Polycycloolefin compositions for low-loss films with improved thermal properties

Abstract

An embodiment according to the present invention relates to a composition comprising one or more polycycloolefinic monomers and at least one multifunctional olefinic monomer, which undergoes bulk polymerization at a suitable temperature to provide a 3D insulating article. The article has a low dielectric constant, low loss properties, and very high thermal properties that could not be achieved in the prior art. The composition of the present invention may further comprise one or more organic or inorganic filler materials that provide very low dielectric properties and further improved thermomechanical properties. The composition is stable at room temperature and undergoes bulk polymerization only when exposed to a suitable elevated temperature, typically above 100°C. The composition of the present invention can be used in a variety of applications, among which it is useful as an insulating material for millimeter wave radar antennas.

Description

[Technical Field]

[0001] Cross-reference to related applications This application claims the benefit of U.S. Provisional Application No. 63 / 107,514, filed October 30, 2020, which is incorporated herein by reference.

[0002] Embodiments of the present invention generally relate to compositions comprising one or more polycycloolefin monomers and at least one multifunctional olefin monomer, which undergo bulk polymerization at suitable temperatures to provide 3D insulating articles exhibiting previously unattainable low dielectric constants, low loss characteristics, and ultra-high thermal properties. More specifically, the present invention relates to compositions comprising a series of substituted norbornene derivatives and at least one bifunctional monomer compound, which undergo bulk polymerization in the presence of specific organopalladium compounds to form 3D articles, such as films, exhibiting very high glass transition temperatures of 300°C or higher, low dielectric constants (less than 2.4 at 10 GHz), and low loss characteristics. Thus, the compositions of the present invention can be used as insulating materials in a variety of applications, including electromechanical devices used in the manufacture of various automotive components. [Background technology]

[0003] It is well known that insulating materials with low dielectric constant (Dk) and low loss (also called low dielectric loss factor (Df)) are important elements in printed circuit boards, which are widely used in electrical products, automotive components, and other applications. Generally, suitable insulating materials for many devices must have a dielectric constant of less than 3 and a loss factor of less than 0.001 at high frequencies, e.g., above 50 GHz. Furthermore, there has been growing interest in the development of organic dielectric materials due to their ease of fabrication.

[0004] However, many technical problems must be solved to develop an insulating material that meets all the requirements. One of these problems is that the insulating material must have a low coefficient of thermal expansion (CTE), preferably less than 50 ppm / K to prevent the copper layer from peeling off. In addition, the insulating material must have a low glass transition temperature (T g ) must be very high, preferably exceeding 150°C or even 250°C, taking into account the process conditions used in the manufacture of printed circuit boards and the harsh conditions to which such devices may be exposed, such as millimeter wave radar antennas used in automobiles.

[0005] For example, films prepared by addition polymerization of norbornene derivatives containing long side chains, such as 5-hexylnorbornene (HexNB) and 5-decylnorbornene (DecNB), have low Dk and Df due to their hydrophobicity, but have high CTE (>200 ppm / K) and low T g is low. See, for example, Japanese Patent Application Laid-Open Nos. 2016-037577 and 2012-121956.

[0006] In addition, certain polymers such as fluorinated polyethylene, polyethylene, and polystyrene are characterized by low Dk / Df, but the glass transition temperature of these polymers is much lower than 150°C, and it has been reported in the literature that they are unsuitable as organic insulating materials. Furthermore, when they contain certain substituted norbornenes substituted with polar groups such as ester or alcohol groups, they generally have low CTE and T g It has also been reported in the literature that it is possible to produce polymers with low Dk and Df. However, the incorporation of such groups results in high Dk and Df due to polarizability under electromagnetic fields, especially at high frequencies. Therefore, norbornenes substituted with such polar groups are not suitable for forming the insulating materials of the present invention.

[0007] Therefore, there remains a demand for the development of new insulating materials that exhibit not only low dielectric constant but also ultra-high thermal properties.

[0008] There is also a need to develop materials that can be formed into thermoset films rather than thermoplastic films, which are generally cross-linked and more stable at high temperatures and do not exhibit thermal mobility like thermoplastic films. Summary of the Invention [Problem to be solved by the invention]

[0009] It is an object of the present invention to provide a composition comprising one or more substituted norbornene monomers and a polyfunctional monomer, which undergoes bulk polymerization to provide an insulating material with previously unattainable properties.

[0010] Further objects and scope of application of the present invention will be set forth in the detailed description below. [Means for solving the problem]

[0011] It has been discovered that compositions comprising one or more monomers of formula (I) as described herein and one or more multifunctional compounds of formula (A1) or (A2) or (A3) as described herein can be used to form 3D articles that provide heretofore unobtainable dielectric and thermal properties.

[0012] In yet another aspect of the invention, kits are provided that include the compositions of the invention.

[0013] Embodiments according to the present invention will now be described with reference to the accompanying drawings and / or images, which show various embodiments of the invention in simplified form and for illustrative purposes only. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 shows comparative thermograms obtained from thermomechanical analysis (TMA) of films formed from compositions of the present invention containing various levels of difunctional crosslinking agents as described herein. DETAILED DESCRIPTION OF THE INVENTION

[0015] Terms used in this specification have the following meanings.

[0016] The use of the articles "a," "an," and "the" is deemed to include a plurality of objects unless expressly limited to one object.

[0017] All numbers, values ​​and / or formulas expressing quantities of ingredients, reaction conditions, and the like described in this specification and the claims appended hereto reflect uncertainties of the measurements performed to arrive at those numbers, values ​​and / or formulas and, therefore, are deemed to include the term "about" unless otherwise indicated.

[0018] When a range of numbers is disclosed herein, the range is considered continuous and includes the maximum and minimum values ​​of the range, as well as all values ​​between the maximum and minimum values. When a range relates to integer values, it includes all integers between the maximum and minimum values ​​of the range. Furthermore, when multiple ranges are presented for the purpose of describing a feature or characteristic, these ranges are combinable. In other words, unless otherwise indicated, all ranges disclosed herein encompass all subranges encompassed by that range. For example, when a range is presented as "1 to 10," that range should be considered to include all subranges between the minimum value of 1 and the maximum value of 10. Examples of subranges between 1 and 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0019] As used herein, "hydrocarbyl" refers to a group containing carbon and hydrogen atoms, including, but not limited to, alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl, etc. "Halohydrocarbyl" refers to a hydrocarbyl group in which at least one hydrogen has been replaced with a halogen. "Perhalocarbyl" is a hydrocarbyl group in which all hydrogens have been replaced with halogens.

[0020] As used herein, "alkyl" refers to a saturated, straight-chain or branched hydrocarbon substituent having the specified number of carbon atoms. Particular alkyl groups include methyl, ethyl, n-propyl, isopropyl, tert-butyl, and the like. Derived expressions such as "alkoxy," "thioalkyl," "alkoxyalkyl," "hydroxyalkyl," "alkylcarbonyl," "alkoxycarbonylalkyl," "alkoxycarbonyl," "diphenylalkyl," "phenylalkyl," "phenylcarboxyalkyl," and "phenoxyalkyl" are to be construed similarly.

[0021] As used herein, "cycloalkyl" includes all known cyclic groups. Representative examples of "cycloalkyl" include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Derived expressions such as "cycloalkoxy," "cycloalkylalkyl," "cycloalkylaryl," and "cycloalkylcarbonyl" should be construed in the same manner.

[0022] As used herein, "perhaloalkyl" refers to an alkyl as defined above, wherein all of the hydrogen atoms of the alkyl group are replaced with halogen atoms selected from fluorine, chlorine, bromine, or iodine. Representative examples include trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl, pentabromoethyl, pentaiodoethyl, linear or branched heptafluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl, nonachlorobutyl, undecafluoropentyl, undecachloropentyl, tridecafluorohexyl, tridecachlorohexyl, and the like. The derived expression "perhaloalkoxy" should be interpreted in the same way. Certain alkyl groups described herein may be partially fluorinated. That is, only a portion of the hydrogen atoms of the alkyl group are replaced with fluorine atoms, and the derived expression should be interpreted in the same way.

[0023] As used herein, "acyl" is synonymous with "alkanoyl" and can be represented by the structural formula "R-CO-," where R is "alkyl" as defined herein having the specified number of carbon atoms. Additionally, "alkylcarbonyl" is synonymous with "acyl" as defined herein. In particular, "(C1-C4)acyl" refers to formyl, acetyl, or ethanoyl, propanoyl, n-butanoyl, and the like. Derived expressions such as "acyloxy" and "acyloxyalkyl" are to be construed similarly.

[0024] As used herein, "aryl" refers to substituted or unsubstituted phenyl or naphthyl. Specific examples of substituted phenyl or substituted naphthyl include o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, etc. Furthermore, "substituted phenyl" or "substituted naphthyl" includes all possible substituents defined herein or known in the art.

[0025] As used herein, "arylalkyl" refers to an aryl, as defined herein, bonded to an alkyl, as defined herein. Representative examples include benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like.

[0026] As used herein, "alkenyl" refers to an acyclic, straight or branched hydrocarbon chain having the specified number of carbon atoms and containing at least one carbon-carbon double bond, including ethenyl, straight or branched propenyl, butenyl, pentenyl, hexenyl, and the like. The derived expressions "arylalkenyl" and 5- or 6-membered "heteroarylalkenyl" are construed similarly. Representative examples of such derived expressions include furan-2-ethenyl, phenylethenyl, 4-methoxyphenylethenyl, and the like.

