A resin composition and an article thereof

Abstract

The present application discloses a resin composition, which comprises 100 parts by weight of a copolymer of phenyl vinyl silane and alkenyl compound, and 20 to 100 parts by weight of styrene-terminated phenol-aldehyde resin; wherein the raw materials of the copolymer of phenyl vinyl silane and alkenyl compound comprise phenyl vinyl silane and alkenyl compound, and the phenyl vinyl silane is 80 to 98 parts by weight and the alkenyl compound is 2 to 20 parts by weight, based on the total weight of 100 parts by weight of the phenyl vinyl silane and the alkenyl compound. The aforementioned resin composition can be made into products such as prepreg, resin film, laminated board, printed circuit board or cured insulator.

Description

Technical Field

[0001] This invention relates to the field of resin compositions, and more specifically to a resin composition and its products that can be used to prepare prepregs, resin films, laminates, printed circuit boards or cured insulators. Background Technology

[0002] In recent years, with the continuous development of information processing in electronic products such as mobile communications, servers, and cloud storage towards higher frequency and higher speed digital signal transmission, low-dielectric-performance resin materials have become the main development direction for high-frequency and high-speed substrates. In the manufacturing of copper-clad laminates (CCLs), the raw material phenylvinylsilane is prone to volatilization due to the high-temperature heating during material processing. Direct use not only results in the waste of expensive raw materials but also alters the properties of the CCL material, failing to meet performance requirements.

[0003] Therefore, optimizing and improving resin materials to reduce their volatility and enhance the overall performance of copper-clad laminate materials, such as improving one or more properties like glass transition temperature, copper foil tensile strength, thermal expansion rate and coefficient of thermal expansion, PCT heat resistance, dielectric constant, and dielectric loss, is a technical challenge that urgently needs to be solved in this field. Summary of the Invention

[0004] In view of the problems encountered in the prior art, the present invention provides a resin composition that can be used to prepare prepregs, resin films, laminates, printed circuit boards or cured insulators, so as to solve the problems of high volatility and inability to meet one or more of the above-mentioned properties in the resin products of the prior art.

[0005] In a first aspect, the present invention provides a resin composition comprising, by weight, 100 parts of a copolymer of phenyl vinyl silane and an alkenyl compound, and 20 to 100 parts of a styrene-terminated phenolic resin.

[0006] The copolymer of phenylvinylsilane and alkenyl compound comprises structural units formed by phenylvinylsilane and alkenyl compound; the raw materials of the copolymer include phenylvinylsilane and alkenyl compound, based on a total weight of 100 parts by weight of phenylvinylsilane and alkenyl compound, wherein phenylvinylsilane comprises 80 to 98 parts by weight and alkenyl compound comprises 2 to 20 parts by weight.

[0007] The phenylvinylsilane has the structure shown in formula (1) and / or formula (2), the alkenyl compound has the structure shown in formula (3), and the styrene-terminated phenolic resin has the structure shown in formula (4).

[0008]

[0009]

[0010] Wherein, Ra, Rb, Rc, and Rd are each independently H or a monovalent organic group, m and n are each independently integers from 0 to 5, and Re, Rf, Rg, and Rh are each independently H or a monovalent alkyl group having 1 to 4 carbon atoms;

[0011] Furthermore, R is a divalent organic group, and n1 is an integer from 1 to 30.

[0012] In an exemplary embodiment, R is at least one of methylene, dicyclopentadienyl, substituted or unsubstituted aryl group, and n1 is an integer from 1 to 10.

[0013] In an exemplary embodiment, the chemical structure of the alkenyl compound is shown in at least one of formula (11), formula (12), or formula (13):

[0014] 2,4-Diphenyl-4-methyl-1-pentene:

[0015] 2,4-Diphenyl-3,4-dimethyl-1-hexene:

[0016] 2,4-Di(p-methoxy)phenyl-4-methyl-1-pentene:

[0017] In a second aspect, the present invention provides an article made of the above-described resin composition, the article comprising a prepreg, a resin film, a laminate, a printed circuit board, or a cured insulator.

[0018] In an exemplary embodiment, the resin composition or article thereof provided by the present invention can be improved in one or more aspects such as glass transition temperature, copper foil tensile strength, dielectric constant, dielectric loss, thermal expansion coefficient, or PCT heat resistance. Attached Figure Description

[0019] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0020] Figure 1 The infrared spectrum of copolymer 3, phenyltrivinylsilane and 2,4-diphenyl-4-methyl-1-pentene of the present invention is shown below; wherein, a is 2,4-diphenyl-4-methyl-1-pentene, b is phenyltrivinylsilane and c is copolymer 3.

[0021] Figure 2 The above is a 1H NMR spectrum of copolymer 3, phenyltrivinylsilane and 2,4-diphenyl-4-methyl-1-pentene of the present invention; wherein, a is phenyltrivinylsilane, b is 2,4-diphenyl-4-methyl-1-pentene and c is copolymer 3.

[0022] Figure 3 This is a gel permeation chromatogram of copolymer 3 of the present invention. Detailed Implementation

[0023] The following embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. The terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art. Unless otherwise specified, the terms defined herein shall prevail. The terms “comprising,” “including,” “containing,” and “having” as used herein are open-ended conjunctions (i.e., they may also include other elements not listed). The terms “composed of” and “consisting of” as used herein are closed-ended conjunctions.

[0024] The numerical range used in this article includes all possible subranges and all individual numerical values ​​(including fractions and integers) within the range.

[0025] The numerical values ​​used herein include all ranges of values ​​that are the same as the value after rounding to the number of significant digits. It should be understood that the invention can be described individually and / or in combination using each member of the Markush group. "Or a combination thereof" as used herein means "any combination thereof". The term "resin" as used herein can include monomers, polymers thereof, combinations of monomers, combinations of polymers thereof, or combinations of monomers and their polymers, etc., and the invention is not limited thereto. For example, "maleimide resin" in this invention includes maleimide monomers (maleimide small molecule compounds), maleimide polymers, combinations of maleimide monomers, combinations of maleimide polymers, and combinations of maleimide monomers and maleimide polymers.

[0026] In the structure of this paper, "*" represents the bonding site.

[0027] The polymers used in this article refer to products formed by the polymerization reaction of monomers. Polymers may include homopolymers (also known as self-polymers), copolymers, prepolymers, etc., but this invention is not limited to these.

[0028] Homopolymers are chemical substances formed by the polymerization, addition polymerization, or condensation polymerization of a single compound. Copolymers are chemical substances formed by the polymerization, addition polymerization, or condensation polymerization of two or more compounds, including random copolymers (structures such as -AABABBBAAABBA-), alternating copolymers (structures such as -ABABABAB-), graft copolymers (structures such as -AA(A-BBBB)AA(A-BBBB)AAA-), and block copolymers (structures such as -AAAAA-BBBBBB-AAAAA-). The copolymers used in this paper refer to polymers obtained by copolymerizing monomers of phenylvinylsilane, divinylbenzene, and styrene. The copolymers used in this paper only need to contain segments of phenylvinylsilane, divinylbenzene, and styrene; there are no particular limitations on whether the polymer backbone and side chain units have been modified or altered.

