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

Abstract

The liquid crystal polymer composite film is formed from a resin composite containing 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 in the frequency range of 1 GHz to 10 GHz, the ratio of the in-plane dielectric constant in the machine direction to the transverse direction is in the range of 1.0 to 1.4. The metal-clad laminate includes a liquid crystal polymer composite film and a metal-clad layer laminated on a major surface of the liquid crystal polymer composite film. The metal-clad laminate may be included as part of an antenna.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application is a PCT international patent application claiming 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 both applications being incorporated herein by reference in their entireties.

[0002] (Technical field) The present invention relates to liquid crystal polymer composites, and in particular to liquid crystal polymer composite films that can be included in metal clad laminates, which can be used in telecommunications products such as antenna assemblies, or in multilayer applications such as multilayer circuit boards, multilayer stackups in rigid multilayer circuits, multilayer stacks in flexible PCBs, or single layers in "hybrid" structures. [Background technology]

[0003] The high-frequency market continues to expand. For example, 5G telecommunications standards provide networks capable of using frequencies up to 40 GHz, while millimeter-wave radar for autonomous driving operates at a higher frequency of 70 GHz. Devices such as mobile phones, tablets, laptops, automobiles, and other devices include antenna substrate assemblies to utilize 5G networks. These antenna assemblies may include a conductive, flexible, or rigid substrate (e.g., copper-clad laminate) onto which the antenna material is mounted. However, providing antenna substrates with suitable electrical and physical / mechanical properties for use in high-frequency applications can be challenging. Summary of the Invention

[0004] The present disclosure relates to liquid crystal polymer ("LCP") composites that can be processed into films. The LCP composite films can be used as part of metal-clad laminate substrates and may be suitable for use in high-frequency products such as antenna assemblies and automotive radar. LCP composite films produced from the LCP composites may have low in-plane dielectric constants and low dissipation factors for high-frequency applications. In some embodiments, films produced from the LCP composites may exhibit low anisotropy in one or more of these properties.

[0005] The present invention relates to the following limitations, options and embodiments, which may be included singly or in combination. A liquid crystal polymer composite film formed from a resin composite, the resin composite comprising one or more liquid crystal polymers present in a range of 40 wt% to 95 wt% based on the total weight of the liquid crystal polymer composite, and one or more fillers present in a range of 5 wt% to 60 wt% based on the total weight of the liquid crystal polymer composite, the thickness of the liquid crystal polymer composite film being in the range of 10 μm to 200 μm, and the ratio of the in-plane dielectric constant in the machine direction of the liquid crystal polymer composite film to the in-plane dielectric constant in the transverse direction of the liquid crystal polymer composite film being in the range of 1.0 to 1.4 in the frequency range of 1 GHz to 10 GHz.

[0006] The liquid crystal polymer composite film, wherein the ratio of the dielectric loss tangent in the machine direction of the liquid crystal polymer composite film to the dielectric loss tangent in the transverse direction of the liquid crystal polymer composite film is in the range of 0.2 to 1.0 in the frequency range of 1 GHz to 10 GHz.

[0007] The liquid crystal polymer composite film, wherein the one or more liquid crystal polymers comprise a polymer having monomer units derived from 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.

[0008] The liquid crystal polymer composite film, wherein the one or more liquid crystal polymers include a polymer having monomer units derived from 4-hydroxybenzoic acid. The liquid crystal polymer composite film, wherein the one or more fillers comprise one or more of zeolite, fused silica, or talc.

[0009] The liquid crystal polymer composite film, wherein the melt viscosity of the resin composite at a melting temperature of 320°C and a shear rate of 1800 (1 / s) is 30 Pa·s or more and less than 120 Pa·s.

[0010] The liquid crystal polymer composite film, wherein the melt viscosity of the resin composite at a melting temperature of 320°C and a shear rate of 1800 (1 / s) is 36 Pa·s or more and less than 80 Pa·s, and the thickness of the liquid crystal polymer composite film is within the range of 10 μm to 100 μm.

[0011] The liquid crystal polymer composite film, wherein the melt viscosity of the resin composite at a melting temperature of 320°C and a shear rate of 1800 (1 / s) is 36 Pa·s or more and less than 57 Pa·s, and the thickness of the liquid crystal polymer composite film is in the range of 10 μm to 100 μm.

[0012] The liquid crystal polymer composite film, wherein the thickness of the liquid crystal polymer composite film is within a range of 25 μm to 200 μm. A metal clad laminate comprising the liquid crystal polymer composite film and a metal layer laminated on a main surface of the liquid crystal polymer composite film, wherein the ratio of the in-plane dielectric constant in the machine direction of the liquid crystal polymer composite film to the dielectric constant in the transverse direction of the liquid crystal polymer composite film is within the range of 0.9 to 1.2 in a frequency range of 1 GHz to 10 GHz.

[0013] The metal clad laminate, wherein the ratio of the in-plane dielectric constant in the machine 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 to 1.1 in the frequency range of 1 GHz to 10 GHz.

[0014] The metal clad laminate, wherein the ratio of the in-plane dielectric constant in the machine direction of the liquid crystal polymer composite film used in the metal clad laminate to the dielectric constant in the transverse direction of the liquid crystal polymer composite film is less than the ratio of the in-plane dielectric constant in the machine direction of the liquid crystal polymer composite film to the dielectric constant in the transverse direction of the liquid crystal polymer composite film before the lamination process.

[0015] The metal clad laminate, wherein the metal is copper, and the roughness of the copper surface measured by ten-point average roughness Rz is less than 5 microns. The metal clad laminate, wherein the peel strength of the copper from the LCP composite film is within the range of 6.0 to 13.0 pounds per inch width (107.2 to 232.2 kilograms per meter width).

[0016] The metal clad laminate, wherein the metal is copper, and the roughness of the copper surface, measured by ten-point average roughness Rz, is less than or equal to 3 microns. The metal clad laminate, wherein the peel strength of the MHT copper from the LCP composite film is within the range of 4.0 to 10.0 pounds per inch width (71.4 to 178.6 kilograms per meter width).

[0017] The metal clad laminate further comprising an additional metal clad layer laminated to an additional major surface of the liquid crystal polymer composite film. The metal-clad laminate, wherein the ratio of the thermal expansion coefficient in the machine direction to the transverse direction (MD / TD) of the liquid crystal polymer composite film is in the range of 0.9 to 1.0.

[0018] The metal clad laminate, wherein the thickness of the laminate is in the range of 15 μm to 50 μm, and the laminate is flexible. The metal clad laminate, wherein the thickness of the laminate is within a range of 50 μm to 200 μm, and the laminate is rigid.

