Curable composition and dielectric material for semiconductor applications

Abstract

A curable composition is provided which can be used to make a dielectric material. The curable composition comprises a polymerizable organic portion. The polymerizable organic portion comprises a polymerizable hydrocarbon resin, at least one crosslinking agent, where the crosslinking agent comprises one or more nitrogen atoms and one or more oxygen atoms, and at least one polymerizable thermoplastic. In some embodiments, an inorganic filler is added to the curable composition. The dielectric material can have a Dk < 3.0 at 10 GHz and a Df < 0.0035 at 10 GHz, as well as a CTE < 50 ppm / °C across a temperature range of 25 to 150 °C.

Description

[0001] CURABLE COMPOSITION AND DIELECTRIC MATERIAL FOR SEMICONDUCTOR APPLICATIONS Field The invention relates to a curable composition that can be formed into a dielectric material that can be used as a build-up film for integrated circuit (IC) construction. The dielectric material exhibits low dielectric loss, a low coefficient of thermal expansion (CTE), and reduced warpage. The present invention also relates to an IC article that includes the dielectric material. The provided IC articles can be especially useful, for example, in high frequency communication applications, e.g., 5G communications. Background With the recent emergence of artificial intelligence (AI) and 5G, semiconductor packaging requires a higher level of integration and ultra-fine technology. In the server and data center fields, trends include increasing numbers of I / O (input / output) and package layers. As a result, the dielectric materials used need to have low warpage to meet the strict thermal dimensional stability demands. Some components of integrated circuit packaging require curable films that can be thermally laminated onto substrates and then cured in place at elevated temperatures (e.g., 180 to 200 degrees Celsius) to form a thermoset composition with a high glass transition temperature (e.g., greater than 110 degrees Celsius). Although conventional epoxy resins can be used to provide desirable thermosetting materials, they often have a dielectric constant (Dk) and a dielectric loss tangent (i.e., dissipation factor (Df)) that are unacceptably high. Areas requiring high-speed operation and low delay, such as server and autonomous, are required to employ packaging materials with low Dk and low Df at high frequency. Thus, alternative thermosetting compositions are desired, particularly in the integrated circuit (IC) packaging space. Summary of the Invention There is a need for low loss dielectric material solutions for IC packaging substrate applications, in particular, build-up materials and bonding solutions. The claimed invention provides curable and cured resin compositions that have excellent dielectric properties, low warpage, and / or good mechanical strength. In one aspect of the invention, a curable composition is provided. The curable composition comprises a polymerizable organic portion. The polymerizable organic portion comprises a polymerizable hydrocarbon resin, at least one crosslinking agent, wherein the crosslinking agent comprises one or more nitrogen atoms and one or more oxygen atoms, and at least one polymerizable thermoplastic. The curable composition also comprises at least 35% by weight based on solids of an inorganic filler. In another aspect of the invention, a dielectric material is derived from a curable composition. The curable composition comprises a polymerizable hydrocarbon resin, at least one crosslinking agent, wherein the crosslinking agent comprises one or more nitrogen atoms and one or more oxygen atoms, and at least one polymerizable thermoplastic. The curable composition also comprises at least 35% by weight of an inorganic filler based on the total weight of solids in the curable composition. Brief Description of the Drawings The invention will now be described in more detail with reference to the following figures exemplifying particular embodiments of the invention: FIG.1 is a schematic cross section view an IC chip construction that includes a dielectric material according to an aspect of the present invention. It should be understood that numerous other modifications and embodiments can be devised by those skilled in the art, which fall within the scope of the disclosure. The figure may not be drawn to scale. Detailed Description According to an embodiment of the invention, a curable composition can be converted into a cured composition, which is a dielectric material. The dielectric material can be used as an electrically insulating film, such as a low loss build-up film for semiconductor devices, such as for IC chips to be used in 5G communications applications. The dielectric material can have very favorable dielectric and thermal properties. For example, material dielectric property requirements for use in 5G communications applications can include low loss dielectric materials that have a Dk < 3.0 at 10 gigahertz (GHz) and a Df < 0.0100 at 10 GHz. In addition, the build-up film should have a suitably low CTE value to match the CTE values of the core substrate and the copper layer(s) of an IC chip construction in order to avoid potential thermal mismatch issues. Low CTE build-up films can also help reduce potential warpage. In some embodiments, the dielectric material has a CTE < 100 ppm / °C across a temperature range of 25 to 150 °C (inclusive). The addition of one or more inorganic fillers can further lower the CTE. For example, the dielectric material can have CTE < 50 ppm / °C across a temperature range of 25 to 150 °C. The dielectric materials as disclosed herein are made from a curable composition comprising a polymerizable organic portion and optionally, an inorganic filler. The polymerizable organic portion of the curable composition includes those organic chemical components having polymerizable groups that can be linked together to form polymer chains or networks in a polymerization or curing process. The polymerizable organic portion comprises a balance of several resins that help yield a low loss, low CTE material. One such resin is a polymerizable hydrocarbon (HC) resin. In one aspect, the polymerizable hydrocarbon resin comprises a free-radically polymerizable hydrocarbon resin. As such, this resin is a non-epoxy based resin. In some preferred embodiments, the polymerizable hydrocarbon resin comprises an addition-polymerized norbornene-based resin comprising a plurality of addition-polymerized norbornene-based monomeric units. As used herein, the term “addition-polymerized norbornene-based monomeric unit” describes a structure of the following formula (I) In Formula (I), each R1 and R2 is or a C1-C12 hydrocarbyl group (in other words, a group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or even 12 carbon atoms). The C1- C12 hydrocarbyl groups may be saturated or unsaturated, and may contain one or more carbon-carbon double bonds or carbon-carbon triple bonds. In some embodiments, the C1- C12 hydrocarbyl groups are alkenyl or alkylidene groups. Exemplary C1-C12 hydrocarbyl groups include methyl, ethyl, vinyl, ethylidene, propylidene, butylidene, hexylidene, octylidene, decylidene, dodecylidene, butyl, butenyl, hexyl, hexenyl, octyl, octenyl, decyl, decenyl, dodecyl, dodecenyl, phenyl, tolyl, naphthyl, and styryl groups. In some embodiments, R1 and R2 together form a saturated or unsaturated hydrocarbon ring structure fused onto the remainder of the norbornene-based monomeric unit. Examples of such fused- ring-containing monomeric units are shown in the following structures: The asterisks (*) in the above structures indicate sites of attachment to other monomeric units or terminal groups. In some embodiments, the addition-polymerized norbornene-based resin further comprises additional addition-polymerized monomeric units which are not norbornene-based. Such units may be