JP2003128821A - Method for producing thermoplastic liquid crystal polymer molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To newly provide a method for increasing flexural modulus of a molding made of a thermoplastic liquid crystal polymer. SOLUTION: The molding made of a thermoplastic liquid crystal polymer and impregnated with a monomer having a polymerizable functional group is subjected to polymerization of the monomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a molded product made of a thermoplastic polymer capable of forming an optically anisotropic molten phase (hereinafter, this may be abbreviated as a thermoplastic liquid crystal polymer). Regarding

[0002]

2. Description of the Related Art In recent years, demands for FPCs (flexible printed wiring boards) have been increasing in the fields of electronics and electric industries due to demands for downsizing and weight reduction of devices. A general manufacturing method of this FPC is to form an electric circuit after laminating a metal foil such as a copper foil on at least one surface of a base film. A polyimide film, a polyethylene terephthalate film, etc. are often used as a base material film for FPC, but a film made of a thermoplastic liquid crystal polymer is supple and has a high tensile strength and a high elastic modulus. It has attracted attention because of its excellent heat resistance and chemical resistance.

[0003]

However, in wiring board applications, high flexural modulus (bending strength) may be required depending on applications such as packages and motherboards.
As a method of further increasing the bending elastic modulus of the thermoplastic liquid crystal polymer film, a method of heat treating the liquid crystal polymer film is known, but a problem may occur during post-processing. For example, when thermocompression-bonding a metal foil to a film, the necessary pressure-bonding temperature may be raised to a temperature above the working limit of the processing machine. On the contrary, if the degree of heat treatment is suppressed in order to avoid problems during post-processing, the flexural modulus is often not sufficiently increased.

Therefore, the present invention is to provide a new method for increasing the flexural modulus of a molded article made of a thermoplastic liquid crystal polymer.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted earnest research on a method for increasing the flexural modulus of a molded article made of a thermoplastic liquid crystal polymer, and as a result, found that a monomer having a polymerizable functional group in the molded article was used. By injecting a body and then subjecting the monomer to a polymerization treatment, it is possible to increase the flexural modulus of a molded body made of a thermoplastic liquid crystal polymer while avoiding the above-mentioned problems during post-processing, and in addition, to perform tensile As a result of further finding out that the strength is also improved, the present invention has been completed.

[0006] That is, the present invention is characterized in that a molded product, which is made of a thermoplastic liquid crystal polymer and into which a monomer having a polymerizable functional group is injected, is subjected to a polymerization treatment of the monomer. Provided is a method for producing a molded article made of a polymer.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the thermoplastic liquid crystal polymer used as a raw material for a molded article is not particularly limited, and specific examples thereof are classified into the following (1) to (4). The known thermotropic liquid crystal polyesters and thermotropic liquid crystal polyester amides derived from these compounds and their derivatives can be mentioned. However, it goes without saying that there are suitable ranges for the combination of various raw material compounds in order to form the thermoplastic liquid crystal polymer.

(1) Aromatic or aliphatic dihydroxy compounds (see Table 1 for representative examples)

[0009]

[Table 1]

(2) Aromatic or aliphatic dicarboxylic acid (see Table 2 for typical examples)

[0011]

[Table 2]

(3) Aromatic hydroxycarboxylic acid (see Table 3 for representative examples)

[0013]

[Table 3]

(4) Aromatic diamine, aromatic hydroxyamine or aromatic aminocarboxylic acid (see Table 4 for representative examples)

[0015]

[Table 4]

Table 5 shows typical examples of the thermoplastic liquid crystal polymer.
The copolymers (a) to (e) having the structural unit shown in can be mentioned.

[0017]

[Table 5]

The thermoplastic liquid crystal polymer is, in terms of processability,
Those having a transition temperature to the optically anisotropic molten phase in the range of about 200 to about 400 ° C., particularly about 250 to about 350 ° C. are preferable. Further, the thermoplastic liquid crystal polymer, if necessary, a polymer such as polyether ether ketone, polyether sulfone, polyimide, polyether imide, polyamide, polyamide imide, polyarylate, a lubricant,
Additives such as antioxidants, inorganic particles, fillers such as fibers and the like may be blended. These thermoplastic liquid crystal polymers are used as a molded product of any shape such as a flat shape or a tube shape. Specific examples include films, plates, sheets and fibers. Further, woven fabrics, non-woven fabrics and the like made of liquid crystal polymer fibers are also included in the molded body. Of these, films and fibers are preferable, and films are more preferable.

