Black liquid crystal polymer composition with low dielectric loss tangent

Abstract

A polymer composition is provided that includes a liquid crystal polymer matrix and carbon black particles dispersed within the polymer matrix. The carbon black particles comprise about 0.1 wt.% to about 3 wt.% of the composition. The composition has a dielectric loss tangent of less than 0.002 and a lightness (L) of less than about 60 when measured at a frequency of 10 GHz. * ) is shown.

Description

[Background technology]

[0001] Background of the Invention

[0001] Electrical components often contain molded parts formed from liquid crystalline thermoplastic resins. In recent years, the electronics industry has been challenged to reduce the size of such components to achieve desirable performance and space savings. For 5G applications, for example, there is a need to form components (e.g., circuit boards, filters, antenna covers, connectors, etc.) from polymers with low dielectric loss to limit signal attenuation during high-speed transmission. In addition, there is often a need to reduce the reflectance of light from the polymer resin, for example, to better view metal circuit components formed on a liquid crystal polymer film. For this reason, carbon black is often used as a colorant. However, the use of carbon black increases the dielectric loss of the liquid crystalline polymer composition. Therefore, there is a need for a black liquid crystalline polymer composition with low dielectric loss. Summary of the Invention [Means for solving the problem]

[0002]

[0002] In accordance with one embodiment of the present invention, a polymer composition is disclosed that includes a liquid crystalline polymer matrix and carbon black particles dispersed within the polymer matrix. The carbon black particles comprise about 0.1 wt.% to about 3 wt.% of the composition. The composition has a color value (L) of less than about 60. * ) and exhibits a dissipation factor of about 0.002 or less when measured at a frequency of 10 GHz.

[0003] Other features and aspects of the present invention are set forth in more detail below.

[0004] A detailed and enabling disclosure of the present invention, including the best mode thereof, to one skilled in the art, is set forth more particularly in the remainder of the specification, including reference to the accompanying drawings. [Brief explanation of the drawings]

[0004] [Figure 1]

[0005] FIG. 1 illustrates one embodiment of a 5G antenna system that may employ a circuit board or connector formed in accordance with the present invention. [Figure 2A]

[0006] FIG. 2A illustrates a top view of an exemplary user computing device including a 5G antenna. [Figure 2B]

[0007] FIG. 2B illustrates a side view of the example user computing device of FIG. 2A. [Figure 3]

[0008] FIG. 3 illustrates an expanded view of a portion of the user computing device of FIG. 2A. [Figure 4]

[0009] FIG. 4 illustrates a side view of a coplanar waveguide antenna array structure that may be employed in a 5G antenna system. [Figure 5A]

[0010] FIG. 5A illustrates an antenna array for a massive multiple-in-multiple-out structure of a 5G antenna system. [Figure 5B]

[0011] FIG. 5B illustrates a configured antenna array that may be employed in a 5G antenna system. [Figure 5C]

[0012] FIG. 5C illustrates an exemplary antenna structure that may be employed in a 5G antenna system. [Figure 6]

[0013] FIG. 6 is a schematic diagram of one embodiment of a laminate that can be formed in accordance with the present invention. [Figure 7]

[0014] FIG. 7 is a schematic diagram of another embodiment of a laminate that can be formed in accordance with the present invention. [Figure 8]

[0015] FIG. 8 is a schematic diagram of yet another embodiment of a laminate that can be formed in accordance with the present invention. [Figure 9]

[0016] FIG. 9 is a schematic diagram of one embodiment of an electronic device in which the circuit board of the present invention can be employed. [Figure 10A]

[0017] FIG. 10A shows a thin-walled electrical connector in accordance with an embodiment of the present invention. [Figure 10B]

[0018] FIG. 10B shows an enlarged view of a portion of the thin-walled connector of FIG. 1A. [Figure 11]

[0019] FIG. 11 is an exploded perspective view of another embodiment of a thin-walled connector and connector receptacle that can be formed in accordance with the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0005]

[0020] It will be understood by those skilled in the art that the discussion of the present invention is merely a description of exemplary embodiments and is not intended to limit the broader aspects of the invention.

[0021] Generally speaking, the present invention is directed to a polymer composition comprising a liquid crystalline polymer matrix and carbon black particles dispersed within the matrix. By selectively controlling the specific nature and concentrations of the components of the polymer composition, the inventors have surprisingly discovered that the resulting composition can exhibit both a dark color and an extremely low dissipation factor over a wide frequency range, which is particularly useful for forming components of 5G systems, such as antenna circuit boards and high-speed connectors. That is, the dissipation factor of the polymer composition, which is a measure of the rate at which energy is lost, can be about 0.002 or less, in some embodiments about 0.001 or less, in some embodiments about 0.0001 to about 0.001, and in some embodiments about 0.0005 to about 0.0009, over typical 5G frequencies (e.g., 10 GHz). The polymer compositions can also exhibit a low dielectric constant of about 6 or less, and in some embodiments, about 5 or less, in some embodiments, from about 1 to about 4.5, and in some embodiments, from about 2 to about 4, over typical 5G frequencies (e.g., 10 GHz).

[0006]

[0022] The use of carbon black at a selectively controlled concentration can provide a composition with a relatively dark color. Darkness can be quantified by measuring absorbance with an optical reader according to a standard test method known as "CIELAB," which is described in F. Cost's Pocket Guide to Digital Printing, Delmar Publishers, Albany, New York, ISBN 0-8273-7592-1, pages 144 and 145, and "Photoelectric color difference meter," Journal of Optical Society of America, Vol. 48, pages 985-995, S. Hunter (1958), both of which are incorporated herein by reference in their entirety. More specifically, the CIELAB test method produces three "Hunter" scale values, i.e., L, corresponding to three characteristics of perceived color based on the opponent color theory of color perception. * , a * , and b * It defines L * = Brightness (or luminosity) ranges from 0 to 100, where 0 = dark and 100 = light.

[0007]

[0023] The lightness value of the composition (L * ) may be less than about 60, and in some embodiments, may be about 30 to about 57, in some embodiments, about 40 to about 54, in some embodiments, about 45 to about 50, and in some embodiments, about 46 to about 48.

[0008]

[0024] It has traditionally been thought that a polymer composition exhibiting a low dielectric loss tangent would not have sufficiently good thermal and mechanical properties and ease of processing (i.e., low viscosity) to enable its use in certain types of applications, such as forming connectors. However, contrary to conventional belief, it has been discovered that polymer compositions possess both excellent thermal and mechanical properties and processability. For example, the melting temperature of the polymer composition may be, for example, from about 200°C to about 400°C, in some embodiments from about 250°C to about 380°C, in some embodiments from about 270°C to about 360°C, and in some embodiments from about 300°C to about 350°C. Even at such melting points, the ratio of temperature deflection under load ("DTUL"), a measure of short-term thermal resistance, to the melting point may still remain relatively high. For example, this ratio may be in the range of from about 0.5 to about 1.00, in some embodiments from about 0.6 to about 0.95, and in some embodiments from about 0.65 to about 0.85. Specific DTUL values ​​may be, for example, about 200° C. or higher, and in some embodiments, from about 200° C. to about 350° C., in some embodiments, from about 210° C. to about 320° C., and in some embodiments, from about 230° C. to about 290° C. Such high DTUL values ​​allow, among other things, the use of fast and reliable surface mounting processes for mating with other components in an electrical part.

[0009]

[0025] The polymeric composition may also have excellent mechanical properties, which may be useful when forming a substrate. For example, the polymeric composition may exhibit a tensile strength of about 10 MPa or higher, and in some embodiments, about 50 MPa or higher, in some embodiments, about 70 MPa to about 300 MPa, and in some embodiments, about 80 MPa to about 200 MPa. The polymeric composition may exhibit a tensile elongation of about 0.3% or higher, and in some embodiments, about 0.4% or higher, in some embodiments, about 0.5% to about 4%, and in some embodiments, about 0.5% to about 2%. The polymeric composition may exhibit a tensile modulus of about 5,000 MPa or higher, and in some embodiments, about 6,000 MPa or higher, in some embodiments, about 7,000 MPa to about 25,000 MPa, and in some embodiments, about 10,000 MPa to about 20,000 MPa. Tensile properties may be determined at a temperature of 23°C according to ISO Test No. 527:2019. The polymeric compositions may also exhibit a flexural strength of about 20 MPa or greater, in some embodiments about 10 MPa or greater, in some embodiments about 50 MPa or greater, in some embodiments about 70 MPa to about 300 MPa, and in some embodiments about 80 MPa to about 200 MPa. The polymeric compositions may exhibit a flexural elongation of about 0.4% or greater, in some embodiments about 0.5% to about 4%, and in some embodiments about 0.5% to about 2%.The polymeric composition may exhibit a flexural modulus of about 5,000 MPa or higher, and in some embodiments, about 6,000 MPa or higher, in some embodiments, about 7,000 MPa to about 25,000 MPa, and in some embodiments, about 10,000 MPa to about 20,000 MPa. Flexural properties may be determined at a temperature of 23°C in accordance with JIS K 178:2010. Additionally, the polymeric composition may also have high impact strength, which may be useful when forming thin substrates. The polymeric composition may have a flexural modulus of, for example, about 3 kJ / m. 2 or higher, in some embodiments about 5 kJ / m 2 or higher, in some embodiments about 7 kJ / m 2 or higher, in some embodiments about 8 kJ / m 2 ~about 40kJ / m 2 , and in some embodiments, about 10 kJ / m 2 ~about 25kJ / m 2 The impact strength may be measured at a temperature of 23°C according to ISO test number ISO 179-1:2010.

