Laminates based on copolymers of diisoalkenylarenes

Abstract

To provide copper clad laminates (CCL) with improved performance for enhanced electrical and mechanical properties.SOLUTION: The disclosure relates to a multi-layered laminate comprising multiple metal foil layers and multiple dielectric (insulating) layers. At least one of the insulating layers includes a copolymer containing diisoalkenylarene (DIAEA) and divinylarene (DVA) units, optionally combined with a filler and / or another dielectric polymer. Another insulating layer includes another dielectric polymer distinct from the DIAEA-DVA copolymer. At least one copolymer-containing insulating layer is positioned adjacent to a metal foil layer. This copolymer layer enhances thermal stability at elevated temperatures and provides improved electrical performance such as reduced dielectric constant (Dk) and dissipation factor (Df) along with excellent processability.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to multi-layered laminates containing copolymer layers of diisoalkenyl arene copolymers for use in copper clad laminate applications. [Background technology]

[0002] Circuit boards play a vital role in the manufacturing of compact electronic devices. To meet current and future technological demands, there is an increasing need for high-frequency and heat-resistant circuit boards. These high-performance circuit boards consist of multiple layers, each with specific requirements such as low dielectric constant (Dk), minimum dissipation factor (Df), low coefficient of thermal expansion (CTE), strong adhesion to various substrates, and low water absorption.

[0003] To enhance the performance of a circuit board, one or more layers must be placed adjacent to a metal foil. The incorporation of crosslinkable copolymers offers several advantages, including high heat resistance and desirable properties such as low dielectric constant (Dk) and minimum dissipation factor (Df). These copolymers can be modified with reactive functional groups, such as vinyl or epoxy, to promote increased crosslink density during curing. Crosslinkable copolymers are typically incorporated into one or more insulating layers. Summary of the Invention [Problem to be solved by the invention]

[0004] There remains a need for copper clad laminates (CCLs) with improved performance in terms of enhanced electrical and mechanical properties. [Means for solving the problem]

[0005] (Summary of the Invention) In one embodiment, the present disclosure relates to a laminate comprising, consisting essentially of, or consisting of a first metal foil, a first insulating layer, and a second insulating layer. The first insulating layer, having a thickness of 3-20 μm and a Dk of less than 2.8 and a Df of less than 0.002, is disposed between the first metal foil and the second insulating layer and comprises 40-70 wt. % of a copolymer of diisoalkenyl arene and divinylarene, the copolymer having a molar ratio of diisoalkenyl arene to divinylarene ranging from 15:1 to 1:15. The first insulating layer may further comprise 30-60 wt. % of a filler and 0-20 wt. % of another dielectric polymer. The second insulating layer, having a thickness of 60-120 μm greater than the thickness of the first insulating layer, a Dk of less than 5.0, and a Df of less than 0.05, contains 30-60 wt. % glass fiber, 0-30 wt. % filler, and 20-50 wt. % another dielectric polymer. The amounts of glass fiber, filler, and another dielectric polymer are independently selected within the specified ranges to add up to 100 wt. %. The laminate has a Dk of less than 5 and a Df of less than 0.01, measured at 10 GHz according to ASTM D2520.

[0006] In a second embodiment, the laminate further includes a third insulating layer disposed on the second insulating layer, the third insulating layer having the same composition as the first insulating layer, and a second metal foil disposed on the third insulating layer, the second insulating layer being disposed between the first and third insulating layers.

[0007] In a third embodiment, the laminate further comprises a second metal foil, and the second insulating layer is disposed between the first insulating layer and the second metal foil. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a cross-sectional view of a multi-layered laminate structure including first and second metal foils, two outer dielectric layers containing a cross-linkable copolymer, and a central insulating layer including glass fiber and another dielectric polymer. [Figure 2]2 is a cross-sectional view of a multi-layered laminate structure similar to FIG. 1, except that the two outer dielectric layers contain both a cross-linkable copolymer and another dielectric polymer. [Figure 3] FIG. 1 is a cross-sectional view of a four-layer laminate structure including two outer metal foils, a first insulating layer containing a cross-linkable copolymer, and a second insulating layer including glass fiber and another dielectric polymer. [Figure 4] FIG. 4 is a cross-sectional view of a multi-layered laminate structure similar to FIG. 3, except that the first insulating layer also contains another dielectric polymer in addition to the cross-linkable copolymer. [Figure 5] FIG. 5 is a schematic process flow diagram showing a method for constructing the laminate structure described in FIGS. DETAILED DESCRIPTION OF THE INVENTION

[0009] The following terms will be used throughout this specification: "At least one of [a group such as A, B, and C]" or "any of [a group such as A, B, or C]" means a single element from the group, more than one element from the group, or a combination of elements from the group. For example, at least one of A, B, and C includes, for example, A alone, B alone, or C alone, as well as A and B, A and C, B and C; or A, B and C, or any other combination of A, B, and C.

[0010] A list of embodiments presented as "A, B, or C" shall be interpreted to include embodiment A only, B only, C only, "A or B," "A or C," "B or C," or "A, B, or C."

[0011] "Either A, B, or C" refers to one choice from A, B, or C.

[0012] "Any of A, B, and C" refers to one or more choices from A, B, and C.

[0013] "Cured" or "crosslinked" are used interchangeably and refer to the formation of covalent bonds that connect one polymer chain to another, or connect one polymerized repeat unit to another in the same polymer chain, thereby changing the properties of the material.

[0014] "Molecular weight" or M w refers to the polystyrene equivalent molecular weight in g / mol of the polymer block or block copolymer. M w can be measured by gel permeation chromatography (GPC) using polystyrene calibration standards as performed according to ASTM 5296. The GPC detector can be an ultraviolet or refractive index detector, or a combination of these. The chromatograph is calibrated using commercially available polystyrene molecular weight standards. The M of a polymer measured using such a calibrated GPC is w is the polystyrene equivalent molecular weight or apparent molecular weight. w is measured at the peak of the GPC trace, and M p This is generally referred to as the polystyrene equivalent "peak molecular weight" shown as

[0015] "Substantially gel-free" refers to a polymer that contains less than 10% by weight, or less than 8% by weight, or less than 5% by weight, or less than 3% by weight, or less than 2% by weight, or less than 1% by weight of solid material (insoluble) in a hydrocarbon solvent, such as toluene, cyclohexane, methyl-ethyl ketone (MEK), xylene, etc., or a mixture of hydrocarbon solvents.

[0016] "Gel content" refers to the insoluble content of the cured polymer composition in toluene (before immersion in toluene) as a percentage of the cured polymer composition. In embodiments, the gel content is greater than 90% by weight (less than 10% by weight extractable toluene), or greater than 95% by weight (less than 5% by weight extractable toluene), or greater than 98% by weight (less than 2% by weight extractable toluene).

[0017] The "gel content test" refers to the measurement of gel content by placing a sample of a cured polymer composition having a weight G1 in 20 volumes of toluene at room temperature for 4 hours. The toluene content is then filtered to recover the solid portion of the cured polymer composition, which is then dried to fully remove the solvent and weighed to obtain the insoluble content G2. The gel content is calculated as (G2 / G1). In an embodiment, the gel content is measured by soaking a sample of the cured polymer composition at 90°C for 9 hours, after which the solid portion is filtered, dried, and the weight is recorded.

[0018] "Solubility test" refers to the measurement of solubility by placing a polymer / copolymer sample in approximately 10 volumes of a hydrocarbon solvent, such as toluene, shaking thoroughly, and leaving it at room temperature for up to 4 hours. The polymer / copolymer in the solvent is then visually inspected for complete or partial dissolution. The contents are decanted or filtered, the weight of the remaining polymer / copolymer is measured, and after drying, the weight of the dissolved polymer / copolymer is calculated.

[0019] "Swelling content" refers to the weight difference (W%) between the weight of the cured polymer composition after immersion in toluene until it is completely saturated, i.e., the weight of the sample (W2) remains the same after a period of time and is not further immersed in toluene, and the weight of the curable polymer composition before immersion (W1); W% = (W2 - W1) / W1 x 100 It is calculated as:

[0020] Df denotes the "dielectric dissipation factor" or "loss factor" (Df) and is a measure of the rate at which electrical energy is lost in a dissipative system.

[0021] Dk denotes the relative permittivity or permittivity.

[0022] "DIAEA" refers to any of 1,3-diisoalkenylarenes, 1,4-diisoalkenylarenes, and combinations of the 1,3- and 1,4-isomers.

[0023] "DVB" refers to divinylbenzene.

[0024] "DVA" refers to divinylarene.

[0025] "DIPEB" refers to diisopropenylbenzene. For example, 1,3-DIPEB refers to 1,3-diisopropenylbenzene.

[0026] "DIAEA-DVA copolymer" or "DIAEA-DVA polymer" or "DIAEA copolymer" refers to a copolymer of DIAEA and divinylarene (DVA) monomers, and optionally other polymerizable monomer(s) different from DIAEA and DVA.

