JPH0759666B2 - Polyarylene sulfide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention is a resin composition comprising a polyarylene sulfide resin, glass fiber, talc and magnesium hydroxide in a specific composition ratio, The present invention relates to a polyarylene sulfide resin composition having excellent arc resistance and capable of obtaining a good surface appearance of a molded product. The composition of the present invention is used in a wide variety of fields such as electric / electronic parts and automobile parts.

[Prior Art] Polyarylene sulfide resins typified by polyphenylene sulfide resins (PPS resins) have recently been excellent in heat resistance, chemical resistance, rigidity, dimensional stability, and the like. Application development is being attempted in fields such as parts where heat resistance and dimensional accuracy are required.

However, since the resin alone is inferior in impact resistance and mechanical strength, various proposals have been made regarding resin compositions in which various inorganic substances are mixed with the resin for the purpose of improving these properties. Further, a composition having improved arc resistance and the like has been proposed for the purpose of being used particularly in electric / electronic parts and automobile parts (for example, JP-A-53-5252 and JP-A-5452).
-162752, JP-A-59-131653, etc.).

[Problems to be Solved by the Invention]

The previous proposals used for this purpose are:
It was a composition mainly containing inorganic fillers such as talc and clay, but when these are molded into large molded products, especially with an injection molding machine, the inorganic fillers gather on the surface of the molded product and the surface appearance of the molded product is improved. It tended to get worse.

Therefore, it has been desired to improve the surface appearance of the molded product while keeping the characteristics such as arc resistance.

[Means for solving problems]

In order to achieve the object of the present invention, as a result of diligent studies on various compositions, it was found that the problem can be solved by blending talc and magnesium hydroxide in a specific composition, and the present invention was reached.

That is, the object of the present invention can be achieved by adding 20 to 120 parts by weight of glass fiber, 30 to 80 parts by weight of talc, and 10 to 50 parts by weight of magnesium hydroxide to 100 parts by weight of polyarylene sulfide resin.

The polyarylene sulfide resin used in the present invention has, in terms of heat resistance, chemical resistance, and mechanical properties, 70 mol% or more of its repeating units have a structural formula It is preferably a p-phenylene sulfide unit represented by This p-phenylene sulfide unit is 70
If it is less than mol%, the heat resistance is lowered, which is not preferable.
The remaining less than 30% component is m-phenylene sulfide bond Diphenyl ether bond Diphenyl sulfone bond Biphenyl bond Substituted paraphenylene sulfide bond (Wherein R is selected from the group consisting of alkyl groups having 12 or less carbon atoms and nitro groups), trifunctional phenyl sulfide bonds, and the like.

In the present invention, the melt flow rate of the polyarylene sulfide resin having the above structure, measured by using a melt flow tester defined by ASTM D 1238 under the conditions of 315 ° C. and a load of 5 kg is 5 to 10,000 g / 10 min. One, preferably 15 to 5000 g / 10 min is used. In addition, particularly in the case where the fluidity is required, as the polyarylene sulfide resin, those having a melt flow rate of 5 to 300 g / 10 min and those having a melt flow rate of 400 to 10,000 g / 10 min under the above conditions are used. It is preferable to use a resin mixture obtained by mixing in a ratio of 5/95 to 95/5.

Specific examples of the polyarylene sulfide resin include Ryton (trade name of PPS resin, manufactured by Phillips Petroleum Co., Ltd.), Toprene (trade name of PPS resin, manufactured by Topren Co., Ltd.), and Fortron (trade name of PPS resin, Kureha Chemical Co., Ltd.). Manufactured by Tosoh Sustain Co., Ltd., etc.

The glass fiber used in the present invention has a fiber diameter of 5 to 20 μm,
Particularly, those having a fiber length of 6 to 15 μm and a fiber length of 1.0 to 20 mm, particularly 1.5 to 6 mm are preferable. If the fiber diameter is smaller than 5 μm, the kneading may be difficult and the fiber may be easily broken.
When the fiber diameter is larger than 20 μm, the mechanical strength of the composition becomes poor. If the fiber length is shorter than 1.0 mm, the mechanical strength of the composition will decrease. If the fiber length is longer than 20 mm, the kneading may be difficult.

