JP2020079364A - Polyarylene sulfide-based composition - Google Patents

Abstract

To provide a polyarylene-based composition having a low dielectric constant, and a low dielectric tangent, having excellent electromagnetic wave transmissivity from maga hertz band to giga hertz band, and having impact resistance necessary as an exterior component, and having no problem of appearance such as warpage and sink, and a chassis made thereof.SOLUTION: A polyarylene sulfide-based composition containing 30 to 70 wt.% of polyarylene sulfide (A), 3 to 20 wt.% of an ethylene-based polymer (B), 30 to 50 wt.% of glass fiber (C) having dielectric constant of 5.5 or smaller at 2GHz, and a portable terminal chassis made of the polyarylene sulfide-based composition.SELECTED DRAWING: None

Description

  The present invention relates to a polyarylene sulfide-based composition which has a low dielectric constant and a low dielectric loss tangent, and thus is excellent in radio wave transmission in the megahertz to gigahertz band, and is also excellent in impact resistance. Is particularly useful for electronic/electrical parts such as housings of mobile terminal devices such as mobile personal computers, tablets, and mobile phones that use radio waves in the megahertz band to gigahertz band during communication, or for electric parts such as automobile electrical parts. The present invention relates to a polyarylene sulfide composition.

  BACKGROUND ART Polyarylene sulfide represented by poly(p-phenylene sulfide) has excellent mechanical properties, thermal properties, electrical properties, and chemical resistance. Therefore, many electronic/electrical device members, automobile device members, It is also widely used for other office automation equipment components. Such a polyarylene sulfide is mixed with a fibrous filler such as glass fiber, a powdery or granular inorganic filler such as calcium carbonate and talc, and a coloring material such as carbon black to obtain mechanical strength and heat resistance. In addition, the rigidity and dimensional stability can be greatly improved, and coloring can be performed.

  However, since these compounded materials, such as glass fibers, have high dielectric constant and dielectric loss tangent, the polyarylene sulfide composition in which they are compounded has high dielectric constant and dielectric loss tangent. The polyarylene sulfide composition having such a high dielectric constant and a high dielectric loss tangent has a low dielectric constant such as a case of a mobile computer, a tablet, a mobile phone, etc. that uses radio waves in the megahertz band to the gigahertz band during communication. It is not suitable for applications requiring a high dielectric constant and a low dielectric loss tangent, and it has been required to reduce the compounding amount of glass fiber in order to lower the dielectric constant and dielectric loss tangent. However, when the compounding amount of the glass fiber or the like is lowered, sufficient mechanical strength such as impact resistance cannot be obtained, which causes problems in appearance such as warpage and sink marks.

Regarding the attempt to reduce the dielectric constant of polyarylene sulfide, at least 15 to 30 parts by weight of the ethylene polymer (B), 15 to 65 parts by weight of glass fiber (C), and white are used with respect to 100 parts by weight of the polyarylene sulfide (A). A polyarylene sulfide-based composition (15 to 40 parts by weight of the colorant (D), 0.03 to 2 parts by weight of the blue colorant (E), and 0.1 to 5 parts by weight of the purple colorant (F) ( See, for example, Patent Document 1), and a block copolymer composed of at least an ethylene polymer (B1), a vinyl aromatic compound polymer block unit, and a conjugated diene compound polymer block unit per 100 parts by weight of a polyarylene sulfide (A). Polymer mixture (B) 15 to 40 in which the combined hydrogenated product (B2) is mixed at a ratio of (B1)/((B1)+(B2))=0.2 to 0.8 (weight). Polyarylene sulfide composition containing 1 part by weight, 15 to 65 parts by weight of glass fiber (C), and 1 to 15 parts by weight of black colorant (D) or 15 to 40 parts by weight of white colorant (E) as a colorant. (For example, refer to Patent Document 2), and as a low dielectric glass, SiO ₂ 53 to 57%, Al ₂ O ₃ 13 to 16%, B ₂ O ₃ 15 to 19.5%, MgO ₃ % in weight%. Or more to less than 6%, CaO _{2 to} 5%, TiO ₂ 1 to 4%, Li ₂ O 0 to 0.3%, Na ₂ O 0 to 0.3%, K ₂ O 0 to 0.5%, F ₂ 0.2 Is 1% and has a glass composition of MgO+CaO 7-10%, LiO ₂ +Na ₂ O+K ₂ O 0.2-0.5%, and the spinning temperature when the viscosity μ (poise) is log μ=3.0. Low dielectric constant glass fiber characterized by having a volatilization amount of B ₂ O ₃ at the time of 1340° C. or less at the time of spinning of 4 ppm or less (see Patent Document 3, for example), SiO ₂ 50-60% by weight, Al ₂ O ₃ 10-20%, B ₂ O ₃ 20-30%, CaO 0-5%, MgO 0-4%, Li ₂ O+Na ₂ O+K ₂ O 0-0.5%, TiO ₂ 0.5-5% composition. And a low dielectric constant glass fiber having a dielectric loss tangent of 10×10 ⁻⁴ or less at a frequency of 1 MHz (see, for example, Patent Document 4) and the like have been proposed.

