Thermoplastic compositions with low dissipation factor for nanomolding technology (NMT) applications

Abstract

The thermoplastic composition comprises: (a) a polyester component; (b) a polycarbonate copolymer component, including polyester-polycarbonate copolymer, polycarbonate-dimethylbisphenol cyclohexane copolymer (DMBPC) or a combination thereof; (c) an impact modifier component, including a copolymer containing two monomers; and (d) a glass fiber component.

Description

Technical Field

[0001] This disclosure relates to polyester-based compositions with good dielectric properties suitable for nanomolding technology (NMT) applications. Background Technology

[0002] Nanomolding (NMT) is an innovative technology that integrates plastic resins with metals through a convenient injection molding process. NMT materials are widely used in the consumer electronics industry due to their excellent metal-bond reliability, high productivity, and cost-effectiveness, especially in antenna splitting solutions for mobile devices and tablets. These materials also offer good water resistance and antenna efficiency. Polybutylene terephthalate (PBT), polyphenylene sulfide (PPS), and polyamide (PA) are primarily used in NMT processes. However, PBT, with its most balanced overall properties such as high metal-bond strength, good colorability, and color stability (or chemical resistance), has become the most popular base resin in the NMT market.

[0003] 5G telecommunications standards have come into effect. The high operating frequencies of 5G networks place new and different demands on the materials used in 5G devices. Generally, materials with low dielectric constant (Dk) and low dissipation factor (Df) are desirable because they have low impact on RF efficiency and high benefits on antenna performance. Several solutions for low-Dk NMT compositions have been reported. For example, PCT application WO2019 / 130269 (SABIC) describes a technique for a PBT-based composition comprising low-Dk glass fiber and hollow filler as a filler group. CN107365480A (Jianghe Material Tech) describes a high-heat-resistant low-Dk composition comprising poly(cyclohexyl terephthalate) (PCT) as a base resin. However, conventional compositions with ultra-low Df (Df less than 0.007 at frequencies greater than 1 GHz) have not yet been identified. For example, PBT has a Df of approximately 0.006 at 1.9 GHz, but the Df increases as additives are incorporated into the PBT composition. Therefore, maintaining the Df of polyester-based NMT compositions at ultra-low levels is very challenging.

[0004] These and other shortcomings are addressed through various aspects of this disclosure. Summary of the Invention

[0005] Various aspects of this disclosure relate to thermoplastic compositions comprising: (a) a polyester component; (b) a polycarbonate copolymer component, including polyester-polycarbonate copolymer, polycarbonate-dimethylbisphenol cyclohexane copolymer (DMBPC), or combinations thereof; (c) an impact modifier component, including copolymers comprising two monomers; and (d) a glass fiber component.

[0006] In a specific aspect, the thermoplastic composition comprises: about 30 wt% to about 80 wt% of a polyester component; about 3 wt% to about 30 wt% of a polycarbonate copolymer component; about 5 wt% to about 20 wt% of an impact modifier component; and about 10 wt% to about 50 wt% of a glass fiber component. The combined weight percentage of all components does not exceed 100 wt%, and all weight percentages are based on the total weight of the composition. Detailed Implementation

[0007] This paper discloses a novel solution that provides a thermoplastic composition with ultra-low dielectric dissipation factor (Df) and good mechanical properties for use in nanoforming technology (NMT) for electronic and / or telecommunications-related applications.

[0008] This disclosure can be more readily understood by referring to the following detailed description of the disclosure and the embodiments included therein. In various aspects, this disclosure relates to thermoplastic compositions comprising: (a) a polyester component; (b) a polycarbonate copolymer component comprising a polyester-polycarbonate copolymer, a polycarbonate-dimethylbisphenol cyclohexane copolymer (DMBPC), or a combination thereof; (c) an impact modifier component comprising a copolymer containing two monomers; and (d) a glass fiber component.

[0009] Before disclosing and describing the compounds, compositions, articles, systems, devices, and / or methods of the present invention, it should be understood that, unless otherwise specified, they are not limited to specific synthetic methods, or, unless otherwise specified, are not limited to specific reagents, and therefore, they can certainly be modified. It should also be understood that the terminology used herein is for descriptive purposes only and is not intended to be limiting.

[0010] This disclosure covers various combinations of elements of this disclosure, such as combinations of elements from dependent claims that are subordinate to the same independent claim.

[0011] Furthermore, it should be understood that, unless expressly stated otherwise, any method described herein is not intended to be construed as requiring its steps to be performed in a particular order. Therefore, unless a method claim actually describes the order in which its steps are followed, or unless the claims or description specifically state that the steps are limited to a particular order, no inference is intended in any respect of the order. This applies to any possible non-explicit basis of interpretation, including: logical questions concerning the arrangement of steps or the flow of operations; simple meanings derived from grammatical organization or punctuation; and the number or type of aspects described in the description.