[0027] As used herein, "heteroaryl" refers to all known aromatic radicals containing heteroatoms. Representative five-membered heteroaryl radicals include furanyl, thienyl, thiophenyl, pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl, and the like. Representative six-membered heteroaryl radicals include pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like. Representative examples of bicyclic heteroaryl radicals include benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, cinnolyl, benzimidazolyl, indazolyl, pyridofuranyl, pyridothienyl, and the like. As used herein, the term "heterocycle" includes all known reduced heteroatoms, including known cyclic radicals. Representative five-membered heterocyclic radicals include tetrahydrofuranyl, tetrahydrothiophenyl, pyrrolidinyl, 2-thiazolinyl, tetrahydrothiazolyl, tetrahydrooxazolyl, and the like. Representative six-membered heterocyclic radicals include piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, and the like. Heterocyclic radicals include, but are not limited to, aziridinyl, azepanyl, diazepanyl, diazabicyclo[2.2.1]hebut-2-yl, triazocanyl, and the like.

[0028] "Halogen" or "halo" means chloro, fluoro, bromo, and iodo. In the broadest sense, "substituted" can be construed to include all permissible substituents of organic compounds. In certain embodiments disclosed herein, "substituted" means substituted with one or more substituents independently selected from the group consisting of (C-C) alkyl, (C-C) alkenyl, (C-C) perfluoroalkyl, phenyl, hydroxy, -COH, ester, amide, (C-C) alkoxy, (C-C) thioalkyl, and (C-C) perfluoroalkoxy. However, other suitable substituents known to those of ordinary skill in the art may also be used in such embodiments.

[0029] In the text, illustrations, examples, and tables of this specification, when an atom cannot satisfy a valence, it is assumed to have the appropriate number of hydrogen atoms to satisfy the valence.

[0030] As used herein, the terms "dielectric" and "insulating" are used interchangeably. Thus, a reference to an insulating material or insulating layer includes a dielectric material or layer, and vice versa. Also, as used herein, the term "organic electronic device" should be understood to include "organic semiconductor devices," particular embodiments of such devices used, for example, in the automotive industry.

[0031] As used herein, the dielectric constant (Dk) of a material refers to the ratio of the charge stored in an insulating material placed between two metal plates to the charge that can be stored when the insulating material is replaced by a vacuum or air. It is also called the electrical permittivity or dielectric constant. It is also called the relative permittivity because it is measured relative to the permittivity of free space.

[0032] "Low loss" as used herein refers to the dissipation factor (Df), which is a measure of the rate at which a vibration mode (mechanical, electrical, or electromechanical) loses energy in a dissipative system. It is the inverse of the quality factor, which indicates the "quality" or durability of the vibration.

[0033] As used herein, "derived" means that the repeating units of the polymer are polymerized (formed) from polycyclic norbornene-type monomers, such as those according to formula (I), where the resulting polymer is formed from the 2,3 double bond of the norbornene-type monomer:

[0034] [ka]

[0035] The above polymerizations are known as vinyl addition polymerizations which generally occur in the presence of organometallic compounds such as organopalladium or organonickel compounds, as will be explained in more detail below.

[0036] Thus, according to the practice of the present invention, in a film-forming composition: a) one or more olefin monomers of formula (I): [ka] (where, m is 0 or 1, [ka] is a single or double bond, R1, R2, R3, and R4 are the same or different and each independently represent hydrogen, straight-chain or branched (C4-C 16 ) alkyl, straight or branched (C2-C 16 ) alkenyl, (C3-C 10 ) cycloalkyl, (C3-C 10 ) cycloalkenyl, (C6-C 12 )bicycloalkyl, (C6-C 12 ) aryl, and (C6-C 12 )aryl(C1-C6)alkyl; or One of R1 and R2, together with one of R3 and R4 and the carbon atom to which they are attached, may optionally be a substituted or unsubstituted (C5-C 14 )monocyclic ring, (C5-C 14 ) bicyclic ring, or (C5-C 14 ) forms a tricyclic ring. b) at least one compound selected from the group consisting of: Compounds of formula (A1): [ka] (where, b is an integer from 2 to 6, Z is a bond or R9R10 SiOSiR 11 R 12 where R9, R 10 , R 11 and R 12 are the same or different and each independently selected from the group consisting of methyl, ethyl, and straight-chain or branched (C-C) alkyl; R5, R6, R7 and R8 are the same or different and each independently represent hydrogen, methyl, ethyl, and straight-chain or branched (C3-C 16 ) alkyl. Compounds of formula (A2): [ka] (where, R 13 , R 14 , R 15 , and R 16 are the same or different and each independently represent hydrogen, methyl, ethyl, and straight-chain or branched (C3-C 16 ) alkyl; and Compounds of formula (A3): [ka] (where, L is a bond or a methylene, ethylene, straight or branched (C3-C 16 ) alkylene, (C3-C 16 ) cycloalkylene, (C5-C8) heterocycle, (C6-C 12 ) arylene, (C5-C 12 ) heteroarylene, and -(CH2) c O(CH2) c -, c is an integer from 1 to 6, and optionally each CH2 is methyl, ethyl, straight or branched (C3-C 16 ) alkyl, and (C6-C 12 )aryl, where methylene, ethylene or (C-C16 The hydrogen moiety on the alkylene is fluorine, trifluoromethyl, pentafluoroethyl, and straight-chain or branched perfluoro(C3-C 16 ) alkyl; R 17 and R 18 are the same or different and each independently represent methyl, ethyl, straight-chain or branched (C3-C 12 ) alkyl, (C6-C 12 ) aryl, and (C6-C 12 )Aryl(C1-C 12 ) alkyl, where optionally methyl, ethyl or (C-C 12 The hydrogen moiety on the alkyl is fluorine, trifluoromethyl, pentafluoroethyl, and straight or branched (C3-C 12 ) perfluoroalkyl; Ar1 and Ar2 are the same or different and each independently represent (C6-C 12 ) arylene group or (C6-C 12 ) heteroarylene groups, which are optionally selected from (C1-C4) alkyl, (C1-C4) alkoxy, (C6-C 10 ) aryl, (C6-C 12 )aryloxy, (C6-C 12 )aryl(C1-C4)alkyl, and (C6-C 12 ) aryl(C1-C4) alkyloxy. c) an organopalladium compound selected from the group consisting of: Palladium(II) bis(triphenylphosphine) dichloride; Palladium(II) bis(triphenylphosphine) dibromide; Palladium(II) bis(triphenylphosphine) diacetate; Palladium(II) bis(triphenylphosphine)bis(trifluoroacetate); Palladium(II) bis(tricyclohexylphosphine) dichloride; Palladium(II) bis(tricyclohexylphosphine) dibromide; Palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785); Palladium(II) bis(tricyclohexylphosphine)bis(trifluoroacetate); Palladium(II) bis(tri-p-tolylphosphine) dichloride; Palladium(II) bis(tri-p-tolylphosphine) dibromide; Palladium(II) bis(tri-p-tolylphosphine) diacetate; Palladium(II) bis(tri-p-tolylphosphine)bis(trifluoroacetate); Palladium(II) ethylhexanoate; Dichlorobis(acetonato)palladium(II); Dichlorobis(benzonitrile)palladium(II); Platinum(II) chloride; Platinum(II) bromide; and Platinum bis(triphenylphosphine) dichloride; and d) an active agent selected from the group consisting of: Lithium tetrafluoroborate; Lithium triflate; Lithium tetrakis(pentafluorophenyl)borate; Lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA); sodium tetrakis(pentafluorophenyl)borate etherate (NaFABA); Trityl tetrakis(pentafluorophenyl)borate etherate (tritylFABA); Tropylium tetrakis(pentafluorophenyl)borate etherate (tropyliumFABA); Lithium tetrakis(pentafluorophenyl)borate isopropanolate; Lithium tetraphenylborate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; Lithium tetrakis(2-fluorophenyl)borate; Lithium tetrakis(3-fluorophenyl)borate; Lithium tetrakis(4-fluorophenyl)borate; Lithium tetrakis(3,5-difluorophenyl)borate; Lithium hexafluorophosphate; Lithium hexaphenyl phosphate; Lithium hexakis(pentafluorophenyl)phosphate; Lithium hexafluoroarsenate; Lithium hexaphenylarsenate; Lithium hexakis(pentafluorophenyl)arsenate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)arsenate; Lithium hexafluoroantimonate; Lithium hexaphenylantimonate; Lithium hexakis(pentafluorophenyl)antimonate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)antimonate; Lithium tetrakis(pentafluorophenyl)aluminate; Lithium tris(nonafluorobiphenyl)fluoroaluminate; Lithium (octyloxy)tris(pentafluorophenyl)aluminate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate; Lithium methyltris(pentafluorophenyl)aluminate; Dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); wherein a film formed from the composition has a dielectric constant (Dk) of less than 2.4 at a frequency of 10 GHz, a glass transition temperature of greater than 150° C., and a coefficient of thermal expansion (CTE) of less than 150 ppm / K.

[0037] It should be noted that the compositions of the present invention are bulk polymerizable compositions when exposed to appropriate temperature and / or photolytic conditions. That is, when a composition of the present invention, generally comprising one or more monomers of Formula (I), at least one compound of Formula (A1), (A2), or (A3), at least one organopalladium compound, and an activator as described herein, is heated to a specific temperature, the composition undergoes bulk polymerization to form a solid object. Any temperature conditions that result in bulk polymerization are contemplated herein. In one embodiment, the composition of the present invention is heated to a temperature of about 60°C to about 150°C for a sufficient time, e.g., about 1 hour to 8 hours. In another embodiment, the composition of the present invention is heated to a temperature of about 90°C to about 130°C for a sufficient time, e.g., about 1 hour to 4 hours.