[0010]

[0026] Various embodiments of the present invention will now be described in more detail. I. polymer composition A. Liquid Crystal Polymer Matrix

[0027] The polymer composition generally contains one or more liquid crystalline polymers in an amount of about 40 wt.% to about 99.9 wt.%, and in some embodiments, about 50 wt.% to about 90 wt.%, in some embodiments, about 60 wt.% to about 80 wt.%, and in some embodiments, about 65 wt.% to about 70 wt.% of the total polymer composition. Liquid crystalline polymers are generally classified as "thermotropic" to the extent that they have a rod-like structure and can exhibit crystalline behavior in their molten state (e.g., a thermotropic nematic state). Liquid crystalline polymers employed in the polymer composition typically have melting points of about 200°C to about 400°C, and in some embodiments, about 250°C to about 380°C, in some embodiments, about 300°C to about 370°C, in some embodiments, about 330°C to about 360°C, and in some embodiments, about 345°C to about 355°C. The melting point may be determined using differential scanning calorimetry ("DSC") as is known in the art, for example, by ISO test number 11357-3:2011. Such polymers may be formed from one or more types of repeating units, as is known in the art. The liquid crystal polymer may, for example, contain one or more aromatic ester repeating units generally represented by the following formula (I):

[0011] [ka]

[0012] During the ceremony, Ring B is a substituted or unsubstituted 6-membered aryl group (e.g., 1,4-phenylene or 1,3-phenylene), a substituted or unsubstituted 6-membered aryl group fused to a substituted or unsubstituted 5- or 6-membered aryl group (e.g., 2,6-naphthalene), or a substituted or unsubstituted 6-membered aryl group linked to a substituted or unsubstituted 5- or 6-membered aryl group (e.g., 4,4-biphenylene); Y1 and Y2 are independently O, C(O), NH, C(O)HN, or NHC(O).

[0013]

[0028] Typically, at least one of Y1 and Y2 is C(O). Examples of such aromatic ester repeating units include, for example, aromatic dicarboxylic acid repeating units (in Formula I, Y1 and Y2 are C(O)), aromatic hydroxycarboxylic acid repeating units (in Formula I, Y1 is O and Y2 is C(O)), as well as various combinations thereof.

[0014]

[0029] The aromatic hydroxycarboxylic acid repeating unit may be, for example, an aromatic hydroxycarboxylic acid, such as 4-hydroxybenzoic acid, 4-hydroxy-4'-biphenylcarboxylic acid, 2-hydroxy-6-naphthoic acid, 2-hydroxy-5-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxy-3-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, etc., as well as those derived from their alkyl, alkoxy, aryl and halogen substituents, and combinations thereof. Particularly suitable aromatic hydroxycarboxylic acids are 4-hydroxybenzoic acid ("HBA") and 6-hydroxy-2-naphthoic acid ("HNA"). When employed, repeat units derived from hydroxycarboxylic acids (e.g., HBA and / or HNA) typically comprise from about 30 mol.% to about 100 mol.%, in some embodiments from about 40 mol.% to about 80 mol.%, in some embodiments from about 45 mol.% to about 65 mol.%, and in some embodiments, from about 50 mol.% to about 60 mol.% of the polymer.

[0015]

[0030] The aromatic dicarboxylic acid repeating unit may also be derived from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, bis(4-carboxyphenyl)ether, bis(4-carboxyphenyl)butane, bis(4-carboxyphenyl)ethane, bis(3-carboxyphenyl)ether, bis(3-carboxyphenyl)ethane, etc., as well as alkyl, alkoxy, aryl, and halogen substituents thereof, and combinations thereof. Particularly suitable aromatic dicarboxylic acids include, for example, terephthalic acid ("TA"), isophthalic acid ("IA"), and 2,6-naphthalenedicarboxylic acid ("NDA"). When employed, repeat units derived from aromatic dicarboxylic acids (e.g., IA, TA, and / or NDA) typically comprise from about 1 mol.% to about 40 mol.%, in some embodiments from about 10 mol.% to about 35 mol.%, and in some embodiments, from about 20 mol.% to about 30% of the polymer.

[0016]

[0031] Other repeating units may also be employed in the polymer.In certain embodiments, for example, the repeating unit may be derived from aromatic diols, such as hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl (or 4,4'-biphenol), 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, bis(4-hydroxyphenyl)ethane, etc., as well as their alkyl, alkoxy, aryl and halogen substituents, and combinations thereof.Particularly suitable aromatic diols may include, for example, hydroquinone ("HQ") and 4,4'-biphenol ("BP"). When employed, repeat units derived from aromatic diols (e.g., HQ and / or BP) typically comprise from about 1 mol.% to about 40 mol.%, in some embodiments, from about 10 mol.% to about 35 mol.%, and in some embodiments, from about 20 mol.% to about 30% of the polymer. Repeat units may also be employed, for example, those derived from aromatic amides (e.g., acetaminophen (“APAP”)) and / or aromatic amines (e.g., 4-aminophenol (“AP”), 3-aminophenol, 1,4-phenylenediamine, 1,3-phenylenediamine, etc.). When employed, repeat units derived from aromatic amides (e.g., APAP) and / or repeat units derived from aromatic amines (e.g., AP) typically comprise from about 0.1 mol.% to about 20 mol.%, in some embodiments, from about 0.5 mol.% to about 15 mol.%, and in some embodiments, from about 1 mol.% to about 10% of the polymer. It should be understood that various other monomeric repeat units can be incorporated into the polymer. For example, in certain embodiments, the polymer may contain one or more repeating units derived from non-aromatic monomers such as, for example, aliphatic or alicyclic hydroxycarboxylic acids, dicarboxylic acids, diols, amides, amines, and the like.Of course, in other embodiments, the polymer may be "fully aromatic" in that it lacks repeat units derived from non-aromatic (e.g., aliphatic or alicyclic) monomers.

[0017]

[0032] Although not required, the liquid crystal polymer may be a "high naphthenic" polymer so long as it contains a relatively high content of repeat units derived from naphthenic hydroxycarboxylic acids and naphthenic dicarboxylic acids, such as NDA, HNA, or a combination thereof. That is, the total amount of repeat units derived from naphthenic hydroxycarboxylic acids and / or dicarboxylic acids (e.g., NDA, HNA, or a combination of HNA and NDA) is typically about 20 mol.% or higher of the polymer, and in some embodiments, from about 30 mol.% to about 95 mol.%, in some embodiments, from about 35 mol.% to about 80 mol.%, in some embodiments, from about 40 mol.% to about 60 mol.%, and in some embodiments, from about 45 mol.% to about 50 mol.%. Contrary to many conventional "low naphthenic" polymers, the resulting "high naphthenic" polymers are believed to be capable of exhibiting excellent thermal and mechanical properties. In addition, the inventors have discovered that the use of liquid crystal polymers containing a relatively high HNA content can result in compositions with extremely low dielectric loss tangents. For example, repeat units derived from HNA may constitute about 20 mol.% or more of the polymer, in some embodiments about 20 mol.% or more, in some embodiments about 30 mol.% to about 85 mol.%, in some embodiments about 35 mol.% to about 75 mol.%, in some embodiments about 40 mol.% to about 60 mol.%, and in some embodiments about 45 mol.% to about 50 mol.%.In such embodiments, the liquid crystal polymer comprises the naphthenic monomer (e.g., HNA and / or NDA) in the above-specified amounts in combination with various other monomers, for example, about 70 mol.% or less, in some embodiments about 60 mol.% or less, in some embodiments about 40 mol.% or less, in some embodiments about 20 mol.% or less, in some embodiments about 1 mol.% to about 10 mol.%, and in some embodiments about 2 mol.% to about 5 mol.% of an aromatic hydroxycarboxylic acid (e.g., In some embodiments, the amount of the aromatic dicarboxylic acid (e.g., IA and / or TA) may be about 1 mol.% to about 40 mol.%, in some embodiments, about 10 mol.% to about 35 mol.%, and in some embodiments, about 20 mol.% to about 30 mol.%; and / or in combination with an aromatic diol (e.g., BP and / or HQ) in an amount of about 1 mol.% to about 40 mol.%, in some embodiments, about 10 mol.% to about 35 mol.%, and in some embodiments, about 20 mol.% to about 30 mol.%.

[0018]

[0033] Regardless of the specific components and properties of the polymer, liquid crystalline polymers may be prepared by first introducing aromatic monomers used to form the ester repeat units (e.g., aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, etc.) and / or other repeat units (e.g., aromatic diols, aromatic amides, aromatic amines, etc.) into a reaction vessel to initiate a polycondensation reaction. The specific conditions and steps employed in such reactions are well known and are well known in the art. Calundann U.S. Patent No. 4,161,470; Linstid, III et al. U.S. Patent No. 5,616,680; Linstid, III et al. U.S. Patent No. 6,114,492; Shepherd et al. U.S. Patent No. 6,514,611; and WaggonerThis can be described in more detail in WO2004 / 058851. The vessel used for the reaction is not particularly limited, but it is typically desirable to use one commonly used in reactions of high-viscosity fluids. Examples of such reaction vessels include anchor type, multi-stage type, spiral ribbon type, screw shaft type, etc., or stirred tank-type devices having an agitator with a variable-shape stirring blade having a modified shape thereof. Further examples of such reaction vessels include mixing devices commonly used in resin kneading, such as kneaders, roll mills, and Banbury mixers.

[0019]

[0034] If desired, the reaction can proceed via acetylation of the monomer, as is known in the art. This can be accomplished by adding an acetylating agent (e.g., acetic anhydride) to the monomer. Acetylation is generally initiated at a temperature of about 90°C. During the initial stage of acetylation, reflux may be employed to maintain the vapor phase temperature below the point at which acetic acid by-product and anhydride begin to distill. The temperature during acetylation typically ranges from 90°C to 150°C, and in some embodiments, from about 110°C to about 150°C. When reflux is used, the vapor phase temperature typically exceeds the boiling point of acetic acid but remains low enough to retain residual acetic anhydride. For example, acetic anhydride vaporizes at a temperature of about 140°C. Therefore, it is particularly desirable to provide a reactor with a vapor phase reflux at a temperature of about 110°C to about 130°C. To ensure a substantially complete reaction, an excess amount of acetic anhydride may be employed. The amount of anhydride excess is expected to vary depending on the specific acetylation conditions employed, such as the presence or absence of reflux. It is not uncommon to use about a 1 to about 10 mole percent excess of acetic anhydride, based on the total moles of reactant hydroxyl groups present.

