JP2012122009A - Polyarylene sulfide-based composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylene sulfide-based composition which is excellent in electrical properties such as especially tracking resistance, mechanical strength, melt flowability, mold releasability and appearance of a molded article and thereby useful for application of electric components such as electric-electronic components or automotive electric components.SOLUTION: The polyarylene sulfide-based composition comprises 20-50 wt.% of a polyarylene sulfide (A), 0.5-20 wt.% of an ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B), 20-69.5 wt.% of hydrotalcite (C), and 10-50 wt.% of fiber-like filler (D).

Description

  The present invention is excellent in electrical properties such as tracking resistance without impairing the heat resistance, chemical resistance, dimensional stability, etc. inherent to polyarylene sulfide, as well as mechanical strength, melt fluidity, mold releasability. In particular, the present invention relates to a polyarylene sulfide composition that is excellent in appearance of a molded product, and more particularly to a polyarylene sulfide composition that is particularly useful for electrical parts such as electrical / electronic parts or automobile electrical parts.

  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 is greatly inferior in tracking resistance as compared with other engineering plastics such as polyamide, its use in applications where it is exposed to a relatively high voltage has been limited.

  Several attempts have been made to improve the tracking resistance of polyarylene sulfides. For example, (a) polyphenylene sulfide, (b) polyamide, and (c) a metal whose main component is magnesium hydroxide. One or more kinds of heavy materials selected from a resin composition containing a hydroxide (see, for example, Patent Document 1), (a) polyarylene sulfide, (b) polyolefin (co) polymer, silicone, and fluorine resin. (C) magnesium hydroxide and (d) a resin composition containing a fibrous and / or non-fibrous filler (see, for example, Patent Document 2), (a) polyphenylene sulfide, (b) specific Resin composition containing magnesium hydroxide having an average particle size and a specific particle size distribution and (c) fibrous and / or non-fibrous filler (example) Situ Patent Document 3.), And the like have been proposed.

  Further, by adding a polar group-containing polyolefin to polyarylene sulfide to make a resin composition, attempts have been made to improve its characteristics. For example, as a resin composition having improved impact resistance, polyphenylene sulfide resin 70 to 98% by weight And a polyphenylene sulfide resin composition comprising 29 to 1% by weight of a saponified ethylene-vinyl acetate copolymer and 10 to 1% by weight of an unsaturated carboxylic anhydride group-containing product or an epoxy group-containing product (see, for example, Patent Document 4). ), A resin composition with improved adhesion strength and adhesion strength, polyarylene sulfide 67-98.9 wt%, polar group-containing polyethylene copolymer 1-30 wt%, and polyethyleneimine 0.1-5 wt% % Polyarylene sulfide composition (see, for example, Patent Document 5), polyarylene sulfide A polyarylene sulfide composition comprising 67 to 98.9% by weight of a polymer, 1 to 30% by weight of a polar group-containing polyethylene copolymer, and 0.1 to 5% by weight of a hydrazine derivative (see, for example, Patent Document 6). Etc. have been proposed.

JP 05-271542 A (see claims) Japanese Patent Laid-Open No. 08-291253 (refer to the claims) JP 2001-288363 A (refer to the claims) Japanese Unexamined Patent Publication No. 04-296355 (refer to the claims) JP 2009-256438 A (refer to claims) JP 2010-001340 A (refer to claims)

  However, the resin compositions proposed in Patent Documents 1 to 3 have a problem that the tracking resistance is not yet satisfactory. In addition, in these proposed resin compositions, in order to obtain sufficiently excellent tracking resistance, a high magnesium hydroxide content is essential, and therefore the mechanical strength and melt fluidity of the composition are significantly reduced. Furthermore, the mold releasability and the appearance of the molded product deteriorated. That is, it is difficult for these resin compositions to obtain excellent tracking resistance, high mechanical strength, good melt fluidity, mold releasability, and molded product appearance at the same time.

  In addition, the resin compositions proposed in Patent Documents 4 to 6 are resin compositions proposed for improving characteristics different from tracking resistance such as impact resistance, adhesive strength, adhesion strength, and the like. Since the blending amount of polyarylene sulfide was large, it was not satisfactory in terms of tracking resistance.

