JPS61162525A - New copolyamideimide, its production and prepolymer thereof and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] This invention relates to a new polymer composition and a method for producing the same.

More specifically, the present invention relates to copolyamideimide, a method for producing the same, and a carboxy-terminated polyimide prepolymer intermediate thereof.

[Conventional technology]

Various polyamides 9 and polyimides prepared by reacting polycarbic acid and its functional derivatives with polyamides and/or polyisocyanates are known to those skilled in the art. For example, British Patent Application No. 2.080,316 discloses the reaction of a mixture of one or more noanhydrides and trianhydrides with cyamine, noisocyanate or mixtures thereof to produce polymers containing both amide and imide linkages. A method of manufacturing is disclosed. Another reaction of diamines and polycarboxylic anhydrides is disclosed in US Pat. No. 3,975,345. Reacting neuisocyanates with various combinations of dicarboxylic, tricarboxylic, and tetracardic acids and their anhydrides is described in U.S. Pat. No. 3,843,587, 3,92
No. 9.691 and No. 4.061,622. According to U.S. Pat. No. 4,331,799, polymers containing both amide and imide moieties are produced by reacting diamines with mixtures of acyl chlorides and anhydrides of carboxylic acid anhydrides, such as trimellitic anhydride. can be manufactured. This reaction, and the reactions disclosed above, result in polymers having irregular and relatively uncontrollable structures and physical properties. Particularly problematic are its susceptibility to thermal distortion and its low glass transition temperature. Additionally, the use of acyl chlorides as precursors results in the presence of residual chlorine in the polymer, which is unacceptable for applications such as electrical insulators.

[Purpose of the invention]

The main objective of this invention is to provide new copolyamideimides and intermediates thereof. A second object is to provide a copolyamide-imide having a relatively high glass transition temperature and heat distortion resistance. A second object is to provide a relatively simple method for preparing the copolyamideimide. A further object is to provide new prepolymers which can be converted into such copolyamideimides. Other purposes will be apparent from the description below.

[Disclosure of the invention]

This invention consists of two main steps, 1 is Cal? Regarding the x-terminated polyimide prepolymer, the others relate to copolyamideimides prepared therefrom. The method for producing a prepolymer is based on the general formula H2N-R+' -NH2... under conditions where all the reaction water is removed.
...(1) (in the formula, R1 is a divalent hydrocarbon group) at least one diamine (A) J (in the formula, R1 is a divalent hydrocarbon group)
2 is a trivalent hydrocarbon group)
(8) and at least one anhydride represented by the formula (wherein 3 is a tetravalent hydrocarbon group).

The molar ratio of reagent (C') to reagent (B) is at least about 0.025, with reagent (A) and combination reagent (B) + (C
) is approximately 1:1.

Copolyamideimide is a neuisocyanate having the general formula 〇CN-R'-NGO-・-(■) and the general formula R'-NH~几'-NH几6... ・
... (At least one diamine having ■ (in the formula, R4 is a divalent hydrocarbon group or a polymeric group, and V and R6 are each independently hydrogen or a lower hydrocarbon group) (
It is produced by reacting with E).

In the context of this invention, a "hydrocarbon group" refers to a group that has a carbon that is directly bonded to the main body of the molecule and does not contain acetylenic and usually ethylenically unsaturated bonds; , refers to a group that primarily has hydrocarbon properties.

Such groups include:

(1) Hydrocarbon groups such as aliphatic, alicyclic, aromatic, aliphatic or ring-substituted aromatic, or aromatic-substituted aliphatic or ring-ring groups, such groups being understood by those skilled in the art. For example, methyl, ethyl, propyl, butyl, decyl, cyclopentyl, cyclohexyl,
These are phenyl, tolyl, xylyl, α-naphthyl, β-sumethyl, and biphenylyl (including isomers).

(2) Substituted hydrocarbon groups which contain non-hydrocarbon substituents and which, in the context of this invention, do not significantly alter the properties of the hydrocarbon; suitable substituents include e.g. alkoxy), carbalkoxy,
Those skilled in the art will appreciate that there are nitro, cyanogen, alkyl sulfones, and the like.

(6) A group in which an atom other than carbon is substituted at a carbon position in a chain or ring, and in the context of this invention, a heteroatom-containing group that primarily has the characteristics of a hydrocarbon group, where an appropriate heteroatom is As will be apparent to those skilled in the art, these include, for example, nitrogen, oxygen, sulfur, and silicon.