[0012] All publications mentioned herein are incorporated herein by reference to disclose and describe the relevant methods and / or materials used in citing those publications.

[0013] definition

[0014] It should also be understood that the terminology used herein is for descriptive purposes only and is not intended to be limiting. As used in this specification and claims, the term "comprising" may include aspects of "consisting of" and "essentially consisting of". Unless otherwise defined, 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 invention pertains. Reference will be made to several terms as defined herein in this specification and the following claims.

[0015] As used in this specification and the appended claims, the singular forms “a,” “an,” and “the” also include plural references, unless the context clearly specifies otherwise. Thus, for example, a reference to “polyester component” includes a mixture of two or more polyester components.

[0016] As used herein, the term "combination" includes blends, mixtures, alloys, reaction products, etc.

[0017] A range may be expressed herein as a range from one value (first value) to another value (second value). When such a range is expressed, the range includes one or both of the first and second values ​​in some aspect. Similarly, when a value is expressed as an approximation using the antecedent “about”, it will be understood that the particular value forms another aspect. It should also be understood that each endpoint of a range is significant relative to and independent of the other endpoint. It should also be understood that multiple values ​​are disclosed herein, and each value is also disclosed herein as “about” that particular value, in addition to being the value itself. For example, if the numerical value “10” is disclosed, then “about 10” is also disclosed. It should also be understood that each unit between two particular units is also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0018] As used herein, the terms “about” and “at or about” mean that the quantity or value in question can be a specified value, approximately a specified value, or approximately the same as a specified value. It is generally understood that, as used herein, unless otherwise stated or inferred, it represents a variation of ±10% of the nominal value. This term is intended to convey that similar values ​​promote the equivalent results or effects described in the claims. That is, it should be understood that quantities, dimensions, formulations, parameters, and other quantities and characteristics are not and need not be precise, but can be approximate and / or larger or smaller as needed, reflecting tolerances, conversion factors, rounding, measurement errors, and other factors known to those skilled in the art. Generally, quantities, dimensions, formulations, parameters, or other quantities or characteristics are “about” or “approximate,” whether or not explicitly stated so. It should be understood that when “about” is used before a quantitative value, unless otherwise specifically stated, the parameter also includes the specific quantitative value itself.

[0019] As used herein, the terms “optional” or “optionally” mean that the event or situation described below may or may not occur, and the description includes both cases where the event or situation occurs and cases where the event or situation does not occur. For example, the phrase “optional impact modifier” means that an impact modifier may or may not be included, and the description includes compositions that include both impact modifiers and compositions that do not include impact modifiers.

[0020] The components used to prepare the compositions disclosed herein, as well as the compositions themselves to be used in the methods disclosed herein, are disclosed herein. These and other materials are disclosed herein, and it should be understood that while specific references to every different individual and common combination and arrangement of these compounds are not explicitly disclosed when combinations, subsets, interactions, groups, etc., of these materials are disclosed, each case is specifically considered and described herein. For example, if a particular compound is disclosed and discussed, and various modifications that can be made to a number of molecules including that compound are discussed, then each and every combination and arrangement of the compound and possible modifications are specifically considered unless specifically indicated to the contrary. Thus, if a class of molecules A, B, and C and a class of molecules D, E, and F are disclosed, and examples of the combination molecule AD are disclosed, then each is individually and collectively included even if each is not described separately, thus implying that combinations AE, AF, BD, BE, BF, CD, CE, and CF are disclosed. Similarly, any subsets or combinations of these are also disclosed. Thus, for example, subgroups of AE, BF, and CE are considered to be disclosed. This concept applies to all aspects of this application, including but not limited to steps in methods of manufacturing and using the compositions of this disclosure. Therefore, if various additional steps are available, it should be understood that each of these additional steps may be performed in any particular aspect or combination thereof of the methods of this disclosure.

[0021] References to the weight parts of a specific element or component in the composition or article in the specification and concluding claims indicate the weight relationship between that element or component and any other element or component in the expressed weight parts of the composition or article. Therefore, in a compound containing 2 parts by weight of component X and 5 parts by weight of component Y, X and Y are present in a weight ratio of 2:5, and this ratio applies regardless of whether the compound contains other components.

[0022] Unless otherwise stated, the weight percentage of a component is based on the total weight of the formulation or composition including that component.

[0023] As used herein, the term "number-average molecular weight" or "M" refers to... n "Can be used interchangeably, and refers to the statistical average molecular weight of all polymer chains in the sample, and is defined by the following formula:"

[0024]

[0025] Where M i It is the molecular weight of the chain, and N i This refers to the number of chains at that molecular weight. The M of a polymer (e.g., a polycarbonate polymer) nThe molecular weight can be determined using methods well known to those skilled in the art, using molecular weight standards, such as polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards.

