JPS62197449A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent flexibility and adhesion and suitable for use in the production of heat-resistant insulated wires, containing a specified polyester resin and a phenolic resin. CONSTITUTION:An acid component (A) consisting of an imide-acid of formula I (wherein R is a bivalent org. acid) obtd. from one mol of a diamine (e.g., 4,4'-diaminodiphenylmethane) and about two mol of trimellitic anhydride and terephthalic acid (lower alkyl ester) is reacted with an alcohol component (b) [e.g., tris(2-hydroxyethyl)isocyanurate] in an excess amount of 10 to 100% by equivalent based on that of the component (a) in the presence of an esterification catalyst (e.g., tetrabutyl titanate) in a phenol solvent (e.g., cresol) at 170 to 250 deg.C to obtain a polyester resin (A) having imide linkages in the molecular chain. 20-50wt% mixture of the component A and 0.1-5.0wt% (based on the amount of the component A) phenolic resin of formula II (wherein n is a number of 1 to 3) is dissolved in 80-50wt% solvent.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a heat-resistant resin composition, and particularly a heat-resistant resin composition that has improved flexibility, adhesion, etc. and is suitable for use in heat-resistant insulated wires. Regarding.

(Prior Art) Conventionally, polyamide-imide wires, polyimide wires, polyester-imide wires, and polyamide-imide ester wires are known as heat-resistant electric wires for magnet wires. Among these, from the point of view of the balance between properties and price, resins modified from tris(2-hydroxyethyl) isocyanurate polyesters having imide or amide-imide bonds, such as polyester imide wires and polyamide-imide ester wires, are baked. Heat-resistant wires are used in relatively large quantities.

However, these polyester-imide wires and polyamide-imide ester wires have the drawback of poor flexibility and adhesion, which poses a particular problem when used as heat-resistant wires with a large wire diameter.

(Problems to be Solved by the Invention) The purpose of the present invention is to eliminate the drawbacks of the prior art,
It is an object of the present invention to provide a heat-resistant resin composition that provides an insulated wire with excellent flexibility and adhesion.

(Means for Solving the Problems) In order to achieve this objective, the present inventors have conducted various studies on improving the flexibility and adhesion of polyesterimide wires, and as a result, the present inventors have developed a polyesterimide wire to which a specific phenolic resin has been added. The present invention was achieved by discovering that baked polyesterimide wire has excellent flexibility and adhesion.

The present invention provides a polyester resin having an imide bond in its molecular chain, and a polyester resin having a Theo of 1 to 5.
0m1%17), -jL&a phenolic resin represented by formula (I) (in the formula, n is an integer of 1 to 3).

The imidic acid used as the imide component of the polyester resin having an imide bond in the molecular chain (hereinafter abbreviated as polyesterimide resin) used in the present invention has the general formula (II) (wherein R is divalent (meaning an organic acid).

The imide acid of general formula (II) can be obtained, for example, by reacting about 2 moles of trimellitic anhydride with 1 mole of diamine (Japanese Patent Publication No. 40113/1983).

The diamine used at this time is, for example, 4°4'-
Diaminodiphenylmethane, m-phenylenediamine,
p-phenylenediamine, ■, 4-diaminonaphthalene, 4,4'-diaminodiphenyl ether, 4,4'-
Examples include dimethyl hebutamethylene diamine, hexamethylene diamine, 4,4'-dicyclohexylmethane diamine, diaminodiphenylsulfone, and the like. In the present invention, instead of these diamines, diisocyanates corresponding to the diamines mentioned above may be used, and imidic acid obtained by reacting about 2 moles of trimellitic anhydride with 1 mole of this diisocyanate may be used. There are no particular restrictions on the method for producing imidic acid.

The amount of imide acid used is 20% of the total acid component from the viewpoint of heat resistance.
~60 equivalent% is preferred.

As the acid component of the polyesterimide resin, in addition to the above-mentioned imide acid, terephthalic acid or a lower alkyl ester thereof such as dimethyl terephthalate, monomethyl terephthalate, diethyl terephthalate, etc. are used. Optionally, as a part of the acid component, it is also possible to use, for example, isophthalic acid, adipic acid, phthalic acid, sebacic acid, etc., which are commonly used in polyester fibers for enameled wires.

As the alcohol component of the polyesterimide resin, for example, tris (2-hydroxyethyl) isocyanurate is used, and some of the alcohol components include ethylene glycol, butadiene diol, hexane diol, etc., which are commonly used in polyester festivals for enameled wires. , glycerin, trimethylolpropane, pentaerythritol, etc. can also be used.

The ratio of the acid component to the alcohol component of the polyesterimide resin is preferably 10 to 100% alcohol excess in equivalent terms.

Synthesis of polyesterimide resin involves combining an acid component and an alcohol component in the presence of an esterification catalyst at a temperature of 170 to 250
The reaction is carried out by heating at a temperature of °C. As the esterification catalyst, tetraalkyl titanates such as tetrabutyl titanate, lead acetate, dibutyltin laurate, zinc octenoate, zinc naphthenate, etc. are used.

Imidic acid may be synthesized in advance, or components that will become imidic acid such as diamine and trimellitic anhydride may be mixed and heated at the same time as other acid components and alcohol components to simultaneously imidize and esterify. You may do so. Furthermore, since the polyesterimide resin has a high viscosity during synthesis, it is preferable to synthesize the polyesterimide resin in the presence of a phenolic solvent such as phenol, cresol, or xylenol.

General formula used in the heat-resistant resin composition of the present invention (in the formula n
is an integer of 1 to 3), for example, methylone resin (trade name, manufactured by General Electric Company, USA) is preferred.