[0029] The prepolymer used in this article refers to a low molecular weight polymer with a molecular weight between that of the monomer and the final polymer. The prepolymer contains reactive functional groups that can undergo further polymerization to obtain a fully cross-linked or hardened product with a higher molecular weight.

[0030] Polymers also include oligomers, but the present invention is not limited thereto. Oligomers, also known as low-molecular-weight polymers, are polymers composed of 2 to 20 repeating units, typically 2 to 5 repeating units.

[0031] The modified materials (also known as modified products) used in this article include products after modification of the reactive functional groups of various resins, products after prepolymerization of various resins with other resins, products after crosslinking of various resins with other resins, products after homopolymerization of various resins, products after copolymerization of various resins with other resins, etc. For example, modification may involve replacing the original hydroxyl groups with vinyl groups through a chemical reaction, or obtaining terminal hydroxyl groups by chemically reacting the original terminal vinyl groups with p-aminophenol, but the present invention is not limited to these.

[0032] The alkyl, alkenyl, and hydrocarbon groups used in this article include their various isomers. For example, propyl includes n-propyl and isopropyl.

[0033] As used herein, "vinyl-containing" refers to a compound structure containing an vinyl carbon-carbon double bond (C=C) or a derivative thereof. Therefore, examples of vinyl-containing compounds may include those containing vinyl, allyl, vinyl benzyl, or methacrylate functional groups, but the invention is not limited thereto. The aforementioned functional groups may be located at the ends of long-chain structures, but the invention is not limited thereto. Thus, for example, vinyl-containing polyphenylene ether resin represents a polyphenylene ether resin containing vinyl, allyl, vinyl benzyl, or methacrylate functional groups, but the invention is not limited thereto.

[0034] The unsaturated bonds used in this article refer to reactive unsaturated bonds, such as unsaturated double bonds that can undergo cross-linking reactions with other functional groups, such as unsaturated carbon-carbon double bonds that can undergo cross-linking reactions with other functional groups, but the present invention is not limited thereto.

[0035] As used herein, parts by weight represent the number of parts by weight, which can be any unit of weight, such as kilograms, grams, pounds, etc., but the invention is not limited thereto. For example, 100 parts by weight of vinyl polyphenylene ether resin can represent 100 kilograms of vinyl polyphenylene ether resin or 100 pounds of vinyl polyphenylene ether resin.

[0036] Embodiments of the present invention

[0037] In a first aspect, the present invention provides a resin composition comprising, by weight, 100 parts of a copolymer of phenyl vinyl silane and an alkenyl compound, and 20 to 100 parts of a styrene-terminated phenolic resin.

[0038] In one exemplary embodiment, the resin composition comprises 20 to 100 parts by weight of styrene-terminated phenolic resin relative to 100 parts by weight of the copolymer of phenylvinylsilane and alkenyl compound. For example, in one exemplary embodiment, the styrene-terminated phenolic resin is 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, or 95 parts by weight relative to 100 parts by weight, but the invention is not limited thereto.

[0039] In one exemplary embodiment, the copolymer of phenylvinylsilane and alkenyl compound comprises structural units formed of phenylvinylsilane and alkenyl compound. The raw materials for the copolymer include phenylvinylsilane and alkenyl compound, with a total weight of 100 parts by weight of phenylvinylsilane and alkenyl compound, wherein the phenylvinylsilane comprises 80 to 98 parts by weight and the alkenyl compound comprises 2 to 20 parts by weight. For example, in one exemplary embodiment, the weight of the phenylvinylsilane is, for example, 80, 85, 90, 95, or 98 parts by weight; and the weight of the alkenyl compound is, for example, 2, 5, 10, 15, or 20 parts by weight. For example, the weight parts of phenylvinylsilane and alkenyl compound are 80 parts by weight and 20 parts by weight, respectively, but the present invention is not limited thereto; for example, the weight parts of phenylvinylsilane and alkenyl compound are 85 parts by weight and 15 parts by weight, respectively; for example, the weight parts of phenylvinylsilane and alkenyl compound are 90 parts by weight and 10 parts by weight, respectively; for example, the weight parts of phenylvinylsilane and alkenyl compound are 95 parts by weight and 5 parts by weight, respectively; and for example, the weight parts of phenylvinylsilane and alkenyl compound are 98 parts by weight and 2 parts by weight, respectively.

[0040] In an exemplary embodiment, the content of structural units formed by phenylvinylsilane in the copolymer of phenylvinylsilane and alkenyl compound is from 78 mol% to 99 mol%, for example 78 mol%, 79 mol%, 80 mol%, 81 mol%, 82 mol%, 83 mol%, 84 mol%, 85 mol%, 86 mol%, 87 mol%, 88 mol%, 89 mol%, 90 mol%, 91 mol%, 92 mol%, 93 mol%, 94 mol%, 95 mol%, 96 mol%, 97 mol%, 98 mol%, 99 mol%, but the present invention is not limited thereto.

[0041] In an exemplary embodiment, the content of structural units formed by the alkenyl compound in the copolymer of phenylvinylsilane and alkenyl compound is from 1 mol% to 20 mol%, for example, 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, 10 mol%, 11 mol%, 12 mol%, 13 mol%, 14 mol%, 15 mol%, 16 mol%, 17 mol%, 18 mol%, 19 mol%, 20 mol%, but the present invention is not limited thereto.

[0042] In one exemplary embodiment, the weight-average molecular weight of the copolymer of phenylvinylsilane and alkenyl compound is between 2,000 and 50,000, for example 2,000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000 or 50,000, but the invention is not limited thereto. For example, the weight-average molecular weight of the copolymer is 32,071, and for example, the weight-average molecular weight of the copolymer is 3,686.

[0043] In one exemplary embodiment, the method for preparing the copolymer of phenylvinylsilane and an alkenyl compound includes reacting 80 to 98 parts by weight of phenylvinylsilane and 2 to 20 parts by weight of an alkenyl compound. In one exemplary embodiment, the reaction is carried out at 80°C to 150°C for 2 to 10 hours. In one exemplary embodiment, the method for preparing the copolymer further includes purification (i.e., refining, also known as increasing its purity), filtration, or drying steps.

[0044] In one exemplary embodiment, the reaction time may be between 2 hours and 10 hours, for example, between 3 hours and 9 hours, or between 4 hours and 8 hours, or between 5 hours and 7 hours. In one exemplary embodiment, the reaction temperature may be between 80°C and 150°C, for example, between 90°C and 140°C, or between 100°C and 130°C, or between 110°C and 120°C. In one exemplary embodiment, the purification is performed by recrystallization using an alcohol solvent.

[0045] In one exemplary embodiment, the preparation method further includes adding a curing accelerator, which includes an initiator, a catalyst, or a combination thereof. The amount of the curing accelerator is 0.1% to 1.5% of the sum of the weights of the phenylvinylsilane and the alkenyl compound, for example, between 0.2% and 1.4%, or between 0.3% and 1.3%, or between 0.4% and 1.2%, or between 0.5% and 1.1%, or between 0.6% and 1.0%, or between 0.7% and 0.9%.