[0019] A metal clad laminate comprising the liquid crystal polymer composite film and a metal layer laminated on a main surface of the liquid crystal polymer composite film, wherein the laminate film has a relative dielectric constant of less than 3.1.

[0020] An antenna including the metal clad laminate. A substrate comprising said metal clad laminate. The metal clad laminate further comprising a third layer, said third layer comprising a material selected from the group consisting of FR4, PTFE, polyimide, and combinations thereof.

[0021] The above and other features of the present invention will be described in more detail below with reference to the accompanying drawings. [Brief explanation of the drawings]

[0022] [Figure 1] FIG. 1 is a schematic perspective view of an exemplary LCP composite film. [Figure 2] FIG. 2 is a schematic side view of an exemplary metal clad laminate. [Figure 3] FIG. 3 is a schematic side view of an exemplary metal clad laminate. [Figure 4] FIG. 4 is a graph showing X-ray diffraction (XRD) data for an LCP composite film and a metal clad laminate. [Figure 5] FIG. 5 is a graph showing X-ray diffraction (XRD) data for an LCP composite film and a metal clad laminate. [Figure 6] FIG. 6 shows the general layout of a film extruder with associated extrusion dies according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0023] (Detailed Description of the Invention) A liquid crystal polymer composite ("LCP composite") in this disclosure comprises a mixture of one or more liquid crystal polymer materials and one or more fillers.

[0024] As described in U.S. Pat. No. 4,118,372, which is incorporated herein by reference, liquid crystal polymers ("LCPs") are themselves anisotropic polymers when tested by the Thermo-Optical Test (TOT) or any reasonable modification thereof.

[0025] LCP materials are anisotropic materials, meaning that their mechanical and electrical properties can vary parallel to or across the flow direction (machine direction). There are three types of liquid crystal polymers developed for industrial use. All are based on the use of hydroxybenzoic acid. Type 1 was the first, used by Sumitomo and Solvay, has the highest heat deflection temperature, and is used primarily in connectors. Types 2 and 3 are "copolymers" developed to reduce temperature resistance and optimize LCP processing.

[0026] This invention relates to composite systems containing fillers that can be applied to all three types of LCP to tailor their properties, resulting in "composites" with unique properties for high frequency circuit applications. Thus, this invention relates to both homopolymers and copolymers of HBA (hydroxybenzoic acid).

[0027] [ka]

[0028] LCPs are typically derived from monomers including aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, aromatic diols, aliphatic diols, aromatic hydroxyamines, and / or aromatic diamines. For example, the LCP may be an aromatic polyester obtained by polymerizing one or two or more aromatic hydroxycarboxylic acids, an aromatic polyester obtained by polymerizing an aromatic dicarboxylic acid, one or two or more aliphatic dicarboxylic acids, aromatic diols, one or two or more aliphatic diols, or an aromatic hydroxycarboxylic acid, an aromatic polyester obtained by polymerizing one or two or more monomers selected from the group including aromatic dicarboxylic acids, aliphatic dicarboxylic acids, aromatic diols, and aliphatic diols, an aromatic hydroxyamine, one or two or more aromatic diamines, and one or two or more aromatic hydrocarbylamines. The polyester amide may be an aromatic polyester amide obtained by polymerizing an aromatic hydroxyamine, one or two or more aromatic diamines, one or two or more aromatic hydroxycarboxylic acids, an aromatic dicarboxylic acid, and one or two or more aliphatic carboxylic acids; or an aromatic polyester amide obtained by polymerizing an aromatic hydroxyamine, one or two or more aromatic diamines, one or two or more aromatic hydroxycarboxylic acids, an aromatic dicarboxylic acid, one or two or more aliphatic carboxylic acids, an aromatic diol, and one or two or more aliphatic diols.

[0029] Examples of aromatic hydroxycarboxylic acids include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and halogen, alkyl, or allyl substituted derivatives of hydroxybenzoic acid.

[0030] 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 t-butylterephthalic acid and chloroterephthalic acid.

[0031] Examples of aliphatic dicarboxylic acids include cycloaliphatic dicarboxylic acids such as trans-1,4-cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and substituted derivatives thereof.

[0032] Examples of aromatic diols include hydroquinone, biphenol, 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'-naphthalenediol, 1,6'-naphthalenediol, 4,4'-dihydroxybenzophenone, 3,4'-dihydroxybenzophenone, 3,3'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyldimethylsilane, and alkyl-substituted and halogen-substituted derivatives thereof.

[0033] Examples of aliphatic diols include cyclic, linear 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-cyclohexanedimethanol, cis-1,4-cyclohexanedimethanol, and the like, and substituted derivatives thereof.

[0034] Examples of aromatic hydroxyamines and aromatic diamines include 4-aminophenol, 3-aminophenol, p-phenylenediamine, m-phenylenediamine, and substituted derivatives thereof.

[0035] One or more LCPs may be produced using any method known in the art. For example, they can be produced by standard polycondensation techniques (melt polymerization, solution polymerization, and solid-state polymerization). In some embodiments, it is desirable to produce the LCP under anhydrous conditions in an inert gas atmosphere. For example, in the melt acidolysis method, the required amounts of acetic anhydride, 4-hydroxybenzoic acid, diol, and terephthalic acid are stirred and then heated in a reaction vessel equipped with a nitrogen inlet and a distillation head or condenser. By-products, such as acetic acid, are removed through the distillation head or condenser and then recovered. After the amount of recovered by-products becomes constant and the polymerization is nearly complete, the molten mass is heated under vacuum (typically below 10 mmHg) to remove the remaining by-products and complete the polymerization.

[0036] In some embodiments, one or more LCPs have a number average molecular weight ranging from about 2,000 to about 200,000. In other embodiments, the LCP has a number average molecular weight ranging from about 5,000 to about 50,000. In other embodiments, the LCP has a number average molecular weight ranging from about 10,000 to about 20,000. Molecular weight can affect the melt viscosity of the LCP.

[0037] The one or more LCPs included in the LCP composite are preferably thermoplastic polyester polymers with rigid mesogenic bonds. In some embodiments, the one or more LCP polymers have a crystalline melting point in the range of about 250° C. to 375° C. In other embodiments, the one or more LCP polymers further have a crystalline melting point in the range of about 270° C. to 355° C.

[0038] The LCP(s) can be classified as neat polymers in that they are not reinforced, filled / mixed, or modified with additional materials prior to being combined with the filler(s).

