JPH0258567A - Heat-resistant resin composition, enameled wire and heat-resistant paint - Google Patents

Abstract

PURPOSE:To obtain a heat-resistant composition giving an enameled wire having excellent adhesivity to copper, mechanical properties, heat-resistance, refrigerant resistance and electrical insulation property by adding a specific amount of a heterocyclic mercaptan to a polyester imide resin. CONSTITUTION:The objective heat-resistant resin composition is produced by compounding (A) a polyester imide resin containing ester bond and imide bond in the molecular chain with (B) 0.01-1wt.% (based on the component A) of a heterocyclic mercaptan of formula I [A forms 5- or 6-membered heterocyclic group together with the group X and the group of formula II and is bonded through single bond or double bond; X is O, S, C or NR (R is H or 1-4C alkyl) (e.g., 2-mercaptoimidazoline). The composition is diluted with a solvent (e.g., phenol or cresol), optionally added with an additive, applied to a conductor and baked to obtain an enameled wire.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a heat-resistant resin composition, and more particularly to adhesion to steel, 8! The present invention relates to a heat-resistant resin composition capable of providing an enameled wire with excellent mechanical properties, heat resistance, refrigerant resistance, and electrical insulation properties, an enameled wire using the same, and a heat-resistant paint using the same.

(Prior Art) Various resins have been known as coating materials for enameled wires, but in recent years electrical equipment has become smaller and lighter.

As performance increases, there is a demand for further improvements in adhesion to conductor steel, heat resistance, abrasion resistance, thermal shock resistance, refrigerant resistance, etc.

The coating-forming resins for enameled wires currently in use are terephthalic acid polyester resins and polyesterimide resins having ester bonds and imide bonds in their molecular chains. Polyester terephthalate resin has poor abrasion resistance, thermal shock resistance, and heat resistance, and polyesterimide resin is superior to polyester terephthalate resin in terms of cholera properties, but its adhesion to copper, which is a conductor, is poor. It cannot be said that this is sufficient.

(Problems to be Solved by the Invention) The purpose of the present invention is to achieve close adhesion to copper, which is a conductor, without impairing the mechanical properties, heat resistance +'tt refrigerant properties, and electrical insulation properties of polyesterimide resin. An object of the present invention is to provide a heat-resistant resin composition that provides an enameled wire with good properties.

(Means for Solving the Problems) As a result of intensive research, the present inventors added 0.01 to 1 weight of a heterocyclic mercaptan represented by the following general formula (11) to a polyesterimide resin based on the resin. The present inventors have discovered that a heat-resistant resin compound containing the above-mentioned heat-resistant resin in a proportion of 1.5% can achieve the above object, and have thus arrived at the present invention.

The present invention applies a polyesterimide resin having 9 ester bonds and imide bonds in its molecular chains to a polyesterimide resin of the general formula (where A, together with X and the group -N=C-X-, forms a heterocycle consisting of 5 or 6 atoms. I'm here.

bonded by a single bond or a double bond, or 1
consisting of two or three carbon atoms, two nitrogen atoms, or a nitrogen atom bonded to one carbon atom forming part of an aromatic ring, containing an oxygen atom, a sulfur atom, a carbon The heterocyclic mercaptan represented by an atom or a group ~NR (R means a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) is added to the polyesterimide resin in a ratio of 0.01 to 0.01 to NR (R means a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) The present invention relates to a heat-resistant resin composition containing lit%.

The polyesterimide resin used in the present invention is a well-known resin.1 For example, the production method described in Japanese Patent Publication No. 51-40113 is to prepare an acid component, an imidic acid-forming component, or an imidic acid and an alcohol component in an organic solvent. It can be obtained by reacting in the presence of

The acid component is 1, for example, terephthalic acid, 1 isophthalic acid,
Its derivatives such as dimethyl terephthalate and dimethyl isophthalate are used for larel.

The imide acid forming component consists of a tribasic acid anhydride having two adjacent carboxyl groups and a diamine.

These peripheral components react as shown in the following equation to form imidic acid. In place of the imide acid-forming component, an imide acid reacted as described below can also be used.

OO (imidic acid) (wherein the formula means an organic group, R2 means an aromatic group) As is clear from the above formula, about 2 moles of tribasic acid anhydride per mole of diamine, preferably exactly 2 moles. is used.

Examples of tribasic acid anhydrides include trimellitic anhydride,
Butanetricarboxylic anhydride and the like are used, with trimellitic anhydride being preferred.

Examples of the diamine include ethylenediamine.

