Molded dielectric component crosslinked by irradiation and method for producing the same

Abstract

A cured molded dielectric part comprising a crosslinked composite material comprising a thermoplastic polymer, an optional crosslinking coagent, an optional curing initiator, an optional additive composition, and a ceramic filler composition, wherein the cured molded dielectric part has a dielectric constant of 1.1 to 20 at 10 GHz and no melt flow index when tested at 190°C and 2.16 kg in accordance with ASTM D1238-20.

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims the benefit of U.S. Provisional Patent Application No. 62 / 938,983, filed on November 22, 2019. This related application is hereby incorporated by reference in its entirety.

Background Art

[0002] In many high - frequency applications, polymer components with low dielectric loss are required. Dielectrics in components for such applications benefit from thermoplastic materials that provide easy and rapid processing, but for those materials to have sufficient thermal stability to pass solder reflow tests, they need to have a softening temperature above 300 degrees Celsius (°C). Such materials can be relevant to components that are important in any transmission system or wireless communication infrastructure, such as base station antennas for mobile phones and antennas in digital applications where high data transfer speeds are required.

[0003] It is described that both thermoplastic and thermosetting materials are used in dielectric components. Generally, thermoplastic materials having sufficient solder reflow heat resistance (e.g., temperatures from 240 to 280 °C) for use in forming dielectric components have high viscosities, require extreme processing temperatures, and often require special barrels, screws, and heater materials. On the other hand, thermosetting materials can withstand higher processing temperatures after cross - linking, but are not suitable for methods of processing large quantities of plastics such as extrusion, injection molding, blow molding, thermoforming, and rotational molding.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] From the above, there is still a need for an improved composite material for use as a molded dielectric component. Specifically, there is a need for a material that can withstand exposure to reflow temperatures and can be easily formed into a molded dielectric component under the conditions of a general-purpose plastic, which may have low dielectric loss.

Means for Solving the Problems

[0006] Disclosed herein are cured molded dielectric components, methods of making the same, and articles including the same.

[0007] Disclosed herein is a cured molded dielectric component comprising a crosslinked product of a composite material comprising a thermoplastic polymer, an optional crosslinking aid, an optional curing initiator, an optional additive composition, and a ceramic filler composition, having a permittivity at 10 GHz of from 1.1 to 20 and having no melt flow index when tested at 190° C. and 2.16 kg in accordance with ASTM D1238-20.

[0008] A method of making a cured molded dielectric component includes the steps of compounding a composite material comprising a thermoplastic polymer, an optional crosslinking aid, an optional curing initiator, an optional additive composition, and a ceramic filler composition; melting the compounded composite material to form a melt; shaping the melt to form a shaped article; and exposing the shaped article to radiation to generate sufficient free radicals in the thermoplastic polymer to crosslink at least a portion of the thermoplastic polymer to form a cured molded dielectric component.

[0009] Further disclosed is an article including a cured molded dielectric component.

[0010] The above and other features are illustrated by the following detailed description of the invention and the claims.

DETAILED DESCRIPTION OF THE INVENTION

[0011] Described herein are crosslinked molded dielectric components and methods of making such components using radiation. Surprisingly, it has been found that the electrical properties of cured molded components made from thermoplastic polymers are maintained after irradiation and the thermal resistance increases to that of thermosetting materials. The cured molded components have low dielectric loss and can withstand solder reflow. In particular, the cured molded components can be easily manufactured by forming a composite material comprising a thermoplastic polymer. The composite material is molded, e.g., shaped, and then the molded composite material is irradiated to crosslink the thermoplastic polymer. The resulting cured molded components are thermally stable and have low dimensional change.

[0012] Accordingly, the cured molded dielectric component comprises a crosslinked product of a composite material comprising a thermoplastic polymer having a low processing temperature, any crosslinking aid, any curing initiator, any additive composition, and a ceramic filler composition. The cured molded dielectric component has a dielectric constant of 1.1 to 20 at 500 megahertz (MHz) to 10 gigahertz (GHz), a thermal resistance of up to 280 degrees Celsius (°C), or both, and does not flow at the low processing temperature used to form the cured molded component.

[0013] The cured part is obtained by crosslinking (curing) a thermoplastic polymer. Preferably, the thermoplastic polymer is solid at room temperature and can repeat a cycle of melting and solidification multiple times without crosslinking (when irradiation is not performed). The thermoplastic polymer that can be used can be processed, that is, compounded into pellets and formed into a molded body, at a temperature of 280°C or lower, or 220°C or lower, and further at a relatively low temperature of about 150°C (that is, by injection molding, profile extrusion, blow molding, rotational molding, extrusion, melt casting, or three-dimensional printing). For example, the thermoplastic polymer can be processed at a low processing temperature of 150°C to 280°C, or 160°C to 280°C, or 160°C to 220°C, or 170°C to 200°C, or 170°C to 190°C. The thermoplastic polymer can be processed at 150°C to 235°C.

[0014] For example, the thermoplastic polymer may have a melting temperature (Tm) or a glass transition temperature (Tg) of 250°C or lower, or 90°C to 250°C. Tg can be determined by a differential scanning calorimeter (DSC), for example, under a nitrogen gas blanket, at a ramp rate of 10°C / min from -120°C to 300°C. Alternatively, or in addition, the thermoplastic polymer may have a melt flow index (MFI) measured at 190°C and 2.16 kilograms (kg) in accordance with ASTM D1238-20 of at least 5 grams per 10 minutes (g / 10 min), and preferably, the MFI measured at 190°C and 2.16 kg in accordance with ASTM D1238-20 is at least 10 g / 10 min.

[0015] Exemplary thermoplastic polymers that can be crosslinked by irradiation include thermoplastic polyolefins and their copolymers. Exemplary polyolefins include polyethylene such as low density polyethylene (LDPE) and linear low density polyethylene (LLDPE), polypropylene (PP), and polymethylpentene (PMP). Additional low temperature processing thermoplastics include fluoropolymers such as fluorinated ethylene propylene copolymer (EFEP), cyclic olefin polymers such as polynorbornene and copolymers containing norbornenyl units and acyclic olefins such as ethylene or propylene, and styrenic block copolymers such as styrene - ethylene - propylene - styrene block copolymer (SEPS). It is also possible to use a combination of thermoplastic polymers.

[0016] The amounts of the respective components in the crosslinkable composite material can be adjusted to obtain the desired thermal and electrical properties, as will be described in more detail below. In the broadest sense, when using a self - crosslinkable polymer such as polyethylene, the crosslinkable composite material may have up to 100 weight percent (wt%) of the thermoplastic polymer. However, generally, one or more of a crosslinking aid, a curing initiator, a ceramic filler composition, or any other optional additive is additionally present at at least 1 wt%. In certain embodiments, the composite material for a molded part comprises 10 to 99 wt%, or 10 to 95 wt%, or 50 to 99 wt%, or 50 to 95 wt%, or 60 to 90 wt%, or 10 to 50 wt%, or 10 to 30 wt%, or 10 to 25 wt%, or 10 to 20 wt% of the thermoplastic polymer, respectively, based on the total weight of the composite material.

[0017] When the thermoplastic polymer includes polyethylene, such as LDPE or LLDPE, crosslinking by irradiation does not require a crosslinking aid, but the inclusion of a crosslinking aid can increase the density of crosslinking. When there is no crosslinking aid in the composite material, the crosslinked product (cured and formed dielectric component) does not contain residues of the crosslinking aid. When the thermoplastic polymer does not crosslink or is cut in the absence of a crosslinking aid, a crosslinking aid is present in the composite material so that the thermoplastic polymer is crosslinked by irradiation. For example, when the thermoplastic polymer includes a polymer other than polyethylene, such as polypropylene, a crosslinking aid may be present. When a crosslinking aid is present, generally, the crosslinked product contains residues of the crosslinking aid.

