JPH0320327A - Production of thermoplastic resin composite - Google Patents

Abstract

PURPOSE:To obtain the subject composite having excellent heat resistance characteristic of an aromatic condensation polymer and improved processability by polycondensing a starting monomer in a solution of a soluble polymer in an organic solvent to form an aromatic condensation polymer insoluble in the solvent. CONSTITUTION:An aromatic dicarboxylic acid and an aromatic diol, or an aromatic dicarboxylic acid, an aromatic diamine, an aromatic aminocarboxylic acid or the like are polycondensed in the presence of a catalyst, or an aromatic dicarboxylic dihalide and an aromatic diol, or an aromatic dicarboxylic dihalide and an aromatic diamine as starting monomers are polycondensed in the absence of any catalyst in a solution of a soluble polymer in an organic solvent (e.g. a solution of a polyarylate in a mixed chloroform/pyridine solvent) to form an aromatic polyester or an aromatic polyamide insoluble in the solvent. In this way, a thermoplastic resin composite composed of a homogeneous mixture of the polymer soluble in the solvent with the aromatic condensation polymers insoluble in the solvent can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a thermoplastic resin composite containing an aromatic condensation polymer and a method for producing the same.

Specifically, in a solution of a soluble polymer compound dissolved in an organic solvent, the corresponding raw material monomers are subjected to a condensation polymerization reaction,
The present invention relates to a thermoplastic resin composite formed by producing and containing an aromatic condensation polymer such as an aromatic polyester or an aromatic polyamide, and a method for producing the same.

[Prior art]

Aromatic condensation polymers (hereinafter sometimes abbreviated as rigid polymers) such as aromatic polyesters and aromatic polyamides are used for various purposes as heat-resistant resins.

However, these rigid polymers have a common problem that they have a high softening point and are insoluble in common solvents, resulting in poor processability.

On the other hand, among various other resins, some have shortcomings in properties such as heat resistance, rigidity, dimensional stability, and water absorption.

Therefore, there is a strong demand for a resin that improves the disadvantages of such resins, improves the processability of rigid polymers, compensates for the disadvantages of both, and expands its applicability.

It is difficult to satisfy such demands with a single polymer. Therefore, various mixed resins have already been proposed in which rigid polymers are mixed with different types of resins, thereby eliminating the disadvantages of each type and making the most of their advantages.

Among these proposals, as a method of mixing resins, (
1) A melt-kneading method in which two or more resins are physically melted and mixed using various mixers, (2) a method in which the resins to be mixed are dissolved in a common solvent and mixed in the solvent, and (3) ) A method in which one base polymer resin is polymerized into the other resin, and (4) a method in which another polymer is bonded to the base polymer.

However, aromatic polyesters and aromatic polyamides are extremely rigid, have relatively high crystallinity, and have very high plasticization temperatures, making them incompatible with other resins, especially polymers with low plasticization temperatures and low melt viscosities. They have a common property of being extremely difficult to mix. Such properties are a serious problem in the above-mentioned mixture mw.

Because of these problems, among the mixing methods that have been proposed, a method in which raw monomers are condensed in the polymer matrix to be mixed without using a solvent to produce an aromatic condensation polymer has been proposed. Even if applied, this method does not have a sufficient effect of improving the physical properties of the mixed raw materials.

That is, in this method, the condensation conditions for obtaining the aromatic condensation polymer are harsh, and the polymer used as the matrix decomposes, but the molecular weight of the aromatic condensation polymer produced is low and sufficient physical property improvement effects are not achieved. There was a problem.

On the other hand, the method of dissolving an aromatic condensation polymer in a solvent and producing a matrix polymer through polymerization requires only special solvents, is expensive, and is hardly expected to improve physical properties. There was a problem.

[Problem to be solved by the invention]

The object of the present invention is to improve the processability of aromatic condensation polymers, such as aromatic polyesters or aromatic polyamides, without impairing their inherent properties, i.e., to improve the excellent heat resistance inherent to aromatic polyesters or aromatic polyamides. An object of the present invention is to provide a thermoplastic resin composite having the same properties and improved processability, and a method for producing the same.

