JPH07242745A - Polyester-imide resin and its production - Google Patents

Abstract

PURPOSE:To obtain a polyester-imide resin which has a high heat softening temperature, can give an insulated wire capable of being soldered within a short time at a low temperature and is excellent in workability in synthesis. CONSTITUTION:A dihydric imidoalcohol represented by the formula (wherein R1 is a bivalent organic group; and R2 is a 2-6 C bivalent aliphatic group) and a polyhydric alcohol are reacted with a polycarboxylic acid and/or its derivative in an organic solvent to obtain the objective resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester imide resin and a method for producing the same, and more particularly to a novel polyester imide resin which provides an insulated wire excellent in solder releasability, heat resistance and workability, and a method for producing the same. Is.

[0002]

2. Description of the Related Art In recent years, with the reduction in size and weight of electric and electronic devices, the number of thin wire type insulated wires used for motors and transformers has been increasing. In addition, with the increase in brightness and definition of televisions and displays, the number of thin-wire type insulated wires used for cathode ray tube deflection yokes is increasing.

By the way, in order to connect the insulated wire to other parts and terminals, after the insulating coating on the end portion of the insulated wire is removed and the conductor is exposed,
The exposed portion of the conductor is further immersed in a solder bath to cover the surface of the conductor with solder, which is used. The main methods of this terminal stripping include mechanical stripping, thermal stripping, chemical stripping, solder stripping and the like. this house,
The method of removing the solder is to remove the coating and solder the conductor surface at the same time by immersing the end of the wire in a solder bath.The features are that the conductor is not scratched and the processing time is short. When removing the end of the type of insulated wire,
The method of peeling the solder is suitable. However, the method of stripping solder has a problem that the usable insulating film is limited, and therefore development of a resin capable of stripping solder is desired.

In general, as a thin wire type insulated wire, an insulated wire having an insulating film formed by using a polyurethane resin capable of peeling solder is used. However, an insulated wire using a polyurethane resin has a heat-resistant classification of A to E insulation. Therefore, it cannot be used for applications requiring heat resistance higher than this. Polyamide-imide resin is known as a resin that provides an insulated wire having heat resistance equal to or higher than F-type insulation and solder releasability, but it is used only for a limited purpose because of its high price.

Therefore, in order to solve this problem, polyesterimide resin has been developed as a resin having heat resistance and solder releasability higher than those of type F insulation and providing an insulated wire at a relatively low cost. These polyesterimide resins are those in which an imide group is introduced into polyester, and were synthesized by polycondensation of a polyhydric alcohol and a polycarboxylic acid having an imide group in the molecule.

[0006]

However, although the insulated wires using these conventional polyesterimide resins have heat resistance and solder releasability higher than those of type F insulation, in order to completely remove the insulating coating, Immersion conditions of about 10 seconds at 0 ° C. are required, so there is a limit to the improvement of the terminal processing speed. For this reason, there has been a demand for an insulated wire that can be subjected to terminal treatment at a lower temperature and a shorter time.

Most of the divalent carboxylic acids containing an imide group in the molecule, which are commonly used as raw materials for these polyesterimide resins, are cresol and phenol, which are commonly used in the synthesis of insulating coatings for electric wires. It is hardly soluble in solvents such as. Therefore, there are problems that the resin synthesis becomes a heterogeneous reaction, that a large force is required for stirring, or that the addition amount of this divalent carboxylic acid cannot be increased, and the workability during synthesis is poor. Also had.

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, have a high heat-softening temperature capable of having a heat resistance of F type or more, and have a solder peeling property at a low temperature in a short time. The present invention has been accomplished by discovering a specific polyester imide resin which can provide an insulated electric wire having the above properties and is excellent in workability during synthesis, and a method for producing the same.

