JP6766341B2 - Polyarylene sulfide-based composition - Google Patents

Description

Since the present invention has a low dielectric constant and a low dielectric loss tangent, it has excellent radio wave transmission in the megahertz band to the gigahertz band, has an excellent black or white tone as an exterior component, and has impact resistance. It also relates to an excellent polyarylene sulfide-based composition, and more specifically, electronically and electrically for the housing of mobile terminal devices such as mobile personal computers, tablets, and mobile phones that use radio waves in the megahertz band to gigahertz band for communication. It relates to a polyarylene sulfide-based composition useful for component applications or electrical component applications such as automobile electrical components.

Polyarylene sulfide represented by poly (p-phenylene sulfide) has excellent mechanical properties, thermal properties, electrical properties, and chemical resistance, and therefore, many electronic / electrical equipment members and automobile equipment members, It is widely used for other OA equipment members. Such polyarylene sulfide has mechanical strength by blending 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 and titanium oxide. , Heat resistance and rigidity can be greatly improved, and coloring can be performed.

However, since some of these compounding materials have a high dielectric constant and dielectric loss tangent such as glass fiber, carbon black, titanium oxide, etc., the dielectric constant and dielectric constant of the polyarylene sulfide-based composition containing these are mixed. The direct contact is also high. A polyarylene sulfide-based composition having such a high dielectric constant and a high dielectric loss tangent has a low dielectric constant, such as a housing of a mobile personal computer, a tablet, a mobile phone, etc. It is not suitable for applications that require a dielectric constant and low dielectric loss tangent, and it has been necessary to reduce the blending amount of glass fiber, carbon black, titanium oxide, etc. in order to reduce the dielectric constant and dielectric loss tangent. However, if the blending amount of carbon black, titanium oxide, etc. is reduced, the black and white tones required for exterior parts are inferior, and if the blending amount of glass fiber, etc. is lowered, the impact resistance required for exterior parts is reduced. There was a problem that sufficient mechanical strength could not be obtained.

Further, in the polyarylene sulfide-based composition, in order to obtain sufficiently high impact resistance, it is common to add an ethylene-based copolymer or the like. However, such an ethylene-based copolymer contains functional groups such as an epoxy group, an acid anhydride group, and a carboxylic acid ester in order to obtain sufficiently high impact resistance, and ethylene is produced by these functional groups. The dielectric constant and dielectric tangent of the system copolymer itself are high. Therefore, in order to obtain a composition having a low dielectric constant and a low dielectric loss tangent, the blending amount of such an ethylene-based copolymer is limited, and therefore the impact resistance required for exterior parts cannot be sufficiently obtained. There was a problem.

Therefore, as a composition capable of providing a good black molded product by adding a small amount of carbon black, a polyarylene sulfide resin composition containing 0.0005 to 3 parts by weight of iron or an iron compound with respect to 100 parts by weight of polyarylene sulfide. A product (see, for example, Patent Document 1) has been proposed.

Further, as a composition capable of providing a molded product having an excellent whiteness, a polyarylene sulfide resin composition composed of a polyarylene sulfide resin (A), a fibrous filler (B), and zinc sulfide (C) (for example, Patent Document). 2) and silica (B) having a pore volume of 1.00 ml / g or less and an average pore diameter of 100 angstrom or less with respect to 100 parts by weight of polyarylene sulfide (A) from 0.01 to A polyarylene sulfide resin composition containing 15 parts by weight (see, for example, Patent Document 3) and the like have been proposed.

Further, as a technique for improving the impact resistance of polyarylene sulfide, for example, a resin composition in which polyarylene sulfide is blended with an ethylene-based copolymer composed of an α, β-unsaturated carboxylic acid alkyl ester and maleic anhydride. (See, for example, Patent Document 4), a resin composition in which an ethylene-based copolymer composed of α-olefin, α, β-unsaturated acid glycidyl ester and ethylene is blended with polyarylene sulfide (see, for example, Patent Document 5). , Polyphenylene sulfide (A), ethylene having a ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) calculated by gel permeation chromatography (GPC) of 3.0 or less. α-Olefin-based copolymer (B), and a functional group-containing olefin-based copolymer containing at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester. A polyphenylene sulfide resin composition (see, for example, Patent Document 6) containing (C) has been proposed.

JP-A-09-194726 (see, for example, claims) Japanese Patent Application Laid-Open No. 05-039417 (see, for example, claims) Japanese Patent Application Laid-Open No. 09-07723 (see, for example, claims) Japanese Patent Application Laid-Open No. 62-151460 (see, for example, claims) JP-A-58-154757 (see, for example, claims) Japanese Patent No. 3739954 (see, for example, claims)

However, the technique proposed in Patent Document 1 is not sufficient as a black color tone and has a problem in impact resistance and the like. Further, the techniques proposed in Patent Documents 2 to 3 are not sufficient as a white tone, and the dielectric constant and dielectric loss tangent are also mobile personal computers, tablets, mobile phones, etc. that use radio waves in the megahertz band to the gigahertz band during communication. It is not low enough to be used for the housing of mobile terminal devices, etc., and has a problem in impact resistance and the like. Further, in the techniques proposed in Patent Documents 4 to 5, although the impact resistance is excellent, the color tone required for the exterior parts, particularly the black tone or the white tone, is not described at all. Furthermore, the technology proposed in Patent Document 6 has insufficient impact resistance, and the dielectric constant and dielectric loss tangent are also mobile personal computers, tablets, mobile phones, etc. that use radio waves in the megahertz band to gigahertz band during communication. There was also a problem that it was not low enough to be used for the housing of a mobile terminal device. That is, these proposed technologies generally have a low dielectric constant and a low dielectric loss tangent. It was difficult to satisfy impact resistance, black tone or white tone at the same time. In addition, even if all of these proposed technologies are combined, a polyarylene sulfide-based composition having a low dielectric constant, a low dielectric loss tangent, an excellent black or white tone as an exterior component, and an excellent impact resistance. I couldn't get anything.

