JPH01182364A - Heat resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain the title coating composition capable of giving enamel wires of excellent heat and refrigerant resistances, etc., by incorporating a specific polyamide-imide ester resin with compounds including specific heterocyclic mercaptan and aminoimidazole. CONSTITUTION:The objective composition can be obtained by incorporating (A) a polyamide-imide ester resin produced by reaction between an amide-imide oligomer having in the molecule both amide and imide groups prepared by reaction between (i) an isocyate compound, (ii) a tribasic acid anhydride, (iii) a dibasic acid and (iv) a lactam followed by further reaction of the component (ii) and (v) a polycarboxylic acid and (vi) a polyhydric alcohol with (B) compounds including a heterocyclic mercaptan of formula I (Y is one nitrogen atom bonded through single bond, double bond, etc., forming heterocycle having 5 or 6 atoms in combination with X and a fraction of formula II; X is O, S, C or NR) and aminoimidazole.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a heat-resistant resin composition, and more specifically, to an enameled wire having excellent mechanical properties, heat resistance, refrigerant resistance, and electrical insulation properties. The present invention relates to a heat-resistant resin composition.

(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 improves, the heat resistance and abrasion resistance of enamelled wire.

There is a demand for further improvement in thermal shock resistance, refrigerant resistance, etc.

The resins currently most used are terephthalic acid polyester resins and polyesterimide resins. Terephthalic acid-based polyester resins are inferior in abrasion resistance, thermal shock resistance, and heat resistance, and polyesterimide-based resins are superior to polyester-based resins in these properties, but they are not sufficient in terms of refrigerant resistance and craze resistance. It is impossible. Furthermore, polyamide-imide resins and polyimide resins are also known, but these resins are expensive and difficult to handle, so they lack versatility and are only used for some special purposes. Only. Furthermore, resin compositions whose main component is a polyamide-imide ester resin in which a dibasic acid having an amide group and an imide group is used as the acid component of the polyester are also known (for example, Japanese Patent Publication No. 45-13597, Japanese Patent Publication No. 45-18316).
issue.

Special Publication No. 46-5089, Special Publication No. 47-26116,
Special Publication No. 51-7689 and Special Publication No. 51-15859
Publications, etc.) is 1! Although films formed from these resins exhibit a certain degree of performance, they are insufficient in mechanical properties, heat resistance, and especially refrigerant resistance.

(Problem that the invention attempts to solve) The object of the present invention is to eliminate the drawbacks of the prior art.

The object of the present invention is to provide a heat-resistant resin that provides an enameled wire with excellent mechanical properties, heat resistance, refrigerant resistance, electrical insulation properties, and adhesion.

(Means for solving the problem) As a result of intensive research, the present inventors have discovered that a polyamideimide ester resin having a specific structure obtained by introducing a specific amideimide oligomer into the molecular chain and a specific The present invention was achieved by discovering that the above object can be achieved by combining compounds.

The present invention provides an isocyanate compound, a tribasic acid anhydride,
After reacting dibasic acids and lactams.

Furthermore, polyamideimide ester resins obtained by reacting a polycarboxylic acid and a polyhydric alcohol with an amide-imide oligomer having an amide bond and an imide bond in the molecular chain obtained by reacting a tribasic acid anhydride, and general Formula (5) (However, in the formula, 5 or 6 atoms together with yFix and the N=C-X moiety also form a heterocycle.

Y is two or three carbon atoms, or two nitrogen atoms, connected by a single or double bond or forming part of an aromatic ring.

Or one nitrogen atom bonded to one carbon atom [however, the hydrogen bonded to this carbon atom may be substituted], where X is oxygen or sulfur.

selected from the group consisting of heterocyclic mercaptans of carbon or NR (wherein R is hydrogen or an alkyl group containing 1 to 4 carbon atoms), aminoimidazoles, aminothiazoles and barbylic acids The present invention relates to a heat-resistant resin composition containing at least one type of compound.

The amide-imide oligomer used in the present invention is produced by reacting an isocyanate compound, a tribasic acid anhydride, a dibasic acid, and a lactam in a polar solvent such as cresol, phenol, N-methylpyrrolidone, etc. It can be obtained by reacting. Among these polar solvents, phenolic solvents, particularly cresol, are preferred.

