Liquid crystal polymer composite, liquid crystal polymer composite film, and metal-clad laminate including the same

Abstract

A liquid crystal polymer composite film formed from a resin composite including one or more liquid crystal polymers and one or more fillers. The liquid crystal polymer composite film has a thickness in the range of 10 µm to 200 µm and a ratio of in-plane dielectric constant in the longitudinal direction to in-plane dielectric constant in the transverse direction in the range of 1.0 to 1.4 in a frequency range of 1 GHz to 10 GHz. A metal-clad laminate includes the liquid crystal polymer composite film and a metal-clad layer laminated to a major surface of the liquid crystal polymer composite film. The metal-clad laminate can be used as part of an antenna.

Description

[0001] Cross-references to related applications

[0002] This is a PCT international patent application that claims priority to U.S. Provisional Application No. 63 / 128,564, filed December 21, 2020, and U.S. Provisional Application No. 63 / 165,480, filed March 24, 2021, the disclosures of which are incorporated herein by reference in their entirety. Technical Field

[0003] This invention relates to liquid crystal polymer composite materials, and in particular, liquid crystal polymer composite films that can be contained in metal-clad laminates. Metal-clad laminates can be used, for example, in telecommunications products such as antenna assemblies, or in multilayer applications such as multilayer circuit boards, as multilayer stacks in rigid multilayer circuits, multilayer stacks in flexible PCBs, or as single layers in "hybrid" structures. Background Technology

[0004] The high-frequency market continues to expand. For example, 5G telecommunications standards provide networks that can use frequencies up to 40 GHz, while millimeter-wave radar used for autonomous driving operates at even higher frequencies, up to 70 GHz. Devices such as mobile phones, tablets, laptops, vehicles, and other equipment include antenna substrate assemblies to take advantage of 5G networks. These antenna assemblies can include conductive, flexible, or rigid substrates on which antenna materials (e.g., copper-clad laminates) are applied. However, there may be challenges in providing antenna substrates with the electrical and physical / mechanical properties suitable for high-frequency applications. Summary of the Invention

[0005] This disclosure relates to liquid crystal polymer (“LCP”) composite materials that can be processed into films. Such LCP composite films can be used as part of a metal-clad laminate substrate and are suitable for high-frequency products, such as antenna assemblies or automotive radar. For high-frequency applications, LCP composite films produced from LCP composite materials can have low in-plane dielectric constant and low loss tangent. In some embodiments, films produced from LCP composite materials can also have low anisotropy with respect to one or more of these properties.

[0006] The present invention relates to the following limitations, options and embodiments, which may be included individually or in combination.

[0007] A liquid crystal polymer composite film formed from a resin composite material, the resin composite material comprising: one or more liquid crystal polymers, wherein the one or more liquid crystal polymers are present in an amount ranging from 40 wt% to 95 wt% based on the total weight of the liquid crystal polymer composite material; and one or more fillers, wherein the one or more fillers are present in an amount ranging from 5 wt% to 60 wt% based on the total weight of the liquid crystal polymer composite material, wherein the thickness of the liquid crystal polymer composite film is in the range of 10 μm to 200 μm, and wherein, in a frequency range of 1 GHz to 10 GHz, the ratio of the in-plane dielectric constant in the longitudinal direction to the in-plane dielectric constant in the transverse direction of the liquid crystal polymer composite film is in the range of 1.0 to 1.4.

[0008] The liquid crystal polymer composite film, wherein in the frequency range of 1 GHz to 10 GHz, the ratio of the loss tangent in the longitudinal direction of the liquid crystal polymer composite film to the loss tangent in the transverse direction of the liquid crystal polymer composite film is in the range of 0.2 to 1.0.

[0009] The liquid crystal polymer composite film, wherein the one or more liquid crystal polymers comprise polymers containing monomer units derived from 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.

[0010] The liquid crystal polymer composite film, wherein the one or more liquid crystal polymers include polymers containing monomer units derived from 4-hydroxybenzoic acid.

[0011] The liquid crystal polymer composite film includes one or more fillers comprising zeolite, fused silica, or talc.

[0012] The liquid crystal polymer composite film, wherein the resin composite material has a melt viscosity of at least 30 Pa-s and less than 120 Pa-s at a melt temperature of 320°C and a shear rate of 1800 (1 / s).

[0013] The liquid crystal polymer composite film, wherein the resin composite material has a melt viscosity of at least 36 Pa-s and less than 80 Pa-s at a melting temperature of 320°C and a shear rate of 1800 (1 / s), and wherein the thickness of the liquid crystal polymer composite film is in the range of 10 μm–100 μm.

[0014] The liquid crystal polymer composite film, wherein the resin composite material has a melt viscosity of at least 36 Pa-s and less than 57 Pa-s at a melt temperature of 320°C and a shear rate of 1800 (1 / s), and wherein the thickness of the liquid crystal polymer composite film is in the range of 10 μm–100 μm.

[0015] The liquid crystal polymer composite film, wherein the thickness of the liquid crystal polymer composite film is in the range of 25μm-200μm.

[0016] A metal-clad laminate material includes: a liquid crystal polymer composite film; and a metal layer laminated to the main surface of the liquid crystal polymer composite film, wherein the ratio of the in-plane dielectric constant in the longitudinal direction of the liquid crystal polymer composite film to the dielectric constant in the transverse direction of the liquid crystal polymer composite film is in the range of 0.9-1.2 in a frequency range of 1 GHz to 10 GHz.

[0017] The metal-coated laminate material, wherein in the frequency range of 1 GHz to 10 GHz, the ratio of the in-plane dielectric constant in the longitudinal direction of the liquid crystal polymer composite film to the dielectric constant in the transverse direction of the liquid crystal polymer composite film is in the range of 0.9-1.1.

[0018] The ratio of the in-plane dielectric constant in the longitudinal direction to the dielectric constant in the transverse direction of the liquid crystal polymer composite film disposed in the metal-coated laminate is less than the ratio of the in-plane dielectric constant in the longitudinal direction to the dielectric constant in the transverse direction of the liquid crystal polymer composite film before lamination.

[0019] The metal-coated laminate material, wherein the metal is copper, and the surface roughness of the copper is less than 5 micrometers as measured by Rz ten-point average roughness measurement.

[0020] The metal-coated laminate, wherein the peel strength of copper from the LCP composite film is in the range of 6.0 to 13.0 psi width.

[0021] The metal-coated laminate material, wherein the metal is copper, and the roughness of the copper surface is less than or equal to 3 micrometers as measured by Rz ten-point average roughness measurement.

[0022] The metal-coated laminate, wherein the peel strength of MHT copper from the LCP composite film is in the range of 4.0 to 10.0 psi width.

[0023] The metal-coated laminate material further includes an additional metal-coated layer laminated onto an additional main surface of the liquid crystal polymer composite film.