Therefore, since the present invention has a low dielectric constant and a low dielectric loss tangent, it has excellent radio wave transmission in the megahertz band to the gigahertz band, has an excellent black tone or white tone as an exterior component, and further has impact resistance. The purpose is to provide a polyarylene sulfide-based composition with excellent properties, and in particular, electronic / electronic housing for mobile terminal devices such as mobile PCs, tablets, and mobile phones that use radio waves from the megahertz band to the gigahertz band for communication. It is an object of the present invention to provide a polyarylene sulfide-based composition useful for electric component applications or electrical component applications such as automobile electrical components.

As a result of diligent studies to solve the above problems, the present inventor has obtained a polymer mixture, glass fiber, which is a mixture of polyarylene sulfide, an ethylene-based copolymer and a hydrogenated block copolymer in a specific ratio. In addition, since the composition composed of the black colorant or the white colorant, the blending ratio thereof is within a specific range, and the release agent is blended as needed, has a low dielectric constant and a low dielectric positive contact. We have found that it can be a polyarylene sulfide resin composition having excellent transmission of radio waves from the megahertz band to the gigahertz band, having an excellent black or white tone as an exterior component, and also having excellent impact resistance. Has been completed.

That is, the present invention relates to a block copolymer composed of at least an ethylene-based polymer (B1), a vinyl aromatic compound polymer block unit, and a conjugated diene compound polymer block unit with respect to 100 parts by weight of polyarylene sulfide (A). Polymer mixture (B) 15-40 weight by mixing the hydrogenated product (B2) at a ratio of (B1) / ((B1) + (B2)) = 0.2 to 0.8 (weight ratio). A poly comprising 15 to 65 parts by weight of glass fiber (C) and 15 to 40 parts by weight of black colorant (D) or 15 to 40 parts by weight of white colorant (E) as a colorant. It relates to an arylene sulfide-based composition.

The present invention will be described in detail below.

The polyarylene sulfide (A) constituting the polyarylene sulfide-based composition of the present invention may be any one that belongs to the category generally called polyarylene sulfide, and the polyarylene sulfide may be, for example, p-phenylene sulfide. Examples thereof include homopolymers or copolymers composed of units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, and biphenylene sulfide units. Specific examples of the sulfide include poly (p-phenylene sulfide), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, polyphenylene sulfide ether, and the like, among which polyarylene sulfide-based compositions having particularly excellent heat resistance and strength characteristics are used. Therefore, it is preferably poly (p-phenylene sulfide).

The polyarylene sulfide (A) was formed with mechanical strength and molding at a melt viscosity measured under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg with a high-grade flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm. Since a polyarylene sulfide-based composition having excellent fluidity can be obtained, a polyarylene sulfide of 50 to 1000 poise is preferable.

As a method for producing the polyarylene sulfide (A), it can be produced by a method known as a method for producing polyarylene sulfide. For example, an alkali metal sulfide salt and a polyhaloaromatic compound are polymerized in a polar solvent. It can be obtained by doing so. Examples of the polar organic solvent at that time include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, cyclohexylpyrrolidone, dimethylformamide, dimethylacetamide and the like, and examples of the alkali metal sulfide salt include sulfide. Anhydrous or hydrates of sodium, rubidium sulfide, lithium sulfide can be mentioned. Further, the alkali metal sulfide salt may be a reaction of an alkali metal hydroxide salt and an alkali metal hydroxide. Examples of the polyhaloaromatic compound include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 4,4'-dichlorodiphenylsulfone, and 4 , 4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl ether, 4,4'-dichlorobiphenyl and the like.

Further, the polyarylene sulfide (A) may be a linear one or one in which a small amount of a polyhalogen compound of trihalogen or more is added at the time of polymerization to introduce a slight crosslinked or branched structure. , Nitrogen, etc., even if part and / or the terminal of the molecular chain of polyarylene sulfide is modified with a functional group such as a carboxyl group, a carboxymetal salt, an alkyl group, an alkoxy group, an amino group, or a nitro group. It may be heat-treated in a non-oxidizing inert gas of the above, and may be a mixture of these structures. Further, the polyarylene sulfide (A) can be treated with deionization (acid cleaning, hot water cleaning, etc.) or cleaning treatment with an organic solvent such as acetone or methyl alcohol before or after heat curing to obtain ions, oligomers, etc. It may be one in which impurities are reduced. Further, after the polymerization reaction is completed, the polymer may be cured by heat treatment in an inert gas or an oxidizing gas.

The polymer mixture (B) constituting the polyarylene sulfide-based composition of the present invention improves the impact resistance of the polyarylene sulfide-based composition, and is an ethylene-based copolymer (B1) and a vinyl aromatic compound. It is a polymer mixture of a hydrogenated product (B2) of a block copolymer composed of a polymer block unit and a conjugated diene compound polymer block unit.

In the polymer mixture (B), the mixing ratio of the ethylene-based copolymer (B1) and the hydrogenated additive (B2) of the block copolymer is (B1) / ((B1) + (B2)). = 0.2 to 0.8 (weight ratio). If the mixing ratio (B1) / ((B1) + (B2)) is less than 0.2, the resulting composition will be inferior in impact resistance, while the mixing ratio (B1) / ((B1) +). When (B2)) is larger than 0.8, the obtained composition has a high dielectric constant and dielectric loss tangent.

