Composite films for mobile electronic device parts

Abstract

The present disclosure has a thickness of less than 0.10 mm, - a woven fiber fabric (FF) selected from the group of woven glass fiber fabrics or woven quartz fiber fabrics, a composition (C) comprising at least one fluoropolymer (FP) coated on the surface of a fibrous fabric (FF); and the fluoropolymer (FP) comprises - Tetrafluoroethylene-derived repeating units (R TFE )and, - repeating units (R ) derived from a fluoromonomer (F) selected from the group consisting of perfluoro(alkyl vinyl ether) (PAVE), hexafluoropropylene (HFP) and combinations of two or more of the above monomers; F )and, - (i) a monomer containing a functional group (FG) selected from the group consisting of a hydroxy group, an isocyanate group, a carboxylic acid group, and an anhydride group, (ii) a repeating unit (R) derived from at least one monomer (M) selected from the group consisting of chlorotrifluoroethylene (CTFE), and (iii) dichlorodifluoroethylene (R1112). M )and, and the following proportions, expressed in mole %, of: -(R TFE ): at least 75.0 mol%; -(R F ): between 0 mol% and 20.0 mol%; -(R M ) between 0.01 mol% and 5.0 mol%; and these mole % percentages are based on the total amount of moles of repeat units of the fluoropolymer (FP).

Description

[Technical Field]

[0001] This application claims priority to U.S. Provisional Application No. 63 / 483614, filed February 7, 2023, and European Patent Application No. 23160088.3, ​​filed March 6, 2023, the contents of which are incorporated herein by reference in their entireties for all purposes. In the event of any discrepancy between this application and the prior application affecting the clarity of terminology or language, reference should be made solely to the present application.

[0002] Technical Field

[0001] This disclosure relates to flexible composite films (CF) suitable for preparing copper clad laminates (CCL), which are based on a combination of at least one fluoropolymer (FP) and at least one woven fiber cloth (FF) and exhibit good flexibility and good folding endurance. [Background technology]

[0003]

[0002] Due to their light weight and high mechanical performance, polymer compositions are widely used in the manufacture of mobile electronic device components. Currently, there is a high market demand for polymer compositions used in the manufacture of mobile electronic device components with improved dielectric performance (i.e., low dielectric constant and dissipation factor).

[0004]

[0003] In mobile electronic devices, the materials forming various components and housings can significantly degrade radio signals (e.g., frequencies of 1 MHz, 2.4 GHz, and 5.0 GHz) transmitted and received by the mobile electronic device via one or more antennas. The dielectric performance of materials used in mobile electronic devices can be determined by measuring their permittivity and loss tangent, which represent a material's ability to interact with electromagnetic waves and impede electromagnetic signals (e.g., radio signals) passing through the material. Thus, the lower the permittivity of a material at a certain frequency, the less the material will impede electromagnetic signals at that frequency.

[0005]

[0004] Polymer films have been employed in the area of ​​mobile electronic devices. For example, aromatic polyimide films in the form of continuous aromatic polyimide film / copper foil laminate structures have been described for producing flexible printed circuit boards (FPCs), carrier tapes for tape automated bonding (TAB), and tapes for lead-on-chip (LOC) structures. Such films have been shown to exhibit good high-temperature resistance, good chemical properties, high electrical insulation, and high mechanical strength. However, polyimide films do not exhibit the expected dielectric performance, and their dielectric loss tangents are too high for use in high-frequency (≥20 GHz) applications. Furthermore, the dielectric loss tangent of polyimide films at high frequencies further deteriorates in humid environments due to moisture absorption.

[0006]

[0005] U.S. Patent No. 8,741,790 relates to a PTFE / glass fiber composite useful as a conveyor belt. Conveyor belts made from PTFE resin are used in a variety of applications. Because many applications rely on heat transfer through the belt, it is desirable to minimize the thickness of the belt. As described therein, thicknesses typically range from 5 mils (i.e., 0.127 mm) to, in some cases, 20 mils (i.e., 0.508 mm).

[0007]

[0006] WO 2022 / 259981 discloses a method for producing a fluorine-containing polymer having a functional monomer and a 5.5m 2 and an inorganic filler having a specific surface area of ​​less than 1000000 / g, and has improved adhesion to metals.

[0008]

[0007] WO 2023 / 005311 discloses a laminated article comprising a dielectric substrate comprising a perfluorocopolymer matrix comprising a fluorinated perfluoropolymer and a non-fluorinated perfluoropolymer, quartz fibers embedded in the perfluorocopolymer matrix, and an additive material dispersed within the matrix, the additive being capable of absorbing ultraviolet light. The perfluorocopolymer is different from that used in the present invention.

[0009]

[0008] WO 2022 / 158524 (D1) discloses a laminate comprising a copper foil layer, a fluororesin film, and a substrate layer. The laminate has a glass fiber woven layer and a resin film layer. D1 also discloses that the glass fiber woven layer is glass cloth or glass nonwoven fabric. D1 discloses that the fluoropolymer may contain at least one functional group based on a carbonyl group in the fluororesin. The functional group may be an acid anhydride, a carbonate group, or a haloformyl group. D1 further discloses that the functional group may be derived from a monomer, a chain transfer agent, and a polymerization initiator. D1 does not mention the proportion of 0.01 to 5.0 mol% of the repeating unit (RM). The description in D1 thus does not disclose the composite film (CF) of the present invention, which would result from multiple selections from D1. Furthermore, none of the examples in D1 disclose a composite film as defined in claim 1.

[0010]

[0009] US Patent Publication No. 2008 / 107866 (D2) discloses a laminate for flexible printed wiring boards having a three-layer laminate structure in which a reinforcing layer (A), an electrical insulator layer (B), and a conductive layer (C) are laminated in this order, in which the electrical insulator layer (B) is made of a fluorocopolymer containing repeating units (a) based on tetrafluoroethylene and / or chlorotrifluoroethylene, repeating units (b) based on a fluoromonomer other than tetrafluoroethylene and chlorotrifluoroethylene, and repeating units (c) based on a monomer having an acid anhydride residue and a polymerizable unsaturated bond, and in which, based on (a) + (b) + (c)), (a) is 50 to 99.89 mol%, (b) is 0.1 to 49.99 mol%, and (c) is 0.01 to 5 mol%. The reinforcing layer (A) is made of at least one member selected from the group consisting of polyimide resin, polyether ether ketone resin, polyphenylene, oxide resin, LCP resin, aramid fiber woven fabric, aramid fiber nonwoven fabric, aramid paper, glass cloth, and PTFE porous material. D2 does not disclose a composite film (CF) having the same features as claim 1 and a thickness of less than 0.20 mm. D2 also does not disclose the preferred configuration (ii) of the composite film.

[0011]

[0010] U.S. Patent No. 7,687,142 (D3) discloses a laminate for a printed wiring board having a laminate structure including an electrical insulator layer (A) and an electrical conductor layer (B) directly bonded to each other. D3 does not disclose a thickness below 0.20 mm.

[0012] Technical issues

[0011] With the development of 5G devices, there is a need for CCLs that include a polymeric protective layer that exhibits low dielectric properties even under humid conditions, as well as good chemical resistance, good durability, and strong adhesion to copper foil. Additionally, there is a need for CCLs and protective layers that exhibit good flexibility and good folding resistance.

[0013] The composite film and CCL of the present invention aim to solve this technical problem. Summary of the Invention

[0014]

[0013] The invention is set out in the accompanying claims.

[0015]

[0014] The present invention therefore relates to a composite film as defined in any one of claims 1 to 30.

[0016] The present invention also relates to the use of the composite film as defined in claim 31.

[0017]

[0016] The present invention also relates to a copper clad laminate as defined in any one of claims 32 to 35.