[0027] "CCL" as used herein refers to copper clad laminate, as well as other laminates in which other materials can be used in place of copper, for example, aluminum, magnesium, nickel, etc.

[0028] "Film" may be used synonymously with layer or film layer.

[0029] The present disclosure relates to a multilayer laminate comprising multiple metal foils and multiple dielectric (insulating) layers, wherein at least one of the insulating layers contains a copolymer comprising diisoalkenyl arene (DIAEA) and divinylarene (DVA) units as a dielectric polymer, a filler, and optionally a different dielectric polymer, and at least one of the insulating layers contains another dielectric polymer other than the copolymer of DIAEA and DVA, glass fiber, and optional filler. At least one of the insulating layers containing the copolymer of DIAEA and DVA is disposed adjacent to a metal foil. The next section describes various materials incorporated into the layers.

[0030] (metal foil layer): In an embodiment, the metal foil is copper foil. The copper foil can be electrodeposited or rolled (commonly referred to as raw foil). It may be surface treated, meaning that at least one side of the foil has been treated to improve various performance properties, such as corrosion resistance, moisture resistance, chemical and acid resistance, heat resistance, and adhesion to substrates. The surface treatment can be applied to one or both sides of the foil.

[0031] The surface roughness and mechanical properties of metal foils can significantly affect their performance. Average surface roughness can be modified through roughening or flattening / smoothing processes. Average surface roughness is defined as a 10-point average roughness. In embodiments, foils exhibit a surface roughness in the range of 0.5 to 5 mm. Alternatively, the roughness may be described as less than 5 mm, less than 4 mm, greater than 3 mm, greater than 2 mm, greater than 1 mm, greater than 0.8 mm, or greater than 0.5 mm.

[0032] In embodiments, the foil has a maximum surface height (Sz) ranging from 0.15 μm to 6.8 μm, which may be specified as less than 6.5 μm, less than 5 μm, less than 3 μm, greater than 0.20 μm, or greater than 0.30 μm.

[0033] The thickness of the metal foil layer may vary based on the desired performance or specific application. In embodiments, the metal foil has a thickness ranging from 0.1 μm to 85 μm. Alternatively, the thickness may be specified as less than 85 μm, less than 80 μm, less than 70 μm, less than 60 μm, less than 50 μm, or greater than 12 μm.

[0034] In an embodiment, the laminate further comprises a second metal foil having surface roughness and thickness characteristics similar to the first metal foil.

[0035] (Dielectric polymer - crosslinkable DIAEA-DVA copolymer): The dielectric material used herein is a copolymer of (a) diisoalkenyl arene (DIAEA) and (b) divinylarene (DVA), where the ratio of DIAEA to DVA is 15:1 to 1:15. The copolymer of DIAEA and DVA is as disclosed in U.S. Patent Application Publication No. 2022 / 0195109 A1, which is incorporated herein by reference.

[0036] In embodiments, the DIAEA-DVA copolymer has: a Dk (dielectric constant) of less than 2.8, or from 0.5 to 2.8, or from 1.0 to 2.8; a dissipation factor (Df) of less than 0.002, or less than 0.001, from 0.0003 to 0.0009, both measured at 1 and 20 GHz according to ASTM D2520, in accordance with the NTS (National Technical System) and PUS-MRI (Penn State University-Materials Research Institute) test methods.

[0037] DIAEA-DVA copolymers can be obtained from DIAEA, DVA, and optionally other polymerizable monomers by cationic polymerization in the presence of a Lewis acid or Bronsted acid catalyst. In embodiments, the copolymers comprise, relative to the total weight of the copolymer, polymerizable DIAEA in an amount of 30 to 95, or 35 to 90, or 40 to 80, or 20 to 60, or 30 to 70 wt. %, polymerized DVA in an amount of 5 to 70, or 10 to 65, or 20 to 60, or 40 to 80, or 30 to 70 wt. %, and other polymerizable monomers in an amount of 0 to 15, or 1 to 12, or 2 to 10, or 5 to 15 wt. %.

[0038] In embodiments, the DIAEA-DVA copolymer has a molar ratio of DIAEA to DVA of 15:1 to 1:15, or 12:1 to 1:12, or 10:1 to 1:10, or 8:1 to 1:8, or 5:1 to 1:5, or 4:1 to 1:4, or 3:1 to 1:3, or 2:1 to 1:2, or 1:1.

[0039] In embodiments, the copolymerized DIAEA monomer comprises at least one of repeating units (A), (B), (C), and (D) whose structure is as shown below, where R 1 is H or a C1-C8 alkyl group. The DIAEA-DVA copolymer can have the repeat units of the copolymerized DIAEA and DVA monomers in any order.

[0040] [ka] TIFF2025181807000003.tif49169

[0041] Non-limiting examples of DIAEA monomers that produce copolymers include compounds having the structure (I) 1,3-diisoalkenyl arene, (II) 1,4-diisoalkenyl arene, or mixtures thereof, where R 1 is methyl, ethyl, isopropyl, or n-butyl.

[0042] [ka]

[0043] In embodiments, the DIAEA is selected from diisopropenylbenzene (DIPEB) and substituted variants thereof to produce copolymers. Examples of DIPEB include, but are not limited to, 1,3-diisopropenylbenzene; 1,2-diisopropenylbenzene; 1,4-diisopropenylbenzene; 3,4-dicyclohexyl-1,2-diisopropenylbenzene; 5-(3-methylcyclopentyl)-1,3-diisopropenylbenzene; 3-cyclopentyl-methyl-6-n-propyl-1,4-diisopropenylbenzene; 4-(2-cyclobutyl-1-ethyl)-1,2-diisopropenylbenzene; 3-(2-n-propylcyclopropyl)-1,4-diisopropenylbenzene; 2-methyl-5-n-hexyl-1,3-diisopropenylbenzene; 4-methyl-1,2-diisopropenylbenzene; 5-ethyl-1,3-diisopropenylbenzene; 3-methyl-1,4-diisopropenylbenzene; and mixtures thereof.

[0044] In embodiments, the DIAEA is DIPEB, including o-DIPEB, m-DIPEB, and p-DIPEB. In embodiments, the DIPEB contains more than 75 wt.%, or more than 80 wt.%, or more than 85 wt.%, or more than 90 wt.%, or more than 95 wt.%, or more than 98 wt.%, or up to 100 wt.% m-DIPEB based on the total weight of the DIPEB.

[0045] In embodiments, the DIAEA is DIPEB having a moisture content of less than 150 ppm, or less than 120 ppm, or less than 100 ppm, or less than 80 ppm, based on the total weight of the DIPEB.

[0046] In embodiments, the DIAEA is DIPEB having a 4-tert-butylcatechol (p-TBC) content of less than 120 ppm, or less than 100 ppm, or less than 90 ppm, or less than 80 ppm, based on the total weight of the DIPEB.

[0047] In embodiments, the DIAEA is a DIPEB having a Hazen (APHA) color of less than 50, or less than 45, or less than 40, or less than 35, or less than 30, or less than 20, as measured on a 10 wt % solution of the DIPEB in a solvent according to ASTM D1209.

[0048] The DVA monomer is copolymerized with the DIAEA monomer, and the DVA is selected from the group consisting of divinylbenzene (DVB), ethylvinylbenzene (EVB), 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 1,4-divinylnaphthalene, 1,5-divinylnaphthalene, 2,3-divinylnaphthalene, 2,7-divinylnaphthalene, 2,6-divinylnaphthalene, 4,4'-divinylbiphenyl, 4,3'-divinylbiphenyl, 4,2'-divinylbiphenyl, 3,2'-divinylbiphenyl, 3,3'-divinylbiphenyl, 2,2'-divinylbiphenyl, 2,4-divinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,3-divinyl-4,5,8-tributylnaphthalene, 2,2'-divinyl-4-ethyl-4'-propylbiphenyl, and mixtures thereof.

[0049] Examples of DVB include o-DVB (1,2-divinylbenzene), p-DVB (1,3-divinylbenzene), m-DVB (1,4-divinylbenzene), trivinylbenzene, or mixtures thereof. In embodiments, the DVB comprises two or more compounds selected from o-DVB, m-DVB, p-DVB, vinylbenzene, diethylbenzene, EVB, and mixtures thereof.

[0050] In an embodiment, the DVA is DVB, including m-DVB, p-DVB, m-EVB, p-EVB, and mixtures thereof.

[0051] In an embodiment, the DVA is a DVB containing 50 to 99% by weight, or 55 to 95% by weight, or 50 to 85% by weight, or 50 to 80% by weight, or more than 50% by weight, or more than 90% by weight, or more than 97% by weight of m-DVB, based on the total weight of the DVB.