The ethylene-based copolymer (B1) may be any one that belongs to the category of an ethylene-based polymer obtained by polymerizing an ethylene monomer, and among them, ethylene-α and β-unsaturated carboxylic acid alkyl ester-. Maleic anhydride copolymer (B1-1), ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (B1-2), ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer Combined (B1-3), ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (B1-4) and maleic anhydride graft-modified ethylene-based polymer (B1) It is preferable that the modified ethylene polymer is at least one selected from the group consisting of −5).

As the ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (B1-1), any one belonging to this category may be used, and among them, the polyarylene sulfide obtained 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 (B1-1) include (trade name) Bondine LX4110 (manufactured by Alchema Co., Ltd.), (trade name). Examples thereof include bondine TX8030 (manufactured by Alchema Co., Ltd.) and bondine AX8390 (manufactured by Alchema Co., Ltd.).

As the ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (B1-2), any one belonging to this category may be used, and the obtained polyarylene sulfide-based composition is particularly suitable. Since it is excellent in impact resistance and the like, it is preferable that the ethylene residue unit: α, β-unsaturated carboxylic acid glycidyl ester residue unit (weight ratio) = 85-99: 15-1. Specific examples of the ethylene-α and β-unsaturated carboxylic acid glycidyl ester copolymer (B1-2) 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 can be mentioned.

As the ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (B1-3), any one belonging to this category may be used, and among them, the polyarylene sulfide system obtained. 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 (B1-3) 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 (B1-4), any one belonging to this category may be used. Among them, since the obtained polyarylene sulfide-based 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. As a specific example of the ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (B1-4), (trade name) Bond First 7L (Sumitomo Chemical Co., Ltd. (Manufactured by Sumitomo Chemical Co., Ltd.), Bond First 7M (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

As the maleic anhydride graft-modified ethylene-based polymer (B1-5), any one belonging to this category may be used, and the obtained polyarylene sulfide-based composition 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) = 50 to 98: 45 to 1: 5 to 1, and specifically. Examples 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 with a grafting reaction. Is.

The α-olefin constituting the ethylene-based polymer (B1) means an α-olefin having 3 or more carbon atoms, for example, propylene, butene-1, 4-methyl-pentene-1, hexene-1, and the like. Octene-1, etc. can be exemplified. Examples of α and β-unsaturated carboxylic acid alkyl esters include alkyl esters such as acrylic acid and methacrylic acid, and specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, and methacrylic 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 Examples include butyl. Examples of the α, β-unsaturated carboxylic acid glycidyl ester include acrylic acid glycidyl ester and methacrylic acid glycidyl ester.

As the hydrogenated product (B2) of the block copolymer composed of the vinyl aromatic compound polymer block unit and the conjugated diene compound polymer block unit, any hydrogenated product (B2) belonging to this category may be used.

Examples of the vinyl aromatic compound in the block copolymer include styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, p-tert-butylstyrene, and the like, and styrene is particularly common. .. These may use not only one kind but also two or more kinds. The conjugated diene compound in the block copolymer is a diolefin having a pair of conjugated double bonds, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2, Examples thereof include 3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and the most common ones are 1,3-butadiene and isoprene. Can be mentioned. These may use not only one kind but also two or more kinds. Examples of the hydrogenated product of such a block copolymer include a hydrogenated product of a styrene block-butadiene block copolymer, a styrene block-butadiene block-a hydrogenated product of a styrene block copolymer, and a styrene block-. Examples thereof include a hydrogenated product of a copolymer of isoprene block and a hydrogenated product of a copolymer of styrene block-isoprene block-styrene block.

In the hydrogenated product (B2) of the block copolymer, the obtained polyarylene sulfide-based composition has excellent impact resistance, so that the density is 0.91 g / cm ³ or less and the vinyl aromatic compound. The content of the polymer block unit (hereinafter referred to as styrene content) is preferably 5 to 20% by weight.

Specific examples of the hydrogenated product (B2) of the block copolymer include Dynalon 1320P (trade name) (manufactured by JSR Co., Ltd., density = 0.89 g / cm ³ , styrene content = 10% by weight). (Product name) Dynalon 1321P (manufactured by JSR Co., Ltd., density = 0.89 g / cm ³ , styrene content = 10% by weight), (trade name) Dynalon 8300P (manufactured by JSR Co., Ltd., density = 0.88 g / cm ³ , styrene content = 9% by weight), (trade name) Dynalon 8600P (manufactured by JSR Co., Ltd., density = 0.90 g / cm ³ , styrene content = 15% by weight), (trade name) Tough Tech H1221 (trade name) Made by Asahi Kasei Chemicals Co., Ltd., density = 0.89 g / cm ³ , styrene content = 12% by weight), (trade name) Tough Tech H1062 (manufactured by Asahi Kasei Chemicals Co., Ltd., density = 0.89 g / cm ³ , containing styrene) Amount = 18% by weight) and the like.

The blending amount of the polymer mixture (B) constituting the polyarylene sulfide-based composition of the present invention is 15 to 40 parts by weight with respect to 100 parts by weight of the polyarylene sulfide (A). When the blending amount of the polymer mixture (B) is less than 15 parts by weight, the obtained composition is inferior in impact resistance. On the other hand, when the blending amount of the ethylene-based polymer (B) exceeds 40 parts by weight, the obtained composition has a high dielectric constant and dielectric loss tangent.