[0039] Exemplary LCPs that can be used in the films include thermoplastic polyester polymers containing monomer units derived from 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; thermoplastic polyester polymers containing monomer units derived from 6-hydroxy-2-naphthoic acid, terephthalic acid, and acetaminophen; and thermoplastic polyester polymers containing monomer units derived from 4-hydroxybenzoic acid, terephthalic acid, and 4,4'-biphenol.

[0040] Exemplary LCPs are those available under the trademark VECTRA® from Celanese Corporation, Inc. These include VECTRA® A polymers (e.g., VECTRA® A950), VECTRA® B polymers (e.g., VECTRA® B950), and VECTRA® C polymers (e.g., VECTRA® C950).

[0041] VECTRA® A polyester has 73 mole percent monomer units derived from 4-hydroxybenzoic acid (“HBA”) having the formula:

[0042] [ka]

[0043] and 27 mole percent of monomer units derived from 2,6-hydroxynaphthoic acid (“HNA”) having the formula:

[0044] [ka]

[0045] VECTRA® A950 has a melting point of about 278°C. VECTRA® B polyester contains 60 mole percent monomer units derived from HNA, 20 mole percent monomer units derived from TA, and 20 mole percent monomer units derived from acetaminophenol having the formula:

[0046] [ka]

[0047] VECTRA® B950 has a melting point of about 280°C. VECTRA® C polyester contains 80 mole percent of monomer units derived from HBA and 20 mole percent of monomer units derived from HNA. VECTRA® C950 has a melting point of about 320°C.

[0048] The total amount of LCP present in the composite may be in the range of 40 wt% to 95 wt% based on the total weight of the composition. In other embodiments, the total amount of LCP present in the composite may be in the range of 50 wt% to 85 wt% based on the total weight of the composition. In other embodiments, the total amount of LCP present in the composite may be in the range of 60 wt% to 85 wt% based on the total weight of the composition. In other embodiments, the total amount of LCP present in the composite may be in the range of 70 wt% to 80 wt% based on the total weight of the composition.

[0049] Exemplary fillers that may be included as the one or more fillers in the LCP composite include zeolite, fused silica, or talc, or a combination thereof. The one or more fillers included in the LCP composite may have a low dielectric constant (Dk). The one or more fillers included in the LCP composite film may be mechanically robust, temperature stable, and appropriately sized to be combined with one or more LCPs in forming the LCP composite and to allow for the production of a desired product (e.g., a film) without destroying (e.g., crushing, melting, etc.) the filler.

[0050] Zeolites are generally microporous crystalline materials with nearly uniform molecular-sized pores and generally low theoretical dielectric constants. In some embodiments, aluminum, silicon, and oxygen are included in the zeolite framework (e.g., aluminosilicate zeolites). In other embodiments, silicon and oxygen are included in the zeolite framework (e.g., silica zeolites). In other embodiments, zeolites may include one or more additional metals, such as titanium, tin, and / or zinc, in addition to aluminum, silicon, and oxygen, or in addition to silicon and oxygen.

[0051] In some embodiments, the pores of the zeolite may have an average pore size of 2 nm or less. The pores may host water molecules and / or ions. In other embodiments, the pores may contain air. Exemplary zeolites include Pentasil (MFI) zeolites available from Clariant AG. These include Pentasil (MFI) CZP800, Pentasil (MFI) CZP200, Pentasil (MFI) CZP90, Pentasil (MFI) CZP30, and Pentasil (MFI) CZP27.

[0052] Fused silica is a glass composed of silica in an amorphous (non-crystalline) structure. Examples include sol-gel silica and organically templated mesoporous silica. Sol-gel silica offers the ability to tailor the Dk value. Organically templated mesoporous silica is a class of materials that can provide more uniform pores (with pore sizes ranging up to approximately 100 nm) than sol-gel silica and has been shown to have promising Dk values.

[0053] Talc is a hydrous magnesium silicate mineral with the chemical composition MgSiO(OH). The composition of talc usually stays close to this general formula, but some substitution can occur. Small amounts of Al or Ti can substitute for Si, and small amounts of Fe, Mn, Al, and / or Ca can substitute for Mg.

[0054] The total amount of filler present in the LCP composite may be in the range of 5 wt% to 60 wt%, based on the total weight of the composition. In other embodiments, the total amount of filler present in the LCP composite may be in the range of 15 wt% to 50 wt%, based on the total weight of the composition. In other embodiments, the total amount of filler present in the LCP composite may be in the range of 15 wt% to 40 wt%, based on the total weight of the composition. In other embodiments, the total amount of filler present in the LCP composite may be in the range of 15 wt% to 35 wt%, based on the total weight of the composition. In other embodiments, the total amount of filler present in the LCP composite may be in the range of 15 wt% to 30 wt%, based on the total weight of the composition.

[0055] In some embodiments, the LCP composite may include one or more additives in addition to one or more liquid crystal polymer ("LCP") materials and one or more fillers. Exemplary fillers include pigments, carbon black, carbon fiber, glass fiber, and the like. The total amount of additives present in the LCP composite may be in the range of 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 may be in the range of 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 may be in the range of 0.1 wt % to 1 wt %, based on the total weight of the composition. In other embodiments, the LCP composite may be free of one or more additives in addition to one or more liquid crystal polymer ("LCP") materials and one or more fillers.

[0056] An LCP composite may be formed by melting and compounding one or more LCPs with one or more fillers. In some embodiments, one or more LCP materials may be melted and compounded with one or more fillers, and the LCP composite may be formed into pellets or another suitable shape that can be subsequently used as an LCP composite resin in product production. In other embodiments, one or more LCP materials may be melted and compounded with one or more fillers, and the LCP composite resin may be used directly to form a product. For example, the LCP composite may be formed into a film. The film may be formed by a melt extrusion process, an injection molding process, or another suitable process. In an exemplary melt extrusion process, the LCP composite may be extruded onto various casting rolls and allowed to cool. The LCP(s) in the LCP composite then solidify, and the LCP composite becomes a film.