[0052] In an embodiment, the DVA is DVB with a weight ratio of m-DVB to p-DVB of 5:1 to 1:5, or 4:1 to 1:4, or 3:1 to 1:3, or 2:1 to 1:2.

[0053] In an embodiment, the DVA contains 35-45 wt % m-DVB, 35-45 wt % p-DVB, 5-15 wt % m-EVB, and 5-20 wt % p-EVB, based on the total weight of the DVB.

[0054] In embodiments, the DVA has a total of more than 80% by weight, or more than 85% by weight, or more than 90% by weight, or more than 92% by weight, or more than 95% by weight of m-DVB, p-DVB, m-EVB, and p-EVB, based on the total weight of the DVA.

[0055] In an embodiment, the DVA is a DVB having a combination of m-DVB and p-DVB in an amount of 50-99% by weight, or 55-85% by weight, or 50-80% by weight, or 55-80% by weight, or more than 50% by weight, or more than 85% by weight or up to 99% by weight, based on the total weight of the DVB.

[0056] In an embodiment, the DVA is a DVB having a combination of m-EVB and p-EVB in an amount of less than 35% by weight, or less than 30% by weight, or less than 20% by weight, or less than 10% by weight, or less than 5% by weight, or 1-25% by weight, or less than 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight, based on the total weight of the DVB.

[0057] In embodiments, the DVA is DVB having a purity of greater than 90%, or greater than 80%, or greater than 70%, or greater than 60%, or greater than 50% by weight of the total DVB. "Purity" of DVB is defined as the presence of more than a certain percentage of a single isomer in a mixture of all isomers, e.g., o-DVB, m-DVB, or p-DVB.

[0058] In embodiments, the DVA is a DVB having a 4-tert-butylcatechol (p-TBC) content of less than 1200 ppm, or less than 1100 ppm, or less than 1000 ppm, or less than 800 ppm, based on the total weight of the DVB.

[0059] In embodiments, the DVA is a DVB having a naphthalene content of less than 1000 ppm, or less than 800 ppm, or less than 700 ppm, or less than 500 ppm, based on the total weight of the DVB.

[0060] In embodiments, the DIAEA-DVA copolymer further comprises other polymerizable monomers selected from the group consisting of styrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene, α-alkylated styrenes, alkoxylated styrenes, and mixtures thereof.

[0061] Non-limiting examples of α-alkylated styrenes include α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-n-butylstyrene, α-isobutylstyrene, α-t-butylstyrene, α-n-pentylstyrene, α-2-methylbutylstyrene, α-3-methylbutyl-2-styrene, α-t-pentylstyrene, α-n-hexylstyrene, α-2-methylpentylstyrene, α-3-methylpentylstyrene, α-1-methylpentylstyrene, α-2,2-dimethylbutylstyrene, α-2,3-dimethylbutylstyrene, α-2,4-dimethylbutylstyrene, α-3,3-dimethylbutylstyrene, α-3,4-dimethylbutylstyrene, α-4,4-dimethylbutylstyrene, α-2-ethylbutylstyrene, α-1-ethylbutylstyrene, α-cyclohexylstyrene, and mixtures thereof. In embodiments, other alkylated styrene compounds include m-methylstyrene, p-methylstyrene, m-propylstyrene, p-propylstyrene, mn-butylstyrene, pn-butylstyrene, mt-butylstyrene, pt-butylstyrene, mn-hexylstyrene, pn-hexylstyrene, m-cyclohexylstyrene, p-cyclohexylstyrene, and mixtures thereof.Examples of alkoxylated styrenes include o-ethoxystyrene, m-ethoxystyrene, p-ethoxystyrene, o-propoxystyrene, m-propoxystyrene, p-propoxystyrene, on-butoxystyrene, mn-butoxystyrene, pn-butoxystyrene, o-isobutoxystyrene, m-isobutoxystyrene, p-isobutoxystyrene, ot-butoxystyrene, mt-butoxystyrene, pt-butoxystyrene, on-pentoxystyrene, mn-pentoxystyrene, pn-pentoxystyrene, α-methyl-o-butoxystyrene, α-methyl Examples of cyclohexoxystyrene include o-m-butoxystyrene, α-methyl-p-butoxystyrene, ot-pentoxystyrene, mt-pentoxystyrene, pt-pentoxystyrene, on-hexoxystyrene, mn-hexoxystyrene, pn-hexoxystyrene, α-methyl-o-pentoxystyrene, α-methyl-m-pentoxystyrene, α-methyl-p-pentoxystyrene, o-cyclohexoxystyrene, m-cyclohexoxystyrene, p-cyclohexoxystyrene, o-phenoxystyrene, m-phenoxystyrene, p-phenoxystyrene, and mixtures thereof.

[0062] In embodiments, other polymerizable monomers include butadiene, isoprene, piperylene, divinyltoluene, divinylpyridine, divinylxylene, vinyltriisopropenoxysilane, methoxytrivinylsilane, tetravinylsilane, diethoxydivinylsilane, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, 2-vinyl-2'-ethylbiphenyl, 2-vinyl-3'-ethylbiphenyl, 2-vinyl-4'-ethylbiphenyl, 3-vinyl-2'-ethylbiphenyl, 3-vinyl-3'-ethylbiphenyl, 3-vinyl-4'-ethylbiphenyl, 3-vinyl-5'-ethylbiphenyl, 3-vinyl-6'-ethylbiphenyl, 3-vinyl-7'-ethylbiphenyl, 3-vinyl-8'-ethylbiphenyl, 3-vinyl-9'-ethylbiphenyl, 3-vinyl-10'-ethylbiphenyl, 3-vinyl-11'-ethylbiphenyl, 3-vinyl-12'-ethylbiphenyl, 3-vinyl-13'-ethylbiphenyl, 3-vinyl-14'-ethylbiphenyl, 3-vinyl-15'-ethylbiphenyl, 3-vinyl-16'-ethylbiphenyl, 3-vinyl-17'-ethylbiphenyl, 3-vinyl-18'-ethylbiphenyl, 3-vinyl-19 ... Vinyl-4'-ethylbiphenyl, 4-vinyl-2'-ethylbiphenyl, 4-vinyl-3'-ethylbiphenyl, 4-vinyl-4'-ethylbiphenyl, 1-vinyl-2-ethylnaphthalene, 1-vinyl-3-ethylnaphthalene, 1-vinyl-4-ethylnaphthalene, 1-vinyl-5-ethylnaphthalene, 1-vinyl-6-ethylnaphthalene, 1-vinyl-7-ethylnaphthalene, 1-vinyl-8-ethylnaphthalene, 2-vinyl-1-ethylnaphthalene, 2-vinyl-3-ethylnaphthalene, 2-vinyl-4-ethylnaphthalene, 2-vinyl-5-ethyl naphthalene, 2-vinyl-6-ethylnaphthalene, 2-vinyl-7-ethylnaphthalene, 2-vinyl-8-ethylnaphthalene, 2-vinyl-2'-propylbiphenyl, 2-vinyl-3'-propylbiphenyl, 2-vinyl-4'-propylbiphenyl, 3-vinyl-2'-propylbiphenyl, 3-vinyl-3'-propylbiphenyl, 3-vinyl-4'-propylbiphenyl, 4-vinyl-2'-propylbiphenyl, 4-vinyl-3'-propylbiphenyl, 4-vinyl-4'-propylbiphenyl, 1-vinyl-2-propylnaphthalene, 1-vinyl 1-vinyl-3-propylnaphthalene, 1-vinyl-4-propylnaphthalene, 1-vinyl-5-propylnaphthalene, 1-vinyl-6-propylnaphthalene, 1-vinyl-7-propylnaphthalene, 1-vinyl-8-propylnaphthalene, 2-vinyl-1-propylnaphthalene, 2-vinyl-3-propylnaphthalene, 2-vinyl-4-propylnaphthalene, 2-vinyl-5-propylnaphthalene, 2-vinyl-6-propylnaphthalene, 2-vinyl-7-propylnaphthalene, 2-vinyl-8-propylnaphthalene, 1,2,4-trivinylbenzene, 1,3,5-trivinylbenzene, 1,2,4-triisopropenylbenzene, 1,3,5-triisopropenylbenzene, 1,3,5-trivinylnaphthalene, 3,5,4'-trivinylbiphenyl, indene, alkylated indenes such as methylindene, ethylindene, propylindene, butylindene, t-butylindene, sec-butylindene, n-pentylindene, 2-methylbutylindene, 3-methylbutylindene, n-hexylindene, 2-methylpentylindene, 3-methylpentylindene, 4-methylpentylindene, alkyl and mono-, di-, or polyfunctional compounds selected from oxyindenes such as methoxyindene, ethoxyindene, propoxyindene, butoxyindene, t-butoxyindene, sec-butoxyindene, n-pentoxyindene, 2-methyl-butoxyindene, 3-methyl-butoxyindene, n-hexyloxyindene, 2-methyl-pentoxyindene, 3-methyl-pentoxyindene, 4-methyl-pentoxyindene, acenaphthylenes such as alkylacenaphthylenes, halogenated acenaphthylenes, phenylacenaphthylene, and mixtures thereof. Examples of alkylacenaphthylenes include 1-methylacenaphthylene, 3-methylacenaphthylene, 4-methylacenaphthylene, 5-methylacenaphthylene, 1-ethylacenaphthylene, 3-ethylacenaphthylene, 4-ethylacenaphthylene, 5-ethylacenaphthylene, and mixtures thereof. Examples of halogenated acenaphthylenes include 1-chloroacenaphthylene, 3-chloroacenaphthylene, 4-chloroacenaphthylene, 5-chloroacenaphthylene, 1-bromoacenaphthylene, 3-bromoacenaphthylene, 4-bromoacenaphthylene, and 5-bromoacenaphthylene, and mixtures thereof. Examples of phenylacenaphthylene include 1-phenylacenaphthylene, 3-phenylacenaphthylene, 4-phenylacenaphthylene, 5-phenylacenaphthylene, and mixtures thereof.