[0009]

The gist of the polyesterimide resin according to the present invention is represented by the general formula (1):

[Chemical 3] (In the formula, R ₁ is a divalent organic group, and R ₂ is ₂ having 2 to 6 carbon atoms.
A valent aliphatic group is shown. ) A dihydric alcohol containing an imide group represented by), a polyhydric alcohol, and / or a polyvalent carboxylic acid or a derivative thereof as a constituent component.

In such polyesterimide resin,
R ₁ in the general formula (1) is

[Chemical 4] One or more selected from the group shown in.

Next, the gist of the method for producing a polyesterimide resin according to the present invention is that the above-mentioned general formula (1) is used.
The polyhydric alcohol and either or both of the polyhydric carboxylic acid and its derivative are added to the solution of the dihydric alcohol containing an imide group represented by, and the reaction is carried out in an organic solvent to carry out polyesterification. It is in.

The gist of another method for producing a polyesterimide resin according to the present invention is that it is a dihydric alcohol precursor containing an imide group represented by the general formula (1). One or both of a polyhydric alcohol and a polyvalent carboxylic acid and its derivative are added to a solution of alcohol and reacted in an organic solvent to simultaneously perform imidization and polyesterification.

The polyesterimide resin according to the present invention has the general formula (2):

[Chemical 5] (In the formula, R ₁ represents a divalent organic group.) A tetracarboxylic acid represented by the following formula, or an anhydride thereof, or a lower alkyl ester thereof, and a mixture of two or more thereof, and a general formula ( _{3) HO-R 2 -NH 2} (3) ( wherein, R ₂ is an amino alcohol represented by.) that represents a divalent aliphatic group having 2 to 6 carbon atoms, with polyhydric alcohols, polyhydric It can also be obtained by reacting either or both of a carboxylic acid and its derivative in an organic solvent to perform imidization and polyesterification at the same time.

The polyesterimide resin according to the present invention can also be obtained by a method in which a dihydric alcohol containing the imide group is added to a solution of the polyester resin and the imide group is introduced into the polyester by transesterification. it can.

Further, the polyesterimide resin according to the present invention comprises a dihydric alcohol which is a precursor of the dihydric alcohol containing the imide group in a solution of the polyester resin,
Alternatively, it can also be obtained by a method of introducing an imide group into the polyester by adding the tetracarboxylic acid or the like and an amino alcohol and transesterifying at the same time as imidization.

[0016]

The polyesterimide resin of the present invention is obtained by reacting a dihydric alcohol containing an imide group, a polyhydric alcohol, and either one or both of a polycarboxylic acid or a derivative thereof in an organic solvent. Since the dihydric alcohol containing an imide group used in the present invention has excellent solubility in an organic solvent, the synthetic system of the resin becomes a homogeneous system, and the addition amount of the dihydric alcohol containing an imide group is It can be increased. Therefore, the content of the imide group of the obtained polyester imide resin can be increased, and further, a large force is not required for stirring at the time of synthesis, and mechanical properties, electrical properties, and chemical properties as well as workability at the time of synthesis are excellent. Further, it is possible to obtain an insulated electric wire having excellent heat resistance and good solder releasability. That is,
The polyesterimide resin of the present invention has excellent heat resistance of 300 ° C. or higher in heat resistance and solder releasability, which are conventionally considered to be contradictory properties, and is 10 seconds or less at 440 ° C. It is possible to provide an insulated electric wire that can be subjected to a solder peeling treatment under immersion conditions, and it is possible to provide a manufacturing method having excellent workability during synthesis.

[0017]

EXAMPLES Next, the polyesterimide resin of the present invention and the method for producing the same will be described in more detail with reference to the preferred embodiments of the present invention.

The polyesterimide resin of the present invention has the general formula (1)

[Chemical 6] (In the formula, R ₁ is a divalent organic group, and R ₂ is ₂ having 2 to 6 carbon atoms.
A valent aliphatic group is shown. ) A dihydric alcohol having an imide group represented by or a dihydric alcohol having an amic acid structure which is a precursor thereof, a polyhydric alcohol, and either or both of a polyhydric carboxylic acid and a derivative thereof (hereinafter,
It is called polycarboxylic acid. ) And are reacted in an organic solvent.

