JP2016164223A - Polyarylene sulfide composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylene sulfide composition useful for electronic component applications such as electric and electronic components or automobile electric components because it is especially excellent in electrical characteristics such as voltage resistance, and a case containing the same.SOLUTION: There is provided a polyarylene sulfide composition containing at least 10 to 100 pts.wt. of (B) a strontium compound and 10 to 150 pts.wt. of (C) a fibrous filler, based on 100 pts.wt. of (A) polyarylene sulfide.SELECTED DRAWING: None

Description

  The present invention provides a polyarylene sulfide-based composition that is excellent in electrical properties such as voltage resistance and at the same time excellent in mechanical strength without impairing the heat resistance, chemical resistance, dimensional stability, etc. inherent to polyarylene sulfide. More particularly, the present invention relates to a polyarylene sulfide-based composition that is particularly useful for electrical component applications such as electrical / electronic components or automotive electrical components.

  Polyarylene sulfide is a resin that exhibits excellent properties such as heat resistance, chemical resistance, and dimensional stability. Utilizing these excellent properties, it is widely used in electrical and electronic equipment members, automotive equipment members, OA equipment members, etc. Has been. However, since polyarylene sulfide resins are inferior in voltage resistance compared to other engineering plastics such as polyamide, their use in applications where they are exposed to relatively high voltages has been limited.

  On the other hand, in recent years, automobiles have become more and more electrical, and as a result of the demand for smaller parts, high voltage resistance has been required for the resin materials used.

  Improvement of the voltage resistance of polyarylene sulfide has been studied so far. For example, a polyarylene sulfide composition comprising polyarylene sulfide, hexagonal boron nitride, and flat glass fiber has been proposed (see, for example, Patent Document 1). .)

Japanese Patent No. 5525682 (see, for example, the claims).

  However, although the resin composition proposed in Patent Document 1 has the characteristics of excellent dielectric breakdown strength and arc resistance, the voltage resistance when a high voltage is applied has not been studied.

  Accordingly, an object of the present invention is to provide a polyarylene sulfide-based composition that has excellent voltage resistance and at the same time excellent mechanical strength, and more specifically, electrical / electronic parts or automotive electrical parts, etc. It is an object of the present invention to provide a polyarylene sulfide-based composition that is particularly useful for electrical component applications.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have a polyarylene sulfide-based composition containing a polyarylene sulfide, a strontium compound, and a fibrous filler, while having excellent voltage resistance, The present inventors have found that the composition can be excellent in mechanical strength and have completed the present invention.

  That is, the present invention comprises at least 10 to 100 parts by weight of a strontium compound (B) and 10 to 150 parts by weight of a fibrous filler (C) with respect to 100 parts by weight of polyarylene sulfide (A). The present invention relates to a polyarylene sulfide-based composition.

  Hereinafter, the present invention will be described in detail.

  The polyarylene sulfide-based composition of the present invention contains at least 10 to 100 parts by weight of the strontium compound (B) and 10 to 150 parts by weight of the fibrous filler (C) with respect to 100 parts by weight of the polyarylene sulfide (A). .

  As the polyarylene sulfide (A) constituting the polyarylene sulfide-based composition of the present invention, any polyarylene sulfide (A) may be used as long as it belongs to the category referred to as polyarylene sulfide. Since the sulfide-based composition is excellent in mechanical strength and moldability, it was measured with a Koka flow tester using a die with a diameter of 1 mm and a length of 2 mm under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg. A polyarylene sulfide having a viscosity of 50 to 3000 poise is preferable, and a viscosity of 60 to 1500 poise is particularly preferable.

  The polyarylene sulfide (A) preferably contains 70 mol% or more, particularly 90 mol% or more of p-phenylene sulfide units as the structural unit. Examples of other structural units include m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, diphenylene sulfide units, substituent-containing phenylene sulfide units, and branched structures. It may contain a contained phenylene sulfide unit and the like, and among them, poly (p-phenylene sulfide) is preferable.