[0024] The metal-coated laminate material, wherein the ratio of the coefficient of thermal expansion in the longitudinal direction to the coefficient of thermal expansion in the transverse direction (MD / TD) of the liquid crystal polymer composite film is in the range of 0.9 to 1.0.

[0025] The metal-coated laminate material has a thickness in the range of 15μm-50μm and is flexible.

[0026] The metal-coated laminate material has a thickness in the range of 50 μm to 200 μm and is rigid.

[0027] A metal-clad laminate material includes: a liquid crystal polymer composite film; and a metal layer laminated to the main surface of the liquid crystal polymer composite film, wherein the relative permittivity of the composite film is less than 3.1.

[0028] An antenna comprising a metal-clad laminate.

[0029] A substrate comprising a metal-clad laminate.

[0030] The metal-coated laminate further includes a third layer, wherein the layer comprises a material selected from FR4, PTFE, polyimide, and combinations thereof.

[0031] The foregoing and other features of the invention will be described in more detail below with reference to the accompanying drawings. Attached Figure Description

[0032] Figure 1 This is a schematic perspective view of an exemplary LCP composite membrane.

[0033] Figure 2 This is a schematic perspective view of an exemplary metal-coated laminate.

[0034] Figure 3 This is a schematic perspective view of another exemplary metal-coated laminate material.

[0035] Figure 4 and Figure 5 This is a graph showing the X-ray diffraction (XRD) data of LCP composite films and metal-coated laminates.

[0036] Figure 6 The general arrangement of a film extruder with associated extrusion dies according to an embodiment of the present invention is shown. Detailed Implementation

[0037] The liquid crystal polymer composite material (“LCP composite material”) disclosed herein includes a blend of one or more liquid crystal polymer materials and one or more fillers.

[0038] Liquid crystal polymers (“LCPs”) are polymers that are anisotropic when tested using thermo-optical testing (TOT) or any reasonable variation thereof, as described in U.S. Patent No. 118,372, which is incorporated herein by reference.

[0039] LCP materials are anisotropic materials, and their mechanical and electrical properties may differ in directions parallel to or transverse to the flow direction (longitudinal direction).

[0040] Three types of liquid crystal polymers have been developed for industrial applications. All of these are based on the use of p-hydroxybenzoic acid. Type I, the first type, used by Sumitomo and Solvay, has the highest heat distortion temperature and is mainly used for connectors. Types II and III are "polymers" that were developed to reduce temperature resistance and optimize LCP processing.

[0041] This invention relates to composite systems comprising fillers applicable to all three types of LCPs to modulate their properties, making them “composite materials” with unique properties for high-frequency circuit applications. Therefore, this invention relates to homopolymers and copolymers of HBA (hydroxybenzoic acid).

[0042]

[0043] LCPs are typically derived from monomers including aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, aromatic diols, aliphatic diols, aromatic hydroxylamines, and / or aromatic diamines. For example, they can be aromatic polyesters obtained by polymerizing one or more aromatic hydroxycarboxylic acids; aromatic polyesters obtained by polymerizing aromatic dicarboxylic acids, one or more aliphatic dicarboxylic acids, aromatic diols, and one or more aliphatic diols or aromatic hydroxycarboxylic acids; aromatic polyesters obtained by polymerizing one or more monomers selected from aromatic dicarboxylic acids, aliphatic dicarboxylic acids, aromatic diols and aliphatic diols; aromatic polyesteramides obtained by polymerizing aromatic hydroxylamines, one or more aromatic diamines and one or more aromatic hydroxycarboxylic acids; aromatic polyesteramides obtained by polymerizing aromatic hydroxylamines, one or more aromatic diamines, one or more aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids and one or more aliphatic carboxylic acids; and aromatic polyesteramides obtained by polymerizing aromatic hydroxylamines, one or more aromatic diamines, one or more aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, one or more aliphatic carboxylic acids, aromatic diols and one or more aliphatic diols.

[0044] Examples of aromatic hydroxycarboxylic acids include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and halogenated, alkyl, or allyl-substituted derivatives of hydroxybenzoic acid.

[0045] Examples of aromatic dicarboxylic acids include terephthalic acid; isophthalic acid; 3,3′-diphenyldicarboxylic acid; 4,4′-diphenyldicarboxylic acid; 1,4-naphthalenedicarboxylic acid; 1,5-naphthalenedicarboxylic acid; 2,6-naphthalenedicarboxylic acid; and alkyl or halogen-substituted aromatic dicarboxylic acids, such as tert-butylterephthalic acid, chloroterephthalic acid, etc.

[0046] Examples of aliphatic dicarboxylic acids include cyclic aliphatic dicarboxylic acids; such as trans-1,4-cyclohexanedicarboxylic acid; cis-1,4-cyclohexanedicarboxylic acid; 1,3-cyclohexanedicarboxylic acid; and their substituted derivatives.

[0047] Examples of aromatic diols include hydroquinone; bisphenol; 4,4′-dihydroxydiphenyl ether; 3,4′-dihydroxydiphenyl ether; bisphenol A; 3,4′-dihydroxydiphenylmethane; 3,3′-dihydroxydiphenylmethane; 4,4′-dihydroxydiphenyl sulfone; 3,4′-dihydroxydiphenyl sulfone; 4,4′-dihydroxydiphenyl sulfide; 3,4′-dihydroxydiphenyl sulfide; 2,6-naphthodiol; 1,6-naphthodiol; 4,4′-dihydroxybenzophenone; 3,4′-dihydroxybenzophenone; 3,3′-dihydroxybenzophenone; 4,4′-dihydroxydiphenyldimethylsilane; and their alkyl and halogen-substituted derivatives.

[0048] Examples of aliphatic diols include cyclic, straight-chain, and branched aliphatic diols, such as trans-1,4-hexanediol; cis-1,4-hexanediol; trans-1,3-cyclohexanediol; cis-1,2-cyclohexanediol; ethylene glycol; 1,4-butanediol; 1,6-hexanediol; 1,8-octanediol; trans-1,4-cyclohexanediethanol; cis-1,4-cyclohexanediethanol; etc., and their substituted derivatives.

[0049] Examples of aromatic hydroxylamines and aromatic diamines include 4-aminophenol, 3-aminophenol, p-phenylenediamine, m-phenylenediamine, and their substituted derivatives.

[0050] One or more LCPs can be produced using any method known in the art. For example, they can be produced using standard polycondensation techniques (melt polymerization, solution polymerization, and solid-state polymerization). In some embodiments, it is ideal to produce LCPs under anhydrous conditions in an inert gas atmosphere. For example, in a melt acidolysis method, necessary amounts of acetic anhydride, 4-hydroxybenzoic acid, glycol, and terephthalic acid are stirred and then heated in a reaction vessel equipped with a nitrogen conduit and a distillation head or cooler; byproducts, such as acetic acid, are removed by the distillation head or cooler and then collected. After the amount of collected byproducts becomes constant and polymerization is nearly complete, the molten agglomerate is heated under vacuum (typically 10 mmHg or less) and the remaining byproducts are removed, completing the polymerization.