[0020]

[0035] Acetylation may be carried out in a separate reaction vessel or in situ within the polymerization reaction vessel. When separate reaction vessels are employed, one or more of the monomers may be introduced into the acetylation reactor and then transferred to the polymerization reactor. Similarly, one or more of the monomers may also be introduced directly into the reaction vessel without prior acetylation.

[0021]

[0036] In addition to the monomer and optional acetylating agent, other components may be included in the reaction mixture to facilitate polymerization. For example, a catalyst may optionally be employed, including metal salt catalysts (e.g., magnesium acetate, tin(I) acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, etc.) and organic compound catalysts (e.g., N-methylimidazole). Such catalysts are typically used in amounts of about 50 to about 500 ppm, based on the total weight of the repeat unit precursor. When separate reactors are employed, it is typically desirable to apply the catalyst to the acetylation reactor rather than the polymerization reactor, although this is by no means a requirement.

[0022]

[0037] The reaction mixture is typically heated to an elevated temperature in a polymerization reactor to initiate melt polycondensation of the reactants. Polycondensation may be carried out, for example, within a temperature range of about 250°C to about 380°C, and in some embodiments, within a temperature range of about 280°C to about 380°C. For example, one suitable technique for forming an aromatic polyester may involve placing precursor monomers and acetic anhydride in a reactor, heating the mixture to a temperature of about 90°C to about 150°C to acetylate the hydroxyl groups of the monomers (e.g., to form acetoxy groups), and then increasing the temperature to about 280°C to about 380°C to carry out melt polycondensation. As the final polymerization temperature approaches, volatile by-products of the reaction (e.g., acetic acid) may be removed to facilitate attainment of the desired molecular weight. The reaction mixture is typically agitated during polymerization to ensure excellent heat and mass transfer and, subsequently, excellent material uniformity. The agitator rotation speed may vary during the course of the reaction, but is typically in the range of about 10 to about 100 revolutions per minute ("rpm"), and in some embodiments, in the range of about 20 to about 80 rpm. To increase the molecular weight of the melt, the polymerization reaction may be carried out under vacuum, the application of vacuum facilitating the removal of volatiles formed during the final stages of polycondensation. The vacuum may be created by the application of suction pressure, for example, in the range of about 5 to about 30 pounds per square inch ("psi"), and in some embodiments, in the range of about 10 to about 20 psi.

[0023]

[0038] After melt polymerization, the molten polymer may be discharged from the reactor through an extrusion orifice, typically equipped with a die of desired configuration, cooled, and collected. Generally, the melt is discharged through a perforated die to form strands, which are collected in a water bath, pelletized, and dried. In some embodiments, the melt-polymerized polymer may also be subjected to a subsequent solid-state polymerization process to further increase its molecular weight. Solid-state polymerization may be carried out in the presence of a gas (e.g., air, an inert gas, etc.). Suitable inert gases include, for example, nitrogen, helium, argon, neon, krypton, xenon, etc., as well as combinations thereof. The solid-state polymerization reactor may be of virtually any design that will allow the polymer to be maintained at the desired solid-state polymerization temperature for the desired residence time. Examples of such vessels may have a fixed bed, a stationary bed, a moving bed, a fluidized bed, etc. The temperature at which the solid-state polymerization is carried out may vary, but typically ranges from about 250°C to about 350°C. Polymerization times are expected to vary, of course, based on the temperature and target molecular weight, but in most cases, solid state polymerization times are expected to be from about 2 to about 12 hours, and in some embodiments, from about 4 to about 10 hours.

[0024] B. carbon black

[0039] As noted above, carbon black particles may be employed in the polymer composition and distributed throughout the polymer matrix. The carbon black particles may comprise from about 0.1 wt.% to about 3 wt.%, in some embodiments from about 0.2 wt.% to about 2 wt.%, in some embodiments from about 0.4 wt.% to about 1.5 wt.%, in some embodiments from about 0.6 wt.% to about 1 wt.%, and in some embodiments, from about 1 wt.% to about 2 wt.% of the total polymer composition.

[0025]

[0040] Carbon black particles having a relatively low conductivity are particularly suitable. Without intending to be limited by theory, it is believed that the use of carbon black particles having a lower conductivity results in a composition having a lower dielectric loss tangent. For example, carbon black particles having a conductivity of about 1×10 2 It may have a surface resistivity of ohms or greater, and in some embodiments, about 1×10 12 ohms or greater, in some embodiments about 1×10 15 ohm ~ approx. 1 x 10 18 ohms, in some embodiments, about 1×10 16 ohm ~ approx. 1 x 10 17 In some embodiments, when the carbon particles are contained in the masterbatch of the liquid crystalline polymer in an amount of 20 wt.%, the masterbatch may have a surface resistivity of about 1×10 8 It may have a surface resistivity of ohms or greater, and in some embodiments, about 1×10 12 ohms or greater, in some embodiments about 1×10 15 ohm ~ approx. 1 x 10 18 ohms, in some embodiments, about 1×10 16 ohm ~ approx. 1 x 10 17 Similarly, when contained in a masterbatch of a liquid crystal polymer in an amount of 50 wt.%, the masterbatch may have a surface resistivity of about 1×10 ohms. 2 It may have a surface resistivity of ohms or greater, and in some embodiments, about 1×10 3 ohms or greater, in some embodiments about 1×10 4 ohm ~ approx. 1 x 10 8 ohms, in some embodiments, about 1×10 5 ohm ~ approx. 1 x 10 6 It may have a surface resistivity of ohms. Such masterbatches are described in more detail below.

[0026]

[0041] Carbon black particles typically exist in the form of aggregates of primary particles. In this regard, carbon black particles have a primary particle size and a secondary particle size, where the primary particle size represents the smallest visually distinguishable particle when visualized at a magnification level of 20,000x, and the secondary particle size represents the particle size of the carbon black aggregate dispersed in the polymer matrix. In some embodiments, the carbon black particles have a number-average primary particle size of about 5 nm to about 100 nm, in some embodiments about 20 nm to about 70 nm, in some embodiments about 30 nm to about 60 nm, and in some embodiments about 35 nm to about 45 nm. In some embodiments, the number-average secondary particle size of the carbon black particles may be about 1 μm to about 100 μm, in some embodiments about 5 μm to about 50 μm, and in some embodiments about 10 μm to about 30 μm. Number-average primary and secondary particle sizes can be determined in accordance with ASTM D3849-22.

[0027]

[0042] The specific surface area of ​​the carbon black particles is not particularly limited, but in some embodiments, is about 50 m 2 / g~about 1500m 2 / g, in some embodiments, about 100 m 2 / g ~ approx. 1250m 2 The specific surface area can be determined by BET analysis, for example, in accordance with ASTM D6556-21.

[0028]

[0043] The pH of the aqueous dispersion of carbon black particles at 25° C. may, in some embodiments, be from about 2.0 to about 8.5, in some embodiments, from about 2.5 to about 7.5, and in some embodiments, from about 3.5 to about 6. The pH of a carbon black dispersion of a predetermined concentration can be measured using any suitably calibrated pH measuring device, for example, according to ISO 787-9.

[0029]

[0044] In some embodiments, the carbon black particles are selected from channel carbon black, furnace carbon black, lamp carbon black, and thermal carbon black. Preferably, the carbon black particles are uncoated. Additionally, the carbon black particles preferably do not contain carbon nanotubes.

[0030] C. Other additives

[0045] Various additional additives may be included in the polymer composition, including, for example, lubricants, fibrous fillers, thermally conductive fillers, pigments, antioxidants, stabilizers, surfactants, waxes, flame retardants, anti-drip additives, nucleating agents (e.g., boron nitride), flow control agents, coupling agents, antimicrobial agents, pigments or other colorants, impact modifiers, and other materials added to enhance properties or processability.

[0031]

[0046] In one embodiment, for example, a fibrous filler may be employed in the polymer composition in an amount of, for example, from about 1 wt.% to about 40 wt.%, in some embodiments, from about 3 wt.% to about 30 wt.%, in some embodiments, from about 5 wt.% to about 20 wt.%, and in some embodiments, from about 7 wt.% to about 15 wt.% of the polymer composition. The fibrous filler typically comprises fibers having a high tensile strength relative to their mass. For example, the ultimate tensile strength (determined according to ASTM D2101) of the fibers is typically from about 1,000 to about 15,000 megapascals ("MPa"), in some embodiments, from about 2,000 MPa to about 10,000 MPa, and in some embodiments, from about 3,000 MPa to about 6,000 MPa. To help maintain desirable dielectric properties, such high-strength fibers can be formed from materials that are generally insulating in nature, such as glass, ceramic, or mineral (e.g., alumina or silica), aramid (e.g., Kevlar® sold by EI duPont de Nemours, Wilmington, Delaware), mineral, polyolefin, polyester, and the like. The fibrous filler can include glass fiber, mineral fiber, or mixtures thereof. For example, in one embodiment, the fibrous filler can include glass fiber. Particularly suitable glass fibers can include E-glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S1-glass, S2-glass, and the like. In another embodiment, the fibrous filler can include mineral fiber.Mineral fibers include those derived from silicates, such as nesosilicates, sorosilicates, inosilicates (e.g., calcium inosilicates such as wollastonite; calcium magnesium inosilicates such as tremolite; calcium magnesium iron inosilicates such as actinolite; magnesium iron inosilicates such as anthophyllite), phyllosilicates (e.g., aluminum phyllosilicates such as palygorskite), tectosilicates, etc.; sulfates, such as calcium sulfate (e.g., dehydrated or anhydrous gypsum); and mineral wool (e.g., rock wool or slag wool). Particularly suitable are inosilicates, such as wollastonite fibers available from Nyco Minerals under the trade name NYGLOS® (e.g., NYGLOS® 4W or NYGLOS® 8).