The glass fiber (C) constituting the polyarylene sulfide-based composition of the present invention improves the impact resistance and mechanical strength of the polyarylene sulfide-based composition, and the glass fiber (C) is generally used. Any material called glass fiber may be used. Specific examples of the glass fibers include chopped strands having an average fiber diameter of 6 to 14 μm, chopped strands composed of flat glass fibers having a fiber cross-sectional aspect ratio of 2 to 4, milled fibers, roving and other glass fibers; silane fibers. Aluminosilicate glass fiber; hollow glass fiber; non-hollow glass fiber and the like. Among them, since it is a polyarylene sulfide-based composition having excellent impact resistance and molding fluidity, it is composed of chopped strands having an average fiber diameter of 6 to 14 μm and flat glass fibers having a fiber cross-sectional aspect ratio of 2 to 4. It is preferably a chopped strand. Examples of chopped strands having an average fiber diameter of 6 to 14 μm include (trade name) ESC 03T-760H (manufactured by Nippon Electric Glass Co., Ltd.), and chopped strands having a fiber cross-sectional aspect ratio of 4 include. For example, (trade name) CSG-3PA 830 (manufactured by Nitto Boseki Co., Ltd.), and chopped strands having a fiber cross-sectional aspect ratio of 2 include (trade name) CSG-3PL 830 (manufactured by Nitto Boseki Co., Ltd.). Can be mentioned. Two or more of these glass fibers (C) can be used in combination, and if necessary, they are surface-treated in advance with a functional compound or polymer such as an epoxy compound, an isocyanate compound, a silane compound, or a titanate compound. You may use the thing.

The blending amount of the glass fiber (C) constituting the polyarylene sulfide-based composition of the present invention is 15 to 65 parts by weight with respect to 100 parts by weight of the polyarylene sulfide (A). When the blending amount of the glass fiber (C) is less than 15 parts by weight, the obtained composition is inferior in impact resistance and mechanical strength. On the other hand, when the blending amount of the glass fiber (C) exceeds 65 parts by weight, the obtained composition has a high dielectric constant and dielectric loss tangent.

When the polyarylene sulfide-based composition of the present invention has a black tone, a black colorant is used as the colorant, and the black colorant (D) at that time is generally used as a black colorant. It is possible to use whatever is used. Among them, the polyarylene sulfide-based composition has a black tone, excellent impact resistance, a low dielectric constant, and a low dielectric loss tangent, and therefore has a triiron tetroxide (D1) and / or a number average particle diameter of 10 to 20 nm. it is preferred dibutyl phthalate oil absorption of carbon black (D2) is 60~125cm ³ / 100g.

As the triiron tetroxide (D1), any one may be used as long as its chemical formula can be expressed as FeO · Fe ₂ O ₃ and / or Fe ₃ O ₄ and belongs to this category. The particle size of the triiron tetroxide (D1) is preferably 2 μm or less in average particle size because a polyarylene sulfide-based composition having a particularly black tone and excellent impact resistance can be obtained. Specific examples of the triiron tetroxide (D1) include Bayferrox 303T (trade name) manufactured by LANXESS Co., Ltd. (average particle size 0.6 μm).

As the carbon black (D2), any one belonging to the category of carbon black may be used, but since it is a polyarylene sulfide-based composition having a particularly excellent black tone and impact resistance, the number average particle diameter of: 10 to 20 nm, DBP oil absorption amount is carbon black 60~125cm ³ / 100g is preferred. Specific examples of the carbon black (D2), (trade name) # 950 (Mitsubishi Chemical Co., Ltd., number average particle diameter of 16 nm, DBP oil absorption of 79cm ^3/100 g), (trade name) # 2600 (Mitsubishi chemical Co., Ltd., number average particle diameter of 13 nm, DBP oil absorption of 77cm ^3/100 g), and the like (trade name) Vulcan 9A32 (Cabot Corporation, number-average particle diameter 19 nm, DBP oil absorption 118cm ^3/100 g) and the like .. The number average particle size can be measured with an electron microscope.

The blending amount of the black colorant (D) constituting the polyarylene sulfide-based composition of the present invention is 1 to 15 parts by weight with respect to 100 parts by weight of the polyarylene sulfide (A). When the blending amount of the black colorant (D) is less than 1 part by weight, the obtained composition is inferior to the black tone. On the other hand, when the blending amount of the black colorant (D) exceeds 15 parts by weight, the obtained composition has a high dielectric constant and dielectric loss tangent, and is inferior in impact resistance.

When the polyarylene sulfide-based composition of the present invention has a white tone, a white colorant is used as the colorant, and the white colorant (E) at that time may be organic or inorganic. Anything can be used. Among them, at least one white colorant selected from the group consisting of titanium oxide (E1), zinc sulfide (E2) and zinc oxide (E3) because the polyarylene sulfide-based composition is particularly excellent in whiteness. Is preferable.

The titanium oxide (E1) is not particularly limited as long as it is in the category of being used as a white colorant, and among them, it is a polyarylene sulfide-based composition having excellent whiteness and impact resistance. Titanium oxide of rutile crystal or anatas crystal having an average primary particle size of 200 to 400 nm and a specific surface area of 5 to 15 m ² / g is preferable. Specific examples of such titanium oxide include (trade name) Typake CR-60 (manufactured by Ishihara Sangyo Co., Ltd., average primary particle size: 210 nm, specific surface area: 10 m ² / g, rutile crystal) and the like. Can be mentioned.

The zinc sulfide (E2) is not limited in shape or the like as long as it is in the category of being used as a white colorant, and may be, for example, spherical or otherwise isotropic. It may have anisotropy such as spindle-shaped, rod-shaped, needle-shaped, tubular, columnar, and plate-shaped. Further, zinc sulfide can be either coated or uncoated on its surface, and there is no limitation on the surface coating agent when the surface is coated. Specific examples of such zinc sulfide include (trade name) Sactris HD (manufactured by Sachtreben) and the like.

The zinc oxide (E3) is not particularly limited as long as it is in the category of being used as a white colorant, and among them, it is a polyarylene sulfide-based composition having excellent whiteness and impact resistance. Zinc oxide having an average particle size of 300 to 1500 nm and a specific surface area of ^{2 to} 6 m ² / g is preferable. Specific examples of such zinc oxide include (trade name) Ginrei A (manufactured by Toho Zinc Co., Ltd., average particle size: 600 nm, specific surface area: 5 m ² / g) and the like.

