JPH04100856A - Molding of thermoplastic resin composition and preparation thereof - Google Patents

Abstract

PURPOSE:To prepare the title molding excellent in mechanical strengths, heat resistance, etc., by mixing a crystalline polycyanoaryl ether with an optically anisotropic arom. polyester in a specified wt. ratio and molding the resulting mixture at specified temp. and shearing rate. CONSTITUTION:20-95wt.% crystalline polycyanoaryl ether having repeating units of formula I (wherein Ar is a group of formula II, III or IV) is mixed with 80-5wt.% optically anisotropic arom. polyester (e.g. a polyester having repeating units of formulas V and VI). The resulting mixture is molded on an injection molding machine at a temp. in a range wherein the polyester shows an optical anisotropy and at a shearing rate of 10sec<-1>, giving the title article contg. the polyester dispersed in the form of fiber. The article is suitably used as the material of an electric or electronic part, a machine part, etc.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a molded article of a thermoplastic resin composition that is suitably used as a material for parts in the fields of electrical/electronic equipment, machinery, etc., and a suitable manufacturing method thereof. Regarding the method.

[Conventional technology]

In recent years, so-called engineering resins have been used in a wide range of fields. Among these resins, aromatic polyether resins are attracting attention as materials for mechanical parts and parts of electrical and electronic equipment because they have excellent heat resistance, mechanical strength, and chemical stability. However, as the field of use expands, the characteristics required for the material are becoming stricter, and the development of further improved materials is awaited.

Among these aromatic polyether resins, crystalline polycyanoaryl ether has excellent heat resistance, mechanical strength, flame retardance, and chemical stability, but this resin alone cannot be used alone. In some cases, the practical physical properties under harsher conditions were not sufficient. For this reason, attempts have been made to further improve its physical properties (Japanese Patent Application Laid-open No. 60-258250, JP-A No. 61-85470, JP-A No. 62-116).
Publication No. 658). Although improvements in various physical properties can be seen through these improvements, there is a problem in that heat resistance and mechanical strength are not sufficiently improved.

[Problem to be solved by the invention]

The present invention aims to provide a molded thermoplastic resin composition having high mechanical strength and sufficient heat resistance. The present invention also aims to provide a suitable method for producing such a thermoplastic resin composition molded article.

[Means to solve the problem]

As a result of intensive research to solve the above problems, the present inventors found that the composition of a crystalline polycyanoarylether resin in which an optically anisotropic aromatic polyester phase is dispersed in the form of fibers and an optically anisotropic aromatic polyester The inventors have discovered that the object can be achieved by a thermoplastic resin composition molded article, and have completed the present invention based on this knowledge.

That is, the present invention comprises 20 to 95% by weight of crystalline polycyanoaryl ether and 8% by weight of optically anisotropic aromatic polyester.
0 to 5% by weight, and the aromatic polyester phase in the molded product is dispersed in the form of fibers. It is.

The crystalline polycyanoaryl ether used in the present invention has a repeating unit represented by the general formula (Ar in the formula represents either round, (n () or wataru). Specifically, CN CN may be used.

Examples of repeating units that can be included in the copolymer include CN CN CN CN .

The crystalline polycyanoaryl ether used in the present invention is a copolymer containing the following repeating units in addition to the above-mentioned homopolymers within a range that does not lose crystallinity. , dissolved in p-chlorophenol to reduce its concentration to 0.
．． It is preferable to have a molecular weight such that the reduced viscosity [η3p/C) of the solution at 60° C. is 0.4 a/g or more when 2 g/d1. Reduced viscosity [η, p/C
) is less than 0.4 d1/g, which is not preferred because the polycyanoaryl ether molded product will not exhibit sufficient mechanical strength.

Further, as the optically anisotropic aromatic polyester used in the present invention, one that exhibits optical anisotropy when melted is used. The temperature range in which optical anisotropy is exhibited is preferably 100°C or higher, particularly preferably 150°C or higher.