[Means to solve the problem]

The present inventors have made extensive studies on a method for solving the above problems and producing a thermoplastic resin composite with good physical properties. As a result, it was discovered that by producing aromatic polyester or aromatic polyamide using a specific method, a thermoplastic resin composite containing aromatic polyester or aromatic polyamide with excellent physical properties can be obtained, and the present invention has been completed. I ended up doing it.

That is, the present invention provides a thermoplastic resin composite and a thermoplastic resin composite characterized in that raw monomers are subjected to condensation polymerization in a solution in which a soluble polymer is dissolved in an organic solvent to produce an aromatic condensation polymer that is insoluble in the solvent. This is the manufacturing method.

More specifically, in the present invention, in a solution in which a soluble polymer is dissolved in an organic solvent, (1) in the presence of a catalyst, (1) an aromatic dicarboxylic acid and an aromatic diol; (2) an aromatic dicarboxylic acid and an aromatic diol; and aromatic hydroxycarboxylic acid, or (1) condensation polymerization using aromatic hydroxycarboxylic acid as a raw material monomer or in the absence of a catalyst, (2) using aromatic dicarboxylic acid dihalide and aromatic diol as raw material monomers. (2) In the presence of a catalyst, (2) aromatic dicarboxylic acid and aromatic diamine; (2) aromatic dicarboxylic acid, aromatic diamine and aromatic aminocarboxylic acid; or ■ Insoluble in the solvent produced by condensation polymerization using an aromatic aminocarboxylic acid as a raw material monomer, or in the absence of a catalyst, or ■ using an aromatic dicarboxylic acid dihalide and an aromatic diamine as raw material monomers. A thermoplastic resin composite comprising an aromatic polyamide, an aromatic condensation polymer, and a method for producing the same.

The method of the present invention will be explained below.

In the method of the present invention, a polymer (
The soluble polymer (hereinafter referred to as soluble polymer) is not particularly limited and can be used as long as it is soluble in a reaction solvent suitable for producing a rigid polymer and under reaction conditions.

Such resins include polyolefin polymers,
Examples include aromatic vinyl polymers, polyamide polymers, polyester polymers, polycarbonates, polyphenylene oxides, acetal resins, and polysulfones.

More specifically, for example, polyolefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, aromatic vinyl polymers such as polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, and nylon. Polyamide-based polymers such as ethylene glycol-terephthalic acid copolymer, polyester-based polymers such as butylene glycol-terephthalic acid copolymer, polycarbonate produced by the reaction of bisphenol A and phosgene, etc., and polycarbonate with a substituent at the ortho position. Examples include polyphenylene oxide obtained by polycondensing phenols such as 2,6-xylenol, acetal resin having a polyoxymethylene structure obtained by polymerizing formaldehyde, and boris sulfone. Particularly preferred are those that have good compatibility with rigid polymers.

The concentration of the soluble polymer in the solution is usually 0.1 to 50
% by weight. However, it is not particularly limited to this range as long as there is no particularly unfavorable effect on removal of the solvent, mixing and stirring, etc.

The monomers used as raw materials for the rigid-rigid polymer in the method of the present invention are as follows.

Aromatic dicarboxylic acids include benzene, naphthalene,
biphenyl, diphenyl ether, diphenyl ketone,
Compounds in which two hydrogen atoms of an aromatic compound such as phenanthrene are replaced with carboxy groups, and other nuclear substituted derivatives in which some or all of the hydrogen atoms are substituted with hydrocarbon residues, alkoxy groups, nitro groups, halogen atoms, etc. etc.

Typical compounds include dicarboxybenzene, dicarboxynaphthalene, dicarboxybiphenyl, dicarboxybenzophenone, and the like.

Aromatic dicarboxylic acid dihalides are those in which the carboxy group of these aromatic dicarboxylic acids has become a carboxy dihalide, and typical compounds include dihaloformylbenzene, dihaloformylnaphthalene, and dihaloformyl biphthalene. Examples include enyl, dihaloformyl benzophenone, and the like.