The blending amount of the white colorant (D) constituting the polyarylene sulfide-based composition of the present invention is 15 to 40 parts by weight with respect to 100 parts by weight of the polyarylene sulfide (A). When the blending amount of the white colorant (D) is less than 15 parts by weight, the obtained composition is inferior in whiteness. On the other hand, when the blending amount of the white colorant (D) exceeds 40 parts by weight, the obtained composition is inferior in impact resistance and has a high dielectric constant and dielectric loss tangent.

Since the polyarylene sulfide-based composition of the present invention has particularly excellent molding processability, it is preferably further blended with a mold release agent (F). The release agent (F) is preferably one or more selected from the fatty acid amide-based lubricant (F-1) and carnauba wax (F-2), and the fatty acid amide-based lubricant (F-1). ), Carnauba wax (F-2) can be commercially available. Examples of the fatty acid amide-based lubricant (F-1) include polycondensates composed of higher fatty acid amides, ethylene bisstearoamides, higher fatty acids and diamines, and any one belonging to this category can be used. It is possible, and examples thereof include (trade name) Light Amide WH-255 (manufactured by Kyoeisha Chemical Co., Ltd.), which is a polycondensate composed of stearic acid, sebacic acid, and ethylenediamine. Further, as the carnauba wax (F-2), any carnauba wax generally referred to as carnauba wax can be used. For example, (trade name) purified carnauba powder No. 1 (manufactured by Nikko Rika Co., Ltd.) And so on. The amount of the release agent (F) to be blended is 0.1 to 3 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin (A) because it is a polyarylene sulfide-based composition having excellent molding fluidity. Is preferable.

The polyarylene sulfide-based composition of the present invention contains carbon fibers, silicon nitride whiskers, basic magnesium sulfate whiskers, barium titanate whiskers, potassium titanate whiskers, silicon carbide whiskers, and boron whiskers, as long as the effects of the present invention are not impaired. , Whiskers such as zinc oxide whiskers; inorganic fibers such as rock wool, zirconia, barium titanate, silicon carbide, silica, blast furnace slag, and organic fibers such as total aromatic polyamide fibers, phenol resin fibers, and total aromatic polyester fibers. Mineral fibers such as wallastenite and magnesium oxysulfate may be added, or calcium carbonate, lithium carbonate, magnesium carbonate, zinc carbonate, mica, silica, as long as the effects of the present invention are not impaired. Talk, clay, calcium sulfate, kaolin, wallastenite, zeolite, silicon oxide, magnesium oxide, zirconium oxide, tin oxide, magnesium silicate, calcium silicate, calcium phosphate, magnesium phosphate, hydrotalcite, glass powder, glass balloon, glass flakes May be added.

Further, the polyarylene sulfide-based composition of the present invention is a conventionally known crystal nucleating agent such as talc, kaolin, silica, etc.; a polyalkylene oxide oligomer-based compound, a thioether-based compound, and an ester-based compound, as long as the effects of the present invention are not impaired. One or more ordinary additives such as compounds, plasticizers such as organic phosphorus compounds; antioxidants; heat stabilizers; lubricants; UV inhibitors; foaming agents may be added.

Further, the polyarylene sulfide-based composition of the present invention contains various thermosetting resins and thermoplastic resins such as epoxy resin, cyanate ester resin, phenol resin, polyimide and silicone resin, as long as the object of the present invention is not deviated. Mix one or more of polyester, polyamide, polyphenylene oxide, polycarbonate, polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone, polyamideimide, polyamide-based elastomer, polyester-based elastomer, polyalkylene oxide, etc. It may be used.

The production method for producing the polyarylene sulfide-based composition of the present invention is not particularly limited, and a method known as a general mixing / kneading method can be used. For example, all raw materials are blended. Method of melt-kneading; a method of blending a part of raw materials and then melt-kneading, and then blending the remaining raw materials and melt-kneading; or a method of blending a part of raw materials and then melt-kneading with a single-screw or twin-screw extruder. Any method may be used, such as a method of mixing the remaining raw materials with a side feeder inside. Further, a small amount of the added component may be used by kneading the other component by the above method or the like, pelletizing the component, and then adding the component before molding. As a method for performing melt-kneading, a conventionally used heat-melt-kneading method can be used, and examples thereof include a heat-melt-kneading method using a single-screw or twin-screw extruder, a kneader, a mill, lavender, or the like. In particular, a melt-kneading method using a twin-screw extruder having excellent kneading ability is preferable. The kneading temperature at this time is not particularly limited, and can be arbitrarily selected from usually 260 to 350 ° C.

Examples of the method for forming the polyarylene sulfide-based composition of the present invention include an injection molding machine, an extrusion molding machine, a compression molding machine, and the like, and these methods can be used to form an arbitrary shape, particularly injection molding. Is a suitable resin composition.

The polyarylene sulfide-based composition of the present invention has a low dielectric constant and a low dielectric loss tangent, has an excellent black or white tone as an exterior component, and has excellent impact resistance. Therefore, ISO179 The shearpy impact strength measured in accordance with JIS C-2565 exceeds 12 kJ / m ² , the permittivity measured at a measurement frequency of 2 GHz in accordance with JIS C-2565 is 3.70 or less, and the dielectric loss tangent is 0.01 or less. When the black colorant (D) is blended in the molded product injection-molded at a temperature of 310 ° C. and a mold temperature of 135 ° C., the L value (brightness) is 30 or less, or the white colorant (E) is blended. In some cases, it is preferable that the L value is 85 or more at the same time.