[0032]

[0047] Furthermore, while fibrous fillers may have a variety of sizes, fibers having a certain aspect ratio can help improve the mechanical properties of polymer compositions. That is, fibrous fillers having an aspect ratio (average length divided by nominal diameter) of about 2 or higher, in some embodiments from about 4 to about 50, in some embodiments from about 5 to about 20, and in some embodiments from about 6 to about 10, can be particularly useful. Such fibrous fillers may have, for example, a weight average length of about 10 micrometers to about 800 micrometers, in some embodiments from about 25 micrometers to about 500 micrometers, in some embodiments from about 50 micrometers to about 300 micrometers, and in some embodiments from about 60 micrometers to about 100 micrometers. Such fibrous fillers may also have, for example, a volume average length of from about 10 micrometers to about 800 micrometers, and in some embodiments, from about 25 micrometers to about 500 micrometers, in some embodiments, from about 50 micrometers to about 300 micrometers, and in some embodiments, from about 60 micrometers to about 100 micrometers. The fibrous fillers may also have a nominal diameter of about 5 micrometers or greater, and in some embodiments, from about 6 micrometers to about 40 micrometers, in some embodiments, from about 8 micrometers to about 20 micrometers, and in some embodiments, from about 9 micrometers to about 12 micrometers. The relative amount of fibrous filler can also be selectively controlled to help achieve desired mechanical and thermal properties without adversely affecting other properties of the polymer composition, such as its flowability and dielectric properties. In this regard, the fibrous filler may have a dielectric constant at a frequency of 1 GHz of about 6 or less, and in some embodiments, about 5.5 or less, in some embodiments, from about 1.1 to about 5, and in some embodiments, from about 2 to about 4.8.

[0033]

[0048] The fibrous filler may be in a modified or unmodified form, for example, provided with a sizing agent or chemically treated, to improve adhesion to plastics. In some cases, glass fibers may be provided with a sizing agent to protect the glass fibers, smooth the fibers, and improve the adhesion between the fibers and the matrix material. If present, the sizing agent may include silanes, film formers, lubricants, wetting agents, adhesives, and optionally antistatic agents, plasticizers, emulsifiers, and optionally further additives. In one particular embodiment, the sizing agent may include silanes. Specific examples of silanes are aminosilanes such as 3-trimethoxysilylpropylamine, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(3-trimethoxysilanylpropyl)ethane-1,2-diamine, 3-(2-aminoethyl-amino)propyltrimethoxysilane, N-[3-(trimethoxysilyl)propyl]-1,2-ethane-diamine.

[0034]

[0049] Optionally, the composition may also include a particulate filler. Particulate fillers may also be employed in the polymer composition as dielectric fillers to help achieve desired properties and / or color. Particulate clay minerals may be particularly suitable for use in the present invention. Examples of such clay minerals include, for example, talc (MgSiO 10 (OH2), halloysite (Al2Si2O5(OH)4), kaolinite (Al2Si2O5(OH)4), illite ((K,H3O)(Al,Mg,Fe)2(Si,Al)4O 10 [(OH)2,(H2O)]), montmorillonite (Na,Ca) 0.33 (Al,Mg)2SiO 10 (OH)2.nH2O), vermiculite ((MgFe,Al)3(Al,Si)4O 10(OH)2.4H2O), palygorskite (Mg,Al)2SiO 10 (OH).4(H2O)), pyrophyllite (Al2Si4O 10 (OH)2), and the like, as well as combinations thereof. Still other particulate fillers may be employed instead of or in addition to clay minerals. For example, other suitable particulate silicate fillers, such as mica, diatomaceous earth, and the like, may also be employed. For example, mica may be a particularly suitable mineral for use in the present invention. The term "mica," as used herein, generally refers to muscovite (KA12(AlSi3)O 10 (OH)2), Biotite (K(Mg,Fe)3(AlSi3)O 10 (OH)2), phlogopite (KMg3(AlSi3)O 10 (OH)2), lepidolite (K(Li,Al) 2~3 (AlSi3)O 10 (OH)2), goroconite (K,Na)(Al,Mg,Fe)2(Si,Al)4O 10 (OH)2), as well as combinations thereof. Other types of mineral particulate fillers, such as silica, alumina, etc., may also be employed.

[0035]

[0050] In some embodiments, it may be desirable to use plate-like mineral particles, such as mica particles, having a relatively high aspect ratio (e.g., average diameter divided by average thickness), for example, about 4 or greater, in some embodiments from about 10 to about 500, in some embodiments from about 30 to about 300, in some embodiments from about 50 to about 200, and in some embodiments from about 70 to about 100. In such embodiments, the average diameter of the particles may be, for example, in the range of about 5 micrometers to about 200 micrometers, in some embodiments from about 10 micrometers to about 100 micrometers, in some embodiments from about 15 micrometers to about 50 micrometers, and in some embodiments from about 20 micrometers to about 30 micrometers. The average thickness, as determined using laser diffraction techniques, e.g., according to ISO 13320:2020 (e.g., using a Horiba LA-960 particle size distribution analyzer), may similarly be about 2 micrometers or less, and in some embodiments, from about 5 nanometers to about 1 micrometer, from about 10 nanometers to about 500 nanometers, from about 15 nanometers to about 100 nanometers, and in some embodiments, from about 20 nanometers to about 50 nanometers. The plate-like particles may also have a narrow particle size distribution. That is, at least about 70 vol% of the particles, in some embodiments, at least about 80 vol% of the particles, and in some embodiments, at least about 90 vol% of the particles may have a size within the above-mentioned range.

[0036]

[0051] In some embodiments, the polymer composition contains glass flakes. For example, the glass flakes are scale-like glass particles, typically having an average diameter of about 10 micrometers to about 4 millimeters and an average thickness of about 1 micrometer to about 7 micrometers. In some embodiments, the glass flakes are made of E-glass. The use of such glass flakes can provide the composition with excellent dimensional stability while maintaining a low dielectric loss tangent.

[0037]

[0052] To help achieve desirable dielectric properties, the polymer composition may also include hollow inorganic fillers. For example, these fillers may have a dielectric constant at 100 MHz of about 3.0 or less, in some embodiments about 2.5 or less, in some embodiments about 1.1 to about 2.3, and in some embodiments about 1.2 to about 2.0. In addition, hollow inorganic fillers have a specific size and can contribute to the strength of the polymer composition, while their hollow nature can also allow the polymer composition to have a reduced weight and / or density.

[0038]

[0053] Generally, hollow inorganic filler has an internal hollow space or cavity, and can be synthesized by using techniques known in the art.Hollow inorganic filler can be made from conventional materials.For example, hollow inorganic filler can include alumina, silica, zirconia, magnesia, glass, fly ash, borate, phosphate, ceramic, etc.In one embodiment, hollow inorganic filler can include hollow glass filler, hollow ceramic filler, and their mixture.In one embodiment, hollow inorganic filler can include hollow glass filler.

[0039]

[0054] The hollow glass filler can be made from soda-lime borosilicate glass, soda-lime glass, borosilicate glass, sodium borosilicate glass, sodium silicate glass, or aluminosilicate glass. In this regard, in one embodiment, the glass composition may be, but is not limited to, at least about 65 wt. % SiO, 3-15 wt. % NaO, 8-15 wt. % CaO, 0.1-5 wt. % MgO, 0.01-3 wt. % AlO, 0.01-1 wt. % KO, and optionally other oxides (e.g., LiO, FeO, TiO, BO). In another embodiment, the composition may be about 50-58 wt. % SiO, 25-30 wt. % AlO, 6-10 wt. % CaO, 1-4 wt. % NaO / KO, and 1-5 wt. % other oxides. Also, in one embodiment, the hollow glass filler may include more alkaline earth metal oxide than alkali metal oxide. For example, the weight ratio of alkaline earth metal oxide to alkali metal oxide may be greater than 1, in some embodiments about 1.1 or greater, in some embodiments about 1.2 to about 4, and in some embodiments about 1.5 to about 3. Notwithstanding the above, it should be understood that the composition of the glass may be varied depending on the type of glass utilized and still provide benefits as desired according to the present invention.

[0040]

[0055] The hollow inorganic fillers may have at least one dimension that is about 1 micrometer or greater, in some embodiments about 5 micrometers or greater, in some embodiments about 8 micrometers or greater, in some embodiments, an average value between about 1 micrometer and about 150 micrometers, in some embodiments about 10 micrometers and about 150 micrometers, and in some embodiments, about 12 micrometers and about 50 micrometers. In one embodiment, such an average value is d 50 It may point to a value.

[0041]

[0056] Additionally, hollow inorganic fillers have a D of about 3 micrometers or greater. 10 and in some embodiments, a D of about 4 micrometers or greater, in some embodiments, from about 5 micrometers to about 20 micrometers, and in some embodiments, from about 6 micrometers to about 15 micrometers. 10 The hollow inorganic filler may have a D of about 10 micrometers or greater. 90 and in some embodiments, a D of about 15 micrometers or greater, in some embodiments, from about 20 micrometers to about 150 micrometers, and in some embodiments, from about 22 micrometers to about 50 micrometers. 90 may have

[0042]

[0057] In this regard, the hollow inorganic filler may be present in a particle size distribution that may be Gaussian, normal, or non-normal. In one embodiment, the hollow inorganic filler may have a Gaussian particle size distribution. In another embodiment, the hollow inorganic filler may have a normal particle size distribution. In a further embodiment, the hollow inorganic filler may have a non-normal particle size distribution. Examples of non-normal particle size distributions include unimodal and multimodal (e.g., bimodal) particle size distributions.

[0043]

[0058] When referring to the above dimensions, such dimensions may be any dimensions. However, in one embodiment, such dimensions refer to diameters. For example, values ​​for such dimensions refer to the average diameter of spheres. Dimensions, such as average diameters, may be determined according to 3M QCM193.0. In this regard, in one embodiment, hollow inorganic fillers may refer to hollow spheres, such as hollow glass spheres. For example, hollow inorganic fillers may have an average aspect ratio of approximately 1. Generally, the average aspect ratio may be about 0.8 or higher, in some embodiments about 0.85 or higher, in some embodiments about 0.9 to about 1.3, and in some embodiments about 0.95 to about 1.05.