Aromatic diols include compounds in which two hydrogen atoms of an aromatic compound such as benzene, naphthalene, biphenyl, diphenyl ether, diphenyl ketone, and phenanthrene are replaced with hydroxy groups, and other compounds in which some or all of the hydrogen atoms are hydrocarbon residues. , nuclear substitution derivatives substituted with alkoxy groups, nitro groups, halogen atoms, etc.

Representative compounds include dihydro-axybenzene, dihydroxynaphthalene, dihydroxybiphenyl, dihydroxybenzophenone, and the like.

Aromatic diamines include compounds in which two hydrogen atoms of an aromatic compound such as benzene, naphthalene, biphenyl, diphenyl ether, diphenyl ketone, and phenanthrene are replaced with amino groups, and other compounds in which some or all of the hydrogen atoms are hydrocarbon residues. These include nuclear-substituted derivatives substituted with groups, alkoxy groups, nitro groups, halogen atoms, etc.

Representative compounds include diaminobenzene, diaminonaphthalene, diaminobiphenyl, diaminobenzophenone, and the like.

In addition, aromatic hydroxycarboxylic acids include benzene,
Compounds in which two hydrogen atoms of an aromatic compound such as naphthalene, biphenyl, diphenyl ether, diphenyl ketone, and phenanthrene are replaced with a hydroxy group and a carboxy group, and other hydrogens in which some or all of the hydrogen atoms are hydrocarbon residues or alkoxy groups , nuclear substitution derivatives substituted with nitro groups, halogen atoms, etc.

Typical compounds include hydroxybenzene,
Examples include hydroxylupoxynaphthalene, hydroxycarboxybiphenyl, and hydroxycarboxybenzophenone.

Furthermore, aromatic aminocarboxylic acids include benzene,
Compounds in which two hydrogen atoms of an aromatic compound such as naphthalene, biphenyl, diphenyl ether, diphenyl ketone, and phenanthrene are replaced with an amino group and a carboxyl group, and other compounds in which some or all of the hydrogen atoms are hydrocarbon residues, alkoxy groups, These include nuclear-substituted derivatives substituted with nitro groups, halogen atoms, etc.

Representative compounds include aminocarboxybenzene, aminocarboxynaphthalene, aminocarboxybiphenyl, aminocarboxybenzophenone, and the like.

In the case of aromatic dicarboxylic acid and aromatic diol, or aromatic dicarboxylic acid and aromatic diamine, the molar ratio of these monomers is approximately 1:1.

Furthermore, when aromatic hydroxycarboxylic acid or aromatic aminocarboxylic acid is used, it can be used in any amount.

In addition, aromatic hydroxycarboxylic acids or aromatic aminocarboxylic acids alone may be used. Furthermore, if necessary, aliphatic dicarboxylic acids, aliphatic diols, Aliphatic diamines, aliphatic hydroxycarboxylic acids, and aliphatic aminocarboxylic acids may be used in combination. In this case, the amounts used are aromatic dicarboxylic acid and aromatic dicarboxylic acid and/or aromatic hydroxycarboxylic acid,
Or aromatic dicarboxylic acid and aromatic diamine and/or
Alternatively, it can be used up to about twice the mole of the total amount of aromatic aminocarboxylic acids. Exceeding this amount is not preferred because the resulting composite loses the original characteristics of a rigid polymer.

What is important in the method of the present invention is that the aromatic polyester or aromatic polyamide produced by condensation polymerization of the raw material monomers is insoluble in the solvent used under the reaction conditions.

Therefore, the solvents to be used include aromatic hydrocarbons,
Halogenated hydrocarbons are preferred. Among these organic solvents, one may be selected and used that dissolves the soluble polymer used as the matrix but does not dissolve the aromatic polyester or aromatic polyamide to be produced.

As the catalyst used in the present invention, various catalysts that promote the formation of ester bonds or amide bonds can be used, and particularly preferred are dichloride of triphenylphosphine, or triphenylphosphine or a ring-substituted derivative thereof. These catalysts are often used to form ester bonds from hydroxy groups and carboxy groups at relatively low temperatures.