[0018]

[0017] These subjects are defined in detail below. [Brief explanation of the drawings]

[0019] [Figure 1]

[0018] A preferred configuration (ii) of the composite film (CF) of the present invention or as claimed in combination with claim 2 is shown schematically. [Figure 2]

[0019] A preferred configuration (ii) of the composite film (CF) of the present invention is shown in Figure 1. In this figure, the warp fibers (f1) or weft fibers (f2) are oriented at an angle α = 0° with respect to the longitudinal axis of the composite film (CF). [Figure 3]

[0020] A preferred configuration (ii) of the composite film (CF) of the present invention is shown, in which the warp fibers (f1) or weft fibers (f2) are oriented at an angle α=45° with respect to the longitudinal axis of the composite film (CF). DETAILED DESCRIPTION OF THE INVENTION

[0020]

[0021] In these figures, (1) and (3) are layers of composition (C), (2) is the fiber fabric (FF), and (4) indicates the longitudinal axis of the composite film (CF).

[0021] definition

[0022] Unless otherwise stated, these definitions apply throughout the contents of this disclosure.

[0022]

[0023] wt.% is weight percent. Mol.% is mole percent.

[0023]

[0024] Unless otherwise stated, the percentage of a repeat unit in a polymer is given in mol % relative to the total percentage of repeat units in the polymer.

[0024]

[0025] When numerical ranges are given herein, the endpoints of the ranges (even open-ended ranges such as ranges including "at least," "most," "lower," "higher," etc.) are included unless otherwise indicated.

[0025]

[0026] In this application, unless otherwise indicated, any particular embodiment or technical feature relating to one of the subject matters of the present invention is applicable and interchangeable with other embodiments or technical features also relating to that subject matter and disclosed elsewhere in this application, in particular in the claims.

[0026]

[0027] The repeating units derived from a given monomer X are designated by the following nomenclature (R X ). For example, (R TFE ) represents a repeating unit derived from TFE.

[0027] DISCLOSURE OF THE INVENTION

[0028] The present invention relates to a composite film (CF) having a thickness (T) of less than 0.20 mm, preferably less than 0.15 mm, preferably less than 0.10 mm, - woven fiber fabrics (FF) selected from the group of woven glass fiber fabrics or woven quartz fiber fabrics; - a composition (C) comprising at least one fluoropolymer (FP) in contact with at least one surface of a fiber fabric (FF); The fibrous fabric (FF) is a woven fabric, and the fluoropolymer (FP) is - Tetrafluoroethylene-derived repeating units (R TFE ); - repeating units (R ) derived from a fluoromonomer (F) selected from the group consisting of perfluoro(alkyl vinyl ether) (PAVE), hexafluoropropylene (HFP) and combinations of two or more of the above monomers; F ); - (i) a monomer containing a functional group (FG) selected from the group consisting of a hydroxy group, an isocyanate group, a carboxylic acid group, and an anhydride group, (ii) a repeating unit (R) derived from at least one monomer (M) selected from the group consisting of chlorotrifluoroethylene (CTFE), and (iii) dichlorodifluoroethylene (R1112), M ); and the following proportions, expressed in mole %, of: -(R TFE ): at least 75.0 mol%; -(R F ): between 0 mol% and 20.0 mol%; -(R M ): between 0.01 mol% and 5.0 mol%; and these mole % percentages are based on the total amount of moles of repeat units of the fluoropolymer (FP).

[0028]

[0029] The composite film (CF) preferably consists of only one fiber fabric (FF), which ensures good foldability.

[0029]

[0030] Composite films (CF) can be of two configurations: -(i) Composition = composition (C) / fiber fabric (FF); or -(ii) Composition = composition (C) / fiber fabric (FF) / composition (C).

[0030]

[0031] In configuration (i), composition (C) contacts only one side of the woven fiber fabric.

[0031]

[0032] Composition of composite film (CF) (ii)

[0033] In configuration (ii), the composition (C) is in contact with two surfaces (or sides) of the fibrous fabric (FF). Figures 1, 2 and 3 show configuration (ii).

[0032]

[0034] The present invention also relates to a composite film (CF) having a thickness (T) of less than 0.20 mm, preferably less than 0.15 mm, preferably less than 0.10 mm, - a layer (L1) of composition (C); - woven fiber fabrics (FF) selected from the group of woven glass fiber fabrics or woven quartz fiber fabrics; - a layer (L2) of composition (C); in this order, The composition (C) comprises at least one fluoropolymer (FP) in contact with at least one surface of the fibrous fabric (FF), The fiber fabric (FF) is a fabric, and the fluoropolymer (FP) is - Tetrafluoroethylene-derived repeating units (R TFE ); - repeating units (R ) derived from a fluoromonomer (F) selected from the group consisting of perfluoro(alkyl vinyl ether) (PAVE), hexafluoropropylene (HFP) and combinations of two or more of the above monomers; F ); - (i) a monomer containing a functional group (FG) selected from the group consisting of a hydroxy group, an isocyanate group, a carboxylic acid group, and an anhydride group, (ii) a repeating unit (R) derived from at least one monomer (M) selected from the group consisting of chlorotrifluoroethylene (CTFE), and (iii) dichlorodifluoroethylene (R1112), M ); and the following proportions, expressed in mole %, of: -(R TFE ): at least 75.0 mol%; -(R F ): between 0 mol% and 20.0 mol%; -(R M ): between 0.01 mol% and 5.0 mol%; and these mole % percentages are based on the total amount of moles of repeat units of the fluoropolymer (FP).

[0033]

[0035] When the composite film (CF) comprises two layers of composition (C), these two layers are preferably based on the same fluoropolymer (FP) and preferably they are of the same composition.

[0034]

[0036] Next, details regarding the composition (C), the fluoropolymer (FP), the woven fiber fabric (FF) and the composite film (CF) are provided below.

[0035]

[0037] About Fluoropolymers (FP)

[0038] Fluoropolymers (FP) are polymers consisting of repeating units (R TFE ) and repeating units (R F ) and repeating units (R M ) and in the following proportions, expressed in mol%: -(R TFE ): at least 75.0 mol%; -(R F ): between 0 mol% and 20.0 mol%; -(R M ): Between 0.01 mol% and 5.0 mol% It has.

[0036]

[0039] Repeating unit (R F ) is between 0 mol% and 20.0 mol%. This proportion may in particular be between 0.1 mol% and 20.0 mol%, more particularly between 0.1 mol% and 10.0 mol%, and even more particularly between 0.5 mol% and 5.0 mol%. This proportion may also be between 1.0 mol% and 5.0 mol%, or between 1.0 mol% and 3.0 mol%.

[0037]

[0040] Repeating unit (R M) may more particularly be between 0.05 mol% and 5.0 mol%. This proportion may more particularly be between 0.05 mol% and 3.0 mol% or anything therebetween. This proportion is preferably at least 0.08. This proportion is preferably at most 1.5 mol% or at most 1.0 mol%.

[0038]

[0041] According to one embodiment, the repeating unit (R TFE ) is the ratio of repeating units (R F ) and (R M ) proportion remaining. In other words, (R TFE ) percentage = 100% - (R F )-(R M )

[0039]

[0042] Repeating unit (R TFE ) is at least 75.0 mol %. This ensures that the fluoropolymer (FP) has sufficient heat resistance and dielectric properties (D k , D f ) is ensured. This proportion is therefore preferably at least 85.0 mol %, preferably at least 94.0 mol %.

[0040]

[0043] The fluoromonomer (F) is selected from the group consisting of perfluoro(alkyl vinyl ether) (PAVE), hexafluoropropylene (HFP) and combinations of two or more of said monomers.

[0041]

[0044] The fluoromonomer (F) is preferably selected from the group of perfluoro(alkyl vinyl ethers) (PAVE), which have the general formula CF2=CFOR f (I) is a monomer of formula (I), wherein R f is a C1-C8 perfluoroalkyl group, preferably a C1-C3 perfluoroalkyl group. The perfluoroalkyl group may be linear or branched.