First, the raw materials for synthesizing the polyesterimide resin of the present invention will be explained. The dihydric alcohol containing an imide group represented by the general formula (1) used in the present invention is, for example, the general formula (2). ) 7

[Chemical 7] (In the formula, R ₁ represents a divalent organic group.) Any one kind or a mixture of two or more kinds of a tetracarboxylic acid represented by the following formula, an anhydride thereof, or a lower alkyl ester thereof (hereinafter referred to as tetracarboxylic acid). Etc.) and a general formula (3) HO—R ₂ —NH ₂ (3) (wherein R ₂ represents a divalent aliphatic group having 2 to 6 carbon atoms). Can be obtained by reacting with and by a conventionally known method, but is not particularly limited to this method.

The dihydric alcohol having an amic acid structure, which is a precursor of a dihydric alcohol containing an imide group represented by the general formula (1), can be prepared under the same reaction conditions (reaction temperature). , Reaction time, etc.).

Here, R ₁ in the general formula (2) is a divalent organic group, and it is possible to use all kinds of tetracarboxylic acids and the like.

[Chemical 8] One or more kinds of tetracarboxylic acid having an organic group selected from the group shown in 1 above are preferably used. Among them, R
Those in which ₁ is an ethylene group are particularly preferred.

Further, R ₂ in the general formula (3) is a divalent aliphatic group having 2 to 6 carbon atoms.

[Chemical 9] One or more kinds of amino alcohols having an organic group selected from the group shown in are preferably used. Among them, R ₂
Particularly preferably, is an ethylene group.

Next, as the polyhydric alcohol used in the present invention, it is preferable to use an aliphatic dihydric alcohol alone or to use an aliphatic dihydric alcohol and an aliphatic trihydric alcohol in combination.

As the aliphatic dihydric alcohol, for example,
Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, various butane-, pentane-, or hexanediol (eg 1,3- or 1,4- Butanediol,
1,5-pentanediol, 1, 6-hexanediol, hexylene glycol), 1,4-buten-2-diol, 2,2-dimethyl-1,3-diol, 2-ethyl-2-butyl - Propane-1,3-diol, 1,4-dimethylolcyclohexane, 1,4-butenediol, water-added bisphenols (for example, water-added bisphenol A or its homologues),
Cyclic glycols (eg 2,2,4,4-tetramethyl-1,3-
Cyclobutanediol, hydroxynon-di-β-hydroxyethyl ether, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, trimethylene glycol,), octylene glycol and the like, ethylene glycol, propylene glycol, and 1,6-hexanediol is preferable, and ethylene glycol is particularly preferable.

As the aliphatic trihydric alcohol, for example,
Glycerin, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane and the like can be mentioned, with glycerin being particularly preferred. In addition, polyhydric alcohols other than aliphatic ones such as trishydroxyethyl isocyanurate may be used.

As the polyvalent carboxylic acid used in the present invention, it is preferable to use a divalent carboxylic acid alone or to use a divalent carboxylic acid and a trivalent carboxylic acid in combination. Further, a derivative thereof may be used instead of or in combination with the polyvalent carboxylic acid.

Examples of the divalent carboxylic acid include isophthalic acid, terephthalic acid, various naphthalene dicarboxylic acids, diphenyl-2,2'-dicarboxylic acid, diphenyl-2,3'-.
Dicarboxylic acid, diphenyl-3,3'-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenylmethane-2,2'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylethane-4,4 ' -Dicarboxylic acid, diphenyl sulfone
-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, phthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, adipic acid, succinic acid, maleic acid , Sebacic acid, isosebacic acid, dimer acid, tetrachlorophthalic acid, 4,4′-dicarboxy-diphenylpropane and the like. Of these, terephthalic acid and isophthalic acid are particularly preferable.