The thickness of the film made of the thermoplastic liquid crystal polymer is preferably 500 μm or less, more preferably 10 to 250 μm.
Is more preferable.

As a method for producing a molded article from a thermoplastic liquid crystal polymer, known methods such as extrusion molding and press molding can be used. For example, when a film is produced from a thermoplastic liquid crystal polymer, a T-die method, an inflation method and the like can be mentioned. Further, in the case of producing fibers from a thermoplastic liquid crystal polymer, a melt spinning method, a solution spinning method and the like can be mentioned.

In the present invention, a monomer having a polymerizable functional group is injected into a molded product made of a thermoplastic liquid crystal polymer. Here, examples of the polymerizable functional group include a vinyl group, a (meth) acryloyl group, and an epoxy group. Further, a combination in which polymerization occurs between a plurality of types of functional groups such as (a) hydroxyl group and (b) carboxyl group, ester group, acid anhydride group or isocyanate group is also included. Examples of the monomer having a polymerizable functional group used in the present invention include a compound that can be a raw material for a thermoplastic liquid crystal polymer, a compound having a vinyl group, a (meth) acryloyl group, or an epoxy group in the molecule. These compounds may be used alone or in combination of two or more.
Examples of the organic compound having a vinyl group, an acryloyl group, a methacryloyl group, an epoxy group or the like in the molecule include (meth) acrylic acid, methyl (meth) acrylate,
(Meth) acrylamide, (meth) acrylonitrile,
Examples thereof include vinyl acid acrylate, styrene, ethylene, propylene, ethylene oxide and the like.

Examples of the compound as a raw material of the thermoplastic liquid crystal polymer include the compounds represented by the above (1) to (4) and derivatives thereof. (A) Aromatic hydroxycarboxylic acid or its ester forming property Derivative,
(B) A combination of an aromatic dihydroxy compound or an ester-forming derivative thereof and an aromatic dicarboxylic acid or an ester-forming derivative thereof is preferable.

Examples of the aromatic hydroxycarboxylic acid include p-hydroxybenzoic acid and 2-hydroxy-6-.
Examples thereof include naphthoic acid and 4'-hydroxy-4-biphenylcarboxylic acid, with p-hydroxybenzoic acid or 2-hydroxy-6-naphthoic acid being preferred. Examples of the ester-forming derivative of aromatic hydroxycarboxylic acid include esters of aromatic hydroxycarboxylic acid such as p-acetoxybenzoic acid, 2-acetoxy-6-naphthoic acid, 4′-acetoxy-4-biphenylcarboxylic acid, p-
Examples thereof include halides of aromatic hydroxycarboxylic acids such as hydroxybenzoic acid chloride and 2-hydroxy-6-naphthoic acid chloride.

Examples of aromatic dihydroxy compounds include hydroquinone, 2,6-dihydroxynaphthalene,
4,4′-bisphenol and the like can be mentioned, but hydroquinone and 2,6-dihydroxynaphthalene are preferable.
Examples of the ester-forming derivative of an aromatic dihydroxy compound include esters of aromatic dihydroxy compounds such as hydroquinone diacetate and 2,6-diacetoxynaphthalene.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid and the like, and terephthalic acid, isophthalic acid or 2,6-
Naphthalenedicarboxylic acid is preferred. Examples of the ester-forming derivative of aromatic dicarboxylic acid include terephthalic acid dichloride, isophthalic acid dichloride, 2,6-naphthalenedicarboxylic acid dichloride, and halides of aromatic dicarboxylic acid such as 4,4′-biphenyldicarboxylic acid dichloride. Is mentioned.