  Accordingly, an object of the present invention is to provide a polyarylene sulfide-based composition having excellent tracking resistance and excellent mechanical strength, melt fluidity, mold releasability, and molded article appearance, More specifically, the object is to provide a polyarylene sulfide-based composition that is particularly useful for electrical component applications such as electrical / electronic components or automotive electrical components.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors blended polyarylene sulfide, ethylene-fatty acid vinyl ester-vinyl alcohol copolymer, hydrotalcite, and fibrous filler, and further if necessary. It has been found that a polyarylene sulfide composition containing a mold release agent has excellent tracking resistance and can be a composition having excellent mechanical strength, melt fluidity, mold releasability, and molded product appearance. The present invention has been completed.

  That is, the present invention comprises 20 to 50% by weight of polyarylene sulfide (A), 0.5 to 20% by weight of ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B) represented by the following general formula (1), The present invention relates to a polyarylene sulfide composition comprising 20 to 69.5% by weight of hydrotalcite (C) and 10 to 50% by weight of fibrous filler (D).

（ここで、ｘ、ｙ、ｚはいずれもが０を超え、ｘ＋ｙ＋ｚ＝１であり、Ｒは炭素数１〜１０の炭化水素基である。）
以下、本発明に関し詳細に説明する。

(Here, x, y and z are all greater than 0, x + y + z = 1, and R is a hydrocarbon group having 1 to 10 carbon atoms.)
Hereinafter, the present invention will be described in detail.

  The polyarylene sulfide-based composition of the present invention comprises a polyarylene sulfide (A) 20 to 50% by weight, an ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B) 0.5 to 20% by weight, hydrotalcite (C ) 20 to 69.5 wt% and fibrous filler (D) 10 to 50 wt%.

  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 molding processability, it was measured with a Koka flow tester using a die having 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. Polyarylene sulfide having a melt viscosity of 50 to 3000 poise is preferable, and one having a melt 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. The phenylene sulfide unit may be contained, and poly (p-phenylene sulfide) is particularly 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 compounding quantity of the polyarylene sulfide (A) which comprises the polyarylene sulfide type composition of this invention is 20 to 50 weight%. Here, when the blending amount of the polyarylene sulfide (A) is less than 20% by weight, the resulting composition is inferior in mechanical strength, melt fluidity, mold releasability, and molded product appearance. On the other hand, when the blending amount of the polyarylene sulfide (A) exceeds 50% by weight, the resulting composition is inferior in tracking resistance.

  The ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B) represented by the general formula (1) constituting the present invention is used for improving the tracking resistance of the polyarylene sulfide-based composition. is there. In the general formula (1), the ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B) is such that x, y, z are all greater than 0, x + y + z = 1, and R is It consists of a hydrocarbon group having 1 to 10 carbon atoms.

  Here, when x is 0, the resulting composition is inferior in heat resistance. When y and / or z is 0, the resulting composition is inferior in tracking resistance. And since it becomes a polyarylene sulfide type composition which has especially high tracking resistance and favorable mechanical strength, x = 0.69-0.94, y = 0.01-0.15, z = 0. An ethylene-fatty acid vinyl ester-vinyl alcohol copolymer in the range of 02 to 0.30 is preferred.

  R is a hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group. Here, in the case of an ethylene-fatty acid vinyl ester-vinyl alcohol copolymer having more than 10 carbon atoms, the resulting composition is inferior in mechanical strength.

  The method for producing the ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B) is not particularly limited. For example, a method of copolymerizing an ethylene monomer, a fatty acid vinyl ester monomer and a vinyl alcohol monomer; It can be obtained by a method of partially saponifying a vinyl ester copolymer. Among them, an ethylene-fatty acid vinyl ester-vinyl alcohol copolymer obtained by partially saponifying an ethylene-fatty acid vinyl ester copolymer is preferable because it is easily available industrially. The coalescence is most preferable because it is easily available industrially, and particularly becomes a polyarylene sulfide-based composition having excellent tracking resistance.

  The blending amount of the ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B) constituting the polyarylene sulfide-based composition of the present invention is 0.5 to 20% by weight. When the blending amount of the ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B) is less than 0.5% by weight, the resulting composition is inferior in tracking resistance. On the other hand, when the blending amount of the ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B) exceeds 20% by weight, the resulting composition is inferior in mechanical strength and molded article appearance.