[0044]

[0059] Additionally, the hollow inorganic fillers may have relatively thin walls to aid in weight reduction as well as dielectric properties of the polymer composition. The wall thickness may be about 50% or less, in some embodiments about 40% or less, in some embodiments about 1% to about 30%, and in some embodiments about 2% to about 25% of the average dimension of the hollow inorganic filler, such as the average diameter of the hollow inorganic filler.

[0045]

[0060] In addition, the hollow inorganic filler may have a specific true density that allows for easy handling and provides a polymer composition with reduced weight. Generally, true density refers to the quotient obtained by dividing the mass of a sample of the hollow filler by the true volume of the mass of the hollow filler, where the true volume refers to the total volume of the hollow filler. In this regard, the true density of the hollow inorganic filler is about 0.1 g / cm 3 or greater, and in some embodiments, about 0.2 g / cm 3 or greater, and in some embodiments, about 0.3 g / cm 3 or greater than about 1.2 g / cm 3 up to about 0.4 g / cm in some embodiments 3 or greater than about 0.9 g / cm 3True density may be determined in accordance with 3M QCM14.24.1.

[0046]

[0061] The filler, even if hollow, may have mechanical strength that allows it to maintain its structural integrity, resulting in a filler that is less likely to break during processing and / or use. In this regard, the isotactic crush resistance of the hollow inorganic filler (i.e., at least 80 vol.%, e.g., at least 90 vol.%, of the hollow filler survives) may be about 20 MPa or higher, in some embodiments about 100 MPa or higher, in some embodiments about 150 MPa to about 500 MPa, and in some embodiments about 200 MPa to about 350 MPa. Isotactic crush resistance may be determined according to 3M QCM14.1.8.

[0047]

[0062] The alkalinity of the hollow inorganic filler may be about 1.0 meq / g or less, in some embodiments about 0.9 meq / g or less, in some embodiments about 0.1 meq / g to about 0.8 meq / g, and in some embodiments about 0.2 meq / g to about 0.7 meq / g. The alkalinity may be determined according to 3M QCM55.19. To provide a relatively low alkalinity, the hollow inorganic filler may be treated with a suitable acid, such as phosphoric acid.

[0048]

[0063] In addition, the hollow inorganic filler may also include a surface treatment to help provide better compatibility with the polymer and / or other components in the polymer composition. As an example, the surface treatment may be silanization. Specific surface treatment agents include, but are not limited to, aminosilanes, epoxysilanes, and the like.

[0049]

[0064] When employed, hollow inorganic fillers may, for example, comprise about 1 wt. % or more of the polymer composition, in some embodiments about 4 wt. % or more, in some embodiments about 5 wt. % to about 40 wt. %, and in some embodiments about 10 wt. % to about 30 wt. %. Furthermore, to provide beneficial properties, the weight ratio of polymer to hollow inorganic filler may be about 0.1 or higher, in some embodiments about 1 or higher, in some embodiments about 1.5 or higher, in some embodiments about 0.1 to about 10, in some embodiments about 1 to about 10, in some embodiments about 2 to about 10, in some embodiments about 2 to about 6, and in some embodiments about 2 to about 5. However, in other embodiments, the composition achieves desirable dielectric properties without the use of any hollow fillers.

[0050]

[0065] In some embodiments, the composition may contain a combination of a fibrous filler and a plate-like mineral filler. For example, in some embodiments, the composition contains a filler comprising a combination of milled glass fiber and mica. In such embodiments, the ratio of plate-like mineral filler to fibrous filler may be from about 0.1 to about 20, in some embodiments from about 0.5 to about 10, in some embodiments from about 1 to about 5, and in some embodiments from about 2 to about 3.

[0051] II. formation

[0066] The components used to form the polymer composition may be combined using any of a variety of techniques known in the art. In one particular embodiment, for example, the liquid crystal polymer, carbon black, and other optional additives are melt-processed as a mixture in an extruder to form the polymer composition. The mixture may be melt-mixed in a single-screw or multi-screw extruder at a temperature of about 200°C to about 450°C. In one embodiment, the mixture may be melt-processed in an extruder containing multiple temperature zones. The temperature of each zone is typically set within a range of about -60°C to about 25°C relative to the melting point of the polymer. As an example, the mixture may be melt-processed using a twin-screw extruder, such as a Leistritz 18-mm co-rotating fully intermeshing twin-screw extruder. Conventional screw designs for melt-processing mixtures can be used. In one embodiment, the mixture containing all of the components may be fed into the feed throat of the first barrel by a volumetric feeder. In another embodiment, different components may be added at different addition points in the extruder, as is known. For example, the polymer may be applied at the feed throat, and certain additives (e.g., carbon black particles and / or other additives) may be added at the same or different temperature zones located downstream therefrom. In either case, the resulting mixture may then be melted and mixed and extruded through a die. The extruded polymer composition may then be quenched in a water bath to solidify, pelletized in a pelletizer, and subsequently dried.

[0052]

[0067] In some embodiments, the carbon black particles are added to the composition in the form of a masterbatch. The masterbatch may, for example, contain a relatively high concentration of carbon black in a thermoplastic carrier. In some embodiments, the carbon black particles comprise from about 5 wt.% to about 70 wt.%, in some embodiments from about 15 wt.% to about 60 wt.%, and in some embodiments, from about 20 wt.% to about 50 wt.% of the masterbatch. Preferably, the thermoplastic carrier comprises a liquid crystalline polymer, which may be the same as or different from the liquid crystalline polymer matrix. The masterbatch may be blended with the polymer matrix and any optional fillers in an extruder, as described above.

[0053]

[0068] Regardless of the manner in which the components are incorporated into the composition, the resulting melt viscosity is generally low enough to flow easily into a mold cavity to form small-sized circuit boards. For example, in one particular embodiment, the polymer composition may have a melt viscosity of about 5 Pa·s or higher, and in some embodiments about 10 Pa·s or higher, in some embodiments from about 10 Pa·s to about 500 Pa·s, in some embodiments from about 5 Pa·s to about 150 Pa·s, in some embodiments from about 5 Pa·s to about 100 Pa·s, in some embodiments from about 10 Pa·s to about 100 Pa·s, and in some embodiments from about 15 to about 90 Pa·s, as determined at a shear rate of 1,000 / sec.

[0054] III. Applicable

[0069] In some embodiments, the polymer composition can be formed into a film. Generally, any of a variety of techniques can be used to form the polymer composition into a film. Suitable techniques include, for example, solvent casting, melt extrusion (e.g., die casting, blown film casting, extrusion coating, etc.), and the like. In one particular embodiment, a blown film process is employed, in which the composition is fed into an extruder, where it is melt-processed, and then fed through a blown film die to form a molten bubble. Typically, the die contains a mandrel disposed within the outer die body to define a space therebetween. The polymer composition is blown through this space to form a bubble, which may then be stretched, inflated with air, and rapidly cooled to rapidly solidify the polymer composition. If necessary, the bubble may then be collapsed between rollers or, optionally, wound onto a reel. The thickness of the resulting film may vary but is typically about 500 micrometers or less; in some embodiments, from about 1 to about 250 micrometers, in some embodiments, from about 2 to about 100 micrometers, and in some embodiments, from about 5 to about 50 micrometers.

[0055]

[0070] In some embodiments, the film can be used as a layer in a laminate. For example, the film can be placed adjacent to at least one conductive layer to form a laminate. The conductive layer can be provided in various forms, such as a membrane, film, mold, wafer, tube, etc. For example, the conductive layer can have a relatively thin, foil-like structure, such as a thickness of about 500 micrometers or less, in some embodiments about 200 micrometers or less, and in some embodiments, about 1 to about 100 micrometers. Of course, greater thicknesses can also be employed. The conductive layer can also contain various conductive materials, such as metals, such as gold, silver, nickel, aluminum, copper, as well as mixtures or alloys thereof. In one embodiment, for example, the conductive layer can include copper (e.g., pure copper and copper alloys).

[0056]

[0071] The film may be applied to the conductive layer using techniques such as those described above (e.g., casting), or alternatively, the conductive layer may be applied to the film using techniques such as ion beam sputtering, radio frequency sputtering, direct current magnetron sputtering, glow discharge, and the like. If necessary, the film may be subjected to a surface treatment on the side facing the conductive layer to improve adhesion between the film and the conductive layer. Examples of such surface treatments include, for example, corona discharge treatment, UV radiation treatment, plasma treatment, and the like. When applied to the conductive layer, the film may optionally be annealed to improve its properties. For example, annealing may be performed at a temperature of about 250°C to about 400°C, in some embodiments, about 260°C to about 350°C, and in some embodiments, about 280°C to about 330°C, for a period ranging from about 15 minutes to about 300 minutes, in some embodiments, about 20 minutes to about 200 minutes, and in some embodiments, about 30 minutes to about 120 minutes. It is sometimes desirable to secure the film in one or more places (e.g., at the edges) so that it cannot physically move as a whole during annealing. This can be accomplished in a variety of ways, such as by clamps, tape, or otherwise adhering the film to the conductive layer.

[0057]

[0072] Laminates may have a two-layer structure containing only a film and a conductive layer. Referring to FIG. 6, for example, one embodiment of such a two-layer structure 10 is shown, containing a film 11 disposed adjacent to a conductive layer 12 (e.g., copper foil). Alternatively, multi-layer laminates containing two or more conductive layers and / or two or more films can be formed. Referring to FIG. 7, for example, one embodiment of a three-layer laminate structure 100 is shown, containing a film 110 disposed between two conductive layers 112. Yet another embodiment is shown in FIG. 8. In this embodiment, a seven-layer laminate structure 200 is shown, containing a core 201 formed from a film 210 disposed between two conductive layers 212. Similarly, films 220 are laminated onto each of the conductive layers 212, respectively, and an outer conductive layer 222 is laminated onto the film 220. In the embodiments described above, the films of the present invention can be used to form any or all of the film layers. Various conventional processing steps may be employed to provide a laminate with sufficient strength. For example, the laminate may be pressed and / or subjected to a heat treatment, as is known in the art.