This glass fiber is 0.05 to 3 with respect to 100 parts of glass fiber.
Those surface-treated with a part of the silane coupling agent are preferable. Examples of the silane coupling agent include vinylethoxysilane, vinyltrichlorosilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and N-β- (aminoethyl. ) -Γ-Aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-
Aminosilane compounds such as aminopropylmethyldiethoxysilane can be used. In addition, it is preferable to use an appropriate amount of urethane and / or epoxy sizing agent.

The blending ratio of the glass fiber is in the range of 20 to 120 parts by weight, preferably 40 parts by weight based on 100 parts by weight of the polyarylene sulfide resin.
The range is up to 100 parts by weight. If it is less than 20 parts by weight, the mechanical strength is remarkably inferior and it cannot be put to practical use. If it is more than 120 parts by weight, it becomes brittle and cannot be put to practical use.

In the present invention, the arc resistance is expressed by talc and magnesium hydroxide, but the mixing ratio of talc and magnesium hydroxide is 100 to 100 parts by weight of the polyarylene sulfide resin, talc 30 to 80 parts by weight, preferably 40 to 70 parts by weight, and magnesium hydroxide 10 to 50 parts by weight, preferably 15 to 40 parts by weight. Further, in the composition of the present invention, a preferable composition is that the total amount of talc and magnesium hydroxide is a polyarylene sulfide resin 10
0 to 100 parts by weight, particularly preferably 55 to 100 parts by weight
It is in the range of 95 parts by weight. If the amount of talc becomes too small, the arc resistance becomes poor. Too much talc is not suitable because the resulting composition becomes brittle. Further, if the total amount of talc and magnesium hydroxide becomes too large, the composition may become brittle. Furthermore, if the amount of magnesium hydroxide is too small, the surface appearance of the injection-molded product will be significantly deteriorated.

The talc and magnesium hydroxide used herein preferably have an average particle diameter of 0.1 μm to 10 μm. If the average particle size is smaller than 0.1 μm, the mixing properties with the polyarylene sulfide resin may be poor, the electrical characteristics may become unstable, and the mechanical strength may be reduced, such being undesirable. If the average particle size exceeds 10 μm,
The surface appearance of the molded product may be deteriorated, the electrical characteristics may be deteriorated, and the mechanical strength may be deteriorated, which is not preferable.

Talc and magnesium hydroxide used here are fatty acids such as stearic acid and oleic acid and salts thereof, surface treating agents such as stearyl alcohol and / or vinylethoxysilane, vinyltrichlorosilane, γ-glycidoxypropyltrimethoxysilane. , Γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (aminoethyl) -γ-
In order to improve the dispersibility of the composition, it is preferable to use the one surface-treated with a silane coupling agent such as aminopropyltriethoxysilane and N-β- (aminoethyl) -γ-aminopropylmethyldiethoxysilane. .
The treatment amount is preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of talc and magnesium hydroxide.

Specific examples of talc include CHC-11P, CHC-13P, CHC-1.
3A03 (Hayashi Kasei Co., Ltd.), TALCKUP (Fuji Talc Industry Co., Ltd.)
and so on.

Specific examples of magnesium hydroxide include Kisuma 5A, Kisuma 5B (manufactured by Kyowa Chemical Industry Co., Ltd.), D5, D7L (manufactured by Ube Chemical Industry Co., Ltd.).

The resin composition of the present invention, as long as the object of the present invention is not impaired, hindered phenol, hydroquinone, thioethers, phosphites and antioxidants and heat stabilizers such as substitution products thereof, resorcinol, salicylate,
UV absorbers such as benzotriazole and benzophenone, fatty acids and salts thereof such as stearic acid and oleic acid, mold release agents such as stearyl alcohol, sodium dodecylbenzenesulphonate, antistatic agents such as polyalkylene glycols, crystallization accelerators, One or more kinds of additives such as a crystallization retarder, a dye and a pigment can be added.