Any hydrotalcite (C) constituting the polyarylene sulfide-based composition of the present invention can be used as long as it belongs to a category called hydrotalcite. For example, the following general formula What is shown by (2) can be mentioned.
(M _1-a N _a (OH) ₂ ) (C ⁿ⁻ ) _{a / n} · mH ₂ O (2)
(Where M is a divalent metal, N is a trivalent metal, C ⁿ⁻ represents an anion, a is 0 <a <1, m is m ≧ 0, and n is 1, 2 or 3. .)
The hydrotalcite represented by the above general formula (2) is composed of a composite metal hydroxide layer represented by (M _1-a N _a (OH) ₂ ) and C ⁿ⁻ inserted between the layers. It consists of a structure consisting of the anions and water shown. The water inserted between the layers (hereinafter referred to as interlayer water) can be desorbed from the layers by heating to about 200 ° C. When preparing the polyarylene sulfide-based composition of the present invention, it is generally prepared by a hot melt kneading method, and the kneading temperature at that time often reaches 280 ° C. or higher. As the site (C), it is possible to suppress the desorption of interlayer water at the time of heat-melt kneading, and therefore it is preferable that the interlayer water is desorbed in advance. As a method for desorbing interlayer water, for example, a method of heating and drying can be mentioned. Examples of such a heat drying apparatus include a stationary dryer, a rotary / stirring dryer, a transport dryer, and the like. The heating conditions vary depending on the amount of hydrotalcite to be treated and the type and size of the heating / drying apparatus. For example, the heating temperature is 200 to 280 ° C., and the heating time is about 2 hours to half a day. Preferably there is.

And as a bivalent metal which is M of the hydrotalcite shown by said general formula (2), Mg, Zn, Ca, Ni, Co etc. can be mentioned, for example, Trivalent metal which is N Examples thereof include Al, Fe, Mn, and Cr. Examples of the anion that is C ^n- include CO ₃ ²⁻ , SO ₄ ²⁻ , and Cl ⁻ . In addition, a is 0 <a <1, and m representing the amount of interlayer water is m ≧ 0, and the amount of water that is desorbed when preparing the polyarylene sulfide-based composition of the present invention is reduced. To 0 ≦ m ≦ 5.

Specific examples of the hydrotalcite (C) include (Mg _0.75 Al _0.25 (OH) ₂ ) (CO ₃ ²⁻ ) _0.125 · 4H ₂ O, (Mg _0.75 Al _{0. 25} (OH) ₂ ) (CO ₃ ²⁻ ) _0.125 , (Mg _0.67 Al _0.33 (OH) ₂ ) (CO ₃ ²⁻ ) _0.167 · 3H ₂ O, (Mg _0.67 Al _0.33 (OH) ₂ ) (CO ₃ ²⁻ ) _0.167 , (Mg _0.7 Al _0.3 (OH) ₂ ) (CO ₃ ²⁻ ) _0.15 · 3.5H ₂ O or (Mg _0.7 Al _0.3 (OH) ₂ ) (CO ₃ ²⁻ ) _{0.15 and the} like.

The hydrotalcite (C) is a polyarylene sulfide-based composition that is particularly excellent in tracking resistance, mechanical strength, melt flowability, and molded article appearance, and therefore has an average particle diameter (measured by a laser diffraction scattering method). D ₅₀ ) is preferably in the range of 0.3 to 10 μm, particularly preferably in the range of 0.4 to 2 μm. Further, the specific surface area of the hydrotalcite (C) is preferably 20 m ² / g or less because it becomes a polyarylene sulfide-based composition having excellent tracking resistance, mechanical strength, and melt fluidity. .

  Moreover, as for this hydrotalcite (C), the thing by which the surface is coat-processed or what is not carried out can be used. When the surface is coated, the surface coating agent is not particularly limited, and higher fatty acids and / or metal salts of higher fatty acids; anionic surfactants, phosphate esters, silane coupling agents, titanate couplings Agents, aluminate coupling agents, polyhydric alcohols 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 orthophosphoric acid 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 and the like; aluminate coupling agents such as acetoalkoxyaluminum diisopropylate and the like; polyhydric alcohol Examples of the esters of fatty acids such as glycerin monostearate, and the like.