[0038] It has further been found that exposure of the compositions of the present invention to suitable electromagnetic radiation results in bulk polymerization to form a solid object. In one embodiment, the compounds of formula (A1), (A2), or (A3) can be activated with specific wavelengths of electromagnetic radiation, generally in the range of about 240 nm to 400 nm. Thus, any compounds of formula (A1), (A2), or (A3) that are activated with electromagnetic radiation can be used in the compositions of the present invention that are compatible with photolytic bulk polymerization conditions. In one embodiment, the wavelength of radiation used to activate the compounds of formula (A1), (A2), or (A3) is 260 nm. In another embodiment, the wavelength of radiation used to activate the compounds of formula (A1), (A2), or (A3) is 310 nm. In yet another embodiment, the wavelength of radiation used to activate the compounds of formula (A1), (A2), or (A3) is 365 nm, 395 nm, or the like.

[0039] In one embodiment of the present invention, the composition of the present invention may further contain another sensitizer compound capable of activating the compound of formula (A1), (A2), or (A3) to facilitate the bulk polymerization of the monomer of formula (I). Any suitable sensitizer compound can be used in the composition of the present invention for this purpose. Examples of suitable sensitizer compounds include photosensitizers such as anthracene, phenanthrene, chrysene, benzpyrene, fluoranthene, rubrene, pyrene, xanthone, indanthrene, and mixtures thereof. In some exemplary embodiments, a suitable sensitizer component includes a mixture thereof. Generally, a photosensitizer absorbs energy from an emitted light source and transfers the energy to a preferred substrate / reactant used in the composition of the present invention.

[0040] In many cases, the organopalladium compound and activator used to effect the bulk polymerization can be dissolved in the monomers used to form a homogeneous solution. If the activator is not dissolved, the organopalladium compound and activator can be dissolved in a suitable solvent, such as tetrahydrofuran (THF), and then mixed with one or more monomers of Formula (I) and a compound of Formula (A1), (A2), or (A3) to form a homogeneous solution. As described herein, other solvents that can be used to dissolve the organopalladium compound and / or activator include ethyl acetate (EA), toluene, trifluorotoluene (TFT), cyclohexane (CH), methylcyclohexane (MCH), and the like. Such bulk polymerization techniques are well known, and the films of the present invention can be formed by any procedure known to those skilled in the art. See, for example, U.S. Patent No. 6,825,307, incorporated herein by reference.

[0041] In one embodiment, the film-forming composition comprises m is 0, [ka] is a single bond, R1, R2, R3, and R4 are the same or different and each comprise a monomer of formula (I) independently selected from the group consisting of hydrogen, n-butyl, n-hexyl, cyclohexyl, cyclohexenyl, and norbornyl.

[0042] Any monomer of formula (I) can be used to form the film-forming composition of the present invention. The monomer of formula (I) can be selected from the group consisting of, but not limited to:

[0043] [ka] [ka] [ka]

[0044] Additionally, specific compounds within the scope of formula (A1) can be used in the film-forming composition of the present invention to achieve the desired effect. The compound of formula (A1) can be selected from the group consisting of, but not limited to:

[0045] [ka]

[0046] Certain compounds within the scope of formula (A2) can be used in the film-forming compositions of the present invention to achieve the desired effect. The compound of formula (A2) can be selected from the group consisting of, but not limited to:

[0047] [ka]

[0048] Certain compounds within the scope of formula (A3) can be used in the film-forming compositions of the present invention to achieve the desired effect. The compound of formula (A3) can be selected from the group consisting of, but not limited to:

[0049] [ka]

[0050] As described above, the film-forming composition according to the present invention comprises at least one monomer of formula (I) and a compound of formula (A1), (A2), or (A3). The amount of the monomer of formula (I) and the compound of formula (A1), (A2), or (A3) is not particularly limited, as long as it is capable of forming the composition of the present invention and providing the intended benefits, such as the low dielectric constant and / or low thermal / mechanical properties described herein, or other desirable properties depending on the intended end use. Thus, the molar ratio of the monomer of formula (I) to the compound of formula (A1), (A2), or (A3) may be from 95:5 to 5:95. In one embodiment, the molar ratio of the monomer of formula (I) to the compound of formula (A1), (A2), or (A3) is in the range of 90:10 to 10:90, and in another embodiment, it may be in the range of 85:15 to 15:85, 80:20 to 20:80, 70:30 to 30:70, 75:25 to 25:75, 60:40 to 40:60, 50:50, etc.

[0051] In one embodiment, the amount of the compound of formula (A1), (A2), or (A3) is less than 5 mol %. Thus, in one embodiment, the molar ratio of the monomer of formula (I) to the compound of formula (A1), (A2), or (A3) can be 99:1 to 1:99, 98:2 to 2:98, 97:3 to 3:97, 96:4 to 4:96, or fractions thereof. There is no limit to the combination that can be applied to the composition of the present invention, as long as the desired benefits are obtained in the intended application.

[0052] Additionally, one or more monomers of Formula (I) and one or more compounds of Formula (A1), (A2), or (A3) can be used in the compositions of the present invention. Thus, the molar ratio of the first monomer of Formula (I) to the second monomer of Formula (I) can be 1:99 to 99:1. In one embodiment, the molar ratio of the first monomer of Formula (I) to the second monomer of Formula (I) can be in the range of 5:95 to 95:5, and in other embodiments, can be in the range of 10:90 to 90:10, 15:85 to 85:15, 20:80 to 80:20, 30:70 to 70:30, 60:40 to 40:60, 50:50, etc. Similarly, when one or more compounds of Formula (A1), (A2), or (A3) are used in the compositions of the present invention, the one or more monomers of Formula (I) can be used in any suitable amount, such as the various ratios presented herein, when applied to the compositions of the present invention.

[0053] Generally, compositions according to the present invention comprise one or more monomers of formula (I) as described above, and as will be seen below, various composition embodiments can be tailored to suit a variety of specific applications, with the various composition embodiments being selected to suit the application and provide preferred properties. Thus, in one embodiment, a composition of the present invention may comprise two or more monomers of formula (I), for example, three different monomers of formula (I), or four different monomers of formula (I), and any desired number of compounds of formula (A1), (A2), or (A3).

[0054] For example, as already discussed above, by using appropriate combinations of various monomers represented by formula (I), it is possible to obtain compositions that exhibit, among other properties, desirable low dielectric constants and thermo-mechanical properties. It is also preferable to include other compatible polymeric or monomeric materials to provide desirable low loss and low dielectric constants depending on the end use, as described in more detail below.

[0055] It has been discovered that one or more compounds of formula (A1) or (A2) or (A3) can be used to form crosslinked structures within a polymer backbone. In other words, crosslinking can occur intramolecularly (i.e., between two crosslinkable sites on the same polymer chain). This can occur statistically, and all such combinations are part of the present invention. By forming intermolecular or intramolecular crosslinks, polymers formed from the compositions of the present invention can obtain properties not previously available. For example, these can include improved thermal properties, i.e., a glass transition temperature much higher than that observed in non-crosslinked polymers of similar composition. Such crosslinked polymers also remain stable at temperatures above 350°C. High temperature stability can also be measured by thermogravimetric analysis (TGA) methods well known to those skilled in the art. One such measurement is the temperature at which a polymer loses 5% of its weight (T d5 As can be seen from the specific examples below, the T of the polymers formed from the compositions of the present invention d5 Generally, the T of the polymer formed from the composition of the present invention can range from about 270°C to about 320°C. d5 The temperature is in the range of about 280°C to about 300°C.

[0056] It should also be noted that the use of one or more compounds of formula (A1), (A2), or (A3) is not required to achieve crosslinking of the polymer formed from the composition. That is, when the monomer of formula (I) includes one or more separate monomers containing unsaturated double bonds that can function as inter- or intramolecular crosslinkable monomers with other polymer chains, as described above. Thus, in one embodiment, a composition is provided that includes at least two monomers of formula (I), at least one of which contains a double bond. All such combinations are part of the present invention.

[0057] The crosslinked polymers formed from the compositions of the present invention can be thermoset, which can provide additional advantages in certain applications where thermoplastic polymers are undesirable, such as in applications involving high temperatures, where the polymeric material may flow and is not suitable for high temperature environments, including millimeter wave radar antennas, as specifically contemplated herein.

[0058] Polymers formed from one or more monomers of formula (I) can be reacted with one compound of formula (A1), (A2), or (A3) to form the crosslinked thermoset described above. Thus, in one embodiment, a composition is further provided comprising a polymer formed from one or more monomers of formula (I) and at least one compound of formula (A1), (A2), or (A3) in a suitable solvent. The solution thus formed can be cast into a film by any known method, or, as described herein, can be exposed to suitable elevated temperatures or radiation to form a crosslinked film. Suitable solvents include any solvent that dissolves the polymer formed from the monomers of formula (I), such as hydrocarbon solvents such as decane, halohydrocarbon solvents such as dichloromethane or dichloroethane, ester solvents such as ethyl acetate, ether solvents such as tetrahydrofuran or diethyl ether, and alcohol solvents such as diglyme or ethyl alcohol. Suitable temperatures for crosslinking can be from about 100°C to about 180°C or higher for a sufficient period of time, for example, from 30 minutes to 1 hour or more. Suitable actinic radiation may include irradiation at 365 nm or 400 nm, as commonly used in the art.

[0059] As described below, the compositions of the present invention can be formed into films. Films formed from the compositions of the present invention exhibit a previously unobtainable combination of low dielectric constant and high glass transition temperature. Thus, in one embodiment, a film formed from a composition of the present invention has a dielectric constant (Dk) of 2.0 to 2.38 at 10 GHz, a glass transition temperature of about 160°C to about 350°C, and a coefficient of thermal expansion (CTE) of about 100 ppm / K to about 140 ppm / K. In another embodiment, a film formed from a composition of the present invention has a dielectric constant (Dk) of 2.10 to 2.30 at 10 GHz, a glass transition temperature of about 190°C to about 350°C, and a coefficient of thermal expansion (CTE) of about 80 ppm / K to about 140 ppm / K. In another embodiment, a film formed from a composition of the present invention has a glass transition temperature of about 220°C to about 350°C.