  The method for producing the polyarylene sulfide (A) is not particularly limited. For example, the polyarylene sulfide (A) can be produced by a method of reacting an alkali metal sulfide and a dihaloaromatic compound in a generally known polymerization solvent. Possible alkali metal sulfides include, for example, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and mixtures thereof, which may be used in the form of hydrates. These alkali metal sulfides are obtained by reacting an alkali metal hydrosulfide with an alkali metal base and can be prepared in situ prior to addition of the dihaloaromatic compound into the polymerization system, or outside the system. The prepared one can be used. Examples of the dihaloaromatic compound include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 1-chloro-4-bromobenzene, 4,4'-dichlorodiphenyl sulfone, 4,4'-dichlorodiphenyl ether, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl and the like. The charging ratio of the alkali metal sulfide and the dihaloaromatic compound is preferably in the range of alkali metal sulfide / dihaloaromatic compound (molar ratio) = 1.00 / 0.90 to 1.10.

  As the polymerization solvent, a polar solvent is preferable, and an organic amide which is aprotic and stable to alkali at high temperature is particularly preferable. Examples of the organic amide include N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoramide, N-methyl-ε-caprolactam, N-ethyl-2-pyrrolidone, and N-methyl-2-pyrrolidone. 1,3-dimethylimidazolidinone, dimethyl sulfoxide, sulfolane, tetramethylurea and mixtures thereof. Moreover, it is preferable to use this polymerization solvent in 150-3500 weight% with respect to the polymer produced | generated by superposition | polymerization, and it is preferable to use especially in the range used as 250-1500 weight%. The polymerization is preferably carried out at 200 to 300 ° C., particularly 220 to 280 ° C. for 0.5 to 30 hours, particularly 1 to 15 hours with stirring.

  Furthermore, even if the polyarylene sulfide (A) is linear or is treated and crosslinked at a high temperature in the presence of oxygen, a slight amount of trihalo or higher polyhalo compound is added to form a slight crosslink. Alternatively, a branched structure may be introduced, a heat treatment may be performed in a non-oxidizing inert gas such as nitrogen, or a mixture of these structures may be used.

The strontium compound (B) constituting the polyarylene sulfide-based composition of the present invention may be any strontium compound as long as it belongs to the category of strontium compounds. For example, strontium oxide, strontium hydroxide, strontium carbonate, chloride Strontium, strontium sulfate, strontium titanate, and the like can be mentioned. Among them, strontium carbonate and strontium chloride are preferable because a polyarylene sulfide-based composition having particularly excellent voltage resistance is obtained. Then, the strontium compound (B) is in the range especially be an excellent polyarylene sulfide composition voltage resistance, the average particle diameter measured by a laser diffraction scattering method (D ₅₀₎ is 0.1~500μm In particular, it is preferable to have a range of 0.5 to 200 μm, and it is preferable to have a range of 0.5 to 100 μm.

  Moreover, as for this strontium compound (B), the thing by which the surface is coat-processed or what is not carried out can be used. There are no limitations on the surface coating agent when the surface is coated. Examples of the surface coating agent include higher fatty acids and / or metal salts of higher fatty acids, anionic surfactants, phosphate esters, and silane cups. Examples thereof include ring agents, titanate coupling agents, aluminate coupling agents, polyhydric alcohol and fatty acid esters. Examples of higher fatty acids and metal salts thereof include stearic acid, oleic acid, and alkali metal salts thereof; examples of anionic surfactants include sulfates of higher alcohols; examples of phosphate esters include ortholine. Acid and higher alcohol esters, etc .; examples of silane coupling agents include vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like; titanate coupling agents such as isopropyl triisostearoyl titanate; aluminate coupling agents such as acetoalkoxyaluminum diisopropylate and the like; Examples of the esters of the call with fatty acids, for example glycerol monostearate, and the like.