[0046] In one exemplary embodiment, the initiator is at least one of bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, dibenzoyl peroxide, 2,3-dimethyl-2,3-diphenylbutane, dicumyl peroxide, tert-butyl peroxide, tert-butyl percarbonate, and azobisisobutylonitrile, but the present invention is not limited thereto.

[0047] In one exemplary embodiment, the catalyst comprises a metal carboxylate.

[0048] In one exemplary embodiment, the preparation method further includes using a solvent in an amount of 0% to 100% of the sum of the weights of the phenylvinylsilane and the alkenyl compound, for example, between 10% and 90%, or between 20% and 80%, or between 30% and 70%, or between 40% and 60%.

[0049] In one exemplary embodiment, the solvent is at least one selected from methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, and propylene glycol methyl ether, but the present invention is not limited thereto.

[0050] In an exemplary embodiment, the phenylvinylsilane has the structure shown in formula (1) and / or formula (2), and the alkenyl compound has the structure shown in formula (3):

[0051]

[0052] In this context, Ra, Rb, Rc, and Rd are each independently H or a monovalent organic group, m and n are each independently integers from 0 to 5, and Re, Rf, Rg, and Rh are each independently H or a monovalent alkyl group having 1 to 4 carbon atoms.

[0053] In one exemplary embodiment, the monovalent organic group includes at least one selected from alkyl, alkoxy, substituted or unsubstituted aryl or benzyl, substituted or unsubstituted aryloxy or benzyloxy. Examples of the monovalent organic group include methyl, ethyl, propyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, phenyl, benzyl, methoxy, ethoxy, propoxy, butoxy, phenoxy, benzyloxy, etc., but the invention is not limited thereto. In one exemplary embodiment, the monovalent organic group may be a monovalent alkyl or alkoxy having 1 to 10 carbon atoms. In one exemplary embodiment, the monovalent organic group may be a monovalent alkyl or alkoxy having 1 to 4 carbon atoms.

[0054] In an exemplary embodiment, the monovalent alkyl group having 1 to 4 carbon atoms may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl.

[0055] In an exemplary embodiment, the copolymer of phenyl vinylsilane and alkenyl compound includes structural unit A and structural unit B, wherein structural unit A is at least one of the structures shown in formula (5), formula (6), formula (7), formula (8), and formula (9), and the number of structures shown in formula (5), formula (6), formula (7), formula (8), and formula (9) in the copolymer are J1, J2, J3, K1, and K2, respectively.

[0056]

[0057] The structural unit B is the structure shown in formula (10), and the number of structures shown in formula (10) in the copolymer is L1;

[0058]

[0059] Where * represents the bonding position, J1, J2, J3, K1, and K2 are each independently 0 or positive integers, but not all of them are 0 at the same time (that is, at least one of J1, J2, J3, K1, and K2 is not 0), and L1 is a positive integer; and 10≤J1+J2+J3+L1≤268, or 8≤K1+K2+L1≤212, or 8≤J1+J2+J3+K1+K2+L1≤268.

[0060] For example, in one exemplary embodiment, J1 and J2 are each independently an integer greater than or equal to 1, and J3, K1, and K2 are each independently an integer greater than or equal to 0. In another exemplary embodiment, J1, J2, and J3 are each independently an integer greater than or equal to 0, and K1 and K2 are each independently an integer greater than or equal to 1. In yet another exemplary embodiment, J1, J2, K1, and K2 are each independently an integer greater than or equal to 1, and J3 is an integer greater than or equal to 0.

[0061] In an exemplary embodiment, the copolymer includes structures as shown in formulas (5), (6), (7) and (10), the number of which, for example, J1+J2+J3+L1 = 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260 or 268, but the invention is not limited thereto. In an exemplary embodiment, the copolymer includes structures as shown in formulas (8), (9) and (10), the number of which, for example, K1+K2+L1 = 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210 or 212, but the invention is not limited thereto. In an exemplary embodiment, the copolymer includes structures as shown in formulas (5), (6), (7), (8), (9), and (10), in quantities such as J1+J2+J3+K1+K2+L1 = 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, or 268, but the invention is not limited thereto.

[0062] In an exemplary embodiment, the chemical structure of the alkenyl compound is shown in at least one of formula (11), formula (12), or formula (13):

[0063] 2,4-Diphenyl-4-methyl-1-pentene:

[0064] 2,4-Diphenyl-3,4-dimethyl-1-hexene:

[0065] 2,4-Di(p-methoxy)phenyl-4-methyl-1-pentene:

[0066] In an exemplary embodiment, the styrene-terminated phenolic resin used in this invention is a phenolic resin with styrene groups obtained by reacting the hydroxyl groups in the phenolic resin with a compound containing styrene groups. The styrene groups are located at the end of the resin molecule structure or on the side of the molecular chain segment, or simultaneously at the end and on the side.

[0067] In an exemplary embodiment, the styrene-terminated phenolic resin has the structure shown in formula (4):

[0068]

[0069] Where R is a divalent organic group and n1 is an integer from 1 to 30.

[0070] In an exemplary embodiment, the divalent organic group is at least one of alkylene, dicyclopentadienyl, substituted or unsubstituted arylene, a combination of alkylene and arylene (also known as arylene alkylene or alkylene aryl), and aromatic heterocyclic group.

[0071] In an exemplary embodiment, the alkylene group is a straight-chain alkyl or branched alkyl group containing 1 to 4 carbon atoms; the aryl group is at least one selected from phenyl, naphthyl, anthraceneyl, biphenyl, and fluorenyl; the aromatic heterocyclic group is at least one selected from pyridine ring, pyrrole ring, pyrazole ring, pyrimidine ring, pyrazine ring, pyridazine ring, thiophene ring, and furan ring. In an exemplary embodiment, the R group can be exemplified as:

[0072]

[0073] However, this invention is not limited thereto.

[0074] In an exemplary embodiment, R is at least one of methylene, dicyclopentadienyl, substituted or unsubstituted aryl group, and n1 is an integer from 1 to 10.

[0075] In one exemplary embodiment, the styrene-terminated phenolic resin may be any one or more commercially available products, homemade products, or combinations thereof. In one exemplary embodiment, the styrene-terminated phenolic resin is a product obtained by reacting 4-vinylbenzyl chloride with a phenolic resin in the presence of sodium hydroxide and tetrabutylamine iodide, or by reacting 4-vinylbenzyl chloride with a phenolic resin in the presence of sodium alkoxide (e.g., sodium methoxide or sodium ethoxide). Specific examples of styrene-terminated phenolic resins include at least one of styrene-terminated dicyclopentadiene phenolic resins (e.g., KPU-6270 purchased from Kolon Industries, Inc.) (R is a divalent dicyclopentadienyl group, n1 is an integer from 1 to 10), styrene-terminated alkyl phenolic resins (R is a methylene group, n1 is an integer from 1 to 10), and styrene-terminated biphenyl phenolic resins (R is a 4,4'-dimethylenebiphenyl group, n1 is an integer from 1 to 10), but the invention is not limited thereto.

