Polybutylene terephthalate compositions and articles thereof

Abstract

The present invention relates to a polybutylene terephthalate composition and an article derived from the polybutylene terephthalate composition, comprising a polybutylene terephthalate (PBT) resin as component (A), a vinyl aromatic polymer containing units derived from a vinyl aromatic monomer as component (B), and a toughening agent as component (C).

Description

[Technical Field]

[0001] POLYBUTYLENE TEREPHTHALATE COMPOSITIONS AND ARTICLES BASED THEREON FIELD OF THE INVENTION The present invention relates to polybutylene terephthalate compositions and articles derived therefrom. [Background technology]

[0002] With the development of high-frequency communication technology, traditional materials are gradually becoming unable to meet the demands of the electronics industry, such as antenna housings, mobile devices, and integrated circuits. Meanwhile, thermoplastic resins are gradually demonstrating the advantages of design flexibility and superior performance. Polybutylene terephthalate (PBT) resins are a popular category due to their high performance in mechanical properties and processing advantages. However, it is extremely difficult to prepare PBT compositions, especially glass-reinforced compositions with desirable low dielectric properties.

[0003] Dielectric properties refer to the degree to which a material concentrates electric flux and energy loss, typically expressed as the dielectric constant (DK) and the dielectric loss tangent (DF). The high dielectric constant and dielectric loss tangent of PBT compositions are not necessarily desirable in the high-frequency communications industry. As DK and DF increase, the electric flux density and energy loss increase. Charge accumulation disrupts signal transmission, reducing the reliability of electrical circuits and limiting further increases in frequency. A low dielectric loss tangent is a desirable property for PBT compositions when applied to the high-frequency communications industry.

[0004] WO2018 / 196539 disclosed a low dielectric composition containing 45% to 70% by mass of PBT and / or PPS, 20% to 45% by mass of chopped glass fiber, 1% to 3% by mass of a toughening resin, and 0.2% to 0.5% by mass of unmodified glycidyl methacrylate. Kis 4.0-4.4 at 1 MHz. The present invention discloses that the dielectronic properties of PBT can be improved by combining unmodified glycidyl methacrylate with chopped glass fiber.

[0005] JP2013131576A disclosed a resin component used as a high-frequency signal transmission component, which includes a PBT resin, an olefin resin, and a fibrous inorganic filler. The polypropylene has a low D K and D F However, the mechanical properties of the composition are rapidly reduced by the addition of polypropylene.

[0006] Miniaturization and high density of electronic components is a trend in E&E fields, such as thin-walled goods, but while it rapidly drives efficiency, it also brings about the problem of component heating. F Materials with this property can effectively overcome the heating problem.

[0007] On the other hand, the excellent mechanical and processing properties of the polybutylene terephthalate composition, especially the bond strength with the metal unit, are also required.

[0008] Therefore, there remains a need to reduce the dissipation factor of polybutylene terephthalate compositions while maintaining their good mechanical properties. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] WO2018 / 196539 [Patent Document 2] JP2013131576A Summary of the Invention

[0010] Therefore, it is an object of the present invention to provide a polybutylene terephthalate composition that exhibits a much lower dielectric loss tangent and good mechanical properties, thereby causing fewer problems when applied to high frequency communication articles.

[0011] This object has been achieved by a polybutylene terephthalate composition according to the present invention, which comprises as component (A) at least one polybutylene terephthalate (PBT) resin, as component (B) at least one vinyl aromatic polymer containing units derived from a vinyl aromatic monomer, and as component (C) at least one toughening agent.

[0012] Therefore, another object of the present invention is to provide an article made from the PBT composition according to the present invention.

[0013] Another object of the present invention is to provide a method for producing the polybutylene terephthalate composition according to the present invention.

[0014] Another object of the present invention is to provide a method of using the vinyl aromatic polymer (B) in reducing the dielectric constant and dielectric loss of polybutylene terephthalate resin.

[0015] Another object of the present invention is to provide a method of using a polybutylene terephthalate composition as a material for a frame, housing or package of a mobile phone, sensor or laptop, or a part or component of a mobile phone or vehicle antenna.

[0016] As used herein, the terms "a," "an," and "the" are used interchangeably with the term "at least one." The phrases "at least one of" and "comprising at least one of," followed by a list, refer to any one item in the list, and any combination of two or more items in the list. All numerical ranges, unless otherwise specified, include endpoints and non-integer values ​​between the endpoints.

[0017] The terms "first," "second," and "third" are used in this disclosure for convenience only in describing one or more embodiments, and it will be understood that unless otherwise specified, these terms are used in a relative sense only. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention provides a polybutylene terephthalate composition comprising, as component (A), at least one polybutylene terephthalate (PBT) resin, as component (B), at least one vinyl aromatic polymer containing units derived from a vinyl aromatic monomer, and as component (C), at least one toughening agent.

[0019] Polybutylene terephthalate resin (A) The polybutylene terephthalate composition according to the present invention contains a polybutylene terephthalate resin (A). The polybutylene terephthalate resin includes a polybutylene terephthalate homopolyester or copolyester (polybutylene terephthalate, polybutylene terephthalate copolyester). The polybutylene terephthalate resin contains butylene terephthalate as the main component, which can be obtained by a common method, for example, by polycondensation of polymerization monomers including a first dicarboxylic acid component containing at least one terephthalic acid and / or its ester derivative and a first glycol component containing at least one 1,4-butanediol and / or its ester derivative.

[0020] Any known polybutylene terephthalate resin can be used in the present invention, and the present invention is not limited by the crystallization characteristics, the type or amount of end groups of the polybutylene terephthalate, the intrinsic viscosity, the molecular weight, the linear or branched structure, the type or amount of the polymerization catalyst, and the polymerization method.

[0021] The polybutylene terephthalate resin may contain units derived from other monomers other than terephthalic acid, its ester derivatives, and 1,4-butanediol or its ester derivatives, as long as the characteristics are not impaired. For example, the amount of the other monomers is preferably 40 mol % or less, particularly 20 mol % or less, based on the total monomers constituting the polybutylene terephthalate resin.

[0022] Examples of other monomers include aliphatic dicarboxylic acids having 20 or less carbon atoms, alicyclic dicarboxylic acids having 7 to 12 carbon atoms, and / or aromatic dicarboxylic acids having 8 to 16 carbon atoms, and preferably succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, azelaic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanoic acid, hexadecanedioic acid, dimer acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, himic acid, and the like. The other monomers are selected from the group consisting of 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, and 4,4'-diphenylketonedicarboxylic acid, and more preferably succinic acid, glutaric acid, adipic acid, pimelic acid, isophthalic acid, and / or phthalic acid. These other monomers can be used alone or in combination of two or more thereof.

[0023] Examples of other monomers include aliphatic glycols having 2 to 12 carbon atoms, alicyclic glycols having 6 to 12 carbon atoms, polyoxyalkylene glycols having multiple oxyalkylene units each having 2 to 4 carbon atoms, and / or aromatic glycols having 6 to 14 carbon atoms. Preferably, these monomers are selected from the group consisting of ethylene glycol, propylene glycol, 1,3-butylene glycol, trimethylene glycol, 1,6-hexanediol, neopentanediol, 1,3-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, ditetramethylene glycol, decanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bis-1,4-(hydroxymethyl)cyclohexane, diethylene glycol, polytetramethylene glycol, bisphenol, xylylene glycol, and naphthalenediol. Ethylene glycol and / or diethylene glycol are more preferred. These other monomers may be used alone or in combination.

[0024] Examples of polybutylene terephthalate resins include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene (terephthalate / naphthalate), and poly(butylene / ethylene) terephthalate.

[0025] The viscosity number of polybutylene terephthalate resin is 90 to 170 cm, measured in a 0.005 g / ml phenol / 1,2-dichlorobenzene solution (mass ratio 1:1) according to ISO 1628-5. 3 / g, preferably 100 to 135 cm 3 / g, more preferably 100 to 120 cm 3 / g range is appropriate.

[0026] The polybutylene terephthalate composition preferably contains 20% to 80% by weight of the polybutylene terephthalate resin, based on the total weight of the polybutylene terephthalate composition. For example, the polybutylene terephthalate resin disclosed herein may be in the range of 20% to 70% by weight, 20% to 60% by weight, 20% to 50% by weight, or 20% to 40% by weight, based on the total weight of the polybutylene terephthalate composition.

[0027] In one embodiment of the present invention, the polybutylene terephthalate resin is a linear polybutylene terephthalate resin.

[0028] Vinyl aromatic polymer (B) The polybutylene terephthalate composition according to the present invention contains at least one vinyl aromatic polymer (B-1) and / or (B-2).

[0029] Vinyl aromatic polymer (B-1) The vinyl aromatic polymer (B-1) contains units derived from at least one vinyl aromatic monomer (b1) in an amount of about 50 mol % to about 100 mol %, preferably 60 mol % to 99.5 mol %, and most preferably 70 mol % to 99.5 mol %, based on all monomers constituting the vinyl aromatic polymer (B-1).

[0030] In one preferred embodiment of the present invention, the vinyl aromatic polymer (B-1) may also contain units derived from at least one ethylenically unsaturated monomer (b2) and / or at least one conjugated diene monomer (b3).

[0031] Suitable vinyl aromatic monomers (b1) are those of formula I: [ka] [wherein R1 may be the same or different and is hydrogen, C1 to C 10 Alkyl groups, C1-C6 alkenyl groups, C4-C 10 Alicyclic group, C6~C 12is selected from the group consisting of an aromatic hydrocarbon group, a C1-C4 alkoxy group and a halogen atom, and is preferably hydrogen, C1-C 10 R2 is an alkyl group and / or a halogen atom, more preferably a hydrogen atom and / or a C1-C4 alkyl group, and most preferably a hydrogen atom, a methyl group, and / or an ethyl group; R2 is a hydrogen atom and / or a C1-C4 alkyl group, and preferably a hydrogen atom, a methyl group, and / or an ethyl group. The monomers corresponding to

[0032] Examples of vinyl aromatic monomers (b1) are styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, para-alpha-dimethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-isopropylstyrene, 3-isopropylstyrene, 4-isopropylstyrene, ortho-divinylbenzene, meta-divinylbenzene, para-divinylbenzene, ethoxystyrene, chlorostyrene, bromostyrene, dibromostyrene, dichlorostyrene, tribromostyrene, trichlorostyrene, 2-vinylnaphthalene and 2-isopropenylnaphthalene, preferably styrene, alpha-methylstyrene, 4-methylstyrene, chlorostyrene, para-divinylbenzene, bromostyrene, dibromostyrene, trichlorostyrene, 2-vinylnaphthalene and / or 2-isopropenylnaphthalene, more preferably styrene, alpha-methylstyrene and 4-methylstyrene.