derived from any unsaturated hydrocarbon monomers, including linear, branched or cyclic C2-C12 alkenes. In some embodiments, these non-norbornene-based addition-polymerized monomeric units are derived from hydrocarbon monomers with one or more unsaturated groups, such as ethylene, propylene, 1-butene, butadiene, 1-hexene, hexadiene, 1-octene, octadiene, 1-decene, decadiene, 1-dodecene, dodecadiene, styrene, divinylbenzene, trivinylcyclohexane, and the like. For the polymerizable hydrocarbon resin to be polymerizable at least one of the addition-polymerized monomeric units must comprise a pendent unsaturated group. In some embodiments, the addition-polymerized norbornene- based resin comprises at least 1%, 2%, 3%, 5%, 10%, 15%, 20%, 25%, 30%, or 40% (by mol %) of monomeric units comprising a pendent unsaturated group. In some aspects, a polymerizable HC resin can be formed as a mixture of different hydrocarbon resins that help provide low dielectric loss levels. In some aspects, the polymerizable HC resin can be formed as a mixture of polymerizable hydrocarbon resins with different molecular weights. In particular, the polymerizable HC resin can include a low-molecular-weight polymerizable HC resin having a number average molecular weight (Mn) less than 300, 500, 800 or 1000 grams per mole (g / mol), a medium-molecular-weight polymerizable HC resin having a Mn of at least 300, 500, 800 or 1000 g / mol and at most 10000, 15000, 20000 or 30000 g / mol, and a high- molecular-weight polymerizable HC resin having a Mn no less than 10000, 15000, 20000 or 30000 g / mol. The molecular weight may be determined by gel permeation chromatography as known in the art. The low-molecular-weight polymerizable HC resin can comprise a cyclic olefin, such as a norbornene-based compound having a pendent polymerizable group as shown in Formula (II) where the pendent group R3 is an alkenyl or alkylidene group. The alkenyl or alkylidene group can have 2 or more carbon atoms such as, for example, 2 to 10 carbon atoms. The number of carbon atoms can be at least 2, at least 3, or at least 4 and up to 10, up to 8, up to 6, or up to 4 carbon atoms. Examples of the norbornene-based compound of Formula (II) are of Formula (II-A) or (II-B). Suitable amounts of HC resin can be from about 1, 2, 3, 4, or 5 % to 10, 11, 12, 13, 14 or 15 wt.% of the polymerizable organic portion. In general, the medium- and high-molecular-weight polymerizable HC resins used in the examples provided herein are polymers called addition-polymerized polynorbornene copolymers. As used herein, the term “addition-polymerized polynorbornene copolymers” refers to addition-polymerized norbornene-based resins that comprise two or more different norbornene-based monomeric units along their main polymeric backbone (ignoring side chains and terminal groups) and do not comprise any non-norbornene-based monomeric units in the main polymeric backbone. The monomeric units in addition-polymerized polynorbornene copolymers ay be randomly distributed along the main polymeric backbone. In some embodiments, the addition-polymerized polynorbornene copolymer has the following structure: , y or 0.40, or 0.50; y / (x + y + z) is at least 0.10, 0.20, 0.25, 0.30, 0.35, 0.40, or 0.45 to at most 0.50, 0.60, 0.70, 0.80, or 0.90; z / (x + y + z) is at least 0.10, 0.20, 0.25, 0.30, 0.35, 0.40, or 0.45 to at most 0.50, 0.60, 0.70, 0.80, or 0.90; and the polymer comprises no additional monomeric units in its main polymeric backbone beyond those represented by x, y, and z. In some embodiments, the monomeric units represented by x, y, and z are present in the ratio of 10 / 45 / 45, and the monomeric units are randomly distributed throughout the chain. Such addition polymerized polynorbornene copolymers can be synthesized as described in further detail below, and in accordance with the procedures described in PCT Publication No. WO2024 / 100476 (Townsend et al.), incorporated by reference herein in its entirety. In some examples, the polymerizable organic portion comprises two polymerizable hydrocarbon resins having the same chemical composition (meaning they are made from identical mixtures of monomers). By using a mixture of different molecular weight polymerizable HC resins, the CTE of the resulting cured composition may be controlled. The low-molecular-weight polymerizable HC resin can provide low CTE and low Df. The higher- molecular-weight polymerizable HC resins can provide low Dk and Df across a range of frequencies and temperatures, but with a higher CTE in the cured composition. Suitable amounts of the medium-molecular-weight polymerizable HC resin can be from about 10, 12, 15, or 20 wt.% to 40, 45, 50, or 55 wt.% of the polymerizable organic portion. Suitable amounts of the high-molecular-weight polymerizable HC resin can be from about 3, 4, 5, or 7 wt.% to 8, 10, 12, or 15 wt.% of the polymerizable organic portion. In some embodiments, the polymerizable HC resin is an addition-polymerized polynorbornene copolymer having norbornene-based monomeric units with pendent polymerizable groups thereon; such polymerizable groups include alkenyl, or alkylidene groups. The polymerizable organic portion of the curable composition further comprises at least one crosslinking agent. A crosslinking agent is a compound that comprises at least two polymerizable groups, which can react with pendent polymerizable groups on polymer chains to link the chains together during curing. In some embodiments, the curable composition can comprise a total crosslinking agent amount of 12, 15, 18, 20, or 25 wt.% to 30, 35, 40, 45, or 50 wt.% of the polymerizable organic portion. In one embodiment, the curable composition comprises a crosslinking agent having one or more nitrogen atoms and one or more oxygen atoms. Exemplary crosslinking agents include tri(methyl)allyl isocyanurate (TMAIC), triallyl isocyanurate (TAIC), tri(methyl)allyl cyanurate, poly-triallyl isocyanurate (poly-TAIC), triallyl cyanurate (TAC), xylylene- bis(diallyl isocyanurate) (XBD), N,N'-m-phenylene bismaleimide, and combinations thereof. In some embodiments, the curable composition can comprise TAIC. In some embodiments, the curable composition can comprise TAIC at 1, 2, 3, 4, or 5 wt.% to 6, 8, 10, 12, or 15 wt.% of the polymerizable organic portion. In other embodiments, the crosslinking agent comprises a maleimide, such as a bismaleimide (BMI) compound. In one example, the bismaleimide compound includes two maleimido groups and at least one C36 hydrocarbon group that has 36 carbon atoms and 0 to 3 carbon-carbon double bonds. These C36 groups typically have 69, 70, 71, or 72 hydrogen atoms. Although these groups are typically predominantly aliphatic, some C36 groups include a single 6-membered aromatic ring. In some embodiments, the crosslinking agent comprises are at least two or more C36 groups. Generally, crosslinking agents tend to decrease the CTE of the cured composition. While this is a desirable feature, many crosslinking agents tend to increase the Dk and the Df of the cured composition. For use of the cured composition as a dielectric material in the preparation of integrated circuit packaging systems, both a low Dk and a low Df are desired. Surprisingly, the bismaleimide crosslinking agents having at least one C36 group with 0 to 3 carbon-carbon double bonds tend to decrease both the Dk and the Df relative to other common crosslinking agents. Thus, using these bismaleimide crosslinking agents advantageously can result in the formation of cured compositions with low Dk at 10 GHz (e.g., less than 3.0), low Df at 10 GHz (less than 0.0035), and low coefficient of thermal expansion (less than 100 ppm / °C or less than 50 ppm / °C) in the temperature range of 25 to 150 °C. Several BMI compounds are commercially available from Designer Molecules, Inc. (San Diego, CA, USA), such as BMI-2500. In one embodiment, the BMI compound is a BMI oligomer with the following chemical structure:

[0002] In some embodiments, the curable composition can comprise a BMI compound at 5, 10, 15, 20 or 25 wt.% to 30, 32, 35, 40, or 45 wt.% of the polymerizable organic portion. The polymerizable organic portion of the curable composition further comprises at least one polymerizable thermoplastic. The at least one polymerizable thermoplastic can help improve film rheology and lower the overall CTE in the cured composition. For example, the at least one polymerizable thermoplastic can provide flexibility, strength, thermal stability, and processing stability. One such class of polymerizable thermoplastics is polyphenylene ethers (PPE). These materials can promote a rigid structure and high heat resistance properties in the cured composition. In some embodiments, the at least one polymerizable thermoplastic comprises a polyphenylene ether that includes at least two free-radically polymerizable groups. In one embodiment, the PPE has the following chemical structure: are integers > 1, and wherein x + y = 5-30. In some embodiments, the curable composition comprises polymerizable thermoplastic at 10, 15, or 20 wt.% to 25, 30, 35, 40, 45, or 50 wt.% of the polymerizable organic portion. In some embodiments, the weight ratio of the polymerizable hydrocarbon resin (A) to the total amount of crosslinking agent (B) and polymerizable thermoplastic (C) in the curable composition (in other words(A) / ((B)+(C)) is at least 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, or 0.8. In some embodiments, (A) / ((B)+(C)) is at most 0.5, 0.7, 0.8, 0.9, 1.0.1.5, 2.0, 2.5, or 3.0. In some embodiments, the weight ratio of the addition-polymerized norbornene-based resin (AA) to the total amount of crosslinking agent (B) and polymerizable thermoplastic (C) in the curable composition (in other words, (AA) / ((B)+(C)) is at least 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, or 0.8. In some embodiments, (AA) / ((B)+(C)) is at most 0.5, 0.7, 0.8, 0.9, 1.0.1.5, 2.0, 2.5, or 3.0. In some embodiments, the curable composition comprises a solvent, which is used to assist in the coating out of the composition to achieve thin formats. Such solvents include non-polar solvents such as toluene, hexanes, benzene, etc. In some embodiments, the curable composition comprises at least 25, 30, 40 or even 50 % and at most 60, 70, 80, or even 90 % by weight of solvent. Because the curable composition may comprise large amounts of solvent, the amounts of inorganic filler and other additives in the curable composition are herein reported based on solids weight. In other words, the amount of inorganic filler present is reported as a weight percent versus the weight of the solids (i.e., non-solvent) present in the composition. To further improve the CTE, an inorganic filler may be used. In one aspect, the curable composition comprises at least 35, 50, 60, 70, 75, 80, or even 90 wt.% inorganic filler based on the total weight of solids in the curable composition (i.e., the total weight of the polymerizable hydrocarbon resin, crosslinking agent, polymerizable thermoplastic, inorganic fillers and any other solids used). Generally, the high amounts of inorganic filler provide improved thermal properties, however some polymerizable component (for example at least 10, 15, or 20 wt.%) is necessary, to act as a matrix for the inorganic filler. Exemplary inorganic fillers include hollow silica, spherical silica, quartz powder, aluminum nitride, boron nitride, zinc oxide, and combinations thereof. In these examples, hollow silica refers to microspheres having a hollow core and a shell of silicon dioxide, whereas spherical silica refers to solid (non-hollow) microspheres of silicon dioxide. Typically, the inorganic fillers have an average particle size of at least 0.3, 0.5, 0.8, or even 1 micron up to at most 2, 4, 5, 8, or even 10 microns. Such particle sizes may be measured using techniques known in the art such as laser diffraction or microscopy. The shape of the inorganic filler is not limited and may be any of spherical, ellipsoid, flake-shaped or irregular. In some embodiments, inorganic fillers may be surface-functionalized with organic groups (e.g, silyl, aryl, alkyl, alkenyl, alkylsilyl, alkenylsilyl, or arylsilyl groups). Such surface-modified inorganic fillers are considered as inorganic fillers for purposes of this description and would not be included in the percentages given for the polymerizable organic portions provided herein. In some embodiments, the inorganic filler comprises at least one silica. In some embodiments, the silica filler has a particle size distribution (D50) preferably less than 10 μm. In this context, (D50) represents a 50thpercentile particle size for the given size distribution of particles. In some embodiments, the curable composition comprises 0.5, 1, 2, or 4 wt.% to about 10, 11, 12, 13, 14, 15 or 20 wt.% hollow silica versus the total weight of the solids in the composition. In some embodiments, the curable composition comprises about 10, 12, 15, 20, 25, 30, 31, 32, 33, 34 or 35 wt.% to about 50, 55, 60, 65, or 70 wt.% spherical silica versus the total weight of the solids in the composition. In some embodiments, the inorganic filler comprises boron nitride (BN). In some embodiments, the BN filler has a particle size distribution (D50) of at least 0.3, 0.4, 0.8, or 1 μm and at most 1, 2, 3, 4, 5, or preferably 10 μm. In one example, the BN filler has a particle size distribution (D50) from about 0.3 μm to about 5.0 μm. In one embodiment, the curable composition comprises about 10, 15, 20, or 25 wt.% to about 35, 40, 45, 50, or 55 wt.% BN based on the total solids weight of the curable composition. In some embodiments the curable composition comprises about 15 wt.% to about 55 wt.% BN based on the total solids weight and at least one of hollow silica and spherical silica, wherein optionally the combined amount of hollow silica and / or spherical silica is from about 10 wt.% to about 70 wt.% based on the total solids weight of the curable composition. In some embodiments, non-polymerizable organic additives, such as styrene and ethylene / butylene copolymer available under the trade designation “Kraton G1657” from Kraton Corp., (Houston, TX, USA), can be incorporated in the curable composition. The curable composition can comprise from about 0.1, 0.5, 1, 2, or 3 wt.% to about 5, 10, 15, or 20 wt.% of these additives based on the total solids weight of the curable composition. Other additives, such as initiators, catalysts, colorants and stabilizers, can also be utilized. In some embodiments, the curable composition comprises a thermal radical initiator, such as those available under the trade designation “Luperox 101” from Arkema (Colombes, France). The curable composition as disclosed herein may be coated onto a substrate using techniques known in the art such as knife-coating, die-coating, gravure coating, etc. Generally, the curable composition is coated such that the resulting dried curable composition or cured dielectric layer has a thickness from about 1, 3, 5, 10, 15, or 20 microns to about 30, 40, 50, 75, 100, 200, 300, or 400 microns. After depositing the curable composition on the substrate, the curable composition may be dried at room temperature or by heating at temperatures up to 100 °C to remove any solvents. The curable composition is then heated (or cured) at temperatures of about 150, 160, 170, or 180 °C to 190, 200, 220, or 250 °C. Generally, the temperature is selected to polymerize the polymerizable components without adversely impacting (for example, decomposing) the constituents. A resulting dielectric material is produced. In some embodiments, the dielectric material comprises 0.5, 1, 2, or 4 wt.