As the divalent carboxylic acid, it is also possible to use a divalent carboxylic acid containing an imide group. The divalent carboxylic acid containing an imide group can be obtained by reacting a tricarboxylic acid anhydride with a diamine or a diisocyanate by a conventionally known method. Alternatively, it can be synthesized from tetracarboxylic dianhydride and aminocarboxylic acid. Of these, divalent carboxylic acids containing an imide group obtained from tricarboxylic acid anhydride and aromatic diamine or aromatic diisocyanate are particularly preferable.

As the tricarboxylic acid anhydride, trimellitic acid anhydride, various naphthalene tricarboxylic acid anhydrides, 3,4,4'-diphenyltricarboxylic acid anhydride, 3,
4,4'-diphenylmethanetricarboxylic anhydride, 3,4,4 '
-Diphenyl ether tricarboxylic acid anhydride, 3,4,4'-
Examples thereof include benzophenone tricarboxylic acid anhydride, and trimellitic acid anhydride is particularly preferable.

Further, as the aromatic diamine, for example,
4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone,
4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl, 3,3'-
Diaminodiphenyl sulfone, 3,3'-dimethyl-4,4'-
Bisphenyldiamine, 1,4-diaminonaphthalene, 1,5-
Examples thereof include diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine and the like.

As the aromatic diisocyanate,
Diisocyanates corresponding to the above aromatic diamines can be mentioned.

Examples of the trivalent carboxylic acid include trimellitic acid, hemimellitic acid, various naphthalenetricarboxylic acids, 3,4,4'-diphenyltricarboxylic acid, 3,4,4'-diphenylmethanetricarboxylic acid, 3,4, Examples thereof include 4'-diphenyl ether tricarboxylic acid and 3,4,4'-benzophenone tricarboxylic acid, with trimellitic acid being particularly preferred.

Examples of the derivatives of these polyvalent carboxylic acids include carboxylic acid esters, carboxylic acid halides, and carboxylic acid anhydrides. These substituents are
All of the carboxyl groups of the polycarboxylic acid may be substituted, or some of them may be substituted. Particularly preferred among these derivatives are carboxylic acid lower alkyl esters, particularly methyl ester or ethyl ester, and carboxylic acid halides and carboxylic acid anhydrides such as dimethyl terephthalate, dimethyl isophthalate and trimellitic anhydride. Is preferably used.

It is also possible to use, as a raw material for the polyesterimide resin, a polyhydric alcohol obtained by esterifying the carboxyl group of the polyhydric carboxylic acid with one hydroxyl group of the aliphatic dihydric alcohol. .

Examples of the solvent for synthesizing the polyesterimide resin of the present invention include solvents having a phenolic hydroxyl group, such as phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2 , 4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,
4-xylenol, 3,5-xylenol, o-n-propylphenol, 2,4,6-trimethylphenol, 2,3,5-trimethylphenol, 2,4,5-trimethylphenol, 4-ethyl-2- Mention may be made of methylphenol, 5-ethyl-2-methylphenol, and cresylic acid which is a mixture thereof. Further, polar solvents such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-dimethylsulfoxide, and N-methyl-2-pyrrolidone are also included.

Further, the above solvent is used as an aliphatic hydrocarbon, aromatic hydrocarbon, ethers, acetals, ketones,
It is also possible to use it after diluting it with a solvent such as ester.

Examples of the aliphatic hydrocarbons and aromatic hydrocarbons include n-heptane, n-octane, cyclohexane, decalin, dipentene, pinene, p-menthane,
Decane, dodecane, tetradecane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, p-cymene, tetralin, or a mixture thereof, petroleum naphtha, coal tar naphtha, solvent naphtha and the like can be mentioned.