[0033] The vinyl aromatic polymer (B-1) may also contain units derived from at least one ethylenically unsaturated monomer (b2) and / or one conjugated diene monomer (b3).

[0034] The ethylenically unsaturated monomer (b2) is preferably one having suitable compatibility with polybutylene terephthalate resin. The ethylenically unsaturated monomer (b2) in the vinyl aromatic polymer (B-1) is preferably an ethylenically unsaturated nitrile monomer, an ethylenically unsaturated acid monomer, or a derivative thereof. The derivative of the ethylenically unsaturated acid monomer is preferably an acid anhydride, ester, molten salt, amide, imide, and / or epoxy compound of the ethylenically unsaturated acid, more preferably an acid anhydride, ester, or epoxy compound of the ethylenically unsaturated acid.

[0035] In one preferred embodiment, the vinyl aromatic polymer (B-1) is composed of a vinyl aromatic monomer (b1), a first ethylenically unsaturated monomer (b2) selected from an ethylenically unsaturated acid monomer, an acid anhydride, and / or an epoxy compound of an ethylenically unsaturated acid, and optionally a second ethylenically unsaturated monomer (b2) selected from an ethylenically unsaturated nitrile monomer and / or an ester of an ethylenically unsaturated acid. The vinyl aromatic polymer (B-1) disclosed herein may be present in an amount ranging from 2 to 10% by weight, based on the total weight of the polybutylene terephthalate composition.

[0036] The ethylenically unsaturated nitrile monomer is preferably selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile and α-cyanoethylacrylonitrile, more preferably acrylonitrile and / or methacrylonitrile, and most preferably acrylonitrile.

[0037] The ethylenically unsaturated acid monomer has at least one carbon-carbon double bond and at least one acid group, such as a carboxyl or sulfonic acid group, and the ethylenically unsaturated carboxylic acid monomer is preferred. Examples of the ethylenically unsaturated carboxylic acid monomer are monoolefin and polyolefin unsaturated mono- and poly-carboxylic acids (di-, tri-carboxylic acids), preferably acrylic acid, methacrylic acid, 2-chloroacrylic acid, 2-ethylacrylic acid, angelic acid, crotonic acid, isocrotonic acid, cinnamic acid, p-chlorocinnamic acid, sorbic acid, alpha-chlorosorbic acid, alpha-cyanoacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, 3-(acryloyloxy)propanoic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3 ,6-tetrahydrophthalic acid, bicyclo(2.2.2)-oct-5-ene-2,3-dicarboxylic acid, 4-methylcyclohex-4-ene-1,2-dicarboxylic acid, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid, bicyclo(2.2.1)oct-7-ene-2,3,5,6-tetracarboxylic acid, maleopimaric acid, 7-oxabicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid and aconitic acid, more preferably acrylic acid, methacrylic acid, maleic acid, fumaric acid and / or citraconic acid.

[0038] An acid anhydride of an ethylenically unsaturated carboxylic acid that does not impair compatibility with polybutylene terephthalate resin is preferably used. Examples of acid anhydrides of ethylenically unsaturated carboxylic acids include maleic anhydride (MAH), acrylic anhydride, methacrylic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, itaconic anhydride, citraconic anhydride, fumaric anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, bicyclo(2.2.2)oct-5-ene-2,3-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic anhydride, norborn-5-ene-2,3-dicarboxylic anhydride, and nadic anhydride. anhydride), methylnadic anhydride, himic anhydride, methyl himic anhydride and / or x-methylbicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic anhydride (XMNA), more preferably maleic anhydride, (meth)acrylic anhydride and / or fumaric anhydride.

[0039] Esters of ethylenically unsaturated acids that do not impair compatibility with polybutylene terephthalate resins are preferably used, and preferably alkyl esters and / or hydroxyalkyl esters of ethylenically unsaturated acids, such as C1-C6 alkyl esters of ethylenically unsaturated carboxylic acids. 18 , more preferably C1 to C 12 , most preferably C1-C4 alkyl esters and / or C1-C 18 , more preferably C1 to C 12Examples of esters of ethylenically unsaturated acids include methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, octyl acrylate, octyl methacrylate, decyl acrylate, decyl methacrylate, isodecyl acrylate, isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, dimethyl maleate, monomethyl maleate, hydroxyethyl acrylate, methyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, octyl acrylate, octyl methacrylate, decyl acrylate, decyl methacrylate, isodecyl acrylate, isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, dimethyl maleate, monomethyl maleate, hydroxyethyl acrylate, methyl meth ... Preferred are methyl methacrylate (HEMA), stearyl methacrylate, stearyl acrylate, isobornyl acrylate, isobornyl methacrylate, hydroxypropyl methacrylate, and vinyl acetate, more preferably methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, and / or isobutyl methacrylate, and most preferably methyl methacrylate and / or methyl acrylate.

[0040] An epoxy compound of an ethylenically unsaturated acid that does not impair compatibility with the polybutylene terephthalate resin is preferably used. The epoxy compound of an ethylenically unsaturated acid may be a carboxylic acid glycidyl ester, a glycidyl ether, or the like. Examples of the epoxy compound of an ethylenically unsaturated acid include glycidyl acrylate, glycidyl methacrylate, 1-glycidyl maleate, diglycidyl maleate, monoglycidyl itaconic acid, diglycidyl itaconic acid, monoglycidyl citraconic acid, diglycidyl citraconic acid, monoglycidyl butene tricarboxylic acid, diglycidyl butene tricarboxylic acid, triglycidyl butene tricarboxylic acid, vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, phenyl glycidyl ether, and 4-vinylbenzyl glycidyl ether. Glycidyl acrylate and / or glycidyl methacrylate are more preferred.

[0041] Preferably, an amide of an ethylenically unsaturated acid is used that does not impair compatibility with polybutylene terephthalate resin. Examples of amides of ethylenically unsaturated acids include allylamine, aminoethyl methacrylate, aminopropyl methacrylate, dimethylaminoethyl methacrylate, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid N-monoethylamide, maleic acid N,N-diethylamide, fumaric acid monoamide and / or fumaric acid diamide.

[0042] The imide of an ethylenically unsaturated acid is preferably selected from the group consisting of maleimide, N-butylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide.

[0043] The molten salt of an ethylenically unsaturated acid is preferably selected from the group consisting of sodium acrylate, calcium acrylate, sodium methacrylate and calcium methacrylate.

[0044] The conjugated diene monomer (b3) is preferably selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene and 3-butyl-1,3-octadiene, more preferably 1,3-butadiene, 1,3-pentadiene and / or isoprene, and most preferably 1,3-butadiene and / or isoprene.

[0045] In the present invention, the polymerization method of the vinyl aromatic polymer (B-1) is not limited, and the suitable vinyl aromatic polymer (B-1) may be a linear copolymer, such as a block copolymer, an alternating copolymer, a periodic copolymer, a random copolymer, or a branched copolymer, such as a graft copolymer or a star copolymer.

[0046] In one preferred embodiment of the present invention, the vinyl aromatic polymer (B-1) is composed of a vinyl aromatic monomer (b1) and at least one selected from the group consisting of an ethylenically unsaturated monomer (b2) and a conjugated diene monomer (b3). The vinyl aromatic polymer (b1) is preferably selected from the group consisting of styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, and 4-methylstyrene. The ethylenically unsaturated monomer (b2) is preferably selected from the group consisting of acrylonitrile, methacrylonitrile, (meth)acrylic acid, maleic acid, fumaric acid, citraconic acid, 2-chloroacrylic acid, 2-ethylacrylic acid, angelic acid, crotonic acid, isocrotonic acid, cinnamic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, fumaric anhydride, methyl (meth)acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, and glycidyl (meth)acrylate, more preferably meth)acrylic acid, maleic acid, fumaric acid, maleic anhydride, fumaric anhydride, methyl (meth)acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, and glycidyl (meth)acrylate. The conjugated diene monomer (b3) is preferably selected from the group consisting of 1,3-butadiene, 1,3-pentadiene and isoprene.

[0047] In one preferred embodiment of the present invention, the vinyl aromatic polymer (B-1) is composed of a vinyl aromatic monomer (b1) selected from the group consisting of styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, and 4-methylstyrene, a component (i) selected from the group consisting of (meth)acrylic acid, maleic acid, maleic anhydride, methyl (meth)acrylate, and glycidyl (meth)acrylate, and optionally a component (ii) selected from the group consisting of 1,3-butadiene, 1,3-pentadiene, acrylonitrile, and methacrylonitrile. The vinyl aromatic polymer (B-1) disclosed herein can be in the range of 2 to 10% by weight based on the total weight of the polybutylene terephthalate composition.

[0048] In one preferred embodiment of the present invention, the vinyl aromatic polymer (B-1) may be a block, alternating, random or graft copolymer of styrene-maleic anhydride, styrene-acrylonitrile-maleic anhydride, styrene-(meth)acrylate, styrene-methyl(meth)acrylate, styrene-glycidyl(meth)acrylate, styrene-acrylonitrile-glycidyl(meth)acrylate, styrene-acrylic acid, styrene-acrylic acid-α-methylstyrene, styrene-butadiene, styrene-acrylonitrile and styrene-butadiene-acrylonitrile.

[0049] The polybutylene terephthalate composition preferably contains 40% by mass or less of the vinyl aromatic polymer (B-1) relative to the total mass of the polybutylene terephthalate composition. For example, the vinyl aromatic polymer (B-1) disclosed herein may be in the range of 0.1 to 30% by mass, 0.3 to 20% by mass, or 2 to 10% by mass relative to the total mass of the polybutylene terephthalate composition.

[0050] The weight average molecular weight (Mw) of the vinyl aromatic polymer (B-1) is generally in the range of 1,000 to 15,000 g / mol, preferably 2,000 to 10,000 g / mol, as measured by GPC using tetrahydrofuran as an eluent.