% to about 10, 11, 12, 13, 14, 15 or 20 wt.% hollow silica. In some embodiments, the dielectric material comprises about 10, 12, 15, 20, 25, 30, 31, 32, 33, 34 or 35 wt.% to about 50, 55, 60, 65, or 70 wt.% spherical silica. In some embodiments, the dielectric material comprises about 10, 15, 20, 25 to about 35, 40, 45, 50, or 55 wt.% BN. In some embodiments, the dielectric material comprises about 0.1, 0.5, 1, 2, or 3 wt.% to about 5, 10, 15, or 20 wt.% of non-polymerizable organic additives. In some embodiments, the dielectric material has acceptable mechanical properties, such as high modulus (e.g., at least 2.5 GPa) and good flexibility, where elongation is greater than 1.0, 1.4, 1.6, 1.8, or even 2.0%. As such, the dielectric material exhibits low warpage, for example less than 0.5, 0.4, 0.3, or even 0.25 millimeters (mm). In some embodiments, the dielectric material of the present disclosure has a glass transition temperature (Tg) of greater than 130, 140, 150, 160 or 170 °C. In some embodiments, the dielectric material used as an insulating film has a Dk value no more than 3.0, 2.8, 2.5, 2.3, or even 2.2 (at 10 GHz). In some embodiments, the dielectric material has a coefficient of thermal expansion (CTE) value less than 125, 100, 75, 50, 30, 25, 20, 15, or even 10 ppm / °C across a range of 25 °C to 150 °C. In some embodiments, the dielectric material used as an insulating film has a Df of less than 0.0100, 0.0050, 0.0040, 0.0035, 0.0025, or even 0.0020 (at 10 GHz). As further shown in the experiment section, the dielectric material described herein exhibits good thermal, mechanical, and / or dielectric properties. Accordingly, the dielectric material is suitable for use in semiconductor device applications, such as for integrated circuit construction. Fig.1 shows an example implementation of the dielectric material described herein as part of an integrated circuit chip 100. In this example, a dielectric material formed from the curable compositions described herein is utilized as a build-up film 110 that is disposed within a build-up film 110 / copper layer 130 stack that is disposed on either or both sides of an IC core substrate 120. By utilizing the curable compositions and cured compositions / build-up films described herein, the IC construction can interfere with electromagnetic signals to a lesser extent (due to the low Dk and Df values of the build-up film), especially as compared to conventional epoxy-based build-up films. Experiments and Examples Table 1: Materials Material Description Source Acetone Acetone MilliporeSigma (Burlington, MA, USA) Activated Carbon Activated carbon available under the trade Thermo Fisher Scientific designation DARCO G-60 (Waltham, MA, USA) Allyl[1,3-bis(2,6- Allyl[1,3-bis(2,6-diisopropylphenyl)imidazol- Strem Chemicals diisopropylphenyl)imidazol-2- 2-ylidene]chloropalladium(II) (Newburyport, MA, USA) ylidene]chloropalladium(II) Addition-polymerized polynorbornene copolymer (medium-m Synthesized as described in AP Polymer-1 olecular-weight polymerizable hydrocarbon resin; Mn < 20,000 Preparative Example 1 g / mol) below. Addition-polymerized polynorbornene Synthesized as described in AP Polymer-2 copolymer (high-molecular-weight Preparative Example 2 polymerizable hydrocarbon resin; Mn > 20,000) below. Bismaleimide oligomer available under the BMI-2500 trade designation BMI-2500 (crosslinking Designer Molecules Inc. agent) (San Diego, CA, USA) Boron Nitride Cooling Filler Platelets (D50 = BN 0.5μm) available under the trade designation 3M (St. Paul, MN, USA) CFP-001 Decyl norbornene 5-Decyl-2-norbornene Wiley Companies (Coshocton, OH, USA) 1,2-Dichloroethane 1,2-Dichloroethane Alfa Aesar (Ward Hill, MA, USA) Heptane n-Heptane MilliporeSigma Non-functionalized hollow silica available Hollow silica under the trade designation XF-600, having a Better Circuit Material reported average diameter of 0.7 µm. (Kaohsiung, TW) Styrene-ethylene-butylene-styrene linear Kraton G1657 triblock copolymer (non-polymerizable organic Kraton (Houston, TX, additive) available under the trade designation USA) KRATON G1657 2,5-Bis(tert-butylperoxy)-2,5-dimethylhexane LUPEROX 101 (thermal radical initiator) available under the Arkema trade designation LUPEROX 101 (Colombes, France) MEK Methyl ethyl ketone MilliporeSigma Norbornene 2-Norbornene Alfa Aesar 1-Octene 1-Octene Alfa Aesar Methacrylate-functionalized polyphenylene PPE ether oligomer available as NORYL SA-9000 SABIC (polymerizable thermoplastic) (Riyadh, Saudi Arabia) Pyridine Pyridine Alfa Aesar Sodium tetrakis[3,5- Sodium tetrakis[3,5- Alfa Aesar bis(trifluoromethyl)phenyl]borate bis(trifluoromethyl)phenyl]borate Vinyl silane functionalized spherical silica Spherical silica (1 μm) (D50 = 1.0μm) available under the trade Sibelco designation SSL-105 (Antwerp, Belgium) TAIC Triallyl isocyanurate (crosslinking agent) Mitsubishi Chemical (Tokyo, Japan) Toluene Toluene MilliporeSigma Tricyclohexylphosphine Tricyclohexylphosphine Alfa Aesar 5-Vinyl-2-norbornene (low-molecular-weight Vinyl norbornene polymerizable hydrocarbon resin; Mn < 500 MilliporeSigma g / mol) Test Methods Gel Permeation Chromatography (GPC) measurement The GPC equipment includes a 1260 Infinity II liquid chromatography system (comprised of isocratic pump, autosampler, column compartment and variable wavelength UV / vis detector) from Agilent Technologies (Santa Clara, CA, USA) operated at a flow rate of 1.0 mL / minute. The size exclusion column set was comprised of two PLgel 5 μm MIXED- C (300 millimeter (mm) length x 7.5 mm internal diameter) and a PLgel 5 μm guard column (50 millimeter (mm) length x 7.5 mm internal diameter) all from Agilent Technologies. The detection consisted of a miniDAWN 3 angle Light Scattering detector and an OPTILAB differential refractive index detector, both from Wyatt Technology Corporation (Santa Barbara, CA, USA). Data were collected and analyzed using software ASTRA version 8 from Wyatt Technology Corporation. The column compartment, UV / vis detector, and differential refractive index detector were set to 40 °C. The solvent and eluent (or mobile phase) consisted of tetrahydrofuran (stabilized with 250 parts per million of butylated hydroxytoluene) OMNISOLV grade from EMD Millipore Corporation (Burlington, MA, USA). Dielectric property measurement: Each cured composition was cut into a test piece with a width of 5 centimeters (cm) and a length of 5 cm. The test piece was measured using a TE mode Cavity Resonator (AET Inc., Kanagawa, Japan) and measured by an IPC-TM6502.5.5.13 method (The Institute for Interconnecting