Isocyanate compounds include aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic diisocyanates, such as ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate. , cyclobuteso 1,3-diisocyanate, cyclohexane 1.
3- and 1,4-diisocyanate, isophorone diisocyanate 1° 3- and 1,4-phenylene diisocyanate, λ4- and 2,6-) lylene diisocyanate and mixtures of these isomers, diphenylmethane-44
'~diisocyanate, diphenylmethane-4,4'-
Diisocyanate, diphenyl ether-4,4'-diisocyanate, xylylene diisocyanate.

naphthalene-1,4-diisocyanate, naphthalene-
1,5-diisocyanate, 1-methoxybenzene-2
, 4-diisocyanate, diphenylsulfone-4,
Examples include diisocyanates such as 4'-diisocyanate. If necessary, trivalent or higher polyisocyanates can be used in combination, such as compounds having three or more isocyanate groups in one molecule obtained by multiplying the above diisocyanates, polyphenylmethylene polyisocyanate ( For example, it can be obtained by treating a condensate of aniline and formaldehyde with phosgene).

As the tribasic acid anhydride, for example, a compound represented by formula (2) or (3) is used.

Formula (2) Formula (3) (X
is -C&- (R is H or C mountain) s -co-, -s ha, -〇-, etc.) Specific examples of compounds represented by the structural formula of formula (2) or formula (3) are Mellitic anhydride, 2-(34-dicarboxyphenyl)-2-(3-carboxyphenyl)propane anhydride, (a4-dicarboxyphenyl)(3-
Examples include carboxyphenyl) methane anhydride, (3,4-dicarboxyphenyl>(3-carboxyphenyl) ether anhydride, and 1(4-tricarboxybenzophenone anhydride).

In addition, L2,4-butanetricarboxylic anhydride.

λkame 5-naphthalene tricarboxylic acid anhydride 11h, az6
- Naphthalene tricarboxylic anhydride, 1,2,4-naphthalene tricarboxylic anhydride. Examples include tin 3-biphenyltricarboxylic anhydride. From the viewpoint of heat resistance and cost, it is preferable to use trimellitic acid anhydride.

As the dibasic acid, for example, terephthalic acid, isophthalic acid, phthalic acid, adipic acid, sebacic acid, etc. are used, but aromatic dibasic acids are preferred.

As the lactam, β-propiolactam, r-butyrolactam, δ-valerolactam, C-cabrolactam, etc. are used, but ε-caprolactam is preferable. The amount of lactam to be used is determined to be 5% of the total amount of isocyanane 11 from the viewpoint of uniform transparency and heat resistance of the enamel wire appearance 9 composition.
~50 equivalents are preferred, and 10 to 40 equivalents are particularly preferred. In this case, the lactam is calculated assuming that 1 mole is 2 equivalents.

Also, isocyanate compounds, tribasic acid anhydrides.

When reacting a dibasic acid and a lactam, the blending equivalent ratio of carboxyl group to 1 isocyanate group is 0.8 to 1.
．． 2 is preferable, and 0.9 to 1.1 is more preferable. When the blending equivalent ratio is less than 0.8, the heat resistance tends to be poor, and when it exceeds 1.2, the solubility of the resin solution tends to be poor. Furthermore, the blending equivalent ratio of the carboxyl group of the tribasic acid anhydride added in the second stage is 0.1 to 0.5 to 1 isocyanate group.
Preferably.

If the blending equivalent ratio is less than 0.1, the appearance of the enameled wire will not be sufficient, and if it exceeds O or S, the heat resistance will tend to decrease. The blending equivalent ratio of all carboxyl groups to the final isocyanate group IK is preferably α9 to L7, and 1.1 to
1.5 is more preferred. In this case, the carboxyl group of the tribasic acid anhydride is calculated assuming that 1 mole of the tribasic acid anhydride is 2 equivalents.

When producing an amide-imide oligomer, the isocyanate compound, tribasic acid anhydride, dibasic acid, and lactam may be charged simultaneously in the -th stage reaction, or the first reaction may be carried out in stages depending on the purpose. . The main reaction is 190~
Preferably, the temperature is 220°C. After the reaction is allowed to proceed until the molecular weight is reached as required for the purpose, it is cooled, a required amount of tribasic acid anhydride is added, and the temperature is raised again to cause the reaction to occur. The reaction temperature is preferably 190 to 220°C.

As the polycarboxylic acid used in the present invention, polycarboxylic acids having a valence of two or more or derivatives thereof are usually used. Examples of dicarboxylic acids or derivatives thereof include dimethyl terephthalate and terephthalic acid.