[0026] As used herein, the term "weight-average molecular weight" or "M" refers to... w "They can be used interchangeably and are defined by the following formula:

[0027]

[0028] Where M i It is the molecular weight of the chain, and N i This represents the number of chains with that molecular weight. (M) n In comparison, M w The molecular weight of a given chain is considered when determining its contribution to the average molecular weight. Therefore, the larger the molecular weight of a given chain, the greater its contribution to M. w The greater the contribution, the better. The M of polymers (e.g., polycarbonate polymers) w The molecular weight can be determined using methods well known to those skilled in the art, using molecular weight standards, such as polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards.

[0029] As used herein, the terms “polydispersity index” or “PDI” are used interchangeably and are defined by the following formula:

[0030]

[0031] When the PDI value is equal to or greater than 1, but the PDI tends to be uniform when the chain length of the polymer chain tends to be uniform.

[0032] The terms “BisA,” “BPA,” or “bisphenol A” are used interchangeably, as they are used herein, to refer to compounds having the structure shown in the following formula:

[0033]

[0034] BisA can also be represented by the names 4,4'-(propane-2,2-diyl)diphenol, p,p'-isopropylidene bisphenol, or 2,2-bis(4-hydroxyphenyl)propane. BisA has CAS #80-05-7.

[0035] As used herein, “polycarbonate” refers to an oligomer or polymer comprising residues of one or more dihydroxy compounds (e.g., dihydroxy aromatic compounds) linked by carbonate bonds; it also encompasses homopolymers, copolymers, and (co)polyesters.

[0036] Throughout the specification, the terms “residue” and “structural unit” are used synonymously when referring to the components of the polymer.

[0037] As used herein, unless otherwise stated, the terms "weight percentage," "wt%," and "wt.%" are used interchangeably to indicate the weight percentage of a given component based on the total weight of the composition. That is, unless otherwise stated, all wt% values ​​are based on the total weight of the composition. It should be understood that the sum of the wt% values ​​of all components in the disclosed compositions or formulations equals 100.

[0038] Unless otherwise stated herein, all test standards are current and valid at the time of submission of this application.

[0039] Each material disclosed herein is commercially available and / or its preparation method is known to those skilled in the art.

[0040] It should be understood that the compositions disclosed herein have certain functions. This document discloses certain structural requirements for performing the disclosed functions, and it should be understood that various structures exist that can perform the same functions associated with the disclosed structures, and these structures will generally achieve the same results.

[0041] thermoplastic composition

[0042] Various aspects of this disclosure relate to a thermoplastic composition comprising: (a) a polyester component; (b) a polycarbonate copolymer component, including a polyester-polycarbonate copolymer, a polycarbonate-dimethylbisphenol cyclohexane copolymer (DMBPC), or a combination thereof; (c) an impact modifier component, including a copolymer comprising two monomers; and (d) a glass fiber component. In a particular aspect, the thermoplastic composition comprises: about 30 wt% to about 80 wt% of a polyester component; about 3 wt% to about 30 wt% of a polycarbonate copolymer component; about 5 wt% to about 20 wt% of an impact modifier component; and about 10 wt% to about 50 wt% of a glass fiber component. The combined weight percentage of all components does not exceed 100 wt%, and all weight percentages are based on the total weight of the composition.

[0043] In some aspects, the polyester component includes polybutylene terephthalate (PBT), polyethylene terephthalate (PET), poly(cyclohexanediol terephthalate) (PCT), polyethylene terephthalate diol (PETG), polycyclohexanediol terephthalate diol (PCTG), polycyclohexylenedimethylene terephthalate (PCTA), copolymers thereof, or combinations thereof. PCT is a crystalline polyester formed from cyclohexanediol (CHDM) and dimethyl terephthalate (DMT) or terephthalic acid (TPA). PETG and PCTG are copolyesters formed by including ethylene glycol (EG) in the polymerization reaction. If the diol content in the copolyester is less than 50% CHDM, PETG is formed; if the diol content in the copolyester is greater than 50% CHDM, PCTG is formed. PCTA is formed by including additional diacids (such as isophthalic acid (IPA)). In certain aspects, the polyester component includes PBT.