Further, as a glass fiber reinforced resin molded product having a low dielectric constant and a low dielectric loss tangent, a glass fiber in the range of 10 to 90 mass% and a resin in the range of 90 to 10 mass% with respect to the total amount of the glass fiber reinforced resin molded product a glass fiber reinforced resin molded product containing, the glass fiber has a SiO ₂ in the range of 52.0 to 57.0 wt% with respect to glass fiber based on the total amount of the range of 13.0 to 17.0 wt% Al ₂ O ₃ , B ₂ O _{3 in} the range of 15.0 to 21.5 mass %, MgO in the range of 2.0 to 6.0 mass %, and 2.0 to 6.0 mass %. CaO in the range, TiO _{2 in} the range of 1.0 to 4.0% by mass, and F _{2 in} less than 1.5% by mass, and the total amount of Li ₂ O, Na ₂ O and K ₂ O. Is less than 0.6% by mass, and a glass fiber reinforced resin molded product (for example, see Patent Document 5) having a number average fiber length of 30 to 5000 μm is proposed as the glass fiber.

JP, 2017-88690, A JP, 2017-88691, A Patent No. 6352186 Japanese Patent No. 3269937 JP, 2017-52974, A

  However, in the resin compositions proposed in Patent Documents 1 and 2, the low dielectric constant cannot be sufficiently satisfied, and it is necessary to reduce the compounding amount of glass fiber in order to sufficiently lower the dielectric constant of the resin composition. There was a problem called.

  Further, in Patent Documents 3 and 4, a low dielectric constant glass fiber is proposed, but it is proposed for reinforcing a printed wiring board for a high-density circuit, and there is nothing about lowering the dielectric constant of polyarylene sulfide. Not considered or mentioned.

  Further, in Patent Document 5, a glass fiber reinforced resin molded product having a low dielectric constant and a low dielectric loss tangent is proposed, but no study or reference is made on the reduction of the dielectric constant of polyarylene sulfide.

  Therefore, the present invention has a low dielectric constant and a low dielectric loss tangent, and therefore has excellent radio wave permeability in the megahertz band to the gigahertz band, and has the shock resistance required as an exterior part, and has a good appearance in terms of warpage and sink marks. The present invention aims to provide a polyarylene sulfide-based composition free from the problem of, and more specifically, a casing of a mobile terminal device such as a mobile personal computer, a tablet or a mobile phone that utilizes radio waves in the megahertz band to the gigahertz band particularly during communication. Another object of the present invention is to provide a polyarylene sulfide-based composition that is useful for electronic/electrical component applications such as the above, or electrical component applications such as automobile electrical components.

  The present inventor, as a result of extensive studies to solve the above problems, at least polyarylene sulfide, ethylene-based polymer, by using a polyarylene sulfide-based composition containing a specific glass fiber, low dielectric constant, low dielectric constant Since it is a tangent, it has been found that it can be excellent in radio wave transmission from the megahertz band to the gigahertz band, and can also be excellent in impact resistance, and has completed the present invention.

  That is, the present invention provides 30 to 70% by weight of polyarylene sulfide (A), 3 to 20% by weight of ethylene polymer (B), and 30 to 50% by weight of glass fiber (C) having a dielectric constant of 5.5 or less at 2 GHz. % Of the polyarylene sulfide-based composition.

  Hereinafter, the present invention will be described in detail.