Examples include dimethyl isophthalate, isophthalic acid, adipic acid, etc., and examples of trivalent or higher polycarboxylic acids or derivatives thereof include trimellitic anhydride, trimellitic acid, trimesic acid, 3,3:4,4'-benzophenone tetra Carboxylic acid, 1,2,3.4-butanetetracarboxylic acid, 1
, 2,4-butanetricarboxylic acid, etc. are used. Characteristic 9 From the viewpoint of price balance, it is preferable to use dimethyl terephthalate or terephthalic acid.

In addition, from the viewpoint of heat resistance, etc., it is particularly preferable to use so-called imidic acid having an imide bond in the molecular chain as part or all of the polyhydric carboxylic acid. It is preferable to use it as an imidic acid forming component by a known method as shown below. Namely.

The imidic acid-forming component consists of two, for example, a tribasic acid anhydride having two adjacent carboxyl groups and a diamine. Both of these components react as shown below to form imidic acid.

(Imidic acid) (In the formula, R means an organic group or a vague aromatic group) As is clear from the above formula, about 2 moles, preferably exactly 2 moles, of tribasic acid anhydride per mole of diamine. used.

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

Examples of diamines include 4,4'-methylene dianiline, 4,4'-diamino-λ3'-dimethyldiphenylmethane, and 44'-diaminodiphenylmethane.

4.4'-diaminodiphenyl ether, 4.4'-diaminodiphenylsulfone, 33'-diaminodiphenylsulfone, paraphenylenediamine, metaphenylenediamine, 4-tolylenediamine, 2゜6-tolylenediamine, metaxylenediamine Aromatic diamines such as 4,4'-diaminodiphenylmethane, 44
'-Diaminodiphenyl ether is preferred.

In addition to this, a combination of a tribasic acid anhydride and an aminocarboxylic acid can also be used as the imide acid forming component.
There is no limit to 49.

The polyhydric alcohol used in the present invention is not particularly limited, but alcohols having 9 or more valences are usually used. Examples of dihydric alcohols include ethylene glycol, neopentyl glycol, 1,4-butanediol, 1.6hexanediol, 1,6cyclohexanedimethanol, and trihydric or higher alcohols such as glycerin, Trimethylolpropane, tris-2-hydroxyethyl isocyanurate, tris-2-hydroxypropyl isocyanurate, pentaerythritol, etc. are used. From the viewpoint of heat resistance, it is preferable that 30 or more of the total alcohol components be trihydric or higher alcohols.

More preferably, the amount is 50 equivalents or more. Further, from the viewpoint of crazing resistance, it is particularly preferable to use glycerin, and from the viewpoint of heat resistance and refrigerant resistance, it is particularly preferable to use tris-(2-and droxyethyl) isocyanurate.

The reaction amount ratio of the acid containing the imidic acid forming component and the alcohol is 20 to 100% alcohol excess, preferably 30 to 100%.
It is 70%.

When reacting the amide-imide oligomer with a polyhydric carboxylic acid and a polyhydric alcohol, the heating reaction conditions are essentially an imidization reaction and an esterification reaction.

There are no particular limitations as long as the conditions are such that reactions such as transesterification and amide transesterification occur.

Usually eg tetrabutyl titanate, lead acetate.

In the presence of trace amounts of a catalyst such as dibutyltin dilaurate, 1
The heating is carried out at a temperature of 20 to 240°C for 3 to 10 hours. It is also possible to synthesize by adding a solvent such as cresol according to the viscosity. At this time, the ratio of the amide-imide oligomer used is preferably 1 to the polyamide-imide ester resin produced.
0-80% by weight.

It is preferably 20 to 50% by weight. If the proportion used is less than 10% by weight, the resulting resin tends to have insufficient properties such as thermal shock resistance and refrigerant resistance, but if it exceeds 80% by weight, the resin tends to have insufficient softening resistance.

The polyamideimide ester resin thus obtained is diluted with a suitable solvent to facilitate the production of enameled wire. In this case, as a solvent, a phenolic solvent such as phenol, cresol, or xylenol is mainly used, and these solvents include, for example, toluene or xylene.

It can also be used in combination with a diluting solvent such as Solpuntona 7s1 petroleum naphtha or carpitol.

A compound represented by the above general formula (5) is used together with the polyamideimide ester resin thus obtained.

This compound is usually 0.001 parts per 100' resin content.
It is used in an amount of ~0.5 parts by weight, preferably 0.01 to 0.15 parts by weight, more preferably 0.03 to 0.11 parts by weight. If the amount added is less than 0.001 parts by weight, the effect of improving adhesion to electrical conductors, which is one of the objectives of the present invention, will be poor.
On the other hand, if the amount exceeds 0.5 fi parts, although the adhesion is good, there will be problems such as a decrease in the flexibility of the enameled wire after heat deterioration. Two or more of these compounds may be used in combination.