In the production of aromatic polyester or aromatic polyamide according to the method of the present invention, there are no particular restrictions on the detailed conditions for using the triphenylphosphine dichloride or the mixture of triphenylphosphine dichloride or its nucleocyclic substituted derivative and the polyhalogen compound; For example, J.O.U.
RNAL OF POLYMERSCIENCE PO
LYMER CHEMISTRY t! DITION
The conditions disclosed in VOL 22 2705 (1984) as a method for producing triphenylphosphine dichloride and a method for producing aromatic polyester using the same can be applied.

In addition, in the method of the present invention, it is preferable to use a solvent such as a halogenated hydrocarbon or an aromatic hydrocarbon as at least a part of the solvent, and to use a deoxidizing agent such as triethylamine, triphenylamine, or pyridine in combination, which is more effective. Aromatic polyesters or aromatic polyamides can be produced automatically.

The reaction temperature is usually in the range of 0 to 250°C, and if the condensation polymerization reaction is carried out at a temperature below the boiling point of the reaction solvent, aromatic polyester or aromatic polyamide can be produced without using special equipment such as a pressure vessel. It is possible to do so. Usually at room temperature! The reaction proceeds satisfactorily.

In the method of the present invention, the catalyst is used, for example, in a halogenated hydrocarbon solvent, triphenylphosphine is converted to triphenylphosphine dichloride using various chlorinating agents; Using i-sphine and polyhalogen compounds directly, in the presence of these catalysts and amines as deoxidizing agents, ■ aromatic dicarboxylic acids and aromatic diols, ■ aromatic dicarboxylic acids, aromatic diols, and Aromatic hydroxycarboxylic acid, or ■ aromatic hydroxycarboxylic acid, or ■ aromatic dicarboxylic acid and aromatic diamine, ■ aromatic dicarboxylic acid, aromatic diamine, and aromatic aminocarboxylic acid, or ■ condensation of aromatic aminocarboxylic acid. An example is an embodiment in which an aromatic condensation polymer is produced by a polymerization reaction.

In the method of the present invention, if an aromatic dicarboxylic acid dihalide is used instead of an aromatic dicarboxylic acid, an aromatic condensed polymer can be produced without using a catalyst such as triphenylphosphine dichloride. . In this case, if aromatic dicarboxylic acid dihalide is used as a raw material monomer instead of aromatic dicarboxylic acid, an aromatic condensation polymer can be produced under the same reaction conditions as described above in the absence of a catalyst.

In the thermoplastic resin composite produced by the method of the present invention, there is no particular restriction on the quantitative ratio of the soluble polymer to the aromatic condensation polymer, and a preferable range can be selected depending on the intended use of the resin composite. . Usually, for 100 parts by weight of soluble polymer, aromatic condensation polymer i-to
It is about ooo parts by weight.

For example, if the purpose is to improve the impact resistance of aromatic polyester or aromatic polyamide, a relatively small amount of soluble polymer is used, and even if the purpose is to improve the rigidity and heat resistance of the soluble polymer. For example, a relatively small amount of aromatic condensation polymer may be used.

In the method of the present invention, after completion of the condensation polymerization reaction, a thermoplastic resin composite containing a soluble polymer and an aromatic condensation polymer is separated from a mixture of a soluble polymer, an aromatic condensation polymer, a solvent, etc. There is no particular restriction on the method, and examples include a method of removing the solvent by evaporation, and a method of adding a poor solvent for both the soluble polymer and the aromatic condensation polymer to precipitate and separate the thermoplastic resin composite. By performing such separation step or molding after separation, a molded thermoplastic resin composite with good physical properties can be obtained.

〔Effect of the invention〕

According to the method of the present invention, a thermoplastic resin composite containing a uniform mixture of a solvent-soluble polymer and a solvent-insoluble aromatic condensation polymer can be obtained.

The method of the present invention easily produces and provides a thermoplastic resin composite with excellent physical properties, and is extremely valuable industrially.