Since the polyarylene sulfide-based composition of the present invention has a low dielectric constant and a low dielectric loss tangent, it has excellent radio wave transmission in the megahertz band to the gigahertz band and has an excellent black tone or white tone as an exterior component. Furthermore, because of its excellent impact resistance, it is used for electronic and electrical parts such as housings of mobile terminal devices such as mobile PCs, tablets, and mobile phones that use radio waves in the megahertz to gigahertz band for communication, or automobile electrical components, etc. It is useful for electrical component applications.

Since the present invention has a low dielectric constant and a low dielectric loss tangent, it has excellent radio wave transmission in the megahertz band to the gigahertz band, has an excellent black or white tone as an exterior component, and has impact resistance. Also provides an excellent polyarylene sulfide-based composition, and the polyarylene sulfide-based composition is a housing for mobile terminal devices such as mobile personal computers, tablets, and mobile phones that use radio waves in the megahertz band to the gigahertz band for communication. It is useful for electronic / electrical parts applications such as, or for electrical parts applications such as automobile electrical components.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

Polyarylene sulfide (A), ethylene polymer (B1), block copolymer hydrogenated product (B2), glass fiber (C), black colorant (D), white used in Examples and Comparative Examples. The colorant (E) and the release agent (F) are shown below.

<Polyarylene sulfide (A)>
Poly (p-phenylene sulfide) (hereinafter referred to as PPS (A-1)): melt viscosity 370 poise.
Poly (p-phenylene sulfide) (hereinafter referred to as PPS (A-2)): melt viscosity 350 poise.
Poly (p-phenylene sulfide) (hereinafter referred to as PPS (A-3)): melt viscosity 470 poise.

<Ethylene copolymer (B1)>
Ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (B1-2-1) (hereinafter referred to as ethylene-based copolymer (B1-2-1)): manufactured by 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 (B1-4-1) (hereinafter referred to as ethylene-based copolymer (B1-4-1)). .): Made by Sumitomo Chemical Co., Ltd. (trade name) Bond First 7M.

<Hydrogenated block copolymer (B2)>
Hydrogenated block copolymer (B2-1): manufactured by JSR Corporation, (trade name) Dynalon 1321P, density 0.89 g / cm ³ , styrene content 10% by weight.
Hydrogenated block copolymer (B2-2): manufactured by JSR Corporation, (trade name) Dynalon 8300P, density 0.88 g / cm ³ , styrene content 9 % by weight.
Hydrogenated block copolymer (B2-3): manufactured by Asahi Kasei Chemicals Co., Ltd. (trade name) Tough Tech H1221, density 0.89 g / cm ³ , styrene content 12% by weight.

<Glass fiber (C)>
Glass fiber (C-1): Chopped strand manufactured by Nippon Electric Glass Co., Ltd., (trade name) ECS 03T-760H, fiber diameter 10.5 μm.
Glass fiber (C-2); chopped strand manufactured by Nitto Boseki Co., Ltd., (trade name) CSG-3PA 830, aspect ratio of fiber cross section 4.

<Black colorant (D)>
Triiron tetroxide (D1-1): manufactured by LANXESS, (trade name) Bayferrox 303T, average particle size 0.6 μm.
Carbon black (D2-1); Mitsubishi Chemical Co., Ltd., (trade name) # 950, the number-average particle diameter of 16 nm, DBP oil absorption of 79cm ³ / 100g.
Carbon black (D2-2); manufactured by Cabot Corporation, (trade name) Vulcan 9A32, number average particle diameter of 19 nm, DBP oil absorption 118cm ³ / 100g.

<White colorant (E)>
Titanium oxide (E1-1); (trade name) Typake CR-60 (manufactured by Ishihara Sangyo Co., Ltd., average primary particle size: 210 nm, specific surface area: 10 m ² / g, rutile crystal).
Zinc sulfide (E2-1); (trade name) Sactris HD (manufactured by Sachtleben).
Zinc oxide (E3-1); (trade name) Ginrei A (manufactured by Toho Zinc Co., Ltd., average particle size: 600 nm, specific surface area: 5 m ² / g).

<Release agent (F)>
Fatty acid amide lubricant (hereinafter referred to as mold release agent (F-1)); manufactured by Kyoeisha Chemical Co., Ltd., (trade name) Light Amide WH-255.
Carnauba wax (hereinafter referred to as mold release agent (F-2)); manufactured by Nikko Rika Co., Ltd., (trade name) purified carnauba powder No. 1.

<Synthesis Example 1 (Synthesis of PPS (A-1))>
To 15 liters autoclave equipped with a stirrer was charged with flaky sodium sulfide _{(Na 2 S · 2.9H 2 O} ) 1854g, 30% sodium hydroxide solution (30% NaOHaq) 48g and N- methyl-2-pyrrolidone 3679G, nitrogen flow The temperature was gradually raised to 200 ° C. with stirring, and 380 g of water was distilled off. After cooling to 190 ° C., 2140 g of p-dichlorobenzene and 985 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 and polymerized at 225 ° C. for 1 hour, then heated to 250 ° C. over 25 minutes, and further polymerized at 250 ° C. for 3 hours. After the polymerization, N-methyl-2-pyrrolidone was recovered from the polymerized slurry under reduced pressure by a distillation operation. The final temperature reached was 170 ° C. and the pressure was 4.7 kPa. Warm water at 80 ° C. was added to the obtained cake and washed to a slurry concentration of 20%, and warm water was added again in the same manner to raise the temperature to 175 ° C. and the poly (p-phenylene sulfide) was washed twice in total. The obtained polyphenylene sulfide was dried at 105 ° C. for 24 hours. Next, the dried polyphenylene sulfide was filled in a batch type rotary kiln type firing device, heated to 240 ° C. in a nitrogen atmosphere, and cured by holding for 1 hour, whereby PPS (A-) having a melt viscosity of 370 poise was performed. 1) was obtained.