  The amount of the hydrotalcite (C) constituting the polyarylene sulfide-based composition of the present invention is 20 to 69.5% by weight. When the amount of the hydrotalcite (C) is less than 20% by weight, the resulting composition is inferior in tracking resistance. On the other hand, when the blending amount of the hydrotalcite (C) exceeds 69.5% by weight, the resulting composition is inferior in mechanical strength, melt fluidity, mold releasability, and molded product appearance.

  The fibrous filler (D) constituting the polyarylene sulfide-based composition of the present invention is blended in order to improve the mechanical strength and dimensional stability of the polyarylene sulfide-based composition. Any fibrous filler can be used as long as it can achieve the above. Examples of the fibrous filler (D) 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. Since the fibrous filler (D) has high mechanical strength of the polyarylene sulfide-based composition, it can be surfaced 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 compounding quantity of the fibrous filler (D) which comprises the polyarylene sulfide type composition of this invention is 10 to 50 weight%. When the compounding quantity of this fibrous filler (D) is less than 10 weight%, the composition obtained will be inferior to mechanical strength. On the other hand, when the compounding quantity of this fibrous filler (D) exceeds 50 weight%, the composition obtained will be inferior to melt fluidity | liquidity and a molded article external appearance.

  The polyarylene sulfide-based composition of the present invention is preferably formed by blending a release agent (E) in order to further improve the mold releasability and appearance of the obtained molded product. The release agent (E) can be used as long as it belongs to a category known as a release agent. For example, carnauba wax (E1), polyethylene wax (E2), polypropylene wax (E3), Metal stearates (E4), acid amide waxes (E5) and the like can be mentioned. Among them, a polyarylene sulfide composition excellent in mold releasability and appearance of molded products can be obtained. To carnauba wax (E1).

  As the carnauba wax (E1), a general commercially available 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 release agent (E) is a polyarylene sulfide-based composition having excellent mold releasability and molded product appearance. It is preferable that it is 0.05-5 weight part with respect to 100 weight part of total amounts of a polymer (B), a hydrotalcite (C), and a fibrous filler (D).

  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 polyolefin, 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. Further, the polyarylene sulfide-based 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, or the like.

  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 current transformer, a voltage regulator, a rectifier, an inverter, a multipolar rod, an electrical component cabinet, a light socket, and a plug. In particular, it can be suitably used for applications such as a capacitor sealing plate.

  The present invention provides a polyarylene sulfide composition which is excellent in electrical characteristics such as tracking resistance, mechanical strength, melt flowability, mold releasability, and molded article appearance. The composition is particularly useful for electrical component applications such as electrical / electronic components or automotive electrical components.

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

  Details of the polyarylene sulfide, ethylene-fatty acid vinyl ester-vinyl alcohol copolymer, hydrotalcite, fibrous filler, and carnauba wax used in Examples and Comparative Examples are shown below.

<Polyarylene sulfide>
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.

<Ethylene-fatty acid vinyl ester-vinyl alcohol copolymer>
Ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B-1) (hereinafter simply referred to as copolymer (B-1)): manufactured by Tosoh Corporation, (trade name) Mersen H6820, x = 0. 817, y = 0.021, z = 0.162, R is a methyl group.
Ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B-2) (hereinafter simply referred to as copolymer (B-2)): manufactured by Tosoh Corporation, (trade name) Mersen H6410, x = 0. 851, y = 0.065, z = 0.084, R is a methyl group.

<Hydrotalcite>
Hydrotalcite (C-1); manufactured by Sakai Chemical Industry Co., Ltd., (trade name) STABIACE HT-1; (Mg _0.67 Al _0.33 (OH) ₂ ) (CO ₃ ²⁻ ) _0.167 · 3H ₂ O, average particle size 0.58 μm, BET specific surface area 10 m ² / g.
Hydrotalcite (C-2); Hydrotalcite (C-1) is heat-treated, and interlayer water is desorbed and removed. (Mg _0.67 Al _0.33 (OH) ₂ ) (CO ₃ ²⁻ ) _0.167 .

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

<Carnauba wax>
Carnauba wax (E1-1); Nikko Fine Products, (trade name) purified carnauba No. 1 powder.

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 a 47% aqueous solution of sodium hydrogen sulfide and 1142 g of a 48% aqueous solution of sodium hydroxide. 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 separated into solid and liquid. 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.