Typical structures of the Y part shown in the general formula are 10 C ru, -CH=CH+, -11J=C-
, phenylene, naphthalene-t'l), general formula (5)
Examples of heterocyclic mercaptans include 2-
Mercapto-thiazoline, 2-mercapto-imidacillin, 2-mercapto-1-methyl-imidazole, 2-
Mercapto-benzoxazole, 2-mercapto-benzimidazole, 2-mercapto-benzothiazole, 5-amino-1, turtle 4-thiadiazole-2-thiol, IH-1, λ4-triazole-3-thiol, 2
-mercapto-quinoline, 2-mercapto-pyridine.

Examples include 1.2-naphthyl(2-mercapto)oxazole. Also, aminoimidazoles.

Examples of aminothiazoles and barbylic acids include 2-
Aminoimidazole, 2-amino-benzimidazole, 2-amino-naphthylimidazole, 2-aminothiazole, 2-amino-benzothiazole, 2-amino-
Naphthylthiazole.

Examples include barbylic acid, 2-thiobarbylic acid, thiobental and the like. Among these various compounds, particularly preferred are IH-1,λ4-triazole-3-thiol, 5-amino-1°-4-thiadiazole-2-thiol, 2-amino-benzothiazole, 2-
Amino-benzimidazole and 2-thiobarbic acid are discovered.

The heat-resistant resin composition of the present invention obtained in this manner may contain various additives, if necessary. For example, various metal compounds added to improve curability and flow characteristics during curing.

Titanium compounds such as tetralinepropyl titanate, tetrabutyl titanate, tetrahexyl titanate, zinc octenoate, zinc naphthenate, manganese octenoate,
Jeoncheon soaps such as cobalt naphthenate and iron octenoate are added.

These additives are added in a proportion of 0.1 to 25% by weight based on the polyamideimide ester resin content.

It is made into an enameled wire by applying and baking it directly onto an electrical conductor or together with other insulating coatings. Conditions normally used for manufacturing enamelled wire are used, and there are no particular restrictions.

(Effect of the invention) The heat-resistant resin composition of the present invention has 9 mechanical properties,
Enameled wires with excellent heat resistance, refrigerant resistance, electrical insulation, and adhesion can be obtained.

(Example) The present invention will be explained in detail. - Production Example A Cresol 7939. #-Caprolactam 99.19 and 4. Add idiphenylmethane diisocyanate 54 & 29.

After heating at 160°C for 1 hour, trimellitic anhydride 29
4.79 and isophthalic acid 109.29 and 21
The reaction was carried out at 0°C for 4 hours. Then cooled to 150°C,
Further, 42.19 g of trimellitic anhydride was added to this solution, and after reacting at 210° C. for 15 hours, cresol was added to obtain a transparent amide-imide oligomer (A) having a resin content of 30 g. When we measured the infrared absorption spectrum of this substance, we found that
The absorption of amide and imide groups was shown.

Production example B 3I with thermometer, nitrogen introduction tube, cooling tube and stirrer! In a four-loaf flask, add cresol 8199. ε-caprolactam 47.59 and 4,4'-diphenylmethane diisocyanate 525.99 were added.

After heating at 160°C for 1 hour, trimellitic anhydride 30
199 and isophthalic acid 87.59.

The reaction was carried out at 210°C for 4 hours. Then, an additional 121.29 g of trimellitic anhydride was added to this solution.

After reacting at 210°C for 15 hours, cresol was added to give a transparent amide-imide oligo (Blt-
Obtained.

Production Example A2 Polyamideimide oligomer solution obtained in Production Example A 14619, 4.4'-diaminodiphenylmethane 201.99. Trimellitic anhydride 391.19. Dimethyl terephthalate 296.59, ethylene glycol 6SL 99. ) Lis(2-hydroxyethyl)in cyanurate 53179 and tetrabutyl titanate 1.2
g was added thereto, the temperature was raised to 200°C over 2 hours, and the mixture was heated and reacted at the same temperature for 5 hours. After that, cresol and xylene 8
The resin concentration is 35 using a 0/20 (J1 quantity ratio) mixed solution.
The mixture was diluted by weight, and tetrabutyl titanate and zinc naphthenate were added as metals in amounts corresponding to 0.8% by weight and 0.2% by weight of the resin content, respectively.