[0044] In some aspects, the thermoplastic composition includes a polycarbonate copolymer component, said polycarbonate copolymer comprising a polyester-polycarbonate copolymer. In a particular aspect, the polyester unit is derived from a reaction between isophthalic acid, terephthalic acid, and resorcinol (also known as an ITR resin). The polyester unit has the following structure:

[0045]

[0046] Where x corresponds to the molar ratio of isophthalate, y corresponds to the molar ratio of resorcinol, and z corresponds to the molar ratio of terephthalate; x, y, and z are added to 100% of the polyester unit. This type of polyester-polycarbonate can be used as… SLX resin is obtained from SABIC. The concentration of the polyester (ITR) resin can be at least 5% based on the molar amount in the polymer. In other respects, the polyester and polycarbonate are used in a molar ratio of about 5:95 to about 40:60, or more particularly about 5:95 to about 35:65, depending on the desired properties. The weight-average molecular weight of the polyester-polycarbonate can be about 1500 to about 100000, or more particularly about 2000 to about 40000. The polyester-polycarbonate polymer can be a copolymer, especially a block copolymer.

[0047] In other respects, the polycarbonate copolymer component comprises a polycarbonate-dimethylbisphenol cyclohexane copolymer (DMBPC) containing at least 50 mol% dimethylbisphenol cyclohexane monomer. DMBPC has the following formula:

[0048]

[0049] Where x and y represent the molar ratio of dimethylbisphenol cyclohexane monomer and polycarbonate monomer, respectively. Therefore, when x is 50, y is also 50, and the copolymer comprises 50 mol% dimethylbisphenol cyclohexane monomer and 50 mol% polycarbonate monomer. In some aspects, x is from 20 to 100.

[0050] Impact modifiers include copolymers comprising two monomers. In a particular aspect, the copolymer comprising two monomers includes an ethylene-glycidyl methacrylate copolymer. In some aspects, the copolymer is a diblock copolymer. In a particular aspect, the impact modifier component does not include terpolymers (e.g., but not limited to ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA)). In other aspects, the impact modifier component includes a copolymer composed of two monomers. In still other aspects, the impact modifier component consists of a copolymer composed of two monomers.

[0051] In some aspects, the composition comprises about 1 wt% to about 5 wt% of an ethylene-glycidyl methacrylate copolymer.

[0052] In some aspects, the glass fiber composition may include low Dk / Df glass fibers, such as, but not limited to, glass fibers with Dk less than 5.0 at 1 GHz and Df less than 0.002 at 1 GHz, wherein Dk and Df are tested according to ASTM D150.

[0053] In some aspects, the composition further includes additional impact modifiers, including ionomers, styrene-ethylene / 1-butene-styrene (SEBS), or combinations thereof. In some aspects, the ionomer includes, but is not limited to, zinc, sodium, magnesium, or calcium. In certain aspects, the ionomer includes ethylene-zinc acrylate.

[0054] In other respects, the composition also contains up to 10 wt% of a polyolefin additive. The polyolefin additive may include, but is not limited to, polypropylene (PP), polystyrene (PS), cyclic olefin copolymers (COC), or combinations thereof.

[0055] This thermoplastic composition exhibits improved properties compared to conventional NMT compositions. Specifically, when tested according to the SABIC method, the composition shows a Df of less than 0.007 at frequencies from 1 to 5 GHz. The SABIC method for determining Dk and Df involves measuring these values ​​using a QWED split post dielectric resonator and an Agilent network analyzer. For measurements at 1.1 GHz, the minimum sample size is 120 mm x 120 mm; the maximum sample thickness is 6 mm. For measurements at 1.9 GHz, the minimum sample size is 70 mm x 70 mm; the maximum sample thickness is 4 mm. For measurements at 5.0 GHz, the minimum sample size is 30 mm x 30 mm; the maximum sample thickness is 2 mm.

[0056] Manufacturing method

[0057] One or any of the aforementioned components described herein may be dry-mixed with each other, or with any combination of the aforementioned components, and then fed into the extruder from one or more feeders, or fed into the extruder individually from one or more feeders. The fillers used in this disclosure may also be processed into masterbatch before being fed into the extruder. Components may be fed into the extruder from the throat hopper or any side feeder.

[0058] The extruder used in this disclosure may have a single screw, multiple screws, intermeshing screws rotating in the same or opposite directions, non-intermeshing screws rotating in the same or opposite directions, reciprocating screws, screws with pins, screws with screens, cylinders with pins, rollers, plungers, helical rotors, co-kneaders, disc processors, various other types of extrusion equipment, or combinations thereof.

[0059] The components can also be mixed together and then melt-blended to form a thermoplastic composition. Melt blending of the components involves the use of shear force, tensile force, compressive force, ultrasonic energy, electromagnetic energy, thermal energy, or a combination of at least one of the above-mentioned forms of force or energy.

[0060] If the resin is a semi-crystalline organic polymer, the barrel temperature on the extruder during compounding can be set to a temperature at which at least a portion of the polymer has reached a temperature greater than or equal to approximately the melt temperature; or if the resin is an amorphous resin, the barrel temperature can be set to the flow point (e.g., the glass transition temperature).