  The polyarylene sulfide (A) constituting the present invention is obtained by subjecting the polyarylene sulfide after the polymerization to a post-treatment as it is or in an inactive state, and heat-treating the linear polyarylene sulfide to be used with oxygen, air or an acidic atmosphere. The cross-linked polyarylene sulfide that has undergone the curing reaction is further roughly classified into nitrogen-treated polyarylene sulfide that has been heat-treated in an inert atmosphere such as nitrogen, and the polyarylene sulfide composition of the present invention is Polyarylene sulfide can also be used, and a mixture of these polyarylene sulfides may be used. And as the unit of the polyarylene sulfide constituting the polyarylene sulfide, for example, p-phenylene sulfide unit, m-phenylene sulfide unit, o-phenylene sulfide unit, phenylene sulfide sulfone unit, phenylene sulfide ketone unit, phenylene sulfide ether unit. , A biphenylene sulfide unit, and the like, and the polyarylene sulfide is a homopolymer or copolymer of these units. Specific examples of the polyarylene sulfide include, for example, polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, polyphenylene sulfide ether, and the like. Sulfide) is preferable, and linear type poly(p-phenylene sulfide) and nitrogen-treated poly(p-phenylene sulfide) are particularly preferable.

  Since the polyarylene sulfide (A) constituting the present invention efficiently removes impurities and the like and is excellent in quality, when the polyarylene sulfide is produced, high-pressure hot water of the polyarylene sulfide after polymerization is used. It is preferably treated and washed. Examples of the high-pressure hot water treatment condition at that time include a method of washing with water having a temperature of 150° C. or higher and 240° C. or lower.

  The method for producing the polyarylene sulfide is not particularly limited, and it may be produced by a method known as a general method for producing polyarylene sulfide. For example, in a polymerization solvent, an alkali metal sulfide and a polyhalogenated compound are used. It can be produced by a method of reacting with an aromatic compound.

  Here, the polymerization solvent is preferably a polar solvent, and particularly preferably an aprotic organic amide solvent that is stable against alkali at high temperature. As the organic amide solvent, any one can be used as long as it belongs to the category of organic amide solvents, for example, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoramide, N -Methyl-ε-caprolactam, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, dimethylsulfoxide, sulfolane, tetramethylurea and mixtures thereof, and the like. Among them, N-methyl-2-pyrrolidone is preferable because a polyarylene sulfide having a particularly high molecular weight and excellent mechanical properties can be obtained more easily.

  As the polyhalogenated aromatic compound, any compound can be used as long as it belongs to the category of polyhalogenated aromatic compounds. For example, p-dichlorobenzene, m-dichlorobenzene and o-dichlorobenzene. , P-dibromobenzene, m-dibromobenzene, o-dibromobenzene, p,p'-dichlorodiphenyl, p,p'-dibromodiphenyl, 2,6-dichloronaphthalene, 2,6-dibromonaphthalene, 1,3,3. Examples thereof include 5-trichlorobenzene and 1,2,4-trichlorobenzene. Among them, p-dichlorobenzene is preferable because a polyarylene sulfide having a high molecular weight and excellent mechanical properties can be easily obtained.

  As the alkali metal sulfide, any one can be used as long as it belongs to the category of alkali metal sulfides, and for example, anhydrous sodium sulfide, 2.8 sodium hydrate hydrochloride, sodium hydrate pentahydrate, etc. Sodium, lithium sulfide, rubidium sulfide, sodium hydrogen sulfide, lithium hydrogen sulfide and the like can be mentioned. Among them, sodium sulfide, lithium sulfide, since polyarylene sulfide excellent in mechanical properties with a particularly high molecular weight is more easily obtained, Sodium hydrogen sulfide and lithium hydrogen sulfide are preferred. A sulfide hydride such as sodium hydrogen sulfide or lithium hydrogen sulfide can also be used as an alkali metal sulfide salt by using it together with an alkali metal hydroxide salt.

  As the polyarylene sulfide, a part and/or the end of the molecular chain of the polyarylene sulfide is modified with a functional group such as a carboxyl group, a carboxy metal salt, an alkyl group, an alkoxy group, an amino group or a nitro group. And the like, and may be a mixture of these polyarylene sulfides. The polyarylene sulfide is subjected to acid washing, hot water washing, or washing treatment with an organic solvent such as acetone or methyl alcohol to obtain sodium atom, polyarylene sulfide oligomer, sodium chloride, 4-(N-methyl-chlorophenylamino). ) It may have reduced impurities such as sodium salt of butanoate.