[0018] Exemplary crosslinking aids include triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, functional phosphazenes, triallyl phosphate, polybutadiene, zinc carboxylate salts such as zinc diacrylate and zinc dimethacrylate, vinyl-terminated compounds such as divinylbenzene and vinyl-terminated polyphenylene ether oligomers, m-phenylene dimaleimide, trimethylolpropane trimethacrylate, tetramethylene glycol diacrylate, polyfunctional (meth)acrylates such as trifunctional acrylate esters and dipentaerythritol pentacrylate, and combinations thereof. Incorporating a crosslinking aid such as a functional phosphazene can be beneficial because it can also function as a flame retardant. For example, there is tribinyl functional phosphazene such as SPV-100 commercially available from Otsuka Chemical Co., Ltd. Incorporating a crosslinking aid such as triallyl trimellitate can reduce the generation of smoke.

[0019] In one aspect, the crosslinkable composite material for a molded part contains 0 to 10% by mass, or 0.25 to 10% by mass, or 0.5 to 8% by mass, or 1 to 3% by mass of a crosslinking aid, respectively based on the total mass of the composite material.

[0020] The crosslinkable composite material may further optionally contain a curing initiator. Suitable curing initiators form initiating species, preferably free radicals, upon absorption of radiation. Photoinitiator systems may be used, including a photoinitiator that, upon irradiation, forms free radicals by absorbing hydrogen or electrons from a second compound, usually called a coinitiator, to provide the initiating free radical. Curing (crosslinking) can be achieved by two or more types of radiation with different wavelengths. In some cases, it may be preferable to use two or more curing initiators together.

[0021] Examples of specific curing initiators include quinones, benzophenone and substituted benzophenones, hydroxyalkyl phenylacetophenone, dialkoxyacetophenone, α-halo-acetophenone, aryl ketones (1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-(4-morpholinophenyl)butan-1-one, etc.), thioxanthones (isopropyl thioxanthone, etc.), benzyldimethyl ketal, bis(2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, trimethylbenzoylphosphine oxide derivatives (2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc.), methylthiophenylmorpholinoketone (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, etc.), morpholinophenylaminoketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 5,7-diiodo-3-butoxy-6-fluorone, diphenyliodonium fluoride, triphenylsulfonium hexafluorophosphate, benzoin ether, peroxide, bi-imidazoles, aminoketone, benzoyloxime ester, camphorquinones, ketocoumarin, Michler's ketone, poly(1,4-diisopropylbenzene) (CUROX® CC-P3 of United Initiators), and 2,3-dimethyl-2,3-diphenylbutane. These can be used even when the filler blocks all UV irradiation. Suitable curing initiators are commercially available, for example, under the trade names of IRGACURE® (BASF), LUCERIN® TPO (BASF AG), PERKADOX® (Nouryon), and ESACURE® (LAMBERTI). In certain embodiments, the curing initiator has an onset temperature or decomposition temperature that is higher than the processing temperature of the thermoplastic polymer, for example, at least 10 °C, at least 20 °C, or at least 30 °C higher than the processing temperature of the thermoplastic polymer. For example, when the compounding is carried out at 180 °C and the molding is carried out at 190 °C, it is preferred that the curing initiator does not decompose during these processes.For example, the half-life temperatures of PERKADOX® 30 are 284°C in 0.1 hour, 259°C in 1 hour, and 237°C in 10 hours. The curing initiator may have a half-life of 0.05 to 1 hour at a temperature of 284°C, or a half-life of 0.5 to 5 hours or 0.5 to 2 hours at a temperature of 259°C, or a half-life of 5 to 15 hours at a temperature of 237°C. Since compounding and molding are generally carried out with a residence time of 2 to 10 minutes, the decomposition of the curing agent is minimal.

[0022] The curing initiator may be present in an amount of 0 to 5% by mass, or 0.01 to 5% by mass, or 0.1 to 3% by mass, or 1 to 2% by mass, respectively, based on the total mass of the composite material.

[0023] The composite material described herein may also include a ceramic filler composition to adjust the properties of the formed cured part as a dielectric or other properties. Preferably, the ceramic filler composition is present. The ceramic filler composition may include at least one of fumed silica, titanium dioxide, barium titanate, strontium titanate, corundum, wollastonite, Ba2Ti9O 20 , hollow ceramic spheres, boron nitride, aluminum nitride, silicon carbide, beryllia, alumina, alumina trihydrate, magnesia, mica, talc, nanoclay, magnesium hydroxide, solid glass spheres, hollow glass spheres, or a combination thereof. The ceramic filler composition may include silica, titanium dioxide, or a combination thereof. The titanium dioxide particles may have an irregular shape with a plurality of flat surfaces. The ceramic filler may have a D90 particle size on a mass basis of 0.1 to 10 micrometers or 0.5 to 5 micrometers. The ceramic filler may have a D90 particle size on a mass basis of 2 micrometers or less or 0.1 to 2 micrometers.

[0024] In one aspect, the ceramic filler composition has a multimodal particle size distribution, and the peak of the first peak of the multimodal particle size distribution is at least 7 times the peak of the second peak of the multimodal particle size distribution. The multimodal particle size distribution can result in a lower viscosity composite material. The multimodal particle size distribution may be, for example, bimodal, trimodal, or tetramodal. In other words, the ceramic filler may include a first plurality of particles having a first average particle size and a second plurality of particles having a second average particle size, and the first average particle size is 7 times or more, or 10 times or more, or 7 to 60 times, or 7 to 20 times the second average particle size. As used herein, the term particle size refers to the diameter of a sphere having the same volume as the particle, and the average particle size refers to the number average of the particle sizes of a plurality of particles. The peak of the first peak (the first average particle size) may be 2 micrometers or more, or 2 to 20 micrometers. The peak of the second peak (the second average particle size) may be 0.2 micrometers or more, or 2 micrometers or less, or 0.2 to 1.5 micrometers.

[0025] The first plurality of particles and the second plurality of particles may comprise the same ceramic filler. For example, the first plurality of particles and the second plurality of particles may comprise titanium dioxide. Conversely, the first plurality of particles and the second plurality of particles may also comprise different ceramic fillers. For example, the first plurality of particles may comprise silica, and the second plurality of particles may comprise titanium dioxide.

[0026] The first plurality of particles may have an average particle size of 1 to 10 micrometers, or 2 to 5 micrometers. The second plurality of particles may have an average particle size of 0.01 to 1 micrometer, or 0.1 to 0.5 micrometer. The ceramic filler may include a first plurality of particles comprising titanium dioxide having an average particle size of 1 to 10 micrometers and a second plurality of particles having an average particle size of 0.1 to 1 micrometer.

[0027] The ceramic filler compositions may each be present in an amount of 1 to 90% by weight, or 5 to 90% by weight, or 1 to 50% by weight, or 5 to 50% by weight, or 10 to 40% by weight, or 50 to 90% by weight, or 70 to 90% by weight, or 75 to 90% by weight, or 80 to 90% by weight, based on the total weight of the composite material.

[0028] In another aspect, the composite material includes more than 20 volume percent (volume %) of ceramic filler based on the total volume of the composite material.

[0029] In one aspect, the composite material includes more than 40 volume % of ceramic filler based on the total volume of the composite material.