[0076] In one exemplary embodiment, the resin composition may further comprise 0.1 to 40 parts by weight, preferably 5 to 30 parts by weight, of a polyolefin resin, in addition to 100 parts by weight of the copolymer of phenylvinylsilane and an alkenyl compound. In one exemplary embodiment, the polyolefin resin is 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, or 25 parts by weight, but the invention is not limited thereto. In another exemplary embodiment, the resin composition does not include a polyolefin resin.

[0077] In an exemplary embodiment, the polyolefin resin includes at least one of unsaturated polyolefin resin and hydrogenated unsaturated polyolefin resin. The unsaturated polyolefin resin of this invention can be any one or more polyolefin resins containing unsaturated carbon-carbon double bonds used in the production of prepregs, resin films, laminates, printed circuit boards, or cured insulators. Specific examples include at least one of styrene-butadiene-divinylbenzene terpolymers, maleic anhydride-added styrene-butadiene polymers, maleic anhydride-added polybutadiene, styrene-butadiene-styrene block polymers, vinyl-polybutadiene-urethane oligomers, styrene-butadiene copolymers, styrene-isoprene copolymers, polybutadiene, ethylene propylene diene monomer (EPDM) rubber, methylstyrene homopolymers, petroleum resins, and cyclic olefin copolymers, but this invention is not limited thereto. The hydrogenated unsaturated polyolefin resin described in this invention is obtained by hydrogenating unsaturated polyolefin resin. It can be any one or more hydrogenated unsaturated polyolefin resins that do not contain unsaturated carbon-carbon double bonds and are used in the production of prepregs, resin films, laminates, printed circuit boards, or cured insulators. Specific examples include at least one of hydrogenated styrene-butadiene copolymers, hydrogenated styrene-butadiene-styrene block polymers, and hydrogenated styrene-isoprene copolymers, but this invention is not limited thereto.

[0078] In an exemplary embodiment, the resin composition further includes at least one of vinyl polyphenylene ether resin, maleimide resin, maleimide triazine resin, small molecule vinyl resin, small molecule vinyl resin prepolymer, styrene maleic anhydride resin, epoxy resin, phenolic resin, benzoxazine resin, cyanate ester resin, polyester resin, polyamide resin, and polyimide resin.

[0079] For example, in one exemplary embodiment, the vinyl-containing polyphenylene ether resin may include various polyphenylene ether resins with ends modified via vinyl or allyl groups, such as vinyl benzyl polyphenylene ether resin, or the vinyl-containing polyphenylene ether resin may be a polyphenylene ether resin containing (meth)acrylate. For example, the aforementioned vinyl-containing polyphenylene ether resins include vinyl benzyl biphenyl polyphenylene ether resin, methacrylate polyphenylene ether resin, vinyl benzyl bisphenol A polyphenylene ether resin, vinyl chain extender polyphenylene ether resin, or combinations thereof, but the invention is not limited thereto. The amount of vinyl-containing polyphenylene ether resin used is not particularly limited.

[0080] For example, in one exemplary embodiment, the aforementioned vinyl-containing polyphenylene ether resin may include various vinyl-containing polyphenylene ether resins known in the art. The vinyl-containing polyphenylene ether resin of the present invention may be any one or more commercially available products, homemade products, or combinations thereof, but the invention is not limited thereto. In some embodiments, any one or more of the following vinyl-containing polyphenylene ether resins may be used: vinyl benzyl biphenyl polyphenylene ether resin (e.g., OPE-2st, available from Mitsubishi Gas Chemical Company), methacrylate polyphenylene ether resin (e.g., SA9000, available from Sabic Company), vinyl benzyl bisphenol A polyphenylene ether resin, vinyl chain-extended polyphenylene ether resin, or combinations thereof. The aforementioned vinyl chain-extended polyphenylene ether resin may include various polyphenylene ether resins as described in U.S. Patent Application Publication No. 2016 / 0185904A1, the entire contents of which are incorporated herein by reference.

[0081] For example, in one exemplary embodiment, the maleimide resin used in this invention refers to a compound or mixture having one or more maleimide functional groups in its molecule. The maleimide resin used in this invention may be any one or more maleimide resins used in the manufacture of prepregs, resin films, laminates, printed circuit boards, or cured insulators, but this invention is not limited thereto. Specific examples include 4,4'-diphenylmethane bismaleimide, benzene maleimide oligomers, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide-(2,2,4-trimethyl)hexane, 2,3-dimethylbenzenemaleimide, 2,6-dimethylbenzenemaleimide, N-phenylmaleimide, maleimide resins containing aliphatic long-chain structures, or combinations thereof, but the present invention is not limited thereto. Furthermore, the maleimide resin described in this invention also includes prepolymers of the aforementioned resins, such as prepolymers of diallyl compounds and maleimide resins, prepolymers of polyfunctional amines (including two or more amino groups) and maleimide resins, or prepolymers of acidic phenolic compounds and maleimide resins, etc., but this invention is not limited thereto.

[0082] For example, maleimide resins can be those produced by Daiwakasei Corporation under trade names such as BMI-1000, BMI-1000H, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H, BMI-4000H, BMI-5000, BMI-5100, BMI-7000, and BMI-7000H, or those produced by KI Chemicals Corporation under trade names such as BMI-70 and BMI-80.

[0083] For example, maleimide resins containing aliphatic long-chain structures can be maleimide resins manufactured by the designer's subsidiary under trade names such as BMI-689, BMI-1400, BMI-1500, BMI-1700, BMI-2500, BMI-3000, BMI-5000, and BMI-6000. For example, maleimide resins containing aliphatic long-chain structures can have at least one maleimide functional group linked to a substituted or unsubstituted long-chain aliphatic group. The long-chain aliphatic group can be an aliphatic group with C5 to C50 carbon atoms, for example, C10 to C50, C20 to C50, C30 to C50, C20 to C40, or C30 to C40, but the invention is not limited thereto.

[0084] For example, in an exemplary embodiment, the maleimide triazine resin of the present invention may be any one or more maleimide triazine resins used in the manufacture of prepregs, resin films, laminates, printed circuit boards, or cured insulators, but the present invention is not limited thereto. For example, the maleimide triazine resin may be obtained by polymerizing a cyanate ester resin with a maleimide resin. The maleimide triazine resin may be obtained, for example, by polymerizing a bisphenol A cyanate ester resin with a maleimide resin, a bisphenol F cyanate ester resin with a maleimide resin, a phenolic phenolic cyanate ester resin with a maleimide resin, or a dicyclopentadiene-containing cyanate ester resin with a maleimide resin, but the present invention is not limited thereto. For example, the maleimide triazine resin may be obtained by polymerizing a cyanate ester resin with a maleimide resin in any molar ratio. For example, relative to 1 mole of maleimide resin, the cyanate ester resin may be 1 to 10 moles. For example, the amount of cyanate resin is 1, 2, 4 or 6 moles relative to 1 mole of maleimide resin, but the invention is not limited thereto.

[0085] For example, in an exemplary embodiment, the small molecule vinyl-containing resin refers to a vinyl compound with a molecular weight less than or equal to 1,000, preferably with a molecular weight between 100 and 900, and more preferably with a molecular weight between 100 and 800. For example, the small molecule vinyl-containing resin includes styrene, divinylbenzene, bis(vinylbenzyl)ether, 1,2,4-trivinylcyclohexane (TVCH), bis(vinylphenyl)ethane (BVPE), divinylphenylhexane, divinylphenyldimethyl ether, divinylphenyldimethylbenzene, triallyl isocyanurate (TAIC), and / or triallyl cyanurate (TAC), but the invention is not limited thereto.

