JPS6369831A - Heat-treating method for thioether based resin - Google Patents

Abstract

PURPOSE:To increase intrinsic viscosity and heat distortion temperature and make it possible to improve heat resistance while holding excellent water and solvent resistance, by heat-treating a specific amorphous aromatic thermoplastic resin at a specific temperature for a specific time. CONSTITUTION:An amorphous aromatic thermoplastic resin, consisting essentially of thioether bonds and further containing amide groups and/or imide groups, preferably aromatic polyamide and/or imide resin having repeating units expressed by formulas I-III (Ar is bifunctional aromatic residue; formula IV is formula V or VI) is heat-treated under temperature condition below the glass transition temperature of the resin - above [(glass transition temperature of the resin) - 100 deg.C] for >=3hr.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for heat treating thioether resins. The thioether resin obtained by the method of the present invention has particularly excellent heat resistance and is useful as engineering plastics, fibers, films, and coating materials used at high temperatures.

[Conventional technology]

Aromatic polythioetheramide resins, aromatic polyamide copolymers with thioether bonds, aromatic polythioetheramide imide resins, aromatic polyamideimide copolymers with thioether bonds, aromatic polythioetherimide resins, etc. that require thioether bonds. The amorphous aromatic thermoplastic resin (hereinafter abbreviated as thioether resin) which further contains an amide group and/or an imide group as a component has an imbalance between excellent moldability and heat resistance,
It also has excellent mechanical properties, water resistance, and solvent resistance, and is expected to be used as a new engineering material, fiber, film, coating material, etc.

However, when used at room temperature, it is desirable to have even better heat resistance.

Generally speaking, aromatic polyimide resin (DuPont's MVespe
1, etc.), aromatic polyamide-imide resins (Torlon, manufactured by Atnoco, etc.), aromatic polyamide resins (Kofux CMR, manufactured by Banjin Co., Ltd., etc.), aromatic polyester resins (Econol, manufactured by Sumitomo Chemical, etc.), etc. Many of these resins have heat distortion temperatures equal to or higher than those of thioether resins, but these resins have poor moldability. On the other hand, thermosetting resins such as aromatic bismaleimide resins, aromatic polyfunctional maleimide resins, polyfunctional (meth)acrylate resins, acetylene-terminated aromatic resins, and polyfunctional epoxy resins have heat resistance equivalent to or higher than that of thioether resins. However, these are inferior in molding cycle, mechanical properties, thermal stability, etc.

[Problem that the invention seeks to solve]

By the way, aromatic polyamide-imide resin and ether amide (imide) resin (which has an ether bond as an essential component,
Furthermore, it is known that the heat distortion temperature can be improved by heat treating an aromatic thermoplastic resin containing an amide group or an imide group (Torlon
Technical data, JP-A-59-140232, etc.), it was difficult to linearly improve the molecular weight.

-□ □ Resins containing S atoms in the main chain, as typified by Luborif-22-Sulfide (hereinafter abbreviated as PPS), undergo cross-linking/chain cleavage due to the cleavage/recombination of C-8 bonds during heat treatment. It is known to cause prolongation. At this time, -C- or -8
It is also known that when an electron-withdrawing group such as O2- is present in the system, this reaction tends to proceed slowly and the chain tends to be extended slowly. However, this reaction is considered to be a characteristic phenomenon only in PPS, which is a crystalline resin, and also occurs in one-chill resins, and it not only can improve the heat distortion temperature but also increase the intrinsic viscosity (bimolecular weight). Moreover, the glass transition temperature does not change and essentially no gel content is produced, so it is thought that the chain is linearly extended, and therefore the excellent properties of thioether resins are maintained. find out that it will be done,
The present invention has now been completed.

[Structure of the invention]

The present invention makes it possible to improve heat resistance while maintaining excellent mechanical properties, water resistance, and solvent resistance by heat-treating a thioether resin.

That is, the present invention provides an amorphous aromatic thermoplastic resin having a thioether bond as an essential component and further containing an amide group and/or an imide group, at a temperature below the glass transition temperature of the resin.
[Providing a method for heat treating a thioether resin, which is characterized by heat treating for 3 hours or more under a temperature condition of [[glass transition temperature of resin] -100°C] or higher to increase its intrinsic viscosity and heat distortion temperature. It is.

The thioether resin used in the present invention is preferably an aromatic polyamide and/or imide resin having repeating units represented by the following formulas (I) to (Ill), in which -6=C, Ar is a divalent It is an aromatic residue. In addition, (j is.) Among them, the above formulas (I) to (1■) are used as repeating units.
Aromatic polyamide and/or imide resin having only repeating units represented by formula (I), aromatic polyamide copolymer containing 50 to 99 moles of repeating units represented by formula (I),
The repeating unit represented by formula (1) is a polyamide copolymer, (in the formula, Ar' is a divalent aromatic residue having 6 to 20 carbon atoms.) CH3 (J IJ (V) (Vl) and The repeating unit represented by formula (III) and the following formula (1m
An aromatic polyamide-imide copolymer consisting of a repeating unit represented by (wherein Ar'' is a divalent aromatic residue) is particularly preferred.

[Heat treatment method]

The heat treatment method of the present invention includes [(glass transition temperature of resin) -
It is necessary to carry out the process at a temperature of 100° C. or higher and lower than the glass transition temperature of the resin. Below the lower limit of the temperature range, hardly any effect of the present invention can be expected, and above the upper limit, deformation etc. occur when processing the molded product, which is not preferable.

The heat treatment of the present invention requires at least 31 days, preferably 8 hours or more.