and Packaging Electronic Circuits. This method describes the nondestructive measurement of the Dk and Df of unclad dielectric substrates at microwave frequencies using a split cylinder resonator) at a measurement frequency of 10 GHz and a measurement temperature of 25 ℃. Dielectric constant (Dk) and dielectric loss tangent (Df) data were obtained. Coefficient of thermal expansion (xy-CTE): For each cured composition, a linear coefficient of thermal expansion was measured in a temperature range of 24 °C to 250 °C on a Q400 TMA instrument (TA Instruments, New Castle, DE, USA). The temperature ramp rate was 10 °C / min and the applied force was 50 Newtons (N). The values reported in the examples are for the portion of the temperature range from 25 °C to 150 °C. Glass transition temperature (Tg) Each cured composition was tested on a Discovery HR 20 Rheometer (TA Instruments). A tan δ curve was obtained across a temperature range of 0 °C to 300 °C, with a ramp rate of 10° C / min, a constant frequency of 10 Hertz (Hz), and a gap of 24 mm. The glass transition temperature (Tg) was determined by locating the peak in the tan δ curve. Thermal conductivity measurement: Each cured composition was cut into a test piece with a length of 25 mm and a width of 25 mm. The test piece was measured using a LW-9389 TIM Thermal Resistance and Conductivity Measurement Apparatus (LonGwin, Taoyuan, Taiwan) and measured by the ASTM D5470-17 (2017) method. This measurement used a pressure of 40 psi, a hot side temperature of 80 ℃, and a thermal equilibrium time of 30 minutes to obtain the thermal impedance. Thermal conductivity is calculated using the linear correlation between thermal impedance and thickness. The results are reported in Watts per meter Kelvin (W / m K). Young's modulus measurement Each cured composition was cut into a test piece with a length of 165 mm, a width of 13 mm, and a gauge length of 50 mm. The test piece was measured using an Instron 5564 Tensile Tester (Instron, Norwood, MA, USA) and measured by the ASTM D1000 (2017) method, at an extension rate of 305 mm / min at room temperature. The results are reported in gigapascals (GPa). Elongation measurement Each cured composition was cut into a test piece with a length of 165 mm, a width of 13 mm, and a gauge length of 50 mm. The test piece was measured using an Instron 5564 Tensile Tester (Instron, Norwood, MA, USA) and measured by the ASTM D1000 (2017) method, at an extension rate of 305mm / min at room temperature. The results are reported in percent (%). Warpage measurement A sheet of the curable composition (with a width of 15 cm, a length of 15 cm, and thickness of 100μm) was laminated on a 700μm-thick glass substrate. The laminated construction was measured using an FSM 413 C2C TTV (Frontier Semiconductor, Milpitas, CA, USA). The warpage was measured after heating the laminated construction at 180 ℃ for 1 h. A warpage value below 0.5 mm is considered desirable. Examples Preparative Example 1: AP Polymer-1 (medium-molecular-weight polymerizable hydrocarbon resin) 1-Octene (2.35 L) and heptane (78 mL) were added to a 5 liter flask equipped with mechanical stirrer, thermocouple, heating mantle, and nitrogen inlet. The temperature of the reaction flask was then increased to 50 °C while stirring at 150 rpm (revolutions per minute). Decyl norbornene (799 g), vinyl norbornene (409 g), and norbornene (71.8 g) were combined in a separate flask and agitated until a clear, homogenous solution was obtained. The catalyst solution was prepared by combining allyl(1,3-bis(2,6-diisopropylphenyl)imidazol-2- ylidene]palladium(II) chloride (0.859 g), tricyclohexylphosphine (0.841 g), sodium tetrakis(3,5-bis(trifluoromethyl)phenyl]borate (6.647 g), and 1,2-dichloroethane (50 mL) followed by stirring at room temperature for 30 minutes. The catalyst solution was then introduced to the reactor held at 50 °C and stirred for 1 minute before addition of monomer premix was initiated. Monomer premix was added at a constant rate of 8 mL / min to yield a total addition time of approximately 3 hours. As the viscosity of the polymerization increased, the stirring rate was likewise increased to a final rate of 270 rpm. The polymerization was allowed to proceed at 50 °C for 6.5 hours after initiation of monomer addition. Termination of the polymerization was then accomplished by adding pyridine (10 mL). To purify the polymer, the polymerization solution was diluted with additional heptane (100 mL) and activated carbon (10.6 g) was added before the solution was stirred for 1 hour. The polymerization solution was then filtered to remove activated carbon. The norbornene addition polymer was then precipitated from the filtrate using excess acetone (~ 6 L). The white polymeric solid was isolated by filtration and dried under reduced pressure to yield 1105 g of the product “AP-Polymer-1”. This polymer was analyzed by GPC and found to have Mn = 14700 g / mol. Preparative Example 2: AP Polymer-2 (high-molecular-weight polymerizable hydrocarbon resin) A preliminary monomer mixture of decyl norbornene (4008.6 g, 17.10 mol), vinyl norbornene (2055.3 g, 17.1 mol), and norbornene (357.8 g, 3.8 mol) was made by combining the components in a 20 L pail and stirring by hand. A preliminary catalyst mixture of 1,2- dichloroethane (1265.0 g), allyl[1,3-bis(2,6-diisopropylphenyl)imidazol-2- ylidene]palladium(II) chloride (4.35 g, 0.0076 mol), sodium tetrakis[3,5- bis(trifluoromethyl)phenyl]borate (33.68 g, 0.0380 mol), and tricyclohexylphosphine (4.26 g, 0.0152 mol) was made by combining the components in a 2 L amber glass bottle and stirring with a magnetic stir bar and plate at room temperature for 1 hour. A 20-gallon chemical reactor was inerted with nitrogen gas and charged with heptane (16204 g) and 1-octene (4264.4 g, 38.00 mol). The entirety of the preliminary catalyst solution was added to the reactor just after its 1 hour of stirring was complete. The reactor was sealed, the agitator was set to 100 rpm, and nitrogen gas was bubbled through the contents for 30 min. The reactor was then heated to 50 °C. Next, while the headspace of the reactor was still under a nitrogen flow, the preliminary monomer mixture was slowly added to the reactor at a rate of ~3175 g / hour (total addition time ~2 hours). Following monomer addition, the mixture was stirred and heated (50 °C) under nitrogen gas for an additional 3 hours. After the 3-hour period, the reaction was quenched by addition of 40 mL pyridine. The reactor was cooled to 21 °C and the contents were drained into 5-gallon (19-L) pails. The polymer was isolated from this crude reaction mixture as follows. The crude reaction mixture (roughly 21 wt.