[0086] For example, in one exemplary embodiment, the small-molecule vinyl resin prepolymer may include styrene prepolymer, divinylbenzene prepolymer, di(vinylbenzyl)ether prepolymer, 1,2,4-trivinylcyclohexane prepolymer, di(vinylphenyl)ethane prepolymer, di(vinylphenyl)hexane prepolymer, divinylphenyldimethyl ether prepolymer, divinylphenyldimethylbenzene prepolymer, triallyl isocyanurate prepolymer, triallyl cyanurate prepolymer, or combinations thereof, but the invention is not limited thereto. For example, in one exemplary embodiment, styrene prepolymer means that the styrene content in the prepolymer is greater than or equal to 50 wt%, or, for example, the styrene content in the styrene prepolymer is between 50 wt% and 99 wt%, while the content of the second monomer unit in the styrene prepolymer is less than or equal to 49 wt%, for example, between 1 wt% and 49 wt%. For example, in one exemplary embodiment, the styrene prepolymer includes 60 wt% styrene monomer units, 30 wt% divinylbenzene monomer units, and 10 wt% ethylstyrene monomer units. In another exemplary embodiment, the divinylbenzene prepolymer comprises 60 wt% divinylbenzene monomer units, 30 wt% ethylstyrene monomer units, and 10 wt% styrene monomer units.

[0087] For example, in an exemplary embodiment, the ratio of styrene (S) to maleic anhydride (MA) in the styrene-maleic anhydride resin used in this invention can be 1:1, 2:1, 3:1, 4:1, 6:1, or 8:1. Examples include styrene-maleic anhydride copolymers sold by Cray Valley Corporation under trade names SMA-1000, SMA-2000, SMA-3000, EF-30, EF-40, EF-60, and EF-80, or styrene-maleic anhydride copolymers sold by Polyscope Corporation under trade names C400, C500, C700, and C900. However, this invention is not limited to these. Furthermore, the styrene-maleic anhydride resin can also be an esterified styrene-maleic anhydride copolymer, such as esterified styrene-maleic anhydride copolymers purchased from Cray Valley Corporation under trade names SMA1440, SMA17352, SMA2625, SMA3840, and SMA31890. The above-mentioned styrene-maleic anhydride resin can be added independently or in combination to the resin composition of the present invention.

[0088] For example, in an exemplary embodiment, the epoxy resin used in this invention may be any type of epoxy resin known in the art, including, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD ​​epoxy resin, phenolic (novolac) epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin, multifunctional phenolic epoxy resin, dicyclopentadiene (DCPD) epoxy resin, phosphorus-containing epoxy resin, p-xylene epoxy resin, naphthalene-type epoxy resin (e.g., naphthol-type epoxy resin), benzofuran-type epoxy resin, and isocyanate-modified epoxy resin, but this invention is not limited thereto. The phenolic epoxy resin may be phenolnovolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, biphenyl novolac epoxy resin, phenolbenzaldehyde epoxy resin, phenol aralkyl novolac epoxy resin, or o-cresol novolac epoxy resin; the phosphorus-containing epoxy resin may be DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) epoxy resin, DOPO-HQ epoxy resin, or a combination thereof.The aforementioned DOPO epoxy resin may be selected from one or more of the following: DOPO-containing phenolic novolac epoxy resin, DOPO-containing cresol novolac epoxy resin, and DOPO-containing bisphenol-A novolac epoxy resin; the aforementioned DOPO-HQ epoxy resin may be selected from at least one of the following: DOPO-containing phenolic novolac epoxy resin, DOPO-containing cresol novolac epoxy resin, and DOPO-containing bisphenol-A novolac epoxy resin.

[0089] For example, in an exemplary embodiment, the phenolic resin described in this invention may be a monofunctional, polyfunctional (including two or more phenolic hydroxyl groups) phenolic resin or a combination thereof. There is no particular limitation on the type of phenolic resin mentioned above; all phenolic resins currently used in the industry are within the scope of phenolic resins to which this invention applies. Preferably, the phenolic resin is selected from phenoxyresin, phenolic resin, or a combination thereof.

[0090] For example, in an exemplary embodiment, the benzoxazine resin of the present invention may be a bisphenol A type benzoxazine resin, a bisphenol F type benzoxazine resin, a phenolphthalein type benzoxazine resin, a dicyclopentadiene benzoxazine resin, or a phosphorus-containing benzoxazine resin, such as Huntsman's trade name LZ-8270 (phenolphthalein type benzoxazine resin), LZ-8280 (bisphenol F type benzoxazine resin), LZ-8290 (bisphenol A type benzoxazine resin), or Showa Polymer Co., Ltd.'s trade name HFB-2006M.

[0091] For example, in an exemplary embodiment, the cyanate resin of the present invention may be any type of cyanate resin known in the art, including cyanate resins having an Ar-OC≡N structure (where Ar is an aromatic group, such as benzene, naphthalene or anthracene), phenolic cyanate resins, bisphenol A cyanate resins, bisphenol A cyanate resins, bisphenol F cyanate resins, bisphenol F cyanate resins, cyanate resins containing a dicyclopentadiene structure, cyanate resins containing a naphthalene ring structure, phenolphthalein cyanate resins, or combinations thereof, but the present invention is not limited thereto. Examples of cyanate ester resins include those manufactured by Lonza under trade names such as Primaset PT-15, PT-30S, PT-60S, BA-200, BA-230S, BA-3000S, BTP-2500, BTP-6020S, DT-4000, DT-7000, ULL950S, HTL-300, CE-320, LVT-50, and LeCy, but the present invention is not limited thereto.

[0092] For example, in an exemplary embodiment, the polyester resin of the present invention is formed by esterification of an aromatic compound having a dicarboxylic acid group and an aromatic compound having a dihydroxyl group, such as HPC-8000, HPC-8150 or HPC-8200 available from Dai Nippon Ink Chemical, but the present invention is not limited thereto.

[0093] For example, in an exemplary embodiment, the polyamide resin of the present invention may be any type of polyamide resin known in the art, including various commercially available polyamide resin products, but the present invention is not limited thereto.

[0094] For example, in an exemplary embodiment, the polyimide resin of the present invention may be any type of polyimide resin known in the art, including various commercially available polyimide resin products, but the present invention is not limited thereto.

[0095] There are no particular restrictions on the ratio of copolymers and resin additives.

[0096] In one exemplary embodiment, the resin composition further includes at least one selected from amine curing agents, flame retardants, inorganic fillers, curing accelerators, polymerization inhibitors, colorants, solvents, toughening agents, and silane coupling agents.

[0097] For example, in an exemplary embodiment, the amine curing agent of the present invention may be at least one of dicyandiamide, diaminodiphenyl sulfone, diaminodiphenylmethane, diaminodiphenyl ether, and diaminodiphenyl sulfide, but the present invention is not limited thereto.

