JPH0559279A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene sulfide resin composition improved in flow and mold release and excellent in moldability. CONSTITUTION:A resin composition prepared by adding 0.1-20 pts.wt. aromatic sulfonamide compound to 100 pts.wt. polyphenylene sulfide resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) which originally has high heat resistance,
The present invention relates to a PPS resin composition which retains mechanical strength and is excellent in molding processability such as fluidity and releasability.

[0002]

2. Description of the Related Art PPS resin has excellent heat resistance, chemical resistance, abrasion resistance, favorable creep resistance, high dimensional stability and the like due to its high crystalline structure, and is mainly used for injection molding. It is used for various electrical parts, mechanical parts, automotive parts, etc. However, it is sometimes pointed out that the PPS resin is slow to be solidified and its releasability is insufficient because the PPS resin is usually molded at a high mold temperature of 120 ° C. or higher in its injection molding. Since the reinforcing material and the filler are used in a relatively large amount, the lack of fluidity may be a problem. Several proposals have been made so far for the improvement of the moldability of such a PPS resin. For example, as a means for improving the releasability of the PPS resin, a method of adding polyethylene, polyethylene wax or the like (Japanese Patent Laid-Open No. 54-54
47752), a method of adding glycerin triester (JP-A-58-74751), and a method of adding pentaerythritol tetraester (JP-A-63).
-289068 gazette) and PPS.
As a means for improving the fluidity of the resin, a method of adding a bisamide compound or the like (Japanese Patent Laid-Open No. 64-51463) has been proposed. However, it is difficult to say that these known conventional techniques have sufficiently satisfactory results because they are not sufficiently effective, and that they have adverse effects such as poor appearance of molded products and bleed-out of additives. Met.

[0003]

Therefore, according to the present invention, the PP
PPS with excellent moldability by improving fluidity and releasability without impairing the heat resistance and strength of S resin.
An object is to obtain a resin composition.

[0004]

That is, the present invention is a PP
Provided is a PPS resin composition obtained by adding 0.1 to 20 parts by weight of an aromatic sulfonamide compound to 100 parts by weight of S resin. Since the resin composition of the present invention has improved fluidity and mold releasability, the molding cycle can be shortened, and the mold temperature can be lowered to around 100 ° C. for better fluidity. It has a secondary effect that a molded product with good appearance and physical properties can be obtained, and it can be said that the contribution to the improvement of productivity is extremely large. The PPS resin used in the present invention has the structural formula (I)

[0005]

[Chemical 1]

It is a polymer containing 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by: When the content of the repeating unit is less than 70 mol%, heat resistance is impaired, which is not preferable. The PPS resin used in the present invention can comprise less than 30 mol% of its repeating unit with a repeating unit having the following structural formula.

[0007]

[Chemical 2]

Although PPS resins obtained by any method can be used in the present invention, essentially linear and relatively high molecular weight polymers are preferred.

The aromatic sulfonamide compound used in the present invention is represented by the following general formula (II).

[0010]

[Chemical 3]

(Here, Ar represents a monovalent aromatic hydrocarbon group, and R ¹ and R ² are each a hydrogen atom or a carbon number of 1.
Selected from the alkyl groups of 6 to 6, R ¹ and R ² may be the same or different from each other. ) Specific examples of the aromatic sulfonamide compound used in the present invention include N-butylbenzenesulfonamide, N-ethyl-o-toluenesulfonamide, N-ethyl-p-toluenesulfonamide and N-isopropylbenzenesulfone. Amide, N-ethylbenzenesulfonamide, N, N'-dibutylbenzenesulfonamide, N, N'-diethylbenzenesulfonamide, N, N'-diethyl-o-toluenesulfonamide, N, N'-diethyl-p-toluene Examples thereof include sulfonamide, and these compounds can be used alone or in the form of a mixture of two or more aromatic sulfonamide compounds. The compounding amount of the aromatic sulfonamide compound in the present invention is 0.1 to 20 parts by weight, preferably 0.3 to 1 part by weight with respect to 100 parts by weight of the PPS resin.
Within the range of 5 parts by weight. If the blending amount is less than 0.1 part by weight, the effect of improving the releasability and fluidity will not be exhibited, which is not preferable. On the contrary, if the blending amount exceeds 20 parts by weight, the drawing phenomenon during molding and the strength of the molded product are not achieved. It is not preferable because the decrease of