〔Example〕

EXAMPLES The present invention will be explained in more detail with reference to Examples below.

Example 1 14.4 g of polyarylate (Ardl00: polycondensate of isophthalic acid dichloride, terephthalic acid dichloride 50:50, and bisphenol A, manufactured by Amoco) was dissolved in a mixed solvent of chloroform 1501 nI and pyridine 50, and then p - After dissolving 5.5 g of aminobenzoic acid and 12.6 g of triphenylphosphine, a solution of 14.2 g of ethane dissolved in 50% chloroform was added and stirred at 25°C for 10 hours, followed by l5CI.
After casting to a size of IIX15an and removing the solvent by drying, the film was thoroughly washed with a mixed solvent of methanol and acetone (1:l) and further dried to obtain a composite film. The tensile yield strength and tensile modulus of this film are 2
When measured at 3℃, 100℃, and 150℃, the results were 3.8, 21G (at 23℃), 2.5, and 130 (at 100℃), respectively.
), 1.45, 110 (150°C) kg/mm”.

Comparative Example 1 Polyarylate was dissolved in chloroform, and then a film was obtained in the same manner as in Example 1. The physical properties of the obtained film are tensile yield strength and tensile modulus of 4.2, 180 (23°C), and 2.0, respectively.
, too (100°C), 0.74, 28 (150"
C) kg/mm! Met. In addition, p-aminobenzoic acid was polycondensed in the absence of polyester to prepare a polyamide dispersion solution, and polyarylate was dissolved in it and cast in the same manner to produce a film and its physical properties were measured. .8, 190 (23℃), 2.1S105 (1
00℃), 0.80, 40 (150℃) kg/mm”
Therefore, almost no reinforcing effect was obtained.Example! The result is that the physical properties, especially at high temperatures, are inferior compared to that of .

Example 2 4-hydroxy- in place of 5.5 g of p-aminobenzoic acid
4゜-carboxy 1. The same procedure as in Example 1 was carried out except that 6 g of l-biphenyl was used. Physical properties are 4.3 and 2, respectively.
20 (23℃), 2.3, 140 (100℃), 1.3
, 60 (150°C) kg/mm”.

Comparative Example 2 A composite was prepared in the same manner as in Example 2 using the same procedure as in Comparative Example 1, in which an aromatic polyester dispersion was synthesized without first dissolving the polyarylate, and then the polyarylate was dissolved. are 3.8 and 185, respectively (
23℃), 2.2, 100 (100℃), 0.75, 3
5 (150° C.) kg/mm”, hardly any reinforcing effect was obtained, and compared to Example 2, the physical properties especially at high temperatures were inferior.

Example 3 Hydroquinone 5 was replaced with 5.5 g of p-aminobenzoic acid.
．． The same procedure as in Example 1 was carried out, except that 5 g of terephthalic acid dichloride and 8.95 g of terephthalic acid dichloride were used, and triphenylphosphine and hexachloroethane were not used.

The physical properties are 4. L 220 (23°C), 2. L 1
60 (100℃), 1.4, 120 (150℃) kg
/mo+”.

Comparative Example 3 A composite was prepared in the same manner as in Example 3 using the same procedure as in Comparative Example 1, in which an aromatic polyester dispersion was synthesized without first dissolving the polyarylate, and then the polyarylate was dissolved. are 3.8 and 185, respectively (
23℃>, 2.2, 100 (100℃), 0.75, 3
5 (150°C) kg/mm', hardly any reinforcing effect was obtained, and the physical properties at high temperatures were inferior compared to Example 3.

Example 4 The same procedure as Example 2 was performed except that polycarbonate (trade name Panlite, Teijin Kaseiichi 12) was used instead of polyarylate, and the physical properties were 4.3 and 210 (at 23°C), respectively.
, 3.1, 198 (100°C), 2.3, 89 (15
0°C) kg/mm”.