As a compounding quantity of the strontium compound (B) which comprises the polyarylene sulfide type composition of this invention, it is 10-100 weight part with respect to 100 weight part of polyarylene sulfide (A). When the compounding quantity of this strontium compound (B) is less than 10 weight part, the composition obtained will be inferior to withstand voltage property. On the other hand, when the compounding amount of the strontium compound (B) exceeds 100 parts by weight, the resulting composition is inferior in mechanical strength. The fibrous filler constituting the polyarylene sulfide-based composition of the present invention (C ) Is compounded to improve the mechanical strength and dimensional stability of the polyarylene sulfide composition, and any fibrous filler can be used as long as it can achieve this purpose. It is. Examples of the fibrous filler (C) include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, asbestos fiber, stone koji fiber, and metal fiber. Among them, glass fiber is preferable. The fibrous filler (C) has a high mechanical strength of the polyarylene sulfide-based composition, so that the surface is coated with an isocyanate compound, a silane coupling agent, a titanate coupling agent, an epoxy compound, or the like. It is preferable that it has been processed.

  The blending amount of the fibrous filler (C) constituting the polyarylene sulfide-based composition of the present invention is 10 to 150 parts by weight with respect to 100 parts by weight of the polyarylene sulfide (A). When the blending amount of the fibrous filler (C) is less than 10 parts by weight, the resulting composition is inferior in mechanical strength. On the other hand, when the amount of the fibrous filler (E) exceeds 150 parts by weight, the resulting composition is inferior in voltage resistance.

  In the polyarylene sulfide-based composition of the present invention, a mold release agent can be blended in order to improve the mold releasability and appearance of the obtained molded product. Any mold release agent may be used as long as it belongs to the category known as a mold release agent. Examples thereof include carnauba wax, polyethylene wax, polypropylene wax, metal stearate, acid amide wax, and the like. be able to. As the carnauba wax, a general commercial product can be used, and examples thereof include (trade name) purified carnauba No. 1 powder (manufactured by Nikko Fine Products).

  The compounding amount of the mold release agent is a polyarylene sulfide-based composition excellent in mold releasability and molded product appearance, so that polyarylene sulfide (A), strontium compound (B), and fibrous filler (C ) Is preferably 0.05 to 5 parts by weight per 100 parts by weight.

  The polyarylene sulfide-based composition of the present invention may contain a non-fibrous filler without departing from the object of the present invention. Examples of the non-fibrous filler include wollastonite, zeolite, and sericite. Silicates such as sight, kaolin, mica, clay, pyrophyllite, bentonite, talc, alumina silicate; oxides such as aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, zinc oxide, iron oxide; calcium carbonate And carbonates such as magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; nitrides such as silicon nitride, boron nitride and aluminum nitride; and glass flakes and glass beads, among which mica, clay, Talc, calcium carbonate, glass flakes and glass beads are preferred. The non-fibrous filler may be a surface treated with an isocyanate compound, a silane coupling agent, a titanate coupling agent, an epoxy compound, or the like.

  Furthermore, the polyarylene sulfide-based composition of the present invention includes various thermosetting resins and thermoplastic resins such as epoxy resins, cyanate ester resins, phenol resins, polyimides, silicone resins, and the like within a range not departing from the object of the present invention. One or more of polyester, polyamide, polyphenylene oxide, polycarbonate, polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone and the like can be mixed and used.

  As a method for producing the polyarylene sulfide-based composition of the present invention, a conventionally used hot melt kneading method can be used. For example, a heat melt kneading method using a single screw or twin screw extruder, a kneader, a mill, a Brabender or the like can be mentioned, and a melt kneading method using a twin screw extruder excellent in kneading ability is particularly preferable. Moreover, the kneading | mixing temperature in this case is not specifically limited, Usually, it can select arbitrarily from 280-400 degreeC. The polyarylene sulfide composition of the present invention can be molded into an arbitrary shape using an injection molding machine, an extrusion molding machine, a transfer molding machine, a compression molding machine, etc. It can be molded as a case of a mechanical device.

  Further, the polyarylene sulfide-based composition of the present invention is a conventionally known heat stabilizer, antioxidant, ultraviolet absorber, crystal nucleating agent, foaming agent, mold corrosion inhibitor within the scope of the present invention. In addition, one or more additives such as flame retardants, flame retardant aids, colorants such as dyes and pigments, and antistatic agents may be used in combination.