[0058]

[0073] The laminates of the present invention can be employed in a variety of different applications. For example, as described above, the laminates can be employed in the circuit board (e.g., printed circuit board) of an electronic device provided with an antenna element. The antenna element can be applied (e.g., printed) directly onto the circuit board, or alternatively, can be provided in an antenna module supported by and connected to the circuit board. Referring to FIG. 9 , for example, one embodiment of an electronic device 140 is shown containing a substrate 154 supporting various electrical components 142, such as integrated circuits (e.g., transceiver circuitry, control circuitry, etc.), discrete components (e.g., capacitors, inductors, resistors), switches, etc. An encapsulant 156 can be applied over the components 142 and printed circuit board 154, containing conductive traces 152 and contact pads 150 for forming electrical signal paths, for example, as described herein. Semiconductor dies 144 can also be employed, which are adhered to the printed circuit board and embedded within a package body to form the respective components 142. More particularly, component 142 may have contacts 146 (e.g., solder pads) and may be attached to contacts 150 on printed circuit board 154 using a conductive material 148 (e.g., solder) that connects contacts 146 and 150. In the illustrated embodiment, antenna element 160 is formed on the exposed surface of encapsulant 156. Antenna element 156 may be electrically connected to printed circuit board 154 via transmission lines 158 (e.g., metal posts).

[0059]

[0074] In certain embodiments, the printed circuit board is specially designed for use in a 5G antenna system. As used herein, "5G" generally refers to high-speed data communication over radio frequency signals. 5G networks and systems are capable of communicating data at speeds significantly faster than previous generations of data communication standards (e.g., "4G," "LTE"). Various standards and specifications have been released to quantify the requirements for 5G communication. As an example, the International Telecommunications Union (ITU) released the International Mobile Telecommunications-2020 ("IMT-2020") standard in 2015. The IMT-2020 standard specifies various data transmission criteria (e.g., downlink and uplink data rates, latency, etc.) for 5G. The IMT-2020 standard defines uplink and downlink peak data rates as the minimum data rates for uploading and downloading data that a 5G system must support. The IMT-2020 standard sets the downlink peak data rate requirement at 20 Gbit / s and the uplink peak data rate requirement at 10 Gbit / s. As another example, the Third Generation Partnership Project (3GPP) recently released a new 5G standard called "5G NR." In 2018, 3GPP published "Release 15," which defines "Phase 1" for the standardization of 5G NR. 3GPP defines 5G frequency bands as "Frequency Range 1" (FR1), which generally includes sub-6 GHz frequencies, and "Frequency Range 2" (FR2), which refers to frequency bands in the 20-60 GHz range. However, as used herein, "5G frequencies" may refer to systems utilizing frequencies greater than 60 GHz, e.g., up to 80 GHz, 150 GHz, or 300 GHz."5G frequency," as used herein, may refer to a frequency of about 2.5 GHz or higher, in some embodiments about 3.0 GHz or higher, in some embodiments about 3 GHz to about 300 GHz or higher, in some embodiments about 4 GHz to about 80 GHz, in some embodiments about 5 GHz to about 80 GHz, in some embodiments about 20 GHz to about 80 GHz, and in some embodiments about 28 GHz to about 60 GHz.

[0060]

[0075] 5G antenna systems typically employ high-frequency antennas and antenna arrays for use in base stations, repeaters (e.g., "femtocells"), relay stations, terminals, user devices, and / or other suitable components of 5G systems. Antenna elements / arrays and systems may qualify or be considered "5G" under standards released by 3GPP, such as Release 15 (2018), and / or the IMT-2020 standard. To achieve such high-speed data communications at high frequencies, antenna elements and arrays typically employ small feature sizes / spacings (e.g., fine-pitch technology) and / or advanced materials that can improve antenna performance. For example, feature sizes (spacing between antenna elements, width of antenna elements), etc., typically depend on the wavelength ("λ") (e.g., nλ / 4, where n is an integer) of the desired transmit and / or receive radio frequencies propagating through the circuit board on which the antenna elements are formed. Additionally, beamforming and / or beamsteering can be employed to facilitate reception and transmission across multiple frequency ranges or channels (e.g., multiple-in-multiple-out (MIMO), massive MIMO). High-frequency 5G antenna elements may have various structures. For example, 5G antenna elements may include coplanar waveguide elements, patch arrays (e.g., mesh grid patch arrays), other suitable 5G antenna structures. Antenna elements may be designed to provide MIMO, massive MIMO functionality, beamsteering, etc. "Massive" MIMO functionality, as used herein, generally refers to providing a large number of transmit and receive channels in an antenna array, e.g., providing eight transmit (Tx) and eight receive (Rx) channels (abbreviated as 8x8). Massive MIMO functionality may be provided in 8x8, 12x12, 16x16, 32x32, 64x64, or more.

[0061]

[0076] Antenna elements may be fabricated using various manufacturing techniques. As an example, antenna elements and / or associated elements (e.g., ground coils, feedlines, etc.) may employ fine-pitch technology. Fine-pitch technology generally refers to small or minute spacing between their components or leads. For example, feature dimensions and / or spacing between antenna elements (or between antenna elements and ground planes) may be about 1,500 micrometers or less, in some embodiments 1,250 micrometers or less, in some embodiments 750 micrometers or less (e.g., center-to-center spacing of 1.5 mm or less), 650 micrometers or less, in some embodiments 550 micrometers or less, in some embodiments 450 micrometers or less, in some embodiments 350 micrometers or less, in some embodiments 250 micrometers or less, in some embodiments 150 micrometers or less, in some embodiments 100 micrometers or less, and in some embodiments 50 micrometers or less. However, it should be understood that smaller and / or larger feature sizes and / or spacings may also be employed. As a result of such small feature dimensions, antenna structures and / or arrays having a large number of antenna elements in a small footprint may be achieved. For example, the antenna array may have an average antenna element density of more than 1,000 antenna elements per square centimeter, and in some embodiments, more than 2,000 antenna elements per square centimeter, in some embodiments, more than 3,000 antenna elements per square centimeter, in some embodiments, more than 4,000 antenna elements per square centimeter, in some embodiments, more than 6,000 antenna elements per square centimeter, and in some embodiments, more than about 8,000 antenna elements per square centimeter.Such a compact arrangement of antenna elements can provide a greater number of channels for MIMO functionality per unit area of ​​antenna area, for example, the number of channels may correspond to (e.g., be equal to or proportional to) the number of antenna elements.

[0062]

[0077] 1 , for example, a 5G antenna system 100 may include a base station 102, one or more relay stations 104, one or more user computing devices 106, one or more Wi-Fi repeaters 108 (e.g., “femtocells”), and / or other suitable antenna components for a 5G antenna system 100. The relay stations 104 may be designed to facilitate communication with the base station 102 by the user computing devices 106 and / or other relay stations 104 by relaying or “repeating” signals between the base station 102 and the user computing devices 106 and / or relay stations 104. The base station 102 may include a MIMO antenna array 110 configured to receive and / or transmit radio frequency signals 112 at the relay stations 104, the Wi-Fi repeaters 108, and / or directly with the user computing devices 106. The user computing device 306 is not necessarily limited by the present invention, and examples thereof may include devices such as 5G smartphones.

[0063]

[0078] The MIMO antenna array 110 can employ beam steering to focus or direct radio frequency signals 112 toward the relay station 104. For example, the MIMO antenna array 110 can be designed to adjust an elevation angle 114 relative to the XY plane and / or a yaw angle 116 relative to the Z direction defined in the ZY plane. Similarly, one or more of the relay station 104, user computing device 106, and Wi-Fi repeater 108 can employ beam steering to improve reception and / or transmission capabilities for the MIMO antenna array 110 by adjusting the sensitivity and / or transmission direction of the devices 104, 106, and 108 relative to the MIMO antenna array 110 of the base station 102 (e.g., by adjusting one or both of the relative elevation angle and / or relative azimuth angle of the respective devices).

[0064]

[0079] 2A-2B similarly illustrate top and side views, respectively, of an exemplary user computing device 106. The user computing device 106 may include one or more antenna elements 200, 202 (e.g., arranged as a respective antenna array). With reference to FIG. 2A, the antenna elements 200, 202 may be designed to perform beam steering in the XY plane (as illustrated by arrows 204, 206, which correspond to relative azimuth angles). With reference to FIG. 2B, the antenna elements 200, 202 may be designed to perform beam steering in the ZY plane (as illustrated by arrows 204, 206).

[0065]

[0080] FIG. 3 shows a simplified schematic diagram of multiple antenna arrays 302 connected (e.g., with a front-end module) using respective feed lines 304. The antenna arrays 302 may be mounted on a side 306 of a substrate 308, for example, as described and illustrated with respect to FIGS. 5A-5C. The substrate 308 may be, for example, a circuit board, such as those described herein. The antenna array 302 may include multiple vertically connected elements (e.g., as a mesh grid array). Thus, the antenna array 302 may extend generally parallel to the side 306 of the substrate 308. Optionally, a shield may be provided on the side 306 of the substrate 308 such that the antenna array 302 is positioned outside the shield relative to the substrate 308. The vertical spacing distance between the vertically connected elements of the antenna array 302 may correspond to the "feature size" of the antenna array 320. Thus, in some embodiments, these spacing distances may be relatively small (eg, less than about 750 micrometers) such that the antenna array 302 is a “fine pitch” antenna array 302 .