[0061] If desired, the mixture comprising the above components can undergo multiple blending and molding steps. For example, the thermoplastic composition can first be extruded and formed into pellets. The pellets can then be fed into a molding machine, where they can be formed into any desired shape or product. Alternatively, the thermoplastic composition emanating from a single melt blender can be formed into sheets or wires and subjected to post-extrusion processes such as annealing, uniaxial or biaxial orientation.

[0062] In some aspects, the melt temperature in this method can be kept as low as possible to avoid excessive thermal degradation of the components. In other aspects, the melt temperature is maintained between about 230°C and about 350°C, but higher temperatures can be used provided that the residence time of the resin in the processing equipment is kept relatively short. In some aspects, the melt-treated composition exits the processing equipment (e.g., an extruder) through a small outlet orifice in a die. The resulting molten resin filament can be cooled by passing the filament through a water bath. The cooled filament can be cut into pellets for packaging and further processing.

[0063] manufactured products

[0064] In some aspects, this disclosure relates to articles comprising a thermoplastic composition that have been shaped, molded, or molded. The thermoplastic composition can be molded into a useful shaped article by various means (e.g., injection molding, extrusion, rotational molding, blow molding, and thermoforming) to form an article. In certain aspects, the article can be incorporated into electronic or telecommunications equipment.

[0065] This disclosure covers various combinations of elements of this disclosure, such as combinations of elements from dependent claims that are subordinate to the same independent claim.

[0066] Aspects of publicly disclosed content

[0067] In all respects, this disclosure relates to and includes at least the following aspects.

[0068] Aspect 1. A thermoplastic composition comprising, consisting of, or substantially consisting of the following:

[0069] (a) Polyester component;

[0070] (b) A polycarbonate copolymer component comprising a polyester-polycarbonate copolymer, a polycarbonate-dimethylbisphenol cyclohexane copolymer (DMBPC), or a combination thereof;

[0071] (c) An impact modifier component comprising a copolymer containing two monomers, consisting of two monomers, or substantially consisting of two monomers; and

[0072] (d) Glass fiber component.

[0073] Aspect 2. The thermoplastic composition according to aspect 1, wherein the composition comprises:

[0074] Approximately 30 wt% to approximately 80 wt% polyester component;

[0075] Approximately 3 wt% to approximately 30 wt% of polycarbonate copolymer components;

[0076] Impact modifier components of about 5 wt% to about 20 wt%; and

[0077] Glass fiber component of approximately 10 wt% to approximately 50 wt%,

[0078] The combined weight percentage of all components does not exceed 100 wt%, and all weight percentage values ​​are based on the total weight of the composition.

[0079] Aspect 3. The thermoplastic composition according to aspect 1 or 2, wherein the polyester component comprises polybutylene terephthalate (PBT), polyethylene terephthalate (PET), poly(cyclohexanediol terephthalate) (PCT), polyethylene terephthalate diol (PETG), polycyclohexanediol terephthalate diol (PCTG), polycyclohexanediol terephthalic acid (PCTA), copolymers thereof, or combinations thereof.

[0080] Aspect 4. The thermoplastic composition according to any one of Aspects 1 to 3, wherein the polyester component comprises PBT.

[0081] Aspect 5. The thermoplastic composition according to any one of Aspects 1 to 4, wherein the polycarbonate copolymer component comprises a polyester-polycarbonate copolymer comprising polycarbonate and polyester units (ITR) derived from the reaction of isophthalic acid, terephthalic acid and resorcinol.

[0082] Aspect 6. The thermoplastic composition according to any one of Aspects 1 to 5, wherein the polycarbonate copolymer component comprises a polycarbonate-dimethylbisphenol cyclohexane copolymer (DMBPC) containing at least 50 mol% of dimethylbisphenol cyclohexane monomer.

[0083] Aspect 7. The thermoplastic composition according to any one of Aspects 1 to 6, wherein the impact modifier component is composed of a copolymer of two monomers.

[0084] Aspect 8. The thermoplastic composition according to any one of Aspects 1 to 7, wherein the impact modifier component comprising a copolymer containing two monomers comprises an ethylene-glycidyl methacrylate copolymer.

[0085] Aspect 9. The thermoplastic composition according to aspect 7 or 8, wherein the impact modifier component does not include a terpolymer.

[0086] Aspect 10. The thermoplastic composition according to any one of Aspects 7 to 9, wherein the composition comprises about 1 wt% to about 5 wt% of an ethylene-glycidyl methacrylate copolymer.

[0087] Aspect 11. The thermoplastic composition according to any one of Aspects 1 to 10, wherein the glass fiber component comprises glass fibers having a dielectric constant (Dk) of less than 5.0 at 1 GHz and a dissipation factor (Df) of less than 0.002 at 1 GHz, wherein Dk and Df are tested according to ASTM D150.