[0051] Vinyl aromatic polymer (B-2) The vinyl aromatic polymer (B-2) is a core-shell polymer comprising a core and a shell, wherein the core is derived from a first monomer system comprising at least one vinyl aromatic monomer (b1) and, optionally, at least one monomer selected from the group consisting of an ethylenically unsaturated monomer (b2) and a conjugated diene monomer (b3); the shell is derived from a second monomer system comprising at least one monomer selected from the group consisting of the vinyl aromatic monomer (b1) and the ethylenically unsaturated monomer (b2); and the mass ratio of the core to the shell in the core-shell polymer is 90:10 to 10:90.

[0052] The ethylenically unsaturated monomer (b2) in the vinyl aromatic polymer (B-2) is preferably an ethylenically unsaturated nitrile monomer, an ethylenically unsaturated acid monomer, or a derivative thereof. The ethylenically unsaturated acid derivative is preferably an ethylenically unsaturated acid anhydride, ester, molten salt, amide, imide, and / or epoxy compound, more preferably an ethylenically unsaturated acid anhydride and / or ester.

[0053] In one preferred embodiment of the present invention, the ethylenically unsaturated monomer (b2) in the vinyl aromatic polymer (B-2) is an ethylenically unsaturated nitrile monomer, an ethylenically unsaturated acid monomer, an acid anhydride of an ethylenically unsaturated acid monomer, and / or an ester of an ethylenically unsaturated acid monomer.

[0054] The core of the core-shell polymer is a polymer or copolymer derived from a first monomer system, which is desirably emulsion polymerized to produce the core.

[0055] Suitable vinyl aromatic monomers (b1) in the core or shell may be the same or different and may be represented by formula I: [ka] [wherein R1 may be the same or different and is hydrogen, C1 to C 10 Alkyl groups, C1-C6 alkenyl groups, C4-C 10 Alicyclic, C6~C 12 is selected from the group consisting of an aromatic hydrocarbon group, a C1-C4 alkoxy group and a halogen atom, and is preferably hydrogen, C1-C 10 R2 is an alkyl group and / or a halogen atom, more preferably a hydrogen atom and / or a C1-C4 alkyl group, and most preferably a hydrogen atom, a methyl group, and / or an ethyl group; R2 is a hydrogen atom and / or a C1-C4 alkyl group, and preferably a hydrogen atom, a methyl group, and / or an ethyl group. The monomers corresponding to

[0056] Examples of vinyl aromatic monomers are styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, para-alpha-dimethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-isopropylstyrene, 3-isopropylstyrene, 4-isopropylstyrene, ortho-divinylbenzene, meta-divinylbenzene, para-divinylbenzene, ethoxystyrene, chlorostyrene, bromostyrene, dibromostyrene, dichlorostyrene, tribromostyrene, trichlorostyrene, 2-vinylnaphthalene and 2-isopropenylnaphthalene, preferably styrene, alpha-methylstyrene, 4-methylstyrene, chlorostyrene, para-divinylbenzene, bromostyrene, dibromostyrene, trichlorostyrene, 2-vinylnaphthalene and / or 2-isopropenylnaphthalene, more preferably styrene, alpha-methylstyrene and / or 4-methylstyrene.

[0057] The conjugated diene monomer (b3) is preferably selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene and 3-butyl-1,3-octadiene, more preferably 1,3-butadiene, 1,3-pentadiene and / or isoprene, and most preferably 1,3-butadiene and / or isoprene.

[0058] The ethylenically unsaturated nitrile monomer of the core or shell is preferably selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile and / or α-cyanoethylacrylonitrile, more preferably acrylonitrile and / or methacrylonitrile, and most preferably acrylonitrile.

[0059] The ethylenically unsaturated acid monomer of the core or shell has at least one carbon-carbon double bond and one acid group, such as a carboxyl or sulfonic acid group, and is preferably an ethylenically unsaturated carboxylic acid monomer, such as monoolefin- and polyolefin-unsaturated mono- and poly-carboxylic acids (di- and tri-carboxylic acids). Examples of the ethylenically unsaturated carboxylic acid monomer are C3 to C6 ethylenically unsaturated carboxylic acids, preferably selected from the group consisting of acrylic acid, methacrylic acid, 2-ethylacrylic acid, angelic acid, crotonic acid, isocrotonic acid, sorbic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, and aconitic acid, and more preferably acrylic acid, methacrylic acid, and / or itaconic acid.

[0060] Examples of ethylenically unsaturated acid anhydride monomers for the core or shell are maleic anhydride (MAH), acrylic anhydride, methacrylic anhydride, itaconic anhydride, citraconic anhydride, butenedioic anhydride and / or fumaric anhydride, more preferably acrylic anhydride, methacrylic anhydride, itaconic anhydride and / or butenedioic anhydride.

[0061] The ester monomer of an ethylenically unsaturated acid in the core or shell is preferably an alkyl ester and / or a hydroxyalkyl ester of an ethylenically unsaturated acid, for example, a C1 to C18, more preferably a C1 to C12, most preferably a C1 to C4 alkyl ester and / or a C1 to C18, more preferably a C1 to C12, most preferably a C1 to C4 hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid. Examples of esters of ethylenically unsaturated acids are methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, octyl acrylate, octyl methacrylate, decyl acrylate, decyl methacrylate, isodecyl acrylate, isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, dimethyl maleate, monomethyl maleate, hydroxyethyl methacrylate (HEMA), stearyl methacrylate, stearyl acrylate, isobornyl acrylate, isobornyl methacrylate, hydroxypropyl methacrylate and / or biphenyls. Preferred are methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl methacrylate, stearyl methacrylate, stearyl acrylate and / or vinyl acetate, and most preferred are methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, propyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, stearyl methacrylate, stearyl acrylate and / or decyl acrylate.

[0062] Examples of the epoxy compounds, amides, imides and molten salts of ethylenically unsaturated acids in the core or shell of the vinyl aromatic polymer (B-2) may be the same as those in the vinyl aromatic polymer (B-1).

[0063] In one preferred embodiment of the present invention, the core of the core-shell polymer comprises units derived from at least one vinyl aromatic monomer (b1) and at least one conjugated diene monomer (b3). The vinyl aromatic monomer (b1) is preferably styrene, alpha-methylstyrene, and / or 4-methylstyrene; the conjugated diene monomer (b3) is preferably 1,3-butadiene, 1,3-pentadiene, and / or isoprene. The core of the core-shell polymer is preferably a diblock polymer of 1,3-diene and styrene (e.g., butadiene-styrene copolymer, isoprene-styrene copolymer).

[0064] In one preferred embodiment of the present invention, the core of the core-shell polymer comprises units derived from at least one vinyl aromatic monomer (b1), at least one conjugated diene monomer (b3), and at least one monomer selected from the group consisting of ethylenically unsaturated nitriles and C1-C4 alkyl esters of ethylenically unsaturated acids. The ethylenically unsaturated nitrile is preferably acrylonitrile and / or methacrylonitrile; and the C1-C4 alkyl ester of ethylenically unsaturated acids is preferably methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and / or isobutyl (meth)acrylate. The core of the core-shell polymer is preferably a butadiene-styrene-(meth)acrylate terpolymer or a butadiene-styrene-acrylonitrile terpolymer.

[0065] In one preferred embodiment of the present invention, the core of the core-shell polymer comprises units derived from at least one vinyl aromatic monomer (b1) and at least one monomer selected from the group consisting of ethylenically unsaturated acids, C1-C4 alkyl esters of ethylenically unsaturated acids, and ethylenically unsaturated nitriles. The C1-C4 alkyl esters of ethylenically unsaturated acids are preferably methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and / or isobutyl (meth)acrylate; the ethylenically unsaturated acids are preferably acrylic acid, methacrylic acid, and / or itaconic acid; and the ethylenically unsaturated nitriles are preferably acrylonitrile and / or methacrylonitrile.

[0066] In one preferred embodiment of the present invention, the core comprises 5% to 80% by mass, preferably 15% to 35% by mass, of units derived from at least one vinyl aromatic monomer (b1), relative to the total units of the core.

[0067] In one preferred embodiment of the present invention, the core comprises 5% by mass to 80% by mass, preferably 15% by mass to 35% by mass, of units derived from at least one vinyl aromatic monomer (b1) and 20% by mass to 95% by mass, preferably 65% ​​by mass to 85% by mass, of units derived from at least one conjugated diene monomer (b3), preferably a 1,3-diene, based on the total units of the core.

[0068] In one preferred embodiment of the present invention, the shell of the core-shell polymer comprises units derived from at least one ester of an ethylenically unsaturated acid and / or at least one vinyl aromatic monomer (b1). The ester of an ethylenically unsaturated acid is preferably a C1-C4 alkyl ester and / or a C1-C4 hydroxyalkyl ester of (meth)acrylic acid or acetic acid, more preferably methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, and / or isobutyl methacrylate, more preferably methyl methacrylate, methyl acrylate, propyl methacrylate, and / or butyl methacrylate. The vinyl aromatic monomer (b1) is preferably styrene, alpha-methylstyrene, 4-methylstyrene, chlorostyrene, bromostyrene, dibromostyrene, dichlorostyrene, and / or tribromostyrene, more preferably styrene, alpha-methylstyrene, and / or 4-methylstyrene.

[0069] In one preferred embodiment of the present invention, the shell of the core-shell polymer comprises at least one selected from the group consisting of C1-C4 alkyl esters of ethylenically unsaturated acids and vinyl aromatic monomers (b1), and an ethylenically unsaturated nitrile monomer, an ethylenically unsaturated acid monomer, an acid anhydride and / or a C1-C4 alkyl ester of an ethylenically unsaturated acid. 10 ~C 20The vinyl aromatic monomer (b1) preferably includes units derived from one monomer (iii) selected from the group consisting of alkyl esters. The C1-C4 alkyl ester of an ethylenically unsaturated acid is preferably methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, and / or isobutyl methacrylate, more preferably methyl methacrylate, methyl acrylate, propyl methacrylate, and / or butyl methacrylate. The vinyl aromatic monomer (b1) is preferably styrene, alpha-methylstyrene, 4-methylstyrene, chlorostyrene, bromostyrene, dibromostyrene, dichlorostyrene, and / or tribromostyrene, more preferably styrene, alpha-methylstyrene, and / or 4-methylstyrene. Examples of monomer (iii) include acrylonitrile, methacrylonitrile, 2-ethylhexyl acrylate, decyl acrylate, lauryl methacrylate, stearyl methacrylate, and / or stearyl acrylate.