By using such an optically anisotropic aromatic polyester and molding it at a shear rate of 10 sec-' or more in the above temperature range, the optically anisotropic aromatic polyester is oriented in a fibrous form within the molded body, and the molding The body's heat resistance and mechanical strength are improved. Polyester without optical anisotropy does not exhibit such properties.

Specific examples of such optically anisotropic aromatic polyesters include those having repeating units shown below.

In the thermoplastic resin composition molded article of the present invention, the composition ratio of the crystalline polycyanoaryl ether and the optically anisotropic aromatic polyester is 20 to 95% by weight of the former: 8% of the latter.
It is 0 to 5% by weight. If the blending ratio of the optically anisotropic aromatic polyester is less than 5% by weight, the heat resistance and mechanical strength will not be improved sufficiently, and if it exceeds 80% by weight, the mechanical strength of the weld portion will decrease. Particularly preferably 50 to 90
Weight %: 50 to 10 weight %.

Furthermore, in the thermoplastic resin composition molded article of the present invention, the aromatic polyester phase in the molded article is dispersed in the form of fibers.

The aromatic polyester phase in the composition of crystalline polycyanoaryl ether and aromatic polyester is separated from the crystalline polycyanoaryl ether phase during melt-kneading and exists as an independent phase in the composition. When the composition is cooled in this state to form a molded article, the aromatic polyester phase forms a substantially spherical aromatic polyester phase with a diameter of about 1 to 10 μm. However, in the present invention, the aromatic polyester phase is dispersed in the composition in the form of fibers by applying shear to the composition in a molten state. The fibrous material of the aromatic polyester phase is along the flow direction of the resin composition during production of the molded article, and the ratio of fiber length/fiber diameter is 5 or more.

The optically anisotropic aromatic polyester phase that has become fibrous in this way has extremely high mechanical strength and elastic modulus in the fiber axis direction, and this strengthens the crystalline polycyanoarylether phase in the composition. This contributes to improving the mechanical strength of molded articles made of this composition.

As a method for producing such a thermoplastic resin composition molded article, the above-mentioned crystalline polycyanoaryl ether 20 to 95
% by weight and 80 to 5% by weight of an optically anisotropic aromatic voluster in a temperature range where the aromatic polyester exhibits optical anisotropy at a shear rate of 10 sec-' or more. suitable.

First, the above crystalline polycyanoaryl ether 20-9
5% by weight and 80 to 5% by weight of the optically anisotropic aromatic polyester are kneaded using a hot roll, a kneader, a Banbury mixer-1 melt molding machine, or the like. The kneading temperature is 300~
400″C is preferable, especially 350 to 400″C.
It is preferable to set it to °C.

Next, the kneaded composition is molded.

The molding temperature is a temperature range in which the aromatic polyester in the composition exhibits optical anisotropy. Outside this temperature range, the optically anisotropic aromatic polyester phase is difficult to orient into fibers;
In addition, although the fibers may be oriented in an apparent fibrous manner, no improvement in mechanical strength in the axial direction of the fibers is observed. The preferred molding temperature is 300 to 400°C, particularly preferably 350 to 3
The temperature is 70°C.

Further, during molding, shear is applied to the composition at a shear rate of 10 sec-' or more. The reason why the molding is carried out under conditions where the shear rate is 10 sec-' or more is that the optically anisotropic aromatic polyester phase in the composition is arranged in the form of fibers parallel to the flow direction of the composition and dispersed in the composition. This is because the mechanical strength of the obtained molded article is improved. Shear rate is 1
If it is less than 0 sec-', the aromatic polyester phase is not fibrous but dispersed in a spherical shape, so that no particular effect can be obtained. A particularly preferred shear rate is 100-50. 000se
It is c-'.

Extrusion molding and injection molding are suitable as the molding method.