% polymer in solvent) was poured in a very thin stream into a 4-L beaker filled with ~2500 mL acetone. This resulted in agglomerations of thin, white polymer strings. These strings were cut up with scissors, stirred in a fresh beaker of acetone, filtered, and dried at 75 °C for 4 hours to yield the isolated polymer product “AP Polymer-2”. This polymer was analyzed by GPC and found to have Mn = 50200 g / mol.. General Procedure: Preparation of Coating Solutions The appropriate amounts of BMI-2500 and PPE (if applicable) were added to a plastic high-speed rotary mixer cup with lid, followed by a portion of toluene to dissolve them. The contents of the cup were mixed to form a solution. The appropriate amounts of all remaining components (other than inorganic filler) were then added to the cup. The contents of the cup were uniformly dispersed with a high-speed rotary mixer. For Examples without inorganic filler: this uniform dispersion was the coating solution. For Examples with inorganic filler(s): the inorganic filler(s) was / were then added to the cup, and the contents of the cup were uniformly dispersed with a high-speed rotary mixer to give the coating solution. The appropriate amounts of each component in each coating solution can be found below in the descriptions of each individual Example. General Procedure: Preparation of Curable Compositions from Coating Solutions A release-treated polyethylene terephthalate (PET) sheet (dimensions: 50 microns (μm) x 300 millimeters (mm) x 300 mm) for was used as a backing. Each coating solution was uniformly coated on the release-treated PET sheet using a die coater and dried at 90-100 degrees Celsius (℃) for 5 minutes (min) to obtain a dried curable composition layer on the release-treated side of the PET sheet. The coating was done such that the thickness of the dried curable composition was 40 microns (μm). General Procedure: Preparation of Cured Compositions from Curable Compositions The curable composition was transferred from the release-treated PET sheet to copper foil (thickness: 38 μm) using a heated-roll laminator at 90-105 ℃. The release-treated PET sheet was removed during this process. Next, the curable composition on copper foil was heated at 180-200 ℃ in an oven for 70-90 minutes to produce a cured composition. After heat curing, an etching solution (10 wt.% Ammonium persulfate solution in water) was used to remove the copper foil. Then, the sheet-like cured composition was rinsed with water and dried at 100 ℃ for 1 hour. Please note that the values provided for each Example are parts by weight of the coating solution and that the values shown in Tables 2 and 3 are weight percentages of the curable composition after the solvent has been removed. Comparative Example 1 (C-1) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight Vinyl norbornene 10 AP Polymer-1 70 AP-Polymer-2 10 TAIC 5 Kraton G1657 5 Luperox 101 1.1 Toluene 110 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Comparative Example 2 (C-2) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight BMI-2500 5 PPE 5 Vinyl norbornene 10 AP Polymer-1 60 AP-Polymer-2 10 TAIC 5 Kraton G1657 5 Luperox 101 1 Toluene 100 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Comparative Example 3 (C-3) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight BMI-2500 45 PPE 45 TAIC 5 Kraton G1657 5 Luperox 101 1 Toluene 100 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Example 1 (Ex 1) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight BMI-2500 20 PPE 10 Vinyl norbornene 10 AP Polymer-1 40 AP-Polymer-2 10 TAIC 5 Kraton G1657 5 Luperox 101 1 Toluene 100 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Example 2 (Ex 2) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight BMI-2500 10 PPE 20 Vinyl norbornene 10 AP Polymer-1 40 AP-Polymer-2 10 TAIC 5 Kraton G1657 5 Luperox 101 1 Toluene 100 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Example 3 (Ex 3) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight BMI-2500 30 PPE 15 Vinyl norbornene 5 AP Polymer-1 35 AP-Polymer-2 5 TAIC 5 Kraton G1657 5 Luperox 101 1 Toluene 100 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Example 4 (Ex 4) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight BMI-2500 15 PPE 30 Vinyl norbornene 5 AP Polymer-1 35 AP-Polymer-2 5 TAIC 5 Kraton G1657 5 Luperox 101 1 Toluene 100 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Example 5 (Ex 5) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight BMI-2500 40 PPE 20 Vinyl norbornene 7.5 AP Polymer-1 15 AP-Polymer-2 7.5 TAIC 5 Kraton G1657 5 Luperox 101 1 Toluene 100 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Example 6 (Ex 6) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight BMI-2500 20 PPE 40 Vinyl norbornene 7.5 AP Polymer-1 15 AP-Polymer-2 7.5 TAIC 5 Kraton G1657 5 Luperox 101 1 Toluene 100 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Example 7 (Ex 7) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight BMI-2500 9 PPE 4.5 Vinyl norbornene 1.5 AP Polymer-1 10.5 AP-Polymer-2 1.5 TAIC 1.5 Kraton G1657 1.5 Spherical Silica 70 Luperox 101 0.3 Toluene 138 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Example 8 (Ex 8) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight BMI-2500 9 PPE 4.5 Vinyl norbornene 1.5 AP Polymer-1 10.5 AP-Polymer-2 1.5 TAIC 1.5 Kraton G1657 1.5 Spherical silica 55 Hollow silica 15 Luperox 101 0.3 Toluene 138 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Example 9 (Ex 9) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight BMI-2500 9 PPE 4.5 Vinyl norbornene 1.5 AP Polymer-1 10.5 AP-Polymer-2 1.5 TAIC 1.5 Kraton G1657 1.5 Spherical silica 35 BN 35 Luperox 101 0.3 Toluene 138 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Example 10 (Ex 10) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight BMI-2500 9 PPE 4.5 Vinyl norbornene 1.5 AP Polymer-1 10.5 AP-Polymer-2 1.5 TAIC 1.5 Kraton G1657 1.5 Spherical silica 55 BN 15 Luperox 101 0.3 Toluene 138 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Example 11 (Ex 11) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight BMI-2500 9 PPE 4.5 Vinyl norbornene 1.5 AP Polymer-1 10.5 AP-Polymer-2 1.5 TAIC 1.5 Kraton G1657 1.5 Spherical silica 15 BN 55 Luperox 101 0.3 Toluene 138 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Example 12 (Ex 12) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight BMI-2500 9 PPE 4.5 Vinyl norbornene 1.5 AP Polymer-1 10.5 AP-Polymer-2 1.5 TAIC 1.5 Kraton G1657 1.5 Spherical silica 45 Hollow silica 5 BN 20 Luperox 101 0.3 Toluene 138 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Example 13 (Ex 13) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight BMI-2500 6 PPE 3 Vinyl norbornene 4.5 AP Polymer-1 12 AP-Polymer-2 4.5 TAIC 1.5 Kraton G1657 1.5 Spherical silica 35 BN 35 Luperox 101 0.33 Toluene 142 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. Comparative Example 4 (C-4) A coating solution was made according to the General Procedure for Preparation of Coating Solutions and the components provided below: Component Parts by weight Vinyl norbornene 3 AP Polymer-1 21 AP-Polymer-2 3 TAIC 1.5 Kraton G1657 1.5 Spherical silica 35 BN 35 Luperox 101 0.3 Toluene 138 The coating solution was converted into a curable composition according to the General Procedure for Preparation of Curable Compositions from Coating Solutions. The curable composition was converted into a cured composition according to the General Procedure for Preparation of Cured Compositions from Curable Compositions. The following Tables provide component values as a weight percentage of the curable compositions after the solvent has been removed.3-0C0% .06% .4 6.