  The amount of the polyarylene sulfide (A) constituting the polyarylene sulfide-based composition of the present invention is 30 to 70% by weight, and preferably 35 to 65% by weight. Here, when the compounding amount of polyarylene sulfide is less than 30% by weight, the resulting composition has a high dielectric constant and a high dielectric loss tangent. On the other hand, if it exceeds 70% by weight, the resulting composition will have poor appearance such as impact resistance and warpage and sink marks when it is used as a molded article, particularly a casing.

  The ethylene-based polymer (B) constituting the polyarylene sulfide-based composition of the present invention improves impact resistance of the polyarylene sulfide-based composition, and is an ethylene-based polymer obtained by polymerizing an ethylene monomer. Any one may be used as long as it belongs to the category of combination, and among them, ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (B-1), ethylene-α, β-unsaturated carboxylic acid glycidyl ester. Copolymer (B-2), ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (B-3), ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β- It is at least one modified ethylene polymer selected from the group consisting of an unsaturated carboxylic acid alkyl ester copolymer (B-4) and a maleic anhydride graft modified ethylene polymer (B-5). preferable.

  As the ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (B-1), any one may be used as long as it belongs to this category, and the polyarylene sulfide obtained among them can be used. Since the system composition is excellent in impact resistance and the like, ethylene residue unit: α, β-unsaturated carboxylic acid alkyl ester residue unit: maleic anhydride residue unit (weight ratio)=50 to 98:40 to 1 It is preferably in the range of 10 to 1. Specific examples of the ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (B-1) include (trade name) Bondine LX4110 (manufactured by Arkema Ltd.) and (trade name). Examples thereof include Bondine TX8030 (manufactured by Arkema Co., Ltd.) and (trade name) Bondine AX8390 (manufactured by Arkema Co., Ltd.).

  As the ethylene-α,β-unsaturated carboxylic acid glycidyl ester copolymer (B-2), any one may be used as long as it belongs to this category, and among them, the obtained polyarylene sulfide composition is From the viewpoint of excellent impact resistance and the like, it is preferable that the ethylene residue unit: α,β-unsaturated carboxylic acid glycidyl ester residue unit (weight ratio) be in the range of 85 to 99:15 to 1. Specific examples of the ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (B-2) include (trade name) Bond First 2C (manufactured by Sumitomo Chemical Co., Ltd.) and (trade name) Bond First. E (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

  As the ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (B-3), any one may be used as long as it belongs to this category. Since the composition is excellent in impact resistance and the like, ethylene residue unit: α,β-unsaturated carboxylic acid glycidyl ester residue unit: vinyl acetate residue unit (weight ratio)=50 to 98:15 to 1:35 It is preferably in the range of -1. Specific examples of the ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (B-3) include (trade name) Bond First 2B (manufactured by Sumitomo Chemical Co., Ltd.), (trade name) ) Bond First 7B (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

  As the ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer (B-4), any one may be used as long as it belongs to this category. In particular, since the obtained polyarylene sulfide composition is excellent in impact resistance and the like, ethylene residue unit: α, β-unsaturated carboxylic acid glycidyl ester residue unit: α, β-unsaturated carboxylic acid alkyl ester residue The base unit (weight ratio) is preferably in the range of 50 to 98:10 to 1:40 to 1. Specific examples of the ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (B-4) include (trade name) Bond First 7L (Sumitomo Chemical ( Ltd.), (Brand name) Bond First 7M (Sumitomo Chemical Co., Ltd.), (Brand name) LOTDER AX8700 (Arkema Co., Ltd.), (Brand name) LOTDER AX8750 (Arkema Co., Ltd.), etc. Can be mentioned.

  As the maleic anhydride graft-modified ethylene polymer (B-5), any one may be used as long as it belongs to this category, and among them, the polyarylene sulfide composition obtained is excellent in impact resistance and the like. Therefore, it is preferable that the ethylene residue unit: α-olefin residue unit: maleic anhydride residue unit (weight ratio) be in the range of 50 to 98:45 to 1:5-1. Examples thereof include maleic anhydride graft-modified linear low-density polyethylene, maleic anhydride graft-modified ethylene-propylene rubber, and the like. The maleic anhydride graft-modified ethylene-α-olefin copolymer can be obtained, for example, by coexisting an ethylene-α-olefin copolymer, a peroxide and maleic anhydride, and proceeding the grafting reaction. Is.