[0051] In some embodiments, the number-average molecular weight of one or more LCPs is in the range of about 2,000 to about 200,000. In other embodiments, the number-average molecular weight of the LCP is in the range of about 5,000 to about 50,000. In still other embodiments, the number-average molecular weight of the LCP is in the range of about 10,000 to about 20,000. Molecular weight may affect the melt viscosity of the LCP.

[0052] One or more LCPs included in the LCP composite are preferably thermoplastic polyester polymers containing rigid mesocrystalline linkages. In some embodiments, the melting point of one or more LCP polymers is in the range of about 250°C to 375°C. In other embodiments, the melting point of one or more LCP polymers is in the range of about 270°C to 355°C.

[0053] One or more LCPs can be classified as pure polymers because they are not reinforced, filled / blended, or modified with additional materials before being combined with one or more fillers.

[0054] Exemplary LCPs that can be used in membranes are: thermoplastic polyester polymers comprising monomer units derived from 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; thermoplastic polyester polymers comprising monomer units derived from 6-hydroxy-2-naphthoic acid, terephthalic acid and acetaminophen; and thermoplastic polyester polymers comprising monomer units derived from 4-hydroxybenzoic acid, terephthalic acid and 4,4'-biphenyl.

[0055] An exemplary LCP is available from Celanese Corporation under a trademark. Those that were obtained. These include... A polymer (e.g., A950) B polymers (e.g., B950) C polymers (e.g., C950).

[0056] Polyester A contains 73 mol% of monomer units derived from 4-hydroxybenzoic acid (“HBA”) having the following formula.

[0057]

[0058] and 27 mol% of monomeric units derived from 2,6-hydroxynaphthoic acid ("HNA") having the following formula:

[0059]

[0060] The melting point of A950 is approximately 278°C.

[0061] Polyester B comprises 60 mol% monomer units derived from HNA, 20 mol% monomer units derived from TA, and 20 mol% monomer units derived from acetaminophen having the following formula:

[0062]

[0063] B950 has a melting point of approximately 280°C.

[0064] C polyester comprises 80 mol% of monomer units derived from HBA and 20 mol% of monomer units derived from HNA. The melting point of C950 is approximately 320°C.

[0065] Based on the total weight of the composition, the total amount of LCP present in the composite material can range from 40 wt% to 95 wt%. In other embodiments, based on the total weight of the composition, the total amount of LCP present in the composite material can range from 50 wt% to 85 wt%. In other embodiments, based on the total weight of the composition, the total amount of LCP present in the composite material can range from 60 wt% to 85 wt%. In other embodiments, based on the total weight of the composition, the total amount of LCP present in the composite material can range from 70 wt% to 80 wt%.

[0066] Exemplary fillers that can be included as one or more fillers in LCP composites include zeolites, fused silica, talc, or combinations thereof. One or more fillers included in LCP composites may have a low dielectric constant (Dk). One or more fillers included in LCP composite films may be fillers with high mechanical strength, temperature stability, and suitable dimensions, allowing them to bond with one or more LCPs during the formation of the LCP composite and allowing the manufacture of the desired product (e.g., a film) without damaging (e.g., crushing, melting, etc.) the filler.

[0067] Zeolites are typically microporous crystalline materials with pores of generally uniform molecular size and generally low theoretical dielectric constant. In some embodiments, aluminum, silicon, and oxygen are contained within the framework of the zeolite (e.g., aluminosilicate zeolite). In other embodiments, silicon and oxygen are contained within the framework of the zeolite (e.g., silica zeolite). In still other embodiments, in addition to aluminum, silicon, and oxygen or silicon and oxygen, the zeolite may include one or more additional metals, such as Ti, Sn, and / or Zn.

[0068] In some embodiments, the average pore size of the zeolite pores can be 2 nm or smaller. These pores can be hosts for water molecules and / or ions. In other embodiments, the pores can include air. Exemplary zeolites include Pentasil (MFI) zeolites purchased from Clariant AG. These include Pentasil (MFI) CZP 800, Pentasil (MFI) CZP 200, Pentasil (MFI) CZP 90, Pentasil (MFI) CZP 30, and Pentasil (MFI) CZP 27.

[0069] Fused silica is a glass composed of silica in an amorphous (non-crystalline) form. Examples include sol-gel silica and organically templated mesoporous silica. Sol-gel silica offers the ability to tune the Dk value. Organically templated mesoporous silica is a class of materials that can provide more uniform pores (pore sizes up to about 100 nm) than sol-gel silica and has shown promising Dk values.

[0070] Talc is a hydrated magnesium silicate mineral with the chemical formula Mg3Si4O10(OH)2. Although the composition of talc is generally close to this general formula, some substitutions may occur. Small amounts of Al or Ti can replace Si; small amounts of Fe, Mn, Al and / or Ca can replace Mg.

[0071] Based on the total weight of the composition, the total amount of filler present in the composite material can range from 5% to 60% by weight. In other embodiments, based on the total weight of the composition, the total amount of filler present in the LCP composite material can range from 15% to 50% by weight. In other embodiments, based on the total weight of the composition, the total amount of filler present in the LCP composite material can range from 15% to 40% by weight. In other embodiments, based on the total weight of the composition, the total amount of filler present in the LCP composite material can range from 15% to 35% by weight. In other embodiments, based on the total weight of the composition, the total amount of filler present in the LCP composite material can range from 15% to 30% by weight.

[0072] In some embodiments, in addition to one or more liquid crystal polymer (“LCP”) materials and one or more fillers, the LCP composite material may include one or more additives. Exemplary fillers include pigments, carbon black, carbon fibers, glass fibers, etc. The total amount of additives present in the LCP composite material may range from 0.001 wt% to 5 wt% based on the total weight of the composition. In other embodiments, the total amount of additives present in the LCP composite material may range from 0.01 wt% to 3 wt% based on the total weight of the composition. In other embodiments, the total amount of additives present in the LCP composite material may range from 0.1 wt% to 1 wt% based on the total weight of the composition. In other embodiments, the LCP composite material may not include one or more additives in addition to one or more liquid crystal polymer (“LCP”) materials and one or more fillers.

[0073] LCP composites can be formed by melting and combining one or more LCPs with one or more fillers. In some embodiments, after melting one or more LCP materials and combining them with one or more fillers, the LCP composite can be formed as granules or another suitable form that can be used as an LCP composite resin in subsequent production of the product. In other embodiments, after melting one or more LCP materials and combining them with one or more fillers, the LCP composite can be used directly for product formation. For example, the LCP composite can form a film. This film can be formed by melt extrusion, injection molding, or other suitable processes. In an exemplary melt extrusion process, the LCP composite can be extruded onto various casting rolls and cooled, causing one or more LCPs in the LCP composite to solidify, and the LCP composite is provided in film form.