Generally, there are 9 for each 10 carbon atoms in a hydrocarbon group.
There are no more than two substituents or heteroatoms. An exception is when silicon is a complex atom, in which case it may contain, for example, as few as four carbon atoms or as many as six complex atoms.

Reagent A is at least one diamine of general formula m. At this time, Bl is an aromatic hydrocarbon group containing about 6 to 20 carbon atoms or a halocyanated group thereof,
or alkylene or cycloalkylene containing about 2 to 20 carbon atoms, or bis-alkylene poly(noalkylsiloxane) groups.

Aromatic hydrocarbon groups are preferred.

Suitable examples of diamines of general formula (I) include ethylenediamine, zolobylenenoamine, trimethylenetriamine, noethylenetriamine, triethylene-tetraamine, heptamethylenezamine, octamethylenezamine, 2.1
1-dodecane cyamine, 1,12-octadecanediamine, 6-methylhegetamethylenezamine, 4.4'-
Tsumethylhexamethyleneziamine, 5-methylnonamethylenediamine, 2,5-tsumethylhexamethylenediamine, 2,2-tsumethylpropylenezamine, N-methyl-bis(3-aminopropyl)-amine, 6 -Methoxyhexamethylenezamine, 1,2-bis(6-aminopropyl)ethane, bis(3-aminopropyl)sulfide, 1,4-cyclohexanediamine, bis(4-aminocyclohexyl)methane, m-phenylenediamine , p-phenylenediamine, 2,4-noaminotoluene, 2,6-noaminotoluene, m-xylylenediamine, p-xylylenediamine, pentunone, 5,3'-
trimethylbentunone, 3,3'-nomethoxypennonone, 1,6-noaminonaphthalene, 4,4'-diaminodiphenylmethane, 4,4'-noamino-diphenylpropane, 2,4-bis-(β -amino-1-butyl)toluene, bis(p-β-methyl-〇-aminophenyl)benzene, 1,3-diamino-4-isozolobylbenzene, 4,4'-noaminodiphenylsulfone, 4
゜4'-noaminonophenyl ether and bis(ro-aminoprobyl)tetramethylnosiloxane. Mixtures of these diamines may also be used.

Aromatic diamines, especially m-phenylenediamine and 4,4
'-Soaminosophenylmethane is a special case.

In the reagent (B) (carboxylic acid anhydride) defined by general formula (n), V is a hexavalent aliphatic group usually containing about 2 to 20 carbon atoms, preferably about 6 to 20 carbon atoms. It is a hexavalent aromatic group containing an atom. Examples of carboxylic anhydrides include trimellitic anhydride, 5-chlorotrimellitic anhydride, benzene-1,2,31-carboxylic anhydride, and carboxysuccinic anhydride.

Preferred carboxylic anhydrides are those in which R2 is aromatic, especially an aromatic hydrocarbon group. Most preferred is trimellitic anhydride.

In the reagent (C) (dianhydride) defined by the general formula ([1)], R3 is a tetravalent radical completely similar to that described above regarding R1 and R2. Yoneyama Patent No. 4.061,6
No. 22 and No. 4,331,799 disclose many suitable anhydrides, and the reader is referred to the disclosures of both patents. A particularly preferable group of anhydrides represented by the general formula (III) is one in which R3 is C, where R4 is oxygen, chlorous acid, -5on-1 lower alkylene (lower here means having 7 or less carbon atoms) or preferably -0-R'-0- (wherein a is a divalent aromatic hydrocarbon group). R
In most cases, 5 is a divalent group derived from benzene or substituted benzene, biphenyl or substituted biphenyl, or nophenylalkane which may have a substituent on one or both aromatic groups. The following groups are preferable as R5.

[In the formula, R6 is each independently hydrogen or methyl, n,
7 is a straight or branched alkylene containing 1 to 5 carbon atoms, often impropylidene, and each Y is independently hydrogen or (usually chlorine or bromine) ] It is also conceivable to use a mixture of these compounds. The most preferred is bisphenol A
, 2'-his(4-hydroxyphenyl)-propane)
It is a group derived from , and by removing both hydroxyl groups therefrom, it has a structure in which R7 of formula (VIII) is impropylidene and Y is hydrogen. Then,
The most preferred anhydride used as reagent C is 2,2
'-bis(4-(3,4-socaldexyphenoxy)phenyl)pro/anhydride, hereinafter referred to as bisphenol A anhydride.