Heat treatment of hydrotalcite Hydrotalcite (C-1) is placed in a blowing constant temperature dryer (trade name: FC-610, manufactured by Advantech Co., Ltd.), heat treated at 220 ° C. for 5 hours, and hydrotalcite interlayer water Was removed and hydrotalcite (C-2) was obtained. By this heat treatment, hydrotalcite (C-1) was reduced by 11% by weight, and interlayer water was desorbed and removed.

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

~ Measurement of tracking resistance ~
A disk-shaped test piece having a diameter of 50 mm and a thickness of 3 mm was produced by injection molding, and a comparative tracking index (hereinafter referred to as CTI) was measured using the test piece according to ICE112. A CTI of 450 (V) or higher was judged to be excellent in tracking resistance.

~ Measurement of bending strength ~
A test piece having a length of 127 mm, a width of 12.7 mm, and a thickness of 3.2 mm was prepared by injection molding, and the bending strength was measured using the test piece according to ASTM D-790 Method-1 (three-point bending method). did. The measuring device (trade name) AG-5000B (manufactured by Shimadzu Corporation) was used, and the test was performed under the test conditions of a distance between fulcrums of 50 mm and a measurement speed of 1.5 mm / min. A bending strength exceeding 120 MPa was judged to be excellent in mechanical strength.

~ 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 device (manufactured by Shimadzu Corporation, (trade name) AG-5000B), the test was performed under the test conditions of a distance between chucks of 110 mm and a measurement speed of 5 mm / min. A tensile strength exceeding 60 MPa was judged to be excellent in mechanical strength.

~ Measurement of bar flow length ~
The bar flow length (hereinafter referred to as BFL) was measured as an index of melt fluidity. An injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE75) is mounted with a mold having a groove with a depth of 1 mm and a width of 10 mm, and the cylinder temperature is 310 ° C. and the injection pressure is The polyarylene sulfide-based composition was charged into a hopper of the injection molding machine set to 190 MPa, injection speed maximum, injection time 1.5 seconds, and mold temperature set to 135 ° C., and injected. And the length which melted and flowed the spiral groove | channel in a metal mold | die was measured as BFL. A BFL exceeding 80 mm was judged to be excellent in melt fluidity.

~ Mold releasability ~
The injection molding machine is mounted with a mold of a box-shaped product having a length of 120 mm, a width of 60 mm, a depth of 20 mm, and a thickness of 2 mm. Under conditions, the polyarylene sulfide-based composition was injected, and after cooling, the releasability of the box-shaped molded product from the mold core was evaluated. The state where it was possible to release from the mold core without any resistance was judged as ◯, the state where there was resistance but the time taken to release the mold was Δ, and the state where the resistance was large and time taken for release was judged as x. The state where the releasability was ○ was judged to be excellent.

~ Appearance of molded product ~
The same disk-shaped test piece as the measurement of tracking resistance was prepared, and the surface state of the test piece was visually observed. A case where the entire surface was glossy was evaluated as ◯, a portion where the surface was glossy was determined as Δ, and a case where the surface was not glossy was determined as ×. Those having a molded product appearance of ◯ were judged to be excellent in the molded product appearance.

Example 1
PPS (A-2) 46.7% by weight, copolymer (B-1) 13.3% by weight and hydrotalcite (C-1) 40.0% by weight, cylinder temperature 310 ° C. To a hopper of a twin-screw extruder (manufactured by Technobell, (trade name) KZW15TW-60MG-NH). On the other hand, glass fiber (D-1) was thrown into the hopper of the side feeder of the twin screw extruder. Fully degassed from the vent ports at two locations to remove intercalated water of hydrotalcite, melt and knead at a screw rotation speed of 200 rpm, and cool and cut the molten composition flowing out from the die. A polyarylene sulfide-based composition was prepared. The composition ratio of the polyarylene sulfide composition at that time is PPS (A-2) / copolymer (B-1) / hydrotalcite (C-1) / glass fiber (D-1) = 35/10. / 30/25 (wt%).

  The polyarylene sulfide-based composition is charged 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 CTI is measured to evaluate the appearance of the molded product. A disk-shaped test piece, a test piece for measuring bending strength, and a test piece for measuring tensile strength were respectively formed. Further, the mold releasability was evaluated and BFL was measured. These results are shown in Table 1.