4.4'-methylene dianiline, 4.4'-diamino-
&3'-dimethyldiphenylmethane, 4.4'-diaminodiphenylmethane, 4.4'-diaminodiphenyl ether, 4.4'-diaminodiphenylsulfone, 3°3'-SchiffS nodiphenylsulfone, paraphenylenediamine, metaphenylenediamine, 2.4-tolylene diamine, 2.6-)lylene diamine, metaxylene diamine, etc. are used, and 4.4'-diaminodiphenyl methane and 4.4'-diaminodiphenyl ether are preferred.

As the alcohol component, an alcohol having a valence of 1 or more is usually used. What about the dihydric alcohol component?

For example, ethylene glycol, diethylene glycol, fluoropylene glycol, dipropylene glycol, neopentyl glycol + 1 + 3-phthanediol, 1
．． 4-butanediol, 1,6-hexanediol, etc. are used, and examples of trivalent or higher alcohols include glycerin, trimethylolpropane, tris-(2-hydroquinethyl)isocy7nuL'-), and pentaerythritol. etc. are used.

From the viewpoint of heat resistance and abrasion resistance, it is preferable to use trihydric or higher alcohols for at least 30 fk of the total alcohol components. In addition, glycerin is good for crazing resistance, and tris(2) is good for heat resistance and refrigerant resistance.
-hydroxyethyl) isocyanurate is particularly preferred.

The reaction amount ratio of the acid component, the imidic acid-forming component, and the alcohol component is preferably in the range of 20 to 100 inches, more preferably 30 to 70 inches in alcohol excess.

Examples of organic solvents include N-methylpyrrolidone, dimethylacetamide dimethylformamide, dimethylsulfoxide, and N-methylcaprolactam.

Xylene, phenol, cresol, xylenol, etc. may be used alone or in combination, and phenolic solvents such as e, if, phenol, cresol, xylenol, etc. are preferred.

When manufacturing polyesterimide resin.

The reaction conditions are not particularly limited as long as they are conditions that substantially allow reactions such as imidization, esterification, and transesterification. Usually in the presence of trace amounts of esterification catalysts such as, for example, tetrabutyl titanate, lead acetate, dibutyltin dilaurate.

It is carried out at 120-200°C for 3-10 hours.

The polyesterimide resin obtained in this way has
The heterocyclic mercaptan represented by the general formula [11] is added to the polyesterimide resin in an amount of 0.01 to i
The adhesion to copper is significantly improved by adding and containing it in a proportion of t.

Examples of the heterocyclic mercaptan represented by the general formula (11) include 2-mercaptoimidacillin, 2-mercaptothiazoline, 2-mercapto-1-methylimitazole, 5-amino-1,3,4-thiadiazole- 2-thiol, 2-mercaptobenzoxazole,
2-mercaptobenzimidazole, 2-mercaptobenzthiazole.

I H-1,44-triazole-3-thiol, 2-
Mercaptopyridine, 2-mercaptoquinoline.

1.2-naphthyl(2-mercapto)oxazole and the like are used.

The polyesterimide resin containing heterocyclic mercaptan thus obtained is diluted with a suitable solvent in order to facilitate the production of enameled wire.

In this case, the solvent may be 1, for example, phenol, cre/ol,
Phenolic solvents such as xylenol are mainly used, and in addition to these solvents, for example, toluene, xylene,
It is also possible to use a mixture of diluting solvents such as solvent naphtha, petroleum + futha, and calpitols.

The heat-resistant resin assembly of the present invention may also contain a titanium compound or a zinc compound as an additive in order to improve curability and flow characteristics during curing.

As the titanium compound, for example, tetraisoglobil titanate, tetrabutyl titanate, tetrahexyl titanate, etc. are used, and as the zinc compound, for example, zinc naphthenate, zinc octenoate, etc. are used.

When using the heat-resistant resin composition of the present invention [7].

Add the above additive to the polyesterimide resin at 0.00%.
It is added at a weight of 0.01 to 1 to 1,000 ml, and is coated and baked directly onto a 1 ML gas conductor or together with other insulating coatings to form an enamelled wire. For the tM manufacturing of enamelled wires, commonly used conditions are employed, and there are no particular limitations.

The heat-resistant resin composition can also be used as a heat-resistant paint applied to copper or other metals.

(Example) The present invention will be explained below with reference to examples. In addition.

In the examples, ``chi'' means weight.

Production example 1 51 with thermometer, nitrogen inlet tube, 1 fractionating tube and stirrer! In a four-bottle flask, add cresol 11169°4.4'-diaminodiphenylmethane 36SL49 (3,66 equivalents).
, 703.2 g (7,32 equivalents) of trimellitic anhydride,
Dimethyl terephthalate 532.89 (per 5.4 g)
, ethylene glycol 106.59 (3,45 equivalents),
Tris-(2-hydroxyethyl)in cyanurate 8
96.19 (10.2 g equivalent) and tetrabutyl titanate) 2.49 were blended.

Gradually warm up to 200°C without removing the distillate.