The reaction to make the prepolymers of this invention usually involves simply a reagent (A
), (B) and (C) are mixed and heated to a temperature at which the reaction occurs. Reactions with two anhydrides (i.e., sharing of reagents (B) and (C)) may be simultaneous or sequential (i.e., first adding reagent (C) and then (B)).
) may be added. However, since adding them sequentially does not have the advantage of adding them separately, simultaneous addition is usually preferred.

The reaction temperature is typically in the range of about 100-200°C, and at least slightly above about 160°C to ensure removal of reaction water and complete imidization of the amic acid produced. is good.

It is usually convenient to carry out the reaction in a substantially inert organic diluent. Typical diluents are aprotic solvents such as benzene, toluene, xylene, O-nochlorobenzene, trimethylformamide, dimethylacetamide, trimethylsulfoxide, or N-methyl-pyrrolidone.

A factor in the formation of a prepolymer is that the intramolecular anhydride and the carboxylic acid moiety differ in their reactivity with the reagent. The reaction of Noami/ with the anhydride moiety in the molecule is highly preferential to that with the carboxylic acid moiety. This selectivity ensures the production of caloxy-terminated prepolymers. It is often preferred to contain a catalytic amount of at least one aliphatic, cycloaliphatic or heterocyclic tertiary amine in the reaction mixture. Suitable amines include triethylamine, N-methylbiperinone, and 4-tumethylaminopyridine. The amount of 6th amine required is small and is typically used as a reagent (Al,
(B), (approximately 0.05-0 based on the total amount of C1
．． It is 5% by weight.

The molecular weight of the prepolymer intermediate depends to a large extent on the molar ratio of reagents (C) and (B), with higher molecular weight prepolymers obtained as the ratio of reagent (C1 to Bl) increases. The molar ratio of (C) is at least about 0.
25 is within the scope of this invention. This molar ratio is at least 0
．． A ratio of 5 is preferred because lower ratios result in prepolymers having portions consisting only of reagents (A) and (B). Although there appears to be no upper limit to this molar ratio, there is usually no particular advantage to increasing it above about 5.

The proportion of reagent (A) in the reaction mixture is determined to such an extent that a carboxy-terminated prepolymer is produced. That is, the ratio of the equivalent of reagent to the anhydride equivalent of the mixture of reagents (Bl and (C)) is about 1:1, typically about 0.95 to 1.05:
This is achieved using a ratio of 1. Here, "anhydride equivalent" depends on the number of anhydride groups theoretically present per molecule, and free carboxylic acid groups are not included in the number. So 1
Moles of reagent (Bl and (C) have 1 and 2 anhydride equivalents, respectively. 1 mole of reagent (A) has 2 equivalents since there are two amine groups per molecule. Under these conditions, anhydride Only the chemical groups react with the reagent (A), and the free carboxy groups become terminal groups in the prepolymer.

The structural formula of the prepolymer of this invention is as follows.

(In formula 1-3 are as described above) In formula (IX), the value of n is theoretically twice the molar ratio of reagent fcl and component (Bl). The molar ratio is 025:1
Since it varies from 5:1 to 5:1, the average value of n is 0.5 to 1.
0, preferably at least 1. formula (rx)
The prepolymers shown are embodiments of this invention.

〔Example〕

The preparation of the prepolymer of this invention will be explained below with reference to Examples. All parts represent parts by weight.

Example 1-6 192 mmol (0.1 mol) of trimellitic anhydride [reagent (
B)] and bisphenol sonohydrate [Reagent (C)], and the stoichiometric Ji in terms of the anhydride equivalents of Reagents (B) and (C).
(D m-7 22 diamine (MPD) or 4.
A mixture of 4'-diaminodiphenylmethane (MDA) (reagent), 0.01 parts of 4-methylaminopyrinone, 30 parts of N-methylpyrrolidone, and 47 parts of toluene were gradually heated to 160 °C. During this time, the mixture became homogeneous and distillation of toluene-water azeotrope began. Heating was continued to about 180°C while water was removed by distillation. The residue was a solution of the desired prepolymer. Table 1 shows reagent names, ratios, etc. related to Examples 1-6.
- indicates evening.

I MPD 0852
MPD 0.255 MPD
1.04 MDA 0
．． 5S MDA 1.0 To produce the polyamideimide of this invention, the prepolymer or its functional derivative [reagent (D)] is reacted with a reagent (E) which is a diisocyanate or a diamine. If the reagent (Dl is the prepolymer itself), the lyamide-imide formation reaction proceeds very effectively when the reagent (El) is a noisocyanate, and one carboxylic acid moiety and one isocyanate moiety are condensed to form one mole of carbon dioxide. Since the reaction of the corresponding carginic acid with an amine is somewhat slow and difficult, the reagent (if El is cyamine, the reagent (D) is a functional derivative of the prepolymer, e.g. its halocyanate). It is preferable to use acyl. However, when the polyamideimide is used for electrical purposes and the presence of haloke9 ion is harmful, or because of the ease of production, it is preferable to use acyl.
Preference is given to the reaction of prepolymers with noisocyanates.