[0074] Like molecular weight, the amount and type of filler also affect melt viscosity. For example, a pure resin with a viscosity of 21 Pa⁻¹ was compared to a high molecular weight resin with a viscosity of 27 Pa⁻¹. Both resins were mixed with fillers (45 wt% filler for the pure resin and 20 wt% filler for the high molecular weight resin). The melt viscosity of the mixed resins was significantly affected: the viscosity of the pure resin after mixing was 57 Pa⁻¹, while the viscosity of the high molecular weight resin after mixing was 36 Pa⁻¹. All viscosity measurements were performed at a melting temperature of 320 °C and a shear rate of 1800 (1 / s) using an LCR 7000 capillary rheometer from Dynsico with a barrel diameter of 0.376 inches, a die diameter of 0.762 mm, a die length of 30.48 mm, and a cone angle of 120 degrees. Melt viscosity can be adjusted to produce unprocessable composite materials, and preferably, the melt viscosity is kept below 120 Pa⁻¹. It is preferable to keep the melt viscosity equal to or below 80 Pa-s, but it is also preferable to increase the viscosity relative to the pure resin to at least 30 Pa-s.

[0075] A “membrane” is a manufactured article having opposing main surfaces, each extending in the length direction and in the width direction perpendicular to the width direction, and the opposing main surfaces being spaced apart from each other in the thickness direction perpendicular to the length direction and the width direction. Figure 1 An exemplary LCP composite membrane 100 is shown, comprising opposing main surfaces 102, 104.

[0076] Each main surface extends in a length direction 120 and a width direction 122 perpendicular to the width direction. In embodiments where the film is produced by a method such as extrusion, the length direction may also be referred to as the longitudinal direction and the width direction as the transverse direction. The main surfaces 102 and 104 are spaced apart from each other in a thickness direction 124 perpendicular to the length direction 120 and the width direction 122.

[0077] In some embodiments, the LCP composite membrane is produced as a sheet having a given length and a given width. In other embodiments, the membrane is produced as a continuous roll having a given width, which can then be cut into lengths.

[0078] LCP composite films can possess mechanical properties suitable for use as part of antenna components.

[0079] For example, the thickness of the LCP composite membrane (i.e., the thickness in the direction extending between the main surfaces of the membrane) can be in the range of 1 μm to 250 μm. In some embodiments, the thickness of the LCP composite membrane can be in the range of 10 μm to 200 μm. In other embodiments, the thickness of the LCP composite membrane can be in the range of 25 μm to 150 μm. In other embodiments, the thickness of the LCP composite membrane can be in the range of 25 μm to 100 μm. In other embodiments, the membrane thickness can be in the range of 25 μm to 50 μm. In some embodiments, the thickness tolerance of the LCP composite membrane is ±1 μm. In other embodiments, the thickness tolerance of the LCP composite membrane is ±0.05 μm.

[0080] The tensile modulus of LCP composites can be measured according to IPC-TM-650 2.4.19 Tensile Strength and Elongation and ASTM D882, the disclosures of which are incorporated herein by reference in their entirety. In some embodiments, the tensile modulus of the LCP composite membrane in both the longitudinal and transverse directions is in the range of 50 MPa–10 GPa. In other embodiments, the tensile modulus of the LCP composite membrane in both the longitudinal and transverse directions is in the range of 90 MPa–10 GPa. In other embodiments, the tensile modulus of the LCP composite membrane in both the longitudinal and transverse directions is in the range of 98 MPa–10 GPa. In other embodiments, the tensile modulus of the LCP composite membrane in both the longitudinal and transverse directions is in the range of 1 GPa–10 GPa. In other embodiments, the tensile modulus of the LCP composite membrane in both the longitudinal and transverse directions is in the range of 5 GPa–10 GPa.

[0081] Elongation can be measured according to IPC-TM-650 2.4.19 Tensile Strength and Elongation, the disclosure of which is incorporated herein by reference in its entirety. In some embodiments, the equilibrium elongation of the LCP composite membrane in both the longitudinal and transverse directions is in the range of 2% to 20%. In other embodiments, the equilibrium elongation of the LCP composite membrane in both the longitudinal and transverse directions is in the range of 2% to 15%. In other embodiments, the equilibrium elongation of the LCP composite membrane in both the longitudinal and transverse directions is in the range of 2% to 10%. In other embodiments, the equilibrium elongation of the LCP composite membrane in both the longitudinal and transverse directions is in the range of 5% to 10%.

[0082] CTE (or dimensional stability) can be measured according to IPC-TM-650 2.2.4 dimensional stability, the disclosure of which is incorporated herein by reference in its entirety. In some embodiments, the coefficient of thermal expansion (CTE) of the LCP composite film in both the longitudinal and transverse directions is in the range of -20 ppm / °C to 100 ppm / °C. In other embodiments, the coefficient of thermal expansion (CTE) of the LCP composite film in both the longitudinal and transverse directions is in the range of 0 ppm / °C to 85 ppm / °C.

[0083] LCP composite films can possess electrical properties suitable for use as part of antenna assemblies. For example, LCP composite films can have low in-plane dielectric constant (Dk) and low loss tangent (tan(δ)) in the high-frequency range, making them suitable for use as part of antenna assemblies. The in-plane dielectric constant (Dk) and loss tangent (Df) of the formed LCP composite film can be measured according to ASTM D2520-13, the disclosure of which is incorporated herein by reference in its entirety.

[0084] The "dielectric constant" (Dk) of a material is expressed as the ratio of its (absolute) dielectric constant to its electrical constant (i.e., the absolute dielectric constant relative to classical vacuum). This dimensionless quantity can also be called the "relative dielectric constant".

[0085] The “in-plane” dielectric constant (Dk) is the dielectric constant measured along the length direction (e.g., longitudinal) or width direction (e.g., transverse) aligned with the field direction.

[0086] The loss tangent (tan(δ)) is a measure of the inherent electromagnetic energy dissipation (absorption of electromagnetic waves by dielectric materials) of a material. The loss tangent is also known as the dissipation factor (Df). A lower loss tangent results in lower electromagnetic energy dissipation, meaning the dielectric material that originally transmitted the electromagnetic wave absorbs less of it. A larger loss tangent means greater dielectric absorption, meaning the dielectric material that originally transmitted the electromagnetic wave absorbs more of it.

[0087] In some embodiments, at 10 GHz, the in-plane dielectric constant (Dk) of the LCP composite film in each longitudinal and transverse direction is in the range of 2.40–4.00. In other embodiments, at 10 GHz, the in-plane dielectric constant (Dk) of the LCP composite film in each longitudinal and transverse direction is in the range of 2.60–3.80. In other embodiments, at 10 GHz, the in-plane dielectric constant (Dk) of the LCP composite film in each longitudinal and transverse direction is in the range of 2.80–3.70. In other embodiments, at 10 GHz, the in-plane dielectric constant (Dk) of the LCP composite material in each longitudinal and transverse direction is in the range of 2.80–3.50.

