JP2625881B2 - Polycyano arylene thioether film - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polycyanoarylene thioether film having excellent heat resistance and mechanical strength.

[Problems to be Solved by Conventional Techniques and Inventions] Resin films excellent in heat resistance, mechanical strength, electric properties, and the like are frequently used in electric and electronic devices. In recent years, as these devices have become smaller and lighter, it has been demanded that film materials used have better heat resistance and mechanical strength.

Conventionally, films of this type have been used such as polyethylene and polyamide. However, since these films are not sufficiently satisfactory in both heat resistance and mechanical strength, development of industrial films having higher heat resistance and mechanical strength is desired.

[Means for Solving the Problems] An object of the present invention is to provide a resin film excellent in heat resistance and mechanical strength in response to such a conventional demand.

The present inventors have made intensive efforts to achieve the above object, and as a result, a film obtained from a polycyanoarylene thioether having a specific structure and a molecular weight as described below is an excellent film satisfying the above-mentioned requirements. This led to the completion of the present invention.

That is, the polycyanoarylene thioether film of the present invention has the formula (I) M repeating units of the formula (II) Has n repeating units represented by and the value of m / (m + n) is
Reduced viscosity at 50 ° C. of a 0.5 g / d1 solution having a concentration of 0.01 to 0.99 and N-methylpyrrolidone as a solvent [ηsp /
c] is 0.2d1 / g or more.

 Hereinafter, the present invention will be described in detail.

The polycyanoarylene thioether used in the present invention is composed of both repeating units represented by the formulas (I) and (II) connected to each other in a random or ordered linear manner, and the terminal thereof is -SH , −X, −CH ₃ , (However, X represents a halogen atom).

It is necessary that the number m of repeating units in the formula (I) and the number n of repeating units in the formula (II) satisfy m / (m + n) = 0.01 to 0.99. If m / (m + n) is less than 0.01, the tensile modulus becomes small, and if m / (m + n) exceeds 0.99, the workability decreases.

Further, when the above-mentioned polymer is applied to the film of the present invention, 5 g / dl of a solvent adjusted to 0.5 g / dl with an N-methylpyrrolidone solvent.
The reduced viscosity (ηsp / c) at 0 ° C. must be 0.2 dl / g or more.

When the reduced viscosity [ηsp / c] of the polycyanoarylene thioether polymer is less than 0.2 dl / g, heat resistance and mechanical strength are reduced. Preferably it is 0.3 dl / g or more.

The reduced viscosity can be adjusted by setting the reaction conditions (for example, temperature and time) during the polymerization reaction to a predetermined value or by adding a predetermined amount of a molecular weight modifier.

Examples of the molecular weight regulator in the latter case include, for example, methyl chloride, chlorobenzonitrile and the like.

An example of the method for producing the above-described polycyanoarylene thioether is shown below. That is, a dihalogenobenzonitrile, 4,4-dihalogenodiphenylsulfone, and a thioetherifying agent (sodium sulfide) are reacted at 200 ° C. for 5 hours in the presence of a solvent, and then treated with water or an alcohol.

The polycyanoarylene thioether thus obtained can be formed into a film by a conventional method, for example, a melt extrusion molding method, a press molding method, or the like. The molding temperature at this time is 250 to 350 ° C, preferably 280 to 3 ° C.
20 ° C.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Sodium sulfide 2.8 hydrate 90.34 g (0.70 mol), 2,6-dichlorobenzonitrile 36.86 g (0.21 mol), 4,4'-dichlorodiphenylsulfone 140.00 g (0.49 mol), N-
700 ml of methylpyrrolidone was charged into a 21 autoclave, the temperature was raised to 200 ° C. with stirring, and the reaction was carried out for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was poured into water, followed by filtration, washing with water, and washing with methanol. The yield of the obtained polymer was 145.07 g (97% yield).

The reduced viscosity [ηsp / c] of the polymer was 0.62.

Further, the copolymer composition ratio m / (m + n) of the polymer is 0.33
Met.

Thermal analysis of this polymer showed a glass transition temperature of 20
It was 9 ° C and the thermal decomposition onset temperature was 476 ° C, confirming that it had sufficient heat resistance for practical use.

Next, the polymer was melt-extruded to form pellets, and then the vacuum-dried pellets were press-formed at 300 ° C. to obtain a transparent film having a size of 100 mm × 100 mm and a wall thickness of 0.06 mm.

The mechanical properties of the resulting film, ie, tensile strength,
The elongation and elastic modulus were measured and the results are shown in Table 1.

Examples 2 to 4 The procedure of Example 1 was repeated except that the polycyanoarylene thioether having a reduced viscosity as shown in Table 1 was produced in the same manner as in Example 1 by changing the reaction time at 200 ° C. A film was formed in the same manner as described above. The heat resistance of the obtained polymer was as good as in Example 1.

Comparative Example 1 A polycyanoarylene thioether having a reduced viscosity of 0.18 dl / g was obtained by shortening the polymerization reaction time at 200 ° C. in Example 1. This polymer was press-molded in the same manner as in Example 1, but the obtained film was brittle and could not be measured for mechanical properties.

Comparative Example 2 A film was formed in the same manner as in Example 1 except that the thermoplastic resin polyethylene terephthalate (manufactured by Teijin Limited) was used as the resin component, and the measurement was performed in the same manner.

[Effect of the Invention] The polycyanoarylene thioether film according to the present invention is a film having high mechanical strength and excellent heat resistance. Therefore, the film of the present invention is useful as an industrial film in the fields of electronics, electric equipment, machinery and the like.

Claims (1)

(57) [Claims] (1) Formula (I) M repeating units of the formula (II) Has n repeating units represented by and the value of m / (m + n) is
Reduced viscosity at 50 ° C. of a 0.5 g / d1 solution having a concentration of 0.01 to 0.99 and N-methylpyrrolidone as a solvent [ηsp /
c] is 0.2d1 / g or more, a film comprising a polycyanoarylene thioether.