The thermoplastic resin composition molded article of the present invention obtained as described above has high mechanical strength and sufficient heat resistance.

Additionally, additives such as fibrous reinforcing materials, inorganic fillers, colorants, oxidation stabilizers, etc. can be added to the thermoplastic resin composition used in the present invention as desired during manufacture or use. .

Suitable fibrous reinforcement materials include glass fiber, carbon fiber,
Examples include titanate whiskers, wollastonite, and ceramic fibers 1i (SiC, etc.).

Suitable inorganic fillers include calcium carbonate, mica, titania, silica, alumina, silicon carbide, silicon nitride, boron nitride, and the like.

These additives can be used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the resin composition. By blending these, the heat resistance of the molded article obtained from the composition is further improved.

〔Example〕

Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.

Production Example 1 (Production of crystalline polycyanoaryl ether) Dichlorobenzonitrile 5.
．． 211 kg, resorcinol 3.30 kg, potassium carbonate 4.27 kg, lithium carbonate 430 g, N- as a solvent
Methylpyrrolidone 4.31! ,, put toluene 21,
The mixture was stirred at room temperature for 1 hour while blowing argon gas therein, and then the temperature was raised to 195°C and the reaction was carried out for 3.5 hours. After the reaction is complete, the reaction product is poured into methanol to precipitate a polymer, and the precipitated polymer is pulverized using a high-speed mixer (manufactured by Fukae Kogyo), and then mixed with 100% water.
It was washed three times with N and twice with 1 oz of methanol and dried to obtain 6.15 kg (yield: 95%) of crystalline polyarylene ether nitrile having the following repeating units.

When the thermal properties of this polymer were measured, the melting point was 340°C and the thermal decomposition onset temperature was 490''C.

Production Example 2 (Production of crystalline polycyanoaryl ether copolymer) Internal volume 200I equipped with stirring device, rectification device, and argon gas blowing pipe! 1.548 kg of dichlorobenzonitrile, 5.58 kg of 4.4'-dihydroxybiphenyl, 4.975 kg of potassium carbonate, and N-methylpyrrolidone 502 as a solvent were placed in a reactor, and the mixture was heated for 1 hour while blowing argon gas into the reactor. from room temperature to 195
After the temperature was raised, a small amount of toluene was added and the produced water was removed from the reaction system by azeotropy.
The reaction was carried out for 30 minutes at a temperature of °C. Then 4.4'
-4.5822 kg of difluorobenzophenone to 70 I of N-methylpyrrolidone! , and the reaction was further carried out for 1 hour. After completion of the reaction, the reaction product was pulverized using a high-speed mixer (manufactured by Fukae Kogyo ■), washed five times with 100 f of water, and dried to obtain a crystalline polycyanoaryl ether having the following repeating units in a ratio of 70:30. 10.2 kg of copolymer (yield 100%) was obtained.

N Be ◇ CO @ 0 (X ◇ 0 half [11) When the thermal properties of this polymer were measured, the melting point was 379°C and the thermal decomposition onset temperature was 562''C.

Production Example 3 (Production of optically anisotropic aromatic polyester) Internal volume 301. equipped with a stirring device, argon gas blowing pipe and vacuum line. In a reactor, 1 part acetoxybenzoic acid
．． 08kg, 4.4'-diacetoxydiphenyl 5.4
0kg, terephthalic acid 0.249kg, isophthalic acid 0
．． 083kg was added, and while blowing in argon gas,
Raise the temperature from room temperature to 280°C over 1 hour. After raising the temperature, the acetic acid formed was flowed out using an argon gas stream, then the argon gas line was closed, and the vacuum line was used to remove the acetic acid.
While reducing the pressure to 0 torr and further to 1 torr,
The mixture was warmed to 0°C and the acetic acid was allowed to flow out over 3 hours. An aromatic polyester having the following repeating units in a ratio of 75:19:6 in a reactor and exhibiting optical anisotropy when melted at 360 to 500°C was obtained.