[0070] In one preferred embodiment of the present invention, the core comprises units derived from at least one vinyl aromatic monomer (b1) and at least one conjugated diene monomer (b3), and the shell comprises units derived from a C1-C4 alkyl ester and / or a C1-C4 hydroxyalkyl ester of (meth)acrylic acid or acetic acid. The vinyl aromatic monomer is preferably styrene, alpha-methylstyrene, and / or 4-methylstyrene. The conjugated diene monomer is preferably 1,3-butadiene, 1,3-pentadiene, and / or isoprene. The C1-C4 alkyl ester and / or a C1-C4 hydroxyalkyl ester of (meth)acrylic acid or acetic acid is preferably methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, and / or isobutyl methacrylate, more preferably methyl methacrylate, methyl acrylate, propyl methacrylate, and / or butyl methacrylate.

[0071] The mass ratio of core to shell in the core-shell polymer is 90:10 to 10:90, preferably 90:10 to 50:50, more preferably 90:10 to 70:30, and most preferably 90:10 to 80:20.

[0072] The core-shell polymer may also comprise one internal graft stage comprising units derived from a graft-linking monomer comprising at least one vinyl aromatic monomer, and / or at least one C1-C4 alkyl ester of a (meth)acrylic acid monomer; and optionally one intermediate sealer stage comprising at least one of the following monomers: a C1-C8 alkyl acrylate or a polyunsaturated crosslinker, the intermediate sealer stage being between the internal graft stage and the shell.

[0073] The vinyl aromatic monomers in the internal grafting stage are preferably styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, para-alpha-dimethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-isopropylstyrene, 3-isopropylstyrene, 4-isopropylstyrene, ortho-divinylbenzene, meta-divinylbenzene, para-divinylbenzene, ethoxystyrene, chlorostyrene, bromostyrene, dibromostyrene, dichlorostyrene, tribromostyrene, trichlorostyrene, 2-vinylnaphthalene and / or 2-isopropenylnaphthalene, preferably styrene, alpha-methylstyrene and / or 4-methylstyrene.

[0074] The C1-C4 alkyl ester of the (meth)acrylic acid monomer is preferably methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, acrylate, isobutyl acrylate and / or isobutyl methacrylate, more preferably methyl methacrylate, methyl acrylate, ethyl methacrylate, butyl methacrylate and / or propyl methacrylate.

[0075] The internal grafting step is carried out using the following monomers: acrylonitrile, methacrylonitrile, 2-ethylhexyl acrylate, decyl acrylate, vinyl naphthalene, isopropenyl naphthalene, as well as higher carbon (C 12 ~C 20 ) alkyl methacrylates and acrylates, for example, units derived from any one or more of lauryl methacrylate, lauryl acrylate, stearyl methacrylate, stearyl acrylate, and isobornyl methacrylate.

[0076] Suitable C1-C8 alkyl acrylates include methyl methacrylate, methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate and octyl acrylate, more preferably butyl acrylate.

[0077] Suitable polyunsaturated crosslinkers include butylene glycol dimethacrylate, alkane polyol polyacrylates or polymethacrylates such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, oligoethylene glycol diacrylate, oligoethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate or trimethylolpropane trimethacrylate, and unsaturated carboxylic acid allyl esters such as allyl acrylate, allyl methacrylate and diallyl maleate, preferably divinylbenzene.

[0078] In one preferred embodiment, the core-shell polymer comprises 70 to 85 parts by weight of the core; 8 to 14 parts by weight of the internal graft stage; 0.1 to 5 parts by weight of the intermediate sealer stage; and 10 to 16 parts by weight of the shell. The core preferably comprises, relative to the total units of the core, 15% to 35% by weight of units derived from at least one vinyl aromatic monomer (b1) and 65% to 85% by weight of units derived from at least one conjugated diene monomer (b3).

[0079] The core of the core-shell polymer preferably has a weight average molecular weight, as determined by gel permeation chromatography, of greater than about 8,000, more preferably greater than 50,000.

[0080] The shell of the core-shell polymer preferably has a weight average molecular weight of about 5,000 to about 100,000, more preferably about 10,000 to about 80,000, as determined by gel permeation chromatography.

[0081] The core-shell polymer may be any one or more of the core-shell polymers described in EP1514883A1, EP0985692A1 and EP0348565A1, the contents of each of which are incorporated herein by reference.

[0082] The core-shell polymers of the present invention may be prepared via conventional polymerization methods such as those described in EP 0348565 A1 or EP 1514883 A1.

[0083] emulsion polymerizing a first monomer system to form a core, and then emulsion polymerizing a second monomer system in the presence of the core to form a shell; or a method for making a core-shell polymer comprising emulsion polymerizing a second monomer system to form a shell, and then emulsion polymerizing a first monomer system in the presence of the shell to form a core.

[0084] In one preferred embodiment, the method for producing the core-shell polymer can be any one of the following I to III: I. Emulsion polymerization of the core in the presence of a graft-linking monomer; emulsion polymerization of the shell and grafting the shell onto the core.

[0085] II. The core is emulsion polymerized; the graft-linking monomer is added and immersed into the core, and the graft-linking monomer is polymerized; the shell is emulsion polymerized in the presence of the core and chemically grafted to the core.

[0086] III. Emulsion polymerization of the shell in the presence of a graft-linking monomer; emulsion polymerization of the core and grafting the core onto the shell.

[0087] In one preferred embodiment, the method for producing the core-shell polymer comprises: i. polymerizing in emulsion, in the presence of an emulsifier and a free radical initiator, a first monomer system comprising 65% to 85% by weight of a diolefin monomer and 15% to 35% by weight of a vinyl aromatic monomer until a conversion of 60% to 90% of the monomers to polymer is achieved; ii. continuing the polymerization of the first monomer system while adding a graft-linking monomer comprising at least one vinyl aromatic monomer, and / or at least one C1-C4 alkyl ester of a (meth)acrylic acid monomer; iii. continuing the polymerization of the graft linking monomer until at least 90% conversion to polymer is achieved; iv. adding a second monomer system comprising at least one C1-C4 alkyl ester of an ethylenically unsaturated acid and / or at least one vinyl aromatic monomer, adding a free radical initiator, and continuing polymerization until at least 95% conversion of monomer to polymer is achieved, wherein the reaction temperature during steps (i) to (iv) is in the range of 20°C to 100°C, preferably 60°C to 70°C; Includes:

[0088] After step (iii), preferably at least one C1-C8 alkyl acrylate or at least one polyunsaturated crosslinking agent and a free radical initiator are added.

[0089] Free radical initiators that can be used in the various steps of the process are those conventionally utilized in free radical polymerizations conducted at temperatures ranging from about room temperature to about 100°C, preferably from 55°C to 80°C. Suitable initiators include thermally activated initiators such as persulfates, peroxides, or peroxyesters. Suitable initiators also include "redox" initiators such as oxidizing agents, e.g., hydroperoxides, persulfates, or peroxides, in combination with reducing agents, e.g., sodium formaldehyde sulfoxylate, sodium sulfite, sodium hydrosulfite, or isoascorbic acid. Oil-soluble initiators with a water solubility less than styrene (3.5 mM at 25°C-50°C) are preferred, examples of which include diisopropylbenzene hydroperoxide, t-butyl perbenxoate, tert-butylperoxyisopropylcarbonate, t-butylperoxyisobutyrate, t-butylperoctoate, diisopropylperoxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, etc. The redox reaction can also be promoted by reagents such as iron salts, e.g., ferrous-ethylenediaminetetraacetic acid ("Fe-EDTA").

[0090] The polybutylene terephthalate composition contains preferably 1 to 20 mass %, more preferably 2 to 15 mass %, and most preferably 2 to 10 mass % of the vinyl aromatic polymer (B-2) relative to the total mass of the polybutylene terephthalate composition.

[0091] The polybutylene terephthalate composition containing the vinyl aromatic polymer (B-2) exhibits better bond strength and dielectric loss, and has more applications.

[0092] Reinforcer (C) The reinforcing agent according to the present invention may be any reinforcing agent selected within a range that does not impair the effects of the present invention.

[0093] Examples of reinforcing agents can be glass fibers, carbon fibers, metal fibers, aramid fibers, one or more whiskers, talc, mica, clay, and mixtures thereof.

[0094] The present invention is not limited to the diameter, shape (cylindrical or cocoon-shaped), length, or glass cutting method, e.g., chopped strands or rovings of glass fiber. Furthermore, the present invention is not limited to the type of glass, e.g., E-glass fiber, D-glass fiber, S-glass fiber, C-glass fiber, or T-glass fiber. E-glass fiber or corrosion-resistant glass containing zirconium is preferred from the viewpoint of quality. There is no limitation on the type of glass fiber; conventional E-glass fiber can meet the requirement of low dielectric loss. D-glass fiber, with a relative dielectric constant of 5.0 or less, is also preferred.

[0095] The reinforcing agent is used in an amount of 5 to 40% by mass, preferably 5 to 35% by mass, and more preferably 15 to 30% by mass, relative to the total mass of the polybutylene terephthalate composition.

[0096] Low melting point polyester (D) The polybutylene terephthalate composition of the present invention contains, as component (D), a polybutylene terephthalate having a melting point (T m ) may further contain a polyester copolymer having a temperature of 105°C to 185°C, preferably 110°C to 160°C.

[0097] In the present invention, the melting point (T mPolyester copolymers with a t / a of 105°C to 185°C (hereinafter simply referred to as "polyester copolymers") are also called "low-melting-point polyesters" and have a lower melting point than unmodified polyesters. The melting point is measured by differential scanning calorimetry (DSC) in accordance with ISO 11357 at a heating rate of 10°C / min. The polyester copolymers can be obtained by partially substituting a second dicarboxylic acid component and / or a second glycol component of polyethylene terephthalate and / or polybutylene terephthalate with a copolymerizable monomer. The second dicarboxylic acid component contains at least terephthalic acid and / or an ester derivative thereof, and the second glycol component contains at least one of 1,4-butanediol, ethylene glycol, and / or an ester derivative of 1,4-butanediol and ethylene glycol, preferably ethylene glycol and / or an ester derivative thereof.