[0063] In embodiments, the DIAEA-DVA copolymer further comprises repeat units derived from monomers including (i) cyclodiene or dimers thereof, (ii) adducts of cyclodiene and acyclic dienes, (iii) allylic compounds having two or more allylic groups, and any combination or subcombination thereof. Examples of cyclically polymerizable monomers include 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,3-cyclopentadiene, alkylcyclopentadienes, trivinylcyclohexane, 2,4,6,8-tetravinyl-2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentavinylcyclopentasiloxane, or mixtures thereof.

[0064] In embodiments, the DIAEA-DVA copolymer comprises low molecular weight species in an amount of 0.25-25 wt%, or 0.50-20 wt%, or 1-15 wt%, or 0.25-10 wt%, or 0.5-20 wt%, of the total mass of the copolymer. Low molecular weight species are defined as having a molecular weight of less than 0.5 kg / mol.

[0065] (DIAEA-DVA copolymer structure): In embodiments, the DIAEA-DVA copolymer is either a random or block copolymer, or the copolymer can contain a homopolymer of DIAEA monomer end-capped with a DVA comonomer to obtain a DVA end-capped polyDIAEA.

[0066] The DIAEA-DVA copolymer can have at least one end group selected from (E), (F), (G), and (H) having the structure shown below.

[0067] [ka] TIFF2025181807000006.tif141169

[0068] The copolymers can be functionalized with functional groups such as isocyanate, anhydride, carboxylic acid, carboxylic acid ester, hydroxyl, vinyl, urethane, amino, phosphino, silane, acrylate, methacrylate, or epoxy groups using methods known in the art.

[0069] In an embodiment, the DIAEA-DVA copolymer is a DIPEB-DVB copolymer.

[0070] (Properties of DIAEA-DVA copolymer): In embodiments, DIAEA-DVA copolymers are resinous materials that have a good combination of molecular weight range and relatively broad molecular weight distribution (polydispersity index), which in part makes them more soluble in non-polar solvents, thereby enhancing their processability.

[0071] In embodiments, the DIAEA-DVA copolymer has a solubility of at least 10 wt %, or more than 20 wt %, or more than 30 wt %, or more than 50 wt %, or more than 70 wt %, or less than 99 wt %, or 10-75 wt %, or 20-65 wt %, or 10-60 wt %, based on the total weight of the solvent, over a period of less than 4 hours in a hydrocarbon solvent at 25° C. Examples of solvents include hexane, heptane, octane, isooctane, cyclohexane, varnish maker and painter's naphtha (VM&P naphtha), petroleum ether, toluene, xylene, and mixtures thereof.

[0072] In embodiments, the DIAEA-DVA copolymer as a solid when dissolved in a hydrocarbon solvent forms a substantially gel-free solution, with less than 2% by weight, or less than 5% by weight, or less than 10% by weight, or less than 15% by weight of the solids remaining insoluble in the solvent.

[0073] In embodiments, the DIAEA-DVA copolymer solution in the hydrocarbon solvent has a gel content of 0.05 to 5 wt %, or 0.1 to 4.5 wt %, or 1 to 4 wt %, or less than 5 wt %, or less than 2 wt %, or less than 1 wt %, based on the total weight of the copolymer.

[0074] In embodiments, the DIAEA-DVA copolymer has a temperature at which decomposition occurs between 200 and 450°C, or between 220 and 420°C, or between 240 and 400°C, or less than 600°C, or less than 500°C, or greater than 300°C.

[0075] In embodiments, the DIAEA-DVA copolymer has a glass transition temperature (T ) of 50-300°C, or 60-250°C, or 70-220°C, or 80-200°C, or 100-250°C, or 120-220°C, or greater than 150°C, or less than 250°C, or less than 220°C, as measured using differential scanning calorimetry (DSC) or dynamic mechanical analyzer (DMA) according to ASTM D3418. g )

[0076] In embodiments, the DIAEA-DVA copolymer has a moisture absorption coefficient, measured at 25°C by ASTM D570, of less than 0.1, or less than 0.08, or less than 0.05.

[0077] In embodiments, the DIAEA-DVA copolymer has a density greater than 0.9, or greater than 1.0, or between 1.0 and 2.0, or between 1.0 and 1.50 g / cc.

[0078] (Other dielectric polymers): In embodiments, the dielectric layer comprising the DIAEA-DVA copolymer further comprises a second dielectric polymer (the "other" dielectric polymer) which may be the same as or different from the "other" dielectric polymer used in the insulating dielectric layer that does not contain the DIAEA-DVA copolymer.

[0079] In embodiments, the other dielectric polymer has: a Dk (dielectric constant) of less than 5, or between 2 and 5, or between 2.1 and 4; a dissipation factor (Df) of less than 0.05, or less than 0.0002, between 0.0003 and 0.05, both Dk and Df measured at 10 GHz according to NTS (National Technical Systems) and PUS-MRI (Penn State University-Materials Research Institute) test methods and according to ASTM-D2520.

[0080] Examples of other dielectric polymers include epoxy resins, polyimide resins, bismaleimide-triazine (BT) resins, cyanate ester resins, benzoxazine resins, phenolic resins, maleimide resins, styrenic block copolymers (SBC), hydrogenated styrenic block copolymers (HSBC), polytetrafluoroethylene (PTEE), polyphenylene ether (PPE), polyetherimide (PEI), polyphenylene sulfide (PPS), polyethersulfone (PES), polysulfone (PSU), polyetherketone (PEEK), polycarbonate (PC), polyolefins including polyethylene and polypropylene, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyesterimide, polyurethane, and fluororesins including polyvinylidene fluoride (PVDF), and mixtures thereof.

[0081] In embodiments, the dielectric polymer is an epoxy resin containing any of glycidyl groups, cycloaliphatic epoxy groups, oxirane groups, ethoxyline groups, and the like. Examples of epoxy resins include novolac-type epoxy resins, cresol-novolac epoxy resins, triphenolalkane-type epoxy resins, aralkyl-type epoxy resins, aralkyl-type epoxy resins having a biphenyl skeleton, biphenyl-type epoxy resins, dicyclopentadiene-type epoxy resins, heterocyclic-type epoxy resins, epoxy resins containing a naphthalene ring, bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, stilbene-type epoxy resins, trimethylolpropane-type epoxy resins, terpene-modified epoxy resins, linear aliphatic epoxy resins obtained by oxidizing an olefin bond with peracetic acid or a similar peracid, alicyclic epoxy resins, sulfur-containing epoxy resins, N,N,N',N'-tetraglycidyl-m-xylylenediamine, N,N,N',N'-tetraglycidylmethylenedianiline, anthracene-based epoxy resins, pyrene-based epoxy resins, naphthalene-based epoxy resins, and mixtures thereof. In embodiments, naphthalene-based epoxy resins include dinaphthalene-based epoxy resins, tetranaphthalene-based epoxy resins, oxazolidone-containing dinaphthalene-based epoxy resins, and the like.

[0082] In embodiments, the other dielectric polymer is a cyanate ester resin containing at least one -O-CN unit. The cyanate ester can contain an Ar-O-CN unit, where Ar is substituted or unsubstituted benzene, biphenyl, naphthalene, phenol novolac, bisphenol A, bisphenol A novolac, bisphenol F, bisphenol F novolac, or phenolphthalein. Ar can be linked to a substituted or unsubstituted dicyclopentadienyl.The cyanate ester resin is a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate compound, a polyfunctional aromatic isocyanate compound, such as trimethylene diisocyanate, tetramethylene diisocyanate, methylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like, 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate , 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenylether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, benzenemethylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate The isocyanate may be obtained from compounds selected from, but not limited to, carbodiimide modified products of methyl methyl ketone, polymethylene polyphenyl polyisocyanate, toluidine diisocyanate, xylene diisocyanate, tetramethyl xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, norbonane diisocyanate, biuret modified hexamethylene diisocyanate, dimer acid diisocyanate, and the like.