When the thermal properties of this polymer were measured, the glass transition temperature and melting point were unclear, but it showed fluidity at temperatures above 350°C. Moreover, the thermal decomposition temperature was 542°C.

Example 1 The crystalline polycyanoaryl ether obtained in Production Example 1 and the optically anisotropic aromatic polyester obtained in Production Example 3 were blended so that the weight ratio of the former to the latter was 90=IO. The mixture was then supplied to a twin-screw extruder and melted and kneaded at 350''C for 3 minutes to obtain a thermoplastic resin composition.

The obtained resin composition was heated to a cylinder temperature of 3 using an injection molding machine.
80”C, shear rate at nozzle tip 2000se
A plate-shaped molded product was obtained by injection molding under the conditions of c-". When a part of this molded product was cut out and the cut piece was observed with an electron microscope, it was found that the aromatic polyester phase was in the injection direction of the molded product. It was confirmed that the particles were dispersed in the form of fibers with a length of 20 μm or more and a diameter of 2 μm.

Next, a test piece was prepared from the molded body, and the ASTM D-648
The heat distortion temperature was measured based on fJL. In addition, bending strength was measured for the welded portion and the non-welded portion. These results are shown in Table 1.

Examples 2 to 3 Crystalline polycyanoaryl ether obtained in Production Example 1,
Example 1 except that the blending ratio with the optically anisotropic aromatic polyester obtained in Production Example 3 was changed to the ratio shown in Table 1.
I did the same thing. The results are shown in Table 1.

Examples 4 to 6 Crystalline polycyanoaryl ether obtained in Production Example 2,
The same procedure as in Example 1 was carried out except that the optically anisotropic aromatic polyester obtained in Production Example 3 was used in the proportion shown in Table 1. The results are shown in Table 1.

Examples 7 to 9 Crystalline polycyanoaryl ether obtained in Production Example 1,
The same procedure as in Example 1 was carried out, except that VECTRA A950 manufactured by Hoechstsenies was used as the optically anisotropic aromatic polyester at the blending ratio shown in Table 1. Here, the VECTRA A950 used was 300 to 400
It exhibited optical anisotropy at °C and fluidity at temperatures above 290 °C. The results are shown in Table 1.

Example 10 To 70 parts by weight of the resin composition obtained in Example 2, 3 parts by weight of glass fiber was added.
The same procedure as in Example 1 was carried out except that 0 parts by weight was added. The results are shown in Table 1.

Comparative Example 1 The resin composition obtained in Example 1 was press-molded at 350°C to obtain a plate-shaped molded body. Shear rate during molding is 0
sec-'. When a part of the obtained molded body was cut out and observed under an electron microscope, it was confirmed that the aromatic polyester phase had a substantially spherical shape with a diameter of 2 to 5 μm and was dispersed in the polycyanoaryl ether phase.

Next, a test piece was prepared from this molded body, and its heat resistance and bending strength were measured. The results are shown in Table 1.

(The following is a blank space) [Effects of the Invention] The thermoplastic resin composition molded article of the present invention has high mechanical strength and sufficient heat resistance.

Moreover, the manufacturing method of the present invention can suitably manufacture the above-mentioned thermoplastic resin composition molded article.

Claims (1)

[Scope of Claims] 1. A molded article consisting of a composition of 20 to 95% by weight of crystalline polycyanoaryl ether and 80 to 5% by weight of optically anisotropic aromatic polyester, and A thermoplastic resin composition molded article characterized in that an aromatic polyester phase is dispersed in the form of fibers. 2. A composition of 20 to 95% by weight of crystalline polycyanoaryl ether and 80 to 5% by weight of optically anisotropic aromatic polyester was heated at a shear rate of 10 sec in a temperature range where the aromatic polyester exhibits optical anisotropy. ^-^ A method for producing a thermoplastic resin composition molded article, characterized by molding with 1 or more.