[0057] Like molecular weight, the amount and type of filler can affect melt viscosity. For example, a neat resin with a viscosity of 21 Pa·s is compared to a higher molecular weight resin with a viscosity of 27 Pa·s. Both resins are blended with filler (45 wt% filler for the neat resin and 20 wt% filler for the high molecular weight resin). The melt viscosity of the blended resins is significantly affected. After blending, the neat resin has a viscosity of 57 Pa·s, while the blended high molecular weight resin has a viscosity of 36 Pa·s. All viscosity measurements were performed using a Dynisco LCR7000 capillary rheometer 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°, at a melt temperature of 320°C and a shear rate of 1800 (1 / s). The melt viscosity may be adjusted to produce a non-processable blend; it is preferable to maintain the melt viscosity below 120 Pa·s. It is more preferred to maintain the melt viscosity below 80 Pa·s, but it is also preferred to increase the viscosity to at least 30 Pa·s relative to the neat resin.

[0058] A "film" is a manufactured article having opposing major surfaces, each extending in a length direction and a width direction perpendicular to the length and width directions. The opposing major surfaces are separated from each other in a thickness direction perpendicular to the length and width directions. Figure 1 shows an exemplary LCP composite film 100 including opposing major surfaces 102, 104.

[0059] Each of the major surfaces extends in a length direction 120 and a width direction 122 that is perpendicular to the length direction. In embodiments in which the film is produced by a process such as extrusion, the length direction may also be referred to as the machine direction, and the width direction may also be referred to as the cross direction. The major surfaces 102, 104 are spaced apart from one another in a thickness direction 124 that is perpendicular to the length direction 120 and the width direction 122.

[0060] In some embodiments, the LCP composite film is produced as a sheet having a given length and a given width, while in other embodiments, the film may be produced as a continuous roll having a given width and then cut to length.

[0061] The LCP composite film may have mechanical properties that may make it suitable for use as part of an antenna assembly. For example, the thickness of the LCP composite film (i.e., in the thickness direction extending between the major surfaces of the film) may be in the range of 1 μm to 250 μm. In some embodiments, the thickness of the LCP composite film may be in the range of 10 μm to 200 μm. In other embodiments, the thickness of the LCP composite film may be in the range of 25 μm to 150 μm. In other embodiments, the thickness of the LCP composite film may be in the range of 25 μm to 100 μm. In other embodiments, the thickness of the LCP composite film may be in the range of 25 μm to 50 μm. In some embodiments, the thickness tolerance of the LCP composite film is ±1 μm. In other embodiments, the thickness tolerance of the LCP composite film is ±0.05 μm.

[0062] The tensile modulus of the LCP composite 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 entireties. In some embodiments, the tensile modulus of the LCP composite film in the machine direction and cross direction is in the range of 50 MPa to 10 Gpa. In other embodiments, the tensile modulus of the LCP composite film in the machine direction and cross direction is in the range of 90 MPa to 10 Gpa. In other embodiments, the tensile modulus of the LCP composite film in the machine direction and cross direction is in the range of 98 MPa to 10 Gpa. In other embodiments, the tensile modulus of the LCP composite film in the machine direction and cross direction is in the range of 1 Gpa to 10 Gpa. In other embodiments, the tensile modulus of the LCP composite film in the machine direction and cross direction is in the range of 5 Gpa to 10 Gpa.

[0063] Elongation can be measured according to IPC-TM-650 2.4.19 Tensile Strength and Elongation, the disclosures of which are incorporated herein by reference in their entireties. In some embodiments, the elongation of the LCP composite film balanced in the machine and cross directions is in the range of 2% to 20%. In other embodiments, the elongation of the LCP composite film balanced in the machine and cross directions is in the range of 2% to 15%. In other embodiments, the elongation of the LCP composite film balanced in the machine and cross directions is in the range of 2% to 10%. In other embodiments, the elongation of the LCP composite film balanced in the machine and cross directions is in the range of 5% to 10%.

[0064] CTE (or dimensional stability) can be measured according to IPC-TM-650 2.2.4 Dimensional Stability, the disclosures of which are incorporated herein by reference in their entireties. In some embodiments, the coefficient of thermal expansion (CTE) of the LCP composite film in the machine and cross 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 the machine and cross directions is in the range of 0 ppm / °C to 85 ppm / °C.

[0065] The LCP composite film may have electrical properties that may make it suitable for use as part of an antenna assembly. For example, the LCP composite film may have a low in-plane dielectric constant (Dk) and a low dissipation factor (tan(δ)) in the high frequency range, making the LCP composite film suitable for use as part of an antenna assembly. The in-plane dielectric constant (Dk) and dissipation factor (Df) of the formed LCP composite film may be measured according to ASTM D2520-13, the disclosure of which is incorporated herein by reference in its entirety.

[0066] The "dielectric constant" (Dk) of a material is the (absolute) permittivity of that material expressed as a ratio to the electric constant (i.e., to the value of the absolute permittivity of classical vacuum). This dimensionless quantity may also be referred to as the "relative permittivity."

[0067] The "in-plane" dielectric constant (Dk) is the dielectric constant measured in the length direction (e.g., machine direction) or width direction (e.g., cross direction), which is aligned with the direction of the electric field. The "dissipation factor" (tan(δ)) is a measure of the specific loss of electromagnetic energy (electromagnetic wave absorption by a dielectric material) of a material. The dissipation factor may also be referred to as the loss factor (Df). A lower dissipation factor means lower loss of electromagnetic energy, which means less electromagnetic wave absorption by the dielectric material of the initially transmitted electromagnetic wave. A higher dissipation factor means greater dielectric absorption, which means greater electromagnetic wave absorption by the dielectric material of the initially transmitted electromagnetic wave.

[0068] In some embodiments, the in-plane dielectric constant (Dk) of the LCP composite film in each of the machine and cross directions at 10 GHz is in the range of 2.40 to 4.00. In other embodiments, the in-plane dielectric constant (Dk) of the LCP composite film in each of the machine and cross directions at 10 GHz is in the range of 2.60 to 3.80. In other embodiments, the in-plane dielectric constant (Dk) of the LCP composite film in each of the machine and cross directions at 10 GHz is in the range of 2.80 to 3.70. In other embodiments, the in-plane dielectric constant (Dk) of the LCP composite film in each of the machine and cross directions at 10 GHz is in the range of 2.80 to 3.50.

[0069] In some embodiments, the LCP composite may have a relatively constant in-plane dielectric constant (Dk) over a frequency range. For example, in some embodiments, the in-plane dielectric constant (Dk) of the LCP composite film in each of the machine and cross directions may be in the range of 2.40 to 4.00 over a frequency range of 1 GHz to 10 GHz. In other embodiments, the in-plane dielectric constant (Dk) of the LCP composite film in each of the machine and cross directions may be in the range of 2.60 to 3.80 over a frequency range of 1 GHz to 10 GHz. In other embodiments, the in-plane dielectric constant (Dk) of the LCP composite film in each of the machine and cross directions may be in the range of 2.80 to 3.70 over a frequency range of 1 GHz to 10 GHz. In other embodiments, the in-plane dielectric constant (Dk) of the LCP composite film in each of the machine and cross directions may be in the range of 2.80 to 3.50 over a frequency range of 1 GHz to 10 GHz.