The blending amount of the phenolic resin of formula (I) is 0.1 to 5.0% by weight based on the polyesterimide resin from the viewpoint of mechanical properties such as flexibility and adhesion of the obtained insulated wire.
, preferably 0.5 to 2.5% by weight. If the blending amount is less than 0.1% by weight, flexibility will not be improved, and if it exceeds 5.0% by weight, wear resistance will decrease.

The heat-resistant resin composition of the present invention is produced by dissolving the polyesterimide resin and the phenol resin in a solvent and adjusting the viscosity to an appropriate value.

The solvent used at this time is not particularly limited as long as it dissolves the polyesterimide resin and the phenol resin represented by the general formula (I), but examples include cresol, xylene, Nl5SEKI HISOL-100 (
Nippon Petrochemical Co., Ltd., aromatic hydrocarbon), methyl ethyl ketone, dimethyl succinate, methyl calpitol, etc. are used.

The heat-resistant resin composition of the present invention contains the polyesterimide resin and the phenol resin in a total amount of 20 to 50%.
It is preferable that the solvent be contained in an amount of 80 to 50% by weight.

The heat-resistant resin composition of the present invention may optionally contain, for example, a titanium compound, a polyisocyanate generator, an organic acid metal salt, a polyamide resin, a polyamideimide ester resin, a polyhydantoin resin, an alkoxy-modified amino resin, a polysulfone resin, etc. 0.1-25 per minute
It may be added and contained in a proportion of % by weight.

The heat-resistant resin composition of the present invention is made into an enameled wire by a conventional method by applying and baking it directly onto an electric conductor or together with another insulating film.

(Effects of the Invention) With the heat-resistant resin composition of the present invention, an insulated wire with significantly improved flexibility, adhesion, etc. can be obtained.

The heat-resistant resin composition of the present invention is widely used for heat-resistant insulated wires and the like.

(Example) Comparative Example 1 (Synthesis of polyesterimide resin composition 4.
4'-diaminodiphenylmethane 74 g (0.75 equivalents), trimellitic anhydride 144 g (I°5 equivalents), dimethyl terephthalate 194 g (2.0 equivalents 1 t), ethylene glycol 34 g (I, 1 equivalent), tris (2 -hydroxyethyl)isocyanurate 377 g (4,3 equivalents)
, 342 g of cresol and 0 tetrabutyl titanate
．． 8 g was placed in a four-bottle flask equipped with a thermometer, a stirrer, and a fractionating tube, and the temperature was raised to 170° C. in a nitrogen stream to react for 60 minutes. This solution was then heated to 210°C for 2
The gelation time at 5θ°C (by JISC-2104 hot plate gel time measurement method, the same applies hereinafter) was measured, and the reaction was allowed to occur until the gelation time reached 80 seconds. The amount of resin used for measuring gelation time was 0.3 g, calculated as 100% resin content.

After the reaction is completed, it is cooled and then cresol/xylene-7
/3 (weight ratio) solution until the Gardner seconds were 50 seconds.

Furthermore, 15 g of tetrabutyl titanate and 20 g of zinc naphthenate were added to this resin solution to obtain a polyesterimide resin composition. The nonvolatile content of this resin composition is 4
0% by weight (200°C - 2 hours), and the viscosity is 50% by weight.
poise (30°C).

Example 1 Polyesterimide resin composition 10 obtained in Comparative Example 1
20 g of Methylone Resin 75108 (manufactured by General Electric Company) was added to 00 g to obtain a heat-resistant resin composition of the present invention.

Example 2 4.4'-diaminodiphenylmethane 59.4 g (0
, 6 equivalents), 115.2 g of trimellitic anhydride (I, 2
135.8 g (I, 4 eq), dimethyl terephthalate, 20.3 g (0,45 eq) 1,4-butanediol, 221.9 g (2,55 eq) tris(2-hydroxyethyl)isocyanurate equivalent), resol 152.8g, lead acetate 0.6g and toluene 40.0
Put 4 pieces of g into a flask and heat at 170°C in a nitrogen stream.
The reaction was carried out for 60 minutes while dehydrating the toluene by refluxing it. Next, this solution was heated to 220°C and
The reaction was continued until the gelation time at 50°C reached 2 minutes. After the reaction was completed, the temperature was lowered, and then 380 g of cresol and 130 g of xylene were added to the reaction solution.

Further, this resin solution was kept at 110°C, 15 g of tetrabutyl titanate and 12 g of zinc naphthenate were added thereto, and then 8 g of methylone resin 75108 (manufactured by General Electric Company) was added to prepare the heat-resistant resin composition of the present invention. Obtained.

The resin compositions obtained in Test Example Comparative Example 1, Examples 1 and 2,
Each copper wire with a diameter of 1 m was baked with a type 0 finish to make an insulated wire, and the characteristics of each insulated wire were measured. The result is the first
Shown in the table.

Margin below Chapter 1 Table ID baking furnace: mold furnace, furnace length 4m Baking temperature (℃) Two person rotor/center/outlet =260/360/400 The test was vague in accordance with JI SC3003.

Table 1 shows that the heat-resistant resin composition of the present invention provides an insulated wire with excellent flexibility and adhesion as compared to the conventional resin composition (Comparative Example 1). Furthermore, Table 1 shows that the heat-resistant resin composition of the present invention has excellent resistance to elongation and impact during coil winding, and resistance to thermal stress during heat cycling.

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Claims (1)

[Scope of Claims] 1. A polyester resin having an imide bond in the molecular chain, and a compound having the general formula (I) OCH_2-CH=CH_2 ▲ in an amount of 0.1 to 5.0% by weight based on the polyester resin. There are mathematical formulas, chemical formulas, tables, etc.▼(I) A heat-resistant resin composition containing a phenolic resin represented by (in the formula, n represents an integer from 1 to 3).