<Synthesis Example 2 (Synthesis of PPS (A-2))>
To 15 liters autoclave equipped with a stirrer, flaky sodium sulfide _{(Na 2 S · 2.9H 2 O} ) 1814g, granular caustic soda (100% NaOH: Wako Pure Chemical special grade) 8.7 g and N- methyl-2-pyrrolidone 3232 g was charged, the temperature was gradually raised to 200 ° C. while 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 and polymerized at 225 ° C. for 1 hour, then heated to 250 ° C. over 25 minutes and polymerized at 250 ° C. for 2 hours. Next, 509 g of distilled water was press-fitted into this system at 250 ° C., the temperature was raised to 255 ° C., and a polymerization reaction was further carried out 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 by a centrifugal filter. The cake was washed repeatedly with N-methyl-2-pyrrolidone and acetone under a nitrogen stream three times in sequence, and further washed sequentially with 0.2% hydrochloric acid and warm water under a nitrogen stream. The obtained poly (p-phenylene sulfide) was dried at 105 ° C. for 24 hours to obtain PPS (A-2) having a melt viscosity of 350 poise.

<Synthesis Example 3 (Synthesis of PPS (A-3))>
To 15 liters autoclave equipped with a stirrer, flaky sodium sulfide _{(Na 2 S · 2.9H 2 O} ) 1814g, granular caustic soda (100% NaOH: Wako Pure Chemical special grade) 8.7 g and N- methyl-2-pyrrolidone 3232 g was charged, the temperature was gradually raised to 200 ° C. while 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 and polymerized at 225 ° C. for 1 hour, then heated to 250 ° C. over 25 minutes and polymerized at 250 ° C. for 2 hours. Next, 509 g of distilled water was press-fitted into this system at 250 ° C., the temperature was raised to 255 ° C., and a polymerization reaction was further carried out 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 by a centrifugal filter. The cake was washed twice in sequence with N-methyl-2-pyrrolidone and acetone under a nitrogen stream, and further washed sequentially with 0.2% hydrochloric acid and warm water under a nitrogen stream. The obtained poly (p-phenylene sulfide) was dried at 105 ° C. for 24 hours to obtain PPS (A-3) having a melt viscosity of 470 poise.

The evaluation / measurement method of the obtained polyarylene sulfide and polyarylene sulfide-based composition is shown below.

Evaluation / measurement method of polyarylene sulfide-Measurement of melt viscosity of polyarylene sulfide-
Measurement of melt viscosity under the conditions of measurement temperature 315 ° C and load 10 kg with a high-grade flow tester (manufactured by Shimadzu Corporation, (trade name) CFT-500) equipped with a die with a diameter of 1 mm and a length of 2 mm. Was done.

Evaluation / measurement method of polyarylene sulfide-based composition-Measurement of L value (brightness) of polyarylene sulfide-based composition-
The polyarylene sulfide-based composition was injection-molded by an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE-75S) at a cylinder temperature of 300 ° C. and a mold temperature of 135 ° C., and 70 mm × 70 mm × 2 mm. A thick molded plate was prepared, and the L value (brightness) was measured at room temperature using a color difference meter (manufactured by Suga Test Instruments Co., Ltd., (trade name) SM color computer). .. The L value is a numerical value indicating the lightness of the color, L = 0 represents a completely black body, and L = 100 represents a completely white body. In the composition of the present invention, it was determined that the black one is excellent in black tone when the L value is 30 or less, and the white one is excellent in white tone when the L value is 85 or more. ..

~ Measurement of permittivity and dielectric loss tangent ~
The polyarylene sulfide-based composition was injection-molded by an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE-75S) at a cylinder temperature of 300 ° C. and a mold temperature of 135 ° C., and 70 mm × 70 mm × 1 mm. A thick molded plate was produced, and a test piece for measuring the dielectric constant having a thickness of 70 mm × 3 mm × 1 mm was produced from this molded plate by cutting. With this test piece, a permittivity measuring device (manufactured by AT Co., Ltd., (trade name) cavity resonator) is used to measure the permittivity and dielectric loss tangent at a measurement frequency of 2 GHz in accordance with JIS C-2565. It was measured. Those having a dielectric constant of 3.70 or less and a dielectric loss tangent of 0.01 or less were judged to have sufficiently low dielectric properties for practical use.

~ Impact resistance measurement ~
A test piece for measuring Charpy impact strength was prepared by using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE-75S) in which the polyarylene sulfide-based composition had a cylinder temperature of 300 ° C and a mold temperature of 135 ° C. Manufactured, notched with a notching machine (manufactured by Toyo Seiki Seisakusho Co., Ltd., (trade name) A-3 type), Charpy impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., (trade name) DG-CB type) The measurement was performed in accordance with ISO179. It was judged that a Charpy impact strength exceeding 12 kJ / m ² shows a practically sufficient value.

Example 1
10 parts by weight of ethylene-based copolymer (B1-2-1) and 10 parts by weight of hydrogenated block copolymer (B2-1) with respect to 100 parts by weight of PPS (A-1) obtained in Synthesis Example 1. Hopper of a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd. (trade name) TEM-35-102B) in which 13 parts by weight of triiron tetroxide (D1-1) was uniformly mixed in advance and heated to a cylinder temperature of 310 ° C. I put it in. On the other hand, the glass fiber (C-1) was charged from the hopper of the side feeder of the twin-screw extruder so as to be 25 parts by weight with respect to 100 parts by weight of PPS (A-1), and melt-kneaded to pelletize. A polyarylene sulfide-based composition was prepared. From the obtained polyarylene sulfide-based composition, a 70 mm × 70 mm × 2 mm thick molded plate for evaluating brightness, a 70 mm × 70 mm × 1 mm thick molded plate for evaluating dielectric constant and dielectric loss tangent, and impact resistance. A test piece for measuring Charpy impact strength for evaluating the properties was prepared, and the brightness, dielectric constant, dielectric loss tangent, and Charpy impact strength were evaluated. The evaluation results are shown in Table 1.

