and measured the friction coefficient similarly. The results are shown in Table 1.

(Comparative Example 2)
Instead of the polyesteramide composition of Example 1, in Comparative Example 2, the compound (CC-2) described in Example 1 of JP-A-2007-70289 was used. The compound described in Example 1 of JP-A-2007-70289 was obtained from 2- (perfluorooctyl) ethanol, succinic anhydride, and stearyl alcohol according to the method described in Example 1 of JP-A-2007-70289.
Except having used said compound, it carried out similarly to Example 1, and prepared the composite polyesteramide composition, respectively, and measured the friction coefficient similarly. The results are shown in Table 1.

(Comparative Example 3)
Instead of the polyesteramide composition of Example 1, in Comparative Example 3, the compound (CC-32) described in Example 6 of JP-A-2007-70289 was used. The compound described in Example 6 of JP-A-2007-70289 was obtained from 2- (perfluorooctyl) ethanol, succinic anhydride, and stearylamine according to the method described in Example 1 of JP-A-2007-70289.
Except having used said compound, it carried out similarly to Example 1, and prepared the composite polyesteramide composition, respectively, and measured the friction coefficient similarly. The results are shown in Table 1.

As can be seen from Table 1, the friction coefficients of the samples of Examples 1 to 21 are lower than those of the samples of Comparative Examples 1 to 3. In particular, in Examples 2 to 4, 7, and 10 to 14, a trihydric or higher alcohol is used as the polyhydric alcohol, and a dimer acid having 24 to 68 carbon atoms is used as the polyhydric carboxylic acid. Therefore, it can be seen that the coefficient of friction is lower.
Further, it can be seen that Examples 1 to 21 have excellent hydrolysis resistance. In particular, Examples 2 to 4, 7, and 10 to 14 have a high hydrolysis resistance in addition to a low friction coefficient.

According to the present invention, a composite polyesteramide composition that can exhibit high lubricating performance can be obtained. Furthermore, according to the present invention, a composite polyesteramide composition capable of exhibiting excellent hydrolysis resistance can be obtained. For this reason, the composite polyesteramide composition of the present invention can be suitably used as a lubricant for metalworking and has high industrial applicability.

Claims

A composite polyesteramide composition comprising a polyesteramide obtained by condensing a polyamine having at least two hydroxyl groups, a polycarboxylic acid having at least two carboxyl groups, and a monoamine.
2. The composite polyesteramide composition according to claim 1, wherein the polyhydric alcohol contains three or more hydroxyl groups.
The composite polyesteramide composition according to claim 1 or 2, wherein the polyhydric alcohol is pentaerythritol, trimethylolpropane, glycerin or dipentaerythritol.
The composite polyesteramide composition according to claim 1, wherein at least one of the polyesteramides is represented by the following general formula (1).

In general formula (1), R represents an n-valent atomic group, R 1 represents an m + 1-valent atomic group, and represents a residue of the polyvalent carboxylic acid. R 2 and R 3 each independently represents 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 substituent. The heteroaryl group which may have is represented. R 2 and R 3 may be bonded to each other to form a cyclic structure. N represents an integer of 2 to 4, and m represents an integer of 1 to 3.
In the general formula (1), n is an integer of 3 or 4, The composite polyesteramide composition according to claim 4,
In the general formula (1), m is an integer of 1 or 2, The composite polyesteramide composition according to claim 4 or 5,
The composite polyesteramide composition according to any one of claims 4 to 6, wherein in the general formula (1), R 1 has 22 to 66 carbon atoms.
The composite polyesteramide composition according to any one of claims 4 to 7, wherein in the general formula (1), R 1 is a dimer acid residue or a trimer acid residue.
The composite polyesteramide composition according to any one of claims 4 to 8, wherein in the general formula (1), the total number of carbon atoms of R 2 and R 3 is 6 or more.
The composite polyester according to any one of claims 4 to 9, wherein, in the general formula (1), R 2 and R 3 are each independently an alkyl group which may have a substituent. Amide composition.
The composite polyester according to any one of claims 4 to 10, wherein in the general formula (1), R is an atomic group composed of a saturated aliphatic hydrocarbon which may have a substituent. Amide composition.
The composite polyesteramide composition according to any one of claims 1 to 11, wherein the viscosity at 40 ° C is 50 to 1650 mPas.
The composite polyesteramide composition according to any one of claims 1 to 12, an antiwear agent, a viscosity index improver, an antioxidant, a detergent, a dispersant, a flow, a curing agent, a corrosion inhibitor, and seal compatibility A composition containing one or more additives selected from an agent, an antifoaming agent, a rust inhibitor, a corrosion inhibitor, a friction modifier, and a thickener.
The composite polyesteramide composition according to any one of claims 1 to 12, or the composition according to claim 13, and mineral oil, oil and fat compound, polyolefin oil, silicone oil, perfluoropolyether oil, aromatic A composition comprising at least one group ester oil and one or more media selected from polyol ester lubricating oils.
A lubricant comprising the composite polyesteramide composition according to any one of claims 1 to 12, or the composition according to claim 13 or 14.
Grease lubricants, mold release agents, engine oils for internal combustion engines, metal processing or cutting oils, bearing oils, combustion engine fuels, vehicle engine oils, gear oils, automotive hydraulic oils, marine and aircraft lubricants , Machine oil, turbine oil, bearing oil, hydraulic oil, compressor / vacuum pump oil, refrigeration oil, lubricant for metal processing, lubricant for magnetic recording media, lubricant for micromachine, lubricant for artificial bone, shock The lubricant according to claim 15, which is used as an absorber oil or a rolling oil.
It comprises a step of mixing a polyhydric alcohol containing at least two hydroxyl groups, a polyvalent carboxylic acid containing at least two carboxyl groups, and a monoamine to obtain a mixture, and a step of dehydrating and condensing the mixture. A method for producing a composite polyesteramide composition.
The step of obtaining the mixture is performed such that the equivalent ratio of mixing the polyvalent carboxylic acid is 1 to 3 and the equivalent ratio of mixing the monoamine is 0.5 to 3 with respect to the polyhydric alcohol. The method for producing a composite polyesteramide composition according to claim 17, which is a process.
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 advancing dehydrating condensation while azeotropically distilling water. The manufacturing method of the composite polyesteramide composition of Claim 17 or 18 characterized by the above-mentioned.