[0088] Aspect 12. The thermoplastic composition according to any one of Aspects 1 to 11, wherein the composition further comprises an additional impact modifier comprising an ionomer, styrene-ethylene / 1-butene-styrene (SEBS), or a combination thereof.

[0089] Aspect 13. The thermoplastic composition according to aspect 12, wherein the composition comprises an ionomer, and the ionomer comprises ethylene-zinc acrylate.

[0090] Aspect 14. The thermoplastic composition according to any one of Aspects 1 to 13, wherein the composition further comprises up to 10 wt% of a polyolefin additive.

[0091] Aspect 15. The thermoplastic composition according to aspect 14, wherein the polyolefin additive comprises polypropylene (PP), polystyrene (PS), cyclic olefin copolymer (COC), or a combination thereof.

[0092] Aspect 16. The thermoplastic composition according to any one of Aspects 1 to 15, wherein, when tested according to the SABIC method, the dissipation factor of the composition at frequencies from 1 to 5 GHz is less than 0.007.

[0093] Example

[0094] The following examples are provided to provide those skilled in the art with a complete disclosure and description of how to prepare and evaluate the compounds, compositions, articles, apparatus, and / or methods claimed herein, and are intended to be purely exemplary and not to limit the scope of this disclosure. Efforts have been made to ensure the accuracy of figures (e.g., amounts, temperatures, etc.), but some errors and deviations should be accounted for. Unless otherwise stated, parts are by weight, temperatures are in °C or ambient temperature, and pressures are atm or near atm. Unless otherwise stated, percentages of compositions are expressed in wt%.

[0095] Reaction conditions (e.g., component concentrations, desired solvents, solvent mixtures, temperature, pressure, and other reaction ranges and conditions that can be used to optimize the purity and yield of the product obtained from the process) can have many variations and combinations. Only reasonable and routine experiments are needed to optimize these process conditions.

[0096] The composition described herein was extruded and injection molded. Typical extrusion properties of the composition are provided in Table 1:

[0097] Table 1 – Extrusion Characteristics

[0098]

[0099]

[0100] Table 2 shows the typical injection molding characteristics of this composition:

[0101] Table 2 – Molding Properties

[0102]

[0103]

[0104] The compositions are formed as shown in Table 3; the properties of these compositions are shown in Table 4.

[0105] Table 3 – Comparative Composition (C) and Example Composition (E)

[0106]

[0107] The properties of the compositions are shown in Tables 4–3.

[0108]

[0109]

[0110] For all tested compositions, the “SABIC method” for determining Dk and Df involves measuring these values ​​using a QWED split-column dielectric resonator and an Agilent network analyzer. For measurements at 1.1 GHz, the minimum sample size is 120 mm x 120 mm; the maximum sample thickness is 6 mm. For measurements at 1.9 GHz, the minimum sample size is 70 mm x 70 mm; the maximum sample thickness is 4 mm. For measurements at 5.0 GHz, the minimum sample size is 30 mm x 30 mm; the maximum sample thickness is 2 mm.

[0111] As shown in Table 3: Composition C1.1 is a control composition using PBT as the base resin. SLX90 / 10 is a bonding promoter, SEBS is an impact modifier, and the filler is low-Dk glass fiber. Compositions E1.1-E1.3 are compositions according to this disclosure. Example composition E1.1 has the same total impact modifier loading as C1.1 (i.e., 12%), and also includes 3% ethylene-glycidyl methacrylate copolymer (AX8840). Example composition E1.2 adds 2% AX8840. Example composition E1.3 adds 2% AX8840 and 2% ethylene-zinc acrylate ionomer in place of some SEBS.

[0112] As shown in Table 4, the notched Izod impact (NII) performance is low when SEBS is used alone as the impact modifier (C1.1). The addition of AX8840 significantly improves impact strength and tensile elongation (see E1.1 and E1.2). Furthermore, it improves bond strength. Although the dissipation factor (Df) of the composition is slightly higher when AX8840 is included, it remains very low (<0.007 at 1–5 GHz) when the AX8840 loading is low. The addition of the ionomer further improves the ductility of the composition, while having little effect on other properties such as bond strength and Dk / Df. E1.3 is compared with E1.2.

[0113] In summary, using a building block of polyester (e.g., PBT base resin), bonding promoter (e.g., SLX90 / 10), low-Dk glass fiber (filler), and impact modifiers of AX8840+SEBS and / or ionomers, the example compositions exhibit high metal bond strength (greater than 28 MPa under both “T” and “TRI” treatments), good impact resistance, and ultra-low Df (<0.007 at 1-5 GHz).

[0114] Additional compositions were formed as shown in Table 5; the properties of these compositions are shown in Table 6.