[0070] The LCP composites of the present disclosure may exhibit low anisotropy with respect to the dielectric constant (Dk) of the formed LCP composite film. In some embodiments, for films having a thickness of 10 μm to 200 μm, the ratio of the dielectric constant (Dk) in the machine direction to the dielectric constant (Dk) in the transverse direction at 10 GHz is in the range of 1.0 to 1.4. In other embodiments, for films having a thickness of 10 μm to 200 μm, the ratio of the dielectric constant (Dk) in the machine direction to the dielectric constant (Dk) in the transverse direction at 10 GHz is in the range of 1.0 to 1.35. In other embodiments, for films having a thickness of 10 μm to 200 μm, the ratio of the dielectric constant (Dk) in the machine direction to the dielectric constant (Dk) in the transverse direction at 10 GHz is in the range of 1.0 to 1.25. In another embodiment, the ratio of the dielectric constant (Dk) in the machine direction to the dielectric constant (Dk) in the transverse direction at 10 Ghz is in the range of 1.0 to 1.20 for films having a thickness of 10 μm to 200 μm.

[0071] In some embodiments, the dissipation factor (Df) of the LCP composite film in each of the machine and cross directions at 10 Ghz is less than 0.003. In other embodiments, the dissipation factor (Df) of the LCP composite film in each of the machine and cross directions at 10 Ghz is in the range of 0.003 to 0.0001.

[0072] In some embodiments, the LCP composite may have a relatively constant dissipation factor (Df) over a frequency range. For example, in some embodiments, the dissipation factor (Df) of an LCP composite film in each of the machine and cross directions over a frequency range of 1 GHz to 10 GHz may be less than 0.003. In other embodiments, the dissipation factor (Df) of an LCP composite film in each of the machine and cross directions over a frequency range of 1 GHz to 10 GHz may be between 0.003 and 0.0001.

[0073] The LCP composites of the present disclosure may exhibit low anisotropy with respect to the dielectric loss tangent (Df) of the formed LCP composite film. In some embodiments, the ratio of the dielectric loss tangent (Df) in the machine direction to the dielectric loss tangent (Df) in the transverse direction at 10 GHz for films having a thickness of 10 μm to 200 μm is in the range of 0.2 to 1.0. In other embodiments, the ratio of the dielectric loss tangent (Df) in the machine direction to the dielectric loss tangent (Df) in the transverse direction at 10 GHz for films having a thickness of 10 μm to 200 μm is in the range of 0.5 to 1.0.

[0074] Example - LCP composite film LCP composite films are formed by melt extrusion. Neat LCP resin is melted and mixed with fillers and extruded to a predetermined thickness. Table 1 lists the composition and thickness of each extruded film.

[0075] [Table 1]

[0076] Table 2 describes the electrical properties of the LCP composite examples described in Table 1. The in-plane dielectric constant (Dk) and dissipation factor (Df) of the formed LCP composite films were measured in accordance with IPC-TM-650 2.5.5.3 (or ASTM D2520-13-compliant) Dielectric Constant (Dielectric Constant) and Dissipation Factor (Loss Factor) of Materials, the disclosures of which are incorporated herein by reference in their entirety. Each specimen of Examples 1-10 was tested according to such test procedure, and the results are set forth in the table. The films were measured as a function of frequency, and Table 2 shows the average dielectric constant (Dk) of the examples at 10 GHz. Film specimens of Examples 1 and 2 were also tested to measure the dissipation factor (Df) in both the machine and cross directions, and Table 2 shows the average dissipation factor (Df) of the examples at 10 GHz.

[0077] [Table 2]

[0078] The in-plane dielectric constant (Dk) versus frequency was measured over the frequency range 2 Ghz to 11 Ghz. The in-plane dielectric constant (Dk) in the machine and cross directions remains relatively constant.

[0079] Table 3 sets forth the tensile modulus of Examples 1-4 described in Table 1. Tensile modulus is measured in accordance with IPC-TM-650 2.4.19 Tensile Strength and Elongation. Specimens of each of Examples 1-4 were tested in accordance with such test procedure, and the results are set forth in the table.

[0080] [Table 3]

[0081] Table 4 sets forth the coefficient of thermal expansion (CTE) of Examples 1-4 described in Table 1. CTE (or dimensional stability) is measured in accordance with IPC-TM-650 2.2.4 Dimensional Stability. Specimens of each of Examples 1-4 were tested in accordance with such test procedure, and the results are set forth in the table.

[0082] [Table 4]

[0083] Table 5 describes the elongation of the examples described in Table 1. Elongation is measured in accordance with IPC-TM-650 2.4.19. Specimens of each of Examples 1-4 were tested according to such test procedures, and the results are described in the table.

[0084] [Table 5]

[0085] 4 and 5, a metal clad laminate may include the LCP composite film of the present disclosure. The metal clad laminate may include a structure in which one or more metal clad layers are laminated to an LCP composite film. FIG. 2 illustrates an exemplary embodiment in which a metal clad layer 150 is on one major surface 102 of the LCP composite film and another metal clad layer 152 is on the other major surface 104 of the LCP composite film 100. FIG. 3 illustrates an exemplary embodiment in which a metal clad layer 150 is on one major surface 102 of the LCP composite film 100.

[0086] The metal-clad laminate may include a third component layer comprising a film laminated to the interior of the metal-clad laminate to provide functionality. The third component layer (not shown) may include polytetrafluoroethylene, glass-reinforced epoxy laminate films such as FR-4, polyimide films, and combinations thereof. The functionality provided by such a third component layer may provide for the metal-clad laminate to function as a printed circuit board.

[0087] Exemplary metals that can be used for the metal clad layer(s) include one or more conductive metals such as copper, aluminum, copper alloys, aluminum alloys, etc. Exemplary coppers include MHT copper and rolled annealed (RA) copper. The metal(s) can provide good adhesion to the LCP composite. In embodiments with more than one metal clad layer, the material of one metal clad layer can be the same as or different from the material of the other clad layers. RA copper foil is produced by a rolling process after copper is cast into a block, while ED copper foil is produced by a galvanic process in which copper is deposited on a rotating drum. RA copper foil can be rolled to a preferred thickness of approximately 6 to 500 microns. It is desirable that each surface be smooth, but can also be roughened. ED copper foil has both a rough and smooth side and is typically 6 to 25 microns thick. In some embodiments, the roughness of the surface adjacent to the LCP composite film may be selected to be less than 5 microns, or equal to or less than 3 microns (ten-point average roughness Rz), as measured by the method described in JIS B 0601-2001.