  And the α-olefin constituting the ethylene polymer (B) means an α-olefin having 3 or more carbon atoms, for example, propylene, butene-1,4-methyl-pentene-1, hexene-1, Octene-1 etc. can be illustrated. Examples of the α,β-unsaturated carboxylic acid alkyl ester include alkyl esters such as acrylic acid and methacrylic acid, and specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic acid. Isopropyl, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-methacrylate. Butyl and the like can be mentioned. Examples of the α,β-unsaturated carboxylic acid glycidyl ester include acrylic acid glycidyl ester and methacrylic acid glycidyl ester.

  The amount of the ethylene polymer (B) constituting the polyarylene sulfide-based composition of the present invention is 3 to 20% by weight, preferably 4 to 16% by weight. Here, when the blending amount of the ethylene polymer (B) is less than 3% by weight, the resulting composition is inferior in impact resistance when it is used as a molded article, particularly as a case. On the other hand, when the blending amount of the ethylene polymer (B) exceeds 20% by weight, the resulting composition has a high dielectric constant and a high dielectric loss tangent.

  The glass fiber (C) constituting the polyarylene sulfide-based composition of the present invention is a glass fiber having a dielectric constant of 5.5 or less at 2 GHz, and has improved impact resistance and mechanical strength of the polyarylene sulfide-based composition. To do. Specific examples of the glass fibers include chopped strands having an average fiber diameter of 6 to 14 μm, chopped strands made of flat glass fibers having an aspect ratio of the fiber cross section of 2 to 4, glass fibers such as milled fibers, and 2 GHz. As specific examples of the glass fiber having a dielectric constant of 5.5 or less, (trade name) CN3J-941S (manufactured by Nittobo Co., Ltd.) and (trade name) CN3J-256S (manufactured by Nitto Boseki Co., Ltd.) Etc. These glass fibers (C) can be used in combination of two or more kinds, and if necessary, surface-treated in advance with a functional compound or polymer such as an epoxy compound, an isocyanate compound, a silane compound and a titanate compound. You may use the thing. Here, when the glass fiber has a dielectric constant of more than 5.5 at 2 GHz, the resulting composition has a high dielectric constant and is likely to be restricted in use as a casing for electric/electronic devices. Will be things.

  The glass fiber (B) constituting the polyarylene sulfide composition of the present invention is incorporated in an amount of 30 to 50% by weight. If the glass fiber content is less than 30% by weight, the resulting composition will be inferior in impact resistance and warp and sink appearance when formed into a molded product. On the other hand, when it exceeds 50% by weight, the resulting composition has a high dielectric constant and a high dielectric loss tangent.

  The polyarylene sulfide composition of the present invention preferably contains a mold release agent (D) in order to improve mold releasability and appearance when forming a molded product. As the release agent (D), for example, polyethylene wax, polypropylene wax, and fatty acid amide wax are preferably used. As the polyethylene wax and polypropylene wax, general commercial products can be used. Further, the fatty acid amide wax is a polycondensate composed of a higher aliphatic monocarboxylic acid, a polybasic acid and a diamine, and any wax can be used as long as it belongs to this category, for example, stearic acid. , (Trade name) Light Amide WH-255 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like, which are polycondensates of sebacic acid and ethylenediamine.

  The polyarylene sulfide-based composition of the present invention may contain a non-fibrous filler within a range not departing from the object of the present invention, and examples of the non-fibrous filler include wollastonite, zeolite, and serium. Silicates such as site, kaolin, mica, pyrophyllite, talc, alumina silicate; oxides such as aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, zinc oxide, iron oxide; calcium carbonate, magnesium carbonate, Examples include carbonates such as dolomite; sulfates such as calcium sulfate and barium sulfate; nitrides such as silicon nitride, boron nitride and aluminum nitride; glass flakes and glass beads, among which mica, talc, calcium carbonate and glass. Flakes and glass beads are preferred. Further, the non-fibrous filler may be surface-treated with an isocyanate compound, a silane coupling agent, a titanate coupling agent, an epoxy compound or the like.