[0098] For example, in an exemplary embodiment, the flame retardant of the present invention may be any one or more flame retardants used in the production of prepregs, resin films, laminates, printed circuit boards, or cured insulators. Specific examples include phosphorus-containing flame retardants, such as those selected from at least one, two, or a combination of two or more of the following groups: ammonium polyphosphate, hydroquinone bis-(diphenylphosphate), bisphenol A bis-(diphenylphosphate), tri(2-carboxyethyl)phosphine (TCEP), trichloroisopropyl phosphate, trimethyl phosphate (TMP), dimethyl methylphosphonate (DMMP), and resorcinol bis-(xylmethylphosphate). The invention may contain at least one of the following: dixylenylphosphate (BBS), RDXP (such as commercially available products like PX-200, PX-201, PX-202), phosphazene compounds (such as commercially available products like SPB-100, SPH-100, SPV-100), melamine polyphosphate, DOPO and its derivatives or resins, diphenylphosphine oxide (DPPO) and its derivatives or resins, melamine cyanurate, tri-hydroxy ethylisocyanurate, and aluminum phosphonate (such as OP-930, OP-935, etc.), but is not limited thereto.

[0099] For example, the flame retardant used in this invention can be a DPPO compound (such as a bisDPPO compound), a DOPO compound (such as a bisDOPO compound), a DOPO resin (such as DOPO-HQ, DOPO-NQ, DOPO-PN, DOPO-BPN), or a DOPO-bonded epoxy resin, etc., wherein DOPO-PN is a DOPO phenolic compound, and DOPO-BPN can be a bisphenolic compound such as DOPO-BPAN (DOPO-bisphenol Anovolac), DOPO-BPFN (DOPO-bisphenol F novolac), or DOPO-BPSN (DOPO-bisphenol Snovolac).

[0100] For example, in an exemplary embodiment, the inorganic filler of the present invention can be any one or more fillers used in the manufacture of resin films, prepregs, laminates, printed circuit boards, or cured insulators. Specific examples include: silica (molten, non-molten, porous, or hollow), alumina, aluminum hydroxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, silicon aluminum carbide, silicon carbide, titanium dioxide, zinc oxide, zirconium oxide, mica, boehmite (AlOOH), calcined talc, talc, silicon nitride, or calcined kaolin, but the present invention is not limited thereto. Furthermore, the aforementioned inorganic filler can be spherical, fibrous, plate-like, granular, flake-like, or needle-like, and can be selectively pretreated with a silane coupling agent.

[0101] In an exemplary embodiment, for example, the curing accelerator (including curing initiator) of the present invention may include a Lewis base or Lewis acid catalyst. The Lewis base may include one or more of the following: imidazole, boron trifluoride amine complex, ethyltriphenyl phosphonium chloride, 2-methylimidazole (2MI), 2-phenyl-1H-imidazole (2PZ), 2-ethyl-4-methylimidazole (2E4MI), triphenylphosphine (TPP), and 4-dimethylaminopyridine (DMAP). The Lewis acid may include metal salt compounds, such as manganese, iron, cobalt, nickel, copper, zinc, etc., and metal catalysts such as zinc octanoate and cobalt octanoate. Curing accelerators also include curing initiators (i.e., initiators), such as peroxides that can generate free radicals. Curing initiators include: 2,3-dimethyl-2,3-diphenylbutane, dicumyl peroxide, tert-butyl peroxybenzoate, dibenzoyl peroxide (BPO), 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (25B), bis(tert-butylperoxyisopropyl)benzene, azobisisobutyronitrile, or combinations thereof, but the present invention is not limited thereto.

[0102] In an exemplary embodiment, for example, the polymerization inhibitor described in this invention is not particularly limited, and may be any type of polymerization inhibitor known in the art, including various commercially available polymerization inhibitor products, but this invention is not limited thereto. For example, the above-mentioned polymerization inhibitor may include 1,1-diphenyl-2-trinitrophenylhydrazine, methacrylonitrile, disulfide, nitrogen oxide stabilized free radical, triphenylmethyl free radical, metal ion free radical, sulfur free radical, hydroquinone, p-methoxyphenol, p-benzoquinone, phenathiazide, β-phenylnaphthylamine, p-tert-butylcatechol, methylene blue, 4,4'-butylenebis(6-tert-butyl-3-methylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) or combinations thereof, but this invention is not limited thereto.

[0103] For example, the aforementioned stable nitroxide radicals may include nitroxide radicals derived from cyclic hydroxylamines, such as 2,2,6,6-substituted-1-piperidinoxy radicals or 2,2,5,5-substituted-1-pyrrolidineoxy radicals, but the present invention is not limited thereto. As substituents, alkyl groups with 4 or fewer carbon atoms, such as methyl or ethyl, are preferred. Specific examples of nitroxide radical compounds include 2,2,6,6-tetramethyl-1-piperidinoxy radicals, 2,2,6,6-tetraethyl-1-piperidinoxy radicals, 2,2,6,6-tetramethyl-4-oxo-1-piperidinoxy radicals, 2,2,5,5-tetramethyl-1-pyrrolidineoxy radicals, 1,1,3,3-tetramethyl-2-isodihydroindole oxygen radicals, and N,N-di-tert-butylamine oxygen radicals. Stable radicals such as galvinoxyl radicals may also be used instead of nitroxide radicals.

[0104] The polymerization inhibitors suitable for the resin compositions of the present invention can also be products derived from the substitution of hydrogen atoms or groups of atoms in the polymerization inhibitor by other atoms or groups of atoms. For example, products derived from the substitution of hydrogen atoms in the polymerization inhibitor by groups such as amino, hydroxyl, or ketone carbonyl.

[0105] In one exemplary embodiment, for example, the dyeing agent of the present invention may include dye or pigment, but the present invention is not limited thereto.

[0106] In an exemplary embodiment, for example, the main function of adding a solvent is to change the solid content of the resin composition and adjust its viscosity. For example, the solvent may include methanol, ethanol, ethylene glycol monomethyl ether, acetone, butanone (also known as methyl ethyl ketone), methyl isobutyl ketone, cyclohexanone, toluene, xylene, methoxyethyl acetate, ethoxyethyl acetate, propoxyethyl acetate, ethyl acetate, dimethylformamide, dimethylacetamide, propylene glycol methyl ether, and other solvents or mixtures thereof, but the present invention is not limited thereto. In some embodiments, the solvent added to the resin composition may evaporate and be removed during the processing of the resin composition into a prepreg or resin film, so that the insulating layer of the prepreg or resin film contains no solvent or only a trace amount of solvent less than or equal to 3 wt% (i.e., 3% by weight). Therefore, the presence or absence of solvent in the resin composition does not affect the properties of the product.

[0107] In one exemplary embodiment, for example, the main function of adding a toughening agent is to improve the toughness of the resin composition. The toughening agent may include compounds such as carboxyl-terminated butadiene acrylonitrile rubber (CTBN), core-shell rubber, or combinations thereof, but the invention is not limited thereto.

[0108] In an exemplary embodiment, for example, the silane coupling agent used in this invention may include silane compounds (such as siloxane compounds, but this invention is not limited thereto), which may be further classified according to the type of functional group as amino silane compounds, epoxy silane compounds, vinyl silane compounds, acrylate silane compounds, methacrylate silane compounds, hydroxy silane compounds, isocyanate silane compounds, methacryloxy silane compounds, and acryloyloxy silane compounds.