[0083] In embodiments, other dielectric polymers include benzoxazine resins, such as bisphenol A benzoxazine, bisphenol F benzoxazine, phenolphthalein benzoxazine, and the like, and mixtures thereof.

[0084] In embodiments, other dielectric polymers include polyphenylene ethers, such as polyphenylene oxide (PPO), polyphenylene ether oligomers or polymers. The polyphenylene ethers can be functionalized with hydroxyl, vinyl, isocyanate, anhydride, carboxylic acid, carboxylic acid ester, urethane, amino, phosphino, epoxy, silane, acrylate, methacrylate, and mixtures thereof. In embodiments, the polyphenylene ethers have 1.2 to 2.8 phenolic hydroxy groups per molecule, a polydispersity index of 1.2 to 3, and an intrinsic viscosity of 0.03 to 0.2 deciliters per gram.

[0085] In embodiments, another dielectric polymer is a polyurethane obtained by reacting an isocyanate and a polyol in the presence of a thermal or photoinitiator. Examples of isocyanates can include those described above under the cyanate ester resin. Examples of polyols include alkylene oxide adducts of bisphenol A, alkylene oxide adducts of aromatic diols, polyester polyols, acrylic polyols, polyether polyols, polycarbonate polyols, polyalkylene polyols, and the like. Other types of hydroxyl-containing compounds that can be used as polyols in preparing polyurethanes include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxy-n-butyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-n-butyl (meth)acrylate, 3-hydroxy-n-butyl (meth)acrylate, and mixtures thereof. The molar ratio of the isocyanate group (NCO) of the isocyanate compound to the hydroxyl group (OH) of the polyol is 0.7 to 1.5, or 0.8 to 1.3, or 0.8 to 1.0.

[0086] In embodiments, other dielectric polymers include styrenic block copolymers (SBCs). The SBCs may be unhydrogenated, hydrogenated, partially hydrogenated, selectively hydrogenated, or mixtures thereof. In embodiments, the SBCs may be either linear or branched (e.g., multi-arm) block copolymers comprising at least one polymer block A derived from a vinyl aromatic monomer and at least one polymer block B derived from a conjugated diene monomer. The vinyl aromatic monomers may be incorporated into or copolymerized with the conjugated diene block in any sequence and distribution. In embodiments, the styrenic block copolymers are hydrogenated SBCs having a general configuration selected from S-EB-S, SE / P, SE / B, S-EP-S, and mixtures thereof. In these configurations, each "S" block is derived from a vinyl aromatic monomer, "EB" indicates an ethylene-butylene block, and "EP" indicates an ethylene-propylene block.

[0087] (Filler): In embodiments, fillers are added to dielectric layers containing DIAEA-DVA copolymers in an amount of 30-60 wt%, or greater than 30 wt%, or greater than 40 wt%, or greater than 50 wt%, or less than 60 wt%, based on the total weight of the layer. In embodiments, fillers are also added to dielectric layers containing other dielectric polymers (other than DIAEA-DVA copolymers) in an amount of 0-30 wt%, or greater than 30 wt%, or greater than 25 wt%, or greater than 20 wt%, or greater than 15 wt%, or greater than 10 wt%, or greater than 5 wt%, or greater than 2 wt%, based on the total weight of the layer.

[0088] Examples of fillers include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate, and mixtures thereof.

[0089] In embodiments, the filler is a silica selected from the group consisting of aerogel silica, silica xerogel, fumed silica, precipitated silica, amorphous silica, crystalline silica, hollow silica, and mixtures thereof. The silica can be derived from a silicate, such as an alkali metal silicate or ammonium silicate. In embodiments, the silica has a spherical shape with an aspect ratio of less than 2, or less than 1.5, or less than 1. In embodiments, the silica has a spherical shape with an aspect ratio of less than 1 m 2 / g or more or 2m 2 / g or more or 5m 2 / g or more, or 1 to 60m 2 / g, or 5 to 30 m 2 / g, or 10 to 50 m 2 / g, or 1 to 15m 2 / g of surface area.

[0090] In embodiments, the filler is an elongated particle having an aspect ratio of 2.0 or greater, or 1.5 or greater, or 1.0 or greater, In embodiments, the filler has an average particle size of 10 nm or greater, or 20 nm or greater, or 50 nm or greater, or 100 nm or greater, or 150 nm or greater, or 10 nm to 1 micron, 20 nm to 500 nm, 20 nm to 200 nm, or 10 nm to 100 nm, 50 nm to 300 nm, or less than 5 μm, or less than 2 μm, or less than 1 μm, or less than 0.8 μm, or less than 0.6 μm.

[0091] In an embodiment, the filler is silica that has been surface-treated with at least one surface treatment agent to enhance the dispersibility of the filler in the copolymer layer, in an amount of 0.1 to 10, or 0.5 to 5, or 0.1 to 3, or 0.2 to 2.5 wt % of the surface treatment agent, based on the total weight of the filler. Examples of surface treatment agents include silane coupling agents, titanium coupling agents, aluminum coupling agents, organosilazane compounds, and the like. Other examples include methacrylsilane, acrylsilane, aminosilane, imidazole silane, vinylsilane, epoxysilane, fluorine-containing silane, mercaptosilane, alkoxysilane, and mixtures thereof. Examples of silanes include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldisilazane, phenyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, vinyltrimethoxysilane (VTMOS), vinyltriethoxysilane (VTEOS), vinyltributoxysilane, vinyldimethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, allyltrimethoxysilane, allyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, dimethoxymethylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, and mixtures thereof.

[0092] (glass fiber): In embodiments, the insulating layer containing the other dielectric polymer (and not the DIAEA-DVA copolymer) further contains glass fibers in an amount of at least 75%, at least 80%, at least 85%, or at least 90% by weight, with the remainder being the second dielectric polymer; or the ratio of glass fibers to the other dielectric polymer is in a weight ratio of 70:30 to 95:5, or 75:25, or 80:20, or 82:18, or 85:15, or 90:10. Examples of glass fibers include glass cloth, aramid cloth, polyester cloth, glass nonwoven cloth, aramid nonwoven cloth, polyester nonwoven cloth, pulp paper, and linter paper.

[0093] In some embodiments, the glass fibers are added to other dielectric polymers forming a varnish mixture. In other embodiments, the other dielectric polymers are impregnated into the glass fiber cloth. In some embodiments, the weight ratio of glass fibers to other dielectric polymers is 75:25, or 80:20, or 82:18, or 85:15, or 90:10, or 95:5.

[0094] (Optional Additives): In an embodiment, a scorch inhibitor is added to the dielectric layer containing the copolymer of DIAEA and DVA. Examples of scorch inhibitors include styrene, alpha-methylstyrene monomer (AMSM), alpha-methylstyrene dimer (AMSD), alpha-methylstyrene oligomer (AMSO), hindered phenolic compounds substituted with an alkyl group, a phenyl group, or the like, at the ortho position relative to at least one phenolic OH group, non-hindered phenolic compounds, amine compounds, thiourea compounds, benzimidazole, and mixtures and derivatives thereof. The alpha-methylstyrene derivatives can have one or more functional groups located on each ring, which can all be the same or different. In embodiments, the alpha-methylstyrene dimer is selected from the group consisting of 2,4-diphenyl-4-methyl-1-pentene, 2,4-diphenyl-4-methyl-2-pentene, 1,2-dimethyl-3-phenylindane, cis-1,3-dimethyl-1,3-diphenylcyclobutene, trans-1,3-dimethyl-1,3-diphenylcyclobutene, and mixtures thereof.

[0095] In embodiments, the scorch inhibitor is added to the DIAEA-DVA copolymer in solution in an amount of 0.001 to 10, or 0.005 to 10, or 0.010 to 10, or 0.050 to 10, or 0.001 to 5, or 0.005 to 5, or 0.010 to 5, or 0.050 to 5, or up to 5 weight percent based on the total weight of the DIAEA-DVA copolymer.

[0096] In embodiments, depending on the dielectric polymer(s) used, the dielectric layer further contains at least an additive selected from initiators, activators, stabilizers, neutralizers, thickeners, coalescing agents, slip agents, release agents, antioxidants, anti-ozonants, color-changing pH indicators, plasticizers, tackifiers, film-forming additives, dyes, pigments, UV stabilizers, fillers, flame retardants, viscosity modifiers, wetting agents, degassing agents, toughening agents, adhesion promoters, heat stabilizers, lubricants, flow control agents, anti-drip agents, anti-static agents, processing aids, stress relief additives, accelerators, water resistance agents, waterproofing agents, heat conductivity agents, agents for imparting electromagnetic wave shielding properties, radical scavengers, and mixtures thereof.