The fibrous or non-fibrous filler used in the present invention includes glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, metal fibers and titanic acid. Fibrous fillers such as potassium whiskers and carbon fibers are included. As the non-fibrous filler, wollastenite, sericite,
Kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, alumina, silicon chloride, magnesium oxide, zirconium oxide,
Metal compounds such as titanium oxide, carbonates such as magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, non-fibrous fillers such as boron nitride, silicon carbide and silica, and the like. May be hollow. These fibrous and non-fibrous fillers can be used alone or in combination of two or more. The blending amount of these fillers in the present invention is 10 to 100 parts by weight of the PPS resin.
In the range of 400 parts by weight, preferably 15 to 350 parts by weight,
It is more preferably in the range of 20 to 300 parts by weight, and by appropriately selecting the compounding amount within this range, a resin composition having excellent strength of the molded product can be obtained. If necessary, these fillers can be pretreated with a coupling agent such as a silane-based, titanium-based or aluminum-based coupling agent.

Further, the PPS resin composition of the present invention contains an antioxidant, a heat stabilizer, a lubricant, a crystal nucleating agent, an anti-UV agent, a coloring agent, a flame retardant, etc. within a range not impairing the effects of the present invention. Ordinary additives may be added, and for the purpose of controlling the degree of crosslinking of the PPS resin, ordinary peroxides and crosslinking of thiophosphinic acid metal salts described in JP-A-59-131650 and the like may be added. Accelerator or JP-A-58-20
4045 and JP-A-58-204046, and the like, dialkyltin dicarboxylates,
It is also possible to incorporate a crosslinking inhibitor such as aminotriazole.

Further, the PPS resin composition of the present invention is a polyamide, polyphenyleoxide, polysulfone, tetrafluoropolyethylene, polyetherimide, polyamideimide, polyimide, polycarbonate, polyether as long as the effect of the present invention is not impaired. Resins such as sulfone, polyether ketone, polyether ether ketone, epoxy resin, phenol resin, polyethylene, polystyrene, polypropylene, ABS resin, polyester, polyamide elastomer, and polyester elastomer may be contained.

The method for preparing the PPS resin composition of the present invention is not particularly limited, and after the PPS resin, the aromatic sulfonamide compound and, if necessary, the reinforcing material are dry blended using a ribbon blender, a Henschel mixer, a V blender or the like. , A method of directly molding into the hopper of a molding machine, or a method of dry-blending the above mixture and then melt-kneading it using a Banbury mixer, a mixing roll, a single-screw or twin-screw extruder and a kneader. Be done. Of these, a typical method is melt kneading using a single-screw or twin-screw extruder having a sufficient kneading force.

[0016]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The characteristics described in Examples and Comparative Examples are measured as follows.

Tensile strength: ASTM D638 Bending strength: ASTM D790 Izod impact strength: ASTM D256 Releasability: A 40 × 15 × 1 mm flat plate molded product having a rib portion with a height of 2 mm in the central portion and a clamping force of 20 tons The mold release force at the time of injection molding was measured using a injection molding machine under the conditions of a cylinder temperature of 310 ° C. and a mold temperature of 120 ° C., and used as a guide for mold releasability.

Fluidity: At the time of molding the above-mentioned molded article, the minimum lower limit filling pressure was measured and used as a measure of fluidity.

Appearance of molded product: The surface condition of the molded product was visually observed.

