JPS61275327A - Polyamide resin composition and its production - Google Patents

Abstract

PURPOSE:To obtain the titled high-MW composition excellent in mechanical properties, hot curing resistance characteristics and solubility, by reacting a polycarboxylic acid (derivative) with a polyamine in the presence of an aromatic polyamide resin. CONSTITUTION:The titled composition is obtained by reacting a polycarboxylic acid (derivative) (e.g., trimellitic anhydride) with a polyamine (e.g., 4,4'- diaminodiphenylmethane) at an equivalent ratio of about 1:1 at 150-250 deg.C for 2-20hr in the presence of 3-40wt% (based on the total resin) aromatic polyamide resin obtained by a reaction of an aromatic dicarboxylic acid with an aromatic diamine in an organic solvent such as a phenolic solvent with the aid of, optionally, 0.01-5wt% catalyst (e.g., lead naphthenate). If required, this composition is mixed with 3-40wt% aromatic polyisocyanate masked with a phenol to obtain another titled composition excellent also in film formability.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a novel polyamide resin composition useful as electrically insulating panels and the like, and a method for producing the same.

(Technical background of the invention and its problems) Necessity of resource and energy conservation and miniaturization of peripheral equipment, @
In recent years, as electrical equipment itself has become more efficient and more compact due to increased quantification, polyamide-imide Nanboku, which has a good balance of heat resistance, mechanical strength, electrical properties, and economic efficiency, has been used for electrical insulation panels and other applications. Its popularity in the field of insulating materials is increasing.

Traditionally, trimesin) & anhydride and aromatic diamine,
For example, it is known that a polyamide-imide resin composition with a high degree of polymerization can be obtained by reacting in an aprotic polar solvent such as N-methyl-2-pyrrolidone or dimethylacetamide. The polar solvent used in the festival has strong hygroscopicity, and pseudo-gelling phenomena and cloudy phenomena are likely to occur when the festival is used, making it difficult to store and manage the festival. It also has the disadvantage of being expensive and lacking in usefulness due to the use of tC.

For this reason, many proposals have been made for polyamide-imide resins using phenolic solvents, which are extremely commonly used as solvents for electrical insulating varnishes (for example,
No. 23999, Special Publication No. 56-17374, Special Publication No. 17374
-22330, Special Publication No. 56-34210).

However, even if an attempt is made to obtain polyamideimide/lipemia by simply reacting trimellitic anhydride with aromatic diamine gold 7-enol solvent such as 4,4'-diaminodiphenylmethane, a cloudy precipitate or Even if the reaction is carried out at a high temperature above the boiling point of the phenolic solvent to obtain a homogeneous solution, aryl esters, etc. are generated at the terminals, making it impossible to obtain a high molecular weight polymer that can be used as a practical wire varnish. It's like that.

In addition, when aliphatic dicarboxylic acids, lactams, etc. are used, the solubility in phenolic solvents improves, but on the other hand, the heat resistance and the heat softening temperature when used as insulated wires are lower than that of aromatic polyamideimide resins. The disadvantage is that it is inferior to
-V is on.

(Purpose of the invention) Akashi, the inventor of the invention, has repeatedly studied the reaction between polycarboxylic acids and polyamines, and has found that a polymer with excellent heat resistance and an extremely high degree of polymerization can be obtained in the reaction in the coexistence of an aromatic polyamide resin. (and the coexisting aromatic polyamide resin and the produced aromatic polyamide resin are integrated) to obtain a heat-resistant, soluble, flat, regular polyamide resin, and a phenolic solution of the resin. It has been discovered that a resin with excellent film-forming properties can be obtained by completely blending an aromatic polyinocyanate masked with phenols in the resin.The present invention was made based on this knowledge. In other words, the polyamide resin composition of the present invention is intended to provide a polyamide-based 4R resin composition free from the above-mentioned conventional drawbacks and a method for producing the same. A polyamide resin composition characterized by reacting a derivative and a polyamine in the coexistence of an aromatic polyamide resin, and the resin composition further contains an aromatic polyisocyanate masked with a phenol. It is an object of the present invention to provide polyamide-based resin compositions and methods for producing them.

The polycarboxylic acids used in the present invention include dibasic acids or their derivatives, tribasic acid anhydrides or their derivatives, tetrabasic acid anhydrides or their derivatives, dibasic acid anhydrides or their derivatives, and tribasic acids. Anhydrides or derivatives thereof can be used alone or by partial replacement with other polycarboxylic acids, and tetrabasic acid anhydrides or derivatives can be used by mixing with other polycarboxylic acids. Examples of dibasic acids or derivatives thereof that may be used include oxalic acid and dibasic acids and dibasic acid esters represented by formula (1).

Among these dibasic acids or derivatives thereof, aromatic dibasic acids or derivatives thereof are suitable for leopards from the viewpoint of heat resistance.