[0097] The additives may be added to the layers in amounts up to 30, or 0.1 to 30, or 0.1 to 20, or 1 to 10, or 0.5 to 5, or 0.1 to 5 weight percent based on the total weight of the dielectric polymer in the particular layer.

[0098] (Laminate structure): The laminate is characterized as having a multilayered sandwich construction of alternating metal foil layers and insulating layers, the insulating layers containing the above-described materials, and an insulating dielectric layer containing the DIAEA-DVA copolymer adjacent to the metal foil layer.

[0099] In embodiments, the insulating dielectric layer adjacent to the metal foil layer comprises the DIAEA-DVA copolymer in an amount of 40-70 wt. %, or 45-65 wt. %, or 50-60 wt. %, based on the total weight of the composition of the first layer (see FIG. 1 and description below). In embodiments, in addition to the DIAEA-DVA copolymer and filler, other dielectric polymers can be added to this layer in weight ratios of other dielectric polymer to DIAEA-DVA copolymer of about 1:20 to 1:4, or 1:15 to about 1:5, or 1:10 to 1:6. See also the description of FIG. 2 below.

[0100] In embodiments, the thickness of the insulating layer containing the DIAEA-DVA copolymer and filler ranges from 3 to 25 μm, or from 5 to 15 μm, or from 7.5 to 12 μm, or is less than 25 μm, less than 20 μm, less than 15 μm, or greater than 3 μm, or greater than 5 μm, greater than 7.5 μm.

[0101] In embodiments, insulating dielectric layers containing DIAEA-DVA copolymers are characterized as having a Dk less than 2.8, or less than 2.5, or less than 2.1, or less than 2.0, or less than 1.8, and a Df less than 0.002, or less than 0.001, or less than 0.0008, or less than 0.0007, or less than 0.0005.

[0102] In embodiments, the insulating layer adjacent to the layer containing the DIAEA-DVA copolymer contains glass fiber(s) and at least one other dielectric polymer in an amount of 15-50%, or 20-40%, or 25-35%, or greater than 15%, or greater than 20%, or greater than 25%, or greater than 30%, or less than 50%, or less than 45%, or less than 40%.

[0103] In embodiments, the thickness of the insulating layer containing other dielectric polymers (other than DIAEA-DVA copolymer) and glass fibers ranges from 50 to 200 μm, 60 to 150 μm, or greater than 50 μm, or greater than 60 μm, or greater than 65 μm, or greater than 75 μm, or greater than 85 μm, or greater than 100 μm, or greater than 115 μm, or less than 200 μm.

[0104] In embodiments, insulating dielectric layers containing other dielectric polymers (other than DIAEA-DVA copolymers) are characterized as having a Dk of less than 5.0, or less than 4.8, or less than 4.5, or less than 4.0, or less than 3.8, or less than 3.5, or less than 3.0, and a Df of 0.0003 to 0.05, or less than 0.05, or less than 0.01, or less than 0.005, or less than 0.002, or less than 0.001.

[0105] An embodiment of a multilayer laminate is illustrated in the figures. In Figure 1, the multilayer laminate structure includes a first metal foil layer (101) and a second metal foil layer (105). First and second dielectric insulating layers (102) and (104), containing a DIAEA-DVA copolymer and a filler, are disposed adjacent to the first and second metal foils, respectively. Between these two DIAEA-DVA copolymer-containing dielectric insulating layers is a layer (103) containing glass fiber and at least another dielectric polymer (other than the DIAEA-DVA copolymer). This symmetrical laminate architecture allows for a scalable and repeatable lamination strategy, where thin, low-loss dielectric layers (i.e., containing the DIAEA-DVA copolymer) are alternated with thicker, mechanically strengthened dielectric layers to achieve optimal performance in high-frequency applications.

[0106] Figure 2 shows another embodiment of a multilayered laminate structure that is structurally similar to the configuration of Figure 1, except that the dielectric layer adjacent to the metal foil layer further comprises another dielectric polymer in addition to the DIAEA-DVA copolymer. The dielectric layer with the DIAEA-DVA copolymer is positioned for a low-loss interface that would optionally be positioned between the metal foil conductor and the glass-reinforced dielectric layer (203).

[0107] 3 shows a further embodiment of a multilayered laminate stack including two outer metal foils (301 and 304), with a dielectric layer (302) having a DIAEA-DVA copolymer disposed adjacent to the metal foil layer (301) and a dielectric layer (303) containing another dielectric polymer (other than the DIAEA-DVA copolymer) disposed adjacent to the metal foil layer (304). This configuration provides a dual dielectric configuration with metal layers on both outer surfaces, which can be particularly advantageous for controlled impedance and EMI shielding.

[0108] Figure 4 shows yet another embodiment of a multilayered laminate architecture. This configuration is similar to the structure of Figure 3, except that in addition to the DIAEA-DVA copolymer and filler, the dielectric layer (402) further comprises another dielectric polymer (other than the DIAEA-DVA copolymer). The resulting architecture enables the design of high-density multilayered circuit boards with excellent signal strength, low dielectric loss, and tight impedance control across the laminated signal and ground planes.

[0109] (Method of preparing a multi-layered laminate): Construction of laminates can be carried out by a variety of methods that may differ in the order in which the layers are assembled, the technique by which the dielectric layers are applied, and the source or form of intermediate materials used, including prepregs (which may be commercially available) or dielectric varnishes.

[0110] FIG. 5 is a schematic process flow diagram illustrating a method of constructing a multilayered laminate structure that includes one or more metal foil layers, at least one thin dielectric layer containing a DIAEA-DVA copolymer, and at least one thicker insulating layer that includes a glass fiber component and another dielectric polymer that is distinct from the DIAEA-DVA copolymer.

[0111] In one illustrated embodiment, the process begins with a core insulation layer (a layer that does not contain DIAEA-DVA copolymer), which can be fabricated in-house (Option 2) or is a commercially available prepreg (Option 1). Either option serves as a base layer for subsequent laminate buildup. Commercially available prepregs are sheets containing glass fibers embedded in another dielectric polymer, such as epoxy or cyanate ester. This prepreg can be cured or semi-cured. To fabricate the core insulation layer, the glass fiber substrate is impregnated with a dielectric polymer(s) other than the DIAEA-DVA polymer. The impregnation solution may optionally contain fillers to enhance performance.

[0112] In the next step, a composition (uncured or partially cured) containing DIAEA-DVA copolymer, filler, and optional other dielectric polymers is applied to both sides of the core insulation layer. This can be done via methods such as brushing, roll coating, or die coating, depending on the process setup. One or two metal foil layers (typically copper or other conductive metal) are then placed on the copolymer-coated side of the core layer. These layers serve as the conductive planes or signal layers of the final laminate. The assembled stack is then subjected to lamination, which involves the application of heat and pressure using a hot press or vacuum forming. This step promotes interlayer adhesion and simultaneously completes the curing of the DIAEA-DVA copolymer.

[0113] In another embodiment, the process begins with a metal foil die-coated with a partially cured DIAEA-DVA copolymer composition (including fillers and optional other dielectric polymers) on its surface. The coated foil is then contacted with a cured insulating layer to form part of a laminate structure. This sequence can be repeated to generate a symmetrical laminate configuration. The completed structure is then subjected to heat and pressure to complete bonding and curing.

[0114] In yet another embodiment, the insulation layer (in-house) can be prepared by impregnating a fiberglass mat with a separate dielectric polymer solution in varnish form, thereby forming a prepreg. A partially cured DIAEA-DVA copolymer (including fillers and optional other dielectric polymers) is then applied to one or both sides of this prepreg, after which one or more metal foils are placed on the coated surface. Lamination under appropriate conditions results in a fully cured and bonded laminate.

[0115] If improved adhesion between layers is desired, the metal foil surface can be chemically treated prior to assembly. For example, a silane coupling agent may be used to treat the interior surface of the metal foil. The method proceeds by first preparing a cured prepreg insulation layer, followed by application of a DIAEA-DVA copolymer formulation to both sides of the prepreg. Chemically treated metal foil is then placed on either side of the coated prepreg. Vacuum lamination is performed at an elevated temperature, e.g., between 180°C and 250°C, to ensure cure of the copolymer and the formation of a strong adhesive bond throughout the laminate.

[0116] In another embodiment, commercially available prepreg sheets containing fiberglass and cured or semi-cured dielectric resin are used directly as the core insulation layer. This alternative allows for faster assembly of the laminate, as a DIAEA-DVA copolymer layer can be applied directly to the surface of the commercial prepreg, which is then laminated with one or more metal foil layers.

[0117] To further strengthen the bond, an optional intermediate adhesive layer or dielectric varnish can be included in the laminate stack. These varnishes incorporate one or more additives such as tackifiers, dielectric resins, fillers, pigments, and curing agents. Such varnishes may be applied to any of the relevant surfaces, including the prepreg, metal foil, or DIAEA-DVA copolymer layer, prior to final lamination.