[0088] In some embodiments, the LCP composite material can have a relatively stable in-plane dielectric constant (Dk) within a certain frequency range. For example, in some embodiments, the in-plane dielectric constant (Dk) of the LCP composite film in each longitudinal and transverse direction can be in the range of 2.40–4.00 in the frequency range of 1 GHz to 10 GHz. In other embodiments, the in-plane dielectric constant (Dk) of the LCP composite film in each longitudinal and transverse direction can be in the range of 2.60–3.80 in the frequency range of 1 GHz to 10 GHz. In other embodiments, the in-plane dielectric constant (Dk) of the LCP composite film in each longitudinal and transverse direction can be in the range of 2.80–3.70 in the frequency range of 1 GHz to 10 GHz. In other embodiments, the in-plane dielectric constant (Dk) of the LCP composite film in each longitudinal and transverse direction can be in the range of 2.80–3.50 in the frequency range of 1 GHz to 10 GHz.

[0089] The LCP composite material disclosed herein can provide low anisotropy regarding the dielectric constant (Dk) of the formed LCP composite film. In some embodiments, for films with a thickness of 10 μm to 200 μm, the ratio of the longitudinal dielectric constant (Dk) to the transverse dielectric constant (Dk) at 10 GHz is in the range of 1.0 to 1.4. In other embodiments, for films with a thickness of 10 μm to 200 μm, the ratio of the longitudinal dielectric constant (Dk) to the transverse dielectric constant (Dk) at 10 GHz is in the range of 1.0 to 1.35. In other embodiments, for films with a thickness of 10 μm to 200 μm, the ratio of the longitudinal dielectric constant (Dk) to the transverse dielectric constant (Dk) at 10 GHz is in the range of 1.0 to 1.25. In other embodiments, for films with a thickness of 10 μm to 200 μm, the ratio of the longitudinal dielectric constant (Dk) to the transverse dielectric constant (Dk) at 10 GHz is in the range of 1.0 to 1.20.

[0090] In some embodiments, at 10 GHz, the loss tangent (Df) of the LCP composite membrane in each longitudinal and transverse direction is less than 0.003. In other embodiments, at 10 GHz, the loss tangent (Df) of the LCP composite membrane in each longitudinal and transverse direction is in the range of 0.003–0.0001.

[0091] In some embodiments, the LCP composite material can have a relatively stable loss tangent (Df) over a certain frequency range. For example, in some embodiments, the loss tangent (Df) of the LCP composite film in each longitudinal and transverse direction can be less than 0.003 in the frequency range of 1 GHz to 10 GHz. In other embodiments, the loss tangent (Df) of the LCP composite film in each longitudinal and transverse direction can be in the range of 0.003–0.0001 in the frequency range of 1 GHz to 10 GHz.

[0092] The LCP composite material disclosed herein can provide low anisotropy with respect to the loss tangent (Df) of the formed LCP composite film. In some embodiments, for films with a thickness of 10 μm to 200 μm, at 10 GHz, the ratio of the longitudinal loss tangent (Df) to the transverse loss tangent (Df) is in the range of 0.2 to 1.0. In other embodiments, for films with a thickness of 10 μm to 200 μm, at 10 GHz, the ratio of the longitudinal loss tangent (Df) to the transverse loss tangent (Df) is in the range of 0.5 to 1.0.

[0093] Example - LCP composite film

[0094] LCP composite membranes are formed by melt extrusion. Pure LCP resin is melted and combined with fillers, and then extruded to a predetermined thickness. Table 1 lists the composition and thickness of each extruded membrane.

[0095] Table 1: Exemplary LCP Composite Materials

[0096]

[0097]

[0098] Table 2 lists the electrical properties of the LCP composite material examples described in Table 1. The in-plane dielectric constant (Dk) and loss tangent (Df) of the formed LCP composite films were measured according to IPC-TM-650 2.5.5.3 (or ASTM D2520-13-confirm), the permittivity (dielectric constant) and loss tangent (dissipation factor) of the materials, the disclosure of which is incorporated herein by reference in its entirety. Samples of each of Examples 1-10 were tested according to these test procedures, and the results are listed in the table. Measuring the films as a function of frequency, Table 2 shows the average dielectric constant (Dk) of the examples at 10 GHz. The film samples of Examples 1 and 2 were also tested to measure the dissipation factor (Df) in both the longitudinal and transverse directions, and Table 2 shows the average dissipation factor (Df) of the examples at 10 GHz.

[0099] Table 2: Electrical Performance

[0100]

[0101]

[0102] The in-plane dielectric constant (Dk) relative to frequency was measured in the frequency range of 2 GHz to 11 GHz. The in-plane dielectric constant (Dk) in the longitudinal and transverse directions remained relatively constant.

[0103] Table 3 lists the tensile moduli of Examples 1-4 described in Table 1. The tensile moduli were measured according to IPC-TM-6502.4.19 tensile strength and elongation. Samples from each of Examples 1-4 were tested according to these test procedures, and the results are listed in the table.

[0104] Table 3: Mechanical Properties - Tensile Modulus (GPa)

[0105]

[0106] Table 4 lists the coefficients of thermal expansion (CTE) of Examples 1-4 described in Table 1. The CTE (or dimensional stability) was measured according to IPC-TM-6502.2.4. Samples from each of Examples 1-4 were tested according to these test procedures, and the results are listed in the table.

[0107] Table 4: Mechanical Properties - CTE (ppm)

[0108]

[0109]

[0110] Table 5 lists the elongation of the embodiments described in Table 1. Elongation was measured according to IPC-TM-650 2.4.19. Samples from each of Examples 1-4 were tested according to these test procedures, and the results are listed in the table.

[0111] Table 5: Mechanical Properties - Elongation (%)

[0112]

[0113] Now go to Figure 4 and 5 The metal-coated laminate may include the LCP composite membrane disclosed herein. The metal-coated laminate may include a structure in which one or more metal-coated layers are laminated onto the LCP composite membrane. Figure 2 An exemplary embodiment is shown, wherein a metal-coated layer 150 is disposed on one main surface 102 of the LCP composite membrane, and another metal-coated layer 152 is disposed on another main surface 104 of the LCP composite membrane 100. Figure 3 An exemplary embodiment is shown in which a metal-coated layer 150 is disposed on a main surface 102 of an LCP composite membrane 100.

[0114] Metal-clad laminates may include a third component layer comprising a film laminated into the metal-clad laminate to provide functionality. The third component layer (not shown) may include polytetrafluoroethylene, glass-reinforced epoxy laminates such as FR-4, polyimide films, and combinations thereof. The functionality provided by such a third component layer can provide a metal-clad laminate suitable for use as a printed circuit board.