[0088] In some embodiments, the thickness of the metal clad layer is in the range of 5 μm to 50 μm. In other embodiments, the thickness of the metal clad laminate (e.g., copper) is in the range of 10 μm to 40 μm. In other embodiments, the thickness of the metal clad laminate is in the range of 10 μm to 30 μm. In other embodiments, the thickness of the metal clad laminate is in the range of 10 μm to 20 μm. In some embodiments where there is more than one metal clad layer, the thickness of one metal clad layer may be different from the thickness of another clad layer. In other embodiments where there is more than one metal clad layer, the thicknesses of the metal clad layers may be the same.

[0089] In an exemplary lamination process, a metal-clad laminate may be produced by preheating platens, placing a stack of an LCP composite film and one or more metal layers between the platens, and applying a predetermined amount of pressure to the layers while heating the layers to a predetermined temperature for laminate formation. After a predetermined length of time, the formed laminate may be removed from the platens 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 other embodiments, the predetermined temperature is greater than 250°C and less than 300°C. In some embodiments, the predetermined pressure used in the lamination process 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 may be low enough to allow for lamination of the LCP laminate film to the one or more metal layers, but to avoid melting the LCP composite to an extent that would cause it to flow out of the laminate.

[0090] The formed stack may then undergo one or more post-formation steps. For example, the metal clad layer may be etched to form the desired metal layer shape. After etching, the stack may be rinsed.

[0091] Such lamination processes may include release layers placed between the platens and adjacent films to minimize adhesion between the films and associated platens. Such release layers are designed to maintain a smooth surface on the film and allow heat flow from the platens to the film. The lamination method may be used to produce a single-layer metal-clad laminate, as shown in FIG. 35, or a dual-layer metal-clad laminate, as shown in FIG. 2. A dual-layer metal-clad laminate can be converted to a single-layer metal-clad laminate by partially or completely etching one of the outer metal layers.

[0092] In one embodiment of the lamination process, a monolayer clad laminate is formed by combining film extrusion and calendering. Referring to Figure 8, a general layout of a film extruder 310 with an associated extrusion die 320 is shown. The extrusion die 320 includes a flat die that, via die bolt adjustments, can produce a planar liquid film of LCP at a desired thickness and width. The extruder operates to produce a planar LCP film in the shape of a hot melt curtain 330.

[0093] The metal foil substrate 340 is placed adjacent to a calendar 350 that includes both a first roll 351 and a second roll 352. The first roll 351 and the second roll 352 are placed adjacent to each other, creating an area of ​​minimum roll separation. This area is called the nip area 353. In the nip area 353, the first and second roll surfaces are approximately parallel. To create pressure in the nip area 353, the rolls can be biased toward each other. The second roll 352 includes a heated surface capable of transferring heat to a substrate carried over the surface of the roll.

[0094] The metal foil 340 is placed on the second roll 352, where it is heated and tensioned to remove and prevent wrinkles. The surface temperature of the second roll is variable, starting from 180°C, to heat the metal foil to a temperature range of 180-220°C. As the metal foil 340 is heated by the second roll 352, it enters the nip region and merges with the hot melt curtain. The hot melt curtain exits the extrusion die 320 and extends into the nip region 353 by gravity.

[0095] The hot metal curtain 330 comes together with the metal foil in the nip area, creating a molten pool (not shown), and is then calendered between two calender rolls, with the thickness of the single layer metal clad laminate 360 ​​being formed in the nip area.

[0096] Additionally, the calender 350 includes a third roll 354 capable of pulling the single layer metal clad laminate 360 ​​through the nip area. Other post-calendering steps can include measuring the thickness of the laminate, trimming the laminate, and winding.

[0097] One aspect of the lamination process is the uniformity of the produced film thickness in both the machine and cross-machine directions. Variations in the gap area due to roll dimensions, thermal effects, and roll distortion due to potential high pressures in the gap can cause product non-uniformity in the cross-machine direction. To prevent non-uniformity in the machine direction, roll eccentricity relative to the roll axis, as well as roll vibration and feed uniformity, must be tightly controlled. Fluid forces generated in the nip area that deflect the rolls can cause uniform empty gap size distortion during operation. This can result in the resulting laminate being thicker in the middle and thinner at the ends. Thus, rolls 351 and 352 are ground, hardened, and polished to maintain a cross-roll diameter within 5 microns per 50 mm along each roll. The roll surfaces are coated with a diamond-like coating (DLC) with high hardness and high release properties, maintaining a Ra of 0.2 microns after coating. A maximum nip force of 0.13 kN / mm is maintained in the nip region between the rolls to produce a 65 micron thick laminate containing 12-35 micron thick metal foil and 50 micron thick LCP film.

[0098] In some embodiments, for an LCP composite film having a thickness of 10 μm to 200 μm and included in a metal-clad laminate, the ratio of the dielectric constant (Dk) in the machine direction to the dielectric constant (Dk) in the transverse direction at 10 GHz is in the range of 1.0 to 1.2. In other embodiments, for an LCP composite film having a thickness of 10 μm to 200 μm and included in a metal-clad laminate, the ratio of the dielectric constant (Dk) in the machine direction to the dielectric constant (Dk) in the transverse direction at 10 GHz is in the range of 1.0 to 1.1. In other embodiments, for an LCP composite film having a thickness of 10 μm to 200 μm and included in a metal-clad laminate, the ratio of the dielectric constant (Dk) in the machine direction to the dielectric constant (Dk) in the transverse direction at 10 GHz is in the range of 1.0 to 1.05.

[0099] The low anisotropy of metal clad laminates may enable them to be used in telecommunications applications, such as, for example, as part of an antenna assembly. The in-plane dielectric constant (Dk) of an LCP laminate film included in a metal-clad laminate can be measured according to the measurement method described in "IPC-D24C Task Group Round Robin of High Frequency Test Methods," Oliver et al., the disclosures of which are incorporated herein by reference in their entireties. Oliver et al. describes other exemplary microstrip transmission line measurement methods, including extraction from impedance, group delay extraction from phase, and differential phase length. Free-space propagation measurement methods, methods involving a perturbed resonant cavity with an electric field oriented in the plane of the dielectric, and methods involving an aperture-coupled stripline with an electric field oriented perpendicular to the plane of the dielectric, are also included. Metal-clad laminates including LCP composite films may 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 entireties.