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

  Further, the polyarylene sulfide composition of the present invention is a conventionally known heat stabilizer, antioxidant, ultraviolet absorber, crystal nucleating agent, foaming agent, mold corrosion inhibitor within a range not departing from the object of the present invention. One or more additives such as a flame retardant, a flame retardant aid, a coloring agent such as a dye or a pigment, and an antistatic agent may be used in combination.

  The polyarylene sulfide-based composition of the present invention has a low dielectric constant and a low dielectric loss tangent, particularly in a high frequency region, and is suitable for applications such as parts and housings of mobile terminal devices. According to 2565, the dielectric constant measured at a measurement frequency of 2 GHz is preferably 3.5 or less and the dielectric loss tangent is 0.010 or less, and particularly, the dielectric constant is 2.0 or more and 3.5 or less and the dielectric loss tangent is It is preferably 0.001 or more and 0.010 or less.

  As the method for producing the polyarylene sulfide-based composition of the present invention, a conventionally used heat-melt kneading method can be used. For example, a heat-melting and kneading method using a single-screw or twin-screw extruder, a kneader, a mill, a Brabender, etc. may be mentioned, and a melt-kneading method using a twin-screw extruder having an excellent kneading ability is particularly preferable. The kneading temperature at this time is not particularly limited and can be arbitrarily selected from the range of 280 to 400°C. Further, 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, or the like.

  INDUSTRIAL APPLICABILITY The polyarylene sulfide composition of the present invention is excellent in impact resistance and product appearance, and thus can be used for various applications such as electric/electronic devices and automobile parts. Particularly, dielectric constant and dielectric loss tangent in a high frequency region. Since it is low, it can be used for parts and housings of mobile terminal devices.

  INDUSTRIAL APPLICABILITY The present invention has a low dielectric constant and a low dielectric loss tangent, and thus is excellent in radio wave transmission from the megahertz band to the gigahertz band, has the impact resistance required as an exterior part, and has a problem in appearance such as warpage and sink mark. In particular, the present invention relates to a polyarylene sulfide composition, and more specifically, electronic/electrical parts such as casings of mobile terminal devices such as mobile computers, tablets, and mobile phones that use radio waves in the megahertz to gigahertz band during communication. The present invention relates to a polyarylene sulfide composition which is useful for applications or electrical parts such as automobile electrical parts.

  Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

  Details of the polyarylene sulfide, the ethylene-based copolymer, the glass fiber and the release agent 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 350 poise.
Poly(p-phenylene sulfide) (A-2) (hereinafter simply referred to as PPS (A-2)): Melt viscosity 470 poise.

<Ethylene polymer (B)>
Ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (B-1-1) (hereinafter, simply referred to as ethylene-based polymer (B-1-1)): Arkema Ltd. Manufactured, (trade name) Bondine AX8390.
Ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (B-2-1) (hereinafter, simply referred to as ethylene-based polymer (B-2-1)): Sumitomo Chemical Co., Ltd., ( Product name) Bond First E.
Ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (B-4-1) (hereinafter, simply referred to as ethylene-based polymer (B-4-1) ): Sumitomo Chemical Co., Ltd., (brand name) Bond First 7M.

<Glass fiber (C)>
Glass fiber (C-1); manufactured by Nitto Boseki Co., Ltd., (trade name) CN3J-941S, dielectric constant 4.8 at measurement frequency 2 GHz.
Glass fiber (C-2); manufactured by Nitto Boseki Co., Ltd., (trade name) CN3J-256S, dielectric constant 4.8 at measurement frequency 2 GHz.
Glass fiber (C-3); made by Taishan, (trade name) TLD-T443, dielectric constant 4.5 at measurement frequency 2 GHz.
Glass fiber (C-4); manufactured by Nippon Electric Glass Co., Ltd. (trade name) T-760H, dielectric constant 6.8 at measurement frequency 2 GHz.

<Release agent (D)>
Release agent (D-1); Kyoeisha Chemical Co., Ltd. (trade name) Light Amide WH-255.