[0060] It has been found that the low dielectric constant of films formed from the compositions of the present invention can be further improved by including one or more fillers. The fillers can be organic or inorganic. Any of the well-known fillers can be used in the present invention, provided that they provide the intended benefits.

[0061] Therefore, in one embodiment, the film-forming composition according to the present invention contains an inorganic filler. Suitable inorganic fillers have a coefficient of thermal expansion (CTE) lower than that of the film formed from the composition of the present invention. Examples of inorganic fillers include, but are not limited to, oxides such as silica, alumina, diatomaceous earth, titanium oxide, iron oxide, zinc oxide, magnesium oxide, and metal ferrites; hydroxides such as aluminum hydroxide and magnesium hydroxide; calcium carbonate (hard and heavy); carbonates such as magnesium carbonate, dolomite, and dolomite; sulfates such as calcium sulfate, barium sulfate, ammonium sulfate, and calcium sulfite; silicates such as talc, mica, clay, glass fiber, calcium silicate, montmorillonite, and bentonite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; carbon black; carbon such as carbon fiber; iron powder; copper powder; aluminum powder; zinc oxide; molybdenum sulfide; boron fiber; potassium titanate; and lead zirconate.

[0062] In another embodiment, the film-forming composition according to the present invention further comprises an organic filler. The organic filler may be a synthetic resin, typically in powder form, or in other suitable forms or polymers. Examples of polymer fillers include, but are not limited to, poly(α-methylstyrene), poly(vinyl-toluene), and copolymers of α-methylstyrene and vinyl-toluene. Further examples of synthetic resin powders include powders of various thermosetting or thermoplastic resins, such as alkyd resins, epoxy resins, silicone resins, phenolic resins, polyesters, acrylic and methacrylic resins, acetal resins, polyethylene, polyethers, polycarbonates, polyamides, polysulfones, polystyrenes, polyvinyl chlorides, fluororesins, polypropylenes, and ethylene-vinyl acetate copolymers, or powders of copolymers of these resins. Further examples of organic fillers include aromatic or aliphatic polyamide fibers, polypropylene fibers, polyester fibers, and aramid fibers.

[0063] In one embodiment, the filler is an inorganic filler, which can effectively reduce the coefficient of thermal expansion. Furthermore, heat resistance can be improved. In one embodiment, the inorganic filler is silica. This can reduce the coefficient of thermal expansion and improve dielectric properties. Various silica fillers known in the art can be used in the compositions of the present invention. Examples of silica fillers include, but are not limited to, fused silica, including fused spherical silica, fused ground silica, and crystalline silica. In one embodiment, fused silica is used. It has been found that the use of spherical silica allows for the formation of compositions containing the maximum silica loading, e.g., 80% by weight. The use of an appropriate silica filler can result in particularly excellent dielectric properties. Generally, the amount of filler can vary from about 5% by weight to 80% by weight or more. In one embodiment, the filler content in the composition is about 30-80% by weight, based on the total solids content of the composition when polymerized to form a film / sheet, as described herein. By appropriately adjusting the filler content, the balance between dielectric properties and the coefficient of thermal expansion can be improved. In another embodiment, the amount of filler in the composition is about 40-70% by weight based on the total solids content of the composition.

[0064] Generally, the filler is treated with a silane compound having an alkoxysilyl group and an organic functional group such as an alkyl group, an epoxy group, a vinyl group, a phenyl group, or a styryl group in a single molecule. Examples of the silane compound include silanes having an alkyl group such as ethyltriethoxysilane, propyltriethoxysilane, and butyltriethoxysilane (alkylsilanes); silanes having a phenyl group such as phenyltriethoxysilane, benzyltriethoxysilane, and phenethyltriethoxysilane; silanes having a styryl group such as styryltrimethoxysilane, butenyltriethoxysilane, propenyltriethoxysilane, and vinyltrimethoxysilane (vinylsilane); silanes having an acrylic group or a methacrylic group such as γ-(methacryloxypropyl)trimethoxysilane; silanes having an amino group such as γ-aminopropyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltriethoxysilane; and silanes having an epoxy group such as γ-(3,4-epoxycyclohexyl)ureidotriethoxysilane. Silanes having a mercapto group, such as γ-mercaptopropyltrimethoxysilane, can also be used. One or more of the aforementioned silane compounds may be used in combination.

[0065] It should also be noted that when inorganic fillers are used as fillers, they are generally treated with a "non-polar silane compound." This can improve the adhesion between the cyclic olefin polymer formed from the composition of the present invention and the filler. As a result, the mechanical properties of the molded article can be improved. It has been found that treatment with a "non-polar silane compound" can eliminate or reduce the adverse effects on dielectric properties. As used herein, "non-polar silane compound" refers to a silane compound that does not contain a polar substituent. A polar substituent is a group that can hydrogen bond or ionically dissociate. Examples of polar substituents include -OH, -COOH, -COOM, NH3, and NR4. + A -, -CONH2, etc., where M is a cation such as an alkali metal, alkaline earth metal, or quaternary ammonium salt, R is H or an alkyl group of up to 8 carbon atoms, and A is an anion such as a halogen atom.

[0066] In one embodiment, the surface of the filler is modified with a vinyl group. The vinyl group is a non-polar substituent that provides the low dielectric constant required for the present invention, so it is preferable to use a vinyl group. For example, when modifying the surface of the filler with a vinyl group, a vinylsilane can be used. Specific examples of vinylsilane are as described above.

[0067] Generally, the average particle size of the filler ranges from about 0.1 to 10 μm. In one embodiment, it is about 0.3 to 5 μm, and in another embodiment, it is about 0.5 to 3 μm. The average particle size is defined as the average diameter of the particles measured by light scattering. When two or more fillers are used, the average particle size of at least one of the fillers falls within the aforementioned range. A suitably small average particle size of the filler reduces the specific surface area of ​​the filler. As a result, the number of polar functional groups that adversely affect the dielectric properties is reduced, easily improving the dielectric properties. Furthermore, when the average particle size of the filler is suitably small, it becomes easy to polymerize and form a film from the composition of the present invention. The film / sheet thus formed has the uniform thickness and flatness required for various applications.

[0068] The composition of the present invention may contain components other than those described above. These components include coupling agents, flame retardants, mold release agents, antioxidants, etc. Examples of coupling agents include, but are not limited to, silane coupling agents such as vinyl silane, acrylic and methacrylic silane, styryl silane, and isocyanatosilane. The use of a silane coupling agent can improve the adhesion between the composition of the present invention and a substrate, etc.

[0069] Examples of flame retardants include, but are not limited to, phosphorus-based flame retardants such as trixylenyl phosphate, xylenyl phosphate, 10(2,5-dihydroxyphenyl)-10H-9-oxa-10phosphaphenanthrene-10-oxide, halogen-based flame retardants such as brominated epoxy resins, and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.

[0070] The compositions of the present invention may further comprise one or more compounds or additives that have utility such as adhesion promoters, surface leveling agents, synergists, plasticizers, cure accelerators, free radical initiators, and the like. The use of one or more thermal free radical generators can accelerate the crosslinking of polymers formed from the compositions of the present invention to produce crosslinked polymers that exhibit further improved thermal properties. For example, the glass transition temperature (T g ) and the temperature at which a 5 wt% weight loss of the polymer occurs (T d5 ) will be higher. T g The increase in T may range from about 10°C to 50°C. In one embodiment, the T g The T of the polymer can be increased by 20 to 40°C using an appropriate amount of thermal free radical generator. d5 The temperature will also rise by about 3 to 10 degrees Celsius.

[0071] Any compound that forms radicals when exposed to heat can be used for this purpose, with general examples including peroxides, peracids, azo compounds, N-alkoxyamines, N-acyloxyamines, etc., and specific examples of thermal free radical generators including, but not limited to, benzoyl peroxide, dicumyl peroxide (DCP), m-chloroperbenzoic acid, methyl ethyl ketone peroxide, azobisisobutyronitrile (AIBN), 1-phenyl-3,3-dipropyltriazene, 1-(phenyldiazenyl)pyrrolidine, 1-(phenyldiazenyl)piperidine, 1-(phenyldiazenyl)azepane, etc.

[0072] The thermal free radical generator can be used in various amounts in the composition of the present invention as long as it produces the intended effect. Generally, the amount ranges from about 2 parts per hundred parts of resin (pphr) to 10 pphr or more. In one embodiment, the amount of thermal free radical generator used is about 3 pphr to 6 pphr.

[0073] Examples of the film-forming composition of the present invention can be selected from the group consisting of, but not limited to:

[0074] 5-decylbicyclo[2.2.1]hept-2-ene (DecNB), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethanonaphthalene (TDD), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-decylbicyclo[2.2.1]hept-2-ene (DecNB), 5-phenylbicyclo[2.2.1]hept-2-ene (PhNB), 1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethanonaphthalene (TDD), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-decylbicyclo[2.2.1]hept-2-ene (DecNB), 2,2′-bi(bicyclo[2.2.1]heptan-5-ene) (NBANB), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (NBC2DMSC2NB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 2,2′-bi(bicyclo[2.2.1]heptan-5-ene) (NBANB), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (NBC2DMSC2NB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 3a,4,7,7a-tetrahydro-1H-4,7-methanoindene (DCPD), 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 3a,4,7,7a-tetrahydro-1H-4,7-methanoindene (DCPD), 5-phenethylbicyclo[2.2.1]hept-2-ene (PENB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyHexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hepta-2,5-diene (NBD), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-(cyclohex-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (CyclohexeneNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethanonaphthalene (TD), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), bicyclo[2.2.1]hepta-2,5-diene (NBD), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-cyclohexylbicyclo[2.2.1]hept-2-ene (CyhexNB), 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), 3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene (CPD3), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 3,3′-((oxybis(methylene))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazirine) (bis-diazirine ether), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB), dicumyl peroxide (DCP), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); and 5-Butylbicyclo[2.2.1]hept-2-ene (BuNB), 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene (ButenylNB), dicumyl peroxide (DCP), silica (SC2300), palladium(II) bis(tricyclohexylphosphine) diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA).