[0109] In a second aspect, the present invention provides an article made of the above-described resin composition, the article comprising a prepreg, a resin film, a laminate, a printed circuit board, or a cured insulator, but the present invention is not limited thereto.

[0110] For example, the resin compositions of various embodiments of the present invention can be made into a prepreg, which includes a reinforcing material and a layer disposed on the reinforcing material. The layer is obtained by heating the aforementioned resin composition at a high temperature to form a semi-cured state (B-stage). The baking temperature for making the prepreg can be between 100°C and 200°C. The reinforcing material can be any of a fiber material, woven fabric, or nonwoven fabric, and the woven fabric preferably includes glass fiber cloth. The glass fiber cloth can be commercially available glass fiber cloth suitable for various printed circuit boards, such as E-type glass fiber cloth, D-type glass fiber cloth, S-type glass fiber cloth, T-type glass fiber cloth, L-type glass fiber cloth, or Q-type glass fiber cloth, wherein the fiber type includes yarn and roving, and the form can include open or closed fibers, but the present invention is not limited thereto. The aforementioned nonwoven fabric preferably includes liquid crystal resin nonwoven fabric, such as polyester nonwoven fabric, polyurethane nonwoven fabric, etc., but the present invention is not limited thereto. The aforementioned woven fabric may also include liquid crystal resin woven fabric, such as polyester woven fabric or polyurethane woven fabric, etc., but the present invention is not limited thereto. This reinforcing material increases the mechanical strength of the prepreg. In a preferred embodiment, the reinforcing material may also be selectively pretreated with a silane coupling agent. The prepreg subsequently undergoes heat curing (C-stage) to form an insulating layer.

[0111] For example, the resin compositions of various embodiments of the present invention can be made into resin films, which are obtained by baking and heating the aforementioned resin compositions to achieve semi-curing. The resin composition can be selectively coated onto polyethylene terephthalate film (PET film), polyimide film (PI film), copper foil, or adhesive-backed copper foil, and then baked and heated to form a semi-cured state, thereby forming a resin film.

[0112] For example, the resin compositions of various embodiments of the present invention can be made into a laminate comprising at least two metal foils and an insulating layer disposed between these metal foils. The insulating layer can be obtained by curing the aforementioned resin composition under high temperature and high pressure conditions (C-stage), wherein a suitable curing temperature is between 180°C and 250°C, preferably between 200°C and 230°C, and the curing time is 90 to 180 minutes, preferably 120 to 150 minutes. The insulating layer can be formed by curing the aforementioned prepreg or resin film (C-stage). The metal foils may include copper, aluminum, nickel, platinum, silver, gold, or alloys thereof; for example, the metal foil may be copper foil.

[0113] Preferably, the aforementioned laminate is a copper clad laminate (CCL).

[0114] Furthermore, the aforementioned multilayer board can be further processed into a circuit board, such as a printed circuit board, through circuit fabrication processes. One method of manufacturing the printed circuit board of this invention involves using a double-sided copper-clad laminate (e.g., product EM-890, available from Taikoo Electronics Materials) with a thickness of 28 mils and 0.5 ounces (HVLP) of copper foil. After drilling, electroplating is performed to create electrical conductivity between the upper and lower copper foil layers. The upper and lower copper foil layers are then etched to form the inner layer circuitry. Next, the inner layer circuitry undergoes a browning roughening treatment to create a surface texture and increase roughness. Then, the copper foil, the aforementioned prepreg, the aforementioned inner layer circuit board, the aforementioned prepreg, and the copper foil are stacked sequentially, and then heated in a vacuum lamination apparatus at a temperature of 180°C to 250°C for 90 to 180 minutes to cure the insulating layer material of the prepreg. Next, various circuit board processes known in the art, such as blackening, drilling, and copper plating, are performed on the outermost copper foil to obtain a printed circuit board.

[0115] For example, the resin compositions of various embodiments of the present invention can be made into cured insulators, which include the cured resin composition, the cured resin composition containing reinforcing materials, or a combination thereof. In an exemplary embodiment, the present invention provides a method for preparing a cured insulator, comprising: directly curing the aforementioned resin composition or curing the aforementioned resin composition through a multiple curing process. Multiple curing refers to two or more curing processes. For example, the aforementioned resin composition can be semi-cured first to obtain a semi-cured resin composition, and then the semi-cured resin composition can be further cured to obtain a cured resin composition. The curing is preferably heat curing.

[0116] In one exemplary embodiment, the heating is baking heating, and the semi-cured resin composition is heated to a semi-curing temperature, which may be between 100°C and 200°C. In one exemplary embodiment, the direct curing of the resin composition or the curing of the semi-cured resin composition is heating to a curing temperature, which may be between 180°C and 250°C, preferably between 200°C and 230°C, and the curing time is 90 to 180 minutes, preferably 120 to 150 minutes. In one exemplary embodiment, the curing includes applying pressure to the resin composition or the semi-cured resin composition.

[0117] In one exemplary embodiment, the cured insulator comprises a cured resin composition thereof, which may be obtained by curing the aforementioned resin film. In another exemplary embodiment, the cured insulator comprises a cured resin composition thereof containing reinforcing material thereof, which may be obtained by curing the aforementioned prepreg.

[0118] In one exemplary embodiment, the method for preparing the cured insulator further includes a molding process. For example, the resin composition or a semi-cured resin composition can be placed into a mold, and the resin composition or semi-cured resin composition can be molded and cured in the mold under a curing temperature and a certain pressure to obtain a cured insulator of a specific shape.

[0119] In an exemplary embodiment, the cured insulator is an insulating layer with a surface free of metal, obtained by removing the surface metal foil from the aforementioned multilayer board or the aforementioned printed circuit board.

[0120] Preferably, the resin composition or product thereof provided by the present invention can be improved in one or more aspects such as glass transition temperature, copper foil tensile strength, dielectric constant, dielectric loss, thermal expansion coefficient, or PCT heat resistance.

[0121] In one exemplary embodiment, the glass transition temperature of the article, measured with reference to the method of IPC-TM-650 2.4.24.4, is greater than or equal to 220°C, for example greater than or equal to 221°C, or for example between 221°C and 260°C.

[0122] In one exemplary embodiment, the glass transition temperature of the article, as measured with reference to the method described in IPC-TM-650 2.4.24.5, is greater than or equal to 200°C, for example greater than or equal to 201°C, or for example between 201°C and 230°C.

[0123] In one exemplary embodiment, the copper foil tensile strength of the article of manufacture, measured with reference to the IPC-TM-650 2.4.8 method, is greater than or equal to 2.00 lb / in, for example, between 2.00 lb / in and 3.00 lb / in;

[0124] In one exemplary embodiment, the article of thermal expansion along the Z-axis, as measured with reference to the IPC-TM-650 2.4.24.5 method, is less than or equal to 1.4%, for example, between 0.70% and 1.40%.