As a compound which is a raw material of the thermoplastic liquid crystal polymer, p-hydroxybenzoic acid is particularly preferable.
2-hydroxy-6-naphthoic acid, p-acetoxybenzoic acid and 2-acetoxy-6-naphthoic acid. Also,
A combination of (a1) hydroquinone or 2,6-dihydroxynaphthalene and (b1) terephthalic acid, isophthalic acid or 2,6-naphthalenedicarboxylic acid;
1) a combination of hydroquinone or 2,6-dihydroxynaphthalene and (b2) terephthalic acid dichloride, isophthalic acid dichloride or 2,6-naphthalenedicarboxylic acid dichloride, (a2) hydroquinone diacetate or 2,6-diacetoxynaphthalene hydroquinone and (a2) The combination of b1) terephthalic acid, isophthalic acid or 2,6-naphthalenedicarboxylic acid is also particularly suitable as a compound as a raw material for the thermoplastic liquid crystal polymer.

The injection amount of these monomers is not particularly limited and may be appropriately selected depending on the desired physical properties of the molded product obtained by subjecting it to a polymerization treatment as will be described later. 0.1-based on the weight of the previous compact
5% by weight.

In the present invention, the supercritical method can be preferably used as a method for injecting the monomer having a polymerizable functional group into the molded product made of the thermoplastic liquid crystal polymer.
Here, the supercritical method is a method in which the temperature and pressure of a fluid are maintained in a supercritical state, a solute is dissolved in this fluid, and the solute is efficiently injected into a molded body made of a thermoplastic liquid crystal polymer. The supercritical method itself is known, and, for example, US Pat. No. 4,598,006, US Pat. No. 4,820,
No. 752 specification, Japanese Patent Laid-Open No. 8-506612, JP-A No. 11-255925, etc., describes a method of impregnating a base material made of a polymer with a physiologically active substance, a monomer and the like by a supercritical method. There is.

In the present invention, the fluid in the supercritical state used when injecting the monomer having a polymerizable functional group into the molded article made of the thermoplastic liquid crystal polymer by the supercritical method is, for example, carbon dioxide, Nitrous oxide, nitrogen, ethane, propane, cyclohexane, isopropanol, benzene, toluene, water, tetrafluoromethane, trichlorofluoromethane, chlorotrifluoromethane, tetrafluoromethylene, etc. (Carbon dioxide) is preferred. In addition to the above fluids, if desired, water, ethanol,
Liquids such as methanol and hexane can also be used.

Injection by the supercritical method is usually carried out by contacting a molded body made of a thermoplastic liquid crystal polymer and a monomer having a polymerizable functional group with a fluid in a supercritical state in a pressure vessel. The temperature and pressure at the time of injecting the monomer having a polymerizable functional group into the molded product made of the thermoplastic liquid crystal polymer depend on the type of the thermoplastic liquid crystal polymer, the shape of the molded product, the type of the injected monomer, etc. The critical temperature of the fluid used is Tc and the critical pressure is Pc.
Then, the temperature is usually in the range of Tc to Tc + 100 ° C. and the pressure is in the range of Pc to Pc + 30 MPa. Further, the time of contact with the fluid in the supercritical state is appropriately determined depending on the type of the thermoplastic liquid crystal polymer, the shape of the molded body, the type of the monomer to be injected, and the temperature and pressure of the fluid in the supercritical state. To be selected. The monomer having a polymerizable functional group is preferably injected up to the center of the molded product made of a thermoplastic liquid crystal polymer, but the object of the present invention can be achieved even if it is injected only near the surface of the molded product. Is possible.
The time of contact with the fluid in the supercritical state may be set in consideration of the degree of injection of the monomer having a polymerizable functional group. When the molded product into which the monomer having a polymerizable functional group has been injected is taken out from the pressure vessel, it is preferable to gradually reduce the pressure and then take out the molded product.

Further, in the present invention, the molding of the thermoplastic liquid crystal polymer in which the monomer having the polymerizable functional group is injected as described above is subjected to the polymerization treatment of the monomer. By such an operation, the bending elastic modulus of the molded body is improved. The method of polymerization treatment at this time, heat treatment, ultraviolet irradiation treatment,
Although a known method such as radiation irradiation treatment can be used, heat treatment is most preferable from the viewpoint of the apparatus used and operability.