Next, the method for producing the polyesterimide resin of the present invention will be described. First, in an organic solvent, the tetracarboxylic acid or the like and an amino alcohol are mixed at a molar ratio of 1: 2, and the reaction is performed at 150 to 200 ° C. for about 1 to 8 hours while removing water generated in the reaction process. And a solution of a dihydric alcohol containing an imide group represented by the general formula (1) is obtained. Next, this solution is cooled to room temperature, then the polyhydric alcohol and polycarboxylic acid are added to the solution, and the temperature is slowly raised to about 200 ° C.,
The polyesterimide resin of the present invention can be obtained by reacting at 200 ° C to 210 ° C for 3 hours to 10 hours for polyesterification. The ratio of using each raw material at this time is
Although not particularly limited, a dihydric alcohol containing an imide group (referred to as imide alcohol) may be used because of the heat resistance of the obtained polyester imide resin, solder peelability, and the like.
The lower limit is preferably 5 equivalent%, more preferably 10 equivalent%, and the upper limit is preferably 50 equivalent%, further preferably 40 equivalent%.
In addition, the total of all alcohols including imido alcohol,
It is preferable that the lower limit is 50 equivalent%, further 55 equivalent%, and the upper limit is 70 equivalent%, and further 60 equivalent% based on the ratio with the total polycarboxylic acid.

Imido alcohol has excellent solubility in the solvent used, and evenly dissolves in the solvent even at room temperature.
The amount of imide alcohol added can be increased to the above ratio. In addition, this synthesis is a homogeneous system, and compared with the conventional method in which a polyesterimide resin is synthesized from a divalent carboxylic acid containing an imide group and a polyhydric alcohol, a large force is not required for stirring, and the work during the synthesis is performed. The property is improved.

As another method for producing the polyesterimide resin of the present invention, the above-mentioned tetracarboxylic acid and the like and amino alcohol are mixed in the same manner as above, and 0-100
After stirring at 10 ° C for several minutes to several hours to obtain a dihydric alcohol which is a precursor of an imide group-containing alcohol, it is reacted with a polyhydric alcohol and a polycarboxylic acid in the same manner as above to give an imide. You may synthesize | combine by carrying out polyesterification simultaneously with conversion.

Furthermore, the tetracarboxylic acid or the like, amino alcohol, polyhydric alcohol, and polyhydric carboxylic acid are mixed in the same manner as above, and the temperature is slowly raised to about 200 ° C., and 200 ° C. to 210 ° C. You may use the method of reacting at 3 degreeC for 3 hours-10 hours, and making it imidize and polyester-form simultaneously.

Further, first, a polyester resin is obtained from a polyhydric alcohol and a polycarboxylic acid by a known method, and then the dihydric alcohol containing the imide group is added to the solution, and the imide is added to the polyester by transesterification. The polyesterimide resin of the present invention can also be obtained by introducing a group. Alternatively, in a solution of a polyester resin composed of a polyhydric alcohol and a polycarboxylic acid, a dihydric alcohol which is a precursor of the dihydric alcohol containing an imide group, or the tetracarboxylic acid and the like which are raw materials thereof and an amino acid. A method of introducing an imide group into the polyester by adding an alcohol and transesterifying at the same time as the imidization may be used.

In these methods, a catalyst or the like generally used for polyester synthesis may be added.

By the above method, the polyesterimide resin of the present invention can be obtained. The polyesterimide resin is diluted to a desired concentration with the solvent used for the synthesis or other appropriate solvent, and the copper wire is then subjected to the appropriate method. It is possible to obtain an insulated electric wire by forming an insulating film by coating and baking on a conductor such as. The obtained insulated wire has a heat resistant softening temperature of 30.
It has excellent heat resistance of 0 ℃ or more and 440 ℃
It is possible to remove the solder under immersion conditions of 10 seconds or less.
INDUSTRIAL APPLICABILITY The polyesterimide resin of the present invention can be suitably used as a resin that provides a thin wire type insulated electric wire, and is also excellent in workability during synthesis. Further, an additive or the like may be added to the polyesterimide resin of the present invention in order to improve workability in obtaining an insulated electric wire.