[0100] The CTE of an LCP composite film included in a metal-clad laminate can be measured according to IPC-TM-650 2.2.4 Dimensional Stability, the disclosures of which are incorporated herein by reference in their entireties. In some embodiments, the ratio of the CTE in the machine direction to the transverse direction (MD / TD) of an LCP composite film included in a metal-clad laminate is in the range of 0.01 to 1.0. In other embodiments, the ratio of the CTE in the machine direction to the transverse direction (MD / TD) of an LCP composite film included in a metal-clad laminate is in the range of 0.2 to 0.8. In other embodiments, the ratio of the CTE in the machine direction to the transverse direction (MD / TD) of an LCP composite film included in a metal-clad laminate is in the range of 0.4 to 0.7.

[0101] The peel strength of the metal clad laminate can be measured according to IPC-TM-650 2.4.9 Peel Strength, Flexible Dielectric Materials, the disclosures of which are incorporated herein by reference in their entireties. In some embodiments, the metal clad is MHT copper and the peel strength of the MHT copper from the LCP composite film is within a range of 6.0 to 13.0 pounds / inch (107.2 to 232.2 kilograms / meter). In other embodiments, the metal clad is MHT copper and the peel strength of the MHT copper from the LCP composite film is within a range of 8.0 to 12.0 pounds / inch (142.9 to 214.3 kilograms / meter). In some embodiments, the metal clad is RA copper and the peel strength of the RA copper from the LCP composite film is within a range of 4.0 to 10.0 pounds / inch (71.4 to 178.6 kilograms / meter). In another embodiment, the metal clad is RA copper and the peel strength of the RA copper from the LCP composite film is within the range of 5.0 to 8.0 pounds per inch width (89.3 to 142.9 kilograms per meter width).

[0102] Example - Metal Clad Laminate with LCP Composite Film The LCP composite films produced according to Examples 4 and 5 are laminated with RA copper having a thickness of 12 μm. The LCP composite films are laminated with a layer of RA copper on each major surface, resulting in a metal-clad laminate layer resembling the stack shown in FIG. 2. To form the laminate, the lamination process is carried out using a predetermined amount of pressure and a specified temperature. The specific pressure and temperature used for each lamination process are shown in Table 6.

[0103] Exemplary metal-clad laminates, including LCP composite films, were tested in accordance with IPC-4204 and IPC-4204A, the disclosures of which are incorporated herein by reference in their entireties, including specification IPC-4202 / 24, used for testing copper-clad liquid crystal polymers.

[0104] Table 6 describes the in-plane dielectric constant (Dk) of the formed metal clad laminate containing the LCP composite film. The in-plane dielectric constant (Dk) of the metal clad laminate containing the LCP composite film is measured according to the microstrip transmission line method - impedance extraction, as described in "IPC-D24C Task Group Round Robin of High Frequency Test Methods," Oliver et al.

[0105] [Table 6]

[0106] FIG. 4 shows XRD analysis results for unlaminated and laminated samples of Example 4 compared to a sample of a commercially available liquid crystal polymer film used in radio frequency circuits ("Comparative Example"). The Comparative Example sample is also laminated with RA copper having a thickness of 12 μm. As shown, the unlaminated sample of Example 4 has a profile with peaks at 90° and -90°. FIG. 7 shows XRD analysis results for unlaminated and laminated samples of Example 5 compared to the Comparative Example sample. As shown, the unlaminated sample of Example 5 has a profile with peaks at 90° and -90°. For the sample of Example 5 laminated at 270°C, these peaks are significantly smaller.

[0107] Table 7 sets forth the coefficient of thermal expansion (CTE) of formed metal-clad laminates containing LCP composite films produced according to Example 4. CTE is measured according to IPC-TM-650 2.2.4 Dimensional Stability. Specimens of metal-clad laminates containing LCP composite films produced according to Example 4 were tested according to such test method, and the results are set forth in the table.

[0108] [Table 7]

[0109] Table 8 describes the peel strength of metal-clad laminates containing LCP composite films produced according to Examples 1-7, as well as comparative metal-clad laminates produced using the comparative examples. Each example was laminated to create two 11-inch by 7-inch (27.9 centimeters by 17.8 centimeter) clads: one on 1 ounce (28.35 grams) MHT copper and one on 1 ounce (28.35 grams) RA copper. Peel strength was measured in accordance with IPC-TM-650 2.4.9 Peel Strength, Flexible Dielectric Materials. Specimens of each Example 1-7 were tested according to such test procedure, and the results are set forth in the table.

[0110] [Table 8]

[0111] The results in Table 8 demonstrate the improved peel strength of metal-clad laminates containing LCP composite films produced according to Examples 1-7 compared to metal-clad laminates produced using the comparative example. The improved adhesion provided by metal-clad laminates containing LCP composite films allows for the use of RA copper, which is smoother and less prone to adhesion compared to MHT copper.

