JPH0576489B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing a polyamide-imide polymer, which has excellent flexibility and flexibility not found in conventional heat-resistant polymers, and is also heat-resistant. The present invention relates to a method for producing a heat-resistant polymer that has excellent properties such as electrical insulation, chemical resistance, and hydrolysis resistance, and also has excellent coating workability such as film-forming properties. [Prior Art] In recent years, heat-resistant polymers such as polyimide, polyamideimide, polyhydantoin, polyamideimide ester, and polyesterimide have been researched and developed and are commercially available. However, when these heat-resistant polymers are put to practical use industrially, for example, when they are used for wire coatings, films, laminates, adhesives, etc. that require heat resistance, they do not only have heat resistance, but also flexibility and bendability. There are many required properties such as electrical insulation, chemical resistance, refrigerant resistance, adhesion, electrical insulation, chemical resistance, refrigerant resistance, etc., and an appropriate balance among these properties is required, and a polymer with excellent film forming properties is desired. It is rare. Polyimide has excellent heat resistance but poor mechanical strength, polyhydantoin has excellent film forming properties but poor refrigerant resistance, and polyamide ester lacks heat resistance as a heat-resistant polymer. ,
Although polyesterimide is advantageous in terms of price, it lacks refrigerant resistance and heat resistance. Among heat-resistant polymers, polyamide-imide has excellent and well-balanced properties in heat resistance, mechanical properties, chemical resistance, and refrigerant resistance. However, conventional polyamide-imide has shortcomings in flexibility, flexibility, and adhesion, and it also has poor film forming properties, which are common shortcomings of heat-resistant polymers. Appearance: Easy to cause rough skin 1
The method used is to reduce the amount of paint per coat, increase the number of coats, and bake at low speed. Therefore, compared to other conventional materials, the working efficiency is poor and the manufacturing cost of enamelled wire is high. [Problems to be Solved by the Invention] The purpose of the present invention is to solve the problems of the prior art and to obtain a heat-resistant polymer that has various required properties and satisfies an appropriate balance. It has excellent flexibility and bendability that are not found in heat-resistant polymers, and also has excellent properties such as heat resistance, electrical insulation, chemical resistance, and hydrolysis resistance, as well as film-forming properties. An object of the present invention is to provide a method for producing a heat-resistant polymer that also has excellent coating workability. Another object of the present invention is to provide a polymer useful for coating metals, particularly wires, and producing films or laminates, which can be adapted to any required properties by changing the composition, and which can be used as a molding resin. It is an object of the present invention to provide a method for producing a polymer that can be used in a wide range of applications such as laminates, adhesives, etc. and is extremely useful in practice. Further objects of the present invention will become apparent from the entire description of the present specification. [Means for Solving the Problems] As a result of intensive studies on these heat-resistant polymers, the present inventors have found that long-chain polyvalent isocyanates derived from dimer acids and organic isocyanates other than the isocyanates are used as isocyanates. By reacting these isocyanates with tricarboxylic acid or its derivative alone or with tricarboxylic acid or its derivative and dimer acid, the above-mentioned disadvantages can be improved without impairing the advantages of conventional polyamide-imide. We have discovered that it is possible to obtain a heat-resistant polymer of high commercial value, and based on this we have arrived at the present invention. The present invention is based on the general formula O=C=NR-N=C=O (where R is an aliphatic hydrocarbon having a carbon number of 36 and forming the skeleton of the long-chain polyvalent isocyanate), which may be masked. It is characterized by reacting a long-chain polyvalent isocyanate represented by the group ) and derived from a dimer acid, an organic isocyanate other than the isocyanate, which may be masked, and a tricarboxylic acid or a derivative thereof. and the general formula O=C=N-R-N=C=O (wherein R is the long chain polyvalent polymer having 36 carbon atoms) A long-chain polyvalent isocyanate derived from a dimer acid, an organic isocyanate other than the isocyanate, which may be masked, and a tricarboxylic acid or Its derivatives and the general formula HOOC−R′−
Reacts with a higher dibasic acid whose main component is a long chain dibasic acid represented by COOH (in the formula, R′ is an aliphatic hydrocarbon group having 18 to 34 carbon atoms and forming the backbone of the long chain dibasic acid) The present invention relates to a method for producing a polyamide-imide polymer. The long chain polyvalent isocyanate used in the present invention has the general formula O=C=NR-N=C=O (wherein,
R is an aliphatic hydrocarbon group that forms the skeleton of the long-chain polyvalent isocyanate having 36 carbon atoms, and is an isocyanate derived from a dimer acid. A diisocyanate derived from dimer acid consisting of
There is one commercially available as DDI diisocyanate from Henkel Japan. This long-chain polyvalent isocyanate may be masked in the same manner as the organic isocyanate described below. One or more of these may be used. The organic isocyanate used in the present invention is other than the above-mentioned isocyanates, such as toluylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diisocyanate diphenylmethane, 4,4'-diisocyanate. Examples include diphenyl ether and xylylene diisocyanate.
Isocyanate derivatives obtained by masking the isocyanate groups of these isocyanates with phenol, cresol, xylenol, etc. can also be used. One or more of these may be used. The tricarboxylic acid or its derivative used in the present invention has the general formula