As additives, metal desiccants, titanic acid or zirconate compounds, stabilized polyisocyanates,
Examples thereof include phenol formaldehyde resins, epoxy resins, and silicone resins.

As the metal desiccant, zinc, calcium,
Or lead octoate or linoleate, for example,
Examples thereof include zinc octoate, calcium naphthenate, zinc naphthenate, lead naphthenate, lead linoleate, calcium linoleate, zinc resinate, and others, and manganese naphthenate, cobalt naphthenate, and the like.

Examples of the titanic acid compound include tetraalkyl titanates such as tetraisopropyl titanate, tetrabutyl titanate, tetrahexyl titanate, tetramethyl titanate, tetrapropyl titanate and tetraoctyl titanate. Also useful are tetraalkyltitanium chelates obtained by reacting tetraalkyltitanate with octyleneglycol, triethanolamine, 2,4-pentadiene, acetoacetic acid ester and the like. Further, tetraalkyl titanium acylate obtained by reacting tetraalkyl titanate with stearic acid is also useful.

Examples of zirconate compounds include tetraalkylzirconates, zirconium chelates, and zirconium acylates corresponding to the above titanic acid compounds.

As the stabilized polyisocyanate, for example, a cyclic trimer of 2,4-tolylene diisocyanate, 2,6-
Cyclic trimer of tolylene diisocyanate, dimer of diphenylmethane-4,4'-diisocyanate, reaction product of diphenylmethane-4,4'-diisocyanate and trimethylolpropane in a molar ratio of 3: 1, 2,4-tri Reaction product of diisocyanate and trimethylolpropane in a molar ratio of 3: 1, reaction product of 2,6-tolylenediisocyanate and trimethylolpropane in a molar ratio of 3: 1, 2,4-tolylenediisocyanate and trimethylolethane Molar ratio of 3 to 1
And a stabilized polyisocyanate obtained by blocking the reaction product of 2,6-tolylene diisocyanate and trimethylolethane in a molar ratio of 3: 1 with phenol or cresol. Also, diphenylmethane-
Also included are stabilized isocyanates in which 4,4'-diisocyanate is blocked with xylenol.

Examples of phenol formaldehyde resins include melamine formaldehyde resin, cresol formaldehyde resin, and xylene formaldehyde resin.

Although the examples of the polyesterimide resin and the method for producing the same according to the present invention have been described above, the present invention is not limited to these examples, and the present invention is within the scope of the present invention. Based on the knowledge of those skilled in
The present invention can be implemented with various improvements, changes and modifications.

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 2 equipped with a stirrer, a nitrogen gas introducing pipe, a thermometer and a cooling pipe
In a liter 4-neck flask, 500 g of cresol and 205 g of ethylene glycol bistrimellitic dianhydride.
(0.5 mol) was added and dispersed. In this dispersion,
61 g (1 mol) of monoethanolamine was gradually added dropwise, 100 ml of xylene was further added, and the mixture was heated to 180 ° C for 3 times.
After the temperature was raised over a period of time, the reaction was allowed to proceed for 3 hours at this temperature while removing the produced water to obtain a dihydric alcohol solution containing an imide group. This dihydric alcohol was uniformly dissolved in cresol. Next, after cooling the system to around room temperature, 62 g (1 mol) of ethylene glycol, 96 g (0.5 mol) of trimellitic anhydride, 49 g (0.25 mol) of dimethyl terephthalate and 2.3 g of tetrabutyl titanate as a catalyst were added. And stir 20
The temperature was raised to 0 ° C. over 6 hours, and the reaction was further performed at this temperature for 5 hours to obtain the polyesterimide resin of the present invention.