The obtained polyarylene sulfide-based composition had a lightness sufficiently low for practical use as a black tone, and had a dielectric constant and dielectric loss tangent sufficiently low for practical use. The Charpy impact strength was also good.

Example 2-8
PPS (A-1, A-2, A-3), ethylene-based copolymers (B1-2-1, B1-4-1), block copolymer hydrogenated products (B2-1, B2-2) , B2-3), triiron tetroxide (D1-1), carbon black (D2-1, D2-2), titanium oxide (E1-1), zinc sulfide (E2-1), zinc oxide (E3-1) ) And the mold release agent (F-1, F-2) are blended in the composition ratios shown in Table 1 and charged into the hopper of the twin-screw extruder, and the glass fibers (C-1, C-2) are added. It was put into the hopper of the side feeder of the twin-screw extruder so as to have the composition ratio shown in Table 1, a polyarylene sulfide-based composition was prepared by the same method as in Example 1, and evaluated by the same method as in Example 1. did. The evaluation results are shown in Table 1.

All the obtained polyarylene sulfide-based compositions have a lightness sufficiently low for practical use in a black tone and a lightness sufficiently high for practical use in a white tone, and have a dielectric constant and a dielectric constant sufficiently low for practical use. It was a direct connection. The Charpy impact strength was also good.

Comparative Examples 1-9
PPS (A-1, A-2), ethylene-based polymers (B1-2-1, B1-4-1), block copolymer hydrogenated products (B2-1, B2-2), tritetraoxide Iron (D1-1), carbon black (D2-1), and mold release agent (F-1) are blended in the composition ratios shown in Table 2 and charged into the hopper of a twin-screw extruder to obtain glass fiber (C). -1, C-2) were put into the hopper of the side feeder of the twin-screw extruder so as to have the composition ratio shown in Table 2, and a polyarylene sulfide-based composition was prepared by the same method as in Example 1. , Evaluated by the same method as in Example 1. The evaluation results are shown in Table 2.

The composition obtained in Comparative Example 1 did not have a sufficiently low brightness in black tones. The composition obtained in Comparative Example 3 did not have a sufficiently high brightness in white tones. The compositions obtained in Comparative Examples 2, 4, 5 , 7 , and 9 did not have sufficient performance in terms of dielectric constant and dielectric loss tangent. Moreover, the compositions obtained in Comparative Examples 2, 4, 6 and 8 were inferior in impact strength.

Since the polyarylene sulfide-based composition of the present invention has a low dielectric constant and a low dielectric loss tangent, it has excellent radio wave transmission in the megahertz band to the gigahertz band and has an excellent black tone or white tone as an exterior component. In addition, because it has excellent impact resistance, it is used for electronic and electrical parts such as housings of mobile terminal devices such as mobile PCs, tablets, and mobile phones that use radio waves in the megahertz to gigahertz band for communication, or automobiles. It is expected as a resin composition used for electric parts such as electric parts.

Claims (6)

A block copolymer hydrogenated product (B2) composed of at least an ethylene-based polymer (B1), a vinyl aromatic compound polymer block unit, and a conjugated diene compound polymer block unit with respect to 100 parts by weight of polyarylene sulfide (A). And (B1) / ((B1) + (B2)) = 0.2 to 0.8 (weight) of the polymer mixture (B) 15 to 40 parts by weight, glass fiber (C). It contains 25 to 60 parts by weight and 1 to 15 parts by weight of the black colorant (D) or 15 to 40 parts by weight of the white colorant (E) as the colorant, and the ethylene-based polymer (B1) contains ethylene-α. , Β-Unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (B1-1), ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (B1-2), ethylene-α, β-unmodified Saturated carboxylic acid glycidyl ester-vinyl acetate copolymer (B1-3), ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (B1-4) and anhydrous A polyarylene sulfide-based composition, which is at least one modified ethylene-based polymer selected from the group consisting of maleic acid graft-modified ethylene-based polymers (B1-5). Further, claim 1 is characterized in that it contains at least one release agent (F) selected from the group consisting of a fatty acid amide lubricant (F-1) and carnauba wax (F-2). The polyarylene sulfide-based composition according to the above. The hydrogenated product of the block copolymer (B2) is a hydrogenated product of the block copolymer having a density of 0.91 g / cm ³ or less and a content of 5 to 20% by weight of the vinyl aromatic compound polymer block unit. The polyarylene sulfide-based composition according to claim 1 or 2, wherein the composition is. Black colorant (D) is, triiron tetroxide (D1) and / or a number average particle diameter of: 10 to 20 nm, that dibutyl phthalate oil absorption of carbon black (D2) is 60~125cm ³ / 100g The polyarylene sulfide-based composition according to any one of claims 1 to 3. The claim is that the white colorant (E) is at least one white colorant selected from the group consisting of titanium oxide (E1), zinc sulfide (E2), and zinc oxide (E3). The polyarylene sulfide-based composition according to any one of 1 to 4. Cylinder temperature 300 ° C., notched Charpy impact strength measurement test piece at a mold temperature of 135 ° C., compliant measured Charpy impact strength ISO179 exceeds 12 kJ / ^{m 2,} a cylinder temperature of 300 ° C., the mold A 70 mm × 3 mm × 1 mm thick dielectric constant measurement test piece prepared by cutting from a 70 mm × 70 mm × 1 mm thick molded plate injected and molded at a temperature of 135 ° C. was measured at a measurement frequency of 2 GHz in accordance with JIS C-2565. The polyarylene sulfide-based composition according to any one of claims 1 to 5, wherein the dielectric constant is 3.70 or less and the dielectric loss tangent is 0.01 or less at the same time.