[0030] The ceramic filler may include treated titanium dioxide. For example, titanium dioxide can be sintered to increase the amount of the desired phase. Without intending to be bound by theory, sintering is thought to help the composition achieve lower dielectric loss. The first plurality of titanium dioxide particles having an average particle size of 1 to 10 micrometers, or 2 to 5 micrometers, may be sintered. The first plurality of titanium dioxide particles having an average particle size of 0.1 to 1 micrometer, or 0.1 to 0.5 micrometer, may be sintered.

[0031] The ceramic filler can be surface-treated with, for example, a surfactant, silane, titanate, zirconate, organic polymer, or other inorganic material to assist in its dispersion in the thermoplastic polymer. For example, the particles can be coated with a surfactant such as oleylamine oleic acid. Silanes can include N-β(aminoethyl)-γ-aminopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, 3-chloropropyl-methoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, phenylsilane, trichloro(phenyl)silane, 3-(triethoxysilyl)propyl succinic anhydride, tris(trimethylsiloxy)phenylsilane, vinylbenzylaminoethylaminopropyltrimethoxysilane, vinyl-trichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(beta-methoxyethoxy)silane, or combinations thereof. Silanes can include phenylsilane. Silanes can include substituted phenylsilanes, such as those described in U.S. Patent No. 4,756,971. Titanate coatings can include isostearyl titanate [tris(isooctadecanoato-O)(propan-2-olato)titanium], neopentyl(diallyl)oxy, trineodecanonyl titanate, neopentyl(diallyl)oxy, tri(dodecyl)benzene-sulfonyl titanate, neopentyl(diallyl)oxy, tri(dioctyl)phosphato titanate, neopentyl(diallyl)oxy, tri(dioctyl)pyro-phosphato titanate, neopentyl(diallyl)oxy, tri(N-ethylenediamino)ethyl titanate, neopentyl(diallyl)oxy, tri(m-amino)phenyl titanate, and neopentyl(diallyl)oxy, trihydroxy It can be formed from caproyl titanate, or a combination thereof. In certain embodiments, the titanate coating is isostearyl titanate such as TYTAN® CP-317 (Borica) [tris(isooctadecanoato-O)(propan-2-olato)titanium]. The zirconate coating can be formed from neopentyl(diallyloxy)tri(dioctyl)pyrophosphate zirconate, neopentyl(diallyloxy)tri(N-ethylenediamino)ethyl zirconate, or a combination thereof.

[0032] The coating can be present at 0.01 to 2 wt% or 0.1 to 1 wt% based on the total mass of the coated ceramic filler. The ceramic filler can be coated with SiO2, Al2O3, MgO, or a combination thereof. The ceramic filler can be coated by a base-catalyzed sol-gel process, polyetherimide (PEI) wet and dry coating processes, or poly(ether ketone) (PEEK) wet and dry coating processes.

[0033] In one aspect, the composite material includes an additive composition to adjust the desired properties of the cured molded part. The additive composition can include an antioxidant, a metal deactivator, a processing aid (e.g., polyethylene wax or stearic acid derivative), an adhesion promoter, or a combination thereof. Non-limiting examples of antioxidants are poly[[6-(1,1,3,3-tetramethylbutyl)amino-s-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl-)imino]] commercially available under the trade name CHIMASSORB® 944 from BASF, or IRGANOX® 1010 (pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)) also commercially available from BASF. Non-limiting examples of metal deactivators are 2,2-oxalyldianamide bis[ethyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] commercially available under the trade name NAUGARD® XL-1 from ADDIVANT®. A preferred metal deactivator is SONGNOX® 1024, 1,2-bis(3,5-di-tert-butylhydroxyhydrocinnamoyl)hydrazine commercially available from Songwon. An exemplary processing aid includes Honeywell A-C® 6A LDPE wax. Exemplary adhesion promoters include maleic anhydride grafted polyolefins such as SCONA® TSPE 1112 GALL commercially available from BYK Chemie.

[0034] Each additive, if present, may be used in an amount of from 0 to 2 wt%, or from 0.0001 to 2 wt%, or from 0.0005 to 1.6 wt% based on the total mass of the composite material, respectively. Generally, the additive composition may be present in a total amount of from 0.0001 to 5 wt% or from 0.001 to 3 wt% based on the total mass of the composite material, respectively.

[0035] Accordingly, a method of fabricating a cured and formed dielectric component may include compounding a composite material including a thermoplastic polymer having a low processing temperature, an optional crosslinking aid, an optional curing initiator, an optional additive composition, and a ceramic filler composition. The compounded composite material may be melted to form a melt, and the melt may be formed into a formed article. Thereafter, the formed article may be exposed to radiation to generate sufficient free radicals in the thermoplastic polymer to crosslink at least a portion of the thermoplastic polymer to form a cured and formed dielectric component.

[0036] In a method of fabricating a cured and formed dielectric component, compounding can be carried out using known apparatuses suitable for melting and blending thermoplastic polymers, such as single-screw or twin-screw extruders, Buss kneaders, Farrel continuous mixers, Banbury mixers, or two-roll mills. Various components may be directly mixed or sequentially fed. In one aspect, the formulation is extruded as strands and cut into cylindrical pellets. Compounding or other processing can be carried out at a temperature of 150 °C to 250 °C, or 160 °C to 220 °C, or 170 °C to 200 °C, or 170 °C to 190 °C.

[0037] After compounding, the crosslinkable composite material may have an MFI measured at 190 °C and 2.16 kg in accordance with ASTM D1238-20 of at least 5 g / 10 min, preferably an MFI measured at 190 °C and 2.16 kg in accordance with ASTM D1238-20 of at least 10 g / 10 min.

[0038] Thereafter, the crosslinkable composite material may be melted and formed. The melting and forming can be carried out at a temperature of 150°C to 250°C, or 160°C to 220°C, or 170°C to 200°C, or 170°C to 190°C. The forming can be achieved, for example, by molding (such as injection molding, rotational molding, or blow molding), extrusion (such as profile or layer extrusion), or otherwise forming layers to form a solid shape, sheet, layer, rod, tube, or hollow article. For example, the forming may include forming a layer on a copper substrate such as a conductive copper layer. In a preferred embodiment, the forming is achieved by molding. In one embodiment, a blowing agent may be added during melting and forming to obtain a low-density shape, sheet, rod, or tube. In one embodiment, the melted crosslinkable composite material can be injected into a mold or overmolded onto a substrate to obtain a formed article while minimizing secondary handling and joining processes.

[0039] The formed article may initiate crosslinking by irradiation to generate free radicals in the polymer backbone or side chains, thereby forming a three-dimensional network in the cured formed part. Exemplary irradiation methods include electron beam irradiation, gamma ray irradiation, ultraviolet irradiation, and the like.

[0040] In another embodiment, the formulation is melted and formed on a substrate and irradiated on the substrate. A mask can be used to cover the area of the substrate to be protected from irradiation. Thus, in one embodiment, the formed article is formed on the substrate, a mask is used to cover the radiation-sensitive area of the substrate to be protected from irradiation, and the unmasked area of the formed article is exposed to irradiation to effect crosslinking of the formed article while protecting the radiation-sensitive area of the substrate.

[0041] The cured molded part includes a cured composite material, in particular, a cross-linked product of a thermoplastic polymer, any remaining cross-linking aids, curing agents, and additives if used, and a ceramic filler composition. Of course, if there are no cross-linking aids, curing agents, or additives in the composite material, there will be no remaining cross-linking aids, curing agents, or additives.

[0042] Importantly, after curing, the molded dielectric part does not have melt flow at the above processing temperatures, for example, from 150 °C to 250 °C, or from 160 °C to 220 °C, or from 170 °C to 200 °C, or from 170 °C to 190 °C. As used herein, the phrase "does not have melt flow" may mean that the MFI is equal to 0 g / 10 min. This characteristic can be characterized by the molded dielectric part having no MFI (i.e., the MFI is unmeasurable) when tested at 190 °C and 2.16 kg according to ASTM D1238-20.