The temperature of the heat treatment may be a temperature at which a monomer having a polymerizable functional group can be polymerized, but it is usually 200 to 350 ° C., preferably 250.
It is carried out at a temperature of ˜350 ° C. The heat treatment time can be appropriately set in consideration of the desired physical properties of the molded product after the heat treatment, but is usually in the range of 1 to 10 hours, preferably 2 to 5 hours. The heat treatment can be performed using, for example, a hot air drying furnace or a heated metal roll. Further, during the heat treatment, the molded body can be appropriately tensioned. Further, the molded body may be heat-treated after being brought into contact with a support such as a metal. Also,
The heat treatment may be carried out by a batch method, or may be carried out by a continuous method for films, sheets, fibers and the like. When the molded product is a film, sheet or fiber, it can be stretched if desired.
The stretching may be performed prior to the heat treatment or may be performed simultaneously with the heat treatment (hot stretching). The heat treatment may be performed in either an inert atmosphere or an inert atmosphere, but in order to achieve a high bending elastic modulus in a shorter time, the heat treatment should be performed in an inert atmosphere after the treatment in the inert atmosphere. Treatment is preferred.

Here, the term "inert atmosphere" means in an inert gas such as nitrogen or argon or under reduced pressure, and means that the active gas such as oxygen is 0.1 vol% or less. Also,
The active atmosphere means an atmosphere containing 1% or more of an active gas such as oxygen, preferably an oxygen-containing gas of 10% or more, and from the industrial point of view, it is most advantageous in terms of cost to use air. It is more preferable to use dry air having a dew point of −40 ° C. or lower. Such low dew point dry air is
For example, it can be easily obtained by using a desiccant such as molecular sieves, silica gel, sulfuric acid or calcium carbonate.

As the heat treatment method, many documents including the above-mentioned conditions are known, for example, JP-A-11-291329 and JP-A-2000-44797. In the present invention, it is possible to apply the methods described in these known documents within a range that does not hinder the physical properties desired in the obtained molded product.

According to the above-mentioned manufacturing method, even if the heat treatment conditions are relaxed, the flexural modulus can be improved to the same degree or more as compared with the case where the molded body is simply heat-treated.
Therefore, it is possible to avoid the above-mentioned problems in post-processing. The molded product obtained by the production method of the present invention has a higher flexural modulus than the molded product before the injection and polymerization treatment of the monomer having a polymerizable functional group and the mechanical strength such as tensile strength. It has been found that the properties are also improved. Further, the molded body obtained by the production method of the present invention, excellent high-frequency dielectric properties of the thermoplastic liquid crystal polymer, gas barrier properties, since the properties such as low hygroscopicity are not impaired, the electronic such as semiconductor package,
It is preferably used for applications in the electric industry field, packaging field such as retort pouches, and clothing field such as fibers. For example,
When the obtained molded product is a film, it can be suitably used as a wiring board in the form of a laminate with a metal plate, ceramics or the like. The laminate of the film and the metal plate obtained by the production method of the present invention can be produced by a known method such as thermocompression bonding or bonding with an adhesive. In this case, it is preferable to laminate the film after the polymerization treatment with the metal plate, but if desired, it is possible to laminate the film before the polymerization treatment with the metal plate and then subject the polymerization treatment to a heat treatment or the like. It is also possible to perform the lamination and the polymerization treatment at the same time by thermocompressing the film before the polymerization treatment between the metal plate and the heating roll.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. The melting point of the obtained film, the flexural modulus,
And the tensile strength was measured by the following method.

Melting point The film was heated to 20 ° C. using a differential scanning calorimeter (DSC).
After the temperature was raised at a rate of 1 / min to completely melt, the melt was cooled to 5
The endothermic peak temperature that appeared when the sample was rapidly cooled to 50 ° C. at a rate of 0 ° C./minute and heated again at a rate of 20 ° C./minute was measured.

Flexural Modulus It is difficult to measure the flexural modulus of a film having a thickness on the order of micron by the conventional flexural modulus test method performed on a thick plate. Therefore, the measurement was performed using the cantilever method. That is, the film was cut into a size of 1 cm in width and 4 cm in length, one end of the film was fixed, and the other end was free, and the hanging height of the free end was measured. The smaller this value is, the higher the bending elastic modulus is.

Tensile Strength Measured according to ASTM D 882.