[0098] The copolymerizable monomers include one or more monomers selected from a third dicarboxylic acid other than terephthalic acid, and / or a third glycol other than ethylene glycol and 1,4-butanediol.

[0099] The ratio of the dicarboxylic acid (the second dicarboxylic acid and the third carboxylic acid) to the glycol (the second glycol and the third glycol) is 0.9:1.1 to 1.1:0.9.

[0100] The third dicarboxylic acid can be at least one selected from the group consisting of aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and / or aromatic dicarboxylic acids excluding terephthalic acid and reactive derivatives thereof.

[0101] The aliphatic dicarboxylic acids disclosed herein are preferably dicarboxylic acids containing 4 to 40 carbon atoms, more preferably 4 to 24 carbon atoms, 4 to 14 carbon atoms, or 4 to 10 carbon atoms. For example, the aliphatic dicarboxylic acids disclosed herein may be succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, and / or hexadecanedicarboxylic acid, and are preferably succinic acid, glutaric acid, azelaic acid, adipic acid, pimelic acid, and / or sebacic acid.

[0102] The alicyclic dicarboxylic acid preferably contains 7 to 12 carbon atoms. For example, the alicyclic dicarboxylic acid disclosed herein can be hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, and / or himic acid.

[0103] Suitable aromatic dicarboxylic acids other than terephthalic acid preferably contain 8 to 16 carbon atoms, and are more preferably at least one selected from the group consisting of isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylketonedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenoxyetherdicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, C1 to C4 alkyl esters of phthalic acid or isophthalic acid (e.g., dimethylphthalate or dimethylisophthalate (DMI)), and derivatives capable of forming esters, such as acid chlorides or acid anhydrides, and are preferably isophthalic acid and / or phthalic acid.

[0104] The third glycol may be at least one selected from the group consisting of aliphatic alkanediols excluding ethylene glycol or 1,4-butanediol, polyoxyalkylene glycols, alicyclic glycols, and aromatic diols.

[0105] The aliphatic alkanediol disclosed herein is preferably an aliphatic alkanediol containing 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 6 carbon atoms, such as trimethylene glycol, propylene glycol, neopentyl glycol, hexanediol, octanediol, and / or decanediol.

[0106] The polyoxyalkylene glycol disclosed in the present specification is preferably a glycol having a plurality of oxyalkylene units each having 2 to 4 carbon atoms, and more preferably at least one selected from the group consisting of diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, and polytetramethylene glycol.

[0107] The alicyclic glycols disclosed herein preferably contain 6 to 12 carbon atoms, and more preferably are 1,4-cyclohexanediol and / or 1,4-cyclohexanedimethanol.

[0108] The aromatic glycol disclosed herein is preferably an aromatic diol containing 6 to 14 carbon atoms, and more preferably at least one selected from the group consisting of xylylene glycol, hydroquinone, resorcinol, naphthalenediol, biphenyl, bisphenol, and xylylene glycol.

[0109] In a preferred embodiment of the present invention, the third glycol is an aliphatic alkanediol having 2 to 6 carbon atoms, such as trimethylene glycol, propylene glycol, and / or hexanediol, and / or a polyoxyalkylene glycol having about 2 to 4 repeating oxyalkylene units, such as diethylene glycol.

[0110] In a preferred embodiment of the present invention, the third dicarboxylic acid is an aliphatic dicarboxylic acid having 6 to 12 carbon atoms, such as adipic acid, pimelic acid, suberic acid, azelaic acid or sebacic acid, and / or an aromatic dicarboxylic acid, such as isophthalic acid and / or phthalic acid.

[0111] In a preferred embodiment of the present invention, the third glycol may be a polyoxyalkylene glycol having about 2 to 4 repeating oxyalkylene units, such as diethylene glycol, and the third dicarboxylic acid may be an aromatic dicarboxylic acid, such as isophthalic acid and / or phthalic acid.

[0112] In one preferred embodiment, the polyester copolymer may contain 5 mol % to 30 mol %, preferably 5 mol % to 20 mol %, of copolymerizable monomers relative to the total moles of the monomers constituting the polyester copolymer.

[0113] In one preferred embodiment, the polyester copolymer comprises, relative to the total moles of monomers constituting the polyester copolymer, 1 mol % to 10 mol % of a third glycol, such as a polyoxyalkylene glycol, and 4 mol % to 29 mol % of a third dicarboxylic acid, such as an aromatic dicarboxylic acid, in particular isophthalic acid and / or phthalic acid.

[0114] In one preferred embodiment, the polyester copolymer is composed of terephthalic acid, ethylene glycol, a polyoxyalkylene glycol having 2 to 4 oxyalkylene units and having 2 to 4 carbon atoms, such as diethylene glycol, as the third glycol, and an aromatic dicarboxylic acid having 8 to 16 carbon atoms, such as isophthalic acid and / or phthalic acid, as the third carboxylic acid. Preferably, the amount of the third glycol is 1 mol % to 10 mol % relative to the total moles of the monomers constituting the polyester copolymer, the amount of the third dicarboxylic acid is 1 mol % to 10 mol %, and the ratio of the dicarboxylic acid (terephthalic acid and the third carboxylic acid) to the glycol (ethylene glycol and the third glycol) is 0.9:1.1 to 1.1:0.9.

[0115] In one preferred embodiment, the polyester copolymer may contain 5 mol % to 30 mol %, preferably 5 mol % to 20 mol %, of copolymerizable monomers relative to the total moles of the monomers constituting the polyester copolymer.

[0116] In one preferred embodiment, the polyester copolymer comprises 1 mol % to 10 mol % of a third glycol, such as a polyoxyalkylene glycol, and 4 mol % to 29 mol % of a third dicarboxylic acid, such as an aromatic dicarboxylic acid, in particular isophthalic acid and / or phthalic acid.

[0117] The polybutylene terephthalate composition preferably comprises 0% to 40% by weight of the polyester copolymer, based on the total weight of the polybutylene terephthalate composition. For example, the polyester copolymer disclosed herein may range from 10% to 35%, 10% to 30%, 15% to 35%, or 15% to 30% by weight, based on the total weight of the polybutylene terephthalate composition.

[0118] The low melting point polyester preferably has a weight average molecular weight of 8,000 to 80,000 g / mol, preferably 10,000 to 30,000 g / mol, as determined by gel permeation chromatography.

[0119] Glass Bubble (E) The polybutylene terephthalate composition of the present invention may further comprise glass bubbles as component (E).

[0120] The glass bubbles referred to in this invention, also known as "hollow glass bubbles," "hollow glass microspheres," "hollow glass beads," "glass microbubbles," or "glass balloons," have an average diameter of less than about 500 micrometers and include a hollow core and a glass shell surrounding the hollow core, which can be filled with a gas such as air.

[0121] The average diameter is preferably the volume-based median diameter D 50 The volume-based median diameter of hollow glass bubbles, D 50 is preferably in the range of 5 to 50 microns.

[0122] The average true density of the glass bubbles in the present invention is preferably 0.3 to 0.7 g / cc, more preferably 0.3 to 0.6 g / cc. For example, the average true densities of the glass bubbles disclosed herein are 0.32 g / cc to 0.6 g / cc, 0.35 g / cc to 0.6 g / cc, 0.38 g / cc to 0.6 g / cc, 0.43 g / cc to 0.6 g / cc, 0.45 g / cc to 0.6 g / cc, 0.46 g / cc to 0.6 g / cc, 0.49 g / cc to 0.6 g / cc, 0.30 g / cc to 0.55 g / cc, 0.32 g / cc to 0.55 g / cc, 0.35 g / cc to 0.55 g / cc, 0.38 g / cc to 0.55 g / cc, 0.43 g / cc The average true density of the glass bubbles can be in the ranges of 0.55 g / cc, 0.45 g / cc to 0.55 g / cc, 0.46 g / cc to 0.55 g / cc, 0.49 g / cc to 0.55 g / cc, 0.30 g / cc to 0.5 g / cc, 0.32 g / cc to 0.5 g / cc, 0.35 g / cc to 0.5 g / cc, 0.38 g / cc to 0.5 g / cc, 0.40 g / cc to 0.5 g / cc, 0.43 g / cc to 0.5 g / cc, 0.45 g / cc to 0.5 g / cc, 0.46 g / cc to 0.5 g / cc, and 0.43 g / cc to 0.49 g / cc. The average true density of the glass bubbles is the quotient obtained by dividing the mass of a sample of glass bubbles by the true volume of the mass of the glass bubbles measured by a gas pycnometer. "True volume" is the total collective volume of the glass bubbles, not the bulk volume. Average true density can be measured using a pycnometer according to ASTM D2840-69 "Average True Particle Density of Hollow Microspheres." "g / cc" means grams per cubic centimeter.

[0123] The crush strength of the glass bubbles is preferably 5,000 PSI to 30,000 PSI, and more preferably 6,000 PSI to 28,000 PSI. For example, the crush strengths disclosed herein can range from 8,000 PSI to 20,000 PSI, 10,000 PSI to 18,000 PSI, or 16,000 PSI to 18,000 PSI. The crush strength of the glass bubbles is typically measured using ASTM D3102-72, "Hydrostatic Collapse Strength of Hollow Glass Microspheres."

[0124] The glass bubbles according to the present invention have a particle size distribution with a volume-based median diameter ranging from about 8 micrometers to about 60 micrometers. The volume-based median diameter of the glass bubbles can be in the range of, for example, 10 to 55 micrometers, 15 to 55 micrometers, 15 to 50 micrometers, 15 to 45 micrometers, 15 to 40 micrometers, 15 to 35 micrometers, 15 to 30 micrometers, 15 to 25 micrometers, 15 to 20 micrometers, 20 to 55 micrometers, 20 to 50 micrometers, 20 to 45 micrometers, 20 to 40 micrometers, 20 to 35 micrometers, 20 to 30 micrometers, or 20 to 25 micrometers. In some embodiments, the glass bubbles disclosed herein have a size distribution ranging from 5 to 30 micrometers, 10 to 35 micrometers, 10 to 50 micrometers, 15 to 60 micrometers, 20 to 38 micrometers, 20 to 45 micrometers, or 20 to 70 micrometers. The volume-based median diameter is also referred to as the Dv50 diameter, where 50 volume percent of the glass bubbles in the distribution are smaller than the stated size. As used herein, the term size is considered to be equivalent to the diameter and / or height of the glass bubbles. The size distribution of the glass bubbles may be Gaussian, normal, or non-normal. The non-normal distribution may be unimodal or multimodal.