<Synthesis Example 1 (synthesis of PPS(A-1))>
In a 15-liter autoclave equipped with a stirrer, 1814 g of flaky sodium sulfide (Na ₂ S.2.9H ₂ O), 8.7 g of granular caustic soda (100% NaOH: Wako Pure Chemical Industries, Ltd.) and N-methyl-2-pyrrolidone 3232 g was charged, the temperature was gradually raised to 200° C. with stirring under a nitrogen stream, and 339 g of water was distilled off. After cooling to 190° C., 2129 g of p-dichlorobenzene and 1783 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225°C over 2 hours, polymerized at 225°C for 1 hour, heated to 250°C over 25 minutes, and polymerized at 250°C for 2 hours. Next, 509 g of distilled water was pressed into this system at 250° C., the temperature was raised to 255° C., and the polymerization reaction was further carried out for 2 hours. After the completion of the polymerization, the temperature was cooled to room temperature, and the polymerization slurry was subjected to solid-liquid separation with a centrifugal filter. The cake was washed successively with N-methyl-2-pyrrolidone and acetone three times in a nitrogen stream, and further washed with 0.2% hydrochloric acid and warm water in a nitrogen stream. The obtained poly(p-phenylene sulfide) was dried overnight at 105° C. to obtain PPS (A-1) having a melt viscosity of 350 poise.

<Synthesis example 2 (synthesis of PPS (A-2))>
In a 15-liter autoclave equipped with a stirrer, 1814 g of flaky sodium sulfide (Na ₂ S.2.9H ₂ O), 8.7 g of granular caustic soda (100% NaOH: Wako Pure Chemical Industries, Ltd.) and N-methyl-2-pyrrolidone 3232 g was charged, the temperature was gradually raised to 200° C. with stirring under a nitrogen stream, and 340 g of water was distilled off. After cooling to 190° C., 2100 g of p-dichlorobenzene and 1783 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225°C over 2 hours, polymerized at 225°C for 1 hour, heated to 250°C over 25 minutes, and polymerized at 250°C for 2 hours. Next, 509 g of distilled water was pressed into this system at 250° C., the temperature was raised to 255° C., and the polymerization reaction was further carried out for 2 hours. After the completion of the polymerization, the temperature was cooled to room temperature, and the polymerization slurry was subjected to solid-liquid separation with a centrifugal filter. The cake was sequentially washed twice with N-methyl-2-pyrrolidone and acetone under a nitrogen stream, and further washed with 0.2% hydrochloric acid and warm water under a nitrogen stream. The obtained poly(p-phenylene sulfide) was dried overnight at 105° C. to obtain PPS (A-2) having a melt viscosity of 470 poise.

~ Melt viscosity measurement of polyarylene sulfide ~
Melt viscosity was measured under the conditions of a measurement temperature of 315° C. and a load of 10 kg, using a Koka type flow tester (manufactured by Shimadzu Corporation, (trade name) CFT-500) equipped with a die having a diameter of 1 mm and a length of 2 mm. went.

  The evaluation/measurement methods of the polyarylene sulfide composition are shown below.

-Measurement of dielectric constant and dielectric loss tangent-
70 mm x 70 mm x 1 mm of a polyarylene sulfide composition was injection molded by an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE-75S) having a cylinder temperature of 300°C and a mold temperature of 135°C. A thick molded plate was prepared, and a 70 mm×3 mm×1 mm thick dielectric constant measuring test piece was manufactured from this molded plate by cutting. In this test piece, the dielectric constant and dielectric loss tangent were measured at a measurement frequency of 2 GHz in accordance with JIS C-2565 using a dielectric constant measuring device (manufactured by ET Co., Ltd., (trade name) Cavity Resonator). It was measured. Those having a dielectric constant of 3.5 or less and a dielectric loss tangent of 0.010 or less were judged to have sufficiently low dielectric properties in practical use.

-Measurement of impact resistance-
A test piece for measuring Charpy impact strength of a polyarylene sulfide-based composition was measured with an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE-75S) having a cylinder temperature of 300° C. and a mold temperature of 135° C. A notch was made with a notching machine (Toyo Seiki Seisakusho, Ltd., (trade name) A-3 type), and a Charpy impact tester (Toyo Seiki Seisakusho, Ltd., (trade name) DG-CB type) was used. Was measured according to ISO179. A Charpy impact strength of more than 10 kJ/m ² was judged to be a sufficiently high impact characteristic for practical use.