[0075] It should be noted that the composition of the present invention can be formed into any shape or form and is not particularly limited to a film. Thus, in one embodiment, the composition of the present invention can be formed into a sheet. The thickness of the sheet is not particularly limited, but considering its use as a dielectric material, it is 0.01 to 0.5 mm. In another embodiment, the thickness is approximately 0.02 to 0.2 mm. Sheets formed in this manner generally do not have fluidity at room temperature (25°C). The sheet may be provided on an optional support layer or may be provided alone. Examples of support layers include polyimide films or glass sheets, and other well-known peelable film substrates can also be used as support layers.

[0076] As described above, the film / sheet formed by the present invention has excellent dielectric properties. Quantitatively, the relative permittivity, i.e., the dielectric constant (Dk), of the film / sheet at a frequency of 10 GHz is approximately 2.0 to 2.38. The dielectric loss tangent at a frequency of 10 GHz is approximately 0.0003 to 0.005, and in another embodiment, approximately 0.0004 to 0.003. The composition of the present invention can be used in a variety of devices requiring such low dielectric constant materials, such as millimeter-wave radar and antennas. See, for example, Japanese Patent Application Publication Nos. 2018-109090 and 2003-216283. Antennas generally consist of an insulator and a conductor layer (e.g., copper foil). The composition or sheet of the present invention can be used as part or the entire insulator. Antennas using the composition or sheet of the present invention as part or the entire insulator have excellent high-frequency characteristics and reliability (durability).

[0077] The conductor layer of the antenna is formed, for example, from a metal having a desired conductivity. A circuit is formed on the conductor layer using a known circuit processing method. Examples of conductors that form the conductor layer include various conductive metals such as gold, silver, copper, iron, nickel, aluminum, and alloy metals thereof. The conductor layer can be formed by known methods, such as vapor deposition, electroless plating, or electrolytic plating. Alternatively, a metal foil (e.g., copper foil) may be pressure-bonded by thermal compression bonding. The metal foil that forms the conductor layer is a metal foil commonly used for electrical connections. In addition to copper foil, various metal foils such as gold, silver, nickel, and aluminum can be used. An alloy foil containing a significant portion (e.g., 98% by weight or more) of the metal may also be used. Among the metal foils, copper foil is commonly used. The copper foil may be rolled copper foil or electrolytic copper foil.

[0078] As mentioned above, the compositions of the present invention are generally used directly to form films or sheets. However, in one embodiment, the compositions may contain a small amount of solvent to dissolve the catalyst as described herein. The compositions of the present invention may also be used as low-molecular-weight varnish-type materials for specific applications. In such cases, an appropriate amount of a suitable solvent may be added to maintain the solids content of the composition at about 10 to 70% by weight during polymerization. Solvents suitable for forming the solution may be used as a single solvent or a mixture of solvents as required for the application.

[0079] In another aspect of the present invention, a film-forming kit is provided. The composition of the present invention is dispersed within the kit. Thus, in one embodiment, a kit is provided that includes dispersed therein one or more olefin monomers of formula (I) described herein, one or more compounds of formula (A1), (A2), or (A3) described herein, an organopalladium compound described herein, and an activator described herein. In one embodiment, the kit of the present invention includes one or more monomers of formula (I) and one or more compounds of formula (A1), (A2), or (A3) in combination to achieve a desired result or for an intended purpose.

[0080] In another aspect of one embodiment of the present invention, the kits of the present invention undergo bulk polymerization only when exposed to an appropriate temperature for a time sufficient to form a polymer film. In other words, the compositions of the present invention, as described herein, are poured onto a surface or substrate, encapsulated thereon, and upon exposure to an appropriate heat treatment, the monomers undergo polymerization to form a solid polymer in the form of a film or sheet.

[0081] Generally, as noted above, such polymerizations may be carried out at various temperatures, e.g., by heating to 90°C, followed by 110°C, and finally to 150°C, for a sufficient time, e.g., 5 minutes to 2 hours, at each temperature step, with further heating to above 150°C for various periods, e.g., 5 minutes to 15 minutes, if necessary. Polymerization may be carried out at a single temperature between about 100°C and 250°C for a sufficient time, e.g., 1 hour to 3 hours, or longer. By practicing the present invention, it is possible to obtain a polymerized film on a substrate that is a substantially uniform film. The thickness of the film can be adjusted as desired, as specifically noted above, and generally ranges from 50 to 500 microns or more.

[0082] Various well-known heating methods can be used to ensure the flatness of the sheet and suppress unintended shrinkage during sheet production. For example, the sheet is initially heated at a relatively low temperature and then gradually increased in temperature. To ensure the flatness, the sheet may be pressed with a flat plate (glass plate) before heating, or may be heated while being pressed with a flat plate. The pressure used for such pressing may be, for example, 0.1 to 8 MPa, and in another embodiment, may be in the range of about 0.3 to 5 MPa.

[0083] In one embodiment of the present invention, the kit described herein comprises a composition comprising two or more monomers of formula (I) and two or more compounds of formula (A1), (A2), or (A3). Any of the monomers of formula (I) or compounds of formula (A1), (A2), or (A3) described herein can be used in this embodiment in any preferred amount depending on the nature of the intended use.

[0084] In one embodiment, the kits described herein include various exemplary compositions as described above.

[0085] In yet another aspect of the present invention, there is further provided a method of forming a film for the manufacture of various optoelectronic and / or automotive devices, including: forming a homogeneous transparent composition comprising a combination of one or more monomers of Formula (I) with one or more compounds of Formula (A1) or (A2) or (A3); an organopalladium compound as described herein; an activator as described herein, and optionally a filler as described herein; coating or pouring the composition onto a suitable substrate to form a film; It consists of heating the film to an appropriate temperature to induce polymerization of the monomers.

[0086] In the step of coating the composition of the present invention onto a suitable substrate to form a film, the substrate may be coated using one of the coating methods described herein or known to those skilled in the art, such as spin coating. Other suitable coating methods include, but are not limited to, spray coating, doctor blading, meniscus coating, inkjet coating, and slot coating. The mixture may also be poured onto the substrate to form a film. The substrate is not particularly limited as long as it is suitable, and may be a substrate used in electrical, electronic, or optoelectronic devices, such as a semiconductor substrate, a ceramic substrate, or a glass substrate.

[0087] The coated substrate is then heated, i.e., baked, for example, at a temperature of about 50°C to about 150°C for about 1 minute to 180 minutes (temperature and time are adjustable) to promote bulk polymerization. In one embodiment, the substrate is baked at a temperature of about 100°C to about 120°C for 120 minutes to 180 minutes. In another embodiment, the substrate is baked at a temperature of about 110°C to about 150°C for 60 minutes to 120 minutes.

[0088] The electrical properties of the films thus formed were evaluated using any method known to those skilled in the art. For example, the dielectric constant (Dk) or dielectric constant and dielectric loss tangent were measured using a cavity resonator dielectric constant measurement device (manufactured by AET, JIS C 2565 standard) at a frequency of 10 GHz. The coefficient of thermal expansion (CTE) was measured using a thermodynamic analyzer (Seiko Instruments, SS 6000) under the following conditions: a sample size of 4 mm (width) x 40 mm (length) x 0.1 mm (thickness), a measurement temperature range of 30 to 350°C, and a heating rate of 5°C / min. The linear expansion coefficient was measured between 50°C and 100°C. Generally, films formed according to the present invention exhibit excellent dielectric properties and can be tailored to desired dielectric properties as described herein.

[0089] In one embodiment of the present invention, there is provided a film or sheet obtained by bulk polymerization of the composition as described herein, and in another embodiment, there is provided an electronic device comprising the film / sheet of the present invention as described herein.

[0090] In yet another aspect of the present invention, there is also provided a composition comprising a polymer formed from one monomer of formula (I) and at least one compound of formula (A1) or (A2) or (A3), which composition can be crosslinked by exposure to appropriate temperature and / or photolytic conditions as described herein to form a 3D article, such as a film, that exhibits superior properties as described herein.

[0091] The following examples provide detailed descriptions of the preparation and use of specific compounds / monomers, polymers, and compositions of the present invention. The detailed preparation methods fall within the scope of the general preparation methods described above and are further illustrative thereof. The examples are for illustrative purposes only and are not intended to limit the scope of the present invention. In the examples and herein, the ratio of monomer to catalyst is a molar ratio.