[0125] Glass bubbles useful herein for the invention can be obtained commercially and sold by Potters Industries, Valley Forge, PA 19482 under the trade name "Sphericel Hollow Glass Spheres" (e.g., grades 110P8 and 60P18) or by 3M Company under the trade name "3M Glass bubbles", e.g., grades S60, S60HS, S38HS, S38XHS, iM16K, iM30K, K42HS, and K46.

[0126] The polybutylene terephthalate composition preferably contains 0% to 20% by weight of glass bubbles, based on the total weight of the polybutylene terephthalate composition. For example, the glass bubbles disclosed herein may range from 5% to 15% by weight, or from 5% to 10% by weight, based on the total weight of the polybutylene terephthalate composition.

[0127] Examples of the silane coupling agent include epoxy-functional silanes, urethane-functional silanes, and / or aminoureido-functional silanes, preferably at least one selected from the group consisting of epoxycyclohexyl-functional silanes, glycidoxy-functional silanes, isocyanate-functional silanes, and aminoureido-functional silanes, and most preferably 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and at least one selected from N-3-aminopropyl tributoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl diethoxysilane, N-2-(aminoethyl)-3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl methyl diethoxysilane, 3-aminopropyl methyl dimethoxysilane, 3-aminopropyl dimethyl methoxysilane, 3-aminopropyl dimethyl ethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxyysily-N-(1,3 dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyl trimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl trimethoxysilane hydrochloride, 3-ureidopropyl trialkoxysilane, and 3-isocyanatopropyl triethoxysilane.

[0128] Additive (F) The polybutylene terephthalate composition may further comprise other components, which are additives selected by a person skilled in the art depending on the subsequent use of the product, preferably from at least one of the conventional additives defined below, provided that said conventional additives do not have a negative effect on the polybutylene terephthalate composition according to the present invention.

[0129] The customary additives are preferably used in an amount of 0% to 10% by weight, more preferably 0.1% to 5% by weight, and most preferably 0.5% to 3% by weight, based on the total weight of the polybutylene terephthalate composition.

[0130] The conventional additives used according to the present invention are preferably lubricants, stabilizers, antioxidants, release agents, UV stabilizers, heat stabilizers, gamma radiation stabilizers, antistatic agents, flow aids, flame retardants, elastomer modifiers, acid scavengers, emulsifiers, nucleating agents, plasticizers and / or pigments.These and other suitable additives are described, for example, in Gaechter, Mueller, Kunststoff-Additive [Plastics Additives], 3rd Edition, Hanser-Verlag, Munich, Vienna, 1989 and Plastics Additives Handbook, 5th Edition, Hanser-Verlag, Munich, 2001.The additives can be used alone or in admixture, or in the form of a masterbatch.

[0131] In one preferred embodiment of the present invention, the polybutylene terephthalate composition according to the present invention may further contain one or more lubricants and / or processing agents. When lubricants and / or processing agents are included, they are preferably esters or amides of saturated aliphatic carboxylic acids having 10 to 40 carbon atoms and / or saturated aliphatic alcohols or amines having 2 to 40 carbon atoms. A preferred lubricant is pentaerythritol tetrastearate, i.e., a fatty acid ester of pentaerythritol having 10 to 20 carbon atoms.

[0132] The lubricant is preferably present in an amount of about 0% to 3% by weight, more preferably about 0.01% to 2% by weight, and most preferably about 0.2% to 1% by weight, each based on the total weight of the polybutylene terephthalate composition according to the present invention.

[0133] In one preferred embodiment of the present invention, the polybutylene terephthalate composition according to the present invention may further comprise one or more antioxidants, preferably aromatic amine antioxidants, hindered phenol antioxidants, and phosphite antioxidants.

[0134] Examples of aromatic amine antioxidants are poly(1,2-dihydro-2,2,4-trimethyl-quinoline), bis(4-octylphenyl)amine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl)-p-phenylenediamine, and / or N,N'-bis(methylphenyl)-1,4-benzenediamine.

[0135] Examples of hindered phenolic antioxidants are poly(oxy-1,2-ethanediyl)-alpha-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropyl]-omega-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy], 2,4-bis[(octylthio)methyl]-o-cresol, octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, and 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid C7-C9-branched alkyl esters. Further, preferably, the solid hindered phenolic antioxidant is 2,4-bis[(dodecylthio)methyl]-o-cresol, 4,4'-butylidenebis-(3-methyl)-6-tert-butylphenol), 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid octadecyl ester, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), triethylene glycol-bis[3-(3 -tert-butyl-5-methyl-4-hydrophenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0136] Examples of phosphite antioxidants include tris(2,4-di-tert-butylphenyl)phosphite (Irgafos® 168, BASF SE, CAS 31570-04-4), bis(2,4-di-tert-butylphenyl)pentaerythrityl diphosphite (Ultranox® 626, Chemtura, CAS 26741-53-7), bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythrityl diphosphite (ADK Stab PEP-36, Adeka, CAS 80693-00-1), bis(2,4-dicumylphenyl)pentaerythrityl diphosphite (Doverphos® S-9228, Dover Chemical Corporation, CAS 154862-43-8), tris(nonylphenyl)phosphite (Irgafos® TNPP, BASF SE, CAS 26523-78-4), (2,4,6-tri-t-butylphenol)-2-butyl-2-ethyl-1,3-propanediol phosphite (Ultranox® 641, Chemtura, CAS 161717-32-4), and Hostanox® P-EPQ.

[0137] The antioxidants are each present in an amount of about 0% to 2% by weight, more preferably about 0.01% to 1% by weight, and most preferably about 0.2% to 0.8% by weight, based on the total weight of the polybutylene terephthalate composition according to the present invention.

[0138] In one preferred embodiment of the present invention, the polybutylene terephthalate composition according to the present invention may further comprise one or more adhesion promoters.

[0139] Examples of adhesion promoters are epoxides, such as epoxidized alkyl esters of fatty acids, for example, epoxidized linseed oil, epoxidized soybean oil, epoxidized rapeseed oil, and epoxy resins, such as bisphenol A resin.

[0140] The adhesion promoters are each present in an amount of preferably about 0% to 3% by weight, more preferably about 0.01% to 2% by weight, and most preferably about 1% to 2% by weight, based on the total weight of the polybutylene terephthalate composition according to the present invention.

[0141] In one preferred embodiment, the polybutylene terephthalate composition preferably contains, relative to the total mass of the polybutylene terephthalate composition, 20% by mass to 50% by mass, preferably 20% by mass to 40% by mass of polybutylene terephthalate resin (A), 2 to 10% by mass of vinyl aromatic polymer (B), 5% by mass to 40% by mass, preferably 15% by mass to 30% by mass of toughening agent (C), 0% by mass to 40% by mass, preferably 15% by mass to 30% by mass of polyester copolymer (D), 0% by mass to 20% by mass, preferably 5% by mass to 15% by mass of glass bubbles (E), and 0% by mass to 10% by mass, preferably 0.1% by mass to 5% by mass of additive (F).

[0142] In another aspect, the present invention relates to a method for producing a polybutylene terephthalate composition according to the present invention. The polybutylene terephthalate composition can be produced or processed by various known methods, such as extrusion or kneading. For example, the composition according to the present invention can be produced or processed by (1) mixing a polybutylene terephthalate resin (A), a vinyl aromatic polymer (B), an optional low-melting polyester (D), and optional additives (F), (2) adding a toughening agent (C), and optionally (3) adding glass bubbles (E), followed by extruding or kneading. It should be understood that, even if the components are introduced into the same feed zone, the components may be introduced through different hoppers depending on their form or properties. The extruder temperature is a conventional processing temperature for polybutylene terephthalate compositions, preferably 200 to 270°C. A reasonable extruder speed is a conventional processing speed for polybutylene terephthalate compositions, preferably 200 to 500 rpm.

[0143] In another aspect, the present invention relates to the use of vinyl aromatic polymer (B) in reducing the dielectric constant and dielectric loss of polybutylene terephthalate resin.

[0144] In another aspect, the present invention also relates to an article obtained or obtainable with the polybutylene terephthalate composition according to the present invention, which is preferably used in the E&E field, in particular in the high frequency communication field, for example as a part or component of a frame, housing or package for a mobile phone, a sensor or a laptop, or an antenna for a mobile phone or a vehicle.

[0145] In another aspect, the present invention also relates to the use of the polybutylene terephthalate composition according to the present invention as a material for a frame, housing or package of a mobile phone, sensor or laptop, or for parts or components of a mobile phone or vehicle antenna. [Example]

[0146] The present invention will now be further described by reference to the following examples, which are provided by way of illustration and are not intended to limit the scope of the invention.

[0147] [Examples 1 to 6 and Comparative Examples 1 to 6] All ingredients of the examples and comparative examples are listed in Tables 1-5.

[0148] Component A: BASF Ultradur® B2550 (viscosity number 107 cm³ according to ISO 307, 1157, 1628) 3 / g, PBT with a number average molar mass (Mn) of 16500 g / mol).

[0149] Component B: (B-1) Joncryl® ADF1300 manufactured by BASF, a copolymer of styrene, acrylic acid, and alpha-methylstyrene, with a weight average molecular weight of M w= 2800 g / mol, and the styrene content is 90 to 99.5 mol%, T g is 56°C. (B-2) Fine-Blend (trademark) SAG-002 manufactured by Nantong Sunny Polymer New Materials Technology Co. Ltd., a styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer with a styrene content of 70 to 80 mol%. (B-3) TOTAL SMA® 3000 manufactured by Cray Valley Oaklands Corporate Center, poly(styrene-maleic anhydride) copolymer, styrene and maleic anhydride ratio of approximately 3:1 by mole, weight average molecular weight of M w = 9500, and the number average molecular weight is M n =3800. (B-4) Paraloid™ EXL-2655 manufactured by Dow, a core-shell polymer in which the core is poly(butadiene / styrene) and the shell is methyl methacrylate, with a styrene content of 10 to 30 mol %. (B-5) POLYLAC (registered trademark) ABS757k manufactured by Chi Mei Corporation, containing 50 to 70 mol % of styrene.