[0115] Table 5 – Comparison of Compositions and Examples

[0116]

[0117]

[0118] Properties of the compositions in Tables 6–5

[0119]

[0120]

[0121] The results in Tables 5 and 6 show that the dielectric constant (Dk) and dissipation factor (Df) of the compositions according to this disclosure can be further improved. Composition C2.1 is a comparative example. In example compositions E2.1 and E2.2, a cyclic olefin copolymer (COC) and polystyrene (PS) were added, respectively. In example compositions E2.3 and E2.4, the glass fiber content was increased to 30% and 40%, respectively.

[0122] As shown in Table 6, COC and PS can help reduce the Dk and Df of the composition. See Example Compositions E2.1 and E2.2, which have 3% COC and 3% PS, respectively. At 1.9 GHz, the Dk and Df of the composition decreased from 3.013 / 0.0062 to 2.977 / 0.0059 (E2.1) and 2.98 / 0.0060 (E2.2). Furthermore, the bonding strength and mechanical properties of the composition are similar to those of C2.1.

[0123] When the glass fiber content is increased to 30% and 40% (E2.3 and E2.4), the mechanical properties of the composition (including impact strength, modulus, stiffness and thermal stability) are greatly improved, and the Df of the composition remains at a very low level (<0.007 at 1-5 GHz).

[0124] These examples show that polyolefins (e.g., COC and PS) can help reduce the Dk and Df of the composition while maintaining metal bonding and mechanical properties.

[0125] The compositions are formed as shown in Table 7; the properties of these compositions are shown in Table 8.

[0126] Table 7 – Comparison of Compositions and Examples

[0127]

[0128]

[0129] Properties of the compositions in Tables 8–7

[0130]

[0131]

[0132] Referring to Tables 7 and 8, the performance of PC copolymers (SABIC) was evaluated. The effect of adding DMX resin is shown in Table 7. C3.1 includes an ITR copolymer (SLX90 / 10) as a bonding accelerator. Example compositions E3.1 and E3.2 include DMX100 and DMX50 instead of SLX90 / 10. In example compositions E3.3 and E3.4, the loading of DMX100 and DMX50 increases to 15% with higher contents of the impact modifier.

[0133] As shown in Table 8, when using DMX100 and DMX50, the Dk and Df of the compositions decreased significantly, from 3.01 / 0.0065 at 1.9 GHz to 2.943 / 00060 (E3.1) and 2.953 / 0062 (E3.2). The metal bond strength of the DMX-based compositions remained high, >28 MPa under T treatment. The thermal and mechanical properties remained at levels similar to or only slightly lower than those of the SLX-based compositions (i.e., notched Izod) (compare E3.1 and E3.2 with C3.1).

[0134] Furthermore, by increasing the loading of DMX resin and impact modifier, the Dk and Df of the composition can be further reduced. As shown in Examples E3.3 and E3.4, when the loading of DMX resin is increased to 15% and the total impact modifier is increased to 12%, the Dk and Df of the composition decrease to 2.887 / 0.0053 (for DMX100, E3.3) and 2.907 / 0.0055 (for DMX50, E3.4). In addition, good mechanical properties and good bond strength (>25 MPa) are also obtained.

[0135] These examples show that DMX is a good candidate for reducing Dk and Df of NMT compositions.

[0136] The compositions are formed as shown in Table 9; the properties of these compositions are shown in Table 10.

[0137] Table 9 – Comparative Compositions and Example Compositions

[0138]

[0139]

[0140] Properties of the compositions in Tables 10–9

[0141]

[0142]

[0143] Tables 9 and 10 show compositions with higher DMX resin content, resulting in significantly lower dielectric properties. Composition C4.1 comprises 15% DMX50 in the formulation. Example composition E4.1 increases the DMX50 content to 25%. An ionomer was added to example composition E4.2 to improve the impact resistance of the composition. Example composition E4.3 includes different proportions of impact modifiers. In example composition E4.4, the glass fiber content is increased to 40%.

[0144] As shown in Table 10, when the DMX50 loading is increased to 25%, the Df of the composition at 1.9 GHz decreases significantly to 0.0052 (comparing E4.1 to C4.1). Although the bond strength of the composition decreases slightly, it remains at a satisfactory level (>24 MPa under “T” and “TRI” treatments). The impact strength of the composition decreases with increasing DMX50 content (105 J / m in E4.1). However, by adding ionomers, the impact strength can be significantly improved, while all other properties, including bond strength, dielectric properties, and mechanical properties, remain at similar levels (see E4.2). By slightly altering the proportions of the impact modifier, i.e., reducing AX8840 to 2% and increasing SEBS to 10%, the Df of the composition can be even lower, becoming <0.005 at 1.9 GHz (see E4.3). As the glass fiber content increased to 40%, the composition still exhibited very good Df properties, with much higher modulus and stiffness, as well as good bonding properties (see E4.4). In summary, by simultaneously including high loadings of DMX resin and ionomer, NMT compositions with very low Df properties (<0.0055 at 1.9 GHz) and good bonding and mechanical properties can be obtained.