[0112] While the present invention has been shown and described with respect to a particular embodiment or embodiments, it will be apparent to those skilled in the art upon reading and understanding this specification and the accompanying drawings that equivalent alterations and modifications may occur. With respect to various functions performed by elements (components, assemblies, devices, compositions, etc.) described above, particularly those described above, even if they are not structurally equivalent to the disclosed structures that perform the functions of the exemplary embodiment or embodiments of the invention described herein, the terms used to describe such elements (including references to "method") are intended to be equivalent to (i.e., functionally equivalent to) any element that performs the particular function of the described element, unless otherwise indicated. Furthermore, while a particular feature of the invention may be described above with respect to only one or more of the described embodiments, such feature may be combined with one or more other features of other embodiments. At the same time, such feature may be desirable and beneficial for any given or particular application. [Note] [Appendix 21] A method for manufacturing a metal clad laminate, comprising: the metal clad laminate is a metal clad laminate including a liquid crystal polymer composite film and a metal layer laminated on a main surface of the liquid crystal polymer composite film, The laminate film has a dielectric constant of less than 3.1, positioning the metal layer adjacent to a calendar including a first roll and a second roll positioned in a parallel arrangement such that a nip area is created between the surfaces of the first roll and the second roll; positioning the extruder in alignment with the calender so that the extruder exit orifice is located above the nip region; heating a metal layer and moving the heated metal layer into the nip area; extruding a liquid crystal composite film, wherein a melt curtain exits the exit orifice and enters the nip region; laminating the liquid crystal composite film and the metal layer in the nip region to produce the metal clad laminate; A manufacturing method comprising: [Appendix 22] 22. The manufacturing method according to claim 21, wherein in the step of heating the metal layer, the metal layer is heated to a temperature in the range of 180°C to 220°C. [Appendix 23] 23. The manufacturing method according to claim 22, wherein in the step of heating the metal layer, the second roll is heated to a temperature in the range of 180°C to 220°C. [Appendix 24] 22. The manufacturing method of claim 21, wherein in the step of positioning the metal layer, the first roll and the second roll are urged relative to each other to generate a nip force in the nip region when the metal layer and the curtain pass through the nip region. [Appendix 25] 25. The manufacturing method according to claim 24, wherein the nip force is maintained within a range of 0 to 0.13 kN / mm. [Appendix 26] In the step of laminating the liquid crystal composite film, a melt pool is formed from the melt curtain in the nip region, The melt pool is calendered between two rolls, the distance between which determines the thickness of the metal clad laminate. The manufacturing method described in Appendix 21. [Appendix 27] The thickness of the metal foil is within the range of 12 to 35 microns, and the thickness of the LCP film is within the range of 40 to 100 microns. The manufacturing method described in Appendix 26. [Appendix 28] 28. The method of claim 27, wherein the LCP film has a thickness of about 50 microns. [Appendix 29] The LCP film comprises one or more liquid crystal polymers present in an amount ranging from 40 wt% to 95 wt% based on the total weight of the liquid crystal polymer composite, and one or more fillers present in an amount ranging from 5 wt% to 60 wt% based on the total weight of the liquid crystal polymer composite film. The manufacturing method according to any one of appendices 21 to 28.

Claims

1. A liquid crystal polymer composite film formed from a resin composite, The resin composite comprises one or more liquid crystal polymers present in an amount ranging from 40 wt % to 95 wt % based on the total weight of the resin composite; one or more porous fillers present in an amount ranging from 5 wt % to 60 wt %, based on the total weight of the resin composite, the one or more porous fillers comprising one or more of a zeolite having an average pore size of 2 nm or less, or a mesoporous silica having an average pore size of up to 100 nm; The thickness of the liquid crystal polymer composite film is in the range of 10 μm to 200 μm; A liquid crystal polymer composite film, wherein the ratio of the in-plane dielectric constant in the machine direction of the liquid crystal polymer composite film 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 in the frequency range of 1 Ghz to 10 Ghz.

2. 2. The liquid crystal polymer composite film of claim 1, wherein the ratio of the dielectric loss tangent in the machine direction of the liquid crystal polymer composite film to the dielectric loss tangent in the transverse direction of the liquid crystal polymer composite film is in the range of 0.2 to 1.0 in the frequency range of 1 Ghz to 10 Ghz.

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

4. 3. The liquid crystal polymer composite film of claim 1, wherein the one or more liquid crystal polymers comprise a polymer having monomer units derived from 4-hydroxybenzoic acid.

5. The liquid crystal polymer composite film according to any one of claims 1 to 4, wherein the melt viscosity of the resin composite at a melting temperature of 320 ° C. and a shear rate of 1800 (1 / s) is 30 Pa · s or more and less than 120 Pa · s.

6. The melt viscosity of the resin composite at a melting temperature of 320 ° C. and a shear rate of 1800 (1 / s) is 36 Pa · s or more and less than 80 Pa · s, and the thickness of the liquid crystal polymer composite film is 10 μm to 100 μm. The liquid crystal polymer composite film according to any one of claims 1 to 4 is in the range.

7. The melt viscosity of the resin composite at a melting temperature of 320 ° C. and a shear rate of 1800 (1 / s) is 36 Pa · s or more and less than 57 Pa · s, and the thickness of the liquid crystal polymer composite film is 10 μm to 100 μm. The liquid crystal polymer composite film according to any one of claims 1 to 4.

8. The liquid crystal polymer composite film according to any one of claims 1 to 7, wherein the thickness of the liquid crystal polymer composite film is in the range of 25 µm to 200 µm.

9. The liquid crystal polymer composite film according to any one of claims 1 to 8, a metal layer laminated on a main surface of the liquid crystal polymer composite film; A metal clad laminate comprising:

1. A metal clad laminate, wherein the ratio of the in-plane dielectric constant in the machine direction of the liquid crystal polymer composite film to the in-plane dielectric constant in the cross direction of the liquid crystal polymer composite film is in the range of 0.9 to 1.2 in the frequency range of 1 Ghz to 10 Ghz.

10. 10. The metal clad laminate of claim 9, wherein the ratio of the in-plane dielectric constant in the machine direction of the liquid crystal polymer composite film to the in-plane dielectric constant in the cross direction of the liquid crystal polymer composite film is in the range of 0.9 to 1.1 in the frequency range of 1 Ghz to 10 Ghz.

11. the ratio of the in-plane dielectric constant in the machine direction of the liquid crystal polymer composite film used in the metal clad laminate to the in-plane dielectric constant in the cross direction of the liquid crystal polymer composite film is 11. The metal clad laminate of claim 9 or 10, wherein the ratio of the in-plane dielectric constant in the machine direction of the liquid crystal polymer composite film to the in-plane dielectric constant in the cross direction of the liquid crystal polymer composite film prior to lamination is less than the ratio of the in-plane dielectric constant in the machine direction of the liquid crystal polymer composite film to the in-plane dielectric constant in the cross direction of the liquid crystal polymer composite film.

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

13. 13. The metal clad laminate of claim 12, wherein the peel strength of the copper from the liquid crystal polymer composite film is within the range of 6.0 to 13.0 pounds per inch width (107.2 to 232.2 kilograms per meter width).

14. 12. The metal clad laminate according to claim 9, wherein the metal of the metal layer is copper, and the surface roughness of the copper, measured by ten-point average roughness Rz, is less than or equal to 3 microns.

15. 15. The metal clad laminate of claim 14, wherein the peel strength of the copper from the liquid crystal polymer composite film is within the range of 4.0 to 10.0 pounds per inch width (71.4 to 178.6 kilograms per meter width).

16. The metal clad laminate of any one of claims 9 to 15, further comprising an additional metal clad layer laminated to an additional major surface of the liquid crystal polymer composite film.

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

0.

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

19. the thickness of the metal clad laminate is in the range of 50 μm to 200 μm; The metal clad laminate according to any one of claims 9 to 17, wherein the metal clad laminate is rigid.

Images