[0043] The cured molded dielectric part can have a dielectric constant (relative permittivity, Dk) of 1.1 to 20 at 500 MHz to 10 GHz. The cured molded dielectric part can have a thermal resistance up to at least 250 °C. The cured molded dielectric part can be dimensionally stable such that the change in dimensions of the cured molded dielectric part is less than 5%, or from 0 to 1%, up to a high temperature of about 280 °C.

[0044] In one aspect, the cured and formed dielectric component may have a relative permittivity greater than 1.1, such as 1.5 to 20, or 2.5 to 20, or 3 to 18, or 3 to 13, etc., when measured at 10 GHz. In certain aspects, the cured and formed dielectric component has a relative permittivity less than 6 when measured at 10 GHz. In another aspect, the cured and formed dielectric component may have a relative permittivity greater than 1.1, such as 1.6 to 6, or 1.5 to 6, or 2 to 6, etc., when measured at 10 GHz. In yet another aspect, the cured and formed dielectric component may have a relative permittivity greater than 6, or greater than 10, or greater than 12, for example 6 to 20, or 6 to 18, or 6 to 15, or 10 to 20, or 12 to 20, when measured at 10 GHz.

[0045] The cured and formed dielectric component may have a dielectric loss (Df) of 0.007 or less, or 0.005 or less. The dielectric loss can be as low as about 0.001 when measured at 10 GHz. For example, the cured and formed dielectric component may have a dielectric loss of 0.001 to 0.005 at 10 GHz.

[0046] The properties as a dielectric can be measured at a temperature of 23 to 25 °C according to the "Stripline Test for Permittivity and Loss Tangent at X - Band" test method IPC - TM - 650 2.5.5.5.

[0047] The cured and formed dielectric component can pass the 30 - second solder float test at 288 °C without cracking, swelling, or warping of the component.

[0048] The change in the length dimension of the pre - cured component compared to the post - cured component can be less than 2%, preferably less than 1%, in at least one, two, three, or all of the length dimensions such as diameter, length, height, width, etc. In certain aspects, the change in the length dimension of the pre - cured component compared to the post - cured component can be less than 2%, preferably less than 1%, in two or three length dimensions.

[0049] In another aspect, the change in the volume dimension of the part before curing compared to after curing can be less than 2%, preferably less than 1%. The volume change can be measured, for example, by three-dimensional image processing.

[0050] Advantageously, by using a thermoplastic polymer, a cured molded dielectric part can be manufactured using standard equipment. In addition, by using irradiation to crosslink the molded dielectric part, the cured part can function at a temperature much higher than the temperature of the thermoplastic. The cured molded dielectric part has a thermal resistance that is not affected by a solder reflow process at 240°C to 280°C.

[0051] The circuit material including the cured molded dielectric part described herein can be prepared by forming a multilayer material having a substrate layer including the cured molded dielectric part and a conductive layer disposed thereon. Useful conductive layers include, for example, stainless steel, copper, gold, silver, aluminum, zinc, tin, lead, transition metals, and alloys thereof. There is no particular limitation on the thickness of the conductive layer, nor is there any limitation on the shape, size, or surface texture of the conductive layer. The conductive layer may have a thickness of 3 to 200 micrometers or 9 to 180 micrometers. When two or more conductive layers are present, the thicknesses of the two layers may be the same or different. The conductive layer may include a copper layer. Suitable conductive layers include thin layers of conductive metals, for example, copper foils currently used in the formation of circuits, for example, electrodeposited copper foils. The copper foil may have a root mean square (RMS) roughness of 2 micrometers or less or 0.7 micrometers or less, where the roughness is measured using the method of white light interferometry using a Veeco Instruments WYCO® optical profiler.

[0052] The conductive layer can be applied by laminating the conductive layer on the substrate, by direct laser structuring, or by adhering the conductive layer to the substrate via an adhesive layer. If permitted by the specific material and form of the circuit material, other methods known in the art, such as electroplating and chemical vapor deposition, can be used to apply the conductive layer.

[0053] Lamination may involve laminating a multi-layer stack including the substrate, the conductive layer, and any intermediate layers between the substrate and the conductive layer to form a layered structure. The conductive layer may be in direct contact with the substrate layer without an intermediate layer. Thereafter, the layered structure may be placed in a press, such as a vacuum press, for a certain period of time under a pressure and temperature suitable for adhering the layers to form a laminate. Lamination and any curing may be performed by a one-step process using, for example, a vacuum press, or by a multi-step process. In the one-step process, the layered structure may be placed in the press, the lamination pressure (e.g., 150 to 400 pounds per square inch (psi) (1 to 2.8 megapascals)) may be increased, and the lamination temperature (e.g., 260 to 390 °C) may be heated. The lamination temperature and pressure may be maintained for a desired soak time, e.g., 20 minutes, and then cooled to 150 °C or less (while the pressure is applied).

[0054] When present, the intermediate layer may include a polyfluorocarbon film that can be positioned between the conductive layer and the substrate layer, and an optional layer of a microglass-reinforced fluorocarbon polymer may be positioned between the polyfluorocarbon film and the conductive layer. The layer of microglass-reinforced fluorocarbon polymer can enhance the adhesion of the conductive layer to the substrate. The microglass may be present in an amount of 4 to 30 weight percent (wt%) based on the total mass of the layer. The microglass may have a longest length scale of 900 micrometers or less or 500 micrometers or less. The microglass may be of a type commercially available from Johns Manville of Denver, Colorado. The polyfluorocarbon film includes fluoropolymers (e.g., polytetrafluoroethylene (PTFE)), fluorinated ethylene-propylene copolymers (e.g., TEFLON® FEP), and copolymers having a tetrafluoroethylene backbone and a perfluorinated alkoxy side chain (e.g., TEFLON® PFA).

[0055] The conductive layer can be applied by direct laser structuring. Here, the substrate may contain a direct laser structuring additive, and the direct laser structuring may include the steps of irradiating the surface of the substrate using a laser, forming tracks of the direct laser structuring additive, and applying a conductive metal to the tracks. The direct laser structuring additive may contain metal oxide particles (e.g., titanium oxide and copper chromium oxide). The direct laser structuring additive may contain spinel-type inorganic metal oxide particles, such as spinel copper. The metal oxide particles may be coated with a composition containing, for example, tin and antimony (e.g., 50 to 99% by mass of tin and 1 to 50% by mass of antimony based on the total mass of the coating). The direct laser structuring additive may contain 2 to 20 parts of the additive based on 100 parts of each composition. The irradiation can be performed with a YAG laser having a wavelength of 1,064 nanometers (nm) under an output of 10 watts (W), a frequency of 80 kilohertz (kHz), and a speed of 3 meters per second (m / s). The conductive metal can be applied using, for example, a plating process in an electroless plating bath containing copper.

[0056] The conductive layer may be applied by adhesively applying the conductive layer. The conductive layer may be a circuit (a metallized layer of another circuit), for example, a flex circuit. An adhesive layer may be disposed between the one or more conductive layers and the substrate. Where appropriate, the adhesive layer may include a poly(arylene ether), and a carboxy-functionalized polybutadiene or polyisoprene polymer containing butadiene, isoprene, or butadiene and isoprene units and from 0 to 50 weight percent of a co-curable monomer unit. The adhesive layer may be present in an amount of from 2 to 15 grams per square meter. The poly(arylene ether) may include a carboxy-functionalized poly(arylene ether). The poly(arylene ether) may be a reaction product of a poly(arylene ether) and a cyclic anhydride, or may be a reaction product of a poly(arylene ether) and maleic anhydride. The carboxy-functionalized polybutadiene or polyisoprene polymer may be a carboxy-functionalized butadiene-styrene copolymer. The carboxy-functionalized polybutadiene or polyisoprene polymer may be a reaction product of a polybutadiene or polyisoprene polymer and a cyclic anhydride. The carboxy-functionalized polybutadiene or polyisoprene polymer may be a maleated polybutadiene-styrene or maleated polyisoprene-styrene copolymer.