As the tribasic acid anhydride or its derivative, citric acid or, for example, aromatic tricarboxylic acid, aromatic tricarboxylic acid ester, aromatic tricarboxylic acid anhydride, or the like represented by formula (■') or (1) is used.

几2(C00RI)s...Pa・(
1) Generally, trimellitic anhydride is preferred from the viewpoints of heat resistance, high reactivity, economic efficiency, etc.

Tetrabasic acid anhydrides or derivatives thereof include, for example, pyrometic anhydride, 3,3',4,4'-benzophenonetetracarboxylic anhydride, and 3,3',4,4'-diphenyltetracarboxylic anhydride. , naphthalenetetracarboxylic anhydride, butanetetracarboxylic anhydride and other acid anhydrides, acids, esters and other derivatives.

The polyamines used in the present invention include aliphatic, alicyclic,
Aromatic diamines are mainly used.

Suitable diamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, heptamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, trimethylhexamethylenediamine, morpholinediamine, and cyclohexane. -1
, 4-diamine, 3.9-bis(3-aminopropyl)
-Aliphatic and alicyclic diamines such as 2,4,8,10-tetraoxaspiro[5.5]undecane, 4.4'-diaminodiphenylmethane, 4.4'-diaminodiphenyl ether, 4.4'- diaminodiphenylpropane,
4.4'-diaminodiphenylsulfone, 3.3'-diaminodiphenylsulfone, 4.47-diaminodiphenylsulfide, 3°3'-dimethyl-4,4'-diaminodiphenylmethane, 3.3'- dichloro-4,4
'-Diamino diphenylmethane, 3.3'-dimethoxy-4,4'-diaminodiphenyl, 3.3'-dimethyl-4,4'-diaminodiphenyl, 4.4'-diaminodiphenyl m-phenylenediamine, p-phenylene Aromatic diamines such as diamine, 2,4-diaminotoluene, 2#6-diaminotoluene, m-xylylene diamine, and p-xylylene diamine are a), and these can be used alone or in combination. A part of the diamine can be replaced with a trivalent or higher polyamine such as 3#3'#4'-)diaminodiphenylmethane, 3.3', 4.4'-tetraaminodiphenylmethane, etc., for the purpose of reducing all the crosslinking components. .

Among the polyamines, aromatic diamines are preferred from the viewpoint of heat resistance and mechanical properties of the insulating film.

The aromatic polyamide resin that coexists in the reaction between a polycarboxylic acid or its derivative and a polyamine is rich in aromatic rings as an acid or amine component. Good value 0
Furthermore, among wholly aromatic polyamide resins, those that dissolve in phenolic solvents at high temperatures can also be used.

The reaction between a polycarboxylic acid or a derivative thereof and a polyamine in the presence of an aromatic polyamide resin is carried out in the presence of an organic solvent at a temperature of 150 to 250° C. for 2 to 20 hours.

Suitable organic solvents for the present invention include phenol, 0-cresol, m-cresol, p-cresol, xylenolic acid of various extractions, various chlorophenols, nitrobenzene, N-methyl-2-hyrolidone, dimethylformamide, dimethyl Examples of solvents that can be used in combination with these include acetamide, hexitemetherphosphoramide, and dimethyl sulfoside, such as benzene, toluene, and high-boiling hydrocarbons (e.g., Swazol 1000, Swazol 1500, manufactured by Maruichi Oil Co., Ltd.). Nippon Oil Co., Ltd.) - Isol 100°, etc.), ethylene glycol monomethyl ether acetate, etc.

Preferred reaction solvents for the box are phenolic solvents such as phenol, cresol, xylenol, etc. from the viewpoint of solubility for the starting materials, stability of the resulting resin solution, film formability, economic efficiency, etc., and are used as electrical insulation panels. In this case, a mixture of the phenolic solvent and a high-boiling aromatic hydrocarbon solvent is suitable.

The blending ratio of polycarboxylic acid or its derivative and polyamine is 2 equivalents of polycarboxylic acid or its derivative,
When the amino group equivalents of the polyamine are the same, the equivalent ratio is preferably about 1:1. However, either one of the 10
An excess of li% or less is within an acceptable range. The function of the aromatic polyamide resin in the synthesis reaction of the present invention is not clear, but it is believed that the entire reaction between the polycarboxylic acid or its derivative and the polyamine is accelerated, and that the resulting resin is crushed 7L7' (solubility and that the aromatic polyamide resin produced and the aromatic polyamide resin used during synthesis react with each other and become integrated, based on the molecular weight distribution results from infrared charts, thermogravimetric analysis, and gel permeation chromatography. It is assumed that the aromatic polyamide resin exhibits a matrix effect in the reaction between polycarboxylic acid or its derivative and polyamine, and at the same time, a polymerization reaction occurs at the amide radical center of the aromatic polyamide resin. Conceivable.