  The resulting polyarylene sulfide-based composition was excellent in CTI, bending strength, tensile strength, melt fluidity, mold releasability, and molded product appearance.

Examples 2-8
PPS (A-1,2,3), copolymer (B-1,2), hydrotalcite (C-1,2), glass fiber (D-1) and carnauba wax (E1-1) are represented. A polyarylene sulfide-based composition was prepared by the same method as in Example 1 except that the blending ratio shown in 1 was used, 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 CTI, bending strength, tensile strength, melt fluidity, mold releasability, and molded product appearance.

比較例１〜７
ＰＰＳ（Ａ−２）、共重合体（Ｂ−１）、ハイドロタルサイト（Ｃ−１）、ガラス繊維（Ｄ−１）及びカルナバワックス（Ｅ１−１）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ポリアリーレンスルフィド組成物を作製し、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 1-7
PPS (A-2), copolymer (B-1), hydrotalcite (C-1), glass fiber (D-1) and carnauba wax (E1-1) other than the mixing ratios shown in Table 2 Prepared a polyarylene sulfide composition 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 2.

  The compositions obtained in Comparative Examples 1, 3, 4, and 7 were inferior in tracking resistance. The compositions obtained in Comparative Examples 2, 5, and 6 were inferior in bending strength and tensile strength.

  The polyarylene sulfide-based composition of the present invention is excellent in electrical properties such as tracking resistance, mechanical strength, melt fluidity, mold releasability, and molded product appearance, and particularly in electric / electronic parts or automobiles. It is expected to be used for electrical parts such as electrical parts.

Claims (6)

Polyarylene sulfide (A) 20 to 50% by weight, ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B) 0.5 to 20% by weight represented by the following general formula (1), hydrotalcite (C) A polyarylene sulfide-based composition comprising 20 to 69.5% by weight and a fibrous filler (D) of 10 to 50% by weight.

(Here, x, y and z are all greater than 0, x + y + z = 1, and R is a hydrocarbon group having 1 to 10 carbon atoms.) The ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B) is represented by the formula (1) where x = 0.69 to 0.94, y = 0.01 to 0.15, z = 0.02. The polyarylene sulfide composition according to claim 1, which is an ethylene-fatty acid vinyl ester-vinyl alcohol copolymer of 0.30. The polyarylene sulfide composition according to claim 1 or 2, wherein the ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B) is an ethylene-vinyl acetate-vinyl alcohol copolymer. The polyarylene sulfide composition according to any one of claims 1 to 3, wherein the hydrotalcite (C) is a hydrotalcite represented by the following general formula (2).
(M _1-a N _a (OH) ₂ ) (C ⁿ⁻ ) _{a / n} · mH ₂ O (2)
(Where M is a divalent metal, N is a trivalent metal, C ⁿ⁻ represents an anion, a is 0 <a <1, m is m ≧ 0, and n is 1, 2 or 3. .) Hydrotalcite (C) is (Mg _0.75 Al _0.25 (OH) ₂ ) (CO ₃ ²⁻ ) _0.125 · 4H ₂ O, (Mg _0.75 Al _0.25 (OH) ₂ ) (CO ₃ ²⁻ ) _0.125 , (Mg _0.67 Al _0.33 (OH) ₂ ) (CO ₃ ²⁻ ) _0.167 · 3H ₂ O, (Mg _0.67 Al _0.33 (OH) ₂ ) (CO ₃ ²⁻ ) _0.167 , (Mg _0.7 Al _0.3 (OH) ₂ ) (CO ₃ ²⁻ ) _0.15 · 3.5H ₂ O or (Mg _0.7 Al _{0. 3} (OH) ₂ ) (CO ₃ ²⁻ ) _0.15 , The polyarylene sulfide-based composition according to claim 1, wherein the composition is ₃ (OH) ₂ ) (CO ₃ ²⁻ ) _0.15 . For a total amount of 100 parts by weight of polyarylene sulfide (A), ethylene-fatty acid vinyl ester-vinyl alcohol copolymer (B), hydrotalcite (C) and fibrous filler (D), a release agent ( E) 0.05-5 weight part is mix | blended, The polyarylene sulfide type composition in any one of Claims 1-5 characterized by the above-mentioned.