~ Appearance evaluation ~
The polyarylene sulfide composition was injection molded by an injection molding machine (Sumitomo Heavy Industries, Ltd. (trade name) SE-75S) having a cylinder temperature of 300° C. and a mold temperature of 135° C., and 150 mm×150 mm×1 mm. A thick molded plate was prepared, and one having no warp was considered to have an excellent appearance.

Example 1
Proportion of PPS (A-1) 85.8% by weight, ethylene copolymer (B-1-1) 13.4% by weight (C-1), release agent (D-1) 0.8% by weight Was added to the hopper of a twin-screw extruder (manufactured by Japan Steel Works, Ltd. (trade name) TEX-25αIII) heated to a cylinder temperature of 300°C. On the other hand, the glass fiber (C-1) was charged into the hopper of the side feeder of the twin-screw extruder, melt-kneaded at a screw rotation speed of 300 rpm, and the molten composition flowing out from the die was cooled and cut into pellets. A polyarylene sulfide-based composition was prepared. The composition ratio of the polyarylene sulfide composition at that time was 51.5% by weight of PPS (A-1), 8% by weight of ethylene copolymer (B-1-1), and 40% of glass fiber (C-1). The release agent (D-1) was 0.5% by weight.

  The polyarylene sulfide 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 300° C. to measure the dielectric constant and dielectric loss tangent. A test piece and a test piece for measuring impact resistance were molded and evaluated, and the appearance was evaluated. The results are shown in Table 1.

  The obtained polyarylene sulfide composition had a sufficiently low dielectric constant and dielectric loss tangent, and was excellent in impact resistance and appearance.

Examples 2-9
Polyarylene was prepared in the same manner as in Example 1 except that the polyarylene sulfide (A), the ethylene-based copolymer (B), the glass fiber (C), and the release agent (D) were mixed in the proportions shown in Table 1. A sulfide composition was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  All the obtained polyarylene sulfide compositions had sufficiently low dielectric constant and dielectric loss tangent, and were excellent in impact resistance and appearance.

Comparative Examples 1-8
A composition was prepared in the same manner as in Example 1 except that the polyarylene sulfide (A), the ethylene copolymer (B), the glass fiber (C) and the release agent (D) were mixed in the proportions shown in Table 2. Was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

  The compositions obtained from Comparative Examples 2, 3, 5, 7, and 8 had a high dielectric constant. The compositions obtained from Comparative Examples 2, 5, 7, and 8 had a high dielectric loss tangent. The compositions obtained from Comparative Examples 1, 3, 4, and 6 were inferior in impact resistance. The compositions obtained from Comparative Examples 4 and 6 were inferior in appearance.

  The polyarylene sulfide-based composition of the present invention has a low dielectric constant and a low dielectric loss tangent, and thus has excellent radio wave permeability in the megahertz to gigahertz band, and has impact resistance required as an exterior part, and warpage. It has no external appearance problems such as sink marks, and is used for electronic/electrical parts such as mobile PCs, tablets, and mobile terminal devices such as mobile phones that use radio waves in the gigahertz band during communication, or automobiles. It is useful for electric parts such as electric parts.

Claims (5)

30 to 70% by weight of polyarylene sulfide (A), 3 to 20% by weight of ethylene polymer (B), and 30 to 50% by weight of glass fiber (C) having a dielectric constant of 5.5 or less at 2 GHz. A polyarylene sulfide-based composition comprising: The polyarylene sulfide-based composition according to claim 1, further comprising at least one release agent (D) selected from the group consisting of polyethylene wax, polypropylene wax, and fatty acid amide wax. object. The ethylene polymer (B) is an ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (B-1), an ethylene-α,β-unsaturated carboxylic acid glycidyl ester copolymer ( B-2), ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (B-3), ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid It is at least one or more modified ethylene polymers selected from the group consisting of an alkyl ester copolymer (B-4) and a maleic anhydride graft modified ethylene polymer (B-5). Item 3. The polyarylene sulfide-based composition according to Item 1 or 2. The dielectric constant measured at a measurement frequency of 2 GHz according to JIS C-2565 is 3.5 or less, and the dielectric loss tangent is 0.010 or less. Poirylene sulfide composition of. A casing for a mobile device terminal, comprising the polyarylene sulfide composition according to any one of claims 1 to 4.