  The polyarylene sulfide composition of the present invention includes a power module, various terminal boards, a generator, an electric motor, a transformer, a booster, a flyback transformer, a power insulator, a power cable, a current transformer, a voltage regulator, a rectifier, Insulating members used for inverter devices such as refrigerators and air conditioners, multipolar rods, electrical component cabinets, light sockets, capacitor sealing plates, and the like can be particularly suitably used.

  The present invention provides a polyarylene sulfide-based composition having excellent electrical characteristics such as voltage resistance and at the same time excellent in mechanical strength. The polyarylene sulfide-based composition is particularly suitable for electric / electronic parts or automobiles. It is particularly useful for electrical component applications such as electrical components.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention, this invention is not restrict | limited to these examples at all.

  Details of the polyarylene sulfide, strontium compound, and fibrous filler used in Examples and Comparative Examples are shown below.

<Polyarylene sulfide (A)>
Poly (p-phenylene sulfide) (A-1) (hereinafter simply referred to as PPS (A-1))
: Melt viscosity 110 poise.
Poly (p-phenylene sulfide) (A-2) (hereinafter simply referred to as PPS (A-2))
: Melt viscosity 300 poise.
Poly (p-phenylene sulfide) (A-3) (hereinafter simply referred to as PPS (A-3))
: Melt viscosity 350 poise.

<Strontium compound (B)>
Strontium carbonate (B-1); manufactured by Sakai Chemical Industry Co., Ltd., (trade name) SW-K, average particle diameter (D ₅₀ ) 5 μm.
Strontium carbonate (B-2); manufactured by Sakai Chemical Industry Co., Ltd., (trade name) POWDER-N, average particle size (D ₅₀ ) 0.5 μm.
Strontium chloride (B-3); manufactured by Sakai Chemical Industry Co., Ltd., (trade name) STC-K, average particle diameter (D ₅₀ ) 100 μm.

<Fibrous filler (C)>
Glass fiber (C-1); manufactured by NSG Vetrotex Co., Ltd., (trade name) RES03-TP91; fiber diameter 9 μm, fiber length 3 mm.

Synthesis Example 1 (Synthesis of PPS (A-1) and PPS (A-2))
A 15 liter autoclave equipped with a stirrer was charged with 1866 g of Na ₂ S · 2.8H ₂ O and 5 liters of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and gradually heated to 205 ° C. while stirring under a nitrogen stream. The temperature was raised and 407 g of water was distilled off. After cooling the system to 140 ° C., 2280 g of p-dichlorobenzene and 1500 g of NMP were added, and the system was sealed under a nitrogen stream. The system was heated to 225 ° C. and polymerized at 225 ° C. for 2 hours. After completion of the polymerization, the mixture was cooled to room temperature, and the polymer was isolated using a centrifuge. The polymer was washed repeatedly with warm water and dried at 100 ° C. for a whole day and night to obtain poly (p-phenylene sulfide).

  The melt viscosity of the obtained poly (p-phenylene sulfide) (PPS (A-1)) was 110 poise.

  Further, PPS (A-1) was heat-cured at 235 ° C. in an air atmosphere.

  The melt viscosity of the obtained poly (p-phenylene sulfide) (PPS (A-2)) was 300 poise.

Synthesis Example 2 (Synthesis of PPS (A-3))
A 15 liter titanium autoclave equipped with a stirrer was charged with 3232 g of NMP, 1682 g of 47% sodium hydrogen sulfide aqueous solution and 1142 g of 48% sodium hydroxide aqueous solution, gradually heated to 200 ° C. while stirring under a nitrogen stream, and 1360 g of water was added. Distilled. The system was cooled to 170 ° C., 2118 g of p-dichlorobenzene and 1783 g of NMP were added, and the system was sealed under a nitrogen stream. The system was heated to 225 ° C., polymerized at 225 ° C. for 1 hour, then heated to 250 ° C. and polymerized at 250 ° C. for 2 hours. Furthermore, 451 g of water was injected at 250 ° C., the temperature was raised again to 255 ° C., and polymerization was carried out at 225 ° C. for 2 hours. After completion of the polymerization, the mixture was cooled to room temperature, and the polymerization slurry was subjected to solid-liquid separation. The polymer was washed successively with NMP, acetone and water, and dried at 100 ° C. overnight to obtain poly (p-phenylene sulfide).