[0042]

[0045] In the context of the present disclosure, a PAVE may more particularly be selected from the group consisting of CF2=CFOCF3 (or PMVE), CF2=CFOCF2CF3 (or PEVE), CF2=CFOCF2CF2CF3 (or PPVE), CF2=CFOCF2CF2CF2CF3, CF2=CFO(CF2)7CF3, and combinations of two or more of said monomers. In the context of the present disclosure, a PAVE may more particularly be selected from the group consisting of CF2=CFOCF3 (or PMVE), CF2=CFOCF2CF3 (or PEVE), CF2=CFOCF2CF2CF3 (or PPVE), and combinations of two or more of said monomers. In the context of the present disclosure, a PAVE is more particularly a PPVE or a PMVE.

[0043]

[0046] The monomer (M) may contain a hydroxy group as a functional group (FG). The monomer (M) may be, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl crotonate, or allyl alcohol.

[0044]

[0047] The monomer (M) may contain an epoxy group as the functional group (FG). The monomer (M) may be, for example, allyl glycidyl ether, 2-methylallyl glycidyl ether, vinyl glycidyl ether, or glycidyl (meth)acrylate.

[0045]

[0048] The monomer (M) may contain an isocyanate group as a functional group (FG). The monomer (M) may be, for example, 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acryloyloxyethoxy)ethyl isocyanate, or 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate.

[0046]

[0049] The monomer (M) may contain a carboxylic acid group as a functional group (FG). The monomer (M) may be, for example, acrylic acid or methacrylic acid.

[0047]

[0050] The monomer (M) is preferably a monomer containing an anhydride group as functional group (FG). Monomer (M) is, for example, itaconic anhydride, citraconic anhydride and the monomer of the formula: It can be 5-norbornene-2,3-dicarboxylic anhydride (NAH) of TIFF2026504515000001.tif48170.

[0048]

[0051] Monomer (M) may be selected in particular from the group consisting of CTFE, R1112, itaconic anhydride, citraconic anhydride and 5-norbornene-2,3-dicarboxylic anhydride (NAH). Monomer (M) may also be selected in particular from the group consisting of CTFE, R1112, NAH and combinations of two or more of said monomers.

[0049]

[0052] The monomer (M) can be NAH.

[0050]

[0053] The monomer (M) can be CTFE.

[0051]

[0054] Monomer (M) can be R1112. It should be noted that dichlorodifluoroethylene can exist in three isomers: cis-1,2-dichloro-1,2-difluoroethylene, trans-1,2-dichloro-1,2-difluoroethylene, and 1,1-difluoro-2,2-dichloroethylene. All isomers, individually and in mixtures, are suitable for the present invention, and the abbreviation R1112 used herein is intended to encompass all individual isomers and mixtures thereof. However, the 1,2-dichloro-1,2-difluoro isomer, either alone or in mixtures, is preferred.

[0052]

[0055] Monomer (M) can also be a combination of CTFE and R1112.

[0053]

[0056] Embodiment (E1)

[0057] According to embodiment (E1) of the present disclosure, the fluoropolymer (FP) comprises repeating units (R TFE) and at least one PAVE-derived repeat unit (R F ) and a repeating unit (R M ), (M) is preferably NAH, and the proportions of those repeat units are as disclosed herein. More specifically, the fluoropolymer (FP) of this embodiment (E1) comprises repeat units derived from TFE, PPVE, and a monomer (M) containing an anhydride group, preferably NAH, and the proportions of those repeat units are as disclosed herein.

[0054]

[0058] A particular fluoropolymer (FP) according to this embodiment (E1) comprises repeating units derived from TFE, at least one PAVE and at least one monomer (M) containing an anhydride group, preferably NAH, in the following proportions: -(R TFE ): at least 95.5 mol%; -(R PAVE ): between 1.0 mol% and 3.0 mol%; -(R M ): between 0.08 mol% and 1.5 mol%, preferably between 0.08 mol% and 1.0 mol% It has.

[0055]

[0059] A particular fluoropolymer (FP) according to this embodiment (E1) comprises repeating units derived from TFE, at least one PAVE, and NAH in the following proportions: -(R TFE ): at least 95.5 mol%; -(R PAVE ): between 1.0 mol% and 3.0 mol%; -(R NAH ): between 0.08 mol% and 1.5 mol%, preferably between 0.08 mol% and 1.0 mol% It has.

[0056]

[0060] Embodiment (E2)

[0061] According to another embodiment (E2) of the present disclosure, the fluoropolymer (FP) comprises repeating units (R TFE ) and optionally at least one PAVE-derived repeat unit (R F ) and a repeating unit (R M ) and the proportion of their repeat units is as disclosed herein. A specific fluoropolymer (FP) according to this embodiment (E2) is the fluoropolymer C1, C2 or C3 disclosed in claim 1 of WO 2022 / 157099.

[0057]

[0062] A particular fluoropolymer (FP) according to this embodiment (E2) contains repeating units derived from TFE, at least one PAVE, and CTFE in the following proportions: -(R TFE ): at least 82.0 mol%; -(R PAVE ): between 1.0 mol% and 3.0 mol%; -(R CTFE ): Between 0.01 mol% and 5.0 mol% It has. The percentages may be as follows: -(R TFE ): at least 82.0 mol%; -(R PAVE ): between 1.0 mol% and 3.0 mol%; -(R CTFE ): between 0.08 mol% and 1.5 mol%.

[0058]

[0063] A particular fluoropolymer (FP) according to this embodiment (E2) comprises repeating units derived from TFE, optionally at least one PAVE, and R1112 in the following proportions: -(R TFE ): at least 75.0 mol%; -(R PAVE ): between 0 mol% and 20.0 mol%; -(R R1112 ): Between 0.01 mol% and 5.0 mol% It has.

[0059]

[0064] A particular fluoropolymer (FP) according to this embodiment (E2) comprises repeating units derived from TFE, optionally at least one PAVE, R1112 and CTFE in the following proportions: -(R TFE ): at least 75.0 mol%; -(R PAVE ): between 0 mol% and 20.0 mol%; -(R R1112 ): between 0.01 mol% and 5.0 mol%; -(R CTFE ): between 0.01 mol% and 5.0 mol%; where the repeating unit (R R1112 ) and (R CTFE ) does not exceed 5.0 mol%.

[0060]

[0065] In the context of the present disclosure, the repeating units of the fluoropolymer (FP) are preferably the repeating units (R TFE ), (R F ) and (R M The phrase "consist essentially of" in the context of repeat units means that the repeat units of the fluoropolymer (FP) consist essentially of or consist of repeat units (R TFE ), (R F ) and (R M ) and up to 1.5 mol %, preferably up to 1.0 mol %, preferably up to 0.5 mol % of (R TFE ), (R F ) and (R M ) and a repeating unit other than the repeating unit.

[0061]

[0066] Fluoropolymers (FP) are prepared by radical copolymerization of the monomer tetrafluoroethylene (TFE), one or more fluoromonomers (F) and one or more monomers (M).

[0062]

[0067] Polymerization is typically carried out in an aqueous medium, either in suspension or emulsion. Fluoropolymers (FP) can be prepared in an aqueous polymerization medium using emulsion and / or suspension polymerization techniques. Polymerization is initiated using at least a radical initiator. Surfactants, such as fluorinated and / or non-fluorinated surfactants, are typically present in the aqueous medium to stabilize the suspension or emulsion. Chain transfer agents may also be used to control the molecular weight and viscosity of the fluoropolymer (FP).

[0063]

[0068] Typically, fluoropolymers (FP) are prepared by emulsion polymerization techniques, and the resulting material is finely dispersed in an aqueous medium in the form of a latex. For further processing, the fluoropolymer (FP) is extracted from the latex using known techniques (e.g., coagulation by freezing). The extracted polymer is washed with demineralized water and dried at high temperatures (e.g., 150-160°C) to remove residual moisture.

[0064]

[0069] The fluoropolymer (FP) can be prepared according to the conditions described in the descriptions and examples of WO 2022 / 157099, U.S. Pat. No. 5,760,151, or U.S. Pat. Publication No. 2010 / 0036053 A1. The fluoropolymer (FP), particularly the fluoropolymer having NAH units, can be prepared according to WO 2016 / 017801, particularly Section

[0123] of WO 2016 / 017801.