[0115] Exemplary metals that can be used for one or more metallized layers include one or more conductive metals, such as copper, aluminum, copper alloys, aluminum alloys, etc. Exemplary copper includes MHT copper and rolled annealed (RA) copper. One or more metals can provide good adhesion to the LCP composite material. In embodiments where there is more than one metallized layer, the material of one metallized layer may be the same as or different from the materials of the other layers. RA copper foil is manufactured by a rolling process after copper is cast into a block, while ED copper foil is manufactured by an electroplating process in which copper is deposited on a rotating roller. RA copper foil can be rolled to a desired thickness of approximately 6-500 micrometers. Each surface is smooth but can be roughened as needed. ED copper foil has both a rough and smooth side and is typically 6-25 micrometers thick. In some embodiments, the roughness of the surface adjacent to the LCP composite film can be selected to be less than 5 micrometers or equal to or less than 3 micrometers (Rz ten-point average roughness), as measured by the method described in JIS B 0601-2001.

[0116] In some embodiments, the thickness of the metallized layer can be in the range of 5 μm to 50 μm. In other embodiments, the thickness of the metallized laminate (e.g., copper) can be in the range of 10 μm to 40 μm. In other embodiments, the thickness of the metallized laminate can be in the range of 10 μm to 30 μm. In other embodiments, the thickness of the metallized laminate can be in the range of 10 μm to 20 μm. In some embodiments where there is more than one metallized layer, the thickness of one metallized layer can be the same as or different from the thickness of the other layers. In other embodiments where there is more than one metallized layer, the thickness of one metallized layer can be uniform.

[0117] In an exemplary lamination process, a metal-coated laminate can be produced by: preheating a pressure plate, placing a stack of LCP composite film and one or more metal layers between the pressure plates, and applying a predetermined amount of pressure to the layers while heating them to a predetermined temperature to form a laminate. After a predetermined amount of time, the formed laminate can be removed from the pressure plate and allowed to cool. In some embodiments, the predetermined temperature is greater than 225°C and less than 325°C. In other embodiments, the predetermined temperature is greater than 250°C and less than 300°C. In some embodiments, the predetermined pressure used during lamination is greater than 0.25 tons and less than 5 tons. In other embodiments, the predetermined pressure is greater than 0.75 tons and less than 4.25 tons. The temperature and pressure used allow the LCP composite film to be laminated onto one or more metal layers, but can be low enough to prevent the LCP composite from melting to the point of causing it to flow out of the laminate.

[0118] The resulting laminate can then undergo one or more post-forming steps. For example, the metal cladding can be etched to form a metal layer of the desired shape. The laminate can be rinsed after etching.

[0119] Such lamination may include a release layer disposed between the press plate and the adjacent membrane to minimize membrane adhesion relative to the press plate. This release layer is designed to maintain a smooth surface on the membrane and allow heat to flow from the press plate to the membrane. The lamination method can be used to manufacture… Figure 3 The single-layer metal-coated laminate shown, or Figure 2 The image shows a double-layer metal-coated laminate. By partially or completely etching one of the outer metal layers, the double-layer metal-coated laminate can be transformed into a single-layer metal-coated laminate.

[0120] In one aspect of lamination processes, single-layer laminates are formed by combining film extrusion with calendering. (Reference) Figure 6The diagram illustrates the overall arrangement of a film extruder 310 with associated extrusion dies 320. The extrusion die 320 includes a planar die that can be adjusted via die bolts to produce planar LCP liquid films of desired thickness and width. The extruder is used to produce planar LCP films in the form of hot melt curtains 330.

[0121] The metal foil substrate 340 is positioned adjacent to a calender 350 including a first roll 351 and a second roll 352. The first roll 351 and the second roll 352 are positioned adjacent to each other to create a region with minimal roll spacing, referred to as the roll gap region 353. In the roll gap region 353, the surfaces of the first roll and the second roll are nearly parallel. The rolls may be offset relative to each other to generate pressure in the roll gap region 353. The second roll 352 includes a heating surface capable of transferring heat to the substrate on its surface.

[0122] The metal foil 340 is heated by being positioned on the second roller 352 while tension is applied to remove and prevent wrinkles in the foil. The surface temperature of the second roller is variable and can vary from 180°C upwards to heat the metal foil to a temperature in the range of 180-220°C. As the metal foil 340 is heated by the second roller 352, it enters the roll gap region and encounters the hot melt curtain generated by the extrusion die 320, and extends into the roll gap region 353 by gravity.

[0123] The hot metal curtain 330 engages with the metal foil in the roll gap region and creates a molten pool (not shown), which is rolled between two rolling rolls and forms a single metal-coated laminate 360 ​​of thickness in the roll gap region.

[0124] The calender 350 also includes a third roll 354, which is capable of drawing individual metal-coated laminates 360 from the roll gap region. Post-calendering operations may additionally include laminate thickness measurement, laminate trimming, and winding.

[0125] One aspect of the lamination process is the uniformity of film thickness in both the longitudinal and transverse directions. Variations in the gap area due to roller dimensions, thermal effects, and roller deformation caused by high pressure that may arise in the gap can lead to transverse non-uniformity. The eccentricity of the rollers relative to the roller shaft, as well as roller vibration and feed uniformity, must be strictly controlled to avoid longitudinal non-uniformity. Uniform gap dimensions can deform during operation due to hydrodynamic forces generated in the gap area, causing roller deflection. Under such conditions, the resulting laminate is thicker in the middle and thinner at the edges. Therefore, rollers 351 and 352 are ground, hardened, and polished, and the transverse diameter of the rollers is maintained within 5 micrometers per 50 mm along each roller. The roller surfaces are coated with a diamond-like carbon (DLC) coating, which has high hardness and high peel strength and maintains a Ra of 0.2 micrometers after coating. A maximum gap force of 0.13 kN / mm is maintained in the gap area between the rollers to produce a 65-micrometer thick laminate consisting of a 12-35 micrometer thick metal foil and a 50-micrometer thick LCP film.

[0126] In some embodiments, for LCP composite films with a thickness of 10 μm to 200 μm, the ratio of the longitudinal dielectric constant (Dk) to the transverse dielectric constant (Dk) at 10 GHz is in the range of 1.0 to 1.2. In other embodiments, for LCP composite films with a thickness of 10 μm to 200 μm, the ratio of the longitudinal dielectric constant (Dk) to the transverse dielectric constant (Dk) at 10 GHz is in the range of 1.0 to 1.1. In other embodiments, for LCP composite films with a thickness of 10 μm to 200 μm, the ratio of the longitudinal dielectric constant (Dk) to the transverse dielectric constant (Dk) at 10 GHz is in the range of 1.0 to 1.05.

[0127] The low anisotropy of metal-clad laminates allows them to be used in applications such as telecommunications, as part of antenna components.