[0145] These examples demonstrate that NMT compositions exhibiting ultra-low Df properties, good metal bonding strength, and good mechanical properties can be obtained. The developed basic building blocks include a polyester (e.g., PBT) as the base resin, a polycarbonate copolymer (e.g., ITR (e.g., SLX) or DMX) as a bonding promoter, an impact modifier including a diblock copolymer (e.g., ethylene-glycidyl methacrylate copolymer (AX8840)), optionally an impact modifier (e.g., SEBS) or an ionomer as an impact modifier, low-Dk glass fiber as a filler, and optionally a polyolefin (e.g., PS or COC) as a dielectric additive. Using the developed building blocks, compositions according to various aspects of this disclosure exhibit ultra-low Df properties (<0.007 at 1.9 GHz), good metal bonding strength (>23 MPa), and good mechanical and processability properties. The very low Df properties make the compositions promising candidates for 5G applications.

[0146] The above description is intended to be illustrative and not restrictive. For example, the above embodiments (or one or more aspects thereof) may be used in combination with each other. Other aspects may be used, for example, as will be apparent to those skilled in the art upon review of the above description. The abstract is provided to comply with 37 C.FR §1.72(b) and to enable the reader to quickly determine the nature of this disclosure. This document is submitted under the understanding that it is not intended to interpret or limit the scope or meaning of the claims. Furthermore, in the above detailed description, various features may be combined to simplify the invention. This should not be construed as implying that any unclaimed disclosed feature is essential to any claim. Rather, the subject matter of the invention may lie in all features less than a particular aspect disclosed. Therefore, the following claims are incorporated herein as embodiments or aspects of the detailed description, wherein each claim is an independent, separate aspect, and such aspects may be contemplated to be combined with each other in various combinations or arrangements. The scope of this disclosure should be determined by reference to the appended claims and the full scope of their equivalents.

Claims

1. A thermoplastic composition comprising: (a) 30 wt% to 80 wt% polyester component; (b) 3 wt% to 30 wt% of polycarbonate-dimethylbisphenol cyclohexane (DMBPC) copolymer containing at least 50 mol% of dimethylbisphenol cyclohexane monomer; (c) 5 wt% to 20 wt% of an impact modifier component comprising a copolymer containing two monomers; and (d) 10 wt% to 50 wt% glass fiber component, in, The combined weight percentage of all components does not exceed 100 wt%, and all weight percentages are based on the total weight of the composition.

2. The thermoplastic composition according to claim 1, wherein, The polyester component comprises polybutylene terephthalate (PBT), polyethylene terephthalate (PET), poly(cyclohexanediol terephthalate) (PCT), polyethylene terephthalate diol (PETG), polycyclohexanediol terephthalate diol (PCTG), polycyclohexanediol terephthalic acid (PCTA), copolymers thereof, or combinations thereof.

3. The thermoplastic composition according to claim 1, wherein, The polyester component contains PBT.

4. The thermoplastic composition according to claim 1, wherein, The impact modifier component comprising a copolymer containing two monomers comprises an ethylene-glycidyl methacrylate copolymer.

5. The thermoplastic composition according to claim 4, wherein, The impact modifier component does not include terpolymers.

6. The thermoplastic composition according to claim 4, wherein, The composition comprises 1 wt% to 5 wt% of the ethylene-glycidyl methacrylate copolymer.

7. The thermoplastic composition according to any one of claims 1 to 6, wherein, The glass fiber component comprises glass fibers with a dielectric constant (Dk) of less than 5.0 at 1 kilohertz (GHz) and a dissipation factor (Df) of less than 0.002 at 1 GHz, wherein Dk and Df are tested according to ASTM D150.

8. The thermoplastic composition according to any one of claims 1 to 6, wherein, The composition also contains additional impact modifiers, which include ionomers, styrene-ethylene / 1-butene-styrene (SEBS), or combinations thereof.

9. The thermoplastic composition according to claim 8, wherein, The composition comprises the ionomer, and the ionomer comprises ethylene-zinc acrylate.

10. The thermoplastic composition according to any one of claims 1 to 6, wherein, The composition also contains up to 10 wt% of polyolefin additives.

11. The thermoplastic composition according to claim 10, wherein, The polyolefin additive comprises polypropylene (PP), polystyrene (PS), cyclic olefin copolymer (COC), or a combination thereof.

12. The thermoplastic composition according to any one of claims 1 to 6, wherein, When tested according to the SABIC method, the dissipation factor of the composition is less than 0.007 at frequencies from 1 to 5 GHz.

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