Production Example B2 Polyamideimide oligomer solution 14619 obtained in Production Example B in the same manner as Production Example A2, 1 saag of 4,4'-diaminodiphenylmethane, and 35 trimellitic anhydride.
5.69. Dimethyl terephthalate 333.29. Ethylene glycol 65.69. ) Lis(2-hydroxyethyl)in cyanurate 552, Og was reacted with heating in the presence of 1.2 g of tetrabutyl titanate to obtain a solution having a resin concentration of 35% by weight. Tetrabutyl titanate and zinc octenoate were added to this solution in amounts corresponding to 0.8% by weight and 0.15% by weight of the resin content, respectively, as the metal content.

Examples 1 to 6 Heterocyclic mercaptan fields and aminoimidazoles used in the present invention for the polyamideimide ester resins obtained in Production Examples A2 and B2.

Several compounds selected from the group consisting of aminothiazoles and thiobarbic acids were added to form the final composition. Table 1 shows the composition ratio of these compounds to the resin content.

Comparative example 1 The composition obtained in Production Example A2 was used as Comparative Example 1.

Comparative example 2 The composition obtained in Production Example B2 was used as Comparative Example 2.

Comparative Example 3 Cresol 5 was placed in a 3e four-bottle flask similar to Production Example A.
48 g s 44'-diaminodiphenylmethane 2
289 (2,30 equivalents), trimellitic anhydride 4429
(4,60 equivalents), dimethyl terephthalate) 335 g (
145 equivalents), ethylene glycol No. 103 (3,32
Equivalents of tris-(2-hydroxyethyl)isocyanurate 5379 (6,17 equivalents) and tetrabutyl titanate (0.89 equivalents) were added, and the mixture was gradually heated to 200°C.
Further, the mixture was reacted at 200° C. for 5 hours to obtain a polyester/limide resin solution. Cresol was added to this resin solution to make the resin content 35%, and the same amounts of tetrabutyl titanate and zinc naphthenate as in Production Example A were added to obtain a resin composition.

Test Examples The resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were baked into copper wires having a diameter of 1IIlfi by a conventional method to obtain enamelled wires.

Table 1 shows the results of characteristic evaluation of the obtained enameled wire.

The characteristics of the enameled wire were evaluated in accordance with JIS C3214 for polyesterimide copper wire.

As shown in Table 1, when using the heat-resistant resin composition of the present invention, comparisons were made with the case where no specific compound was added (Comparative Example 1 and Comparative Example 2) and the polyesterimide resin (Comparative Example 3). As a result, the adhesion of the coating film has been significantly improved, and it also has better heat resistance and better heat resistance than polyesterimide resin.
It has excellent abrasion resistance and refrigerant resistance, and can be used not only for enameled wire production but also for heat-resistant paints.

Agent Patent Attorney Kunihiko Wakabayashi °1) -ノ

Claims (1)

[Claims] 1. After reacting an isocyanate compound, a tribasic acid anhydride, a dibasic acid, and a lactam, an amide bond and an imide bond are formed in the molecular chain obtained by further reacting the tribasic acid anhydride. Polyamideimide ester resin obtained by reacting polycarboxylic acid and polyhydric alcohol with amideimide oligomer having the formula (A) (A) ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula Y forms a heterocycle with 5 or 6 atoms together with bonded to two or three carbon atoms, or two nitrogen atoms, or one carbon atom forming part of the carbon atom, provided that the hydrogen bonded to this carbon atom may be substituted. heterocyclic mercaptans consisting of one nitrogen atom, X is oxygen, sulfur, carbon or NR [wherein R is hydrogen or an alkyl group containing 1 to 4 carbon atoms] A heat-resistant resin composition comprising at least one compound selected from the group consisting of , aminoimidazoles, aminothiazoles, and parbituric acids. 2. The heat-resistant resin composition according to item 1, wherein the heterocyclic mercaptan represented by general formula (A) is 5-amino-1,3,4-thiazole-2-thiol. 3. Aminoimidazole is 2-aminoimidazole,
2. The heat-resistant resin composition according to item 1, which is 2-amino-benzimidazole or 2-amino-naphthylimidazole. 4. Aminothiazoles are 2-aminothiazole, 2-
2. The heat-resistant resin composition according to item 1, which is amino-benzothiazole or 2-amino-naphthylthiazole. 5. The heat-resistant resin composition according to item 1, wherein the parbituric acid is parbituric acid, 2-thioparbituric acid, or thiopental.