[0150] Component C: (C-1) Chongqing Polycomp International Corp. (CPIC) glass fiber ECS3031H (C-2) Glass fiber ECS303(HL)303N-3 Chongqing Polycomp International Corp. (CPIC)

[0151] Component D: Low melting point polyester 180: Produced from terephthalic acid (TPA), isophthalic acid (IPA), ethyl glycol (EG), and diethylene glycol (DEG), with a molar ratio of TPA:IPA:EG:DEG = 1:0.4:1.3:0.1. g = 68℃, T m =174℃, intrinsic viscosity=0.68dL / g.

[0152] Component E: Glass Bubble iM16K manufactured by 3M Company.

[0153] Component F: (F-1) Vikoflex® 7190, stabilizer manufactured by Arkema Inc. (F-2) Irganox® 1010, an antioxidant manufactured by BASF. (F-3) Loxiol® P861 / 3.5, a long chain fatty acid ester of pentaerythritol manufactured by Emery Oleochemicals. (F-4) MODIPER® CL430-G, a compatibilizer manufactured by NOF Corporation, the main chain is polycarbonate and the branched polymer is a poly(glycidyl methacrylate-acrylonitrile-styrene) copolymer with a styrene content of 1 to 20 mol %. (F-5) Elvaloy® PTW, an elastomer from DuPont, an ethylene terpolymer.

[0154] PP Z1500, Polypropylene from Dawn Group.

[0155] Ingredients of the comparative example PP Z1500 manufactured by Sinopec Yizheng Chemical fiber Co., Ltd. PET WK851, a TPA-based polyethylene terephthalate resin manufactured by Zhejiang Wankai New Materials Co., Ltd.

[0156] Characterization: It is characterized by measuring tensile modulus, elongation at break, and tensile strength at break according to ISO 527-1 / 2 at 23°C using Type 1A test specimens.

[0157] The notched and unnotched Charpy impact strength were tested according to Type A of ISO179-1-2010 at 23°C. The sample stripe is 80*10*4mm (length*width*thickness).

[0158] MVR: Melt Volume-Flow Rate was tested according to ISO1133-2011. The test conditions are 275°C and 2.16 kg load.

[0159] The dielectric constant and dielectric loss were evaluated according to IEC60250 or GB / T12636-90 at 1 GHz.

[0160] Bond strength was tested according to ISO 19095 using Type B test specimens.

[0161] The extrusion conditions in the following examples are as follows: the zone temperature of the screw extruder is 200°C to 250°C, and the throughput is 30 kg / h.

[0162] [Table 1]

[0163] As can be seen from Table 1, the composition containing the vinyl aromatic polymer reduces the dielectric constant and dielectric loss, while the tensile modulus and flowability of the composition increase rapidly.

[0164] [Table 2]

[0165] As can be seen from Table 2, polypropylene is a resin with a low relative dielectric constant (2.1) and dielectric loss (0.0003), but the addition of PP has no obvious effect on improving the dielectric properties and has an obvious negative effect on the deterioration of the tensile properties.

[0166] [Table 3]

[0167] As can be seen from Table 3, the dielectric loss of Example 4 was reduced.

[0168] [Table 4]

[0169] [Table 5]

[0170] As can be seen from Table 5, the core-shell vinyl aromatic polymer exhibits desirable effects on reducing dielectric loss and improving flowability even at very low amounts of core-shell polymer.

Claims

1. A polybutylene terephthalate composition comprising at least one polybutylene terephthalate resin as component (A), at least one vinyl aromatic polymer containing units derived from a vinyl aromatic monomer as component (B), and at least one toughening agent as component (C), wherein the polybutylene terephthalate composition further comprises a polyester copolymer having a melting point (Tm) of 105°C to 185°C as component (D) and / or glass bubbles as component (E); The vinyl aromatic polymer is a vinyl aromatic polymer (B-1) and / or (B-2); The vinyl aromatic polymer (B-1) contains 60 mol % to 99.5 mol % of units derived from at least one vinyl aromatic monomer (b1) relative to all monomers constituting the vinyl aromatic polymer (B-1); and optionally, units derived from at least one ethylenically unsaturated monomer (b2) and / or one conjugated diene monomer (b3); the vinyl aromatic polymer (B-2) is a core-shell polymer comprising a core and a shell, the core being derived from a first monomer system comprising at least one vinyl aromatic monomer (b1) and, optionally, at least one monomer selected from the group consisting of an ethylenically unsaturated monomer (b2) and a conjugated diene monomer (b3); the shell being derived from a second monomer system comprising at least one monomer selected from the group consisting of the vinyl aromatic monomer (b1) and the ethylenically unsaturated monomer (b2); the mass ratio of the core to the shell in the core-shell polymer is 90:10 to 10:90; Component (D) is derived by partially substituting a second dicarboxylic acid component and / or a second glycol component constituting polyethylene terephthalate and / or polybutylene terephthalate with a copolymerizable monomer; the copolymerizable monomer is an aliphatic alkylene diol having 2 to 6 carbon atoms, a polyoxyalkylene glycol having 2 to 4 repeating oxyalkylene units, an aliphatic dicarboxylic acid having 6 to 12 carbon atoms, and / or an aromatic dicarboxylic acid; The glass bubbles (E) have a volume-based median diameter D of 5 to 50 microns. ５０ an average true density of 0.3 to 0.7 g / cc as measured using ASTM D2840-69; a crush strength of 5,000 PSI to 30,000 PSI as measured using ASTM D3102-72; and optionally containing an additive as component (F). Polybutylene terephthalate composition.

2. The vinyl aromatic monomer (b1) is represented by formula I: 【Chemistry 1】 [In the formula, R １ are the same or different and are hydrogen, C １ ~C １０ Alkyl group, C １ ~C ６ Alkenyl group, C ４ ~C １０ Alicyclic group, C ６ ~C １２ Aromatic hydrocarbon group, C １ ~C ４ is selected from the group consisting of an alkoxy group and a halogen atom; R ２ is hydrogen and / or C １ ~C ４ alkyl group] 2. The polybutylene terephthalate composition of claim 1, comprising a monomer corresponding to

3. 3. The polybutylene terephthalate composition of claim 2, wherein the vinyl aromatic monomer (b1) is selected from the group consisting of styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, para-alpha-dimethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-isopropylstyrene, 3-isopropylstyrene, 4-isopropylstyrene, ortho-divinylbenzene, meta-divinylbenzene, para-divinylbenzene, ethoxystyrene, chlorostyrene, bromostyrene, dibromostyrene, dichlorostyrene, tribromostyrene, trichlorostyrene, 2-vinylnaphthalene, and 2-isopropenylnaphthalene.

4. 4. The polybutylene terephthalate composition according to claim 1, wherein the ethylenically unsaturated monomer (b2) is selected from the group consisting of an ethylenically unsaturated nitrile monomer, an ethylenically unsaturated acid monomer, and a derivative thereof; and the derivative of the ethylenically unsaturated acid monomer is an acid anhydride, an ester, a molten salt, an amide, an imide, and / or an epoxy compound of the ethylenically unsaturated acid.

5. The ethylenically unsaturated monomer (b2) in the vinyl aromatic polymer (B-1) is an ethylenically unsaturated nitrile monomer, an ethylenically unsaturated acid monomer, an acid anhydride of an ethylenically unsaturated acid, an ester of an ethylenically unsaturated acid, and / or an epoxy compound of an ethylenically unsaturated acid; or the ethylenically unsaturated monomer (b2) in the vinyl aromatic polymer (B-2) is an ethylenically unsaturated nitrile monomer, an ethylenically unsaturated acid monomer, an acid anhydride of an ethylenically unsaturated acid and / or an ester of an ethylenically unsaturated acid; The polybutylene terephthalate composition according to any one of claims 1 to 3.

6. The ethylenically unsaturated nitrile monomers in the vinyl aromatic polymers (B-1) and (B-2) are independently selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile and / or α-cyanoethyl acrylonitrile; or The ethylenically unsaturated acid monomer in the vinyl aromatic polymer (B-1) is (meth)acrylic acid, 2-chloroacrylic acid, 2-ethylacrylic acid, angelic acid, crotonic acid, isocrotonic acid, cinnamic acid, p-chlorocinnamic acid, sorbic acid, alpha-chlorosorbic acid, alpha-cyanoacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, 3-(acryloyloxy)propanoic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3, 6-tetrahydrophthalic acid, bicyclo(2.2.2)-oct-5-ene-2,3-dicarboxylic acid, 4-methylcyclohex-4-ene-1,2-dicarboxylic acid, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic acid, bicyclo(2.2.1)oct-7-ene-2,3,5,6-tetracarboxylic acid, maleopimaric acid, 7-oxabicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid and aconitic acid; or the ethylenically unsaturated acid monomer of the core or shell in the vinyl aromatic polymer (B-2) is selected from the group consisting of (meth)acrylic acid, 2-ethylacrylic acid, angelic acid, crotonic acid, isocrotonic acid, sorbic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid and aconitic acid; or The acid anhydride of the ethylenically unsaturated carboxylic acid in the vinyl aromatic polymer (B-1) is maleic anhydride, acrylic anhydride, methacrylic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, itaconic anhydride, citraconic anhydride, fumaric anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, bicyclo(2.2.2)oct-5-ene-2,3-dicarboxylic anhydride , 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic anhydride, norborn-5-ene-2,3-dicarboxylic anhydride, nadic anhydride, methyl nadic anhydride, himic anhydride, methyl himic anhydride and x-methylbicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic anhydride; or The acid anhydride monomer of the ethylenically unsaturated acid in the core or shell of the vinyl aromatic polymer (B-2) is selected from the group consisting of maleic anhydride, acrylic anhydride, methacrylic anhydride, itaconic anhydride, citraconic anhydride, butenedioic anhydride and / or fumaric anhydride; or The ester of an ethylenically unsaturated acid in the vinyl aromatic polymer (B-1) or (B-2) is independently selected from the group consisting of C of an ethylenically unsaturated carboxylic acid. １ ~C １８ Alkyl esters and / or C １ ~C １８ Is a hydroxyalkyl ester; or the epoxy compound of an ethylenically unsaturated acid in the vinyl aromatic polymer (B-1) is selected from the group consisting of glycidyl (meth)acrylate, maleic acid 1-glycidyl ester, diglycidyl ester of maleic acid, monoglycidyl ester of itaconic acid, diglycidyl ester of itaconic acid, monoglycidyl ester of citraconic acid, diglycidyl ester of citraconic acid, monoglycidyl ester of butene tricarboxylic acid, diglycidyl ester of butene tricarboxylic acid, triglycidyl ester of butene tricarboxylic acid, vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, phenyl glycidyl ether, and 4-vinylbenzyl glycidyl ether; or the amide of an ethylenically unsaturated acid in the vinyl aromatic polymer (B-1) is selected from the group consisting of allylamine, aminoethyl methacrylate, aminopropyl methacrylate, dimethylaminoethyl methacrylate, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid N-monoethylamide, maleic acid N,N-diethylamide, fumaric acid monoamide, and fumaric acid diamide; or The imide of the ethylenically unsaturated acid in the vinyl aromatic polymer (B-1) is selected from the group consisting of maleimide, N-butylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; or the molten salt of an ethylenically unsaturated acid in the vinyl aromatic polymer (B-1) is selected from the group consisting of sodium acrylate, calcium acrylate, sodium methacrylate, and calcium methacrylate; The polybutylene terephthalate composition according to claim 4 or 5.