Although neuisocyanate is often referred to as reagent (E) in the following description, it is to be understood that cyamine can be substituted under appropriate conditions.

Reagents suitable for use as El are given by the formula (■ and (Jl
) are noisocyanate and noamine, respectively. In these formulas, R4 is the same 2 as R1 in general formula (2).
It may be a valent hydrocarbon group, and may be the same as or different from RI. If the reagent (El is a noamine), each of R5 and R6 may be independently hydrogen or a lower hydrocarbon group, preferably a hydrocarbon group, and even more preferably a lower alkyl (especially methyl) group. R5 and R6 are other than hydrogen. In this case, an N-substituted amide bond is formed by reaction with the acid moiety in the sag polymer.Of course, such a bond is not formed when the reagent (El) is a noisocyanate.

Examples of suitable noamines for use as reagent (E) include those listed above in connection with the reagent carrier, and at the same time, e.g.
, N'-tumethyl compounds. An example of a noisocyanate is p-phenylene noisocyanate, 2.4
-Toluene diisocyanate, 2,6-toluene diisocyanate, quizylene diisocyanate, menothylene diisocyanate, durennoisocyanate, 4-methoxy-1,3-phenylenenoisocyanate, 4-chloro-1,3-phenylenenoisocyanate isocyanate, 4-isozorobyl-1,5-phenyle/soisocyanate, toluene diisocyanate, noaninonnoincyanate), 4
．． 4'-methylenebis(phenylisocyanate), 4
゜4'-methylenebis(o-tolyl isocyanate),
4.4'-methylenebis(cyclo-1xyl isocyanate), 1.5-su7thalene diisocyanate 1-14.
4'-bis(incyanatophenyl)ether, 2
, 4'-bis(isocyanatophenyl)ether and 4,4'-bis(incyanatophenyl)sulfone. Mixtures of cyanocyanates may also be used. Preferred noncyanates in terms of availability, low cost, and particularly suitable for the preparation of the polyamideimide of the present invention are:
2,4-Toluene diisocyanate (2゜4-TDI
), 2,6-torninnoisocyanate) (2,6-
TDI) and 4,4'-methylenebis(phenylisocyanate) (MDI).

The reagent (El may be a isocyanate or amine-terminated polymer such as polyamide or polyurethane. In such a case it is a polymeric group and the product is a polyurethane or similar block linked by amide bonds, polyamide and polyimide. Blockzukasu Martonal.

For the preparation of copolyamideimide, a mixture of reagents (D) and fB) is heated, usually at a temperature in the range of about 150 DEG to 225 DEG C., until carbon dioxide evolution is complete.

The reaction is accomplished in a substantially inert organic diluent as described above for the formation of the prepolymer.

Preferred diluents for polymer production are trimethylformamide, dimethylacetamide, trimethylsulfoxide, N
- dipolar aprotic solvents such as methylpyrrolidone.

Equivalence ratio of reagent (DJ and reagent (E) (each equivalent value is,
half of the molecular weight) is varied according to the desired polymer molecular weight. Roughly speaking, ratios between about 0.5:1 and about 2:1 are conceivable;
The I-mer dimensions fr are the minimum and maximum values that yield products containing diincyanate-derived units. A ratio of about 0.67:1 to about 1.5:1 is preferred, resulting in a high molecular weight product. Most preferred is a ratio of about 1:1.

The reaction between the reagents (Di and (El) usually does not proceed completely, and the free acid in the reaction mixture is analyzed after the initial reaction, and the results reduce the residual acid content to about 1% or less. It is often desirable to additionally add an effective amount of reagent (El).

Approximately 10% by weight of the original amount of reagent (E) is often required for this purpose. Then, the reagent (Di
It is particularly preferred that the equivalent ratio of E1 and reagent (El) is between about 0.9:1 and about 1:1. It is also conceivable to incorporate small amounts of chain terminators or terminating agents into the reaction mixture; Typical are monoisocyanates such as phenyl isocyanate, monoamines such as aniline, monocarboxylic acids such as benzoic acid, or monoanhydrides such as phthalic anhydride.