The proportion of the rounded aromatic polyamide resin to be used can be varied depending on the amount of resin sufficient to produce the matrix effect, the intended use of the resulting resin, and the suitability of the resin. For example, when used as an electrically insulating board, the amount is preferably 3 to 40% by weight based on the total resin content. If the amount is less than 3% by weight, a sufficient matrix effect will not be exhibited, and if it exceeds 40% by weight, the heat resistance of the enameled wire obtained from the insulating face will decrease. On the other hand, when used as a film or molded product, it is possible to use aromatic polyamide resin T-40 in an amount of 1i% or more by weight depending on the demand.

The polycarboxylic acid or its derivative, the polyamine, and the aromatic polyamide resin may be charged at the same time at the start of the reaction, or one may be dissolved in a solvent and the other may be charged at the same time or in several batches. There are no restrictions on However, in order to obtain a high molecular weight polyamide resin, it is preferable to add the aromatic polyamide resin to the layer from the start of the reaction. On the other hand, when used as an electrically insulating face, the reaction proceeds even during the baking step to form an enamel film, so the aromatic polyamide resin can be added relatively late in the reaction in the face synthesis stage.

Although the reaction proceeds under sufficient pressure in the absence of a catalyst, the reaction of the present invention can be accelerated by a catalyst commonly used in reactions of polyamines.

Examples of suitable catalysts include - lead oxide, boric acid, metal salts of naphthenic acids such as lead naphthenate, zinc, phosphoric acid, polyphosphoric acid, triethylamine, etc. The preferred amount used is the solid state at the time of charging. Lunch box 0. O1-511L1%.

The reaction in a phenolic solvent starts at around 70°C with no dehydration, usually at 180-210°C and 3-1°C.
A practical high molecular weight polyamide resin can be obtained under reaction conditions of 2 hours.

The polyamide resin composition thus obtained can be used as it is as an electrically insulating board, etc., but it is particularly suitable for use in recent years at high wire speeds and as an electrically insulating board for enamelled wire production.
When used in a highly efficient printing machine, #! It has the disadvantage that it tends to foam at the edges.

After further investigation into these problems, it was discovered that by blending an aromatic polyincyanate masked with phenols into the polyamide resin solution, the above-mentioned difficulties could be significantly improved.

Examples of aromatic polyisocyanates masked with phenols include 4,4'-diphenylmethane diincyanate, 2.4-tolylene diincyanate), and 2.6
-) lylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 4.4'
-Incyanate foundation of diphenyl ether diisocyanate Polyincyanate derivatives masked with 7 enols such as phenol, cresol, and xylenol can be used.

The ratio of polyisocyanate to the entire resin is 3 to 40! Quantity is suitable. If the amount is less than 3% by weight, the improvement in foaming resistance, flexibility, and softening temperature will not be significant, and if it exceeds 40% by weight, the flexibility and abrasion resistance of the enamelled wire will decrease.

There is no limit to the temperature when adding the masked aromatic polyincyanate gold, but if it is stirred for a long time at around 200°C, the resin solution may become partially opaque and precipitates may form. Therefore, the temperature at which it is added is preferably 140°C or lower.

The resin composition of the present invention may be blended with other resins as necessary. It is also possible to make a modified polyamide resin composition by adding other polyfunctional compounds such as polyols, polyamines, and polycarboxylic acids and reacting them.

(Example of the invention) The present invention will be explained in detail below with reference to Examples.

Example 1 Attach a thermometer, stirrer, cooling pipe, nitrogen introduction pipe, etc. m3/4
192.1 g of trimellitic anhydride (1
0 mol) 4.4'-diaminodiphenylmethane + 98g
(1.0 mol), Lenny (Mitsubishi IS Chemical Co., Ltd.'JMf Io
(M8 L) 5) 4 Q gSm-cresylic acid (JIS K2451. Meta-cresylic acid No. 1 equivalent) 400gt" was prepared and heated in a rat stream for about 1 hour.
Raise the temperature to 00℃. Many foams due to dehydration were observed at temperatures ranging from 70 to 160°C. The reaction temperature was set at 205°C and the reaction was carried out at normal pressure. The contents, which were transparent immediately after the start of the reaction at 205° C., temporarily became opaque, but after about 2 hours became a reddish-brown, transparent, and uniform solution. After 8 hours at 205°C, when the contents became a viscous solution that was difficult to stir, 619 gQ of cresol was added to stop the reaction. This resin solution is reddish-brown and transparent with a non-volatile content (200°C!
1.5 hours) 30.3g, viscosity (30'Q) 3
It has a viscosity of 50 boids. The obtained resin solution was uniformly applied to a copper plate measuring 10cm x 3α and 0.1cm thick so that the film thickness was approximately 15 μm, heated at 230°C for 30 minutes, and then bent at 180°. A flexible coating film that does not cause cracks even when applied is obtained.