[Formula] is exemplified. [Here, R ₁ =H or an alkyl group is exemplified,

[expression] or

[Formula] is exemplified. ] Trimellitic anhydride is generally preferred from the standpoint of heat resistance and economical efficiency, but a portion of the tricarboxylic acid may be replaced by pyromellitic anhydride, 3,3'4,4'benzophenonetetracarboxylic anhydride, Substitution with a tetracarboxylic acid such as butanetetracarboxylic acid or a derivative thereof is also possible. One or more of these may be used. Although various higher dibasic acids can be used in the present invention, a particularly preferred one is a dimer acid obtained by polymerizing purified vegetable unsaturated fatty acids. This dimer acid is mostly composed of dimers of fatty acids, and those obtained from _C18 fatty acids are mainly composed of _C36 dimer acids and contain small amounts of trimer acids and monomer acids. It is something that This type of dimer acid is, for example, Versadime 288, Versadime 216,
Since it is commercially available as Versadime 228 (all of the above are trade names of Henkel Japan Co., Ltd.), such commercial products can be effectively used in the present invention. Other preferred examples of higher dibasic acids include the following. (a) HOOC (CH ₂ ) ₆ CH=CH (CH ₂ ) ₆ COOH 4-9% HOOC (CH ₂ ) ₆ CH=CH (CH ₂ ) CH=CH
( _CH2 ) _6COOH 35-52%

[ka] 2-4%

[C] 30-40% (B) HOOC (CH ₂ ) ₁₄ COOH 4-10% HOOC (CH ₂ ) ₁₈ COOH 85-90% (C)

[ka] 10-20%

[ka] 80-90% (d) Main component,

〔Example〕

Next, the present invention will be further described in detail based on Examples and Comparative Examples. Example 1 230 g of trimethic anhydride was placed in a 2-four-necked flask equipped with a thermometer, stirrer, cooling tube, and nitrogen inlet tube.
4,4'-Diisocyanate diphenylmethane 296
14 g of DDI diisocyanate (trade name, Henkel Japan Co., Ltd.) and 798 g of N-methylpyrrolidone were charged, and the temperature was raised to 80° C. to 90° C. and maintained at this temperature for 4 hours. Next, the temperature was raised to 120°C to 130°C and maintained at this temperature for 4 hours. During this period, a significant amount of carbon dioxide gas was generated. The temperature was further raised to 140°C to 150°C, and the reaction was completed at this temperature over 3 hours. The reaction product was obtained in the form of a reddish-brown transparent viscous solution, and its infrared spectrum showed absorptions characteristic of amidimide groups at 1650 cm ^-1 and 1780 cm ^-1 . The reaction product, N
-30% in mixed solvent of methylpyrrolidone and xylene
A resin solution of 30 poise (30°C) was obtained. This resin solution was heated using a 7m long vertical hot air shield furnace.
Baking coating was performed on a copper wire with a wire diameter of 1.0 mμφ under the conditions shown in Table 1. Example 2 Trimellitic anhydride 230% was added to a 2-4-necked flask equipped with a thermometer, stirrer, cooling tube, and nitrogen inlet tube.
g, 4,4' diisocyanate diphenylmethane
287 g, ddi diicyanate (trade name of Henkel Japan Ltd.), 35 g, and 820 g of N-methylpyrrolidone were charged and reacted in the same manner as in Example 1. The resulting reaction product was dissolved in a mixed solvent of N-methylpyrrolidone and xylene. Diluted to 30% to obtain a 30 poise resin solution. The obtained resin solution was baked and applied onto electric wires in the same manner as in Example 1. Example 3 Trimellitic anhydride 228 was added to a two-four neck flask equipped with a thermometer, stirrer, cooling tube, and nitrogen inlet tube.
g, 7 g of higher acid dibasic acid (Henkel Japan Co., Ltd. trade name Versadime 288), 299 g of 4,4'-diisocyanate diphenylmethane, 7 g of ddi diisocyanate, and 797 g of N-methylpyrrolidone were charged and reacted in the same manner as in Example 1. The resulting reaction product was diluted to 30% with a mixed solvent of N-methylpyrrolidone and xylene to obtain a 30 poise resin solution. The obtained polymer solution was baked on a 0.04 mm thick copper foil in a baking oven, and the resulting coating film had sufficient flexibility, and the infrared absorption spectrum of the coating film was 1650 cm ^-1 At 1780 cm ^-1 , an absorption characteristic of the amide-imide group was observed. Further, the obtained resin solution was applied by baking onto an electric wire in the same manner as in Example 1. Comparative example Trimellitic anhydride 288 was added to a 2-four-necked flask equipped with a thermometer, stirrer, cooling tube, and nitrogen inlet tube.
g, 4,4'-diisocyanate diphenylmethane
Prepared 380g and 1002g of N-methylpyrrolidone.
When the temperature rises to 80°C to 90°C, the generation of carbon dioxide gas is observed. When the temperature was further heated at 130° C. to 140° C. for 1 to 2 hours, the viscosity increased and the reaction was completed after heating for about 3 hours. The obtained reaction product was diluted to 30% with a mixed solvent of N-methylpyrrolidone and xylene, and baked onto an electric wire in the same manner as in Example 1. The general characteristics of the enamelled wires obtained in Examples 1 to 3 and Comparative Examples were determined according to JIS C3003-1976.
The test results were as shown in Table-2.