[0057] The cured and formed dielectric component can be used in electronic devices and electromagnetic components, such as inductors on electronic integrated circuit chips, electronic circuits, electronic packages, modules, housings, transducers, ultra-high frequency (UHF) antennas, very high frequency (VHF) antennas, and microwave antennas for various applications, such as power applications, data storage, and microwave communication. The cured and formed dielectric component can be used in electronic devices, such as mobile Internet devices. The cured and formed dielectric component can be used in electronic devices, such as mobile phones, tablets, notebook computers, and Internet clocks. The cured and formed dielectric component can be used in applications where an external DC magnetic field is applied. In addition, the cured and formed dielectric component can be used with very good results (size and bandwidth) in all antenna designs over a frequency range from 1 to 10 GHz. The antenna may be a planar inverted F antenna, a patch antenna, a dipole antenna, or a meander line antenna. In one aspect, the cured and formed dielectric component is the dielectric portion of a dielectric resonator antenna. The cured and formed dielectric component may be a resonator. The cured and formed dielectric component may be a dielectric resonator antenna. The cured and formed dielectric component may be an electromagnetic waveguide, including, but not limited to, a dielectric waveguide or a metal waveguide having a dielectric in the transmission region. The cured and formed dielectric component may be a dielectric electromagnetic lens, such as a dielectric electromagnetic lens configured to operate at a frequency above 5 GHz and less than 300 GHz. The cured and formed dielectric component can be used in radio frequency (RF) components. The cured and formed dielectric component can be used in microwave components. The cured and formed dielectric component can be used in millimeter-wave components. The cured and formed dielectric component can be used in terahertz components. The cured and formed dielectric component can be used in optical components.

[0058] The cured dielectric component (also referred to as a component) may include a cross-linked product of a composite material. The composite material may include a thermoplastic polymer and a ceramic filler composition. The composite material may optionally include at least one of a cross-linking aid, a curing initiator, or an additive composition. The component may have a dielectric constant of 1.1 to 20 at 10 GHz. The component may not have a melt flow index when tested at 190 °C and 2.16 kg according to ASTM D1238-20. The processing temperature of the thermoplastic polymer may be from 160 °C to 280 °C. The melting temperature of the thermoplastic polymer may be 250 °C or less, or from 90 °C to 250 °C. The melt flow index of the thermoplastic polymer measured at 190 °C and 2.16 kg according to ASTM D1238-20 may be less than 5 grams per 10 minutes. The thermoplastic polymer may include polyethylene, polypropylene, polymethylpentene, fluorinated ethylene propylene copolymer, polynorbornene, styrene-ethylene-propylene-styrene block copolymer, or a combination thereof. The thermoplastic polymer may include low-density polyethylene or linear low-density polyethylene. The cross-linked product may include a residue of the cross-linking aid. Conversely, for example, when the thermoplastic polymer includes a thermoplastic polymer that self-cross-links by irradiation such as polyethylene, the cross-linked product may not include a residue of the cross-linking aid. The composite material may include a curing initiator, and the curing initiator may have an initiation temperature higher than the processing temperature of the thermoplastic polymer, preferably at least 10 °C, at least 20 °C, or at least 30 °C higher than the processing temperature of the thermoplastic polymer. The composite material may include all three of a cross-linking aid, a curing initiator, and an additive composition. The cross-linking aid may be present and may include triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, polybutadiene, zinc diacrylate, zinc dimethacrylate, divinylbenzene, vinyl-terminated polyphenylene ether oligomer, m-phenylene dimaleimide, trimethylolpropane trimethacrylate, tetramethylene glycol diacrylate, trifunctional acrylate ester, dipentaerythritol pentaacrylate, or a combination thereof. The additive composition may be present and may include oxidation It may contain an inhibitor, a metal deactivator, a processing aid, an adhesion promoter, or a combination thereof. The ceramic filler may include fumed silica, titanium dioxide, barium titanate, strontium titanate, corundum, wollastonite, Ba2Ti9O 20 , hollow ceramic spheres, boron nitride, aluminum nitride, silicon carbide, beryllia, alumina, alumina trihydrate, magnesia, mica, talc, nanoclay, magnesium hydroxide, solid glass spheres, hollow glass spheres, or a combination thereof. The ceramic filler may have a multimodal particle size distribution, and the peak of the first peak of the multimodal particle size distribution is at least 7 times that of the peak of the second peak of the multimodal particle size distribution.

[0059] Before crosslinking, the composite materials each may contain, based on the total mass of the composite materials before crosslinking, 10 to 99% by mass of a thermoplastic polymer, 0 to 10% or 0.25 to 10% by mass of a crosslinking aid, 0 to 5% or 0.01 to 5% by mass of a curing initiator, 0 to 2% or 0.0001 to 2% by mass of an additive composition, and 1 to 90% by mass of a ceramic filler composition, with the total being 100% by mass. Before crosslinking, the composite materials each may contain, based on the total mass of the composite materials before crosslinking, 50 to 95% by mass of a thermoplastic polymer, 0 to 10% or 0.25 to 10% by mass of a crosslinking aid, 0 to 5% or 0.01 to 5% by mass of a curing initiator, 0 to 2% or 0.001 to 2% by mass of an additive composition, and 5 to 50% by mass of a ceramic filler composition, with the total being 100% by mass. Before crosslinking, the composite materials each may contain, based on the total mass of the composite materials before crosslinking, 10 to 50% by mass of a thermoplastic polymer, 0 to 10% or 0.25 to 10% by mass of a crosslinking aid, 0 to 5% or 0.01 to 5% by mass of a curing initiator, 0 to 2% or 0.001 to 2% by mass of an additive composition, and 50 to 90% by mass of a ceramic filler composition, with the total being 100% by mass. Before crosslinking, the composite materials each may contain, based on the total mass of the composite materials before crosslinking, 10 to 25% by mass of a thermoplastic polymer, 0 to 10% or 0.25 to 10% by mass of a crosslinking aid, 0 to 5% or 0.01 to 5% by mass of a curing initiator, 0 to 2% or 0.001 to 2% by mass of an additive composition, and 75 to 90% by mass of a ceramic filler composition, with the total being 100% by mass. The composite material may contain more than 20 volume percent, preferably more than 40 volume percent, of ceramic filler based on the total volume of the composite material.

[0060] The dielectric constant of the component may be from 1.1 to 20 when measured at 10 GHz. When the component contains a ceramic filler composition in a reduced amount, for example, 5 to 50% by mass based on the total mass of the composite material before crosslinking, the component may have a lower dielectric constant from 1.1 to 6 when measured at 10 GHz. When the component contains a ceramic filler composition in an increased amount, for example, 50 to 90% by mass or more based on the total mass of the composite material before crosslinking, the component may have a lower dielectric constant greater than 6, preferably greater than 10, preferably greater than 12 when measured at 10 GHz. The change in the length dimension of the component before curing compared to after curing is less than 2%, preferably less than 1% in any or all of the length dimensions.