According to the usual method, the furnace length is 7 m, and the furnace temperature is 430-38°〇-280.
(Top → Bottom), at a linear speed of 10 m/min.
The resulting 7'C ridge fat solution was coated and baked 7 times on a 1.0% copper wire to obtain an insulated wire with a coating thickness of about 38 μm.

Measurements were made according to JIS C3003, and the characteristics were found as shown in Table 1.

Table 1 Comparative Example Using the same equipment as in Example 1, trimellitic anhydride 1
92.1 g (1.0 mol), 4.4'-diaminodiphenylmethane 198.3 g (1.0 mol), m-cresol tR (JIS K2451. Metacresol 1-
Corresponding to Q) i, 300 g was charged, and the reaction was carried out in the same manner as in Example 1. Foaming similar to Example 1 was observed at 70 to 160°C, but unlike Example 1, it became opaque at 205°C and did not become transparent even after 95 hours. After 5 hours, the reaction temperature was raised to 220° C. while all of the resol was being exported, and the reaction was started at 205° C. for an additional 3 hours. The reaction was continued for a total of 8 hours, and a transparent solution was obtained.

Distilled cresol weighed 29 g. At this point, 559 g of cresol was added to stop the reaction. The resulting resin solution was reddish-brown and transparent, had a nonvolatile content of 30.1% by weight, and a viscosity of (3
0°C) had 93 voids. A coating film was formed on a copper plate under the same conditions as in Example 1, but no coating film was obtained that was as flexible as the shifrak metal when bent by 180 degrees.

Example 2 Using the same equipment and starting materials as Example 1, 200 to 20
The reaction was carried out at a temperature of 5° C. for 5 hours. Cresol 400gt
-The reaction was stopped, and when the resin solution reached 70°C, it was masked and nine aromatic polyisocyanate (containing about 50% by weight as M8-50.4#4'-diphenylmethane diisocyanate manufactured by Nippon Polyurethane Co., Ltd.) sogt-
The mixture was added and thoroughly stirred to obtain a homogeneous solution.

The resin solution diluted with a mixed solvent of 210 g of cresol and 90 g of solvent naphtha was reddish-brown and transparent with a nonvolatile content of 31.
8! ii%, and a viscosity of 78 poise at 30°C. The straightness of the insulated wire obtained in the same manner as in Example 1 at a line speed of 12 m/min and having a coating thickness of about 38 μm is shown in Table 2.
90 No. 2 Examples 3 to 5 Using the same equipment as in Example 1 and using the starting materials and synthesis conditions shown in Table M3, a reddish-brown transparent resin solution was obtained in each case.

The furnace length was 7 m as in Example 1.
Furnace temperature 430-380-280 (top → bottom)
, 1 at a linear speed of 12 m/min. Coated and baked on OUφ copper wire 7 times to obtain an insulating film with a thickness of approximately 38 μm +11. ) Table 3 Jujube TMA;) Limelic acid anhydride IPM; Isobutanoic acid BTDA; Benzophenonato dicarboxylic acid anhydride 1) AM; 4.4'-diaminodiphenylmethane aromatic polyamide; Meta-xylene diamine and adipic acid are reacted. Table 4 (Effects of the invention)

Claims (1)

[Claims] 1. A polycarboxylic acid or its derivative and a polyamine,
A polyamide resin composition characterized by being reacted in the coexistence of an aromatic polyamide resin at an equivalent ratio of approximately 1:1. 2. The polyamide resin composition according to claim 1, wherein the polycarboxylic acid or its derivative is an aromatic polycarboxylic acid. 3. The polyamide resin composition according to claim 1 or 2, wherein the aromatic polycarboxylic acid is trimellitic anhydride. 4. The polyamide resin composition according to any one of claims 1 to 3, wherein the polyamine is an aromatic diamine. 5. Aromatic polyisocyanate masked with phenols is added to a resin composition obtained by reacting a polycarboxylic acid or a derivative thereof and a diamine at an equivalent ratio of approximately 1:1 in the coexistence of an aromatic polyamide resin. A polyamide resin composition characterized in that it is made by blending. 6. The polyamide resin composition according to claim 5, wherein the polycarboxylic acid or its derivative is an aromatic polycarboxylic acid. 7. The polyamide resin composition according to claim 5 or 6, wherein the aromatic polycarboxylic acid is trimellitic anhydride. 8. The polyamide resin composition according to any one of claims 5 to 7, wherein the polyamine is an aromatic diamine. 9. Polycarboxylic acid or its derivative and polyamine,
A polyamide resin composition characterized by reacting in a phenolic solvent in the coexistence of an aromatic polyamide resin at an equivalent ratio of approximately 1:1, and then blending an aromatic polyisocyanate masked with a phenol. How things are manufactured.