In order to show the characteristics of the polyesterimide resin, the obtained polyesterimide resin was cooled to 60 ° C., and then an appropriate amount of cresol and 2.5% of tetrabutyl titanate with respect to the nonvolatile content were added to give a nonvolatile content of 3%.
Dilute to 8%, viscosity 30 poise, in a horizontal baking oven,
Die squeeze 7 times, maximum temperature 500 ℃, φ0.40
It was baked on a copper wire of mm to obtain an insulated electric wire having a film thickness of 0.02 mm. The characteristics of this insulated wire are flexibility, adhesion, softening temperature (° C), breakdown voltage (kV), 440 ° C and 460 ° C.
Test for solder releasability (seconds) in JIS C
The test was carried out according to the test method for enamel copper wire and enamel aluminum wire of 3003-1084, and the results are shown in Table 1.

[0055]

[Table 1]

Example 2 The same amount of cresol, bistrimellitic acid ethylene glycol dianhydride, monoethanolamine, and xylene were added to the same apparatus as in Example 1 by the same method, and the mixture was stirred at room temperature for 1 hour, A solution of a dihydric alcohol having an amic acid structure, which is a precursor of a dihydric alcohol containing an imide group, was obtained. To this system, the same amounts of ethylene glycol, trimellitic anhydride, dimethyl terephthalate, and 2.3 g of tetrabutyl titanate as a catalyst were added to this system, and the reaction was carried out under the same conditions as in Example 1 to carry out the reaction of the present invention. A polyesterimide resin was obtained. In order to show the characteristics of the obtained polyester imide resin, in the same manner as in Example 1, the nonvolatile content was diluted to 40% and the viscosity was 30 poise to obtain an insulated electric wire, and its characteristics were investigated. The results are also shown in Table 1. It was

Example 3 By the same method as in Example 1, a dihydric alcohol containing an imide group was obtained. Next, after cooling this system to around room temperature, 124 g (2 mol) of ethylene glycol, 64 g (0.33 mol) of trimellitic anhydride, 49 g (0.25 mol) of dimethyl terephthalate, 4,4'-diaminodiphenylmethane and anhydrous Divalent carboxylic acid containing imide group obtained by reacting trimellitic acid at a molar ratio of 1: 1
3.7 g (0.25 mol) and 2.8 g of tetrabutyl titanate as a catalyst were added and reacted under the same conditions as in Example 1 to obtain a polyesterimide resin of the present invention.
Here, the divalent carboxylic acid containing an imide group was insoluble in cresol and thus formed a dispersion liquid, but dissolved as the reaction proceeded. In order to show the characteristics of the obtained polyesterimide resin, in the same manner as in Example 1 below, the non-volatile content was diluted to 38% and the viscosity was 20 poise to obtain an insulated electric wire, and its characteristics were investigated. The results are also shown in Table 1. It was

Example 4 By the same method as in Example 1, a dihydric alcohol containing an imide group was obtained. Next, after cooling this system to around room temperature, 47 g (0.75 mol) of ethylene glycol, 31 g (0.17 mol) of glycerin, and 9 parts of trimellitic anhydride
6 g (0.5 mol), dimethyl terephthalate 49 g
(0.25 mol) and 2.3 g of tetrabutyl titanate as a catalyst were added to obtain a polyesterimide resin of the present invention. In order to show the characteristics of the obtained polyester imide resin, in the same manner as in Example 1 below, the non-volatile content was diluted to 36% and the viscosity was 30 poise to obtain an insulated electric wire, and its characteristics were examined. The results are also shown in Table 1. It was