[0092] Example (general) The following abbreviations are used herein to describe some of the compounds, instruments and / or methods used to describe certain embodiments of the present invention. PENB: 5-phenethylbicyclo[2.2.1]hept-2-ene; PhNB: 5-phenylbicyclo[2.2.1]hept-2-ene; DecNB: 5-decylbicyclo[2.2.1]hept-2-ene; HexNB: 5-hexylbicyclo[2.2.1]hept-2-ene; BuNB: 5-butylbicyclo[2.2.1]hept-2-ene; ButenylNB: 5-(but-3-en-1-yl)bicyclo[2.2.1]hept-2-ene; NBANB: 2,2'-bi(bicyclo[2.2.1]heptan-5-ene); CyHexNB: 5-cyclohexylbicyclo[2.2.1]hept-2-ene; DCPD: 3a,4,7,7a-tetrahydro-1H-4,7-methanoindene; NBD: bicyclo[2.2.1]hepta-2,5-diene; TDD: 1,4,4a,5,8,8a-hexahydro-1,4:5,8-dimethanonaphthalene; NBC2DMSC2NB: 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane; CPD3: 3a,4,4a,5,8,8a,9,9a-octahydro-1H-4,9:5,8-dimethanocyclopenta[b]naphthalene; Pd785: Palladium(II) bis(tricyclohexylphosphine) diacetate; DANFABA: dimethylanilinium tetrakis(pentafluorophenyl)borate; DCP: dicumyl peroxide; Bis-diazirine ether: 3,3'-((oxybis(methylene))bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazirine); GEN-I BondLynx: 3,3'-((perfluoropropane-2,2-diyl)bis(4,1-phenylene))bis(3-(trifluoromethyl)-3H-diazirine); MCH: methylcyclohexane; EA: ethyl acetate; THF: tetrahydrofuran; DSC: differential scanning calorimetry; TGA: thermogravimetric analysis; TMA: Thermodynamic analysis; pphr: parts per hundred parts of resin or parts per hundred parts of total monomers of formula (I).

[0093] The various monomers used herein are commercially available or can be readily prepared by the procedures described in US Pat. No. 9,944,818.

[0094] Example 1 (DecNB / HexNB / TDD-containing composition - molar ratio 50:30:20) A mixture of Pd-785 (0.003 mmol) and DANFABA (0.15 mmol) was mixed in a vial in a dry box and then sealed. THF (0.24 g) was added to the vial via syringe. The catalyst solution was then added to a mixture of DecNB (3.52 g, 15 mmol), HexNB (1.6 g, 9 mmol), and TDD (0.95 g, 6 mmol). The composition thus formed was coated onto a glass substrate using a doctor blade and cured in an oven at 110 °C for 3 h in air to obtain a film approximately 100–300 μm thick. This film was cut into rectangular strips and used for thermal and dielectric property measurements. The results are summarized in Table 1.

[0095] Example 2 (PhNB / DecNB / TDD containing composition - 50:30:20 molar ratio) A mixture of Pd-785 (0.031 g) and DANFABA (0.176 g) was mixed in a vial in a dry box and then sealed. THF (3.2 g) was added to the vial via syringe, and 0.16 g of this solution was added to a mixture of exo-PhNB (2.13 g, 12.5 mmol), DecNB (1.76 g, 7 mmol), and TDD (0.79 g, 5 mmol). The composition thus formed was coated onto a glass substrate using a doctor blade and cured in an oven at 110 °C for 3 h in air to obtain a film approximately 100–300 μm thick. This film was cut into rectangular strips and used for thermal and dielectric property measurements. The results are summarized in Table 1.

[0096] Example 3 (NBANB / HexNB / NBC2(DMS)2C2NB containing composition - molar ratio 50:30:20) A mixture of Pd-785 (0.031 g) and DANFABA (0.176 g) was mixed in a vial in a dry box and then sealed. THF (3.2 g) was added to the vial via syringe, and 0.16 g of this solution was added to a mixture of NBANB (1.88 g, 10 mmol), HexNB (1.07 g, 6 mmol), and NBC2(DMS)2C2NB (1.5 g, 4 mmol). The composition thus formed was coated onto a glass substrate using a doctor blade and cured in an oven at 110 °C for 3 h in air to obtain a film approximately 100–300 μm thick. This film was cut into rectangular strips and used for thermal and dielectric property measurements. The results are summarized in Table 1.

[0097] Example 4 (NBANB / DecNB / NBC2(DMS)2C2NB containing composition - molar ratio 50:30:20) A mixture of Pd-785 (0.031 g) and DANFABA (0.176 g) was mixed in a vial in a dry box and then sealed. THF (3.2 g) was added to the vial via syringe, and 0.16 g of this solution was added to a mixture of NBANB (1.88 g, 10 mmol), DecNB (1.41 g, 6 mmol), and NBC2(DMS)2C2NB (1.5 g, 4 mmol). The composition thus formed was coated onto a glass substrate using a doctor blade and cured in an oven at 110 °C for 3 h in air to obtain a film approximately 100–300 μm thick. This film was cut into rectangular strips and used for measuring thermal and dielectric properties. The results are summarized in Table 1.

[0098] [Table 1]

[0099] Examples 5 to 8 Stock solutions of Pd-785 (1 wt% in MCH) and DANFABA (5 wt% in EA) were prepared in sealed vials. Various compositions containing different monomers were then prepared with Pd-785 and DANFABA as described herein. Example 5 contains CyHexNB / BuNB / NBD (molar ratio 50 / 40 / 10), Example 6 contains TD / BuNB / NBD (molar ratio 50 / 40 / 10), and Example 7 contains CyHexNB / BuNB / CPD3 (molar ratio 50 / 40 / 10). Example 8 contains CyHexNB / BuNB / CPD3 (molar ratio 50 / 40 / 10) with 4 pphr DCP as the thermal radical initiator. Each composition in Examples 5-8 contains a monomer / Pd-785 / DANFABA molar ratio of approximately 10,000 / 1 / 5. Each composition of Examples 5 to 8 was poured onto a glass substrate and a doctor blade was used to create a rectangle of approximately 10 cm x 6 cm, which was then cured at 110°C for 3 hours to form a rectangular film of approximately 200 to 500 μm thickness. The film was further heated at approximately 120 to 150°C for 3 to 6 hours under vacuum to remove residual monomer. The rectangular film was cut into smaller rectangles for TMA and electrical property measurements, including the dielectric constant (Dk) and dielectric loss factor (Df) at a frequency of 10 GHz. The glass transition temperature (T g ), the temperature at which 5% weight loss of the film occurs (T d5 The thermal decomposition temperatures, coefficients of thermal expansion (CTE), Dk and Df of the films measured at 300°C are summarized in Table 2. From the data shown in Table 2, it can be seen that the films produced with the compositions of Examples 5 to 8 have high T g , high T in the range of 284℃~301℃ d5The compositions of Example 8 exhibit low CTEs in the range of 86 to 89 ppm / K, low Dk in the range of 2.2 to 2.36, and low Df in the range of 0.0008 to 0.0022. Furthermore, when incorporating a thermal free radical generator such as DCP to utilize a second cure pathway to crosslink the film to produce a thermoset, as in Example 8, the second double bond of CPD3 undergoes free radical initiated polymerization, further reducing Df to 0.001 at 10 GHz compared to the composition of Example 7, in which a second cure pathway to crosslink the film is not utilized. The glass transition temperature of the composition of Example 8 is also higher than that of Example 7, indicating the formation of a more robust crosslinked film.

[0100] [Table 2]

[0101] Examples 9 to 14 Stock solutions of Pd-785 (1 wt% solution in MCH) and DANFABA (5 wt% solution in EA) were prepared in sealed vials. Various compositions were then prepared by adding stock solutions of Pd-785 (0.08 g) and DANFABA (0.08 g) to a sample of HexNB (1.68 g, 10 mmol). The monomer:Pd-785:DANFABA ratio was maintained at approximately 10,000:1:5. Various amounts of bis-diazirine ether were then added to each composition, as listed in Table 3. Each of these compositions was individually doctor-bladed onto a glass substrate and cured at 130 °C for 3 hours. Under these curing conditions, the HexNB monomer is expected to bulk polymerize into poly-HexNB, while the bis-diazirine ether decomposes to form a carbene intermediate that inserts into the C-H bonds of the HexNB to form a crosslinked network, as described herein. The dielectric constant (Dk) and dielectric loss factor (Df) were measured at 10 GHz, and as can be seen from the data shown in Table 3, Examples 10 to 14 all produced films with lower Dk. The appearance of a second glass transition temperature above 300°C and a decrease in the coefficient of thermal expansion (CTE) and the first glass transition temperature (T gThe disappearance of the bis-diazirine ether, as measured by TMA, was observed only in the presence of the bis-diazirine ether. The TMA data summarized in Table 3 and Figure 1 indicate that a crosslinked network, i.e., a thermoset film, is formed in the presence of the bis-diazirine ether.

[0102] [Table 3]

[0103] Example 15 Weight average molecular weight (M w A sample of poly-HexylNB, with a pH of approximately 224 K (5 g), was dissolved in decane (20 g) to prepare a 20 wt. % solution. This solution was divided into two equal parts; the first part was designated Example A, and the second part (10 g of solution containing 2 g of polymer) was mixed with bis-diazirine ether (0.24 g, 12 pphr) and designated Example 15B. Both solutions were filtered through a 1 μm PTFE filter. These solutions were applied to glass substrates and baked on a hot plate at 80-90°C for 10 minutes to remove the decane solvent, keeping the bake temperature low enough to avoid thermal decomposition of the bis-diazirine ether. Films formed to a thickness of approximately 100-200 μm were exposed to i-line radiation at 365 nm wavelength at a dose of 1000 mJ / cm. 2 The exposed films were exposed to 120°C for 5 minutes followed by a bake step. The film formed from the composition of Example 15A, which did not contain the bis-diazirine ether, was readily dissolved in THF, indicating that crosslinking did not occur during the light exposure step. On the other hand, the film formed from the composition of Example 15B was not dissolved in THF. This clearly indicates that the film of Example 15B was photocured due to the presence of the bis-diazirine ether, which formed a crosslinked network. The properties of the two films are summarized in Table 4.

