JPH07100759B2 - Molded product of aromatic polyarylketone resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to an aromatic polyarylketone resin composition used as a material for a molded article having heat resistance.

[Conventional technology]

Polyarylketone resins represented by polyetheretherketone resins developed by ICI Corporation in the UK are widely used as so-called engineering plastics with excellent heat resistance, flame retardancy, hydrolysis resistance and chemical resistance. However, for various molded products that are often used at high temperatures, such as insulation coatings for electric wires and cables, aircraft parts, electric / electronic parts, etc., a resin with better mechanical properties at high temperature should be used. There is a strong demand.

Polyarylketone resin is originally a highly crystalline polymer, but has a relatively low glass transition temperature of about 140 to 170 ° C. and cannot be said to have sufficient mechanical properties at a glass transition point or higher, In particular, further improvement in heat resistance is desired as a material for the above-mentioned molded article placed under high temperature.

[Problems to be solved by the invention]

As described above, in the conventional technique, the molded product has excellent heat resistance, hydrolysis resistance, and chemical resistance, and further has excellent mechanical properties under conditions in which a load is applied at a temperature higher than the glass transition temperature of the polyarylketone resin. There is a problem that there is no molded product of the polyarylketone resin composition that exhibits the desired strength.

[Means for solving problems]

In order to solve the above problems, the present invention relates to an aromatic polyarylketone resin comprising a polymer of repeating units represented by the following general formula and a phenol resin in a weight ratio of (40 to 99) to (60). 1) to 1) and melt-molded the mixture to obtain a molded product of the aromatic polyarylketone resin composition. The details will be described below.

First, the aromatic polyaryl ketone resin of the present invention has the general formula Is a polymer represented by. Wherein Z, Z ′ and Z ″ in the formula are divalent aromatic residues containing at least one carbon 6-membered ring, for example , Q is O, CO or a direct bond, and n is 0.
Is an integer of ˜3. And a particularly typical polyarylketone resin has the general formula A crystalline polyetheretherketone resin represented by the following formula (hereinafter abbreviated as PEEK resin), which is commercially available from ICI Corporation in the United Kingdom. For example, according to European Patent No. 1879 (corresponding to JP-A-54-90296), this resin contains 4,4'-difluorobenzophenone and hydroquinone in a solvent of diphenyl sulfone at 150 to 400 ° C. Obtained by reacting under temperature conditions. In the polyarylketone resin of the present invention, in addition to the arylketone structural unit as a main component, other copolymerized units may be partially introduced, if necessary. The method for producing such a copolymer is disclosed in, for example, British Patent No. 1,414,421 and Japanese Patent Laid-Open No. 52-38000.

Next, the phenol resin used in the present invention is preferably one that is not thermally deteriorated even at the molding temperature of the aromatic polyarylketone resin and can be melted at the same time. For example, a phenol / alkyl resin or a phenol / formaldehyde resin is preferable. The phenol / alkyl resin is
For example Examples of the resin having a chemical structure represented by the following are commercially available products such as trade name Millex XL-225 manufactured by Mitsui Toatsu Chemicals, Inc. The phenol / formaldehyde resin is, for example, a phenol / aldehyde resin which is a condensation product of phenols and aldehydes, or a nitrogen-containing phenol / aldehyde copolymer resin which is a condensation product of phenols, nitrogen-containing compounds and aldehydes. is there. Here, as the phenols, phenol, cresol, xylenol, monovalent phenol such as alkylphenol, catechol, resorcin, divalent phenol such as hydroquinone, pyrogallol, trivalent phenol such as phloroglucin, formaldehyde as aldehydes,
Examples thereof include aliphatic saturated aldehydes such as acetaldehyde, paraformaldehyde, trioxane (metaformaldehyde) and the like, and examples of nitrogen-containing compounds include compounds having at least two active hydrogens such as urea, aniline, melamine and guanidine. . A method for producing such a phenol resin is described in, for example, JP-A-57-17.
A large number have already been disclosed in Japanese Patent No. 701, Japanese Patent No. 58-17114, and others.