  The obtained poly (p-phenylene sulfide) (PPS (A-3)) was linear, and its melt viscosity was 350 poise.

  Evaluation and measurement methods used in Examples and Comparative Examples are shown below.

(Performance evaluation of polyarylene sulfide composition)
~ Measurement of withstand voltage ~
A test piece having a 70 mm square and a thickness of 1 mm was produced by injection molding, an AC voltage of 10 kV and a frequency of 100 Hz was applied to the test piece at room temperature, and the time until the test piece breaks down was measured. Those having a dielectric breakdown time of 60 minutes or more were judged to be excellent in voltage resistance.

~ Measurement of tensile strength ~
A No. 1 test piece of ASTM D-638 was prepared by injection molding, and the tensile strength was measured using the test piece according to ASTM D-638. Using a measuring apparatus (manufactured by Shimadzu Corporation, (trade name) AG-5000B), the test was performed under test conditions of a distance between chucks of 110 mm and a measurement speed of 5 mm / min. Those having a tensile strength of 70 MPa or more were judged to be excellent in mechanical strength.

Example 1
A twin screw extruder (trade name: TEM-35, manufactured by Toshiba Machine Co., Ltd.) blended at a ratio of 91% by weight of PPS (A-2) and 9% by weight of strontium carbonate (B-1) and heated to a cylinder temperature of 310 ° C. -102B). On the other hand, the glass fiber (C-1) is put into the hopper of the side feeder of the twin screw extruder, melted and kneaded at a screw rotation speed of 200 rpm, and the molten composition flowing out from the die is cooled and cut into pellets. A polyarylene sulfide-based composition was prepared. The composition ratio of the polyarylene sulfide composition at that time was 10 parts by weight of strontium carbonate (B-1) and 15 parts by weight of glass fiber (C-1) with respect to 100 parts by weight of PPS (A-2). .

  The polyarylene sulfide-based composition is put into a hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE75) heated to a cylinder temperature of 310 ° C., and a test piece for measuring voltage resistance, tension Test pieces for strength and measurement were molded and evaluated. These results are shown in Table 1.

  The obtained polyarylene sulfide-based composition was excellent in voltage resistance and tensile strength.

Examples 2-5
Examples, except that PPS (A-1, 2, 3), strontium carbonate (B-1, 2), strontium chloride (B-3), and glass fiber (C-1) were blended as shown in Table 1. A polyarylene sulfide composition was prepared by the same method as in Example 1 and evaluated by the same method as in Example 1. The evaluation results are shown in Table 1.

  All the obtained polyarylene sulfide-based compositions were excellent in voltage resistance and tensile strength.

比較例１〜４
ＰＰＳ（Ａ−２）、炭酸ストロンチウム（Ｂ−１）、ガラス繊維（Ｃ−１）を表２に示す配合割合とした以外は、実施例１と同様の方法により組成物を作製し、実施例１と同様の方法により評価した。評価結果を表２に示した。

Comparative Examples 1-4
A composition was prepared in the same manner as in Example 1 except that PPS (A-2), strontium carbonate (B-1), and glass fiber (C-1) were mixed in the proportions shown in Table 2. Evaluation was performed in the same manner as in 1. The evaluation results are shown in Table 2.

  The compositions obtained from Comparative Examples 1, 2, and 4 were inferior in voltage resistance. The compositions obtained from Comparative Examples 1, 2, and 3 were inferior in tensile strength.

  The polyarylene sulfide-based composition of the present invention is excellent in electrical characteristics such as withstand voltage, and is particularly expected for use in electrical parts such as electrical / electronic parts or automotive electrical parts.

Claims (2)

A polyarylene sulfide composition comprising at least 10 to 100 parts by weight of a strontium compound (B) and 10 to 150 parts by weight of a fibrous filler (C) with respect to 100 parts by weight of polyarylene sulfide (A). object. The polyarylene sulfide composition according to claim 1, wherein the strontium compound (B) is strontium carbonate and / or strontium chloride.