[0061] The component may be a dielectric resonator antenna, a dielectric part of a dielectric resonator antenna, an electromagnetic waveguide, a dielectric electromagnetic lens, a radio frequency component, a microwave component, a millimeter wave component, a terahertz component, or an optical component. The component may be a dielectric electromagnetic lens, preferably a dielectric electromagnetic lens configured to operate at a frequency greater than 5 GHz and less than 300 GHz. The circuit material or the circuit board may include a cured and formed dielectric component.

[0062] The method of fabricating a cured and formed dielectric component may include the steps of blending a composite material including a thermoplastic polymer, any crosslinking aid, any curing initiator, any additive composition, and a ceramic filler composition; melting the blended composite material to form a melt; shaping the melt to form a shaped article; and exposing the shaped article to radiation to generate sufficient free radicals in the thermoplastic polymer and crosslink at least a part of the thermoplastic polymer to form a cured and formed dielectric component. The method may further include the steps of forming the shaped article on a substrate, masking at least a part of the shaped article against irradiation, and exposing the unmasked part of the shaped article to irradiation to form a cured and formed dielectric component. The shaping may include molding or layer formation, preferably molding.

[0063] The following examples are merely illustrative and are not intended to limit the compositions, cured molded parts, or devices disclosed and made herein, or the processes, conditions, or process parameters disclosed herein.

Examples

[0064] In the examples, the melt flow index (MFI) at 190 °C / 2.16 kg was measured with an extrusion plastometer from Tinius Olsen (registered trademark).

[0065] The melting point of the thermomechanical analysis (TMA) was measured with a TMA Q400 from TA Instruments. The TMA was determined according to ASTM E1545-11 (2016), and the sample was heated, cooled, and reheated from -50 °C to 300 °C at a rate of 10 °C per minute. The first heat cycle was for annealing out orientation and physical external effects, and the second heating was performed to prove that the measurements were reproducible.

[0066] The long strip line dielectric constant (LSL) was measured using a network analyzer 8510 from Hewlett Packard and reported at 10 GHz.

[0067] The solder float at 287 °C was determined with a solder melting unit from Ritehete.

[0068] The components used in the examples are provided in Table 1.

[0069]

Table 1

[0070] (Examples 1 - 6) The compositions in Table 2 were compounded using a twin-screw extruder. The compounded compositions were formed into molded bodies by injection molding at 180°C using an Extrude to Fill E30V molding machine. The formed bodies were then crosslinked at room temperature using an electron beam (0, 8, 16, and 32 MRad). The MFI and TMA of the material before crosslinking (0 MRad) and the properties of the crosslinked bodies were determined and are shown in Table 2.

[0071] [Table 2]

[0072] Example 7 Under the same measurement conditions, a liquid crystal polymer (LCP) filled with TiO2 failed the solder float test after 5 minutes due to cracking.

[0073] (Examples 8 to 19) Examples 8-10, shown in Table 3, were prepared (8) without coagent and curing initiator, (9) with coagent and no curing initiator, and (10) with both coagent and curing initiator, and cured by exposure to 32 MRad of electron beam radiation. The melting peak temperatures and melting efficiencies of the cured compositions are also shown in Table 3.

[0074] [Table 3]

[0075] From the data in Table 3, it can be seen that the polypropylene of Example 8 depolymerizes by cleavage when exposed to an electron beam without a crosslinking agent or initiator, as shown by complete melting. Although significant improvement was brought about by adding a crosslinking aid as in Example 9, the TMA scan still showed a small feature at the melting point, indicating that there is a small amount of uncrosslinked domain present. When both a crosslinking agent and a secondary curing initiator (temperature 284 °C, half-life 0.1 hour) are added at a temperature much lower than the melt mixing temperature of 180 °C, as demonstrated by the TMA scan not showing the characteristics of melting, the last residue of the uncrosslinked polymer is eliminated.

[0076] (Example 20) Dimensional change A molded part containing the following composition was formed, specifically an antenna. 6.93% by mass of LLDPE, 6.93% by mass of HDPE, 78.95% by mass of titanium dioxide, 4.95% by mass of fumed silica / silane, 2.02% of TAIC, 0.198% by mass of PERDADOX® 30 curing initiator, and 0.0396% by mass each of a metal deactivator and an antioxidant. At room temperature, the diameter and height of the part before and after curing were measured in millimeters (mm). The results are provided in Table 4, where samples A to E are the same samples labeled for tracking purposes.

[0077] [Table 4]

[0078] As can be seen from Table 4, the diameter and height of the part changed little after irradiation compared to before irradiation.

[0079] The following are non-limiting aspects of the present disclosure.

[0080] Aspect 1: A cured molded dielectric component comprising a cross-linked product of a composite material containing a thermoplastic polymer, an optional cross-linking aid, an optional curing initiator, an optional additive composition, and a ceramic filler composition, wherein the dielectric constant at 10 GHz is from 1.1 to 20 and has no melt flow index when tested at 190 °C and 2.16 kg according to ASTM D1238-20.

[0081] Aspect 2. The cured molded dielectric component according to Aspect 1, wherein the processing temperature of the thermoplastic polymer is from 160 °C to 280 °C.

[0082] Aspect 3. The cured molded dielectric component according to Aspect 1 or 2, wherein the melting temperature of the thermoplastic polymer is 250 °C or lower, or from 90 °C to 250 °C.

[0083] Aspect 4. The cured molded dielectric component according to any one of Aspects 1 to 3, wherein the melt flow index of the thermoplastic polymer measured at 190 °C and 2.16 kg according to ASTM D1238-20 is less than 5 grams per 10 minutes.

[0084] Aspect 5. The cured molded dielectric component according to any one of Aspects 1 to 4, wherein the thermoplastic polymer comprises polyethylene, polypropylene, polymethylpentene, fluorinated ethylene propylene copolymer, polynorbornene, styrene-ethylene-propylene-styrene block copolymer, or a combination thereof.

[0085] Aspect 6. The cured molded dielectric component according to any one of Aspects 1 to 5, wherein the thermoplastic polymer comprises LDPE or LLDPE.

[0086] Aspect 7. The cured molded dielectric component according to any one of Aspects 1 to 6, wherein the cross-linked product contains residues of the cross-linking aid.

[0087] Aspect 8. The cured molded dielectric component according to any one of Aspects 1 to 6, wherein the crosslinked product does not contain a residue of a crosslinking aid, and the thermoplastic polymer contains a thermoplastic polymer that self-crosslinks by irradiation such as polyethylene.

[0088] Aspect 9: The cured molded dielectric component according to any one of Aspects 1 to 8, wherein the curing initiator is present and has an initiation temperature higher than the processing temperature of the thermoplastic polymer, preferably at least 10 °C, at least 20 °C, or at least 30 °C higher than the processing temperature of the thermoplastic polymer.

[0089] Aspect 10. The cured molded dielectric component according to any one of Aspects 1 to 9, wherein at least one or more of the crosslinking aid, the curing initiator, or the additive composition is present, preferably all three of the crosslinking aid, the curing initiator, and the additive composition are present.

[0090] Aspect 11. The cured molded dielectric component according to any one of Aspects 1 to 10, wherein the crosslinking aid contains triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, polybutadiene, zinc diacrylate, zinc dimethacrylate, divinylbenzene, vinyl-terminated polyphenylene ether oligomer, m-phenylenedimaleimide, trimethylolpropane trimethacrylate, tetramethylene glycol diacrylate, trifunctional acrylate ester, dipentaerythritol pentaacrylate, or a combination thereof.

[0091] Aspect 12. The cured molded dielectric component according to any one of Aspects 1 to 11, wherein the additive composition contains an antioxidant, a metal deactivator, a processing aid, an adhesion promoter, or a combination thereof.