%0%0%0%0%0% 3 1540 324 96 3444.0.0.0.5.5 0.1.2 0.80 1.02-8%81C2. %50%.5 0%.5 9. 49.%99%0%0%0235.9.5.5.1.2070. 496 83. 140 1 1 0snoiti10%80s-0.%0%0%92.%9%9%9%143 10 52oC81.0.0.99 .9.4.4.1.2 0.17 142>1.0 3p6 0moCde664%r x8E.0 .%69.%4%9.%4%%% 5 1420 0528 6193.74 .07.05.05.1.2 0.661.0u1 0Cfose5itx64%6%8 %%9 %%%% 1 8410 7417rE.0 .9.94.. 4 974 .0 0 07.5. . .2 0.651.0e3 1 1 5 1 0porP40% dx 9.nE09% .4 7.%% 90. 7.%%%% 620 213 440.0.0.0.3.2 0.761 7.0 1a 1 2 5 3 5 5 5 1 0)%.tw3( x09% % .7.%%%%%% 4 71888sE09 9.2401. 7. 0543.05.05.05.31.200.7501 6.081noitiso2p x17% % E. %9% 5 91.8.%9. 6. 9%.0. %0%0 2. 0 1896 56. 12m1 991 993 9 5.5.1 2 0.0 1 0oCelb1a x17% %1 8. 8.%9%96.%9%0%0%0 2.10 69 26 16. 52rE191.9.993.9.5.5.1 2 0.0 1 0uCf) 2 7) )o)C(00e 1nre -re 56 10 z z )%1H H℃ / )s's(st+n)5ElyenmmCeB2(-IP niro yl yl I 1Gx G0G℃ A0-m0℃gul )a nonor 1 1 yx pp 5 (nuudPitn( / MPVbr op opTot ep tata ( 1-g o oG( ago)A(BonPau k fE5AP2T Y mnArT K L D D C(olpEmo )CB)( ):CB( ev2 et ilne elC( Htne tielbab zgbaciiAzit el )dAg dare gn rsalba(AAyTmi ezympo ir ni gcs ni iynr tryt trrelsotnkniyl me ermRkniagrot epoep poPelnsosPeh ylls O ait r or rfpo o oo s i pplop rT PorelnI ci l acit maoC Cba errtacm inR CziruteeCelere ahhlgbi hceia cmyD T M eziinlrnWea oitoPmgyrro-nlo p ooN P4- 39C.%70%1.0%0%9.%0% %%9 %%9 % 6 0220 88 10 20 5. 870.0.302.3 5.51.. 0143..0433.0.2 0.8301 4.0.1 1.031x00. % % %% 28.9.4. 6.% % %%9 %% 14.5.5..30. 9.% 0 733.2.120088 125134.8.512.2 2.0sE5 2 4 1 4 1 1 3 0 3 0.0 0noitisop21mx09. %00. %5%% % % 50 32.5.%5%5%59.%09.%3 3. 0 81 2 2534 8. 34. 12.oE9.4 101.1.1.144.591.0 2 0.0 1.0 3 1 0Cderu110 7Cx 9. %0% %5%5 %5%5%%0.%%8 %3 7.10 73 188.1. 22fE0.9 5.4.1 .0 .1.1 5.150.0 .4 .2 0.151 5.3 1.0o1 1 5 0 0 0seitre0p10 % % %%% % %%%%% 120 01 542 95ox 9.0.5.5. 5. 5.5.5. 8. 0. 0. 3.3.0rE0 9 4 101 1 1 145 051 0 2.0 251 3. .04.1 2.0Pdna) 90% % %1 81 1 23%x 9E. %0%5%55.%5%5%59.%09.%3 2. 0 8 5 74 1.7.2..0.9.4.101.1.1.143.043.0 2 0.10 1.0 4 1 0tw(snoi 8tx09%isE.0 0. %5%% 9.54. 5.% % %%8%0 %% 3 41051.2 31 5.51..14.5501.30.0.20003 541.6. 3.2501 1.0 3 1 3.0opmoC7elx09E. %00. %95%%% %.54. 5. 510 .1 5. %581..19 %60. %0% 8 020.3.7.20093 615 81 5.1. 123.b 1 0 0.0 1.0 3 0aruCf)ena )su ) )o)C0en 1 2rre -r 75c6ilaici10 zHzH℃ / ) )lu%(mst (+0n)5EoebmmC1Sllis 1 mx G0Gp℃)K0 ℃.do)a nm o(eB2(-IP roylyl IG AnacwNor 101 p(5 ( m / msPit egn(o / )MPn olPoPTotirolBetataE1-gW('g G( ag apA BynP ParehlpopuLk fT5Tn nrD DC-2(Ku ol ap( iA A KSHyx oY E WmVoCt t:n3 e e)el gelC(C neHegvitlbbaAbzacii gt el )Aiareni )zi sa baAd(gn) da) y ykBTm(re lp zoir nisikB(ciDy(tryt tiv tiryelsotn nilme syslomere men y Rilnsasgrrrel olt epreptc piai oo u orPf noo orPhlooroFtirp r dn pp C T P Cel cnIcplo laoit m bai iaoelzi ner rtaclcainR Cr agucelmre m ahtbhazi c erC i no moyn ei h rID Tehcegiere nait loT M Wmgyrro plo p -onoP N Also, as observed, conventional epoxy-based dielectric materials have CTE values in the range of 70-90 ppm / °C or higher, with Dk values > 3.0 at 10 GHz and Df > 0.01 at 10 GHz. As shown above, the dielectric materials of examples 7-13 show CTE values less than 50 ppm / ℃. In examples noted above, the weight ratio of the polymerizable hydrocarbon resin (A) to the total amount of crosslinking agent (B) and polymerizable thermoplastic (C) in the curable composition (in other words, (A) / ((B)+(C))) can be adjusted to achieve low CTE (< 100 ppm / ℃) and low loss (Dk < 3.0, Df < 0.0035 at 10 GHz). Using a mixed inorganic filler (with two or more of hollow silica / spherical silica / BN) can achieve lower CTE (< 30ppm / ℃) and maintain low loss (Dk < 3.0, Df < 0.0035 at 10 GHz). The Young’s modulus of the cured compositions (which are dielectric materials) can be improved by adding the mixed inorganic fillers. As used herein, the term “preferably” refer to embodiments described herein that can afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful and is not intended to exclude other embodiments from the scope of the invention. The term “about” as used herein can allow for a degree of variability in a value or a range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range and includes the exact stated value or range. As used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a” or “the” component may include one or more of the components and equivalents thereof known to those skilled in the art. Further, the term “and / or” means one or all of the listed elements or a combination of any two or more of the listed elements. It is noted that the term “comprises”, and variations thereof, do not have a limiting meaning where these terms appear in the accompanying description. Moreover, “a,” “an,” “the,” “at least one,” and “one or more” are used interchangeably herein. Reference throughout this specification to “one embodiment,” “certain embodiments,” “one or more embodiments” or “an embodiment” means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. Thus, the appearances of the phrases such as “in one or more embodiments,” “in certain embodiments,” “in one embodiment” “in some embodiments” or “in an embodiment” in various places throughout this specification are not necessarily referring to the same embodiment of the invention. The term “curable” refers to a composition or component that can be cured. The terms “cured” and “cure” refer to joining polymer chains together by covalent chemical bonds to form a polymeric network. A cured polymeric network is generally characterized by insolubility, but it may be swellable in the presence of an appropriate solvent. The terms “polymer” and “polymeric material” are used interchangeably and refer to materials formed by reacting one or more monomers. The terms include homopolymers, copolymers, terpolymers, and the like. Likewise, the terms “polymerize” and “polymerizing” refer to the process of making a polymeric material that can be a homopolymer, copolymer, terpolymer, and the like. The terms “polymer” and “copolymer” can be used interchangeably when the polymeric material includes more than one type of monomeric unit. The term “number average molecular weight” (Mn) is the absolute average mass of all small molecules, polymers, or oligomer chains that make up a material. Mn is expressed in g / mol, which refers to the weight in grams of one mole of the small molecules, polymers, or oligomer chains that make up a material. As used herein, any statement of a range includes the endpoint of the range and all suitable values within the range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). All cited references, patents, and patent applications in the above application for letters patent are herein incorporated by reference in their entirety in a consistent manner. In the event of inconsistencies or contradictions between portions of the incorporated references and this application, the information in the preceding description shall control. The preceding description, given in order to enable one of ordinary skill in the art to practice the claimed disclosure, is not to be construed as limiting the scope of the disclosure, which is defined by the claims and all equivalents thereto.