[0128] The in-plane dielectric constant (Dk) of LCP composite films contained in metallized laminates can be measured according to the measurement methods described in Oliver et al., “High-Frequency Test Method Cycle of the IPC-D24C Task Group,” the disclosure of which is incorporated herein by reference in its entirety. Oliver et al. proposed other exemplary microstrip transmission line measurement methods, including extraction from impedance, extraction from phase, and extraction of group delay and differential phase length; as well as free-space transmission measurement methods, methods involving perturbed resonant cavities with electric field orientation in the dielectric plane, and methods involving aperture-coupled striplines with electric field orientation perpendicular to the dielectric plane. Metallized laminates containing LCP composite films can also be measured according to IPC-TM-650 2.5.5.3, IPC-TM-650 2.5.5.9, and IPC-TM-650 2.5.5.5, the disclosures of which are incorporated herein by reference in their entirety.

[0129] The CTE of an LCP composite membrane included in a metal-coated laminate can be measured according to dimensional stability according to IPC-TM-6502.2.4, the disclosure of which is incorporated herein by reference in its entirety. In some embodiments, the ratio (MD / TD) of the longitudinal CTE to the transverse CTE of the LCP composite membrane included in the metal-coated laminate is in the range of 0.01 to 1.0. In other embodiments, the ratio (MD / TD) of the longitudinal CTE to the transverse CTE of the LCP composite membrane included in the metal-coated laminate is in the range of 0.2 to 0.8. In still other embodiments, the ratio (MD / TD) of the longitudinal CTE to the transverse CTE of the LCP composite membrane included in the metal-coated laminate is in the range of 0.4 to 0.7.

[0130] The peel strength of the metallized laminate can be measured according to IPC-TM-650 2.4.9 Peel Strength, Flexible Dielectric Materials, the disclosure of which is incorporated herein by reference in its entirety. In some embodiments, when the metallization is MHT copper, the peel strength of MHT copper from the LCP composite film is in the range of 6.0 to 13.0 psi width. In other embodiments, when the metallization is MHT copper, the peel strength of MHT copper from the LCP composite film is in the range of 8.0 to 12.0 psi width. In some embodiments, when the metallization is RA copper, the peel strength of RA copper from the LCP composite film is in the range of 4.0 to 10.0 psi width. In other embodiments, when the metallization is RA copper, the peel strength of RA copper from the LCP composite film is in the range of 5.0 to 8.0 psi width.

[0131] Example - Metal clad laminate including LCP composite film

[0132] The LCP composite films produced according to Examples 4 and 5 are laminated with RA copper with a thickness of 12 μm. The LCP composite films are laminated with RA copper on each main surface, such that the layers of the metal-coated laminate are similar to... Figure 2 The laminates are shown. A predetermined pressure and temperature are used to form the laminated material. The specific pressures and temperatures used in each lamination process are shown in Table 6.

[0133] Exemplary metal-coated laminates including LCP composite films are tested according to IPC-4204 and IPC-4204A, the disclosure of which is incorporated herein by reference in its entirety. The specification sheet IPC-4202 / 24 contained therein is for testing copper-coated liquid crystal polymers.

[0134] Table 6 lists the in-plane dielectric constant (Dk) of the metal-coated laminate containing the LCP composite film. The in-plane dielectric constant (Dk) of the metal-coated laminate containing the LCP composite film is measured from the impedance according to the microstrip transmission line method described in "High-Frequency Test Method Cycle of the IPC-D24C Task Group" by Oliver et al.

[0135] Table 6: In-plane dielectric constant (Dk) of the formed metal-coated laminate

[0136]

[0137]

[0138] Figure 4 XRD analysis results of the unlaminated and laminated samples of Example 4 and a commercially available liquid crystal polymer film sample for radio frequency circuitry (“Comparative Example”) are shown. The Comparative Example sample was also laminated with RA copper with a thickness of 12 μm. As shown, the unlaminated sample of Example 4 includes a curve in which the peaks appear at 90° and -90°. Figure 5 The XRD analysis results of the unlaminated and laminated samples of Example 5 are shown, comparing them with the samples of the comparative example. As shown, the unlaminated sample of Example 5 includes curves in which peaks appear at 90° and -90°. For the sample of Example 5 laminated at 270°C, these peaks are significantly reduced.

[0139] Table 7 lists the coefficient of thermal expansion (CTE) of the metal-coated laminates comprising the LCP composite membrane produced according to Example 4. The CTE was measured according to IPC-TM-650 2.2.4 dimensional stability standards. Samples of metal-coated laminates comprising the LCP composite membrane produced according to Example 4 were tested according to these test procedures, and the results are listed in the table.

[0140] Table 7: Coefficient of Thermal Expansion

[0141]

[0142] Table 8 lists the peel strengths of the metal-coated laminates comprising the LCP composite films produced according to Examples 1-7, and the peel strengths of the comparative metal-coated laminates produced using the comparative examples. Each example was laminated into two 11-inch × 7-inch coatings. One had 1 ounce of MHT copper on it. The other had 1 ounce of RA copper on it. Peel strength was measured according to IPC-TM-6502.4.9 Peel Strength, Flexible Dielectric Material. Samples from each of Examples 1-7 were tested according to these test procedures, and the results are listed in the table.

[0143] Table 8: Peel Strength

[0144] Example Copper Peel strength (lb / in width) 1 MHT 8.6 1 RA 6.64 2 MHT 11.64 2 RA 10.06 3 MHT 10.88 3 RA 3.43 4 MHT 6.65 4 RA 6.70 5 MHT 10.85 5 RA 4.12 6 MHT 10.09 6 RA 5.76 7 MHT 10.04 7 RA 5.98 Comparative Example MHT 5.44 Comparative Example RA 3.67

[0145] Table 8 shows the improved peel strength of the metal-coated laminates, including the LCP composite films produced according to Examples 1-7, compared to the metal-coated laminates produced using the comparative examples. The improved adhesion provided by the metal-coated laminates including the LCP composite films allows the use of RA copper, which is smoother and more difficult to adhere to compared to MHT copper.

[0146] Although the invention has been shown and described with respect to one or more embodiments, it will be apparent to those skilled in the art, upon reading and understanding this specification and the accompanying drawings, that equivalent changes and modifications will occur. In particular, with respect to the various functions performed by the foregoing elements (components, assemblies, devices, compositions, etc.), unless otherwise stated, the terminology used to describe such elements (including references to “device”) is intended to correspond to any element performing a particular function of the stated element (i.e., functionally equivalent), even if structurally not equivalent to the disclosed structures that perform the functions of the invention in one or more exemplary embodiments shown herein. Furthermore, while specific features of the invention may have been described above with respect to only one or more of the illustrated embodiments, such features may be combined with one or more other features of other embodiments, which may be desirable and advantageous for any given or particular application.