[0092] Aspect 13. The ceramic filler is fumed silica, titanium dioxide, barium titanate, strontium titanate, cordierite, wollastonite, Ba2Ti9O 20, a hollow ceramic sphere, boron nitride, aluminum nitride, silicon carbide, beryllia, alumina, alumina trihydrate, magnesia, mica, talc, nanoclay, magnesium hydroxide, a solid glass sphere, a hollow glass sphere, or a combination thereof, the cured molded dielectric component according to any one of aspects 1 to 12.

[0093] Aspect 14. The ceramic filler has a multimodal particle size distribution, and the peak of the first peak of the multimodal particle size distribution is at least 7 times the peak of the second peak of the multimodal particle size distribution, the cured molded dielectric component according to any one of aspects 1 to 13.

[0094] Aspect 15. Before crosslinking, the composite material respectively contains, based on the total mass of the composite material before crosslinking, 10 to 99% by mass of the thermoplastic polymer, 0 to 10% by mass or 0.25 to 10% by mass of the crosslinking aid, 0 to 5% by mass or 0.01 to 5% by mass of the curing initiator, 0 to 2% by mass or 0.0001 to 2% by mass of the additive composition, and 1 to 90% by mass of the ceramic filler composition, and the total is 100% by mass, the cured molded dielectric component according to any one of aspects 1 to 14.

[0095] Aspect 16. Before crosslinking, the composite material respectively contains, based on the total mass of the composite material before crosslinking, 50 to 95% by mass of the thermoplastic polymer, 0 to 10% by mass or 0.25 to 10% by mass of the crosslinking aid, 0 to 5% by mass or 0.01 to 5% by mass of the curing initiator, 0 to 2% by mass or 0.0001 to 2% by mass of the additive composition, and 5 to 50% by mass of the ceramic filler composition, and the total is 100% by mass, the cured molded dielectric component according to aspect 15.

[0096] Aspect 17. The dielectric constant measured at 10 GHz is 6 or less, less than 6, or 1.1 to 6, the cured molded dielectric component according to any one of aspects 1 to 16.

[0097] Aspect 18. The composite material before crosslinking contains, respectively, based on the total mass of the composite material before crosslinking, 10 to 50% by mass of the thermoplastic polymer, 0 to 10% by mass or 0.25 to 10% by mass of the crosslinking aid, 0 to 5% by mass or 0.01 to 5% by mass of the curing initiator, 0 to 2% by mass or 0.0001 to 2% by mass of the additive composition, and 50 to 90% by mass of the ceramic filler composition, with the total being 100% by mass. The cured and molded dielectric component according to any one of Aspects 1 to 14.

[0098] Aspect 19. The composite material before crosslinking contains, respectively, based on the total mass of the composite material before crosslinking, 10 to 25% by mass of the thermoplastic polymer, 0 to 10% by mass or 0.25 to 10% by mass of the crosslinking aid, 0 to 5% by mass or 0.01 to 5% by mass of the curing initiator, 0 to 2% by mass or 0.0001 to 2% by mass of the additive composition, and 75 to 90% by mass of the ceramic filler composition, with the total being 100% by mass. The cured and molded dielectric component according to Aspect 18.

[0099] Aspect 20. The composite material contains more than 20% by volume, preferably more than 40% by volume of the ceramic filler based on the total volume of the composite material. The cured and molded dielectric component according to any one of Aspects 1 to 19, or Aspects 1 to 14, or Aspects 16 to 17.

[0100] Aspect 21. The relative permittivity measured at 10 GHz is more than 6, preferably more than 10, preferably more than 12. The cured and molded dielectric component according to any one of Aspects 1 to 20, or Aspects 1 to 14, or Aspects 18 to 20.

[0101] Aspect 22: The change in the length dimension of the component before curing compared to after curing is less than 2%, preferably less than 1% in one, or two, or more length dimensions. The cured and molded dielectric component according to any one of Aspects 1 to 21.

[0102] Aspect 22a. The change in the volume dimension of the part before curing compared to after curing is less than 2%, preferably less than 1%, of the cured molded dielectric part according to any one of Aspects 1 to 21.

[0103] Aspect 23. The part is a dielectric resonator antenna, a dielectric part of a dielectric resonator antenna, an electromagnetic waveguide, a dielectric electromagnetic lens, a radio frequency component, a microwave component, a millimeter wave component, a terahertz component, or an optical component, of the cured molded dielectric part according to any one of Aspects 1 to 22.

[0104] Aspect 24. The part is a dielectric electromagnetic lens, or a dielectric electromagnetic lens configured to operate at a frequency above 5 GHz and less than 300 GHz, of the cured molded dielectric part according to any one of Aspects 1 to 23.

[0105] Aspect 25. A circuit material or a circuit board including the cured molded dielectric part according to any one of Aspects 1 to 24.

[0106] Aspect 26. A method for manufacturing the cured molded dielectric part according to any one of Aspects 1 to 24, the method including: blending a composite material including a thermoplastic polymer with a low processing temperature, any crosslinking aid, any curing initiator, any additive composition, and a ceramic filler composition; melting the blended composite material to form a melt; molding the melt to form a molded article; and exposing the molded article to radiation to generate sufficient free radicals in the thermoplastic polymer and crosslink at least a part of the thermoplastic polymer to form the cured molded dielectric part.

[0107] Aspect 27. The method according to Aspect 26, further including: forming the molded article on a substrate; masking at least a part of the molded article against irradiation; and exposing the unmasked part of the molded article to irradiation to form the cured molded dielectric part.

[0108] Aspect 28: The method according to aspect 27, wherein the shaping comprises molding or layer formation, preferably molding.

[0109] The articles, compositions, and methods may alternatively comprise, consist of, or consist essentially of any suitable materials, steps, or components disclosed herein. The compositions, methods, and articles may additionally or alternatively be formulated so as to lack, or consist essentially of, any materials (or species), steps, or components that are not necessary to achieve the functions or objectives of the compositions, methods, and articles.

[0110] The terms "a" and "an" are not intended to denote a limitation of quantity, but rather to indicate that at least one of the items being referred to exists. The term "or" means "and / or" unless the context clearly indicates otherwise. Throughout this specification, references to "one aspect", "another aspect", "some aspects", etc. mean that a particular element (e.g., feature, structure, step, or property) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it should be understood that the described elements may be combined in any suitable manner in various embodiments. The terms "first", "second", etc. used herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The term "combination" includes blends, mixtures, alloys, reaction products, and the like. Also, "at least one of" or "combinations thereof" is non-limiting and means that the list includes not only each element individually, but also combinations of two or more elements in the list, and combinations of at least one element in the list with other similar elements not explicitly listed. Unless otherwise defined, 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 pertains.

[0111] Unless otherwise specified in this specification, all test standards are the latest standards in effect at the filing date of this application or, if priority is claimed, at the filing date of the earliest priority application in which the test standard is described. All endpoints of all ranges directed to the same component or property are inclusive of the endpoints and may be combined independently, including all intermediate points and ranges. For example, the range "up to 25% by weight, or 5 to 20% by weight" includes the endpoints and the range "5 to 25% by weight", including all intermediate values such as 10 to 23% by weight, etc.

[0112] Compounds are described using standard nomenclature. For example, any position not substituted by any of the indicated groups is understood to have its valence satisfied by a bond or hydrogen atom as shown. A dash ("-") not flanked by two letters or symbols is used to indicate the point of attachment of a substituent. For example, -CHO is attached through the carbon of the carbonyl group. As used herein, the term "(meth)acrylic" encompasses both acrylic and methacrylic groups. As used herein, the term "(iso)cyanurate" encompasses both cyanurate and isocyanurate groups.