After reacting at 200°C for 5 hours, cresol/
Blend xylene = 8/2 (weight ratio) solvent to reduce resin content to 3
Specializes in 6-chi polyesterimide resin solutions.

Production example 2! + Cresol 5489.4.4'-diaminodiphenylmethane 22
8 g (2,30 equivalents), trimellitic anhydride 4429 (
4,60 equivalents), dimethyl terephthalate 3359 (3
, 45 #), ethylene glycol 1039 (3,32
equivalent), tris-(2-hydroxyethyl)in cyanurate 5379 (per 6,17) and tetrabutyl titanate 0.89, and gradually heated to 200'C while removing distillate, and heated to 200°C. After reacting for 5 hours, a solvent of cresol/xylene=8/2 (weight ratio) was blended thereto to obtain a polyesterimide resin solution with a resin content of 36.

Example 1 1 with thermometer, 9 element inlet tube and stirrer! ! Pour the polyesterimide resin solution 10009 obtained in Production Example 1 into a three-neck flask and add 0.369 (0.1 to the resin).
%) of 2-mercaptoimidacillin and 90%
After heating and melting at ℃ for 1 hour.

Furthermore, 3.6 g of tetrabutyl titanate and 129 g of zinc naphthenate were added to obtain a heat-resistant resin composition.

Example 2 Implementation gAJ In a flask similar to 1,! 8! Pour the polyesterimide resin solution 10009 obtained in Preparation Example 1, and add 0.299 (0.08 h based on the resin) of 5-amino-1,3,4-thiadiazole-2-thiol. After heating and dissolving at 90° C. for 1 hour, the same amounts of tetrabutyl titanate and zinc naphthenate as in Example 1 were further added to obtain a heat-resistant resin composition.

Example 3 The polyesterimide resin solution 10009 obtained in Production Example 2 was placed in a flask similar to that in Example 1, and the solution was 0.4
After adding 3 g (0.12% based on the resin) C7) 2=mercapto-1-methylimidazole and dissolving it by heating at 90°C for 1 hour, the same amount of tetrabutyl titanate and naphthenic acid as in Example 1 was added. Zinc was added to obtain a heat-resistant resin composition.

Example 4 The polyesterimide resin solution 10009 obtained in Production Example 2 was placed in a flask similar to that in Example 1, and the solution was 0.3
After adding 2-mercaptobenzthiazole of 69 (0.1 h based on the resin) and dissolving it by heating at 90°C for 1 hour,
Furthermore, the same amounts of tetrabutyl titanate and zinc naphthenate as in Example 1 were added to obtain a heat-resistant resin composition.

Comparative Example 1 The polyesterimide resin solution 10009 obtained in Production Example 1 was placed in a flask similar to Example 1, and the same amounts of tetrabutyl titanate and zinc naphthenate as in Example 1 were added to make it heat resistant. A synthetic resin composition was obtained.

Comparative Example 2 The polyesterimide resin solution 10009 obtained in Production Example 2 was placed in a flask similar to Example 1, and the same amount of tetrabutyl titanate and zinc naphthenate as in Example 1 was added to make it heat resistant. A synthetic resin composition was obtained.

Test Examples Examples 1 to 4 Using the heat-resistant resin compositions obtained in Comparative Examples 1 to 2, steel wires having a diameter of 1 mm were fried in a conventional manner to obtain enamelled wires.

Table 1 shows the results of characteristic evaluation of the obtained enameled wire. The characteristics of the enameled wire are polyesterimide copper wire JIS
Measured according to C3214.

From the results in Table 1, the heat-resistant resin compositions of the present invention (Examples 1 to 4) have 1 mechanical properties, It is shown that the thermal properties, electrical insulation properties, and resistance to heat resistance are the same, but the adhesion to copper is superior.

(Effect of the invention) By using the heat-resistant resin composition of the present invention.

Adhesion to copper 1 Enameled wire with excellent mechanical properties, heat resistance, refrigerant resistance, and electrical insulation properties can be provided.

, Pura Rei・

Claims (3)

[Claims] 1. Polyester resins that have ester bonds and imide bonds in their molecular chains have general formulas (I) ▲mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, A stands for X and the group -N=C-X- 2 or 3 carbon atoms forming a heterocyclic ring of 5 or 6 atoms, connected by single or double bonds, or forming part of an aromatic ring, 2 or a nitrogen atom bonded to one carbon atom; 0.0% of the heterocyclic mercaptan represented by )) relative to the polyesterimide resin.
A heat-resistant resin composition containing 0.01 to 1% by weight. 2. An enameled wire obtained by coating and baking the heat-resistant resin composition according to claim 1 on an electrical conductor. 3. A heat-resistant paint using the heat-resistant resin composition according to claim 1.