7. The polybutylene terephthalate composition of any one of claims 1 to 6, wherein the conjugated diene monomer (b3) is selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene.

8. The vinyl aromatic polymer (B-1) is composed of a vinyl aromatic monomer (b1) and at least one selected from the group consisting of an ethylenically unsaturated monomer (b2) and a conjugated diene monomer (b3); the vinyl aromatic polymer (b1) is selected from the group consisting of styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, and 4-methylstyrene; and the ethylenically unsaturated monomer (b2) is selected from the group consisting of acrylonitrile, methacrylonitrile, (meth)acrylic acid, maleic acid, fumaric acid, citraconic acid, 2-chloroacrylic acid, 2-ethylacrylic acid, angelica acid, crotonic acid, isocrotonic acid, cinnamic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, fumaric anhydride, methyl (meth)acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, and glycidyl (meth)acrylate; and the conjugated diene monomer (b3) is selected from the group consisting of 1,3-butadiene, 1,3-pentadiene, and isoprene; or The vinyl aromatic polymer (B-1) is composed of a vinyl aromatic monomer (b1) selected from the group consisting of styrene, alpha-methylstyrene, 2-methylstyrene, 3-methylstyrene, and 4-methylstyrene, a component (i) selected from the group consisting of (meth)acrylic acid, maleic acid, maleic anhydride, methyl (meth)acrylate, and glycidyl (meth)acrylate, and optionally a component (ii) selected from the group consisting of 1,3-butadiene, 1,3-pentadiene, acrylonitrile, and methacrylonitrile; or The vinyl aromatic polymer (B-1) is a block, alternating, random or graft copolymer of styrene-maleic anhydride, styrene-acrylonitrile-maleic anhydride, styrene-(meth)acrylate, styrene-methyl(meth)acrylate, styrene-glycidyl(meth)acrylate, styrene-acrylonitrile-glycidyl(meth)acrylate, styrene-acrylic acid, styrene-acrylic acid-α-methylstyrene, styrene-butadiene, styrene-acrylonitrile and styrene-butadiene-acrylonitrile, The polybutylene terephthalate composition of any one of claims 1 to 7.

9. In the vinyl aromatic polymer (B-2), the core comprises units derived from at least one vinyl aromatic monomer (b1) and at least one conjugated diene monomer (b3); the vinyl aromatic monomer (b1) is styrene, alpha-methylstyrene, and / or 4-methylstyrene; and the conjugated diene monomer (b3) is 1,3-butadiene, 1,3-pentadiene, and / or isoprene; or The core is a copolymer of at least one vinyl aromatic monomer (b1), at least one conjugated diene monomer (b3), and a C-type copolymer of an ethylenically unsaturated nitrile and an ethylenically unsaturated acid. １ ~C ４ the ethylenically unsaturated nitrile is acrylonitrile and / or methacrylonitrile; the C of the ethylenically unsaturated acid is １ ~C ４ The alkyl ester is methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and / or isobutyl (meth)acrylate; and the core is a butadiene-styrene-(meth)acrylate terpolymer, a butadiene-styrene-acrylonitrile terpolymer; or The core is a copolymer of at least one vinyl aromatic monomer (b1) and a C-type copolymer of an ethylenically unsaturated acid. １ ~C ４ It contains units derived from at least one monomer selected from the group consisting of alkyl esters, ethylenically unsaturated acids, and ethylenically unsaturated nitriles; １ ~C ４ The alkyl ester is methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and / or isobutyl (meth)acrylate; the ethylenically unsaturated acid is acrylic acid, methacrylic acid, and / or itaconic acid; and the ethylenically unsaturated nitrile is acrylonitrile and / or methacrylonitrile; or the shell comprises units derived from at least one ester of an ethylenically unsaturated acid and / or at least one vinyl aromatic monomer (b1); the ester of an ethylenically unsaturated acid is selected from the group consisting of (meth)acrylic acid and acetic acid; １ ~C ４ Alkyl esters and / or C １ ~C ４ hydroxyalkyl esters; and the vinyl aromatic monomer (b1) is styrene, alpha-methylstyrene, 4-methylstyrene, chlorostyrene, bromostyrene, dibromostyrene, dichlorostyrene and / or tribromostyrene; or The shell is an ethylenically unsaturated acid C １ ~C ４ At least one selected from the group consisting of alkyl esters and vinyl aromatic monomers (b1), and C-type monomers of ethylenically unsaturated nitrile monomers, ethylenically unsaturated acid monomers, acid anhydrides and / or ethylenically unsaturated acids １０ ~C ２０ alkyl esters of an ethylenically unsaturated acid; １ ~C ４ the alkyl ester is methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and / or isobutyl (meth)acrylate; the vinyl aromatic monomer (b1) is styrene, alpha-methylstyrene, 4-methylstyrene, chlorostyrene, bromostyrene, dibromostyrene, dichlorostyrene, and / or tribromostyrene; and the monomer (iii) is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, 2-ethylhexyl acrylate, decyl acrylate, lauryl methacrylate, stearyl methacrylate, and / or stearyl acrylate; The polybutylene terephthalate composition of any one of claims 1 to 8.

10. In the vinyl aromatic polymer (B-2), the core contains units derived from at least one vinyl aromatic monomer (b1) and at least one conjugated diene monomer (b3); and the shell contains units derived from C of (meth)acrylic acid or acetic acid. １ ~C ４ Alkyl esters and / or C １ ~C ４ the vinyl aromatic monomer (b1) is styrene, alpha-methylstyrene and / or 4-methylstyrene; the conjugated diene monomer (b3) is 1,3-butadiene, 1,3-pentadiene and / or isoprene; the C of (meth)acrylic acid or acetic acid １ ~C ４ Alkyl esters and / or C １ ~C ４ 10. The polybutylene terephthalate composition of claim 1, wherein the hydroxyalkyl ester is methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate and / or isobutyl methacrylate.

11. The polybutylene terephthalate composition according to any one of claims 1 to 10, wherein the mass ratio of core to shell in the vinyl aromatic polymer (B-2) is 90:10 to 50:

50.

12. The amount of the vinyl aromatic monomer (b1) in the vinyl aromatic polymer (B-1) is 60 mol % to 99.5 mol % based on the total amount of the monomers constituting the vinyl aromatic polymer (B-1); or In the vinyl aromatic polymer (B-2), the core contains 5% by mass to 80% by mass of units derived from at least one vinyl aromatic monomer (b1) and 20% by mass to 95% by mass of units derived from at least one conjugated diene monomer (b3), based on the total units of the core.

12. The polybutylene terephthalate composition of any one of claims 1 to 11.

13. The vinyl aromatic polymer (B-2) is a polymer containing at least one vinyl aromatic monomer and / or at least one C (meth)acrylic acid monomer. １ ~C ４ one internal graft stage comprising units derived from a graft-linking monomer comprising an alkyl ester; and the following monomer: C １ ~C ８ and optionally one intermediate sealer stage comprising at least one of an alkyl acrylate or a polyunsaturated crosslinker, wherein the intermediate sealer stage is between the internal graft stage and the shell.

14. 14. The polybutylene terephthalate composition of claim 1, wherein the vinyl aromatic polymer (B-2) comprises 70 to 85 parts by weight of the core; 8 to 14 parts by weight of the internal graft stage; 0.1 to 5 parts by weight of the intermediate sealer stage; and 10 to 16 parts by weight of the shell.

15. Contains 40% by mass or less of a vinyl aromatic polymer (B-1) relative to the total mass of the polybutylene terephthalate composition; or The polybutylene terephthalate composition contains 1 to 20 mass% of a vinyl aromatic polymer (B-2) based on the total mass of the composition.

15. The polybutylene terephthalate composition of any one of claims 1 to 14.

16. 16. The polybutylene terephthalate composition according to claim 1, comprising, relative to the total mass of the polybutylene terephthalate composition, 20% by mass to 70% by mass of a polybutylene terephthalate resin, 40% by mass or less of a vinyl aromatic polymer (B-1) or 1 to 20% by mass of a vinyl aromatic polymer (B-2), 5% by mass to 40% by mass of a toughening agent (C), 0% by mass to 40% by mass of a component (D), and 0% by mass to 20% by mass of glass bubbles (E).

17. 17. A method for producing the polybutylene terephthalate composition of any one of claims 1 to 16, comprising the steps of: mixing all components of the polybutylene terephthalate composition; (1) mixing the polybutylene terephthalate resin (A), the vinyl aromatic polymer (B), the optional low-melting polyester (D), and the optional additives (F); (2) adding the reinforcing agent (C); and optionally (3) adding glass bubbles (E); and extruding or kneading the resulting mixture.

18. Use of the vinyl aromatic polymer (B) according to any one of claims 1 to 15 in reducing the dielectric constant and dielectric loss of polybutylene terephthalate resin.

19. 17. An article obtainable with the polybutylene terephthalate composition of any one of claims 1 to 16, which is used as a part or component of a frame, housing or package for a mobile phone, a sensor or a laptop, or an antenna for a mobile phone or a vehicle.

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