[0065]

[0070] The melting temperature (Tm) of the fluoropolymer (FP) is preferably at least 280° C., more preferably at least 290° C. Tm is typically at most 320° C. Tm is typically measured according to ASTM D4591-22.

[0066]

[0071] The melt flow rate (MFR) of the fluoropolymer (FP), measured according to ASTM D1238 (372°C, 5 kg), is preferably at least 1.0 g / 10 min. The MFR may advantageously be at least 8.0 g / 10 min. The MFR may more particularly be between 8.0 g / 10 min and 20.0 g / 10 min.

[0067]

[0072] Regarding composition (C)

[0073] The composition (C) of the composite film (CF) comprises or consists of: - at least one fluoropolymer (FP); - optionally, at least one fluoropolymer (FP) other than fluoropolymer (FP * ); and Optionally, at least one additive selected from the group of fillers, pigments, colorants and additive materials capable of absorbing ultraviolet (UV) radiation having a wavelength between 180 nm and 400 nm.

[0068]

[0074] The composition (C) of the composite film (CF) may comprise or consist of: - at least one fluoropolymer (FP); and Optionally, at least one additive selected from the group of fillers, pigments, colorants and additive materials capable of absorbing ultraviolet (UV) radiation having a wavelength between 180 nm and 400 nm.

[0069]

[0075] The components of composition (C) are typically blended to form a homogeneous mixture, which is typically accomplished by using an extruder in which one or more of the polymer components are in a molten state.

[0070]

[0076] The composition (C) is a fluoropolymer (FP) other than fluoropolymer (FP). * Fluoropolymers (FP) may also be included. * ) is composed of between 80.0 mol% and 99.9 mol% repeating units (R TFE) and 0.1 mol % and 20.0 mol % of repeating units derived from at least one perfluoroalkyl vinyl ether (PAVE), M According to one embodiment, the copolymer may be a copolymer containing no fluoropolymer (FP). * ) repeating unit is a repeating unit (R TFE ) and at least one perfluoroalkyl vinyl ether (PAVE)-derived repeat unit, in the proportions indicated herein.

[0071]

[0077] Composition (C) may contain at least one filler, preferably selected from the group consisting of carbon nitride, boron nitride, boron carbide, boron phosphide, phosphorus nitride, boron carbonitride, carbon black, glass fibers, boron fibers, silica fibers, aramid fibers, and mixtures thereof.

[0072]

[0078] Composition (C) may include at least one additive material capable of absorbing ultraviolet (UV) radiation having a wavelength between 180 nm and 400 nm, such additive enabling the CCL to be laser drilled to form circuit structures.

[0073]

[0079] The proportion of one or more additives in composition (C) is usually at most 5.0 wt%, this proportion being based on the total weight of composition (C).

[0074]

[0080] One or more fluoropolymers (FP) in composition (C) and one or more fluoropolymers (FP * ) (if any) is at least 95.0 wt.%, more particularly at least 99.0 wt.%, said proportion being based on the total weight of composition (C).

[0075]

[0081] The proportion of one or more fluoropolymers (FP) may be between 1.0 wt% and 99.0 wt%, preferably between 10.0 wt% and 60.0 wt%, and this proportion is determined by the ratio of one or more fluoropolymers (FP) and one or more fluoropolymers (FP). * ) based on the total weight of the

[0076]

[0082] One or more fluoropolymers (FP * The proportion of one or more fluoropolymers (FP) may be between 1.0 wt% and 99.0 wt%, preferably between 10.0 wt% and 60.0 wt%, and this proportion is determined by the ratio of one or more fluoropolymers (FP) to one or more fluoropolymers (FP). * ) based on the total weight of the

[0077]

[0083] According to one embodiment, the composition comprises, as polymer component, only at least one fluoropolymer (FP) as disclosed herein. The polymer component of composition (C) consists of at least one fluoropolymer (FP).

[0078]

[0084] According to one embodiment, the composition comprises, as polymer component, only one fluoropolymer (FP) disclosed herein. The polymer component of composition (C) consists of only one fluoropolymer (FP).

[0079]

[0085] About Fiber Fabrics (FF)

[0086] The fiber fabric (FF) is a woven fabric selected from the group of glass fiber fabrics or quartz fiber fabrics, which is produced by interlacing warp fibers (f1) and weft fibers (f2) in a regular weave pattern, where f1 and f2 are both made of either glass or quartz, and are at an angle of 90°±2°, preferably 90°±1°, relative to each other.

[0080]

[0087] Fiber fabrics (FF) are typically prepared on looms where fibers are processed into finished fiber fabrics (or cloth).

[0081]

[0088] The fiber fabric (FF) may more particularly follow any one of the following weave patterns: plain weave, satin weave such as 4-harness satin, 5-harness satin and 8-harness satin, or twill weave, in particular 2x2 twill weave. The fiber fabric (FF) is generally a plain weave.

[0082]

[0089] The fibrous fabric (FF) may for example exhibit an average thickness of about 200 μm or less, such as 180 μm or less or 160 μm or less.

[0083]

[0090] The fibers in the fibrous fabric (FF) may exhibit an average diameter of about 25 μm or less, such as about 23 μm or less or 21 μm or less.

[0084]

[0091] In some embodiments, the fiber fabric (FF) has a fiber density of 10 g / m 2 and 100g / m 2 Between, for example, 12 g / m 2 and 90g / m 2 Between 15g / m 2 and 80g / m 2 The average area weight (grams per square meter or g / m 2 The average area weight is preferably 15.0 g / m 2 and 40.0 g / m 2 It is between.

[0085]

[0092] The fibrous fabrics (FF) are such that they have a thickness between 0.01 mm and 0.09 mm, and even between 0.02 mm and 0.07 mm.

[0086]

[0093] The fiber fabric (FF) is preferably characterized by a low dielectric constant and a low dielectric loss tangent. The fiber fabric (FF) has a dielectric constant D at 1 GHz measured using the transmission line method and a vector network analyzer. k is less than 5.5, and / or the dielectric loss tangent D at 1 GHz measured using the transmission line method and a vector network analyzer f is less than 0.0030.

[0087]

[0094] The fiber fabric (FF) preferably has a dielectric constant D at 1 GHz measured using the transmission line method and a vector network analyzer. k is less than 5.0. Dielectric constant D at 1 GHz k is generally 3.0 or higher.

[0088]

[0095] The fiber fabric (FF) preferably has a dielectric loss tangent D at 1 GHz measured using the transmission line method and a vector network analyzer. f is less than 0.0025, or even less than 0.0020. f is generally greater than or equal to 0.0001.

[0089]

[0096] Quartz fiber fabrics having the properties detailed above are available from Saint-Gobain under the trade name Quartzel® Veil. An example of a suitable quartz fiber fabric from this brand is made from non-porous ultra-pure silica fibers with an SiO2 content of 99.95% or more, with a fiber diameter of 9-14 μm, a fiber length of >5 mm, and an average product area weight (grams per square meter, g / m 2 ) is 25.

[0090]

[0097] Glass fiber fabrics having the properties detailed above are available from CTG Taishan Fiberglass as well as Nittobo. An example of a suitable glass fiber fabric that can be used to prepare the composite film is LD1035-127, available from CTG Taishan Fiberglass.

[0091]

[0098] The glass fiber fabric (FF) may be made from fibers containing at least 33.0 to 48.0 parts by mass of silicon oxide, 1.0 to 5.0 parts by mass of alumina, 5.0 to 10.0 parts by mass of titanium oxide, 0.5 to 4.0 parts by mass of zirconium oxide, and at least one of the following oxides: holmium oxide, alkaline earth metal oxide, neodymium oxide, and iron oxide.