The copolyamideimide of this invention has the general formula (wherein B1-1
1 and n are as defined above). However, this structure is well defined by the molecular certainty as well as the method of its preparation. The copolyamideimide of this invention typically has a weight average molecular weight of from about 3.000 to about 150.000. The intrinsic viscosity measured in dimethylformamide at 25°C is approximately 0.2-0.9 dllj? The method for producing the copolyamideimide of the present invention will be described below with reference to Examples.

Example 7 An equivalent mixture of the brepolymer solution of Example 1 and 2.4-1 luene diincyanate was prepared at room temperature and heated slowly to about 180° C. over a period of 6 hours while being heated to a vigorous carbon dioxide concentration. occurred, and the solution viscosity increased significantly. After cooling the solution, it was dissolved in trimethylformamide and poured into methanol to cause precipitation. The copolyamideimide was filtered off and dried in a vacuum oven. Its intrinsic viscosity is 0.53d
The glass transition temperature was 265°C in l/l.

Example 8-17 Compared to 0.1 of the prepolymer of Example 1-6, 0.
50 d − of 1 equivalent of diisocyanate.

-Dichlorobenzene solution t- Gradually added at 150-190°C. After the generation of carbon dioxide had ended, the amount of free acid present was determined by titration, and the calculated amount of diisocyanate necessary to neutralize the acid was added. The polymer was then precipitated as in Example 7 and dried. The physical properties and detailed compositions of the products of Examples 8-17 are shown in Table 2. All percentages are by weight. Heat distortion temperature (HDT) is A8T
The weight average molecular weight is 9 as determined by Dull permeation chromatography.

The copolyamideimide of the invention can be processed into packaging and packaging films and molding compositions. Another use is in the form of a solution as an insulating coating for electrical conductors made of copper, aluminum, etc., especially electric wires. If desired, the insulated conductor may be further coated with polyamide, polyester, silicone, polyvinyl formal, epoxy resin, polyimide, polytetrafluoroethylene, or the like.

Patent applicant General Electric Kan Yanii sub-agent Tadashi Wakabayashi

Claims (1)