Comparative Example 4 The same procedure as Comparative Example 1 was performed except that the polycarbonate of Example 4 was used instead of polyarylate, and the physical properties of polycarbonate alone were 4.0, 140 (at 23°C), 2.4, and 8.
9 (100℃), 1.0, 30 (150”c) with Te,
As a complex, 4.0, 150 (23°C), 2.5, 1
20 (100°C), 1.5, 60 (150°C) kg/
mm', and as compared to Example 4, the physical properties at high temperatures are inferior and the reinforcing effect is also small.

Example 5 Polyoxymethylene (40) was used instead of polycarbonate (
A sheet was prepared in the same manner as in Example 4, except that Mitsubishi Kawado Kagaku ■) was used, and the physical properties were measured. 4.3, 2
05 (23℃), 3.2, 199 (100℃), 2.5
, 95 (150°C) kg/m.

Comparative Example 5 The aromatic polyamide obtained by filtering the aromatic polyamide slurry obtained in Comparative Example 4 and polycarbonate were melt-mixed at 300° C. and then pressed to prepare a sheet, and the physical properties were similarly measured. In addition, as a comparison, we created a sheet without adding aromatic polyester and measured its physical properties.
Polycarbonate 4.2 and 145 (23°C) respectively
, 2.5, 92 (100"C), 1.4, 36 (150"
℃), and as a complex 4.3, 165 (at 23℃),
3.0, 105 (100″C), 1.5, 55 (150
"C) kg/mm", and the reinforcing effect of composite is small.

Example 6 Hydroquinone 3 instead of 5.5 g of p-aminobenzoic acid
, Og and 4.0 g of terephthalic acid were used.
It was carried out in the same way. The physical properties are 4.3 and 240 (
23℃), 2.5, 180 (100℃), 1.5, 13
0 (150°C) kg/mm”.

Comparative Example 6 Comparative Example 1 was repeated except that the polyoxymethylene of Example 4 was used in place of polyoxymethylene, and the physical properties of polyoxymethylene alone were 4. L 150 (23°C), 2.
7, 110 (100℃), 1.6, 45 (150″C)
and as a complex, 4.2, 165 (23°C),
2,5,120 (100℃), 1.5, 60 (150℃
) kg/mm', and as compared with Example 5, the physical properties at high temperatures are inferior, and the reinforcing effect is also small.

Example 7 The same procedure as in Example 6 was carried out except that 3.1 g of p-phenylenediamine was used instead of 3.0 g of hydroquinone.

Physical properties are 4.4, 235 (23℃), 2.6, and 1, respectively.
95 (100℃), 1.8, 125 (150℃) kg/
mm”.

Comparative Example 7 A composite was prepared in the same manner as in Example 7 using the same procedure as in Comparative Example 1, in which a dispersion of aromatic polyamide was synthesized without dissolving the polyarylate in advance, and then the polyarylate was dissolved. are 4.0 and 195 (2
3℃>, 2.2, 110 (100℃), 0.95, 32
(150° C.) kg/mm”, hardly any reinforcing effect was obtained, and the physical properties especially at high temperatures were inferior compared to the examples.

Example 8 The same procedure as in Example 6 was carried out except that p-hydroxybenzoic acid tg was further added and the reaction was carried out. The physical properties are 4. L 240 (23℃), 2.6, 180 (10
0°C), 1.6, 120 (150°C) kg/mm”.

Example 9 The reaction in Example 7 with the addition of 1 g of p-aminobenzoic acid was carried out in the same manner as in Example 6.

The physical properties are 4.2, 235 (23℃), 2.7, and 1, respectively.
85 (100'C), 1.8, 115 (150''C)k
g/mm".

