Polybutylene terephthalate composition for use in high-frequency radio wave applications

Abstract

A polybutylene terephthalate composition for use in high-frequency radio wave applications above 6 GHz comprises a mixture of polybutylene terephthalate and hollow glass bubbles having an average diameter or particle diameter of 5 μm to 80 μm. The polybutylene terephthalate composition further comprises at least one of glass fibers having a length of 0.5 mm to 10 mm and a width or diameter of 5 μm to 15 μm, aluminum oxide fibers having a length of 1 mm to 5 mm and a width or diameter of 1 μm to 30 μm, a cyclic olefin copolymer, and a polycarbonate. The polybutylene terephthalate composition is prepared by modifying polybutylene terephthalate by melt-kneading polybutylene terephthalate with various materials.

Description

Technical Field

[0001] The present invention relates to a polybutylene terephthalate composition for use in high-frequency radio wave applications.

Background Art

[0002] With the emergence of 5G communication technologies and related equipment, there is a demand for low-cost and lightweight polymer materials with low values of dielectric constant (Dk) and dielectric tangent (Df), high metal adhesion strength, low coefficient of thermal expansion (CTE), and good mechanical and thermal properties. Currently, FR-4 glass-reinforced epoxy laminate materials are widely used as antenna substrates for sub-6 GHz frequency applications. FR-4 laminate is considered unsuitable for high-frequency (i.e., >6 GHz) applications because of its high values of Dk (>4) and Df (>0.01).

[0003] On the other hand, materials such as polytetrafluoroethylene (PTFE), liquid crystal polymer (LCP), and modified polyimide (M-PI) are considered suitable materials for high-frequency (>6 GHz) antennas and other sub-segment applications because of their low Dk and Df values. However, these materials are very expensive and do not meet the lightweight criteria required for the intended applications, apart from other specific issues associated with each material. In particular, the use of PTFE poses several problems, such as higher system costs including both material and processing costs, inferior metal adhesion, high CTE in the z-axis direction, and higher density.

[0004] In this regard, since the Dk (about 3 at 10 GHz) and Df (about 0.005 at 10 GHz) are lower compared to FR-4 and the metal adhesion characteristics are excellent compared to PTFE, other commercially available polymer materials such as polybutylene terephthalate (PBT) can be selected. However, the mechanical and thermal properties of neat PBT are not sufficient to meet specific manufacturing processes such as surface mount technology (SMT) processes and usage conditions. Although the mechanical and thermal properties of PBT may be improved by compounding specific additives, the dielectric and metal adhesion properties of PBT may be affected by these additives.

[0005] Therefore, in order for modified PBT to be suitable for high-frequency (i.e., >6 GHz) applications by having low Dk and Df values, high metal adhesion strength, low CTE, as well as good mechanical and thermal properties, it is necessary to modify PBT with additives that bring about a synergistic effect.

Summary of the Invention

[0006] A polybutylene terephthalate (PBT) composition for use in applications of high-frequency radio waves of 6 GHz or higher includes a mixture of polybutylene terephthalate, hollow glass bubbles having an average diameter of 5 microns to 80 microns, and at least one additive. Examples of the additive include glass fibers having a length of 0.5 mm to 10 mm and a width or diameter of 5 microns to 15 microns, aluminum oxide fibers having a length of 1 mm to 5 mm and a width or diameter of 1 micron to 30 microns, polyethylene terephthalate, and / or polycarbonate.

[0007] The hollow glass bubbles may be included in the PBT composition in an amount of 1 wt% to 35 wt%. The hollow glass bubbles may have at least one of a crushing strength of 30 MPa or more, a true density of 0.3 g / cc to 0.8 g / cc, and a gas content of 50% to 90%.

[0008] The PBT composition may contain glass fibers in an amount of 40% by weight or less based on the total weight of the composition. The glass fibers may have at least one of a dielectric constant (Dk) of 6 or less measured at 6 MHz or higher in accordance with ASTM D150, a dielectric tangent (Df) of 0.005 or less measured at 6 MHz or higher in accordance with ASTM D150, and a coefficient of thermal expansion (CTE) of 35×10-6 / °C or less measured in accordance with ASTM D696.

[0009] The PBT composition may further contain aluminum oxide fibers in an amount of 40% by weight or less based on the total weight of the composition.

[0010] The PBT may be a low IV resin with an intrinsic viscosity (IV) of 1.4 dl / g or less, or a high IV resin with an IV of 1.5 dl / g or more, or a mixture of the above resins.

[0011] The PBT composition may also contain polycarbonate in an amount of 30% by weight or less based on the total weight of the composition, and polyethylene terephthalate in an amount of 30% by weight or less based on the total weight of the composition.

[0012] The PBT composition may also contain at least one of a stabilizer, a coupling agent, a nucleating agent, a thermal conductivity agent, a flame retardant additive, a thermal conductivity additive, a binder, an antiblocking agent, an antistatic agent, an antioxidant, a neutralizing agent, an acid scavenger, a foaming agent, a crystallization aid, a dye, a flame retardant, a filler, a rigid filler, a soft filler, an impact modifier, a release agent, an oil, another polymer, a pigment, a processing agent, a reinforcing agent, a light stabilizer, an ultraviolet resistant agent, a lubricant, a fluidity improver, and combinations thereof.

[0013] The PBT composition may have a Dk value of 2.5 or less when measured at 6 GHz or higher, and a Df value of 0.005 or less when measured at 6 GHz or higher, and may also have at least one of the following: a metal adhesion peel strength of 0.1 N / mm or more measured according to ASTM B533 or IPC-TM-650; a coefficient of thermal expansion (CTE) of 35 ppm / °C or less measured according to ASTM D696; a heat distortion temperature (HDT) of 200 °C or more measured according to ASTM D648; a water absorption rate of 0.05 wt% or less measured according to ASTM D570; a tensile modulus of 2000 MPa or more measured according to ASTM D638; a tensile strength of 35 MPa or more measured according to ASTM D638; a density of 1.4 g / cc or less; a UL94 flame retardancy grade of V0@1.5 mm; and a thermal conductivity of 0.3 W / mK or less measured according to ASTM C518.

[0014] The PBT composition is formed into a manufactured article. The manufactured article may be a telecommunications device or component, a high-frequency (>6 GHz) electrical device, a high-frequency (>6 GHz) multi-generation telecommunications device or component, a telecommunications device or component of 5G or higher generation, a telecommunications device housing, a radome cover, a high-frequency (RF) filter, an RF connector, an EMI shield, an antenna substrate, a waveguide substrate or carrier, an antenna substrate of a base station antenna, or an automotive radar component.

[0015] In a method of forming a PBT composition for use in high-frequency radio wave applications of 6 GHz or higher, the polybutylene terephthalate is modified by melt-kneading a material of at least one of hollow glass bubbles having an average diameter of 5 to 80 microns and some additives dispersed throughout the polybutylene terephthalate with the polybutylene terephthalate. These additives may include glass fibers having a length of 0.5 mm to 10 mm and a width or diameter of 5 to 15 microns, aluminum oxide fibers having a length of 1 mm to 5 mm and a width or diameter of 1 to 30 microns, and polycarbonate. Detailed Description of the Invention

[0016] Compared with the high-cost materials currently used for high-frequency radio wave applications, polybutylene terephthalate (PBT) is an easily available and relatively low-cost material. However, due to the drawbacks inherent in neat PBT at high frequencies, PBT has not been widely used for high-frequency radio wave applications. In the present invention, these drawbacks are overcome by melt-kneading a mixture of PBT and synergistic additives that make the PBT composition suitable for use in high-frequency radio wave applications above 6 GHz.

[0017] By adapting the modified PBT, the modified polypropylene is lightweight, has a low dielectric constant (Dk), a low dielectric tangent (Df), a high metal adhesion strength, a low coefficient of thermal expansion (CTE), a high mechanical strength, and good thermal performance. These properties can be achieved by using a blend of PBT and the specific additives described herein.

[0018] In a co-pending patent application filed on the same day under the title "Polypropylene Composition for Use in High-Frequency Radio Wave Applications" identified by Attorney Docket No. 21T&I0030, modified polypropylene (PP) for use in 5G applications of high-frequency radio waves above 6 GHz is disclosed. While the modified polypropylene can be useful for many such applications, due to its lower melting point of polypropylene (about 160 °C), it has limitations with respect to processing conditions and operations that occur at much higher temperatures, such as during soldering in surface mount technology (SMT) applications. In contrast, PBT has a much higher melting point (about 220 °C) and can be used for applications involving high temperatures such as SMT.

[0019] The PBT component of the polymer blend may comprise a homopolymer of polybutylene terephthalate resin. These are dicarboxylic acids containing terephthalic acid or their ester-forming derivatives (e.g., C 1 ~C 6It may be a component formed by polycondensation of an alkyl ester or an acid halide, etc., and a glycol component containing an alkylene glycol having at least 4 carbon atoms (for example, 1,4-butanediol) or its ester-forming derivative.

[0020] Examples of suitable commercially available PBT homopolymers include polymers available as VALOX™ resin 176 or VALOX™ resin 3007 from SABIC USA and SABIC Europe, respectively.

[0021] In other embodiments, as the PBT component, a random PBT-PET copolymer including the selection of a diol component selected from the group consisting of poly(ethylene glycol (PBT-PET multiblock copolymer), PBT-polyethylene oxide terephthalate (PBT-PEOT block copolymer), PBT-r-butylene dilinoleate (PBT-DLA copolymer), ethylene glycol, propylene glycol, and poly(butylene-1,4-cyclohexanedicarboxylate (PBCD), poly(butylene-1,3-cyclopentanedicarboxylate (PBCP), and poly(butylene block-poly(lactic acid) copolymer can be included. When the above copolymers are used, the non-butylene terephthalate comonomer units may be present in an amount of 30% by weight or less in the PBT copolymer, and in many cases, are used in an amount of 5% to 30% by weight. In certain embodiments, the non-butylene terephthalate comonomer component is present in the PBT copolymer in an amount of at least 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, and 30% by weight, an amount equal to the above amount, and / or an amount between any two of the above amounts.

[0022] In some embodiments, the polybutylene terephthalate composition is substantially free of polytetrafluoroethylene (PTFE). As used herein, the phrase "substantially free of" with respect to a component of a composition means that the component is not actively or intentionally added to the composition, but may be present as an impurity in an amount of less than about 0.01% by weight of the composition.

[0023] In this specification, when a numerical value, concentration, or range is indicated, each numerical value should be read once as modified by the term "about" (except when it has already been explicitly so modified), and then again as not so modified, unless the context indicates otherwise. Also, in this specification, it should be understood that ranges of amounts recited or described as useful, suitable, etc. are intended to include every value within the range including the endpoints. For example, the range "from 1 to 10" should be read as indicating every possible numerical value along the continuum between about 1 and about 10. Thus, even if a particular point within the range, or points within the range, are not explicitly specified or mentioned, the inventor understands that any and all points within the range are considered to be specified, and the inventor is considered to own the entire range and all points within the range, including smaller ranges within the larger range.

[0024] As discussed throughout the following description, with respect to the PBT component of the PBT composition, the expression "PBT" means both PBT homopolymers and PBT copolymers, unless explicitly stated otherwise or not apparent from the context.

[0025] The PBT component of the above composition can be characterized by various properties such as average molecular weight, density, intrinsic viscosity, melt flow index (MFI), polydispersity index (PDI), tensile strength at yield, tensile modulus, tensile elongation at yield, Izod notched impact strength, hardness, or combinations thereof.

[0026] The average molecular weight (Mw) of the PBT component may be in the range of 30,000 to 200,000, as determined by high-temperature gel permeation chromatography. In particular, the average molecular weight (Mw) of PBT may be at least 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 110,000, 120,000, 130,000, 140,000, 150,000, 160,000, 170,000, 180,000, 190,000, and 200,000, values equal to the above values, and / or values between any two of the above values, as determined by high-temperature (40 - 50 °C) gel permeation chromatography using 1,1,1,3,3,3-hexafluoroisopropanol (HFIP, as the solvent). Unless otherwise specified, the average molecular weight (Mw) of all polymers described herein is determined by high-temperature gel permeation chromatography.

[0027] The density of PBT can be from 1.3 g / cm 3 or 1.4 g / cm 3 In particular, the density of PBT may be at least 1.30 g / cm 3 , 1.31 g / cm 3 , 1.32 g / cm 3 , 1.33 g / cm 3 , 1.34 g / cm 3 , 1.35 g / cm 3 , 1.36 g / cm 3 , 1.37 g / cm 3 , 1.38 g / cm 3 , 1.39 g / cm 3 , and 1.40 g / cm 3 values, values equal to the above values, and / or values between any two of the above values.

[0028] The PBT can be a PBT having a low IV resin with an IV (intrinsic viscosity) of 1.4 dl / g or less, or a high IV resin with an IV of 1.5 dl / g or more, or a mixture of the above PBT resins. The intrinsic viscosity of the PBT is measured in a dilute solution using a capillary viscometer according to the ISO-1628-5 protocol. In certain embodiments, the low IV PBT can have an IV from at least 0.2 dl / g, 0.3 dl / g, 0.4 dl / g, 0.5 dl / g, 0.6 dl / g, 0.7 dl / g, 0.8 dl / g, 0.9 dl / g, 1.0 dl / g, 1.1 dl / g, 1.2 dl / g, 1.3 dl / g, and 1.4 dl / g, an IV equal to the above values, and / or an IV between any two of the above values. In certain embodiments, the high IV PBT resin can have an IV from 1.5 dl / g, 1.6 dl / g, 1.7 dl / g, 1.8 dl / g, 1.9 dl / g, 2.0 dl / g, 2.1 dl / g, 2.2 dl / g, 2.3 dl / g, 2.4 dl / g, and 2.5 dl / g, an IV equal to the above values, and / or an IV between any two of the above values.

[0029] When a mixture of the above low-IV PBT resin and high-IV PBT resin is used, the low-IV PBT resin is used in an amount of 0.1% to 99.9% by weight based on the total weight of the low-IV PBT resin and the high-IV PBT resin. When a mixture of the low-IV PBT resin and the high-IV PBT resin is used, the low-IV resin is at least 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1.0% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight, 1.7% by weight, 1.8% by weight, 1.9% by weight, 2.0% by weight, 2.1% by weight, 2.2% by weight, 2.3% by weight, 2.4% by weight, 2.5% by weight, 2.6% by weight, 2.7% by weight, 2.8% by weight, 2.9% by weight, 3.0% by weight, 3.1% by weight, 3.2% by weight, 3.3% by weight, 3.4% by weight, 3.5% by weight, 3.6% by weight, 3.7% by weight, 3.8% by weight, 3.9% by weight, 4.0% by weight, 4.1% by weight, 4.2% by weight, 4.3% by weight, 4.4% by weight, 4.5% by weight, 4.6% by weight, 4.7% by weight, 4.8% by weight, 4.9% by weight, 5.0% by weight, 5.5% by weight, 6.0% by weight, 6.5% by weight, 7.5% by weight, 8.0% by weight, 8.5% by weight, 9.0% by weight, 9.Amounts from 5 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, 41 wt%, 42 wt%, 43 wt%, 44 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, 53 wt%, 54 wt%, 55 wt%, 56 wt%, 57 wt%, 58 wt%, 59 wt%, 60 wt%, 61 wt%, 62 wt%, 63 wt%, 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, 71 wt%, 72 wt%, 73 wt%, 74 wt%, 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, 99 wt% and 99.9 wt%, amounts equal to the above amounts and / or amounts between any two of the above amounts may also be used.

[0030] The PBT may have an MFI at 250°C and a load of 2.16 kg of from 0.1 g / 10 min to 40 g / 10 min in accordance with ISO 1133, or may be at least 0.1 g / 10 min, 0.2 g / 10 min, 0.3 g / 10 min, 0.4 g / 10 min, 0.5 g / 10 min, 0.6 g / 10 min, 0.7 g / 10 min, 0.8 g / 10 min, 0.9 g / 10 min, 1 g / 10 min, 2 g / 10 min, 3 g / 10 min, 4 g / 10 min, 5 g / 10 min, 6 g / 10 min, 7 g / 10 min, 8 g / 10 min, 9 g / 10 min, 10 g / 10 min, 11 g / 10 min, 12 g / 10 min, 13 g / 10 min, 14 g / 10 min, 15 g / 10 min, 16 g / 10 min, 17 g / 10 min, 18 g / 10 min, 19 g / 10 min, 20 g / 10 min, 21 g / 10 min, 22 g / 10 min, 23 g / 10 min, 24 g / 10 min, 25 g / 10 min, 26 g / 10 min, 27 g / 10 min, 28 g / 10 min, 29 g / 10 min, 30 g / 10 min, 31 g / 10 min, 32 g / 10 min, 33 g / 10 min, 34 g / 10 min, 35 g / 10 min, 36 g / 10 min, 37 g / 10 min, 38 g / 10 min, 39 g / 10 min, and 40 g / 10 min, values equal to the above values, and / or values between any two of the above values, in accordance with ISO 1133.

[0031] The PBT component may have a polydispersity index (PDI = Mw / Mn) determined by high temperature gel permeation chromatography of from 2 to 10, or may be at least 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, values equal to the above values, and / or values between any two of the above values.

[0032] The tensile modulus of PBT is 1700 MPa to 3000 MPa, or a value from at least 1700 MPa, 1750 MPa, 1800 MPa, 1850 MPa, 1900 MPa, 1950 MPa, 2000 MPa, 2050 MPa, 2100 MPa, 2150 MPa, 2200 MPa, 2250 MPa, 2300 MPa, 2350 MPa, 2400 MPa, 2450 MPa, 2500 MPa, 2550 MPa, 2600 MPa, 2650 MPa, 2700 MPa, 2750 MPa, 2800 MPa, 2850 MPa, 2900 MPa, 2950 MPa, and 3000 MPa, a value equal to the above value, and / or a value between any two of the above values, measured according to ASTM D638. The tensile strength at yield of PBT is 20 MPa to 60 MPa, or a value from at least 20 MPa, 25 MPa, 30 MPa, 35 MPa, 40 MPa, 45 MPa, 50 MPa, 55 MPa, and 60 MPa, a value equal to the above value, and / or a value between any two of the above values, measured according to ISO 527.

[0033] The notched Izod impact strength of the PBT component at -30 °C is at least 2 kJ / m 2 ~8 kJ / m 2 or 3 kJ / m 2 4 kJ / m 2 5 kJ / m 2 6 kJ / m 2 7 J / m 2 and 8 J / m 2 from, a value equal to the above value, and / or a value between any two of the above values. The notched Izod impact strength of the PBT component at 23 °C is 4 kJ / m 2 ~15 kJ / m 2 or at least 4 kJ / m 2 5 kJ / m 2 6 kJ / m 2 7 kJ / m 2 8 kJ / m 2 9 kJ / m 2 10 kJ / m 2, 11 kJ / m 2 , 12 kJ / m 2 , 13 kJ / m 2 , 14 kJ / m 2 , and 15 kJ / m 2 , 22 kJ / m 2 Values from, values equal to, and / or values between any two of the above values may be possible.

[0034] The above PBT component is used as a polymer blend in combination with one or more different primary additives for use in high-frequency radio applications. These primary additives can impart a lower Dk, a lower Df, a higher metal adhesion strength, and a lower CTE to the PBT composition compared to PBT without the primary additive. The PBT composition can also exhibit high mechanical strength and good thermal performance.

[0035] The primary additive includes hollow glass bubbles. The glass bubbles help reduce the bulk density of the PBT and lower the Dk and Df values. This is at least partially due to the presence of air, gas, or a vacuum space within the glass bubbles, resulting in lower Dk and Df values for the glass bubbles themselves.

[0036] A glass bubble is typically a unicellular sphere that is a hollow, thin-walled structure made from soda lime borosilicate glass. The glass bubble may have an average diameter or particle size of from 5 μm to 80 μm, more particularly from 15 μm to 65 μm. In certain embodiments, the average diameter or particle size of the glass bubble is at least 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, and 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, 36 μm, 37 μm, 38 μm, 39 μm, 40 μm, 41 μm, 42 μm, 43 μm, 44 μm, 45 μm, 46 μm, 47 μm, 48 μm, 49 μm, 50 μm, 51 μm, 52 μm, 53 μm, 54 μm, 55 μm, 56 μm, 57 μm, 58 μm, 59 μm, 60 μm, 61 μm, 62 μm, 63 μm, 64 μm, 65 μm, 66 μm, 67 μm, 68 μm, 69 μm, 70 μm, 71 μm, 72 μm, 73 μm, 74 μm, 75 μm, 76 μm, 77 μm, 78 μm, 79 μm, and 80 μm, a value equal to the foregoing values, and / or a value between any two of the foregoing values.

[0037] The hollow glass bubbles may have a wall thickness of 0.4 μm to 1.5 μm, more particularly 0.5 μm to 0.9 μm, and even more particularly 0.6 μm to 0.8 μm. In certain embodiments, the wall thickness of the glass bubbles is at least 0.40 μm, 0.41 μm, 0.42 μm, 0.43 μm, 0.44 μm, 0.45 μm, 0.46 μm, 0.47 μm, 0.48 μm, 0.49 μm, 0.50 μm, 0.51 μm, 0.52 μm, 0.53 μm, 0.54 μm, 0.55 μm, 0.56 μm, 0.57 μm, 0.58 μm, 0.59 μm, 0.60 μm, 0.61 μm, 0.62 μm, 0.63 μm, 0.64 μm, 0.65 μm, 0.66 μm, 0.67 μm, 0.68 μm, 0.69 μm, 0.70 μm, 0.71 μm, 0.72 μm, 0.73 μm, 0.74 μm, 0.75 μm, 0.76 μm, 0.77 μm, 0.78 μm, 0.79 μm, 0.80 μm, 0.81 μm, 0.82 μm, 0.83 μm, 0.84 μm, 0.85 μm, 0.86 μm, 0.87 μm, 0.88 μm, 0.89 μm, 0.90 μm, 0.91 μm, 0.92 μm, 0.93 μm, 0.94 μm, 0.95 μm, 0.96 μm, 0.97 μm, 0.98 μm, 0.99 μm, 1.00 μm, 1.11 μm, 1.12 μm, 1.13 μm, 1.14 μm, 1.15 μm, 1.16 μm, 1.17 μm, 1.18 μm, 1.19 μm, 1.20 μm, 1.21 μm, 1.22 μm, 1.23 μm, 1.24 μm, 1.25 μm, 1.26 μm, 1.27 μm, 1.28 μm, 1.29 μm, 1.30 μm, 1.31 μm, 1.32 μm, 1.33 μm, 1.34 μm, 1.35 μm, 1.36 μm, 1.37 μm, 1.38 μm, 1.39 μm, 1.40 μm, 1.41 μm, 1.42 μm, 1.43 μm, 1.44 μm, 1.45 μm, 1.46 μm, 1.47 μm, 1.48 μm, 1.49 μm and 1.50 μm, values equal to the above values, and / or values between any two of the above values.

[0038] As a result, the gas amount or internal space within the hollow glass sphere can be from 50% to about 90%. Those glass bubbles having a gas amount or internal space of 60% to 80% have been found to be particularly useful. In certain embodiments, the gas amount or internal space within the hollow glass bubble can be at least 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, and values from 90%, values equal to the above values, and / or values between any two of the above values. The internal space of the glass bubble is usually filled with air, but may also be filled with other gases such as nitrogen. Further, there may be no medium (vacuum) in the internal space, or it may be filled with a low dielectric constant liquid that is likely to reduce the Dk value and Df value.

[0039] The glass bubbles may have a true density of 0.3 g / cc to 0.8 g / cc, measured by helium pycnometry. In certain embodiments, the glass bubbles have a true density measured by helium pycnometry that is at least 0.30 g / cc, 0.31 g / cc, 0.32 g / cc, 0.33 g / cc, 0.34 g / cc, 0.35 g / cc, 0.36 g / cc, 0.37 g / cc, 0.38 g / cc, 0.39 g / cc, 0.40 g / cc, 0.41 g / cc, 0.42 g / cc, 0.43 g / cc, 0.44 g / cc, 0.45 g / cc, 0.46 g / cc, 0.47 g / cc, 0.48 g / cc, 0.49 g / cc, 0.50 g / cc, 0.51 g / cc, 0.52 g / cc, 0.53 g / cc, 0.54 g / cc, 0.55 g / cc, 0.56 g / cc, 0.57 g / cc, 0.58 g / cc, 0.59 g / cc, 0.60 g / cc, 0.61 g / cc, 0.62 g / cc, 0.63 g / cc, 0.64 g / cc, 0.65 g / cc, 0.66 g / cc, 0.67 g / cc, 0.68 g / cc, 0.69 g / cc, 0.70 g / cc, 0.71 g / cc, 0.72 g / cc, 0.73 g / cc, 0.74 g / cc, 0.75 g / cc, 0.76 g / cc, 0.77 g / cc, 0.78 g / cc, 0.79 g / cc, 0.80 g / cc, values equal to the above values, and / or values between any two of the above values.

[0040] Furthermore, the hollow glass bubbles may have a crushing strength of 30 MPa to 300 MPa. In certain embodiments, the crushing strength of the glass bubbles is at least 30 MPa, 31 MPa, 32 MPa, 33 MPa, 34 MPa, 35 MPa, 36 MPa, 37 MPa, 38 MPa, 39 MPa, 40 MPa, 41 MPa, 42 MPa, 43 MPa, 44 MPa, 45 MPa, 46 MPa, 47 MPa, 48 MPa, 49 MPa, 50 MPa, 51 MPa, 52 MPa, 53 MPa, 54 MPa, 55 MPa, 56 MPa, 57 MPa, 58 MPa, 59 MPa, 65 MPa, 66 MPa, 67 MPa, 68 MPa, 69 MPa, 70 MPa, 71 MPa, 72 MPa, 73 MPa, 74 MPa, 75 MPa, 76 MPa, 77 MPa, 78 MPa, 79 MPa, 80 MPa, 81 MPa, 82 MPa, 83 MPa, 84 MPa, 85 MPa, 86 MPa, 87 MPa, 88 MPa, 89 MPa, 90 MPa, 91 MPa, 92 MPa, 93 MPa, 94 MPa, 95 MPa, 96 MPa, 97 MPa, 98 MPa, 99 MPa, 100 MPa, 105 MPa, 110 MPa, 115 MPa, 120 MPa, 125 MPa, 130 MPa, 135 MPa, 140 MPa, 145 MPa, 150 MPa, 155 MPa, 160 MPa, 165 MPa, 170 MPa, 175 MPa, 180 MPa, 185 MPa, 190 MPa, 195 MPa, 200 MPa, 205 MPa, 210 MPa, 215 MPa, 220 MPa, 225 MPa, 230 MPa, 235 MPa, 240 MPa, 245 MPa, 250 MPa, 255 MPa, 260 MPa, 265 MPa, 270 MPa, 275 MPa, 280 MPa, 285 MPa, 290 MPa, 295 MPa, and values from 300 MPa, values equal to the above values, and / or values between any two of the above values.

[0041] Examples of suitable commercially available hollow glass bubbles include the hollow glass bubbles available as 3M's iM16K and iM30K glass bubbles in Maplewood, Minnesota. The glass bubbles used in this study (IM30K high-strength glass bubbles) are commercially available from 3M (trademark). The crushing strength and gas volume of the hollow glass bubbles were measured using 3M's internal QCM (internal QCM).

[0042] The hollow glass bubbles may be used in the PBT composition in an amount of 1 wt% to 35 wt% based on the total weight of the PBT composition. In certain embodiments, the glass bubbles are at least 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, and 35 wt% based on the total weight of the polybutylene terephthalate composition, values equal to the above values, and / or values between any two of the above values.

[0043] During the melt-kneading of the polymer composition, a certain amount of the glass bubbles is expected to break. As a result, it is typical for less than 5% of the glass bubbles to break. The breakage of the glass bubbles should be minimized, but the broken glass bubbles essentially become glass powder and can promote the reinforcement of the PBT composition.

[0044] Since the glass bubbles and / or the broken glass bubbles do not provide sufficient reinforcement to the PBT composition by themselves, other materials may also be used in the PBT composition. This includes glass short fiber (SGF) materials and aluminum oxide fiber materials.

[0045] Glass fibers can be used to improve both the mechanical and thermal properties of PBT compositions. Such properties include higher rigidity, higher tensile or flexural modulus, lower CTE, higher heat deflection temperature (HDT), and better dimensional stability. Short glass fibers can also enhance, or can significantly reduce or not change, the enhanced properties provided to polymer compositions with low Dk and / or Df values provided by glass bubbles, by including glass fibers having low Dk and / or Df values.

[0046] The short glass fibers have a length of 0.5 mm to 10 mm and may have a width or diameter of 5 μm to 15 μm. In specific applications, the length of the short glass fibers may be a value from at least 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm, 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, 2.0 mm, 2.1 mm, 2.2 mm, 2.3 mm, 2.4 mm, 2.5 mm, 2.6 mm, 2.7 mm, 2.8 mm, 2.9 mm, 3.0 mm, 3.1 mm, 3.2 mm, 3.3 mm, 3.4 mm, 3.5 mm, 3.6 mm, 3.7 mm, 3.8 mm, 3.9 mm, 4.0 mm, 4.1 mm, 4.2 mm, 4.3 mm, 4.4 mm, 4.5 mm, 4.6 mm, 4.7 mm, 4.8 mm, 4.9 mm, 5.0 mm, 5.1 mm, 5.2 mm, 5.3 mm, 5.4 mm, 5.5 mm, 5.6 mm, 5.7 mm, 5.8 mm, 5.9 mm, 6.0 mm, 6.1 mm, 6.2 mm, 6.3 mm, 6.4 mm, 6.5 mm, 6.6 mm, 6.7 mm, 6.8 mm, 6.9 mm, and 7.0 mm, 7.1 mm, 7.2 mm, 7.3 mm, 7.4 mm, 7.5 mm, 7.6 mm, 7.7 mm, 7.8 mm, 7.9 mm, 8.0 mm, 8.1 mm, 8.2 mm, 8.3 mm, 8.4 mm, 8.5 mm, 8.6 mm, 8.7 mm, 8.8 mm, 8.9 mm, 9.0 mm, 9.1 mm, 9.2 mm, 9.3 mm, 9.4 mm, 9.5 mm, 9.6 mm, 9.7 mm, 9.8 mm, 9.9 mm, and 10.0 mm, a value equal to the above values, and / or a value between any two of the above values. The width or diameter of the short glass fibers may be a value from at least 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, and 15 μm, a value equal to the above values, and / or a value between any two of the above values.

[0047] The short glass fibers may be used in the PBT composition in an amount of 40% by weight or less based on the total weight of the PBT composition, and in many cases, 1% to 30% by weight based on the total weight of the PBT composition is preferred. In certain embodiments, the glass fibers are, based on the total weight of the PBT composition, at least 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, and 40% by weight, an amount equal to the above amount, and / or an amount between any two of the above amounts.

[0048] The PBT composition incorporating the short glass fibers may have a CTE of 35×10 -6 / °C or less as measured according to ASTM D696. In certain embodiments, the CTE value of the PBT composition incorporating the short glass fibers, measured according to ASTM D696, may be 35, 30, 25, 20, 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0.5×10 -6 / °C or less.

[0049] In certain applications, since both low Dk and Df values and high Dk and Df values provide a similar reinforcing effect to the PBT composition, the glass short fibers may be glass short fibers having higher or lower Dk and Df values. When used, the glass short fibers having higher Dk and Df values may be glass short fibers having a Dk value of 5 or more measured at 6 MHz or higher in accordance with ASTM D150 and a dielectric tangent Dk measured at 6 MHz or higher in accordance with ASTM D150 being greater than 0.005. Examples of such glass fibers may include E-CR (E-glass corrosion resistant) glass fibers. Examples of commercially available glass short fibers include glass fibers available as DS2200 13P glass fibers from the Braj Binani Group in Mumbai, India. These glass fibers are distinguishable from glass fibers having low Dk and Df values. These glass fibers are distinguishable from glass fibers having low Dk and Df values.

[0050] Glass fibers with low permittivity or Dk value and Df value may also be used alone or in combination with short glass fibers with higher Dk value and Df value. The low Dk glass fibers may be glass fibers having a Dk value of 4 to 5 measured at 6 MHz or higher in accordance with ASTM D150. In certain embodiments, the low Dk glass fibers may have a Dk value of at least 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, and 5.0, a Dk value equal to the above values, and / or a Dk value between any two of the above values. The glass fibers with low Df may be glass fibers having a Df value of 0.005, 0.004, 0.003, 0.002, 0.001, 0.0009, 0.0008, 0.0007, 0.0006, 0.0005, 0.0004, 0.0003, 0.0002, 0.0001 or less. The glass fibers with low Dk and Df may have one or both of low Dk and low Df. Typically, the fibers with low Dk and Df have both low Dk and low Df. Such glass fibers may include HL-glass fibers. Examples of such commercially available short glass fibers with low Dk value and Df value include short glass fibers available as CS(HL)303N-3 glass fibers from Chongqing Polycomp International Corp in Chongqing, China.

[0051] The glass fibers having a low Dk and a low Df may constitute all or part of all the glass staple fibers. The glass fibers having a low Dk and a low Df may be present in the PBT composition in an amount of 40% by weight or less based on the total weight of the PBT composition. In certain embodiments, when used, the glass fibers having a low Dk and a low Df are, based on the total weight of the polybutylene terephthalate composition, at least 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% and 40% by weight, an amount equal to the above amount, and / or an amount between any two of the above amounts.

[0052] Aluminum oxide fibers may be used in the PBT composition. While improving mechanical properties such as tensile modulus and rigidity, aluminum oxide fibers maintain radio frequency (RF) permeability. The aluminum oxide fibers may be any form of aluminum oxide phase and may be obtained using any suitable process. The aluminum oxide fibers may generally be in a cylindrical shape and / or a flat shape. The length of the aluminum oxide fibers may range from 1 mm to 10 mm, and the diameter or width may range from 1 μm to 15 μm. In certain applications, the length of the aluminum oxide fibers may be at least 1.0 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm, 2.0 mm, 2.1 mm, 2.2 mm, 2.3 mm, 2.4 mm, 2.5 mm, 2.6 mm, 2.7 mm, 2.8 mm, 2.9 mm, 3.0 mm, 3.1 mm, 3.2 mm, 3.3 mm, 3.4 mm, 3.5 mm, 3.6 mm, 3.7 mm, 3.8 mm, 3.9 mm, 4.0 mm, 4.1 mm, 4.2 mm, 4.3 mm, 4.4 mm, 4.5 mm, 4.6 mm, 4.7 mm, 4.8 mm, 4.9 mm, 5.0 mm, 5.1 mm, 5.2 mm, 5.3 mm, 5.4 mm, 5.5 mm, 5.6 mm, 5.7 mm, 5.8 mm, 5.9 mm, 6.0 mm, 6.1 mm, 6.2 mm, 6.3 mm, 6.4 mm, 6.5 mm, 6.6 mm, 6.7 mm, 6.8 mm, 6.9 mm, and 7.0 mm, 7.1 mm, 7.2 mm, 7.3 mm, 7.4 mm, 7.5 mm, 7.6 mm, 7.7 mm, 7.8 mm, 7.9 mm, 8.0 mm, 8.1 mm, 8.2 mm, 8.3 mm, 8.4 mm, 8.5 mm, 8.6 mm, 8.7 mm, 8.8 mm, 8.9 mm, 9.0 mm, 9.1 mm, 9.2 mm, 9.3 mm, 9.4 mm, 9.5 mm, 9.6 mm, 9.7 mm, 9.8 mm, 9.9 mm, and 10.0 mm, values equal to the above values, and / or values between any two of the above values. The width or diameter of the aluminum oxide fibers may be at least 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, and 15 μm, values equal to the above values, and / or values between any two of the above values.Examples of commercially available aluminum oxide fibers include aluminum oxide fibers available as 3M's Nextel 610 fibers in Maplewood, Minnesota.

[0053] The aluminum oxide fibers may be present in the PBT composition in an amount of 40 wt% or less based on the total weight of the PBT composition. When used, in certain embodiments, the aluminum oxide fibers are at least 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt% and 40 wt% based on the total weight of the PBT composition, an amount equal to the above amount, and / or an amount between any two of the above amounts.

[0054] In certain applications, polyethylene terephthalate (PET) is used with PBT. The PET used has an intrinsic viscosity in the range of 0.5 dl / g to 0.8 dl / g, and a density of 800 kg / m 3 ~850 kg / m 3It can be characterized by the bulk density according to ASTM D1895 within the range. When used, the amount of any PET component is present in an amount of 30 wt% or less based on the total weight of the composition. In certain embodiments, when used, PET is at least 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 29 wt%, and 30 wt% based on the total weight of the PBT composition, an amount equal to the above amount, and / or an amount between any two of the above amounts may be used. Examples of commercially available such PETs are PETs available as BC210, BC211, BC212, PCG 60 and PCG 80 of Saudi Basic Industries Corporation in Riyadh, Saudi Arabia. In certain applications, PET is not used in the PBT composition.

[0055] Polycarbonate can also be used in the PBT composition. The weight average molecular weight of the polycarbonate inferred from gel permeation chromatography is in the range of 30,000 to 60,000 on a polystyrene basis. As inferred from NMR analysis, the polycarbonate is completely end-capped. The polycarbonate can improve metal adhesion and reduce warping. Examples of the polycarbonate include, but are not limited to, bisphenol A type polycarbonate and copolycarbonates obtained by varying the ratios of different comonomers (e.g., 20% to 50%). Particularly useful is bisphenol A type polycarbonate.

[0056] The polycarbonate may be used in an amount of 30% by weight or less based on the total weight of the PBT composition, with or without a transesterification catalyst. When used, in certain embodiments, the polycarbonate is at least 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, and 30% by weight based on the total weight of the PBT composition, an amount equal to the above amount, and / or an amount between any two of the above amounts.

[0057] The PBT composition or polymer blend formed during melt compounding can further include at least one additional secondary additive that is distinct from the primary additives described above. The optional or secondary additive may be an additive that does not necessarily affect or increase the dielectric properties (i.e., Dk value and Df value), mechanical properties, or thermal properties of the final product, but there is a possibility of affecting or increasing them. The optional or secondary additive may be added to facilitate processing during the melt compounding and extrusion processes, but may also impart various desired properties to the final PBT composition. Non-limiting examples of additional optional or secondary additives include stabilizers, coupling agents, compatibilizers, thermal conductivity agents, flame retardant additives, thermal conductivity additives, binders, anti-blocking agents, antistatic agents, antioxidants, neutralizing agents, acid scavengers, foaming agents, nucleating agents, crystallization aids, dyes, flame retardants, fillers, hard fillers, soft fillers, impact modifiers, release agents, oils, other polymers, pigments, processing aids, reinforcing agents, light stabilizers, UV resistant agents, lubricants, flow improvers, and combinations thereof.

[0058] Since PBT has polar functional groups throughout the polymer chain, PBT may make it easier to disperse glass bubbles, glass fibers, polycarbonate, etc. throughout the polymer blend. Therefore, in order to achieve a good interface between the glass bubbles and the fibers, the use of coupling agents in the polymer blend can be reduced or eliminated. However, in certain embodiments, coupling agents may be used within the PBT component or the glass fibers. By treating the glass fibers with a silane coupling agent, the uniform dispersion of these materials within the PBT matrix can be further enhanced. The coupling agent may be maleic anhydride grafted PBT (MA-g-PP). The coupling is carried out in situ in the extruder. The use of this coupling agent promotes the dispersion of the glass fibers due to the interaction between the maleic anhydride groups and the amino groups of the aminosilane-treated glass fibers. Examples of coupling agents suitable for PBT include maleic anhydride grafted PBT (MA-g-PP) available as Exxon Mobil's EXELOR P1020. The coupling agent may be present in the polymer blend in an amount of 2 wt% or less based on the total weight of the polymer blend. In certain embodiments, when used, the coupling agent may be used in an amount of at least 0.01 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, and 2.0 wt% based on the total weight of the polymer blend, an amount equal to the above amounts, and / or an amount between any two of the above amounts. When blending polycarbonate with PBT, a transesterification reaction catalyst such as p-toluenesulfonic acid may be added to enable reactive coupling between PBT and polycarbonate. The amount of the transesterification reaction catalyst may be in the range of 0.001 wt% to 0.01 wt% based on the total weight of the polymer blend.

[0059] In some cases, the thermal conductivity additive is present in the polymer blend in an amount from at least 0.01 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, and 1.0 wt% based on the total weight of the polymer blend, an amount equal to the above amount, and / or an amount between any two of the above amounts. Non-limiting examples of the thermal conductivity additive include aluminum oxide, titanium dioxide, graphite compounds, graphene, boron nitride, aluminum nitride, zinc oxide, and the like.

[0060] In some embodiments, the filler is present in the polymer blend in an amount from at least 0.01 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 2.0 wt%, 3.0 wt%, 4.0 wt%, 5.0 wt%, 6.0 wt%, 7.0 wt%, 8.0 wt%, 9.0 wt%, 10.0 wt%, 20.0 wt%, 30.0 wt% based on the total weight of the polymer blend, an amount equal to the above amount, and / or an amount between any two of the above amounts. The filler can be a hard filler. Non-limiting examples of the hard filler include inorganic particulate fillers such as talc, silica, calcium carbonate, and inorganic layered fillers such as clay, mica, and the like. The filler can be a soft filler. Non-limiting examples of the soft filler include immiscible particulate elastomer / polymer resins. The filler can also be a hollow filler. Non-limiting examples of the hollow filler include plastic microspheres, ceramic microspheres such as cenospheres made from aluminosilicate microspheres, metal microspheres made from aluminum and copper / silver microspheres, and phenolic microspheres.

[0061] In certain embodiments, the light stabilizer is present in the polymer blend in an amount from at least 0.01 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, and 1.0 wt% based on the total weight of the polymer blend, an amount equal to the above amounts, and / or an amount between any two of the above amounts. The light stabilizer can be a hindered amine light stabilizer. The term "hindered amine light stabilizer" refers to a group of amine compounds having specific light stabilizing properties. Non-limiting examples of hindered amine light stabilizers (HALS) include 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine; bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(1-acetoxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate; bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(1-acyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate; 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino]-6-(2-hydroxyethylamino-s-triazine; bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate; 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl) butylamino]-6-chloro-s-triazine; 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine; 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine; 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine;Bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; Bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) adipate; 2,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethylamino)-s-triazine; 4-benzoyl-2,2,6,6-tetramethylpiperidine; Di-(1,2,2,6,6-pentamethylpiperidin-4-yl) p-methoxybenzylidene malonate; 2,2,6,6-tetramethylpiperidin-4-yl octadecanoate; Bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate; 1,2,2,6,6-pentamethyl-4-aminopiperidine; 2-undecyl l-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane; Tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate; Tris(2-hydroxy-3-(amino-(2,2,6,6-tetramethylpiperidin-4-yl)propyl) nitrilotriacetate; Tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate; Tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate; 1,1’-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone); 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione; 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione; 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione; 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione; N,N’-bis-formyl-N,N’-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine;Reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-triazine and N,N'-bis(3-aminopropyl)ethylenediamine; condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid; condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine; condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; condensate of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine; condensate of N,N'-bis-(1,2,2,6,6-pentamethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine; condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane; condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane; reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane and epichlorohydrin; poly[methyl,(3-oxy-(2,2,6,6-tetramethylpiperidin-4-yl)propyl)]siloxane, CAS#182635-99-0; reaction product of maleic anhydride-C18-C22-α-olefin-copolymer and 2,2,6,6-tetramethyl-4-aminopiperidine; oligomeric condensate of 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine;Oligomeric condensates of 4,4'-hexamethylenebis(amino-1,2,2,6,6-pentamethylpiperidine) and 2,4-dichloro-6-[(1,2,2,6,6-pentamethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine; oligomeric condensates of 4,4'-hexamethylenebis(amino-1-propoxy-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine; oligomeric condensates of 4,4'-hexamethylenebis(amino-1-acryloyloxy-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-acryloyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine; and products obtained by reacting (a) and (b), wherein (a) is a product obtained by reacting 1,2-bis(3-aminopropylamino)ethane with cyanuric chloride, and (b) is (2,2,6,6-tetramethylpiperidin-4-yl)butylamine, are included. Also included are sterically hindered N-H, N-methyl, N-methoxy, N-hydroxy, N-propoxy, N-octyloxy, N-cyclohexyloxy, N-acryloyloxy and N-(2-hydroxy-2-methylpropoxy) analogs of any of the above compounds. Non-limiting examples of commercially available light stabilizers are available under the trade names Uvinul® 4050H, 4077H, 4092H, 5062H, 5050H, 4092H, 4077H, 3026, 3027, 3028, 3029, 3033P, and 3034 from BASF or Tinuvin® 622.;

[0062] The antistatic agent can be used to suppress the accumulation of dust on plastic articles. The antistatic agent can improve the electrical conductivity of the plastic composition and eliminate any surface charges generated during manufacturing and use. Therefore, dust particles are less likely to be attracted to the surface of the plastic article, and as a result, the accumulation of dust is reduced. In a particular embodiment of the present invention, the antistatic agent can be glycerol monostearate. The polymer blend may contain the antistatic agent in an amount from at least 0.01 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, and 1 wt% based on the total weight of the polymer blend, an amount equal to the above amount, and / or an amount between any two of the above amounts.

[0063] To improve the mold manufacturing characteristics, a lubricant can be added to the polymer blend. The lubricant can be a low molecular weight compound from the group of fatty acids, fatty acid esters, wax esters, fatty alcohol esters, amide waxes, metal carboxylates, montanic acid, montanic acid esters, or a high molecular weight compound such as paraffin or polyethylene wax. In a particular embodiment of the present invention, the lubricant is a metal stearate. Non-limiting examples of metal stearates include zinc stearate, calcium stearate, lithium stearate, or combinations thereof, preferably calcium stearate. The polymer blend may contain the lubricant in an amount from at least 0.01 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, and 1 wt% based on the total weight of the polymer blend, an amount equal to the above amount, and / or an amount between any two points of the above amounts.

[0064] Antioxidants and / or heat stabilizers can provide protection against polymer degradation during processing. Phosphites are known as heat-oxidation stabilizers for polymers and other organic materials. The antioxidant can be a phosphite-based antioxidant. In certain embodiments, phosphite-based antioxidants include, but are not limited to, triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, and tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite. The polymer blend can contain the antioxidant in an amount of at least 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, and amounts from 0.1 wt%, an amount equal to the above amounts, and / or amounts between any two of the above amounts, based on the total weight of the polymer blend. Non-limiting examples of commercially available antioxidants or heat stabilizers include Irganox 1010 and Irgaphos-168 available from BASF, or Doverphos S9228T available from the Dover Chemical Company.

[0065] Nucleating agents may also be used in the polymer blend. The nucleating agent may be considered as an additive added to the polymer to promote crystal growth in the polymer melt. One or more nucleating agents may be used. The nucleating agent may include, but is not limited to, cyclic dicarboxylates and talc. Talc is often used as a filler when used in large amounts. Talc acts as a nucleating agent when used in a low amount (i.e., <5 wt%). The use of a combination of a cyclic dicarboxylate as the first nucleating agent and talc as the second nucleating agent is described in U.S. Patent No. 11,136,446, which is incorporated herein by reference for all purposes. When using such a combination, the nucleating agent may be used in various amounts. For example, the weight ratio of the cyclic dicarboxylate to talc may range from 1:1200 to 2:1. The cyclic dicarboxylate may be used in an amount of 0.0025 wt% to 0.1 wt% based on the total weight of the composition, and the talc nucleating agent may be used in an amount of 0.1 wt% to 5 wt%. Examples of suitable commercially available potassium salts of 1,2-cyclohexanedicarboxylic acid useful as nucleating agents include the potassium salt available as HYPERFORM® HPN 20E from Milliken and Company.

[0066] When forming the PBT composition, the various components of the PBT composition containing the primary additives described can be dry blended with any additional secondary additives. The PBT component may be in the form of pellets, powder, flakes or fluff. The materials are mixed in a conventional mixer, and the PBT and the primary additives are mixed with any additional additives or secondary additives. Any secondary additives can be added at the end or during the processing steps for manufacturing the polymer blend. Suitable machines for such mixing are known to those skilled in the art. Non-limiting examples include mixers, kneaders and extruders. These materials are then fed directly into the feed zone of the extruder. In certain cases, the process can be carried out in an extruder, and the introduction of the additives may be carried out during processing. Non-limiting examples of suitable extruders include single-screw extruders, counter-rotating and co-rotating twin-screw extruders, planetary gear extruders, ring extruders, or co-kneaders. The process can be carried out at a temperature of 240°C to 300°C.

[0067] In some embodiments, the PBT component, the primary additive, and any secondary additives used to produce the PBT polymer blend of the present invention can be melt extruded according to a typical procedure of weighing the required amounts of PBT and additives, then dry blending, and then feeding the mixture into the main feeder of a single-screw or co-rotating twin-screw extruder (length / diameter (L / D) ratio of 25:1 or 40:1) to obtain the final composition. The PBT, the additives, or their blend can be subjected to a high temperature for a sufficient time in the blend. The blend temperature can be a temperature above the melting point of the polymer. In certain embodiments, the extrusion process can be carried out at a temperature of 240°C to 300°C. The primary additive and the secondary additive can be added in-line before the pelletization of the PBT resin during the manufacturing process. The amount of the additive combined with the PBT can be adjusted to provide the weights described above.

[0068] Any secondary additive can be premixed with the polymer blend or its various components or added individually. As an example, by premixing the secondary additives of the present invention, a blend can be formed before adding to PBT or the primary additives. The blend can be subjected to high temperature for a sufficient time during blending of the additives and / or compounding. Incorporation of any secondary additive into the polymer resin can be carried out, for example, by mixing the above components using methods conventional in the process art. The blending temperature can be a temperature exceeding the melting point of the PBT polymer. In a particular embodiment, the process can be carried out at a temperature of 240 °C to 270 °C. By such "melt-kneading" or "melt-mixing", the optional additive is uniformly dispersed in the PBT and / or the primary additives.

[0069] Articles manufactured from the PBT composition prepared as described can be used in high-frequency radio wave applications above 6 GHz. In particular, the PBT and / or articles molded therefrom may have a Dk value of 3.1, 3.0, 2.9, 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, or 2.0 or less when measured at 6 GHz or above. Also, the PBT and / or articles molded therefrom may have a Df value of 0.005, 0.004, 0.003, 0.002, 0.001, 0.0005 or less when measured at 6 GHz or above.

[0070] Furthermore, the PBT composition and / or an article formed therefrom may have a metal adhesion peel strength measured according to ASTM B533 or IPC-TM-650 of 0.1 N / mm, 0.2 N / mm, 0.3 N / mm, 0.4 N / mm, 0.5 N / mm or more. The PBT composition or an article formed therefrom may have a CTE measured according to ASTM D696 of 35 ppm / °C, 30 ppm / °C, 25 ppm / °C, 20 ppm / °C, 15 ppm / °C, 10 ppm / °C, 5 ppm / °C or less. Further, the PBT composition and / or an article formed therefrom may have a HDT measured at 1.8 MPa according to ASTM D648 of 150 °C, 160 °C, 170 °C, 180 °C, 190 °C, 200 °C, 210 °C, 220 °C or more.

[0071] Also, the PBT composition or article may have a water absorption rate measured according to ASTM D570 of 0.05 wt%, 0.04 wt%, 0.03 wt%, 0.02 wt%, 0.01 wt% or less based on the total weight. The composition or article may also have a tensile modulus measured according to ASTM D638 of 2000 MPa, 2100 MPa, 2200 MPa, 2300 MPa, 2400 MPa, 2500 MPa, 2600 MPa, 2700 MPa, 2800 MPa, 2900 MPa, 3000 MPa, 3100 MPa, 3200 MPa, 3300 MPa, 3400 MPa, 3500 MPa, 3600 MPa, 3700 MPa, 3800 MPa, 3900 MPa, 4000 MPa, 4100 MPa, 4200 MPa, 4300 MPa, 4400 MPa, 4500 MPa, 4600 MPa, 4700 MPa, 4800 MPa, 4900 MPa, 5000 MPa, 5100 MPa, 5200 MPa, 5300 MPa, 5400 MPa, 5500 MPa, 5600 MPa, 5700 MPa, 5800 MPa, 5900 MPa, 6000 MPa, 6100 MPa, 6200 MPa, 6300 MPa, 6400 MPa, 6500 MPa, 6600 MPa, 6700 MPa, 6800 MPa, 6900 MPa, 7000 MPa, 7100 MPa, 7200 MPa, 7300 MPa, 7400 MPa, 7500 MPa or more, and a tensile strength measured according to ASTM D638 of 35 MPa, 40 MPa, 45 MPa, 50 MPa, 55 MPa, 60 MPa, 65 MPa, 70 MPa, 75 MPa, 80 MPa, 85 MPa, 90 MPa, 95 MPa, 100 MPa, 105 MPa, 110 MPa, 115 MPa, 120 MPa or more.

[0072] The PBT composition may have a density of 1.4 g / cc, 1.3 g / cc or less. Further, the composition may have a UL94 flame retardancy grade of V0@1.5 mm and a thermal conductivity measured according to ASTM C518 of 0.05 W / mK, 0.1 W / mK, 0.15 W / mK, 0.2 W / mK, 0.25 W / mK, 0.3 W / mK, 0.35 W / mK, 0.4 W / mK, 0.45 W / mK, 0.5 W / mK or more.

[0073] The PBT composition may be useful for specific applications at service temperatures from -40°C to 210°C or higher.

[0074] The compositions of the present disclosure can "comprise", "consist essentially of", or "consist of" the specific ingredients, components, compositions, etc. disclosed throughout this specification.

[0075] The PBT composition formed as described is typically recovered as pellets, which can be stored for some time or used immediately in the molding process. Examples of the molding process include injection molding, blow molding, compression molding, sheet extrusion, film blowing, pipe extrusion, profile extrusion, calendering, thermoforming, rotomolding, or combinations thereof. The finally formed PBT articles can be articles used in high-frequency radio wave applications of 6 GHz or higher. These articles include, for example, telecommunications equipment or components, high-frequency (>6 GHz) electrical equipment, high-frequency (>6 GHz) multi-generation telecommunications equipment or components, electrical communication antennas and end-use equipment or components of 5G or higher generations, telecommunications equipment housings, radome covers, high-frequency (RF) filters, RF connectors, EMI shields, antenna substrates, waveguide substrates or carriers, antenna substrates of base station antennas, and automotive radar components.

[0076] Although the present invention has been shown in several aspects, it will be apparent to those skilled in the art that the present invention is not so limited, and various changes and modifications can be made without departing from the scope of the present invention based on other optimizations considering experimental data or the economy of the whole process. Therefore, the appended claims should be construed broadly and appropriately so as not to conflict with the scope of the present invention.

Claims

1. Polybutylene terephthalate and Hollow glass bubbles with an average diameter of 5 microns to 80 microns, A polybutylene terephthalate composition for use in high-frequency radio wave applications of 6 GHz or higher, comprising a mixture of at least one glass fiber having a length of 0.5 mm to 10 mm and a width or diameter of 5 microns to 15 microns, aluminum oxide fiber having a length of 1 mm to 5 mm and a width or diameter of 1 micron to 30 microns, polyethylene terephthalate, and polycarbonate.

2. The composition according to claim 1, wherein the composition contains the above-mentioned hollow glass bubbles in an amount of 1% to 35% by weight.

3. The composition according to claim 1 or 2, wherein the hollow glass bubble has at least one of the following: Crushing strength of 30 MPa or more, as measured by QCM; True density of 0.3 g / cc to 0.8 g / cc as measured by helium pycnometry; and, The amount of gas between 50% and 90%, as measured by QCM.

4. The composition according to claim 1 or 2, wherein the composition contains the glass fibers in an amount of 40% by weight or less relative to the total weight of the composition.

5. The composition according to claim 1 or 2, wherein the above-mentioned glass fibers have at least one of the following: Dielectric constant (Dk) of 6 or less, measured at 6 MHz or above according to ASTM D150. Dielectric loss tangent (Df) of 0.005 or less, measured at 6 MHz or above according to ASTM D150, and Measured according to ASTM D696, 35 × 10 －６ The coefficient of thermal expansion (CTE) of less than or equal to 1°C.

6. The composition according to claim 1 or 2, wherein the composition contains aluminum oxide fibers in an amount of 40% by weight or less relative to the total weight of the composition.

7. The composition according to claim 1 or 2, wherein the polybutylene terephthalate is a low-IV resin having an intrinsic viscosity (IV) of 1.4 dl / g or less, measured in a dilute solution using a capillary viscometer according to the ISO-1628-5 protocol, or a high-IV resin having an IV of 1.5 dl / g or more, or a mixture thereof.

8. The composition according to claim 1 or 2, wherein the composition contains polycarbonate in an amount of 30% by weight or less relative to the total weight of the composition.

9. The composition according to claim 1 or 2, wherein the composition contains polyethylene terephthalate in an amount of 30% by weight or less relative to the total weight of the composition.

10. The composition according to claim 1 or 2, further comprising at least one of the following: stabilizers, coupling agents, nucleating agents, thermal conductive agents, flame retardant additives, thermal conductive additives, binders, blocking inhibitors, antistatic agents, antioxidants, neutralizing agents, acid scavengers, foaming agents, crystallization aids, dyes, flame retardants, fillers, rigid fillers, flexible fillers, impact modifiers, mold release agents, oils, other polymers, pigments, processing agents, reinforcing agents, light stabilizers, UV resistant agents, lubricants, flow modifiers, and combinations thereof.

11. The polybutylene terephthalate composition described above has a Dk value of 2.5 or less when measured at 6 GHz or higher, a Df value of 0.005 or less when measured at 6 GHz or higher, and has at least one of the following: Metal adhesive peel strength of 0.1 N / mm or greater, as measured according to ASTM B533 or IPC-TM-650; A coefficient of thermal expansion (CTE) of 35 ppm / °C or less, measured according to ASTM D696; Heat distortion temperature (HDT) of 200°C or higher, as measured according to ASTM D648; Water absorption rate of 0.05% by weight or less, as measured according to ASTM D570; Tensile modulus of 2000 MPa or greater, as measured according to ASTM D638; Tensile strength of 35 MPa or greater, as measured according to ASTM D638; Density of 1.4 g / cc or less; V0@1.5mm UL94 flame retardant grade; and, Thermal conductivity of 0.3 W / mK or greater, measured according to ASTM C518.

12. The composition according to claim 1 or 2, wherein the polybutylene terephthalate composition is molded into a manufactured article.

13. The composition according to claim 12, wherein the manufactured article is at least one of the following: telecommunications equipment or components, high-frequency (>6GHz) electrical equipment, high-frequency (>6GHz) multi-generation telecommunications equipment or components, 5G or higher generation telecommunications equipment or components, telecommunications equipment housing, radome cover, high-frequency (RF) filter, RF connector, EMI shield, antenna substrate, waveguide substrate or carrier, antenna substrate for base station antenna, and automotive radar components.

14. Hollow glass bubbles with an average diameter of 5 microns to 80 microns, A material comprising glass fibers having a length of 0.5 mm to 10 mm and a width or diameter of 5 microns to 15 microns, aluminum oxide fibers having a length of 1 mm to 5 mm and a width or diameter of 1 micron to 30 microns, and at least one of polycarbonate, A method for forming a polybutylene terephthalate composition for use in high-frequency radio wave applications of 6 GHz or higher, comprising modifying polybutylene terephthalate by melt-kneading it with polybutylene terephthalate, thereby dispersing the above material throughout the polybutylene terephthalate.