[0092]

[0099] In a specific embodiment, the woven glass fiber fabric (FF) is made of fibers having the following composition: 35.0 to 48.0 parts by weight of silicon oxide, 1.0 to 5.0 parts by weight of alumina, 5.5 to 10.0 parts by weight of titanium oxide, 0.5 to 4.0 parts by weight of zirconium oxide, 3.0 parts by weight or less of holmium oxide, and 32.0 to 47.5 parts by weight of alkaline earth metal oxide, based on the total weight of the fibers. Alternatively, the woven glass fiber fabric is made of fibers having the following composition: 33.0 to 46.0 parts by weight of silicon oxide, 1.5 to 5.0 parts by weight of alumina, 5.0 to 10.0 parts by weight of titanium oxide, 0.5 to 4.0 parts by weight of zirconium oxide, 2.5 parts by weight or less of neodymium oxide, 1.2 parts by weight or less of iron oxide, and 31.0 to 53.0 parts by weight of alkaline earth metal oxide, based on the total weight of the fibers.

[0093]

[0100] In a particular embodiment, the glass fiber fabric (FF) is made of fibers having the following composition: 45.0-70.0 wt% SiO2, 0-20.0 wt% Al2O3, 10.0-35.0 wt% B2O3, 88.0-98.0 wt% SiO2+Al2O3+B2O3, 0-0.7 wt% Li2O+Na2O+K2O, 0.1-12.0 wt%, 0-3.0 wt% TiO2, and a CaO / MgO mass ratio of 1.0 or less.

[0094]

[0101] About Composite Film (CF)

[0102] The composite film has a thickness (T) of less than 0.20 mm (≦0.20 mm), preferably less than 0.15 mm (≦0.15 mm), preferably less than 0.10 mm (≦0.10 mm). T is generally at least 0.01 mm (≧0.01 mm), or at least 0.02 mm (≧0.02 mm), or at least 0.03 mm (≧0.03 mm).

[0095]

[0103] T may be comprised between 0.005 mm and 0.20 mm, or between 0.005 mm and 0.10 mm, preferably between 0.010 mm and 0.09 mm. The thickness may preferably be between 0.02 mm and 0.08 mm, or between 0.03 mm and 0.07 mm.

[0096]

[0104] The composite film (CF) of the present invention typically does not include a conductive layer (eg, a copper layer or copper foil).

[0097]

[0105] The composite film (CF) of the present invention is typically in the form of a square or rectangle. The width w of the composite film (CF) of the present invention is typically at least 250 mm. w is generally between 250 mm and 1500 mm.

[0098]

[0106] The composite film (CF) exhibits high flexibility and can be in the form of a roll film.

[0099]

[0107] The composite film (CF) of the present invention is flexible and exhibits good folding resistance. The MIT folding endurance test according to ASTM D2176-16 can be used to test the resistance of a plastic film to repeated folding. This test provides the number of cycles until the tested film breaks.

[0100]

[0108] The composite film (CF) of the present invention typically exhibits a folding endurance of at least 40,000 cycles, preferably at least 50,000 cycles, and preferably at least 80,000 cycles. The folding endurance is measured in accordance with ASTM D2176-16 under a 0.9072 kg load, a 135° angle, and a temperature of 23±2°C at 90 cycles / min.

[0101]

[0109] The composite film (CF) of the present invention preferably exhibits a coefficient of thermal expansion (CTE) of 80 ppm / °C (1 ppm = μm / (m·°C)) or less, especially in the MD or TD, and the conditions for measuring the CTE are described in the Examples section.

[0102]

[0110] According to the present invention, the composite film (CF) preferably comprises less than 75.0 wt.% of woven fiber fabric (FF) per unit area of ​​the composite film (CF), preferably between 5.0 wt.% and 70.0 wt.%, or between 10.0 wt.% and 60.0 wt.% of woven fiber fabric (FF).

[0103]

[0111] According to the present invention, the composite film (CF) preferably has a volume (V f ) is between 20.0 vol.% and 60.0 vol.%, for example between 25.0 vol.% and 55.0 vol.%, or between 30.0 vol.% and 50.0 vol.%, where Vf is calculated according to the following formula: TIFF2026504515000002.tif11170

[0104]

[0112] Embodiment (E3)

[0113] According to a preferred embodiment (E3), the warp threads (f1) or weft threads (f2) of the fibrous fabric (FF) are oriented at an angle α relative to the longitudinal axis of the composite film (CF), α being between 20° and 80°, preferably between 30° and 70°, preferably between 40° and 60°, preferably between 42° and 58° or between 44° and 46°.

[0105]

[0114] As mentioned above, f1 and f2 are oriented at substantially 90° to each other (in other words, the angle between f1 and f2 is), which means that these fibers f2 are oriented at an angle substantially equal to (90°-α) with respect to the longitudinal axis of the composite film (CF).

[0106]

[0115] Embodiment (E3) makes it possible to have an improved folding resistance, both for the composite film (CF) alone and for the CCL obtained from said composite film.

[0107]

[0116] All details and embodiments relating to composition (C), fluoropolymer (FP) and composite film (CF) disclosed herein are applicable to embodiment (E3).

[0108]

[0117] Dielectric properties of composite film (CF)

[0118] The composite film (CF) of the present invention preferably exhibits several advantageous dielectric properties. In some embodiments, the composite film (CF) exhibits at least one of the following dielectric constants Dk at 5 GHz, as measured by a split post dielectric resonator (SPDR), IEC 61189-2-721:2015: TIFF2026504515000003.tif55170

[0109]

[0119] In some embodiments, the composite film (CF) exhibits at least one of the following dielectric loss tangents Df at 5 GHz, measured by split post dielectric resonator (SPDR), IEC 61189-2-721:2015: TIFF2026504515000004.tif55170

[0110]

[0120] In some embodiments, the composite film (CF) exhibits at least one of the following dielectric constants Dk at 20 GHz, measured by a split cylinder resonator, IPC TM-650 2.5.5.13: TIFF2026504515000005.tif55170

[0111]

[0121] In some embodiments, the composite film (CF) exhibits at least one of the following dielectric loss tangents Df at 20 GHz, measured by a split cylinder resonator, IPC TM-650 2.5.5.13: TIFF2026504515000006.tif55170

[0112]

[0122] In some embodiments, the composite film (CF) has the following combination of dielectric properties: - Dk 5GHz less than 2.6; and / or - Df 5GHz less than 0.0015; and / or - Dk 20GHz less than 2.6; and / or - Df 20 GHz less than 0.0030; and / or - Dk 50GHz less than 3.0, or even less than 2.8; and / or - Df 50 GHz less than 0.0040, or even less than 0.0025; and / or - Dk 77GHz less than 3.0, or even less than 2.8; and / or - Df 77GHz less than 0.0040, even less than 0.0025; where Dk is measured with a split cylinder resonator per IPC TM-650 2.5.5.13 after drying at 100°C for 1 hour and Df is measured with a split post dielectric resonator (SPDR) per IEC 61189-2-721:2015 after drying at 100°C for 1 hour.

[0113]

[0123] Method for preparing composite films (CF)

[0124] The composite film (CF) of the present invention is prepared by a method comprising: a) contacting a composition (C) comprising a fluoropolymer (FP) on one or more surfaces of a fibrous fabric (FF); and b) applying pressure and heat to the composite structure obtained after step a).

[0114]

[0125] More specifically, the composite film (CF) of the present invention can be produced by the steps of: a) contacting a composition (C) containing a fluoropolymer (FP) on a woven fiber fabric (FF); b) applying a pressure P of at least 0.3 MPa and heating the composition (C) to a temperature T so that the composition (C) is in a molten form. process and heating at 400.degree.

[0115]

[0126] The molten form and pressure make it possible to achieve intimate contact and adhesion of composition (C) with the fiber fabric.

[0116]

[0127] Composition (C) may be in the form of a powder. The powder usually has a Dv between 0.1 μm and 100 μm, preferably between 1 μm and 90 μm, or between 5 μm and 80 μm. 50(Median) is shown. Dv of powder 50 can be measured by laser scattering in isopropanol (volume distribution).

[0117]

[0128] Composition (C) may also be in the form of a film prepared from composition (C). This method more particularly comprises the following steps: a) applying a polymer film of composition (C) to at least one surface of a fiber fabric (FF); b) a pressure P and / or temperature T of at least 0.3 MPa process In this process, the polymer film is bonded to the fiber fabric (FF).