[0066]

[0081] FIG. 4 illustrates a side view of the structure of a coplanar waveguide antenna 400. One or more coplanar ground layers 402 may be aligned parallel to antenna elements 404 (e.g., patch antenna elements). Another ground layer 406 may be spaced apart from the antenna elements 404 by a substrate 408, which may be a circuit board as described herein. One or more additional antenna elements 410 may be spaced apart from the antenna elements 404 by a second layer or substrate 412, which may be a circuit board as described herein. The dimensions “G” and “W” may correspond to the “feature size” of the antenna 400. The “G” dimension may correspond to the distance between the antenna elements 404 and the coplanar ground layer 406. The “W” dimension may correspond to the width (e.g., line width) of the antenna elements 404. Thus, in some embodiments, the dimensions "G" and "W" may be relatively small (eg, less than about 750 micrometers) such that the antenna 400 is a "fine pitch" antenna 400.

[0067]

[0082] FIG. 5A illustrates one embodiment of an antenna array 500. The antenna array 500 may include a substrate 510 and a plurality of antenna elements 520 formed thereon. The substrate 510 may be, for example, a circuit board, such as those described herein. The plurality of antenna elements 520 may be approximately equally sized in the X and / or Y directions (e.g., square or rectangular). The plurality of antenna elements 520 may be approximately equally spaced apart in the X and / or Y directions. The dimensions of the antenna elements 520 and / or the spacing therebetween may correspond to the "feature size" of the antenna array 500. Thus, in some embodiments, the dimensions and / or spacing may be relatively small (e.g., less than about 750 micrometers), such that the antenna array 500 is a "fine-pitch" antenna array 500. As illustrated by ellipsis 522, the number of columns of antenna elements 520 illustrated in FIG. 5A is provided by way of example only. Similarly, the number of rows of antenna elements 520 is provided by way of example only.

[0068]

[0083] The tunable antenna array 500 can be used to provide massive MIMO functionality, for example, in a base station (e.g., as described above with respect to FIG. 1). More specifically, radio frequency interactions between various elements can be controlled or tuned to provide multiple transmit and / or receive channels. The transmit power and / or receive sensitivity can be directionally controlled to focus or direct the radio frequency signal, for example, as described with respect to the radio frequency signal 112 of FIG. 1. The tunable antenna array 500 can provide a large number of antenna elements 522 in a small footprint. For example, the tunable antenna 500 may have an average antenna element density of 1,000 antenna elements per square centimeter or greater. Such a compact arrangement of antenna elements can provide a greater number of channels for MIMO functionality per unit area. For example, the number of channels may correspond to (e.g., be equal to or proportional to) the number of antenna elements.

[0069]

[0084] FIG. 5B illustrates an embodiment of an antenna array 540. The antenna array 540 may include multiple antenna elements 542 and multiple feed lines 544 connecting the antenna elements 542 (e.g., with other antenna elements 542, a front-end module, or other suitable components). The antenna elements 542 may have respective widths “w” and spacing distances “S1” and “S2” therebetween (e.g., in the X and Y directions, respectively). These dimensions may be selected to achieve 5G radio frequency communication at desired 5G frequencies. More specifically, the dimensions may be selected to tune the antenna array 540 to transmit and / or receive data using radio frequency signals within the 5G frequency spectrum (e.g., greater than 2.5 GHz and / or greater than 3 GHz and / or greater than 28 GHz). The dimensions may be selected based on the material properties of the substrate. For example, one or more of "w," "S1," or "S2" may correspond to a multiple of the propagation wavelength ("λ") of the desired frequency through the substrate material (e.g., nλ / 4, where n is an integer).

[0070]

[0085] As an example, λ can be calculated as follows:

[0071]

number

[0072] where c is the speed of light in a vacuum and ε R is the dielectric constant of the substrate (or surrounding material) and f is the desired frequency.

[0086] 5C illustrates an exemplary antenna structure 560 in accordance with aspects of the present invention. The antenna structure 560 may include multiple antenna elements 562 aligned parallel to a long edge of a substrate 564. The various antenna elements 562 may have respective lengths "L" (and spacing distances therebetween) that tailor the antenna structure 560 for reception and / or transmission at a desired frequency and / or frequency range. More specifically, such dimensions may be selected based on the propagation wavelength λ at a desired frequency for each substrate material, as discussed above with reference to FIG. 5B, for example.

[0073]

[0087] As mentioned above, the radio communication tower component may be an RF filter. RF filters are a key element in remote radio heads. RF filters are used to reject signals of specific frequencies and are commonly used as the building blocks for duplexers and diplexers, which combine or separate multiple frequency bands. RF filters also play a key role in minimizing interference between systems operating in different bands. RF cavity filters are commonly used RF filters. Common methods for fabricating these filters, which have various designs and physical geometries, are to die-cast aluminum into the desired structure or machine the final geometry from a preform. RF filters, their characteristics, uses, fabrication, machining, and overall production are described, for example, in U.S. Pat. Nos. 7,847,658 and 8,072,298.

[0074]

[0088] In various embodiments, at least a portion of the polymer composite material described above may be metal-plated (i.e., metallized), as is typically done for RF cavity filters. For example, a metal layer such as copper, silver, or gold can be deposited on the polymer composite material via various plating techniques. Examples of suitable plating techniques can be found, for example, in U.S. Provisional Patent Application No. 61 / 577,918.

[0075]

[0089] In other embodiments, the polymer composition may be molded into a desired shape for a particular application. Typically, molded parts are formed using a one-component injection molding process in which dried and preheated plastic granules are injected into a mold. In one embodiment, the molded part or shape may be an electrical connector as described above. The electrical connector may have particular application in 5G radio frequency systems. For example, the electrical connector may communicatively couple any of the devices described in the 5G system, such as antennas and / or antenna arrays, to one or more integrated circuits, processors, memories, etc.

[0076]

[0090] One particularly suitable electrical connector 100, in accordance with an aspect of the present invention, is shown in FIG. 10A. FIG. 10B shows an enlarged view of the electrical connector 100 of FIG. 10A. As illustrated, an insertion passage or space 225 is defined between opposing walls 224 that receive contact pins to facilitate multiple separate electrical connections. The electrical connector 100 may be highly compact. More specifically, the walls 224 may have respective widths "w" that are relatively thin, for example, within the ranges described above.

[0077]

[0091] FIG. 11 shows another embodiment of an electrical connector 200. The board-side portion C2 can be mounted on the surface of a circuit board P. The connector 200 may also include a wiring-side portion C1 structured to connect separate wires 3 to the circuit board P by mating with the board-side connector C2. The board-side portion C2 may include a first housing 10 having a mating recess 10a into which the wiring-side connector C1 is mounted and having an elongated structure in the transverse direction of the housing 10. The wiring-side portion C1 may also include a second housing 20 elongated in the width direction of the housing 20. In the second housing 20, multiple terminal-receiving cavities 22 may be provided parallel to each other in the width direction to create a two-tiered array including upper and lower terminal-receiving cavities 22. Terminals 5 may be attached to the distal ends of separate wires 3 and received in each of the terminal-receiving cavities 22. If desired, a locking portion 28 (mating portion) may be provided on the housing 20 to correspond to a connecting member (not shown) on the board-side connector C2.

[0078]

[0092] As discussed above, the interior walls of the first housing 10 and / or the second housing 20 may be relatively thin (e.g., may have a relatively small width dimension) and may be formed from the polymer composition of the present invention.

[0079]

[0093] Electrical connectors can reduce or prevent interference (e.g., "crosstalk") between signals transmitted to adjacent or nearby pins due to the dielectric properties of the polymeric composition from which they are formed.

[0080]

[0094] The present invention can be better understood with reference to the following examples. [Example]

[0081] Test Method

[0095] Melt viscosity: Melt viscosity (Pa·s) was measured over 1,000 s using a Dynisco LCR7001 capillary rheometer according to ISO test number 11443:20021. -1 and a temperature 15°C above the melting point (e.g., about 350°C). The rheometer orifice (die) had a diameter of 1 mm, a length of 20 mm, an L / D ratio of 20.1, and an entrance angle of 180°. The barrel diameter was 9.55 mm + 0.005 mm, and the rod length was 233.4 mm.

[0082]

[0096] Melting Point: Melting point ("Tm") may be measured by differential scanning calorimetry ("DSC") as known in the art. Melting point is the differential scanning calorimetry (DSC) melting peak temperature as determined by ISO test number 11357-2:2020. Under the DSC procedure, samples were heated and cooled at 20°C / min as stated in ISO standard 10350, with DSC measurements performed on a TA Q2000 instrument.

[0083]

[0097] Deflection Temperature Under Load ("DTUL"): Deflection under load may be measured according to ISO Test No. 75-2:2013 (technically equivalent to ASTM D648-18). More specifically, a test strip sample having a length of 80 mm, a thickness of 10 mm, and a width of 4 mm may be subjected to an edgewise three-point bending test at a specified load (maximum external fiber stress) of 1.8 megapascals. The sample may be submerged in a silicone oil bath, where the temperature is increased at 2°C / min until the sample deflects 0.25 mm (0.32 mm for ISO Test No. 75-2:2013).

[0084]

[0098] Tensile modulus, tensile stress, and tensile elongation: Tensile properties may be tested according to ISO Test No. 527:2019 (technically equivalent to ASTM D638-14). Modulus and strength measurements may be made on the same test strip sample having a length of 80 mm, a thickness of 10 mm, and a width of 4 mm. The test temperature may be 23°C, and the test speed may be 1 or 5 mm / min.

[0085]

[0099] Flexural Modulus, Flexural Stress, and Flexural Elongation: Flexural properties may be tested according to ISO Test No. 178:2019 (technically equivalent to ASTM D790-17). This test may be performed on a 64 mm support span. The test may be performed on the center section of an uncut ISO 3167 multipurpose bar. The test temperature may be 23°C, and the test speed may be 2 mm / min.

[0086]

[0100] Unnotched and Notched Charpy Impact Strength: Charpy properties may be tested according to ISO Test No. ISO 179-1:2010 (technically equivalent to ASTM D6110-10, Method B). This test may be performed using a Type 1 specimen size (80 mm length, 10 mm width, and 4 mm thickness). When testing notched impact strength, the notch may be a Type A notch (0.25 mm base circle radius). The specimen may be cut from the center of a utility bar using a single-tooth milling machine. The test temperature may be 23°C.