Claims (19)

[Claims] (1) A method for producing a thermoplastic resin composite, which comprises condensing and polymerizing raw material monomers in a solution containing a polymer soluble in an organic solvent to produce an aromatic condensation polymer insoluble in the solvent. (2) The method for producing a thermoplastic resin composite according to claim 1, wherein the aromatic condensation polymer is an aromatic polyester or an aromatic polyamide. (3) In a solution of a soluble polymer dissolved in an organic solvent, in the presence of a catalyst, [1] aromatic dicarboxylic acid and aromatic diol; [2] aromatic dicarboxylic acid, aromatic diol, and aromatic hydroxycarbonate; acid, or [3] aromatic hydroxycarboxylic acid, or [4] aromatic dicarboxylic acid and aromatic diamine, [5] aromatic dicarboxylic acid, aromatic diamine, and aromatic aminocarboxylic acid, or [6] aromatic amino 1. A method for producing a thermoplastic resin composite, which comprises carrying out condensation polymerization using carboxylic acid as a raw material monomer to produce and contain an aromatic polyester or an aromatic polyamide insoluble in the solvent. (4) In a solution of a soluble polymer dissolved in an organic solvent, in the absence of a catalyst, [7] aromatic dicarboxylic acid dihalide and aromatic diol, or [8] aromatic dicarboxylic acid dihalide and aromatic diamine 1. A method for producing a thermoplastic resin composite, which comprises condensation polymerizing the following as a raw material monomer to produce and contain an aromatic polyester or an aromatic polyamide insoluble in the solvent. (5) In a solution of a soluble polymer dissolved in an organic solvent, in the presence of a catalyst, [1] aromatic dicarboxylic acid and aromatic diol; [2] aromatic dicarboxylic acid, aromatic diol, and aromatic hydroxycarbonate; An aromatic polyester-based thermoplastic resin composite comprising an acid or [3] aromatic hydroxycarboxylic acid as a raw material monomer by condensation polymerization to produce an aromatic polyester insoluble in the solvent. Production method. (6) In a solution of a soluble polymer dissolved in an organic solvent, in the presence of a catalyst, [4] aromatic dicarboxylic acid and aromatic diamine, [5] aromatic dicarboxylic acid, aromatic diamine, and aromatic aminocarbon An aromatic polyamide-based thermoplastic resin composite comprising an aromatic polyamide insoluble in the solvent produced by condensation polymerization of an acid or [6] aromatic aminocarboxylic acid as a raw material monomer. Production method. (7) In the absence of a catalyst, aromatic dicarboxylic acid dihalide and aromatic diol are subjected to condensation polymerization as raw material monomers in a solution containing a polymer soluble in an organic solvent, resulting in an aromatic polyester insoluble in the solvent. 1. A method for producing an aromatic polyester thermoplastic resin composite, the method comprising producing and containing an aromatic polyester thermoplastic resin composite. (8) Condensation polymerization of aromatic dicarboxylic acid dihalide and aromatic diamine as raw material monomers is carried out in the absence of a catalyst in a solution containing a polymer soluble in an organic solvent to produce an aromatic polyamide insoluble in the solvent. 1. A method for producing an aromatic polyamide-based thermoplastic resin composite, comprising: (9) The method according to claim 1, 3, 4, 5, 6, 7 or 8, wherein the solvent is a halogenated hydrocarbon or an aromatic hydrocarbon. (10) The method according to claim 3, 5 or 6, wherein the catalyst is triphenylphosphine dichloride or a ring-substituted derivative thereof, or a mixture of triphenylphosphine or a ring-substituted derivative thereof and a polyhalogen compound. (11) The solvent is a halogenated hydrocarbon or an aromatic hydrocarbon, and the catalyst is triphenylphosphine dichloride or a nuclear ring substituted derivative thereof, or a combination of triphenylphosphine or its nuclear ring substituted derivative and a polyhalogen compound. 7. The method according to claim 3, 5 or 6, which is a mixture. (12) Claim 3, in which the polycondensation reaction is carried out in the presence of a deoxidizing agent;
4, 5, 6, 7 or 8. (13) A thermoplastic resin composite obtained by the method according to claim 1. (14) A thermoplastic resin composite obtained by the method according to claim 3. (15) A thermoplastic resin composite obtained by the method according to claim 4. (16) An aromatic polyester thermoplastic resin composite obtained by the method according to claim 5. (17) An aromatic polyamide thermoplastic resin composite obtained by the method according to claim 6. (18) An aromatic polyester thermoplastic resin composite obtained by the method according to claim 7. (19) An aromatic polyamide thermoplastic resin composite obtained by the method according to claim 8.