[Claims] (1) General formula H_2N-R^1-NH_2...
...At least one diamine (A) represented by (I) (in the formula, R^1 is a divalent hydrocarbon group) is expressed by the general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼...・・・・・・
(II) (In the formula, R^2 is a trivalent hydrocarbon group) At least one carboxylic acid anhydride (B) and general formula ▲ Numerical formula, chemical formula, table, etc. ▼... ...
(III) reacting with at least one di-acid anhydride (C) represented by (in the formula, R^3 is a tetravalent hydrocarbon group) under conditions such that all reaction water is removed; During the reaction, reagent (B)
The molar ratio of reagent (C) to reagent (C) is at least about 0.25, and the ratio of equivalents of reagent (A) to acid anhydride equivalents of reagents (B) and (C) combined is about 1:1. A method for producing a carboxy-terminated prepolymer comprising a process. (2) R^1 is an aromatic hydrocarbon group containing about 6 to 20 carbon atoms or a halogenated group thereof, or about 2
an alkylene or cycloalkylene group containing from about 20 carbon atoms, or a bis-alkylene-poly(dialkylsiloxane) group, and R^2 and R^3 are each independently an aromatic group containing about 6 to 20 carbon atoms. 2. The method according to claim 1, wherein the reaction mixture contains a catalytic amount of at least one tertiary amine. (3) R^5 is ▲ There are mathematical formulas, chemical formulas, tables, etc. is any one of divalent aromatic hydrocarbon groups] The manufacturing method according to claim 2. (4) The reagent (B) is trimellitic anhydride, the reagent (C) is bisphenol dianhydride, and the reagent (
4. The method of claim 3, wherein the molar ratio of reagent (C) to B) is at least about 0.5. (5) The manufacturing method according to claim 4, wherein R^1 is an aromatic hydrocarbon group. (6) The reagent (A) is m-phenylenediamine, m-
The manufacturing method according to claim 5, which is either toluenediamine or 4,4'-diaminodiphenylmethane. (7) General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (IX) (In the formula, R^1 is a divalent hydrocarbon group, and R^2 is 3
R^4 is a tetravalent hydrocarbon group, and the average value of n is at least 0.5. (8) R^1 is an aromatic hydrocarbon group containing about 6 to 20 carbon atoms or a halogenated group thereof, or about 2
to 20 carbon atoms, or an alkylene or cycloalkylene group, or a bis-alkylene-poly(dialkylsiloxane) group, and R^2 and R^3 are each independently about 6
8. The prepolymer according to claim 7, which is an aromatic hydrocarbon group containing 20 to 20 carbon atoms. (9) R^3 is ▲ There are mathematical formulas, chemical formulas, tables, etc. 9. The prepolymer according to claim 8, which is any one of valent aromatic hydrocarbon groups). (10) Claims in which R^2 is ▲There is a mathematical formula, chemical formula, table, etc.▼, R^3 is ▲There is a mathematical formula, chemical formula, table, etc.▼, and the average value of n is at least 1. Prepolymer according to item 9. (11) The prepolymer according to claim 10, wherein R^1 is an aromatic hydrocarbon group. (12) R^1 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
The prepolymer according to claim 11, which is either ▲ has a mathematical formula, chemical formula, table, etc. ▼ or ▲ has a mathematical formula, chemical formula, table, etc. ▼. (13) General formula H_2N-R^1-NH_2...
・(I) (In the formula, R^1 is a divalent hydrocarbon group)
At least one diamine (A) represented by the general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) (In the formula, R^2 is three hydrocarbon groups) At least one carboxylic acid anhydride (B) and general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼・・・・・・
(III) (In the formula, R^3 is a tetravalent hydrocarbon group) is reacted with at least one dianhydride (C) under conditions where all the reaction water is removed; The molar ratio of reagent (C) to reagent (B) during the reaction is at least about 0.25, and the ratio of the equivalents of reagent (A) to the anhydride equivalents of reagents (B) and (C) combined. A carboxy-terminated prepolymer (D) is produced by adjusting the ratio to about 1:1, and the prepolymer (D) is converted into a diiso-terminated prepolymer (D) represented by the general formula OCN-R^4-NCO (IV). Cyanate and general formula R^5NH-R^4
-NHR^6...Diamine represented by (V) (in the formula R
^4 is a divalent hydrocarbon group or a polymeric group,
A method for producing a copolyamide-imide, which comprises reacting with at least one (E) of R^5 and R^6 each independently hydrogen or a lower hydrocarbon group. (14) The reagent (E) is at least one diisocyanate, and R^1 and R^4 are each independently about 6 to 2
either an aromatic hydrocarbon group or a halogenated group thereof containing 0 carbon atoms, or an alkylene or cycloalkylene group containing about 2 to 20 carbon atoms, or a bis-alkylene poly(dialkylsiloxane) group , R^2 and R^3 are each independently an aromatic group containing about 6 to 20 carbon atoms, and the equivalent ratio of prepolymer (D) to reagent (E) is about 0.67:1. or about 1.5:
1. The manufacturing method according to claim 13, which is (15) Each of R^1 and R^4 is an aromatic hydrocarbon group, R^2 is ▲ has a mathematical formula, chemical formula, table, etc. ▼, and R^3 is ▲ has a mathematical formula, chemical formula, table, etc. ▼ The method according to claim 14. (16) The reagent (E) is 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and 4-toluene diisocyanate.
, 4'-methylenebis(phenylisocyanate). (17) General formula▲ Numerical formulas, chemical formulas, tables, etc.▼・・・・・・(X) (In the formula, R^1 and R^4 are each independently a divalent hydrocarbon group, and R^ 2 is a trivalent hydrocarbon group, R^3
is a tetravalent hydrocarbon group, R^5 and R^6 are each independently hydrogen or a hydrocarbon group, and the average value of n is at least 0.5) copolyamideimide consisting of (18) R^1 and R^4 are each independently an aromatic hydrocarbon group containing about 6 to 20 carbon atoms or a halogenated group thereof, or an alkylene group containing about 2 to 20 carbon atoms; cyclo-alkylene or bis-alkylene poly(dialkylsiloxane) groups, R^2 and R^3 are each independently an aromatic group containing about 6 to 20 carbon atoms, and 18. The copolyamide-imide of claim 17, wherein each of R^5 and R^6 is hydrogen. 1. R^1 and R^4 are each independently an aromatic hydrocarbon group, and R^2 has a ▲ mathematical formula, chemical formula, table, etc. ▼, R^
The copolyamide-imide according to claim 18, wherein 3 is ▲a mathematical formula, a chemical formula, a table, etc.▼, and the average value of n is at least 1. (20) The copolyamideimide according to claim 19, wherein R^4 is at least one of 2,4-tolylene, 2,6-tolylene, and 4,4'-methylenebis-phenyl group.