[0087]

[0101] Permittivity ("Dk") and Dissipation Factor ("Df"): The dielectric constant (or relative static permittivity) and dissipation factor are determined using the well-known split-post dielectric resonator technique, as described, for example, in Baker-Jarvis et al., IEEE Trans. on Dielectric and Electrical Insulation, 5(4), 571 (1998) and Krupka et al., Proc. 7th Ed., International Conference on Dielectric Materials: Measurements and Applications, IEEE Conference Publication No. 430 (September 1996). More specifically, a plaque sample having a size of 80 mm x 80 mm x 1 mm was inserted between two fixed dielectric resonators. The resonators measured the permittivity factor at the face of the sample. Five samples were tested, and the average value was recorded. The split-post resonator can be used to measure dielectric properties in the low gigahertz range, for example, from 2 GHz to 1 GHz.

[0088]

[0102] Surface / Volume Resistivity: Surface and volume resistivity values ​​are typically measured according to IEC 60093 (similar to ASTM D257-14). According to this procedure, a standard sample (e.g., a 1-meter cube) is placed between two electrodes. A voltage is applied for 60 seconds, and the resistance is measured. Surface resistivity is the quotient of the potential gradient (in units of V / m) and the current per unit of electrode length (in units of A / m), and generally represents the resistance to leakage current along the surface of an insulating material. Because the four ends of the electrode define a square, the quotient offsets the length, and surface resistivity is reported in ohms, although it is common to refer to the more descriptive unit ohms / square. Volume resistivity can also be determined as the ratio of the potential gradient parallel to the current in the material to the current density. In SI units, volume resistivity is numerically equal to the DC resistance (ohm m) between the opposing faces of a 1-meter cube of material.

[0089]

[0103] Lightness (L * CIELAB Test for: Color measurements are performed using a DataColor 600 spectrophotometer utilizing an integrating sphere, with measurements made using the specular included mode. Color coordinates are calculated according to ASTM D2244-11 using CIELAB units, with an observer at illuminant D65 / 10°, A / 10°, or F2 / 10°.

[0090] Example 1

[0104] Sample 1 was prepared by blending 40 parts of a carbon black masterbatch containing 50 wt.% carbon black particles in a liquid crystal polymer carrier with 60 parts of a pure liquid crystal polymer resin (LCP1) using a cube blending method. The resulting resin had a carbon black content of 20 wt.%. The surface resistivity of the 50 wt.% carbon black masterbatch was measured to be 7.7 x 10 5 The resistivity was 1.0 ohms. The carbon black particles in the masterbatch were measured to have a number-average primary particle size of 41 nm and a number-average secondary particle size of 22 μm. Sample 2 was a carbon black masterbatch containing 20 wt.% carbon black particles and 80 wt.% LCP2. LCP1 was formed from 43.86 mol.% HBA, 8.57 mol.% TA, 28.57 mol.% HQ, and 20 mol.% NDA. LCP2 was formed from 2 mol.% HBA, 48 mol.% HNA, 25 mol.% BP, and 25 mol.% TA. LCP2 had a melting point of 350°C. The surface resistivities of Samples 1 and 2 were measured and are shown in Table 1.

[0091] [Table 1]

[0092] Example 2

[0105] Samples 3-10 were made from liquid crystal polymer (LCP1 or LCP2), mica, glass powder, glass fiber, lubricant, and carbon black in the amounts shown in Table 2. The glass powder consisted of milled fibers with a weight-average fiber length of 70 μm and a nominal diameter of 10 μm. The mica consisted of plate-shaped particles with an average particle size of 24 μm and an average aspect ratio of 80. Furthermore, the glass fibers employed had an initial length of either 3 mm or 4 mm. The carbon black (CB MB1) used in Samples 3-9 was from the 50 wt.% masterbatch used in Sample 1. The carbon black (CB MB2) used in Sample 10 was from Sample 2, which contained 20 wt.% carbon black. The dielectric properties of Samples 3-10 were measured and were as shown in Table 2.

[0093] [Table 2]

[0094]

[0106] These and other modifications and variations of the present invention may be practiced by those skilled in the art without departing from the spirit and scope of the present invention. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only and is not intended to limit the invention as further described in such appended claims.

Claims

1. A polymer composition comprising a liquid crystal polymer matrix and carbon black particles dispersed within the polymer matrix, the carbon black particles comprising from about 0.1 wt. % to about 3 wt. % of the composition, the composition having a dielectric loss tangent of less than 0.002 and a lightness (L) of about 60 or less when measured at a frequency of 10 GHz. ＊ The polymer composition as described above.

2. 10. The polymer composition of claim 1, wherein the carbon black particles have a number average primary particle size of about 20 to about 60 nm, as measured according to ASTM D3849-22.

3. 10. The polymer composition of claim 1, wherein the carbon black particles have a number average agglomerate particle size of from about 5 μm to about 50 μm as measured according to ASTM D3849-22.

4. 10. The polymer composition of claim 1, further comprising a filler in an amount of about 5 wt. % to about 50 wt. % of the composition.

5. The polymer composition of claim 4 , wherein the filler comprises a fibrous filler.

6. The polymer composition of claim 5 , wherein the fibrous filler comprises glass fibers.

7. 7. The polymer composition of claim 6, wherein the glass fibers have an average length of about 30 μm to about 150 μm.

8. 7. The polymer composition of claim 6, wherein the glass fibers have an aspect ratio of about 3 to about 15.

9. The polymer composition of claim 4 , wherein the filler comprises a platy filler.

10. The polymer composition of claim 9 , wherein the platy filler comprises mica.

11. 11. The polymer composition of claim 10, wherein the mica has an average particle size of about 10 μm to about 50 μm.

12. 11. The polymer composition of claim 10, wherein the mica has an average thickness of from about 0.1 μm to about 1 μm.

13. A masterbatch consisting of 20 wt. % carbon particles and 80 wt. % liquid crystal polymer resin has a viscosity of 1 x 10 when measured according to ASTM D257-14. １５ 10. The polymer composition of claim 1, exhibiting a surface resistivity greater than an ohm.

14. Lightness (L) greater than 30 ＊ 2. The polymer composition of claim 1, wherein

15. Lightness (L) greater than 40 ＊ 2. The polymer composition of claim 1, wherein

16. Lightness (L) greater than 45 ＊ 2. The polymer composition of claim 1, wherein

17. 10. The polymer composition of claim 1, exhibiting a dissipation factor of less than 0.001 when measured at a frequency of 10 GHz.

18. 10. The polymer composition of claim 1, wherein the liquid crystalline polymer contains repeat units derived from one or more aromatic dicarboxylic acids, one or more aromatic hydroxycarboxylic acids, or a combination thereof.

19. 19. The polymer composition of claim 18, wherein the aromatic hydroxycarboxylic acid comprises 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, or a combination thereof.

20. 19. The polymer composition of claim 18, wherein the aromatic hydroxycarboxylic acid comprises terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, or a combination thereof.

21. 20. The polymer composition of claim 18, wherein the liquid crystalline polymer further contains repeat units derived from one or more aromatic diols.

22. 22. The polymer composition of claim 21, wherein the aromatic diol comprises hydroquinone, 4,4'-biphenol, or a combination thereof.

23. The polymer composition of claim 1 , wherein the liquid crystalline polymer is wholly aromatic.

24. 10. The polymer composition of claim 1, wherein the liquid crystal polymer contains repeat units derived from 6-hydroxy-2-naphthoic acid in an amount of about 30 mol. % or more.

25. 10. The polymer composition of claim 1, wherein the liquid crystal polymer contains about 40 mol. % or more of repeat units derived from 6-hydroxy-2-naphthoic acid.

26. 10. The polymer composition of claim 1, wherein the liquid crystal polymer contains repeat units derived from 6-hydroxy-2-naphthoic acid and 4-hydroxybenzoic acid in a molar ratio of about 15 to about 40.

27. The liquid crystal polymer is represented by formula (I), (II), (III), and (IV): 【Chemistry 1】 In an amount of 40 to 75 mol% of structural units (I), 8.5 to 30 mol% of structural units (II), 8.5 to 30 mol% of structural units (III), and 0.1 to 8 mol% of structural units (IV), based on all structural units; In the formula, Ar １ is 2,6-naphthalene, and Ar ２ is at least one group selected from the group consisting of 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene, and Ar ３ is at least one group selected from the group consisting of 1,3-phenylene, 1,4-phenylene, and residues of compounds having two or more phenylene groups bonded to each other at their respective para positions, and Ar ４ The polymer composition of claim 1, wherein is 1,4-phenylene.

28. 10. The polymer composition of claim 1, wherein the thermally conductive filler comprises less than 40 wt.% of the composition.

29. 10. The polymer composition of claim 1, exhibiting a melt viscosity of about 10 Pa·s to about 200 Pa·s when measured at a shear rate of 1,000 / sec.

30. 10. The polymer composition of claim 1, exhibiting a dielectric constant of about 2 to about 4 when measured at a frequency of 10 GHz.

31. 10. The polymer composition of claim 1, wherein the composition is formed by melt blending a carbon black masterbatch containing the carbon black particles with the liquid crystalline polymer.

32. 32. The polymer composition of claim 31, wherein the carbon black masterbatch comprises about 15 wt. % to about 60 wt. % of the carbon black particles and about 40 to about 85 wt. % of the liquid crystalline polymer.

33. The carbon black masterbatch is about 1×10 ２ 32. The polymer composition of claim 31 having a surface resistivity of ohms or greater.

34. A film comprising the composition of claim 1.

35. 35. A laminate comprising the film of claim 34 and a conductive layer adjacent to the film.

36. 36. An antenna comprising a circuit board containing the laminate of claim 35 and an antenna element.

37. A connector comprising a molded part formed from the composition of claim 1.

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