[0118]

[0129] temperature T process is the temperature at which composition (C) is in the molten form. When composition (C) contains only (FP) as the fluoropolymer, T process It is sufficient that the composition has a melting temperature of at least one additional fluoropolymer (FP). * ), (FP * ) must also be considered. In this case, T process is preferably above the highest melting temperature of the fluoropolymers present in composition (C).

[0119]

[0130] Preferably, step b) is carried out at a pressure of at least 0.4 MPa, at least 0.5 MPa. process is such that T≧Tm+5°C.

[0120]

[0131] T process Generally, T is such that 300°C≦T≦400°C. process can be between 300°C and 350°C.

[0121]

[0132] The duration of step b) depends on the composition and the temperature and pressure applied. The duration is generally between 1 and 60 minutes. The duration can be between 1 and 30 minutes, or between 1 and 15 minutes.

[0122]

[0133] The amount of pressure and temperature applied depends on the operability, physical and dimensional properties of the press, as well as the type of fluoropolymer (FP) used and the fiber fabric used and its respective physical and dimensional properties.

[0123]

[0134] The composite film (CF) of the present invention may be prepared using the composite film preparation methods and conditions shown in the Examples section.

[0124]

[0135] Composite Film (CF) End Uses

[0136] The present invention also relates to the use of a composite film (CF) as disclosed herein for the preparation of a copper clad laminate (CCL). The present invention also relates to the use of a composition or a fluoropolymer (FP) for the preparation of a copper clad laminate.

[0125]

[0137] The present invention also relates to a copper clad laminate (CCL) comprising at least one copper foil and the composite film (CF) of the present invention.

[0126]

[0138] According to one embodiment, the CCL comprises one copper foil. According to this embodiment, the CCL has the following configuration: copper foil / composite film (CF).

[0127]

[0139] According to another embodiment, the CCL comprises two copper foils. According to this embodiment, the CCL is of the following type: copper foil / composite film (CF) / copper foil. In the composite film (CF) of configuration (ii), the CCL is of the following type, in this order: copper foil / composition (C) / fiber fabric (FF) / composition (C) / copper foil.

[0128]

[0140] According to one embodiment, the copper foil is in direct contact with the composite film (CF).

[0129]

[0141] According to another embodiment, there is an adhesive layer between one or more copper foils and the composite film (CF), the function of which is to improve the adhesion between the copper foil and the composite film (CF).

[0130]

[0142] The CCL can be obtained by i) contacting one or more copper foils with the composite film (CF) of the present invention, or ii) laminating the composite film (CF) onto one or more copper foils, the one or more copper foils being optionally coated with an adhesive layer. Typical conditions consist of contacting the surfaces and applying a pressure of at least 0.3 MPa and a temperature T>Tm of the fluoropolymer (FP). T is usually at least 300°C.

[0131]

[0143] The composition comprises at least one additional fluoropolymer (FP * ) contains FP * In this case, T is preferably greater than the melting temperature of the highest fluoropolymer present in the composition.

[0132]

[0144] The pressure and heat are applied for a duration sufficient to ensure that the composite film (CF) is bonded sufficiently strongly. The duration can be between 1 and 30 minutes. The duration is preferably at least 5 minutes.

[0133]

[0145] For the preparation of the CCL of the present invention, the conditions (pressure, temperature and contact duration) given in the Examples section can be applied.

[0134]

[0146] The surface of the copper foil to which the composite film is applied may be pretreated to enhance the adhesion of the composite film or adhesive layer, the pretreatment being selected from the group consisting of flame treatment, mechanical abrasion, and chemical treatment. Examples of chemical pretreatment of copper foil can be found in U.S. Patent Publication No. 2023 / 0019067.

[0135]

[0147] The CCL preferably exhibits a peel strength of at least 7.0 N / cm, preferably at least 10.0 N / cm, when measured according to standardized test IPC-TM-650, number 2.4.9, which was developed to measure the peel strength of metal clad laminates.

[0136]

[0148] Other uses: The present invention also relates to the use of at least one composite film for preparing mobile electronic device articles or components, such as flexible printed circuit boards (FPCs). The composite films of the present invention can be particularly used to prepare flexible printed circuit boards (FPCs), carrier tapes for tape automated bonding (TAB), and tapes for lead-on-chip (LOC) structures. [Example]

[0137]

[0149] The present disclosure will now be described in more detail with reference to the following examples, the purpose of which is merely illustrative and is not intended to limit the scope of the present disclosure.

[0138]

[0150] Starting materials

[0151] Fluoropolymer (FP-1): Copolymer TFE (97.9 mol%) / PPVE (2.0 mol%) / NAH (0.1 mol%). Tm = 300°C; MFR = 17.6 g / 10 min (ASTM D1238 (372°C; 5 kg)).

[0139]

[0152] Fluoropolymer (FP-2): Copolymer TFE (96.0 mol%) / PPVE (3.9 mol%) / CTFE 0.1 mol%. Tm = 312°C; MFR = 15.0 g / 10 min (ASTM D1238 (372°C; 5 kg)).

[0140]

[0153] Glass Fabric (FF-1): Glass fiber fabric LD1035-127, commercially available from CTG Taishan Fiberglass; dielectric constant Dk 4.3-4.5 at 1 GHz and dissipation factor Df 0.0016 at 1 GHz. Both Dk and Df are measured using the transmission line method and a vector network analyzer. LD1035-127 has an average area of ​​26.2 gsm. Other characteristics: warp 65 / 25 mm, weft 68 / 25 mm.

[0141]

[0154] Quartz Fabric (FF-2): Quartz fiber fabric, Quartz® Veil, commercially available from Saint-Gobain, average area weight (grams per square meter gsm or g / m 2 )twenty five.

[0142]

[0155] Glass Fabric (FF-3): Glass fiber fabric NTB 1027 (plain weave), commercially available from Nittobo. NTB 1027 exhibits an average area of ​​18.0 gsm. Other characteristics include thickness: 0.020 mm; warp 74.3 / 25 mm, weft 75.7 / 25 mm. The glass fiber is made of glass with a lower alkaline earth metal (CaO, MgO, etc.) content and a higher boric acid (B2O3) content than the general-purpose E-glass typically used in composites. This specific composition ensures that the fiber exhibits a low dielectric constant and low dielectric loss tangent.

[0143]

[0156] Glass Fabric (FF-4): Glass fiber fabric NTB 1017 (plain weave), commercially available from Nittobo. Same composition as FF-3. Other characteristics: Thickness: 0.015 mm. Average area: 13.0 gsm. Warp: 95 / 25 mm, weft: 95 / 25 mm.

[0144]

[0157] All four types of glass fiber fabrics tested are woven fabrics.

[0145]

[0158] Preparation method of composite film (CF): Composite films (CF) were prepared using fluoropolymer films (FP-1 or FP-2) with the following structure: polymer (FP) / (fiber fabric) / polymer (FP).

[0146]

[0159] The resulting combination of components was then pressed into a thin composite film using a double-belt press set at a temperature of 320-330°C and a pressure of 1-3 MPa. The film was heated for approximately 10 minutes. The polymer melted and impregnated the fibers. The composition and properties of the composite film are reported in the Results section below.

[0147]

[0160] Preparation method of copper-clad laminate (CCL): A copper-clad laminate having the following composition: copper / composite film (CF) / copper was obtained by laminating the composite film between two sheets of T49A-DS-HD2-12 copper foil (manufactured by Fukuda) in a Lauffer laminator at 340 °C for 20 minutes under a pressure of 3 MPa.

[0148]

[0161] Test Method

[0162] Dielectric performance (Dk, Df)

[0163] The dielectric constant Dk and dissipation factor Df were measured at 5 GHz by a split post dielectric resonator (SPDR) according to IEC 61189-2-721:2015 after drying at 100 °C for 1 hour and after immersion in water for 24 hours.