◯: Good surface smoothness x: Roughness on the surface Example 1 PPS resin powder (M258 manufactured by Toray-Philips)
8) 100 parts by weight and 3 parts by weight of N-butylbenzenesulfonamide are blended, and 30 mmφ counter rotating type 2
Using a shaft extruder, the mixture was melt-kneaded under the conditions of a cylinder temperature of 300 ° C. and a screw rotation speed of 150 rpm, and the strand was cooled with water and pelletized with a pelletizer. After hot-drying the pellets with hot air at 120 ° C. for 5 hours, a test piece for measuring mechanical properties was used under the conditions of a cylinder temperature of 310 ° C. and a mold temperature of 140 ° C. using an injection molding machine, and the fluidity under the above conditions.
Molded products for releasability and appearance evaluation were molded. The properties of the resin composition obtained here are as shown in Table 1, and it is an excellent PPS resin composition which is excellent in molding processability such as fluidity and releasability and has sufficient mechanical strength. There was found.

Comparative Example 1 Extrusion pelletization of PPS was carried out in the same manner as in Example 1 except that N-butylbenzenesulfonamide was not added.
Various moldings were obtained by injection molding. These characteristics are as shown in Table 1, and the fluidity and releasability were insufficient.

Comparative Example 2 Instead of N-butylbenzenesulfonamide, N, N '
Melt kneading, pelletizing, and injection molding were carried out in the same manner as in Example 1 except that ethylenebisstearoylamide was used to obtain various molded products. The characteristics of the molded product obtained here are as shown in Table 1, and some improvement effects were recognized in terms of fluidity and mold release property, but the appearance of the molded product was non-uniform and the mechanical strength was There was a decline and it was not satisfactory.

[0023]

[Table 1]

Example 2 100 parts by weight of the PPS resin powder used in Example 1, 5 parts by weight of N-butylbenzenesulfonamide and 65 parts by weight of glass fiber chopped strands (fiber diameter 13 μm) were dry blended with a V blender, Using a 40 mmφ single-screw extruder, the mixture was melt-kneaded into pellets under the conditions of a cylinder temperature of 320 ° C. and a screw rotation speed of 80 rpm.
The pellets were dried with hot air at 140 ° C. for 3 hours, then the temperature of the cylinder was 320 ° C. and the mold temperature was 140 ° C. using an injection molding machine.
A test piece for mechanical property measurement was formed under the condition of ° C, and a molded article for fluidity, releasability and appearance evaluation was formed by the procedure described above. The various properties of the molded product obtained here are as shown in Table 2, and it was found that this reinforced PPS resin composition also has good moldability and strength and is of high practical value.

Comparative Example 3 Various moldings were obtained by carrying out melt kneading and injection molding in exactly the same manner as in Example 2 except that N-butylbenzenesulfonamide was removed. These characteristics are as shown in Table 2, and the fluidity and the releasing force were insufficient.

Examples 3 to 5 Resin compositions obtained by carrying out extrusion kneading and injection molding in the same manner as in Example 2 while changing the types and blending amounts of the PPS resin powder, the aromatic sulfonamide compound, and the filler in various ways. The various characteristics of the above are summarized in Table 2. All of these had excellent moldability and mechanical properties.

[0027]

[Table 2]

[0028]

Industrial Applicability The resin composition comprising the PPS resin of the present invention, the aromatic sulfonamide, and the inorganic filler optionally added has good moldability such as fluidity and releasability and is sufficient. It is a material that has mechanical strength and is particularly suitable for injection molding applications.

Claims (2)

[Claims] 1. An aromatic sulfonamide compound is added in an amount of 0.1 to 20 relative to 100 parts by weight of a polyphenylene sulfide resin.
A polyarylene sulfide resin composition obtained by adding and blending parts by weight. 2. 100 parts by weight of a polyphenylene sulfide resin, 0.1 to 20 parts by weight of an aromatic sulfonamide compound, and at least one kind of fibrous or non-fibrous filler.
A polyarylene sulfide resin composition containing about 400 parts by weight.