[0118] This architecture allows for tight control of electrical loss, impedance, and mechanical stiffness, making it suitable for high-frequency circuit boards, antenna components, multilayer signal routing platforms, and other applications requiring low-loss and structurally robust dielectric materials.

[0119] In embodiments, the resulting laminate structure includes one or more thin dielectric layers containing DIAEA-DVA copolymer. These layers have thicknesses ranging from about 3 to 20 micrometers and exhibit a dielectric constant (Dk) of less than 2.8 and a dissipation factor (Df) of less than 0.002 measured at 10 GHz. Thicker insulating dielectric layers containing glass fiber and another dielectric polymer exhibit a dielectric constant of less than 5.0 and a dissipation factor of less than 0.05. Lamination is performed using hot pressing or vacuum lamination at pressures ranging from about 0.5 to 2 MPa.

[0120] (Laminate properties): Laminates containing DIAEA-DVA copolymer layers with thicknesses of 5 to 200 μm exhibit excellent dielectric properties and effectively prevent wiring delamination.

[0121] Adhesion strength to copper foil: In an embodiment, the laminate has a 90° peel strength to copper foil, performed according to IPC 650 2.4.19, of greater than 0.1, or greater than 0.2, or 0.1-1.0, or 0.2-0.9, or 0.3-0.7 N / m.

[0122] In embodiments, the laminate has a decomposition temperature (Td) of less than 500°C, or less than 450°C, or greater than 100°C, or greater than 150°C, or greater than 175°C, or greater than 200°C, as measured using thermogravimetric analysis (TGA) at 5% weight loss.

[0123] In embodiments, the laminate has a glass transition temperature (T) of 150-300°C, or less than 300°C, or less than 280°C, or greater than 150°C, as measured using DSC according to ASTM D3418 or DMA (Dynamic Mechanical Analyzer). g )

[0124] In embodiments, the cured laminate has a coefficient of thermal expansion (CTE) of less than 30 ppm / °C, or less than 28 ppm / °C, or less than 25 ppm / °C, or less than 22 ppm / °C, as measured using TMA over the range of -50 to 300°C.

[0125] In embodiments, the laminate has a Dk (dielectric constant) measured at 10 GHz according to ASTM D2520 of less than 4.5, or less than 4, or less than 3.5, or less than 2.80, or less than 2.70, or less than 2.60, or less than 2.50, or less than 2.40.

[0126] In an embodiment, the laminate has a Df (dielectric loss tangent) measured at 10 GHz according to ASTM D2520 of less than 0.01, or less than 0.005, or less than 0.0018, or less than 0.0015, or less than 0.0005, or less than 0.0006, or from 0.002 to 0.0001, or from 0.0015 to 0.0001.

[0127] Heat Resistance - The heat resistance (T288) of metal clad laminates is evaluated according to IPC TM650. Specifically, a thermomechanical analyzer (TMA) is used to heat the metal clad laminate to 288°C and measure the time it takes for delamination to occur.

[0128] (Applicable): DIAEA-DVA copolymers can be used in automotive coating applications, such as refinish, primer, basecoat, undercoat, overcoat, clearcoat, etc. Power cables can be derived from thermosetting polymers, such as DIAEA-DVA copolymers, particularly cables for high voltage applications, useful for both alternating current (AC) and direct current (DC) applications.

[0129] In embodiments, the DIAEA-DVA copolymer (with fillers and optionally other dielectric polymers) can be used in the preparation of prepregs, laminates, or printed circuit boards (PCBs).

[0130] In embodiments, DIAEA-DVA copolymers (including fillers and optional other dielectric polymers) are used in the manufacture of copper clad laminates (CCLs). Such laminates can be used to fabricate components such as flexible or rigid laminate circuit boards that can be incorporated into end-use devices such as televisions, computers, laptop computers, tablet computers, printers, mobile phones, video games, DVD players, stereos, electronic encapsulants, and other consumer electronic products.

[0131] The laminates can be used in high frequency applications, such as signal frequencies above 10 GHz, including automotive antennas, cell phone base station antennas, high performance servers, collision avoidance radar, base station servers, routers, etc.

[0132] (Analysis method): In an embodiment, the laminate includes a first insulating layer comprising a DIAEA-DVA copolymer optionally blended with another dielectric polymer, further comprising a specified amount of filler. This first insulating layer is disposed adjacent to a second insulating layer comprising a conventional dielectric polymer material, such as glass-filled epoxy. Each layer is defined not only by its composition but also by its electrical properties—specifically, its dielectric constant (Dk) and dissipation factor (Df) at 10 GHz—and by specified relative thicknesses.

[0133] Cross-sectional analysis of the laminate may be performed using cryogenic microtomy, focused ion beam (FIB) milling, or mechanical sectioning to detect the presence of the claimed layered structure. The resulting cross-section may be examined using optical microscopy or scanning electron microscopy (SEM) to determine the number, order, and relative thickness of layers. The first insulating layer may be further characterized for filler loading and morphology using energy dispersive X-ray spectroscopy (EDS / EDX) or thermogravimetric analysis (TGA), confirming that the filler is present in a defined range (e.g., 30-60 wt%) and has a preferred particle size (e.g., 3-5 μm).

[0134] To confirm the dielectric properties of each individual layer, samples of the separated layers may be tested according to ASTM D2520 or equivalent high-frequency methods to measure Dk and Df at 10 GHz. When layer separation is not feasible, spatially resolved dielectric characterization may be performed using scanning microwave microscopy (SMM), which allows local measurement of Dk and Df across the laminate cross-section with micron-scale precision. These methods can confirm that the copolymer layer has a relative permittivity of less than 2.8 and a dissipation factor of less than 0.002, while the adjacent dielectric polymer exhibits a higher Dk and Df, within the limits specified in the claims (e.g., Dk less than 5.0, Df less than 0.05).

[0135] In certain cases, modeling techniques may be used to estimate the dielectric contribution of individual layers from bulk measurements, using known dielectric values ​​and thickness data to reconstruct laminate performance and account for the presence of high-performance copolymer layers. Spectroscopic techniques such as Fourier transform infrared (FTIR) mapping, Raman spectroscopy, or solid-state nuclear magnetic resonance (NMR) may further be used to identify the chemical structure of the copolymer layers and distinguish them from conventional dielectric polymers.

[0136] The molecular composition of the DIAEA-DVA copolymer is 1 H) and carbon ( 13 The copolymers can be detected in the laminates using nuclear magnetic resonance (NMR) spectroscopy, including C) NMR. Characteristic chemical shifts corresponding to the alkenyl and aromatic moieties of both the diisoalkenyl arene and divinylarene units can be identified in the NMR spectrum. Integration of the relevant peaks allows for quantitative determination of the molar ratio of the two monomer units, thereby confirming compliance with the claimed molar ratio range (15:1 to 1:15). Copolymer samples can be dissolved or swollen in a suitable deuterated solvent to enable such analysis using a high-field NMR spectrometer. [Example]

[0137] The following examples are intended to be non-limiting.

[0138] The following materials and test methods are used:

[0139] Metal foil - Cu foil with a thickness of 25 to 50 μm and a surface roughness of 0.5 to 5 mm.

[0140] First insulating layer - DIAEA-DVA copolymer (15:1 to 1:15), filler, optional first dielectric polymer (linear triblock copolymer based on styrene and ethylene / butylene).

[0141] Second insulating layer - Epoxy Resin Impregnated Fiberglass (FR4). Woven fiberglass fabric with a flame-retardant epoxy resin binder.

[0142] The other dielectric polymer (SE / BS) is a linear triblock copolymer based on styrene and ethylene / butylene, having a molecular weight of 55 kg / mol, a butylene unit content of 39%, and a vinyl aromatic unit content of 31% by weight.

[0143] Other dielectric polymers Brominated epoxy-tetrabromobisphenol A epoxy resins having a molecular weight (Mn) of 1000-5000 g / mol, an epoxy equivalent weight (EEW) of 350-500 g / eq, a Tg of 130-150°C, and a viscosity of about 1.2-1.3 g / cm 3 Those with a density of

[0144] Comparative sample 5 - a commercial halogen-free epoxy resin material sandwiched between two metal foils (Cu) with a fiberglass laminate (0.2 mm) as the insulating layer.

[0145] Comparative sample 6 - a commercial PPE material sandwiched between two metal foils (Cu) with a fiberglass laminate (0.2 mm) as the insulating layer.

[0146] Glass transition temperature (T g ) is measured by dynamic mechanical analysis (DMA) according to ASTM 4065. Temperature sweep experiments were performed from -80 to 200 °C with a heating ramp of 2 °C / min and 10 rad / s in shear mode unless otherwise indicated, to obtain the storage modulus (G'), loss modulus (G"), and loss factor (tan δ) as a function of temperature.