Claims

1. A liquid crystal polymer composite film formed from a resin composite material, the resin composite material comprising: One or more liquid crystal polymers are present in an amount ranging from 40% to 95% by weight based on the total weight of the liquid crystal polymer composite material; and One or more porous fillers comprising zeolites with an average pore size of 2 nm or less, wherein the porous fillers are present in an amount ranging from 5% to 60% by weight based on the total weight of the liquid crystal polymer composite material. The thickness of the liquid crystal polymer composite film is in the range of 10 μm-200 μm; and In the frequency range of 1 GHz to 10 GHz, the ratio of the in-plane dielectric constant in the longitudinal direction to the in-plane dielectric constant in the transverse direction of the liquid crystal polymer composite film is in the range of 1.0-1.

4.

2. The liquid crystal polymer composite film according to claim 1, wherein in the frequency range of 1 GHz to 10 GHz, the ratio of the loss tangent in the longitudinal direction of the liquid crystal polymer composite film to the loss tangent in the transverse direction of the liquid crystal polymer composite film is in the range of 0.2-1.

0.

3. The liquid crystal polymer composite film according to claim 1 or 2, wherein the one or more liquid crystal polymers comprise polymers containing monomer units derived from 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.

4. The liquid crystal polymer composite film according to claim 1 or 2, wherein the one or more liquid crystal polymers comprise polymers containing monomer units derived from 4-hydroxybenzoic acid.

5. The liquid crystal polymer composite film according to claim 1 or 2, wherein the resin composite material has a melt viscosity of at least 30 Pa-s and less than 120 Pa-s at a melt temperature of 320°C and a shear rate of 1800 (1 / s).

6. The liquid crystal polymer composite film according to claim 1 or 2, wherein the melt viscosity of the resin composite material at a melting temperature of 320°C and a shear rate of 1800 (1 / s) is at least 36 Pa-s and less than 80 Pa-s, and wherein the thickness of the liquid crystal polymer composite film is in the range of 10 μm–100 μm.

7. The liquid crystal polymer composite film according to claim 1 or 2, wherein the melt viscosity of the resin composite material at a melting temperature of 320°C and a shear rate of 1800 (1 / s) is at least 36 Pa-s and less than 57 Pa-s, and wherein the thickness of the liquid crystal polymer composite film is in the range of 10 μm–100 μm.

8. The liquid crystal polymer composite film according to claim 1 or 2, wherein the thickness of the liquid crystal polymer composite film is in the range of 25 μm to 200 μm.

9. A metal-clad laminate, comprising: The liquid crystal polymer composite film according to claim 1 or 2; And a metal layer laminated onto the main surface of the liquid crystal polymer composite film; In the frequency range of 1 GHz to 10 GHz, the ratio of the in-plane dielectric constant of the liquid crystal polymer composite film in the longitudinal direction to the in-plane dielectric constant of the liquid crystal polymer composite film in the transverse direction is in the range of 0.9-1.

2.

10. The metal-coated laminate according to claim 9, wherein, in the frequency range of 1 GHz to 10 GHz, the ratio of the in-plane dielectric constant of the liquid crystal polymer composite film in the longitudinal direction to the in-plane dielectric constant of the liquid crystal polymer composite film in the transverse direction is in the range of 0.9-1.

1.

11. The metal-coated laminate according to claim 9, wherein the ratio of the in-plane dielectric constant in the longitudinal direction to the in-plane dielectric constant in the transverse direction of the liquid crystal polymer composite film disposed in the metal-coated laminate is less than the ratio of the in-plane dielectric constant in the longitudinal direction to the in-plane dielectric constant in the transverse direction of the liquid crystal polymer composite film before lamination.

12. The metal-coated laminate according to claim 9, wherein the metal is copper, and the roughness of the copper surface is less than 5 micrometers as measured by Rz ten-point average roughness measurement.

13. The metal-coated laminate of claim 12, wherein the peel strength of copper from the LCP composite film is in the range of 6.0 to 13.0 psi width.

14. The metal-coated laminate according to claim 9, wherein the metal is copper, and the roughness of the copper surface is less than or equal to 3 micrometers as measured by Rz ten-point average roughness measurement.

15. The metal-coated laminate of claim 14, wherein the copper is MHT copper, and the peel strength of the MHT copper from the LCP composite film is in the range of 4.0 to 10.0 psi width.

16. The metal-coated laminate of claim 9, further comprising an additional metal-coated layer laminated to an additional main surface of the liquid crystal polymer composite film.

17. The metal-coated laminate according to claim 9, wherein the ratio (MD / TD) of the longitudinal coefficient of thermal expansion of the liquid crystal polymer composite film to the transverse coefficient of thermal expansion is in the range of 0.9 to 1.

0.

18. The metal-coated laminate of claim 9, wherein the thickness of the laminate is in the range of 15 μm to 50 μm, and wherein the laminate is flexible.

19. The metal-coated laminate of claim 9, wherein the thickness of the laminate is in the range of 50 μm to 200 μm, and wherein the laminate is rigid.

20. A method for manufacturing a metal-coated laminate, comprising: The metal-coated laminated material comprises the liquid crystal polymer composite film of claim 1 or 2 and a metal layer laminated to the main surface of the liquid crystal polymer composite film; The relative permittivity of the liquid crystal polymer composite film is less than 3.1; The metal layer is positioned adjacent to a rolling mill, which includes first and second rolls positioned in a parallel configuration to create a roll gap region defined by the surfaces of the first and second rolls. Position the extruder to align with the calender such that the extruder's outlet orifice is located above the roll gap region; The heated metal layer is then moved into the roll gap area. The liquid crystal polymer composite film is extruded, wherein the melt curtain leaves the outlet orifice and enters the roll gap region; A liquid crystal polymer composite film and a metal layer are laminated in the roll gap region to produce a metal-coated laminate.

21. The method of claim 20, wherein in the step of heating the metal layer, the metal layer is heated to a temperature in the range of 180-220°C.

22. The method of claim 21, wherein in the step of heating the metal layer, the second roller is heated to a temperature in the range of 180-220°C.

23. The method of claim 20, wherein in the step of positioning the metal layer, as the metal layer and the molten curtain flow through the roll gap region, the first and second rolls are biased relative to each other to generate a roll gap force in the roll gap region.

24. The method of claim 23, wherein the roll gap force is maintained in the range of 0-0.13 kN / mm.

25. The method of claim 20, wherein in the step of laminating the liquid crystal polymer composite film, a melt pool is formed by a melt curtain in the roll gap region, wherein the melt pool is rolled between two rolls, and the thickness of the metal-coated laminate is determined by the distance between the two rolls.

26. The method of claim 25, wherein the thickness of the metal foil is in the range of 12-35 micrometers, and the thickness of the liquid crystal polymer composite film is in the range of 40-100 micrometers.

27. The method of claim 26, wherein the thickness of the liquid crystal polymer composite film is 50 micrometers.

Images