[0113] All patents, patent applications, and other references cited are hereby incorporated by reference in their entirety. However, if a term in this application conflicts or is inconsistent with a term in the incorporated reference, the term in this application shall prevail over the conflicting term in the incorporated reference.

[0114] Although specific embodiments have been described, alternative, modified, variant, improved, and substantially equivalent forms that are not presently foreseen or that may not be foreseeable may occur to the applicant or to a person of ordinary skill in the art. Accordingly, the appended claims, as filed and as amended if applicable, are intended to cover all such alternative, modified, variant, improved, and substantially equivalent forms.

Claims

1. A thermoplastic polymer, a crosslinking aid, a curing initiator, an additive composition, and a ceramic filler composition comprising a crosslinked product of a composite material, the cured molded dielectric component being wherein the composite material before crosslinking is, respectively, based on the total mass of the composite material before crosslinking, 10 to 99% by mass of the thermoplastic polymer, 0.25 to 10% by mass of the crosslinking aid, 0.01 to 5% by mass of the curing initiator, 0.0001 to 2% by mass of the additive composition, 1 to 90% by mass of the ceramic filler composition and the total is 100% by mass, the cured molded dielectric component having a dielectric constant at 10 GHz of more than 6 and up to 20, and having no melt flow index when tested at 190 °C and 2.16 kg according to ASTM D1238-20, cured molded dielectric component.

2. The cured molded dielectric component according to claim 1, wherein the processing temperature of the thermoplastic polymer is from 160 °C to 280 °C.

3. The cured molded dielectric component according to claim 1 or 2, wherein the melting temperature of the thermoplastic polymer is 250 °C or lower, or from 90 °C to 250 °C.

4. The cured molded dielectric component according to any one of claims 1 to 3, wherein the melt flow index of the thermoplastic polymer measured at 190 °C and 2.16 kg according to ASTM D1238-20 is less than 5 grams per 10 minutes.

5. The cured molded dielectric component according to any one of claims 1 to 4, wherein the thermoplastic polymer comprises polyethylene, polypropylene, polymethylpentene, fluorinated ethylene propylene copolymer, polynorbornene, styrene-ethylene-propylene-styrene block copolymer, or a combination thereof.

6. The cured molded dielectric component according to any one of claims 1 to 5, wherein the thermoplastic polymer comprises low density polyethylene or linear low density polyethylene.

7. The cured molded dielectric component according to any one of claims 1 to 6, wherein the crosslinked product contains a residue of the crosslinking aid.

8. The cured molded dielectric component according to any one of claims 1 to 6, wherein the crosslinked product does not contain a residue of the crosslinking aid and the thermoplastic polymer comprises a thermoplastic polymer that self-crosslinks by irradiation such as polyethylene.

9. ​ The curable molding dielectric component according to any one of claims 1 to 8, wherein the curing initiator is present and has a starting temperature higher than the processing temperature of the thermoplastic polymer, preferably at least 10 °C, at least 20 °C, or at least 30 °C higher than the processing temperature of the thermoplastic polymer.

10. The curable molding dielectric component according to any one of claims 1 to 9, wherein the crosslinking aid is present and includes triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, polybutadiene, zinc diacrylate, zinc dimethacrylate, divinylbenzene, vinyl-terminated polyphenylene ether oligomer, m-phenylene dimaleimide, trimethylolpropane trimethacrylate, tetramethylene glycol diacrylate, trifunctional acrylate ester, dipentaerythritol pentaacrylate, or a combination thereof.

11. The curable molding dielectric component according to any one of claims 1 to 10, wherein the additive composition is present and includes an antioxidant, a metal deactivator, a processing aid, an adhesion promoter, or a combination thereof.

12. The ceramic filler is fumed silica, titanium dioxide, barium titanate, strontium titanate, corundum, wollastonite, Ba 2 Ti 9 O 20 , hollow ceramic spheres, boron nitride, aluminum nitride, silicon carbide, beryllia, alumina, alumina trihydrate, magnesia, mica, talc, nanoclay, magnesium hydroxide, solid glass spheres, hollow glass spheres, or a combination thereof, the cured molded dielectric component according to any one of claims 1 to 11.

13. The curable molding dielectric component according to any one of claims 1 to 12, wherein the ceramic filler has a multimodal particle size distribution, and the peak of the first peak of the multimodal particle size distribution is at least 7 times the peak of the second peak of the multimodal particle size distribution.

14. Before crosslinking, the composite materials each, based on the total mass of the composite materials before crosslinking, 50 to 95% by mass of the thermoplastic polymer, 0.25 to 10% by mass of the crosslinking aid, 0.01 to 5% by mass of the curing initiator, 0.001 to 2% by mass of the additive composition, 5 to 50% by mass of the ceramic filler composition and the total is 100% by mass. The curable molding dielectric component according to any one of claims 1 to 13.

15. Before crosslinking, the composite materials each, based on the total mass of the composite materials before crosslinking, 10 to 50% by mass of the thermoplastic polymer, 0.25 to 10% by mass of the crosslinking aid, 0.01 to 5% by mass of the curing initiator, 0.001 to 2% by mass of the additive composition, 50 to 90% by mass of the ceramic filler composition and the total is 100% by mass. The curable molding dielectric component according to any one of claims 1 to 13.

16. The composite material before crosslinking has, based on the total mass of the composite material before crosslinking, 10 to 25% by weight of the thermoplastic polymer; 0.25 to 10% by weight of the crosslinking coagent; 0.01 to 5% by weight of the curing initiator; 0.001 to 2 wt. % of the additive composition; 75 to 90% by weight of the ceramic filler composition; Including, 16. The cured molded dielectric part of claim 15, wherein the total is 100% by weight.

17. 17. The cured molded dielectric component of claim 1, wherein the composite material comprises more than 20 volume percent, preferably more than 40 volume percent, of the ceramic filler, based on the total volume of the composite material.

18. 18. A cured molded dielectric part according to any one of claims 1 to 17, having a dielectric constant measured at 10 GHz of 10 or more, preferably 12 or more.

19. 19. A cured molded dielectric part according to any one of claims 1 to 18, wherein the change in linear dimension of the part before curing compared to after curing is less than 2%, preferably less than 1%, in any or all linear dimensions.

20. 20. The cured molded dielectric part of claim 1, wherein the part is a dielectric resonator antenna, a dielectric portion of a dielectric resonator antenna, an electromagnetic waveguide, a dielectric electromagnetic lens, a radio frequency part, a microwave part, a millimeter wave part, a terahertz part, or an optical part.

21. 21. A cured molded dielectric part according to any one of claims 1 to 20, wherein the part is a dielectric electromagnetic lens, preferably configured to operate at a frequency greater than 5 GHz and less than 300 GHz.

22. 22. A circuit material or circuit board comprising a cured molded dielectric component according to any one of claims 1 to 21.

23. 20. A method of making a cured molded dielectric component according to any one of claims 1 to 19, comprising the steps of: compounding a composite material comprising the thermoplastic polymer, the optional crosslinking coagent, the optional cure initiator, the optional additive composition, and the ceramic filler composition; melting the blended composite material to form a melt; shaping the melt to form a shaped article; exposing the molded article to radiation to generate sufficient free radicals in the thermoplastic polymer to crosslink at least a portion of the thermoplastic polymer to form the cured molded dielectric component; A method including...

24. A step of forming the shaped article on a substrate, A step of masking at least a part of the shaped article against irradiation, A step of exposing the unmasked part of the shaped article to irradiation to form the cured shaped dielectric component The method according to claim 23, further comprising...

25. The method according to claim 24, wherein the shaping includes molding or layer formation, preferably molding.

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