Reference Example 1 6-hydroxy-2-naphthoic acid unit 27 mol%, p-
A thermotropic liquid crystal polyester composed of 73 mol% of hydroxybenzoic acid unit was 280 using a single screw extruder.
To kneading at a temperature of 300 ° C., extruding from an inflation die having a diameter of 40 mm and a slit interval of 0.6 mm at a shear rate of 550 sec ⁻¹ , melting point 280 ° C., thickness 50 μm
I got a film of. Table 6 shows the flexural modulus and the tensile strength of the obtained film.

Example 1 A benzene solution of p-acetoxybenzoic acid was soaked in a glass fiber filter paper, and then benzene was removed by evaporation. After this filter paper and the thermoplastic liquid crystal polymer film obtained in Reference Example 1 were co-wound, they were loaded into a column of a supercritical device (manufactured by Hisaka Seisakusho Co., Ltd.) and carbon dioxide (carbon dioxide gas) was introduced. Temperature 120 ℃, Pressure 20M
It was set to Pa and left for 10 minutes under these conditions. After reducing the pressure to normal pressure, the film was taken out. The weight increase rate of the film at this point was 0.25%.

Next, the above-mentioned thermoplastic liquid crystal polymer film was introduced into an oven and heat-treated in a 98% nitrogen stream. The nitrogen flow rate during the heat treatment was 0.3 Nm ³ / min, and the temperature inside the oven was set as follows by program control. (1) Preheat to 160 ° C to introduce the film (2) Raise temperature from 160 ° C to 200 ° C in 1 hour (3) Raise temperature from 200 ° C to 240 ° C in 1 hour (4) Temperature increase from 240 ° C to 280 ° C in 1 hour (5) Temperature increase from 280 ° C to 290 ° C in 1 hour (6) Temperature decrease from 290 ° C to 180 ° C in 1 hour Table 6 shows the flexural modulus, tensile strength, and weight increase rate of the thermoplastic liquid crystal polymer film after the above treatment.

Example 2 A thermoplastic liquid crystal polymer film was obtained in the same manner as in Example 1 except that the pressure of carbon dioxide was changed to 25 MPa. Table 6 shows the flexural modulus, tensile strength, and weight gain of the thermoplastic liquid crystal polymer film.

Example 3 A thermoplastic liquid crystal polymer film was obtained in the same manner as in Example 1 except that the pressure of carbon dioxide was 30 MPa. Table 6 shows the flexural modulus, tensile strength, and weight gain of the thermoplastic liquid crystal polymer film.

Example 4 A thermoplastic liquid crystal polymer film was obtained in the same manner as in Example 1 except that styrene was used instead of p-acetoxybenzoic acid. Table 6 shows the flexural modulus, tensile strength, and weight gain of the thermoplastic liquid crystal polymer film.

Example 5 A thermoplastic liquid crystal polymer film was obtained in the same manner as in Example 2 except that styrene was used instead of p-acetoxybenzoic acid. Table 6 shows the flexural modulus, tensile strength, and weight gain of the thermoplastic liquid crystal polymer film.

Example 6 A thermoplastic liquid crystal polymer film was obtained in the same manner as in Example 3 except that styrene was used instead of p-acetoxybenzoic acid. Table 6 shows the flexural modulus, tensile strength, and weight gain of the thermoplastic liquid crystal polymer film.

Comparative Example 1 The thermoplastic liquid crystal polymer film of Reference Example 1 was directly introduced into an oven and heat-treated under the same conditions as in Example 1. Table 6 shows the flexural modulus, tensile strength, and weight gain of the thermoplastic liquid crystal polymer film.

Comparative Example 2 The thermoplastic liquid crystal polymer film of Reference Example 1 was directly introduced into an oven and heat-treated under the same conditions as in Example 1. Table 6 shows the flexural modulus, tensile strength, and weight gain of the thermoplastic liquid crystal polymer film.

Comparative Example 3 The thermoplastic liquid crystal polymer film of Reference Example 1 was directly introduced into an oven and heat-treated under the same conditions as in Example 1. Table 6 shows the flexural modulus, tensile strength, and weight gain of the thermoplastic liquid crystal polymer film.