[0104] [Table 4]

[0105] Examples 16 to 21 Stock solutions of Pd-785 (1 wt % in MCH) and DANFABA (5 wt % in EAH) were prepared in sealed vials. Various compositions containing different monomers were then prepared with Pd-785 and DANFABA as described herein: Example 16 contains HexNB / ButenylNB (80 / 20 molar ratio), Example 17 contains HexNB / ButenylNB (70 / 30 molar ratio), Example 18 contains BuNB / ButenylNB (80 / 20 molar ratio), and Example 19 contains BuNB / ButenylNB (70 / 30 molar ratio). Example 20 contained BuNB / ButenylNB (70 / 30 molar ratio) and DCP (2 pphr) as thermal free radical generators, while Example 21 contained BuNB / ButenylNB (70 / 30 molar ratio), DCP (2 pphr), and silica nanoparticles (75 pphr, SC2300-SVJ) as thermal free radical generators. Sufficient amounts of Pd-785 in MCH and DANFABA in EA were added to each of these compositions to maintain a monomer / Pd-785 / DANFABA molar ratio of approximately 10,000 / 1 / 5. The compositions of Examples 20 and 21 were poured onto glass substrates and, using a doctor blade, created rectangular shapes approximately 10 cm x 6 cm. These were then cured at 120 °C for 3 hours (Cure Condition 1) to form rectangular films approximately 100–300 μm thick. Portions of these films were further heated at approximately 160 °C for 2 hours (Cure Condition 2). The rectangular films were cut into smaller rectangles and the TMA, dielectric constant (Dk), and dielectric loss factor (Df) at 10 GHz were measured. Table 5 summarizes the compositions and curing conditions of Examples 16 to 21. The glass transition temperature (T g ), the temperature at which 5% weight loss of the film occurs (T d5 The thermal decomposition temperature, coefficient of thermal expansion (CTE), Dk and Df of the film at 10 GHz frequency measured by FT-IR spectroscopy are summarized in Table 6.

[0106] [Table 5]

[0107] [Table 6]

[0108] Examples 22 to 25 Weight average molecular weight (M w A 20 wt% solution was prepared by dissolving 15 g of a poly-HexNB sample (with a molecular weight of approximately 190,000) in 60 g of decane. Various compositions were prepared by adding 1 g of poly-HexNB to a 5 g portion of this stock solution: Example 22 contains 10 ppr of bis-diazirine ether, Example 23 contains 10 ppr of GEN-IBondLynx, Example 24 contains 20 ppr of GEN-IBondLynx and an additional 15 g of decane, and Example 25 contains 15 ppr of GEN-IBondLynx. All compositions were filtered through a 1 μm PTFE filter. Films 150–200 μm thick were formed on glass substrates using a doctor blade, followed by a 5-minute bake step on a hot plate at 80 °C to remove the solvent. The films produced in Examples 22–24 were cut in half. Each half of the film was exposed to a dose of 1500 mJ / cm to effect photocuring. 2 Half of the film was exposed to i-line radiation (365 nm wavelength), and the other half was heated in an oven at 130°C for 30 minutes under a nitrogen atmosphere to affect thermal curing. Small sections of the cured films were immersed in decane for approximately 1 hour to test the film's solubility. None of the films that underwent photo- or thermal curing were soluble in decane, but the film that did not contain the bis-diazirine crosslinker was readily dissolved in either the photo- or thermal curing step. The dielectric constant (Dk) and dielectric loss factor (Df) were measured and are listed in Table 7. The film of Example 25 was further cured at 190°C under vacuum for 1.5 hours to yield cured films with thicknesses of approximately 140 μm and 160 μm. The Dk and Df of these films were measured at 10 GHz, 35 GHz, and 80 GHz and are listed in Table 8.

[0109] [Table 7]

[0110] [Table 8]

[0111] As can be seen from the data presented in Table 8, Df does not change significantly at higher frequencies, which provides a valuable advantage for various applications: for devices operating at high frequencies of 50 GHz and above, signal loss must be minimized for optimal performance, which is provided by films formed from the compositions of the present invention.

[0112] Examples 26-27 The compositions of Examples 23 and 24 were spin-coated onto a 4-inch SiO2 wafer at 500 rpm for 40 seconds and then post-baked (PAB) at 80°C for 2 minutes. The film obtained in Example 23 was applied through a mask at 1000 mJ / cm2. 2 The film obtained in Example 24 was exposed to 791 mJ / cm 2 of i-line radiation (365 nm) through a mask to generate lines, pillars, trenches, and contact holes (CH). 2 The compositions were exposed to 1000 nm of i-line radiation to produce lines, pillars, trenches, and contact holes (CH). The exposed films were developed in decane to reveal images of the lines, pillars, trenches, and contact holes (CH). Table 9 summarizes the photoimage properties of the compositions.

[0113] [Table 9]

[0114] Although the present invention has been described by the above examples, the present invention is not limited to the examples and encompasses the general scope disclosed in this specification. Various modifications and embodiments can be made without departing from the spirit of the present invention.

Claims

1. A film-forming composition comprising: a) one or more olefin monomers of formula (I): 【Chemical 1】 (where, m is 0 or 1; 【Chemistry 2】 is a single or double bond, R 1 , R 2 , R 3 , and R 4 are the same or different and each independently represent hydrogen, straight-chain or branched (C 4 -C 16 ) alkyl, straight or branched (C 2 -C 16 ) alkenyl, (C 3 -C 10 ) cycloalkyl, (C 3 -C 10 ) cycloalkenyl, (C 6 -C 12 ) bicycloalkyl, (C 6 -C 12 ) aryl, and (C 6 -C 12 ) aryl (C 1 -C 6 ) alkyl; or R 1 and R 2 One of them is R 3 and R 4 and the carbon atoms to which they are attached, optionally containing one or more double bonds, substituted or unsubstituted (C 5 -C 14 ) monocyclic ring, (C 5 -C 14 ) a bicyclic ring, or (C 5 -C 14 ) forms a tricyclic ring. b) a compound selected from the group consisting of: Compound of formula (A1): 【Chemistry 3】 (where, b is an integer from 2 to 6, Z is a bond or R 9 R 10 SiOSiR 11 R 12 where R 9 , R 10 , R 11 and R 12 are the same or different and each independently represent methyl, ethyl, and straight-chain or branched (C 3 -C 6 ) alkyl; R 5 , R 6 , R 7 and R 8 are the same or different and each independently represent hydrogen, methyl, ethyl, and straight-chain or branched (C 3 -C 16 ) alkyl; and Compound of formula (A3): 【Chemistry 5】 (where, L is a bond, methylene, ethylene, straight or branched (C 3 -C 16 ) alkylene, (C 3 -C 16 ) cycloalkylene, (C 5 -C 8 ) heterocycle, (C 6 -C 12 ) arylene, (C 5 -C 12 ) heteroarylene, and —(CH 2 ) c O (CH 2 ) c -, c is an integer of 1 to 6, and optionally each CH 2 is methyl, ethyl, straight or branched (C 3 -C 16 ) alkyl, and (C 6 -C 12 ) aryl, where methylene, ethylene or (C 3 -C 16 The hydrogen moiety on the alkylene is fluorine, trifluoromethyl, pentafluoroethyl, and straight-chain or branched perfluoro(C 3 -C 16 ) alkyl; R 17 and R 18 are the same or different and each independently represent methyl, ethyl, straight-chain or branched (C 3 -C 12 ) alkyl, (C 6 -C 12 ) aryl, and (C 6 -C 12 ) aryl (C 1 -C 12 ) alkyl, optionally selected from methyl, ethyl or (C 3 -C 12 The hydrogen moiety on the alkyl is fluorine, trifluoromethyl, pentafluoroethyl, and straight or branched (C 3 -C 12 ) perfluoroalkyl; Ar 1 and Ar 2 are the same or different, and each independently represents (C 6 -C 12 ) an arylene group or (C 6 -C 12 ) heteroarylene groups, which are optionally selected from (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, (C 6 -C 10 ) aryl, (C 6 -C 12 ) aryloxy, (C 6 -C 12 ) aryl (C 1 -C 4 ) alkyl, and (C 6 -C 12 ) aryl (C 1 -C 4 ) alkyloxy. c) an organopalladium compound selected from the group consisting of: Palladium(II) bis(triphenylphosphine) dichloride; Palladium(II) bis(triphenylphosphine) dibromide; Palladium(II) bis(triphenylphosphine) diacetate; Palladium(II) bis(triphenylphosphine)bis(trifluoroacetate); Palladium(II) bis(tricyclohexylphosphine) dichloride; Palladium(II) bis(tricyclohexylphosphine) dibromide; Palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785); Palladium(II) bis(tricyclohexylphosphine)bis(trifluoroacetate); Palladium(II) bis(tri-p-tolylphosphine) dichloride; Palladium(II) bis(tri-p-tolylphosphine) dibromide; Palladium(II) bis(tri-p-tolylphosphine) diacetate; Palladium(II) bis(tri-p-tolylphosphine)bis(trifluoroacetate); Palladium(II) ethylhexanoate; Dichlorobis(acetonato)palladium(II); and Dichlorobis(benzonitrile)palladium(II); and d) an active agent selected from the group consisting of: Lithium tetrafluoroborate; Lithium triflate; Lithium tetrakis(pentafluorophenyl)borate; Lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA); Lithium tetrakis(pentafluorophenyl)borate isopropanolate; Lithium tetraphenylborate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; Lithium tetrakis(2-fluorophenyl)borate; Lithium tetrakis(3-fluorophenyl)borate; Lithium tetrakis(4-fluorophenyl)borate; Lithium tetrakis(3,5-difluorophenyl)borate; Lithium hexafluorophosphate; Lithium hexaphenyl phosphate; Lithium hexakis(pentafluorophenyl)phosphate; Lithium hexafluoroarsenate; Lithium hexaphenylarsenate; Lithium hexakis(pentafluorophenyl)arsenate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)arsenate; Lithium hexafluoroantimonate; Lithium hexaphenylantimonate; Lithium hexakis(pentafluorophenyl)antimonate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)antimonate; Lithium tetrakis(pentafluorophenyl)aluminate; Lithium tris(nonafluorobiphenyl)fluoroaluminate; Lithium (octyloxy)tris(pentafluorophenyl)aluminate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate; Lithium methyltris(pentafluorophenyl)aluminate; Dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); wherein a film formed from the composition has a dielectric constant (Dk) of less than 2.4 at a frequency of 10 GHz, a glass transition temperature of greater than 150° C., and a coefficient of thermal expansion (CTE) of less than 150 ppm / K.