Comparative Example 1 3 equipped with a stirrer, nitrogen gas introducing pipe, thermometer and cooling pipe
In a 4-liter 4-liter flask, trimellitic anhydride 19
2 g (1 mol) and 600 g of cresol were added and dispersed. To this dispersion was added 99 g (0.5 mol) of 4,4'-diaminodiphenylmethane, and the mixture was reacted at 150 ° C for 3 hours to obtain a dispersion of a divalent carboxylic acid containing an imide group. This dicarboxylic acid was poorly soluble in cresol and turned into a mud at room temperature. Next, after cooling this system to 100 ° C. or lower, 582 g (3 mol) of dimethyl terephthalate and 342 g (1 mol of trimethylene acid triethylene glycol ester)
mol), 93 g (1.5 mol) of ethylene glycol, 186 g (2 mol) of glycerin and 120 g of xylene are added, and the temperature is raised to 200 ° C. over 6 hours while stirring,
Further, the reaction was carried out at this temperature for 5 hours to obtain a polyesterimide resin. At this time, the divalent carboxylic acid containing an imide group was dissolved as the reaction proceeded. In order to show the characteristics of the obtained polyesterimide resin, the following Example 1 was used.
In the same manner as above, the non-volatile content was diluted to 36% and the viscosity was 40 poise to obtain an insulated electric wire, and its characteristics were examined. The results are also shown in Table 1.

Comparative Example 2 In order to show the characteristics of the polyester imide resin, which has been used in the related art, to provide an insulated electric wire of a heat-resistant category F which is capable of peeling solder, an insulating paint KS-103J-36M (manufactured by Dainichiseika Kogyo Co., Ltd.) was used. An insulated electric wire was obtained by using the same method as in Example 1, the characteristics thereof were investigated, and the results are also shown in Table 1.

From the above results, the insulated wire obtained from the polyesterimide resin according to the present invention has the same characteristics as conventional products in flexibility, adhesion and heat resistance, and has a solder peeling property of 440. Solder releasability at ℃ is 4 ~
7 seconds, which is 10 seconds or more in the insulated wire and the conventional product obtained from the resin obtained by using the imide group-containing polyvalent carboxylic acid without using the imide group-containing dihydric alcohol. It can be seen that the time required for the solder peeling process has been considerably shortened.

[0062]

The polyesterimide resin of the present invention comprises a dihydric alcohol containing an imide group, a precursor thereof or a tetracarboxylic acid or the like which is a raw material thereof, an amino alcohol, a polyhydric alcohol and a polyhydric carboxylic acid. It is a constituent component, and has an excellent heat resistance of 300 ° C. or higher in heat resistant softening temperature, and an insulated wire which can be subjected to solder peeling treatment at 440 ° C. for 10 seconds or less can be provided. That is, the insulated wire obtained from the polyesterimide resin of the present invention has characteristics equivalent to those of the conventional product, and the time required for terminal treatment of the insulated wire can be considerably shortened as compared with the conventional product. The imide resin can be a resin suitable for obtaining an insulated electric wire having heat resistance of F or more. Further, by using a dihydric alcohol containing an imide group or a precursor thereof or an amino alcohol which is a raw material thereof and a tetracarboxylic acid as a raw material, a homogeneous reaction can be achieved, and a force required for stirring may be small, It is possible to provide a manufacturing method having excellent workability.

Claims (4)

[Claims] 1. A compound represented by the general formula (1): (In the formula, R ₁ is a divalent organic group, and R ₂ is ₂ having 2 to 6 carbon atoms.
A valent aliphatic group is shown. And a dihydric alcohol containing an imide group represented by), a polyhydric alcohol, and / or a polyhydric carboxylic acid or a derivative thereof as a constituent component. 2. R ₁ in the general formula (1) is represented by the following formula: The polyesterimide resin according to claim 1, wherein the polyesterimide resin is one or more selected from the group shown in. 3. A solution of a dihydric alcohol containing an imide group represented by the general formula (1), a polyhydric alcohol and one or both of a polyhydric carboxylic acid and a derivative thereof are added to obtain an organic compound. A method for producing a polyesterimide resin, which comprises reacting in a solvent for polyesterification. 4. A polyhydric alcohol, a polyhydric carboxylic acid or a derivative thereof in a solution of a dihydric alcohol which is a precursor of a dihydric alcohol containing an imide group represented by the general formula (1). A method for producing a polyesterimide resin, characterized in that one or both of them is added and reacted in an organic solvent to perform imidization and polyesterification at the same time.