[0051]

[Table 6]

As is clear from Table 6 above, Example 1
The thermoplastic liquid crystal polymer films of the present invention Nos. 6 to 6 have clearly improved flexural modulus and tensile strength as compared with the untreated film of Reference Example 1 and the films of Comparative Examples 1 to 3. Further, as is clear from the table, the thermoplastic liquid crystal polymer film of the present invention has an increased weight, and therefore the compound monomer having a polymerizable functional group is effectively injected into the film. Understand that In addition,
When the films of Comparative Examples 1 to 3 are subjected to heat treatment based on the temperature pattern of Example 1 above, decarboxylation, dephenolation, deacetic acid, etc. occur due to solid-state polymerization, and the weight of the films is reduced.

[0053]

As described above, according to the present invention, the flexural modulus and the tensile strength of a molded article made of a thermoplastic liquid crystalline polymer can be increased.

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Claims (9)

[Claims] 1. A molded article, which is made of a thermoplastic polymer capable of forming an optically anisotropic molten phase and in which a monomer having a polymerizable functional group is injected, is subjected to a polymerization treatment of the monomer. And a method for producing a molded article made of a thermoplastic polymer capable of forming an optically anisotropic molten phase. 2. The method for producing a molded article according to claim 1, wherein a supercritical method is used as a method for injecting the monomer having a polymerizable functional group into the molded article. 3. A thermotropic liquid crystal polyester or thermotropic polymer in which a thermoplastic polymer capable of forming an optically anisotropic molten phase is derived from a compound or a derivative thereof classified into the following (1) to (4): A monomer having a polymerizable functional group, which is a liquid crystal polyesteramide and is injected into a molded article, has a compound capable of being a raw material of a thermoplastic polymer and / or a vinyl group, a (meth) acryloyl group or an epoxy group in a molecule. The method for producing a thermoplastic liquid crystal polymer molded body according to claim 1, which is an organic compound having. (1) Aromatic or aliphatic dihydroxy compound (2) Aromatic or aliphatic dicarboxylic acid (3) Aromatic hydroxycarboxylic acid (4) Aromatic diamine, aromatic hydroxyamine or aromatic aminocarboxylic acid 4. A monomer having a polymerizable functional group, which is injected into a molded article, is at least one compound selected from the group consisting of compounds classified into the following (1) to (4) and derivatives thereof. The method for producing a thermoplastic liquid crystal polymer molded body according to claim 3, wherein (1) Aromatic or aliphatic dihydroxy compound (2) Aromatic or aliphatic dicarboxylic acid (3) Aromatic hydroxycarboxylic acid (4) Aromatic diamine, aromatic hydroxyamine or aromatic aminocarboxylic acid 5. A molding comprising a thermoplastic polymer capable of forming an optically anisotropic molten phase, wherein a monomer having a polymerizable functional group is injected and then the monomer is polymerized. A thermoplastic liquid crystal polymer molding characterized by being treated. 6. A thermotropic liquid crystal polyester or thermotropic polymer in which a thermoplastic polymer capable of forming an optically anisotropic melt phase is derived from a compound or a derivative thereof classified into the following (1) to (4): A monomer having a polymerizable functional group, which is a liquid crystal polyesteramide and is injected into a molded article, has a compound capable of being a raw material of a thermoplastic polymer and / or a vinyl group, a (meth) acryloyl group or an epoxy group in a molecule. The thermoplastic liquid crystal polymer molded article according to claim 5, which is an organic compound having. (1) Aromatic or aliphatic dihydroxy compound (2) Aromatic or aliphatic dicarboxylic acid (3) Aromatic hydroxycarboxylic acid (4) Aromatic diamine, aromatic hydroxyamine or aromatic aminocarboxylic acid 7. A monomer having a polymerizable functional group to be injected into a molded article is at least one compound selected from the group consisting of compounds and derivatives thereof classified into the following (1) to (4): 7. The thermoplastic liquid crystal polymer molded article according to claim 6. (1) Aromatic or aliphatic dihydroxy compound (2) Aromatic or aliphatic dicarboxylic acid (3) Aromatic hydroxycarboxylic acid (4) Aromatic diamine, aromatic hydroxyamine or aromatic aminocarboxylic acid 8. The thermoplastic liquid crystal polymer molded product according to claim 5, wherein the molded product is a film or a fiber. 9. A wiring board comprising the film according to claim 8 and a metal plate.