【table】

[Table] As is clear from the results in the table above, in terms of painting workability, the amide-imide polymer of the present invention shows good appearance even after 6 times of application, whereas the conventional method required 9 times of application. It has excellent work efficiency and can reduce the manufacturing cost of enamelled wire. Also flexible,
As is clear from the results of the twisting peel test, it has excellent flexibility, adhesion, and bendability, and has no inferiority in terms of heat resistance, electrical properties, and chemical properties compared to conventional amide-imide properties. . [Effects of the Invention] (1) According to the present invention, it was possible to obtain a product that has various required properties not found in conventional heat-resistant polymers and can also satisfy an appropriate balance. In other words, it has excellent flexibility and bendability that are not found in conventional heat-resistant polymers, as well as heat resistance, electrical insulation, chemical resistance,
It was possible to obtain a heat-resistant polymer that has excellent properties such as hydrolysis resistance and also excellent coating workability such as film-forming properties. (2) The polyamide-imide polymer obtained by the production method of the present invention has particularly excellent properties in flexibility, flexibility, and film-forming properties compared to conventional wholly aromatic polyamides. It is useful for coating metals, especially wires, and manufacturing films and laminates. By changing the composition, it is possible to suitably meet any required properties, and it can be used for molding resins, laminates, adhesives, etc. It can be used for a wide range of purposes, and has been extremely useful industrially.

Claims (1)

[Claims] 1 General formula that may be masked O=C=N-R-N=C=O (wherein R is a fatty acid forming the skeleton of the long-chain polyvalent isocyanate having 36 carbon atoms) A long-chain polyvalent isocyanate represented by a group hydrocarbon group) and derived from a dimer acid, and an organic isocyanate other than the isocyanate, which may be masked, are reacted with a tricarboxylic acid or a derivative thereof. A method for producing a polyamide-imide polymer, characterized by: 2 General formula that may be masked O=C=N-R-N=C=O (wherein R is an aliphatic hydrocarbon group forming the skeleton of the long-chain polyvalent isocyanate having 36 carbon atoms) A long-chain polyvalent isocyanate derived from a dimer acid, an organic isocyanate other than the isocyanate, which may be masked, a tricarboxylic acid or a derivative thereof, and a general formula HOOC-R'-
Reacts with a higher dibasic acid whose main component is a long chain dibasic acid represented by COOH (in the formula, R′ is an aliphatic hydrocarbon group having 18 to 34 carbon atoms and forming the backbone of the long chain dibasic acid) 1. A method for producing a polyamide-imide polymer, which comprises: