LOW LOSS FACTOR THERMOPLASTIC COMPOSITIONS FOR NANOFORMING TECHNOLOGY APPLICATIONS

Description

FIELD OF THE DISCLOSURE

[0001] The present disclosure relates to polyester-based compositions having good dielectric properties suitable for use in nano molding technology (NMT) applications.BACKGROUND OF THE DISCLOSURE

[0002] Nano molding technology (NMT) is an innovative technology wherein plastic resins are integrated with metal through convenient injection molding processes. Because of the features like excellent metal bonding reliability, high productivity, good cost efficiency, etc., NMT materials have been widely used in the consumer electronics industry, especially in antenna split solutions in the mobile devices and tablets. These materials offer good waterproof performance and antenna efficiency. Polybutylene terephthalate (PBT), Polyphenylene sulfide (PPS), and Polyamide (PA) are primarily used in the NMT process. However, with the most balanced overall performance, for example high metal bonding strength, good color-ability and color stability (or chemical resistance) etc., PBT has become the most popular base resin in the NMT market.

[0003] The 5G telecommunications standard is in effect. The high working frequency of the 5G network imposes new and different requirements on the materials used in 5G devices. In general, materials with low dielectric constant (Dk) and low dissipation factor (Df) are desired due to their low influence on the RF efficiency and high benefit to antenna performance. Some solutions for low Dk NMT compositions have been reported. For example, PCT application WO 2019 / 130269 (SABIC) describes a technology for PBT-based compositions including a low Dk glass fiber and hollow filler as the filler group. CN107365480A (Jianghe Material Tech) describes high heat resistant low Dk compositions including poly(cyclohexanedimethylene terephthalate) (PCT) as the base resin. Conventional compositions having an ultra-low Df (less than 0.007 at greater than 1 GHz) have not been identified, however. For example, PBT has a Df of around 0.006 at 1.9 GHz, but the Df increases as additives are incorporated into the PBT composition. It is thus very challenging to maintain the Df of polyester-based NMT compositions at an ultra-low level.

[0004] US Patent Publication US2020 / 0140679 A1 describes thermoplastic compositions comprising: from about 15 wt. % to about 80 wt. % of a polymer resin; and from about 10 wt. % to about 50 wt. % of a low dielectric constant glass fiber component, wherein the low dielectric constant glass fiber component has a Dk of less than 5.0 at a frequency of from 1 MHz to 1 GHz and a Df of less than about 0.002 at a frequency of from 1 MHz to 1 GHz; from about 3 wt. % to 40 wt. % of a hollow filler; and from about 0.1 wt. % to about 10 wt. % of an impact modifier, wherein the thermoplastic composition exhibits a dielectric constant of less than 3.2 at a frequency of 1.9 GHz when tested using a split post dielectric resonator and network analyzer on a sample size of 100 mm by 70 mm and 1.6 mm thickness; wherein the thermoplastic composition exhibits a dissipation factor Df of less than 0.01 at a frequency of 1.9 GHz when tested using a split post dielectric resonator and network analyzer on a sample size of 100 mm by 70 mm and 1.6 mm thickness, wherein the thermoplastic composition exhibits a nano-molding technology bonding strength of at least 18 MPa when tested in accordance with a bonding strength test adapted from ISO 19095 with a T treatment, wherein the thermoplastic composition exhibits a notched impact strength of at least 70 J / m when tested in accordance with ASTM D256 at 23° C., wherein the thermoplastic composition exhibits a flow rate of less than 25 cm3 / 10 min when tested in accordance with ISO 1133 at 275° C. at 5 kg and 300 seconds

[0005] US Patent Publication 2015 / 0368458 A1 describes blended thermoplastic compositions comprising at least one polycarbonate component, at least one polybutylene component, at least one polyester ether elastomer component, at least one poly(ethylene-co-ethylacrylate) component, at least one ethylene / alkyl acrylate / glycidyl methacrylate terpolymer component, and at least one glass fiber component. The thermal blended polycarbonate compositions can optionally further comprise a transesterification quenching agent and / or epoxy hydrostabilizer agent. The resulting compositions can be used in the manufacture of articles requiring materials that have high impact strength yet have very high stiffness, while retaining desired dielectric properties and are colorable from white to black.

[0006] US Patent Publication 2012 / 0184661 A1 describes a thermoplastic composition comprising, based on the total weight of the composition, (a) from 10 to 80 wt. % of a polybutylene terephthalate; (b) from 10 to 80 wt. % of a copolyestercarbonate having a number average molecular weight of more than 21,500 Daltons; (c) from 7 to 30 wt. % of a particulate filler; (d) from 0.1 to 10 wt. % of a fluoropolymer; and (e) from 3 to 25 wt. % of a polymeric impact modifier.

[0007] PCT Publication WO2017 / 093232 A1 describes a thermoplastic composition comprising: 0 to 50 weight percent of a polycarbonate; 10 to 50 weight percent of a polyester carbonate copolymer; 5 to 20 weight percent of a poly(ethylene terephthalate); 20 to 50 weight percent of a poly(butylene terephthalate); and optionally 5 to 30 weight percent of an impact modifier wherein weight percent is based on the combined amounts of polycarbonate, polyester carbonate copolymer, poly(ethylene terephthalate), poly(butylene terephthalate) and optional impact modifier.

[0008] EP Publication EP1979403 A1 describes an article derived from a molding composition containing: (a) from 5 to 99.99 wt% of a modified polybutylene terephthalate random copolymer; (b) a member selected from the group consisting of (1) fillers, (2) carboxy reactive materials (3) polyalkylene terephthalates, (4) combinations of polycarbonates and impact modifier, (5) impact modifiers, (6) polycarbonates, and (7) combinations thereof; wherein the amount of (1) fillers is at least 0.5 wt.% when the fillers are selected from the group consisting of glass fillers, ceramic fillers, carbon fillers, metal fillers, mineral fillers, nano-fillers, nano-composites, nano-tubes, talc and combinations thereof, and is less than 0.5 wt.% when the fillers are nano-tubes or nano-fillers, (2) carboxy reactive materials ranges from 0.01 - 30 wt.%, (3) polyalkylene terephthalates ranges from 1 - 80 wt.%, (5) impact modifiers ranges from 1 - 50 wt.%, (6) polycarbonates ranges from 5 - 90 wt.%, and when the member is (4) a combination of polycarbonates and impact modifiers, the polycarbonate is present in an amount ranging from 5 to 90 wt%; and the impact modifier is present in an amount that is at least 1 wt. %.

[0009] These and other shortcomings are addressed by aspects of the present disclosure.SUMMARY

[0010] In its main embodiment, encompassed by claim 1, the instant invention is directed to a thermoplastic composition including: (a) a polyester component; (b) a polycarbonate copolymer component including a polycarbonate-dimethyl bisphenol cyclohexane copolymer (DMBPC) comprising at least 50 mol% dimethyl bisphenol cyclohexane monomer; (c) an impact modifier component including a copolymer including two monomers; and (d) a glass fiber component.

[0011] In specific embodiments, the thermoplastic composition includes: from 30 wt% to 80 wt% of the polyester component; from 3 wt% to 30 wt% of the polycarbonate copolymer component; from 5 wt% to 20 wt% of the impact modifier component; and from 10 wt% to 50 wt% of the glass fiber component. The combined weight percent value of all components does not exceed 100 wt%, and all weight percent values are based on the total weight of the composition.DETAILED DESCRIPTION

[0012] This publication discloses a novel solution which offers thermoplastic compositions with ultra-low dielectric dissipation factor (Df) and good mechanical performance used in Nano Molding Technology (NMT) for electronics and / or telecommunication related applications.

[0013] The present invention can be understood more readily by reference to the following detailed description of the invention and the Examples included therein. In its main embodiment, the present invention pertains to thermoplastic compositions including: (a) a polyester component; (b) a polycarbonate copolymer component including a polycarbonate-dimethyl bisphenol cyclohexane copolymer (DMBPC), comprising at least 50 mol% dimethyl bisphenol cyclohexane monomer; (c) an impact modifier component including a copolymer including two monomers; and (d) a glass fiber component.

[0014] Before the present compounds, compositions, articles, systems, devices, and / or methods are disclosed and described, it is to be understood that they are not limited to specific synthetic methods unless otherwise specified, or to particular reagents unless otherwise specified, as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.

[0015] Various combinations of elements of this disclosure are encompassed by this disclosure, e.g., combinations of elements from dependent claims that depend upon the same independent claim.

[0016] Moreover, it is to be understood that unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is in no way intended that an order be inferred, in any respect. This holds for any possible non-express basis for interpretation, including: matters of logic with respect to arrangement of steps or operational flow; plain meaning derived from grammatical organization or punctuation; and the number or type of aspects described in the specification.

[0017] All publications mentioned herein are quoted to disclose and describe the methods and / or materials in connection with which the publications are cited.Definitions

[0018] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and in the claims, the term "comprising" can include the aspects "consisting of" and "consisting essentially of." Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined herein.

[0019] As used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a polyester component" includes mixtures of two or more polyester components.

[0020] As used herein, the term "combination" is inclusive of blends, mixtures, alloys, reaction products, and the like.

[0021] Ranges can be expressed herein as from one value (first value) to another value (second value). When such a range is expressed, the range includes in some aspects one or both of the first value and the second value. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0022] . It is intended to convey that similar values promote equivalent results or effects recited in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. In general, an amount, size, formulation, parameter or other quantity or characteristic is "about" or "approximate" whether or not expressly stated to be such.

[0023] As used herein, the terms "optional" or "optionally" means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not. For example, the phrase "optional impact modifier" means that the impact modifier can or cannot be included and that the description includes compositions that both include and do not include an impact modifier.

[0024] Disclosed are the components to be used to prepare the compositions of the disclosure as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F and an example of a combination molecule, A-D is disclosed, then even if each is not individually recited each is individually and collectively contemplated meaning combinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are considered disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E would be considered disclosed. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions of the disclosure. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific aspect or combination of aspects of the methods of the disclosure.

[0025] References in the specification and concluding claims to parts by weight of a particular element or component in a composition or article, denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.

[0026] A weight percent of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.

[0027] As used herein, the terms "number average molecular weight" or "M n " can be used interchangeably, and refer to the statistical average molecular weight of all the polymer chains in the sample and is defined by the formula: M n = ∑ N i M i ∑ N i , where M i is the molecular weight of a chain and N i is the number of chains of that molecular weight. M n can be determined for polymers, e.g., polycarbonate polymers, by methods well known to a person having ordinary skill in the art using molecular weight standards, e.g. polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards.

[0028] As used herein, the terms "weight average molecular weight" or "M w " can be used interchangeably, and are defined by the formula: M w = ∑ N i M i 2 ∑ N i M i , where M i is the molecular weight of a chain and N i is the number of chains of that molecular weight. Compared to M n , M w takes into account the molecular weight of a given chain in determining contributions to the molecular weight average. Thus, the greater the molecular weight of a given chain, the more the chain contributes to the M w . M w can be determined for polymers, e.g., polycarbonate polymers, by methods well known to a person having ordinary skill in the art using molecular weight standards, e.g., polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards.

[0029] As used herein, the terms "polydispersity index" or "PDI" can be used interchangeably, and are defined by the formula: PDI = M w M n . The PDI has a value equal to or greater than 1, but as the polymer chains approach uniform chain length, the PDI approaches unity.

[0030] The terms "BisA," "BPA," or "bisphenol A," which can be used interchangeably, as used herein refers to a compound having a structure represented by the formula: BisA can also be referred to by the name 4,4'-(propane-2,2-diyl)diphenol; p,p'-isopropylidenebisphenol; or 2,2-bis(4-hydroxyphenyl)propane. BisA has the CAS # 80-05-7.

[0031] As used herein, "polycarbonate" refers to an oligomer or polymer including residues of one or more dihydroxy compounds, e.g., dihydroxy aromatic compounds, joined by carbonate linkages; it also encompasses homopolycarbonates, copolycarbonates, and (co)polyester carbonates.

[0032] The terms "residues" and "structural units", used in reference to the constituents of the polymers, are synonymous throughout the specification.

[0033] As used herein the terms "weight percent," "wt%," and "wt. %," which can be used interchangeably, indicate the percent by weight of a given component based on the total weight of the composition, unless otherwise specified. That is, unless otherwise specified, all wt% values are based on the total weight of the composition. It should be understood that the sum of wt% values for all components in a disclosed composition or formulation are equal to 100.

[0034] Unless otherwise stated to the contrary herein, all test standards are the most recent standard in effect at the time of filing this application.

[0035] Each of the materials disclosed herein are either commercially available and / or the methods for the production thereof are known to those of skill in the art.

[0036] It is understood that the compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.Thermoplastic Compositions

[0037] In its main embodiment, the present invention relates to a thermoplastic composition including: (a) a polyester component; (b) a polycarbonate copolymer component including a polycarbonate-dimethyl bisphenol cyclohexane copolymer (DMBPC) comprising at least 50 mol% dimethyl bisphenol cyclohexane monomer; (c) an impact modifier component including a copolymer including two monomers; and (d) a glass fiber component. In particular embodiments the thermoplastic composition includes: from 30 wt% to 80 wt% of the polyester component; from 3 wt% to 30 wt% of the polycarbonate copolymer component; from 5 wt% to 20 wt% of the impact modifier component; and from 10 wt% to 50 wt% of the glass fiber component. The combined weight percent value of all components does not exceed 100 wt%, and all weight percent values are based on the total weight of the composition.

[0038] In some embodiments the polyester component includes polybutylene terephthalate (PBT), polyethylene terephthalate (PET), poly(cyclohexylenedimethylene terephthalate) (PCT), polyethylene terephthalate glycol (PETG), polycyclohexylene dimethylene terephthalate glycol (PCTG), polycyclohexylene dimethylene terephthalate acid (PCTA), copolymers thereof, or a combination thereof. PCT is a crystalline polyester formed from cyclohexanedimethanol (CHDM) and either dimethyl terephthalate (DMT) or terephthalic acid (TPA). PETG and PCTG are copolyesters formed by including ethylene glycol (EG) in the polymerization reaction. PETG is formed if less than 50% of the diol content in the copolyester is CHDM; PCTG is formed if greater than 50% of the diol content in the copolyester is CHDM. PCTA is formed by including additional diacids such as isophthalic acid (IPA). In a particular embodiment the polyester component includes PBT.

[0039] The thermoplastic composition includes a polycarbonate copolymer component including a polycarbonate-dimethyl bisphenol cyclohexane copolymer (DMBPC) including at least 50 mol% dimethyl bisphenol cyclohexane monomer, as detailed below. In addition to said DMBPC component, the said polycarbonate copolymer component may include a polyester-polycarbonate copolymer. In a specific embodiment, the polyester unit is derived from the reaction of isophthalic acid, terephthalic acid, and resorcinol (also known as an ITR resin). The polyester unit has the following structure: where x corresponds to the molar ratio of the isophthalate, y corresponds to the molar ratio of the resorcinol, and z corresponds to the molar ratio of the terephthalate; x, y, and z adding to 100 percent of the polyester unit. Such polyester-polycarbonates are available as LEXAN ®< SLX resin from SABIC. The concentration of polyester (ITR) resin may be least 5%, based on the number of moles in the polymer. In further embodiments, the polyester and polycarbonate are used in a molar ratio of from about 5:95 to about 40:60 or more particularly from about 5:95 to about 35:65, depending on the properties desired. The polyester-polycarbonates may have a weight average molecular weight of from about 1,500 to about 100,000 or more particularly from about 2,000 to about 40,000. The polyester-polycarbonate polymer can be a copolymer, especially a block copolymer.

[0040] As outlined above, the polycarbonate copolymer component includes, as a compulsory component, a polycarbonate-dimethyl bisphenol cyclohexane copolymer (DMBPC) including at least 50 mol% dimethyl bisphenol cyclohexane monomer. DMBPC has the formula: wherein x and y represent the molar ratio of dimethyl bisphenol cyclohexane monomer and polycarbonate monomer, respectively. Thus when x is 50 y is also 50 and the copolymer includes 50 mol% dimethyl bisphenol cyclohexane monomer and 50 mol% polycarbonate monomer. In some embodiments x is from 50 to 100.

[0041] The impact modifier includes a copolymer including two monomers. In a particular embodiment the copolymer including two monomers includes an ethylene-glycidyl methacrylate copolymer. In some embodiments the copolymer is a diblock copolymer. In specific embodiments the impact modifier component does not include a terpolymer (such as but not limited to ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA)). In further embodiments the impact modifier component includes a copolymer consisting of two monomers. In yet further embodiments the impact modifier component consists of a copolymer consisting of two monomers.

[0042] In certain embodiments the composition includes from about 1 wt% to about 5 wt% of the ethylene-glycidyl methacrylate copolymer.

[0043] The glass fiber component may include in some embodiments a low Dk / Df glass fiber, such as but not limited to glass fiber having a Dk of less than 5.0 at 1 gigahertz (GHz) and a Df of less than 0.002 at 1 GHz, wherein Dk and Df are tested in accordance with ASTM D150.

[0044] In some embodiments the composition further includes an additional impact modifier including an ionomer, styrene-ethylene / 1-butene-styrene (SEBS), or a combination thereof. The ionomer in some embodiments includes but is not limited to zinc, sodium, magnesium, or calcium. In a particular embodiment the ionomer includes ethylene-acrylic acid zinc.

[0045] In further embodiments the composition further includes up to 10 wt% of a polyolefin additive. The polyolefin additive may include, but is not limited to, polypropylene (PP), polystyrene (PS), cyclic olefin copolymer (COC), or a combination thereof.

[0046] The thermoplastic composition has improved properties as compared to conventional NMT compositions. In specific embodiments the composition has a Df of less than 0.007 at a frequency of from 1 to 5 GHz when tested according to the SABIC Method. The "SABIC Method" for determining Dk and Df includes measuring these values using a QWED split post dielectric resonator and an Agilent network analyzer. For the 1.1 Gigahertz (GHz) measurement, the minimum sample size is 120 millimeter (mm) x 120 mm; the maximum sample thickness is 6 mm. For the 1.9 GHz measurement, the minimum sample size is 70 mm x 7 0mm; the maximum sample thickness is 4 mm. For the 5.0 GHz measurement, the minimum sample size is 30 mm x 30mm; the maximum sample thickness is 2 mm.Methods of Manufacture

[0047] The one or any foregoing components described herein may be first dry blended with each other, or dry blended with any combination of foregoing components, then fed into an extruder from one or multi-feeders, or separately fed into an extruder from one or multi-feeders. The fillers used in the disclosure may also be first processed into a masterbatch, then fed into an extruder. The components may be fed into the extruder from a throat hopper or any side feeders.

[0048] The extruders used in the disclosure may have a single screw, multiple screws, intermeshing co-rotating or counter rotating screws, non-intermeshing co-rotating or counter rotating screws, reciprocating screws, screws with pins, screws with screens, barrels with pins, rolls, rams, helical rotors, co-kneaders, disc-pack processors, various other types of extrusion equipment, or combinations including at least one of the foregoing.

[0049] The components may also be mixed together and then melt-blended to form the thermoplastic compositions. The melt blending of the components involves the use of shear force, extensional force, compressive force, ultrasonic energy, electromagnetic energy, thermal energy or combinations including at least one of the foregoing forces or forms of energy.

[0050] The barrel temperature on the extruder during compounding can be set at the temperature where at least a portion of the polymer has reached a temperature greater than or equal to about the melting temperature, if the resin is a semi-crystalline organic polymer, or the flow point (e.g., the glass transition temperature) if the resin is an amorphous resin.

[0051] The mixture including the foregoing mentioned components may be subject to multiple blending and forming steps if desirable. For example, the thermoplastic composition may first be extruded and formed into pellets. The pellets may then be fed into a molding machine where it may be formed into any desirable shape or product. Alternatively, the thermoplastic composition emanating from a single melt blender may be formed into sheets or strands and subjected to post-extrusion processes such as annealing, uniaxial or biaxial orientation.

[0052] The temperature of the melt in the present process may in some embodiments be maintained as low as possible in order to avoid excessive thermal degradation of the components. In certain embodiments the melt temperature is maintained between about 230°C and about 350°C, although higher temperatures can be used provided that the residence time of the resin in the processing equipment is kept relatively short. In some embodiments the melt processed composition exits processing equipment such as an extruder through small exit holes in a die. The resulting strands of molten resin may be cooled by passing the strands through a water bath. The cooled strands can be chopped into pellets for packaging and further handling.Articles of Manufacture

[0053] In certain embodiments, the present disclosure pertains to shaped, formed, or molded articles including the thermoplastic compositions. The thermoplastic compositions can be molded into useful shaped articles by a variety of means such as injection molding, extrusion, rotational molding, blow molding and thermoforming to form the articles. In a particular embodiment the article may be incorporated into an electronic or telecommunications device.

[0054] Various combinations of elements of this disclosure are encompassed by this disclosure, e.g., combinations of elements from dependent claims that depend upon the same independent claim.EXAMPLES

[0055] The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compositions claimed herein are made and evaluated, and are intended to be purely exemplary and are not intended to limit the disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric. Unless indicated otherwise, percentages referring to composition are in terms of wt%.

[0056] There are numerous variations and combinations of reaction conditions, e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions.

[0057] Compositions described herein were extruded and injection molded. A typical extrusion profile for the compositions is provided in Table 1: Table 1 - Extrusion Profile Parameters Unit Condition Compounder TypeNONETEM-37BSBarrel SizeMm1500DieMm4Zone 1 Temp°C100Zone 2 Temp°C200Zone 3 Temp°C250Zone 4 Temp°C250Zone 5 Temp°C250Zone 6 Temp°C260Zone 7 Temp°C260Zone 8 Temp°C260Zone 9 Temp°C260Zone 10 Temp°C260Zone 11 Temp°C260Die Temp°C260Screw speedRpm200Throughputkg / hr50Torque%80-90Vacuum 1Bar-0.08Side Feeder 1 speedRpm250Melt temperature°C265-275

[0058] The typical injection molding profile for the compositions is shown in Table 2: Table 2 -Molding Profile Parameters Unit Condition Pre-drying timeHour4Pre-drying temp°C120Molding MachineNONEFANUC, SE180Mold Type (insert)NONEASTM Tensile, Flexural, & Izod bars 100×70×1.6mm plaquesHopper temp°C50Zone 1 temp°C240Zone 2 temp°C250Zone 3 temp°C260Nozzle temp°C250Mold temp°C120Screw speedrpm100Back pressurekgf / cm 2< 30Cooling times20-30Injection speedmm / s50-100Holding pressurekgf / cm 2< 800-1000Max. Injection pressurekgf / cm 2< 1000-1500

[0059] Compositions were formed as shown in Table 3; the properties of these compositions are shown in Table 4: Table 3 - Comparative Compositions Item Description Unit C1.1 C1.2 C1.3 C1.4 PBT, low viscosity%33.233.233.233.2PBT, high viscosity%30303030SLX 90 / 10 PCP capped, copolymer%6666Kraton SEBS, G1651%129108Ethylene-Acrylic Acid Zinc Ionomer%2AX8840, Ethylene-glycidyl methacrylate copolymer%322CPIC low Dk glass fiber, ECS303N-3-K / HL%18181818Mono zinc phosphate%0.050.050.050.05Pentaerythritol tetrastearate%0.30.30.30.32-(2'hydroxy-5-t-octylphenyl)-benzotriazole%0.250.250.250.25Irganox 1010%0.10.10.10.1Hostanox P-EPQ P%0.10.10.10.1 Table 4 - Properties of the Compositions of Table 3 Typical Property Test Method Test Description Unit C1.1 C1.2 C1.3 C1.4 MVR275°C / 5kgASTM D1238cm 3< / 10 min37.717.823.618.2Bonding strengthT-treatmentISO 19095MPa26.429.028.729.9TRI-treatmentISO 19095MPa27.830.830.132.8Notched Izod23°C, 5 lbf / ftASTM D256J / m106142132152-20°C, 5 lbf / ftASTM D256J / m8110697114Un-notched Izod23°C, 5 lbf / ftASTM D256J / m7548377971030HDT1.82MPa / 3.2 mmASTM D648°C1741851831790.45MPa / 3.2 mmASTM D648°C213214214215Flexural Modulus3.2mm, 1.27mm / minASTM D790MPa4680464046404610Flexural Strength@break, 3.2mmASTM D790MPa129135134140Tensile Modulus5mm / minASTM D638MPa4989504250014978Tensile Strength@breakASTM D638MPa76807981Tensile Elongation@breakASTM D638%3.393.733.734.54Dk1.9 GHzSABIC Method / 2.9502.9472.9402.957Df1.9 GHzSABIC Method / 0.00580.00610.00600.0059Dk5.0 GHzSABIC Method / 2.9972.9932.9872.993Df5.0 GHzSABIC Method / 0.00520.00550.00540.0053

[0060] For all compositions tested the "SABIC Method" for determining Dk and Df includes measuring these values using a QWED split post dielectric resonator and an Agilent network analyzer. For the 1.1 Gigahertz (GHz) measurement, the minimum sample size is 120 millimeter (mm) x 120 mm; the maximum sample thickness is 6 mm. For the 1.9 GHz measurement, the minimum sample size is 70 mm x 7 0mm; the maximum sample thickness is 4 mm. For the 5.0 GHz measurement, the minimum sample size is 30 mm x 30mm; the maximum sample thickness is 2 mm.

[0061] As shown in Table 3; composition C1.1 was a control composition using PBT as the base resin. SLX90 / 10 is a bonding force promoter, SEBS is an impact modifier, and the filler is a low Dk glass fiber. Compositions C1.2-C1.4 were additional comparative compositions. Composition C1.2, with a total impact modifier loading at the same level as that in C1.1 (i.e. 12%) further included 3% ethylene-glycidyl methacrylate copolymer (AX8840). Composition C1.3 added 2% AX8840. Composition C1.4 added 2% AX8840 and 2% Ethylene-acrylic acid zinc ionomer to replace some of the SEBS.

[0062] As shown in Table 4, when only SEBS was used as the impact modifier (C1.1) notched Izod impact (NII) performance was low. Addition of AX8840 can result in greatly improved impact strength and tensile elongation (see C1.2 and C1.3). Further, the bonding strength can also be improved. Although the dissipation factor (Df) of the compositions was slightly higher when AX8840 was included, it was still at a very low level (< 0.007 at 1-5 GHz) when the loading of AX8840 was not high. Addition of ionomer further improved the ductility of the composition with little influence to the other properties like bonding strength and Dk / Df. Compare C1.4 to C1.3.

[0063] In sum, using the building blocks of a polyester (e.g., PBT base resin), a bonding force promoter (e.g., SLX90 / 10), a low Dk glass fiber (filler), and impact modifiers of AX8840 plus SEBS and / or ionomer, the example compositions showed high metal bonding strength (>28 MPa under both 'T' and 'TRI' treatment methods), good impact, and ultra-low Df (< 0.007 at 1-5 GHz) performance.

[0064] Additional comparative compositions were formed as shown in Table 5; the properties of these compositions are shown in Table 6: Table 5 - Comparative Compositions Item Description Unit C2.1 C2.2 C2.3 C2.4 C2.5 PBT, low viscosity%31.230.230.230.230.2PBT, high viscosity%3028282111SLX 90 / 10 PCP capped, copolymer%88888Kraton SEBS, G1651%77777Topas COC 6017S-04%3General purpose Polystyrene%3AX8840%33333CPIC low Dk glass fiber, ECS303N-3-K / HL%2020203040Mono zinc phosphate%0.050.050.050.050.05Pentaerythritol tetrastearate%0.30.30.30.30.32-(2'hydroxy-5-t-octylphenyl)-benzotriazole%0.250.250.250.250.25Irganox 1010%0.10.10.10.10.1Hostanox P-EPQ P%0.10.10.10.10.1 Table 6 - Properties of the Compositions of Table 5 Typical Property Test Method Test Description Unit C2.1 C2.2 C2.3 C2.4 C2.5 MVR275°C / 5kgASTM D1238cm 3< / 10 min20.617.022.713.16.5Bonding strengthT-treatmentISO 19095MPa31.330.231.228.329.2Notched Izod23°C, 5 lbf / ftASTM D256J / m135127125161165-20°C, 5 lbf / ftASTM D256J / m989695120129Un-notched Izod23°C, 5 lbf / ftASTM D256J / m807885881928917HDT1.82MPa / 3.2 mmASTM D648°C1841871831961990.45MPa / 3.2 mmASTM D648°C216216215219220Flexural Modulus3.2mm, 1.27mm / minASTM D790MPa51105200525070709040Flexural Strength@break, 3.2mmASTM D790MPa136139139161178Tensile Modulus5mm / minASTM D638MPa565856995729778410021Tensile Strength@breakASTM D638MPa858888102110Tensile Elongation@breakASTM D638%2.923.153.072.922.46Dk1.9 GHzSABIC Method / 3.0132.9772.9803.1373.243Df1.9 GHzSABIC Method / 0.00620.00590.00600.00620.0063Dk5.0 GHzSABIC Method / 3.0503.0203.0233.1533.257Df5.0 GHzSABIC Method / 0.00520.00500.00500.00540.0056

[0065] The results in Tables 5 and 6 demonstrate that the dielectric constant (Dk) and dissipation factor (Df) of compositions according to the disclosure can be further improved. Composition C2.1 was a control example. In comparative compositions C2.2 and C2.3, cyclic olefin copolymer (COC) and polystyrene (PS), respectively, were added. In example compositions C2.4 and C2.5 the glass fiber content was increased to 30% and 40%, respectively.

[0066] As shown in Table 6, COC and PS can help to decrease the Dk and Df of the compositions. See compositions C2.2 and C2.3, with 3% COC and PS respectively. The Dk and Df of the compositions decreased from 3.013 / 0.0062 to 2.977 / 0.0059 (C2.2) and 2.98 / 0.0060 (C2.3) at 1.9GHz. Further, bonding strength and mechanical performance of the compositions was similar to C2.1

[0067] When the glass fiber content was increased to 30% and 40% (C2.4 and C2.5), mechanical performance of the compositions, including the impact strength, modulus, stiffness, and thermal stability was greatly improved, and the Df of the compositions was maintained at a very low level (< 0.007 at 1-5GHz).

[0068] From these examples it was observed that, polyolefins such as COC and PS can help to decrease the Dk and Df of the compositions while maintaining the metal bonding and mechanical performance.

[0069] Compositions were formed as shown in Table 7; the properties of these compositions are shown in Table 8: Table 7 - Comparative and Example Compositions Item Description Unit C3.1 E3.1 E3.2 E3.3 E3.4 PBT, low viscosity%32.232.232.228.228.2PBT, high viscosity%3131312626SLX 90 / 10 PCP capped, copolymer%10DMX100 (DMBPC including 100 mol% dimethyl bisphenol cyclohexane monomer)%1015DMX50 (DMBPC including 50 mol% dimethyl bisphenol cyclohexane monomer)%1015Kraton SEBS, G1651%5551010AX8840%33322CPIC low Dk glass fiber, ECS303N-3-K / HL%1818181818Mono zinc phosphate%0.050.050.050.050.05Pentaerythritol tetrastearate%0.30.30.30.30.32-(2'hydroxy-5-t-octylphenyl)-benzotriazole%0.250.250.250.250.25Irganox 1010%0.10.10.10.10.1Hostanox P-EPQ P%0.10.10.10.10.1 Table 8 - Properties of the Compositions of Table 7 Typical Property Test Method Test Description Unit C3.1 E3.1 E3.2 E3.3 E3.4 MVR275°C / 5kgASTM D1238cm 3< / 10 min25.923.529.317.822.9Bonding strengthT-treatmentISO 19095MPa30.332.128.825.825.6Notched Izod23°C, 5 lbf / ftASTM D256J / m141115113116115-20°C, 5 lbf / ftASTM D256J / m10493908983Un-notched Izod23°C, 5 lbf / ftASTM D256J / m9299299081080995HDT1.82MPa / 3.2 mmASTM D648°C1811831831681620.45MPa / 3.2 mmASTM D648°C214213214210207Flexural Modulus3.2mm, 1.27mm / minASTM D790MPa48804670474044804490Flexural Strength@break, 3.2mmASTM D790MPa147144147136132Tensile Modulus5mm / minASTM D638MPa54555374536648194849Tensile Strength@breakASTM D638MPa9192918080Tensile Elongation@breakASTM D638%3.693.733.714.173.99Dk1.9 GHzSABIC Method / 3.0102.9432.9532.8872.907Df1.9 GHzSABIC Method / 0.00650.00600.00620.00530.0055Dk5.0 GHzSABIC Method / 3.0672.9973.0132.9472.953Df5.0 GHzSABIC Method / 0.00580.00540.00550.00480.0049

[0070] With reference to Tables 7 and 8, the effect of inclusion of a PC copolymer (SABIC LEXAN ®< DMX resin) was evaluated. As shown in Table 7, C3.1 included an ITR copolymer (SLX90 / 10) as a bonding promoter. Example compositions E3.1 and E3.2 included DMX100 and DMX50 in place of the SLX90 / 10. In example compositions E3.3 and E3.4, the loading of DMX100 and DMX50 was increased to 15% with higher content of impact modifiers.

[0071] As shown in Table 8, when DMX100 and DMX50 was used, Dk and Df of the compositions was substantially lowered, from 3.01 / 0.0065 to 2.943 / 0.0060 (E3.1) and 2.953 / 0.0062 (E3.2) at 1.9GHz. Metal bonding strength of the DMX based compositions was still high, >28 megapascals (MPa) under T-treatment. Thermal and mechanical performance was maintained at a similar level or only slightly lower (i.e. notched Izod) than the SLX-based composition (compare E3.1 and E3.2 to C3.1).

[0072] Further, by increasing the loading of DMX resins and impact modifiers, the Dk and Df of the compositions could be further decreased. As shown in example compositions E3.3 and E3.4, when the loading of the DMX resins was increased to 15% and the total impact modifiers to 12% the Dk and Df of the compositions were decreased to 2.887 / 0.0053 (for DMX100, E3.3) and 2.907 / 0.0055 (for DMX50, E3.4). Moreover, good mechanical performance and good bonding strength (>25 MPa) was also achieved.

[0073] From these examples it is observed that DMX is a good candidate to decrease the Dk and Df of NMT compositions.

[0074] Compositions were formed as shown in Table 9; the properties of these compositions are shown in Table 10: Table 9 - Example Compositions Item Description Unit E4.5 E4.1 E4.2 E4.3 E4.4 PBT, low viscosity%30.223.223.223.218.2PBT, high viscosity%2017161610DMX50 (DMBPC including 50 mol% dimethyl bisphenol cyclohexane monomer)%1525252520Kraton SEBS, G1651%999108Ethylene-Acrylic Acid Zinc Ionomer%111AX8840%33322CPIC low Dk glass fiber, ECS303N-3-K / HL%2222222240Mono zinc phosphate%0.050.050.050.050.05Pentaerythritol tetrastearate%0.30.30.30.30.32-(2'hydroxy-5-t-octylphenyl)-benzotriazole%0.250.250.250.250.25Irganox 1010%0.10.10.10.10.1Hostanox P-EPQ P%0.10.10.10.10.1 Table 10 - Properties of the Compositions of Table 9 Typical Property Test Method Test Description Unit E4.5 E4.1 E4.2 E4.3 E4.4 MVR275°C / 5kgASTM D1238cm 3< / 10 min16.913.710.113.45.7Bonding strengthT-treatmentISO 19095MPa29.124.125.725.423.3TRI-treatmentISO 19095MPa31.125.026.325.725.5Notched Izod23°C, 5 lbf / ftASTM D256J / m116105119110149-20°C, 5 lbf / ftASTM D256J / m87788478129Un-notched Izod23°C, 5 lbf / ftASTM D256J / m8488939058551080HDT1.82MPa / 3.2 mmASTM D648°C1721321301301540.45MPa / 3.2 mmASTM D648°C211198196193206Flexural Modulus3.2mm, 1.27mm / minASTM D790MPa51905030494049208740Flexural Strength@break, 3.2mmASTM D790MPa143136134133186Tensile Modulus5mm / minASTM D638MPa57075615531654429352Tensile Strength@breakASTM D638MPa87837580113Tensile Elongation@breakASTM D638%3.192.732.802.802.94Dk1.9 GHzSABIC Method / 2.9972.9772.9702.9573.173Df1.9 GHzSABIC Method / 0.00560.00520.00510.00490.0054

[0075] Tables 9 and 10 demonstrate compositions with higher DMX resin content resulting in much lower dielectric performance. Composition E4.5 included 15% DMX50 in the formulation. Example composition E4.1 increased the DMX50 content to 25%. Ionomer was added in example composition E4.2 to improve the impact performance of the composition. Example composition E4.3 included a different ratio of impact modifiers. The glass fiber content was increased to 40% in example composition E4.4.

[0076] As shown in Table 10, when the DMX50 loading was increased to 25%, Df of the composition was greatly decreased to 0.0052 at 1.9GHz (compare E4.1 to E4.5). Although bonding strength of the composition decreased slightly, it was still at a satisfactory level (>24 MPa at 'T' and 'TRI' treatment). Impact strength of the composition can be decreased with the increasing of DMX50 in the formulation (105 J / m in E4.1). However, by adding an ionomer impact strength can be greatly improved with all the other performance including bonding strength, dielectric properties, and mechanical performance kept at similar level (see E4.2). By slightly modifying the ratio of the impact modifiers, i.e., decreasing AX8840 to 2% and increasing SEBS to 10%, the Df of the composition can be even lower, becoming < 0.005 at 1.9GHz (see E4.3). And with glass fiber content increased to 40% the composition still showed very good Df performance with much higher modulus and stiffness and good bonding performance (see E4.4). In sum, by including a high loading of DMX resin together with an ionomer, NMT compositions with very low Df properties (< 0.0055 at 1.9GHz) and good bonding and mechanical performance can be achieved.

[0077] From these examples it is concluded that NMT compositions with ultra-low Df property, good metal bonding force and good mechanical performance can be achieved. The developed basic building blocks included a polyester (e.g., PBT) as the base resin, a polycarbonate copolymer such as DMX as a bonding force promoter, an impact modifier including a di-block copolymer (e.g., ethylene-glycidyl methacrylate copolymer (AX8840)), optionally an impact modifier such as SEBS or an ionomer as an impact modifier, a low Dk glass fiber as the filler, and optionally a polyolefin such as PS or COC as a dielectric additive. Using the developed building blocks, compositions according to aspects of the disclosure demonstrated ultra-low Df property (< 0.007 at 1.9GHz), good metal bonding strength (>23 MPa), and good mechanical and processing performance. The very low Df property allows the compositions to be good candidates for 5G applications.

Claims

1. A thermoplastic composition comprising: (a) a polyester component; (b) a polycarbonate copolymer component comprising a polycarbonate-dimethyl bisphenol cyclohexane copolymer (DMBPC) comprising at least 50 mol% dimethyl bisphenol cyclohexane monomer; (c) an impact modifier component comprising a copolymer comprising two monomers; and (d) a glass fiber component.

2. The thermoplastic composition according to claim 1, wherein the composition comprises: from 30 wt% to 80 wt% of the polyester component; from 3 wt% to 30 wt% of the polycarbonate copolymer component; from 5 wt% to 20 wt% of the impact modifier component; and from 10 wt% to 50 wt% of the glass fiber component, wherein the combined weight percent value of all components does not exceed 100 wt%, and all weight percent values are based on the total weight of the composition.

3. The thermoplastic composition according to claim 1 or 2, wherein the polyester component comprises polybutylene terephthalate (PBT), polyethylene terephthalate (PET), poly(cyclohexylenedimethylene terephthalate) (PCT), polyethylene terephthalate glycol (PETG), polycyclohexylene dimethylene terephthalate glycol (PCTG), polycyclohexylene dimethylene terephthalate acid (PCTA), copolymers thereof, or a combination thereof.

4. The thermoplastic composition according to any of claims 1 to 3, wherein the polyester component comprises PBT.

5. The thermoplastic composition according to any of claims 1 to 4, wherein the polycarbonate copolymer component further comprises a polyester-polycarbonate copolymer.

6. The thermoplastic composition according to any of claims 1 to 5, wherein the impact modifier component comprising the copolymer comprising two monomers comprises an ethylene-glycidyl methacrylate copolymer.

7. The thermoplastic composition according to claim 6, wherein the impact modifier component does not include a terpolymer.

8. The thermoplastic composition according to claim 6 or 7, wherein the composition comprises from 1 wt% to 5 wt% of the ethylene-glycidyl methacrylate copolymer.

9. The thermoplastic composition according to any of claims 1 to 8, wherein the glass fiber component comprises glass fiber having a dielectric constant (Dk) of less than 5.0 at 1 gigahertz (GHz) and a dissipation factor (Df) of less than 0.002 at 1 GHz, wherein Dk and Df are tested in accordance with ASTM D150.

10. The thermoplastic composition according to any of claims 1 to 9, wherein the composition further comprises an additional impact modifier comprising an ionomer, styrene-ethylene / 1-butene-styrene (SEBS), or a combination thereof.

11. The thermoplastic composition according to claim 10, wherein the composition comprises the ionomer, and the ionomer comprises ethylene-acrylic acid zinc.

12. The thermoplastic composition according to any of claims 1 to 11, wherein the composition further comprises up to 10 wt% of a polyolefin additive.

13. The thermoplastic composition according to claim 12, wherein the polyolefin additive comprises polypropylene (PP), polystyrene (PS), cyclic olefin copolymer (COC), or a combination thereof.

14. The thermoplastic composition according to any of claims 1 to 13, wherein the composition has a dissipation factor of less than 0.007 at a frequency of from 1 to 5 GHz, wherein the dissipation factor is determined according to the method outlined in the description.