[0149]

[0164] The dielectric constant Dk and dissipation factor Df were measured at 20 GHz with a split cylinder resonator according to IPC TM-650 2.5.5.13 after drying at 100°C for 1 hour and after immersion in water for 24 hours.

[0150]

[0165] MIT flex resistance test (A)

[0166] The MIT flex test was performed in accordance with ASTM D2176-16 using an MIT flex tester under conditions of 0.9072 kg load, 135° angle, and 23 ± 2°C temperature at 90 cycles / min. Details of the tester are described in ASTM D2176-16 (reapproved in 2021).

[0151]

[0167] A Tinius Olsen tester (see https: / / www.tiniusolsen.com / product / mit-folding-endurance-tester / ) can be used.

[0152]

[0168] MIT flex resistance test (B)

[0169] To evaluate the flexibility of the composite film (CF) and CCL, the MIT bending resistance test was performed according to IPC TM-650 2.4.3. Test conditions were: bending radius 0.6 mm, bending frequency 40 cycles / min, bending angle 0-180°.

[0153]

[0170] Tensile strength

[0171] Tensile tests were measured using an Instron® mechanical testing machine according to ASTM D882.

[0154]

[0172] Coefficient of Thermal Expansion (CTE)

[0173] CTE was measured in tensile mode according to ASTM D696-16. During the test, the first heat is from 23°C to 250°C at 5°C / min, the first cool is from 250°C to 23°C at 5°C / min, and the second heat is from 23°C to 210°C at 5°C / min. CTE is measured from the dimensional change during the second heat.

[0155]

[0174] Fiber volume

[0175] The volume of the fiber (Vf) is calculated according to the following formula: TIFF2026504515000007.tif11170

[0156]

[0176] Peeling force

[0177] The copper foil peel force was measured according to IPC-TM-650.2.4.9.

[0157]

[0178] result Table I TIFF2026504515000008.tif153170 *The peel force for the adhesion between the copper foil and the composite film was measured. Table II TIFF2026504515000009.tif139170Table III TIFF2026504515000010.tif144170Table IV TIFF2026504515000011.tif139170Table V TIFF2026504515000012.tif99170 Table VI TIFF2026504515000013.tif99170Table VII TIFF2026504515000014.tif144170 Table VIII TIFF2026504515000015.tif153170

[0158]

[0179] Composite films #1 to #5 have much higher adhesive strength to copper foil than comparative LCP film #8. Composite films #1 to #5 have higher folding endurance than comparative LCP film #8, which strongly indicates their high flexibility.

[0159]

[0180] The composite films CF of #1 to #7 have very good dielectric properties under all conditions.

[0160]

[0181] Table IX also illustrates the present invention with other composite films (CF). The composite films (CF) of the present invention (see CF#9 and CF#10) exhibit a CTE of less than 80 ppm in MD or TD (1 ppm / °C = μm / (m.°C)).

[0161]

[0182] In all examples of composite films #1 to #10, the angle α is 0°. Table IX TIFF2026504515000016.tif73170MD means machine direction and TD means cross direction.

[0162]

[0183] In Table X, the influence of the angle α (see embodiment (E3)) on the flexibility of the composite film (CF) alone or of the CCL can be seen: - In the case of CF: the number of cycles to failure increased from 720 (α = 0°) to 11525 (α = 45°), showing a dramatic increase in the test. -For CCL: The same effect can be seen whether the CCL is single-sided or double-sided.

[0163]

[0184] These results show that the bendability of the CF is improved when α is between 20° and 80°, preferably between 30° and 70°, preferably between 40° and 60°, preferably between 42° and 58°, or between 44° and 46°. Table X TIFF2026504515000017.tif90170°°:Configuration (ii) [Composition (C) layer] / Fiber fabric (FF) / [Composition (C) layer] One side = [Cu layer] / [composition (C) layer] / fiber fabric (FF) / [composition (C) layer] Both sides = [Cu layer] / [composition (C) layer] / fiber fabric (FF) / [composition (C) layer] / [Cu layer] Composition (C) = 100% of FP-1

Claims

1. A composite film (CF) having a thickness (T) of less than 0.20 mm, preferably less than 0.15 mm, more preferably less than 0.10 mm, - a woven fiber fabric (FF) selected from the group of woven glass fiber fabrics or woven quartz fiber fabrics, a composition (C) comprising at least one fluoropolymer (FP) coated on the surface of a woven fiber fabric (FF), wherein the woven fiber fabric (FF) is a woven fabric and the fluoropolymer (FP) is - Tetrafluoroethylene-derived repeating units (R ＴＦＥ )and, - a repeating unit (R ) derived from a fluoromonomer (F) selected from the group consisting of perfluoro(alkyl vinyl ether) (PAVE), hexafluoropropylene (HFP) and a combination of two or more of the above monomers; Ｆ )and, - repeating units (R) derived from at least one monomer (M) selected from the group consisting of (i) a monomer containing a functional group (FG) selected from the group consisting of a hydroxy group, an isocyanate group, a carboxylic acid group, and an anhydride group, (ii) chlorotrifluoroethylene (CTFE), and (iii) dichlorodifluoroethylene (R1112), preferably 1,2-dichloro-1,2-difluoro isomer (cis, trans, or a mixture of cis and trans). Ｍ )and, and the following proportions, expressed in mole percent: - (R ＴＦＥ ): at least 75.0 mol%; - (R Ｆ ): between 0 mol% and 20.0 mol%; - (R Ｍ ): between 0.01 mol% and 5.0 mol%; and these mole percent percentages are based on the total moles of repeat units of the fluoropolymer (FP).

2. A composite film (CF) having a thickness (T) of less than 0.20 mm, preferably less than 0.15 mm, preferably less than 0.10 mm, a layer (L1) of composition (C), - woven fibre fabrics (FF) selected from the group of woven glass fibre fabrics or woven quartz fibre fabrics, a layer (L2) of composition (C), in this order, The composition (C) comprises at least one fluoropolymer (FP) in contact with at least one surface of the fibrous fabric (FF), The fiber fabric (FF) is a fabric, and the fluoropolymer (FP) is - Tetrafluoroethylene-derived repeating units (R ＴＦＥ ), - a repeating unit (R ) derived from a fluoromonomer (F) selected from the group consisting of perfluoro(alkyl vinyl ether) (PAVE), hexafluoropropylene (HFP) and a combination of two or more of the above monomers; Ｆ ), - (i) a monomer containing a functional group (FG) selected from the group consisting of a hydroxy group, an isocyanate group, a carboxylic acid group, and an anhydride group, (ii) a repeating unit (R) derived from at least one monomer (M) selected from the group consisting of chlorotrifluoroethylene (CTFE), and (iii) dichlorodifluoroethylene (R1112). Ｍ ), and the following proportions, expressed in mole percent: - (R ＴＦＥ ): at least 75.0 mol%; - (R Ｆ ): between 0 mol% and 20.0 mol%; - (R Ｍ ): between 0.01 mol% and 5.0 mol%; and these mole percentages are based on the total amount of moles of repeating units of the fluoropolymer (FP).

3. The repeating unit (R Ｆ 3. The composite film (CF) according to claim 1 or claim 2, wherein the proportion of CF is between 0.1 mol% and 10.0 mol%, or between 0.5 mol% and 5.0 mol%, or between 1.0 mol% and 5.0 mol%, or between 1.0 mol% and 3.0 mol%.

4. The repeating unit (R Ｍ ) is between 0.05 mol% and 5.0 mol%, or between 0.05 mol% and 3.0 mol%; and / or at most 1.5 mol% or at most 1.0 mol% A composite film (CF) according to any one of claims 1 to 3, wherein

5. The repeating unit (R ＴＦＥ ) is the ratio of the repeating unit (R Ｆ ) and (R Ｍ 5. A composite film (CF) according to any one of claims 1 to 4, wherein the proportion of the remaining

6. The repeating unit (R ＴＦＥ 6. A composite film (CF) according to any one of claims 1 to 5, wherein the proportion of 2-methyl-2-propanol is at least 75.0 mol%, preferably at least 85.0 mol%, more preferably at least 94.0 mol%.