The mixing ratio of the aromatic polyarylketone resin and the phenol resin is preferably (40 to 99) to (60 to 1) by weight. This is because when the amount of the phenol resin is less than 1 part by weight, the effect of improving the heat distortion temperature of the polyarylketone resin is small, and conversely, when the amount of the resin exceeds 60 parts by weight, there is almost no increase effect on the improvement of the heat distortion temperature. This is because it is not expected and it is not preferable because the original properties of the polyarylketone resin are impaired. It is preferable that the polyarylketone resin is 50 to 95 parts by weight, and the phenol resin is 50 to 5 parts by weight, as a ratio for practical use. Incidentally, also in the composition of the present invention, as in the case of the ordinary resin composition, within a range that does not impair the main purpose of the invention, for example, graphite, carbon, silica powder, molybdenum disulfide, fluorine resin, etc. Abrasivity improver, glass fiber, carbon fiber, boron fiber, silicon carbide fiber, asbestos rock wool, reinforcing (reinforcing) material such as metal fiber, flame retardant such as antimony trioxide, magnesium carbonate, calcium carbonate, clay, mica, Electrical property improvers such as asbestos, silica, graphite, acid resistance improvers such as barium sulfate, silica, calcium metasilicate, thermal conductivity improvers for metal powders such as iron, zinc, aluminum and copper, glass beads , Glass spheres, calcium carbonate, alumina, talc, diatomaceous earth, hydrated alumina, shirasu balloon, and other metal oxides News such as a pigment may be mixed stable materials are more than 350 ° C..

Various operations such as blending, heating, melting, and mixing of the raw materials of the present invention utilize a heat roller, a Banbury mixer, a brabender, an extruder, etc., and usually 340 to 400 ° C., preferably 350 to 380.
It suffices to continue until a uniform mixture is obtained at 0 ° C, and the polyarylketone resin as the base material, the phenol resin, and the fillers added as necessary may be individually supplied to the melt mixer, Alternatively, a part or all of these may be pre-mixed with a mortar, a Henschel mixer, a ball mill, a ribbon blender or the like and then supplied to a melt mixer, or by melt-blending a polyarylketone resin and a filler. A two-stage Brent method of making a master batch and melt-blending this with a phenol resin may be adopted. The heat resistance of the obtained molded product can be further improved by subjecting it to a heat treatment at a temperature not higher than the melting point of the polyarylketone resin.

〔Example〕

Examples 1 to 4: PEEK resin (manufactured by UK ICI, glass transition point 14
3 ° C., melting point 334 ° C.) and phenol resin (Mitsui Toatsu Chemical Co., Inc .: Millex SP-2000 at the ratios shown in the table) were dry-blended and then fed to a melt extruder to obtain a cylinder temperature
The mixture was melt-kneaded at 350 to 360 ° C. and a screw rotation speed of 100 rpm to be granulated, and this was molded into a test piece under the conditions of 360 ° C. and 100 kg / cm ² . Heat distortion temperature of the obtained test piece (according to ASTM-D648), bending stress kg / cm ² (according to ASTM-D790), bending elastic modulus (according to ASTM-D790) and Izod impact strength kg.
cm / cm (according to ASTM-D256) was measured and the results are summarized in the table.

Comparative Examples 1 to 3: Test pieces were prepared by the same procedure as in Example 1 except that the mixing ratio of PEEK resin and phenol resin was out of the range of the present invention as shown in the table. In the same manner, and the obtained results are also shown in the table. I wrote it.

As is clear from the table, in Examples 1 to 4, the heat deformation temperature was much higher than in Comparative Example 1 in which no phenol resin was mixed, and the bending elastic modulus at high temperature was also extremely excellent. The stress and Izod impact strength were well balanced. When the amount of the phenol resin mixed is small as in Comparative Example 3, almost no effect of improving the flexural modulus at high temperature is observed, and when it is large as in Comparative Example 2, the Izod impact strength is significantly reduced. In either case, no favorable result was obtained.

〔effect〕

The molded product of the aromatic polyarylketone resin composition of the present invention retains the heat aging resistance peculiar to the polyarylketone resin, and has high strength, elastic modulus, and further hydrolysis resistance under the usage conditions under high temperature load as a molded material. Since it also has both heat resistance and chemical resistance, it is used as a component in all fields such as aerospace equipment, electric and electronic equipment, nuclear power equipment, automobiles, general industrial equipment, hot water equipment, etc. It can be said that the present invention is extremely significant because it can exhibit excellent properties such as strength, sliding properties, electrical properties, and solvent resistance.

Claims (1)

[Claims] 1. A general formula (In the formula, Z, Z ′ and Z ″ are divalent aromatic residues containing at least one 6-membered carbon ring, Q is O, CO or a direct bond, and n is an integer of 0 to 3) Aromatic polyarylketone resin consisting of a polymer having the repeating unit of (1) as a main structural unit and a phenolic resin are blended in a weight ratio of (40 to 99) to (60 to 1) and melt-molded. A molded article of the aromatic polyarylketone resin composition.