[0147] Example 1 - Preparation of the First Insulating Layer: The first insulating layer is prepared using a copolymer of DIAEA-DVA, a filler, and optionally another dielectric polymer. A film is formed by solution-casting the DIAEA-DVA copolymer composition onto a polyethylene terephthalate (PET) substrate. After casting, the film is dried at room temperature by transferring it onto a PET release liner. It is then heat-cured by heating at temperatures ranging from 120°C to 180°C. The resulting film exhibits the following properties: a gel content greater than 90%, a Dk less than 2.8, and a Df less than 0.002.

[0148] Example 2 - Preparation of Second Insulating Layer: The second insulating layer is produced by impregnating glass fibers (0.3 mm thick) with epoxy resin (a dielectric polymer) in a weight ratio of 80:20 to 90:10 (epoxy:glass fiber). Impregnation is carried out by immersing the glass fibers in an organic solvent selected from methyl ethyl ketone (MEK), cyclohexane, toluene, tetrahydrofuran (THF), or mixtures thereof. After impregnation, the material is dried and subjected to a heat treatment at 80°C to 180°C for a duration of 1 to 10 minutes. The final second insulating layer demonstrates a Dk of less than 5 and a Df of less than 0.05.

[0149] (Examples 3 to 6) Fabrication of laminated plate structure Examples 3 to 6 illustrate various embodiments of the laminate structure, as summarized in Table 1. In each case, a 50 μm thick copper foil is laminated onto the first insulating layer. The assembly is subjected to a vacuum press under the following conditions: pressing temperature: 190° C., holding time: 90 minutes, and pressure: 400 N.

[0150] [Table 1]

[0151] Table 2 summarizes the properties of Samples 1-4 prepared according to Examples 3-6. For comparison, the table also includes the properties of Comparative Samples 5 and 6, which represent conventional products. All samples, including the Comparative Examples, were prepared according to the process outlined in Example 3.

[0152] [Table 2]

[0153] The laminate samples of the present invention (Samples 1-4) demonstrated superior performance across key parameters when compared to conventional samples. Sample 2 exhibited the lowest coefficient of thermal expansion (15.55 ppm / °C), comparable to commercial materials, while Samples 1 and 4 exhibited higher, but controlled, expansion. Thermal stability was significantly improved for Samples 2 and 3, with decomposition thresholds of 450°C, significantly exceeding those of the comparative examples (320-370°C). All samples, including the comparative example, exceeded the thermal decomposition time threshold of 60 minutes (T288), demonstrating adequate resistance to long-term high-temperature exposure. Dielectric properties were significantly enhanced for the inventive samples, with Sample 3 achieving the lowest dielectric constant (Dk = 2.45) and Sample 2 exhibiting the lowest dissipation factor (Df = 0.000478), both of which were substantially superior to the comparative samples (Dk > 3.4, Df max 0.0023). These results collectively demonstrate that the compositions of the present invention provide a balanced combination of thermal dimensional stability, high heat resistance, and low dielectric loss, making them suitable for demanding high frequency electronic applications.

[0154] As used herein, the term "comprising" means inclusive of the element or step identified according to that term, but not exclusive of any such element or step, and that embodiments may include other elements or steps. While the terms "comprising" and "including" have been used herein to describe various aspects, the terms "consisting essentially of" and "consisting of" can be used in place of "comprising" and "including" to provide more specific aspects of the present disclosure, and are also disclosed. [Explanation of symbols]

[0155] 101 First metal foil layer 102 first dielectric insulating layer 103 layers 104 Second Dielectric Insulation Layer 105 Second metal foil layer 203 Glass-reinforced dielectric layer 301 Metal foil layer 302 Dielectric layer 303 Dielectric Layer 304 Metal foil layer 402 Dielectric layer

Claims

1. A laminate comprising: a) a first metal foil; b) a first insulating layer disposed on the first metal foil, the first insulating layer having a thickness of 3 to 20 μm, a Dk of less than 2.8, and a Df of less than 0.002; (i) 40 to 70 weight percent of a first dielectric polymer, a copolymer of (a) a diisoalkenyl arene and (b) a divinylarene, the molar ratio of (a) to (b) being from 15:1 to 1:15; (ii) 30 to 60 wt. % of a filler, and (iii) 0 to 20% by weight of another dielectric polymer a first insulating layer comprising: c) a second insulating layer disposed on the first insulating layer, the second insulating layer having a thickness of 60 to 120 μm greater than the thickness of the first insulating layer, a Dk of less than 5.0, and a Df of less than 0.05; (i) 30 to 60% by weight of glass fibers; (ii) 0 to 30 wt. % filler, and (iii) 20 to 50% by weight of other dielectric polymers a second insulating layer Including, the other dielectric polymer is selected from the group consisting of polyphenylene ether, cyclic polyolefin, polydicyclopentadiene, polyester, styrenic block copolymer, polyolefin, polytetrafluoroethylene, polyetherimide, maleimide resin, cyanate ester resin, epoxy resin, phenolic resin, benzoxazine resin, polyamide resin, polyimide resin, polyphenylene sulfide, polysulfone, polyesterimide, polyethersulfone, polyetherketone, polyurethane, polyetherethersulfone, liquid crystal polymer, polyacrylate, and mixtures thereof; the first insulating layer is disposed between the first metal foil and the second insulating layer; The laminate is a dielectric constant (Dk) of less than 5; Dissipation factor (Df) less than 0.01 and All of the Dk and Df are measured at 10 GHz according to ASTM D2520. Laminated board.

2. (d) a third insulating layer disposed on the second insulating layer, the third insulating layer having the same composition as the first insulating layer; and (e) a second metal foil disposed on the third insulating layer; wherein the second insulating layer is disposed between the first and third insulating layers. The laminate of claim 1 .

3. The laminate of claim 1 further comprising the second metal foil, the second insulating layer being disposed between the first insulating layer and the second metal foil.

4. The first insulating layer 40 to 70% by weight of said copolymer of (a) diisoalkenyl arene and (b) divinylarene; 30 to 60% by weight of the filler, and 2 to 10% by weight of another dielectric polymer The laminate according to any one of claims 1 to 3, comprising:

5. said copolymer of (a) diisoalkenyl arenes and (b) divinylarenes being a decomposition temperature of greater than 350°C by thermogravimetric analysis at 5% weight loss measured according to ASTM E1131, and Glass transition temperature (Tg) above 200°C measured according to ASTM D3418 The laminate according to any one of claims 1 to 3, comprising:

6. The laminate of any one of claims 1 to 3, wherein the second insulating layer is at least 15% thicker than the first insulating layer.

7. The laminate according to any one of claims 1 to 3, wherein the first insulating layer has a thickness in the range of 5 to 10 µm, and the second insulating layer has a thickness in the range of 80 to 100 µm.

8. The laminate according to any one of claims 1 to 3, wherein the first insulating layer has a relative dielectric constant (Dk) of less than 2.5 and a dielectric loss tangent (Df) of less than 0.0015.

9. The laminate according to any one of claims 1 to 3, further comprising an adhesive layer disposed on one or both sides of the second metal foil.

10. 4. The laminate according to claim 1, wherein the divinylarene comprises a combination of m-ethylvinylbenzene and p-ethylvinylbenzene in an amount of less than 35% by weight based on the total weight of the divinylarene.

11. said copolymer of (a) diisoalkenyl arene and (b) divinylarene, based on the total weight of said copolymer (a) 30 to 95 weight percent of polymerized diisoalkenyl arenes; (b) 5 to 70 weight percent of polymerized divinylarene, and (c) 0 to 15% by weight of other polymerizable monomers The laminate according to any one of claims 1 to 3, comprising:

12. 4. The laminate according to claim 1, wherein the diisoalkenyl arene is a diisopropenyl benzene containing more than 75% by weight of m-diisopropenyl benzene based on the total weight of the diisopropenyl benzene.

13. The diisoalkenyl arene a water content of less than 150 ppm; a 4-tert-butylcatechol content of less than 120 ppm, and Hazen (APHA) color of less than 50 measured in a 10 wt % solution of diisoalkenyl arene in solvent according to ASTM D1209 The laminate according to any one of claims 1 to 3, comprising at least one of the following:

14. The divinylarene is a 4-tert-butyrocatechol (p-TBC) content of less than 1200 ppm; a moisture content of less than 130 ppm, and Naphthalene content less than 1000 ppm The laminate according to any one of claims 1 to 3, comprising at least one of the following:

15. The laminate is a coefficient of thermal expansion (CTE) of less than 30 ppm / °C measured using TMA over the range of -50 to 300°C; Heat resistance (T288) at 300°C for more than 60 minutes measured according to IPC TM650, and 90° peel strength to metal greater than 0.6 N / m measured according to IPC 650 2.4.19 The laminate according to any one of claims 1 to 3, comprising:

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