2. m is 0, 【Chemistry 6】 is a single bond, R 1 , R 2 , R 3 , and R 4 The film-forming composition of claim 1, wherein: are the same or different and each independently selected from the group consisting of hydrogen, n-butyl, n-hexyl, cyclohexyl, cyclohexenyl, and norbornyl.

3. 2. The film-forming composition of claim 1, wherein the monomer of formula (I) is selected from the group consisting of: 【Chemistry 7-1】 【Chemistry 7-2】 【Chemistry 7-3】

4. 2. The film-forming composition of claim 1, wherein the compound of formula (A1) or (A3) is selected from the group consisting of: 【Chemistry 8-1】 【Chemistry 8-2】

5. 10. The film-forming composition of claim 1, wherein the composition comprises at least one monomer of formula (I) and one compound of formula (A1) or (A3).

6. 10. The film-forming composition of claim 1, wherein a film formed from the composition has a dielectric constant (Dk) of 2.0 to 2.38 at a frequency of 10 GHz, a glass transition temperature of 160°C to 350°C, and a coefficient of thermal expansion (CTE) of 100 ppm / K to 140 ppm / K.

7. The film-forming composition according to claim 1 , further comprising an inorganic filler.

8. The film-forming composition of claim 1 further comprising an organic filler.

9. 10. The film-forming composition of claim 1 selected from the group consisting of: 5-decylbicyclo[2.2.1]hept-2-ene (DecNB), 2,2′-bi(bicyclo[2.2.1]heptan-5-ene) (NBANB), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (NBC2DMSC2NB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); and 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 2,2′-bi(bicyclo[2.2.1]heptan-5-ene) (NBANB), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (NBC2DMSC2NB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA).

10. A film-forming kit comprising a composition comprising: a) one or more olefin monomers of formula (I): 【Chemistry 10】 (where, m is 0 or 1; 【Chemistry 11】 is a single or double bond, R 1 , R 2 , R 3 , and R 4 are the same or different and each independently represent hydrogen, straight-chain or branched (C 4 -C 16 ) alkyl, straight or branched (C 2 -C 16 ) alkenyl, (C 3 -C 10 ) cycloalkyl, (C 3 -C 10 ) cycloalkenyl, (C 6 -C 12 ) bicycloalkyl, (C 6 -C 12 ) aryl, and (C 6 -C 12 ) aryl (C 1 -C 6 ) alkyl; or R 1 and R 2 One of them is R 3 and R 4 and the carbon atoms to which they are attached, optionally containing one or more double bonds, substituted or unsubstituted (C 5 -C 14 ) monocyclic ring, (C 5 -C 14 ) a bicyclic ring, or (C 5 -C 14 ) forms a tricyclic ring. b) a compound selected from the group consisting of: Compound of formula (A1): 【Chemistry 12】 (where, b is an integer from 2 to 6, Z is a bond or R 9 R 10 SiOSiR 11 R 12 where R 9 , R 10 , R 11 and R 12 are the same or different and each independently represent methyl, ethyl, and straight-chain or branched (C 3 -C 6 ) alkyl; R 5 , R 6 , R 7 and R 8 are the same or different and each independently represent hydrogen, methyl, ethyl, and straight-chain or branched (C 3 -C 16 ) alkyl; and Compound of formula (A3): 【Chemistry 14】 (where, L is a bond, methylene, ethylene, straight or branched (C 3 -C 16 ) alkylene, (C 3 -C 16 ) cycloalkylene, (C 5 -C 8 ) heterocycle, (C 6 -C 12 ) arylene, (C 5 -C 12 ) heteroarylene, and —(CH 2 ) c O (CH 2 ) c -, c is an integer from 1 to 6, and optionally each CH 2 is methyl, ethyl, straight or branched (C 3 -C 16 ) alkyl, and (C 6 -C 12 ) aryl, where methylene, ethylene or (C 3 -C 16 The hydrogen moiety on the alkylene is fluorine, trifluoromethyl, pentafluoroethyl, and straight-chain or branched perfluoro(C 3 -C 16 ) alkyl; R 17 and R 18 are the same or different and each independently represent methyl, ethyl, straight-chain or branched (C 3 -C 12 ) alkyl, (C 6 -C 12 ) aryl, and (C 6 -C 12 ) aryl (C 1 -C 12 ) alkyl, optionally selected from the group consisting of methyl, ethyl or (C 3 -C 12 The hydrogen moiety on the alkyl is fluorine, trifluoromethyl, pentafluoroethyl, and straight or branched (C 3 -C 12 ) perfluoroalkyl; Ar 1 and Ar 2 are the same or different, and each independently represents (C 6 -C 12 ) an arylene group or (C 6 -C 12 ) heteroarylene groups, which are optionally selected from (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, (C 6 -C 10 ) aryl, (C 6 -C 12 ) aryloxy, (C 6 -C 12 ) aryl (C 1 -C 4 ) alkyl, and (C 6 -C 12 ) aryl (C 1 -C 4 ) alkyloxy. c) an organopalladium compound selected from the group consisting of: Palladium(II) bis(triphenylphosphine) dichloride; Palladium(II) bis(triphenylphosphine) dibromide; Palladium(II) bis(triphenylphosphine) diacetate; Palladium(II) bis(triphenylphosphine)bis(trifluoroacetate); Palladium(II) bis(tricyclohexylphosphine) dichloride; Palladium(II) bis(tricyclohexylphosphine) dibromide; Palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785); Palladium(II) bis(tricyclohexylphosphine)bis(trifluoroacetate); Palladium(II) bis(tri-p-tolylphosphine) dichloride; Palladium(II) bis(tri-p-tolylphosphine) dibromide; Palladium(II) bis(tri-p-tolylphosphine) diacetate; Palladium(II) bis(tri-p-tolylphosphine)bis(trifluoroacetate); Palladium(II) ethylhexanoate; Dichlorobis(acetonato)palladium(II); and Dichlorobis(benzonitrile)palladium(II); d) an active agent selected from the group consisting of: Lithium tetrafluoroborate; Lithium triflate; Lithium tetrakis(pentafluorophenyl)borate; Lithium tetrakis(pentafluorophenyl)borate etherate (LiFABA); Lithium tetrakis(pentafluorophenyl)borate isopropanolate; Lithium tetraphenylborate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; Lithium tetrakis(2-fluorophenyl)borate; Lithium tetrakis(3-fluorophenyl)borate; Lithium tetrakis(4-fluorophenyl)borate; Lithium tetrakis(3,5-difluorophenyl)borate; Lithium hexafluorophosphate; Lithium hexaphenyl phosphate; Lithium hexakis(pentafluorophenyl)phosphate; Lithium hexafluoroarsenate; Lithium hexaphenylarsenate; Lithium hexakis(pentafluorophenyl)arsenate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)arsenate; Lithium hexafluoroantimonate; Lithium hexaphenylantimonate; Lithium hexakis(pentafluorophenyl)antimonate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)antimonate; Lithium tetrakis(pentafluorophenyl)aluminate; Lithium tris(nonafluorobiphenyl)fluoroaluminate; Lithium (octyloxy)tris(pentafluorophenyl)aluminate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate; Lithium methyltris(pentafluorophenyl)aluminate; Dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); and e) fillers; wherein a film formed from the composition has a dielectric constant (Dk) of less than 2.4 at a frequency of 10 GHz, a glass transition temperature of greater than 150° C., and a coefficient of thermal expansion (CTE) of less than 150 ppm / K.

11. m is 0, 【Chemistry 15】 is a single bond, R 1 , R 2 , R 3 , and R 4 The kit of claim 10, wherein: are the same or different and each independently selected from the group consisting of hydrogen, n-butyl, n-hexyl, cyclohexyl, cyclohexenyl, and norbornyl.

12. 11. The kit of claim 10, wherein the monomer of formula (I) is selected from the group consisting of: 【Chemistry 16-1】 【Chemistry 16-2】 【Chemistry 16-3】

13. The kit of claim 10, wherein the compound of formula (A1) or (A3) is selected from the group consisting of: 【Chemistry 17-1】 【Chemistry 17-2】

14. 11. The kit of claim 10, wherein the composition comprises at least one monomer of formula (I) and one compound of formula (A1) or (A3).

15. 11. The kit of claim 10, wherein a film formed from the composition has a dielectric constant (Dk) of 2.0 to 2.38 at a frequency of 10 GHz, a glass transition temperature of 160°C to 350°C, and a coefficient of thermal expansion (CTE) of 100 ppm / K to 140 ppm / K.

16. The kit of claim 10, wherein the filler is an inorganic filler.

17. The kit of claim 10 , wherein the filler is an organic filler.

18. The kit of claim 10, selected from the group consisting of: 5-decylbicyclo[2.2.1]hept-2-ene (DecNB), 2,2′-bi(bicyclo[2.2.1]heptan-5-ene) (NBANB), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (NBC2DMSC2NB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); and 5-hexylbicyclo[2.2.1]hept-2-ene (HexNB), 2,2′-bi(bicyclo[2.2.1]heptan-5-ene) (NBANB), 1,3-bis(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (NBC2DMSC2NB), palladium(II) bis(tricyclohexylphosphine)diacetate (Pd785), and dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA).

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