Claims

What is claimed is:

1. A curable composition, comprising: (i) a polymerizable organic portion, comprising (A) a polymerizable hydrocarbon resin; (B) at least one crosslinking agent, wherein the crosslinking agent comprises one or more nitrogen atoms and one or more oxygen atoms; (C) at least one polymerizable thermoplastic; and (ii) at least 35% by weight based on solids of an inorganic filler.

2. The curable composition of claim 1, wherein the polymerizable hydrocarbon resin comprises a free-radically polymerizable hydrocarbon resin.

3. The curable composition of any of the previous claims, wherein the polymerizable hydrocarbon resin comprises an addition-polymerized norbornene-based resin with pendent polymerizable groups.

4. The curable composition of claim 3, wherein the addition-polymerized norbornene-based resin comprises an addition-polymerized polynorbornene copolymer having norbornene-based monomeric units with pendent polymerizable groups.

5. The curable composition of any of the previous claims, wherein the at least one crosslinking agent comprises a bismaleimide (BMI) compound comprising two maleimido groups and at least one C36 hydrocarbon group that has 0 to 3 carbon-carbon double bonds.

6. The curable composition of any of the previous claims, wherein the at least one crosslinking agent comprises a bismaleimide (BMI) oligomer having the following chemical structure:where 1 ≤ n ≤ 5 and 1 ≤ m ≤ 5.

7. The curable composition of any of the previous claims, wherein the at least one cross- linking agent comprises tri(methyl)allyl isocyanurate (TMAIC), triallyl isocyanurate (TAIC), tri(methyl)allyl cyanurate, poly-triallyl isocyanurate (poly-TAIC), triallyl cyanurate (TAC), or xylylene-bis(diallyl isocyanurate) (XBD), N,N'-m-phenylene bismaleimide, or combinations thereof.

8. The curable composition of any of the previous claims, wherein the at least one polymerizable thermoplastic comprises a polyphenylene ether (PPE) that includes at least two free radically polymerizable groups.

9. The curable composition of any of the previous claims, wherein the polymerizable organic portion comprises about 15 wt.% to about 50 wt.% of the at least one crosslinking agent.

10. The curable composition of any of the previous claims, wherein the polymerizable organic portion comprises about 10 wt.% to about 45 wt.% of the at least one polymerizable thermoplastic.

11. The curable composition of any of the previous claims, wherein the inorganic filler comprises silica.

12. The curable composition of any of the previous claims, wherein the inorganic filler comprises boron nitride (BN).

13. The curable composition of claim 12, wherein the BN has a particle size distribution D50 of about 0.3 μm to about 5.0 μm.

14. The curable composition of any of the previous claims, wherein the curable composition comprises (i) hollow silica, spherical silica, or combinations thereof and (ii) about 15 wt.% to about 55 wt.% BN based on a total solids weight.

15. The curable composition of any of the previous claims, wherein a weight ratio of (A) / ((B) + (C)) is between 0.4 and 3.0, inclusive.

16. The curable composition of any one of the previous claims, further comprising a solvent.

17. A dielectric material, wherein the dielectric material is derived from: a polymerizable hydrocarbon resin; at least one crosslinking agent, wherein the crosslinking agent comprises nitrogen and oxygen; at least one polymerizable thermoplastic; and at least 35% wt.% of an inorganic filler, wherein the dielectric material has a glass transition temperature ≥ 150 °C.

18. The dielectric material of claim 17, having a dielectric constant (Dk) value < 3.0 and a coefficient of thermal expansion (CTE) value < 50 (ppm / ºC).

19. The dielectric material of any of claims 17- 18, having a dissipation factor (Df) < 0.0035 at 10 GHz.

20. The dielectric material of any of claims 17-19 having a warpage value below 0.5 mm.

21. An integrated circuit substrate comprising the dielectric material of any of claims 17-20.

22. An integrated circuit chip comprising the integrated circuit substrate of claim 21.

23. A curable composition, comprising: (A) a polymerizable hydrocarbon resin; (B) at least one crosslinking agent, wherein the crosslinking agent comprises one or more nitrogen atoms and one or more oxygen atoms; and (C) at least one polymerizable thermoplastic.

24. The curable composition of claim 23, wherein a weight ratio of (A) / ((B) + (C)) is between 0.4 and 3.0, inclusive.

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