In addition, a small amount of thermoplastic resin such as polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / propylene copolymer, polystyrene, oliamide, polyester, polyacetal, polycarbonate, polysulfone, polyphenylene ether, polyarylate, or phenol resin, Melamine resin, silicone resin,
It is also possible to add a thermosetting resin such as an epoxy resin, or a thermoplastic elastomer such as a styrene / butadiene copolymer, a hydrogenated butadiene / styrene block copolymer, a polyester elastomer and a polyamide elastomer.

Further, various reinforcing materials and fillers can be added within the range not impairing the object of the present invention. Specific examples of the reinforcing material and the filler include asbestos fiber, carbon fiber, silica fiber, silica alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, stainless steel, aluminum, titanium, copper and brass. , Metal fibers such as magnesium, and polyamide fibers,
Fluororesin fibers, polyester fibers, organic fibers such as acrylic resin fibers, copper, iron, nickel, zinc, tin, lead,
Stainless steel, metal powder such as aluminum, gold, silver and magnesium, fumed silica, aluminum silicate, glass beads, glass flakes, carbon black, quartz powder, talc, titanium oxide, iron oxide, calcium carbonate, diatomaceous earth, mica There are powders. Of these, fibrous substances have an average fiber diameter of 3 to 50 μm and a fiber length of 50 μm.
It can be used in the range of m to 30 mm. Further, as these reinforcing materials and fillers, those surface-treated with a known silane coupling agent or titanate coupling agent can also be used.

Production of the resin composition of the present invention, continuous kneaders such as extruders, Banbury mixer, batch-type kneaders such as kneader, can be carried out by a usual melt-kneading processing apparatus, further, injection molding, It can be processed into molded articles for various uses by compression molding, extrusion molding and the like.

The present invention will be described below with reference to examples.

Example of the present invention

Arc resistance, bending strength described in Examples and Comparative Examples,
The bending elasticity and the surface appearance of the molded product were evaluated by the following methods.

(1) Arc resistance According to ASTM D 495, it was tested using an arc resistance tester manufactured by Nissho Denki Seisakusho.

(2) Flexural strength and flexural modulus Measured according to ASTM D 790. (Unit: Kgf / cm ² ) (3) Surface appearance of molded product A disk having a thickness of 3 mm and a diameter of 100 mm was injection molded, and the surface was visually observed.

Examples 1 to 4, Comparative Examples 1 to 6 Toprene T-4 (manufactured by Topren Co., Ltd.), talc 1 (average particle size 5 μm, aminosilane compound treated product), talc 2
(Average particle size 5 μm, stearic acid treated product) Magnesium hydroxide (flakes, average particle size 1.5 μm, stearic acid treated product), glass fiber (fiber diameter 13 μm, fiber length 3 m
m, silane-treated converged product) at a ratio shown in Table 1 was charged into a twin-screw kneader set at 310 ° C., and melt-mixed to produce pellets. Using an injection molding machine, various test pieces were prepared from the pellets under the conditions of a cylinder temperature of 300 ° C. and a mold temperature of 150 ° C., and evaluated under predetermined conditions.

Further, without using magnesium hydroxide (Comparative Example 1),
Increasing the blending ratio of magnesium hydroxide (Comparative Example 2), instead of magnesium hydroxide, calcium carbonate (average particle diameter 1.8 μm) (Comparative Example 3), aluminum hydroxide (synthetic product, average particle diameter 1.5) ( Comparative Example 4), magnesium hydroxide (manufactured by Nippon Lime Co., Ltd., 150 mesh total pass)
Using (Comparative Example 5), further reducing the compounding ratio of the glass fiber (Comparative Example 6), mixing and molding under the same conditions,
An evaluation was performed to compare with a talc / magnesium hydroxide-based composition. The results are shown in Table 1.

[Effects of the Present Invention] According to the present invention, polyarylene that has sufficient mechanical strength, high heat resistance, and arc resistance and is excellent in the appearance of molded products and that can be used in the field of electrical / electronic parts or automobile parts A sulfide resin composition can be provided.

Claims (1)

[Claims] 1. A resin composition containing 20 to 120 parts by weight of glass fiber, 30 to 80 parts by weight of talc, and 10 to 50 parts by weight of magnesium hydroxide to 100 parts by weight of a polyarylene sulfide resin.