The shape of the thioether resin used in the heat treatment of the present invention does not matter. However, if it is in the form of a fine powder, the effect of the present invention is poor, so it is desirable that it be in the form of a molded article or pellet. Particularly in the case of melt-molded products, the intrinsic viscosity increases by 1 degree or more, and the heat distortion temperature increases by 15 degrees C. or more, so the effects of the invention are significant.

The heat treatment of the present invention is carried out by placing the thioether resin in a heating device controlled at a predetermined temperature and heating it for a predetermined period of time. Power a? There are no particular restrictions on the type of device, but it is usually convenient to open with an electric heating method, and the atmosphere in the oven may be, for example, a hot air circulation type,
A hot air flow system can be used.

[Processing/Applications]

When molding the heat-treated thioether resin of the present invention, various known filler components can be included.

Typical examples of filler components include (a) yA fibrous optical filler Nigadis fiber, carbon fiber, poron fiber, alumina fiber, silicon carbide) [fiber, etc., Φ) Inorganic filler: Myriki, talc , clay, graphite, car pump hook, silica, asbestos, molybdenum sulfide, magnesium oxide, calcium oxide, etc.

The heat-treated thioether resin of the present invention can be used to produce various parts in the electrical and electronic fields, car parts, interior materials for aircraft, sliding parts, gears, insulation materials, heat-resistant films, 1111I' thermal varnishes, Although OJ can be used in a wide range of applications such as heat-resistant fiber braiding, it is particularly recommended to take advantage of its excellent heat resistance for use in parts that are used at high temperatures.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to examples, but the scope of the present invention is not limited by these examples.

Example 1.2 and Comparative Example 1.2 Thioether resin [ηinh
= 0.7 s ttt/t (0.2% N-methylpyrrolidone solution, measured at 30°C) oTr = 227°C]
Cm/n"80/20 (molar ratio)] was compression molded at 320°C to create test pieces. Each of the test pieces was placed in a hot air circulation type heating furnace set at the temperature shown in Table 1. Heat treatment was performed for the times shown in Table 1.

Table 1 also shows the measurement results of ηinh, heat distortion temperature, mechanical properties, water absorption, etc. for each test piece after heat treatment.

As is clear from Table 1, when the heat treatment temperature is low (Comparative Example 1), there is almost no effect of improving ηinh or heat distortion temperature. Also, when the heat treatment time is short (Comparative Example 2), η
There is almost no effect of improving inh or heat distortion temperature. On the other hand, according to the heat treatment conditions of the present invention, ηinh and heat distortion temperature were dramatically improved.

Margin below C) [Chapter] Table] 1) Measured by DSC.

2) 0.2% N-methylpyrrolidone solution, 30°C.

33 Load 18.6 kf/ct/.

4), 5) Based on ASTIvi D-638.

6) Based on ASTM D-570 (2411r, &
[η1nh=
o, 65 dt/y (0,2% N-methylpyrrolidone solution, measured at 30°C) o Ty = 260°C] - (m/n
10/p=40/40/IO/10 (molar ratio)] to 3
A test piece was prepared by compression molding at 25°C. This test piece was placed in a hot air circulation type heating furnace set at the temperature shown in Table 2, and heat treated for the time shown in Table 2.

For each test piece after heat treatment, ηinh, heat distortion temperature,
Measurement results regarding mechanical properties, etc. are also shown. As a result, under the heat treatment conditions of the present invention, ηinh and thermal deformation temperature force were significantly improved.

[Table 2] 1) Measured by DSC.

23 0.2% N-methylpyrrolidone solution, 30'C0
3) 18.6 ky/1tti load.

4) Compliant with ASTM D-638.

Example 4 and Comparative Example 3 Thioether resin [ηinh
= 0.57 dl/f (0.2% N-methylpyrrolidone solution, measured at 30°C) o'l'y = 240°C] was compression molded at 320°C to create a test piece. This test piece was placed in a hot air circulation type heating furnace set at the temperature shown in Table 3, and heat-treated for the time shown in Table 3.
Measurement results regarding mechanical properties, etc. are also shown.

As is clear from Table 1, when the heat treatment temperature is high (Comparative Example 3), the effect of improving ηinh and heat distortion temperature is large, but the difference from the heat treatment conditions of the present invention (Example 4) is small. This is not preferable because it may cause sagging in the molded product.

[Table 3] 1) 1) Measured by SC.

21 0.2% N-methylpyrrolidone solution, 30℃33
18.6 kg/ca load.

4) Compliant with ASTM D-63s.

Comparative Example 4 A test piece was prepared by compression molding a polyetherimide resin (C08, Ultem-1000) having the structure shown below at 315°C.

This test piece was placed in a hot air circulation type heating furnace set at the temperature shown in Table 4, and heat treated for the time shown in Table 4.

For each test piece after heat treatment, measurement results regarding ηinh, heat distortion temperature, mechanical properties, etc. are also shown. As a result, although the heat distortion temperature increased, +7 inh hardly changed, and there was no effect like the present invention.

(Margin below) [Table 4] 1) Measured by DSC.

2) 0.2% N-methylpyrrolidone solution, 30°C 0
3) 18.6 m/d load.

4) Compliant with ASTIVl, D-638.

Claims (2)

[Claims] (1) An amorphous aromatic thermoplastic resin containing a thioether bond as an essential component and further containing an amide group and/or an imide group at a temperature below the glass transition temperature of the resin [(glass transition temperature of the resin) -100°C ] A method for heat-treating a thioether-based resin, which is characterized by heat-treating for 3 hours or more under the above temperature conditions to increase its intrinsic viscosity and heat distortion temperature. (2) A patent in which the amorphous aromatic thermoplastic resin described in claim 1 is an aromatic polyamide and/or imide resin having repeating units represented by the following formulas (I) to (III). The method according to claim 1. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, Ar is a divalent aromatic group. It is a residue.Also, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼
It is. )