7. The repeating unit of the fluoropolymer (FP) is the repeating unit (R ＴＦＥ ), (R Ｆ ) and (R Ｍ The term "consisting essentially of" means that the repeating units of the fluoropolymer (FP) are not limited to the repeating units (R ＴＦＥ ), (R Ｆ ), (R Ｍ ) and up to 1.5 mol %, preferably up to 1.0 mol %, preferably up to 0.5 mol % of (R ＴＦＥ ), (R Ｆ ) and (R Ｍ The composite film (CF) according to any one of claims 1 to 6, which means that it consists of a repeating unit other than ).

8. The fluoromonomer (F) is of the general formula CF ２ =CFOR ｆ (I) is selected from the group of perfluoro(alkyl vinyl ether)s (PAVEs) of the formula: ｆ But C １ -C ８ perfluoroalkyl groups, preferably C １ -C ３ A perfluoroalkyl group, preferably CF ２ = CFOCF ３ , C.F. ２ = CFOCF ２ CF ３ , C.F. ２ = CFOCF ２ CF ２ CF ３ 8. A composite film (CF) according to claim 1, wherein the monomer is selected from the group consisting of: and a combination of two or more of said monomers.

9. The composite film (CF) according to any one of claims 1 to 8, wherein the monomer (M) is selected from the group consisting of CTFE, R1112, itaconic anhydride, citraconic anhydride and 5-norbornene-2,3-dicarboxylic anhydride (NAH).

10. The fluoropolymer (FP) is a copolymer comprising repeating units derived from TFE, at least one perfluoro(alkyl vinyl ether) (PAVE), and at least one monomer (M) containing an anhydride group, (M) being preferably NAH, in the following proportions: - (R ＴＦＥ ): at least 95.5 mol %; - (R ＰＡＶＥ ): between 1.0 mol% and 3.0 mol%; - (R Ｍ ): between 0.08 mol% and 1.5 mol%, preferably between 0.08 mol% and 1.0 mol% A composite film (CF) according to any one of claims 1 to 9, having

11. 11. Composite film (CF) according to any one of claims 1 to 10, wherein the fluoropolymer (FP) has a melting temperature (Tm) of at least 280°C, more preferably at least 290°C.

12. 12. The composite film (CF) according to any one of claims 1 to 11, wherein the melt flow rate (MFR) of the fluoropolymer (FP) measured in accordance with ASTM D1238 (372 ° C, 5 kg) is at least 1.0 g / 10 min, preferably between 8.0 g / 10 min and 20.0 g / 10 min.

13. The composition (C) comprises at least one fluoropolymer (FP) and, optionally, at least one fluoropolymer other than the fluoropolymer (FP) (FP ＊ 13. A composite film (CF) according to any one of claims 1 to 12, comprising or consisting of: a polymerizable compound (polymerizable copolymer) of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 39, 38, 39, 40, 39, 41, 42, 43, 44, 45, 46, 47, 48, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122,

14. Fluoropolymer (FP ＊ ) is between 80.0 mol % and 99.9 mol % of the repeating unit (R ＴＦＥ ) and 0.1 mol % and 20.0 mol % of repeating units derived from at least one perfluoroalkyl vinyl ether (PAVE), and Ｍ 14. The composite film (CF) according to claim 13, which is a copolymer free of .

15. One or more fluoropolymers (FP) in composition (C) and one or more fluoropolymers (FP ＊ 15. Composite film (CF) according to claim 13 or 14, wherein the proportion of (if any) of composition (C) is at least 95.0 wt.%, more particularly at least 99.0 wt.%, based on the weight of composition (C).

16. 16. A composite film (CF) according to any one of claims 1 to 15, wherein the composition (C) comprises at least one fluoropolymer (FP) as the only polymer component.

17. Fiber fabric (FF) is 10 g / m ２ and 100 g / m ２ Between 12 g / m and 12 g / m ２ and 90 g / m ２ Between 15 g / m ２ and 80 g / m ２ between 15.0 g / m and 15.0 g / m ２ and 40.0 g / m ２ Average area weight (grams / square meter or g / m ２ 17. A composite film (CF) according to any one of claims 1 to 16, having a

18. Split Post Dielectric Resonator (SPDR), at least one of the following dielectric constants Dk at 5 GHz as measured by IEC 61189-2-721:2015:

18. A composite film (CF) according to any one of claims 1 to 17, which has

19. Split Post Dielectric Resonator (SPDR), at least one of the following dissipation factors Df at 5 GHz as measured by IEC 61189-2-721:2015:

19. A composite film (CF) according to any one of claims 1 to 18, which exhibits:

20. Split cylinder resonator, at least one of the following dielectric constants Dk at 20 GHz as measured by IPC TM-650 2.5.5.13:

20. A composite film (CF) according to any one of claims 1 to 19, which has

21. Split cylinder resonator, at least one of the following dissipation factors Df at 20 GHz as measured by IPC TM-650 2.5.5.13:

21. A composite film (CF) according to any one of claims 1 to 20, which has

22. 22. A composite film according to any one of claims 1 to 21, wherein the fibre fabric (FF) is according to one of the following weave patterns: plain weave, satin weave such as 4-harness satin, 5-harness satin and 8-harness satin, or twill weave, in particular 2x2 twill weave.

23. 23. The composite film (CF) according to any one of claims 1 to 22, which exhibits a folding endurance of 40,000 cycles or more, preferably 50,000 cycles or more, preferably 80,000 cycles or more, when measured in accordance with ASTM D2176-16 under a load of 0.9072 kg, an angle of 135 degrees, and a temperature of 23±2°C, at 90 cycles / minute.

24. 24. A composite film according to any one of claims 1 to 23, exhibiting a coefficient of thermal expansion (CTE) of less than or equal to 80 ppm / °C (1 ppm = μm / (m °C)), particularly in MD or TD, the conditions for measuring the CTE being as set out in the Examples section.

25. 25. A composite film according to any one of claims 1 to 24, wherein the warp threads (f1) or weft threads (f2) of the fibrous fabric (FF) are oriented at an angle α relative to the longitudinal axis of the composite film (CF), α being between 20° and 80°, preferably between 30° and 70°, preferably between 40° and 60°, preferably between 42° and 58°, or between 44° and 46°.

26. 26. A composite film (CF) according to any one of claims 1 to 25, having the following structure: (i) (composition (C)) / fiber fabric (FF)) or (ii) (composition (C)) / fiber fabric (FF)) / (composition (C)).

27. 27. A composite film (CF) according to any one of claims 1 to 26, which does not comprise a conductive layer.

28. 28. A composite film (CF) according to any one of claims 1 to 27, comprising only one woven fibre fabric (FF).

29. 29. A composite film (CF) according to any one of claims 1 to 28, prepared by a process comprising: a) contacting the composition (C) on one or more surfaces of a fibrous fabric (FF); and b) applying pressure and heat to the composite structure obtained after step a).

30. a) contacting a composition (C) containing a fluoropolymer (FP) on a woven fiber fabric (FF); b) applying a pressure P of at least 0.3 MPa and raising the temperature T so that the composition (C) is in a molten form; ｐｒｏｃｅｓｓ 30. A composite film (CF) according to any one of claims 1 to 29, prepared by a process comprising the steps of:

31. 31. Use of a composite film (CF) according to any one of claims 1 to 30 for the preparation of a copper clad laminate (CCL).

32. A copper clad laminate (CCL) comprising at least one copper foil and the composite film (CF) according to any one of claims 1 to 30.

33. 33. The copper clad laminate (CCL) of claim 32 having the following configuration (in this order): copper foil / composite film (CF), or the following configuration: copper foil / composite film (CF) / copper foil.

34. 34. The copper clad laminate (CCL) according to claim 32 or 33, wherein one or more copper foils are in direct contact with the composite film (CF).

35. 34. The copper clad laminate (CCL) according to claim 32 or 33, wherein an adhesive layer is present between the one or more copper foils and the composite film (CF).

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