[0125] In one exemplary embodiment, the coefficients of thermal expansion of the article along the X and Y axes, as measured with reference to the IPC-TM-650 2.4.24.5 method, are less than or equal to 11.0 ppm / °C, for example, between 7.5 ppm / °C and 11.0 ppm / °C.

[0126] In one exemplary embodiment, after a 5-hour pressure cooking test according to the method described in IPC-TM-650 2.6.16.1, followed by a heat resistance test according to the method described in IPC-TM-650 2.4.23, no plate bursting occurred.

[0127] In one exemplary embodiment, the dielectric constant of the article, measured at a frequency of 10 GHz with reference to the JIS C2565 method, is less than or equal to 3.40, for example, between 3.20 and 3.40;

[0128] And / or, the dielectric loss of the article, measured at a frequency of 10 GHz with reference to the JIS C2565 method, is less than or equal to 0.00300, for example, between 0.00240 and 0.00300.

[0129] The present invention will be further described in detail below with reference to specific embodiments. The specific embodiments below are merely illustrative in nature and should not be construed as limiting the scope of protection and uses of the present invention.

[0130] Using various raw materials from the following sources, preparation examples and comparative preparation examples of the present invention were prepared according to the amounts in Table 1, and resin compositions of the embodiments and comparative examples of the present invention were formulated according to the amounts in Tables 4 to 8, and further made into various test samples or articles.

[0131] The chemical raw materials used in the preparation examples, embodiments, and comparative examples of this invention are as follows:

[0132] Phenylacetylsilane: Purchased from Suzhou Sisso, structural formula is:

[0133] Diphenyldivinylsilane: Purchased from Suzhou Sisso, structural formula is:

[0134] Methyltrivinylsilane: Commercially available, source is not limited.

[0135] Tetraphenyldivinyldisiloxane: Commercially available, source is not limited.

[0136] 2,4-Diphenyl-4-methyl-1-pentene: purchased from Aladdin.

[0137] The structural formula is:

[0138] 2,4-Diphenyl-3,4-dimethyl-1-hexene: Synthesized according to the method of Synthetic Example 1.

[0139] The structural formula is:

[0140] 2,4-Di(p-methoxy)phenyl-4-methyl-1-pentene: synthesized according to the method of Synthetic Example 2.

[0141] The structural formula is:

[0142] 1,4-Naphthoquinone: purchased from Aladdin.

[0143] n-Dodecyl mercaptan: purchased from Aladdin.

[0144] KPU-6270: Styrene-terminated dicyclopentadiene phenolic resin, purchased from Kolon Industries, structural formula:

[0145]

[0146] Styrene-terminated alkyl phenolic resin: synthesized according to the method of Synthesis Example 3, with the following structural formula:

[0147]

[0148] Styrene-terminated biphenyl phenolic resin: synthesized according to the method of Synthesis Example 4, with the following structural formula:

[0149]

[0150] H1051: Hydrogenated styrene-butadiene-styrene triblock copolymer (SEBS), purchased from Asahi Kasei.

[0151] MD1648: Hydrogenated styrene-butadiene-styrene triblock copolymer (SEBS), purchased from Kraton.

[0152] SBS-C: Styrene-butadiene-styrene triblock copolymer, purchased from Nippon Soda.

[0153] EBT-4045M: Ethylene propylene diene monomer (EPDM) rubber, purchased from Sinopec Mitsui Chemicals.

[0154] Ricon 100: Styrene-butadiene copolymer, purchased from Cray Valley.

[0155] Ricon 184MA6: Maleic anhydride-added styrene-butadiene polymer, purchased from Cray Valley.

[0156] Ricon 257: Styrene-butadiene-divinylbenzene terpolymer, purchased from Cray Valley.

[0157] SA9000: Terminal dimethacrylate polyphenylene ether resin, purchased from Sabic.

[0158] OPE-2st 1200: Terminal divinyl benzyl polyphenylene ether resin, purchased from Sabic.

[0159] SC-2050SMJ: Spherical silica with a surface treated with silane coupling agent, purchased from Admatechs.

[0160] 25B: 2,5-Dimethyl-2,5-Di(tert-butylperoxy)-3-hexyne, purchased from Nippon Oil Co., Ltd.

[0161] Butyl ketone (MEK): Commercially available, source is not limited.

[0162] Toluene: Purchased from Qiangdi.

[0163] Synthesis example 1

[0164] This synthetic example provides a method for synthesizing 2,4-diphenyl-3,4-dimethyl-1-hexene, comprising the following steps:

[0165] 20 g of but-1-en-2-ylbenzene (purchased from Aladdin) and 10 g of toluene were added to a flask and stirred until homogeneous. Then, 0.2 g of p-toluenesulfonic acid monohydrate was added. The mixture was replaced with N2 and reacted at 20 °C for 20 hours. The reaction was stopped by adding 2 mL of pure water. The reaction mixture was diluted with 20 g of ethyl acetate. The organic phase was washed with pure water to remove impurities, dried, filtered, and the solvent was removed by rotary evaporation to obtain 2,4-diphenyl-3,4-dimethyl-1-hexene.

[0166] Synthesis example 2

[0167] This synthetic example provides a method for synthesizing 2,4-bis(p-methoxy)phenyl-4-methyl-1-pentene, comprising the following steps:

[0168] The difference from Synthesis Example 1 is that 20g of 1-isopropenyl-4-methoxybenzene (purchased from Aladdin) was used to replace but-1-en-2-ylbenzene to obtain 2,4-di(p-methoxy)phenyl-4-methyl-1-pentene.

[0169] Synthesis example 3

[0170] This synthetic example provides a method for synthesizing a styrene-terminated alkyl phenolic resin, comprising the following steps:

[0171] 105 g (containing 1.0 mol phenolic hydroxyl groups) of alkyl phenolic resin (TD-2090, R group is methylene, hydroxyl equivalent 105 g / eq, purchased from DIC), 1.05 mol 4-vinylbenzyl chloride and 150 g toluene were added to a reaction vessel. The temperature was set at 70 °C and the reaction was stirred for 6 hours. Then, 1.05 mol sodium hydroxide and 0.07 mol tetrabutylammonium iodide were added and the reaction was continued for 4 hours. After the reaction was completed, the reaction mixture was washed with methanol and distilled water and dried to obtain styrene-terminated alkyl phenolic resin with methylene R group.

[0172] Synthesis example 4

[0173] This synthetic example provides a method for synthesizing a styrene-terminated biphenyl phenolic resin, comprising the following steps:

[0174] The difference from Preparation Example 3 is that 220g of biphenyl-type phenolic resin (BPNH9781, R group is 4,4'-dimethylene biphenyl, hydroxyl equivalent 215-225g / eq, purchased from Jiashengde) was used to replace the alkyl-type phenolic resin to obtain a styrene-terminated biphenyl-type phenolic resin with R group 4,4'-dimethylene biphenyl.

[0175] Preparation of copolymers

[0176] The weight parts of each raw material in the various preparation examples and comparative preparation examples of the copolymers prepared in this invention are shown in Table 1. Blanks in the table represent "0".

[0177] Table 1 Raw material composition of the preparation examples and comparative preparation examples

[0178]

[0179] Preparation Example 1

[0180] This preparation example provides a method for preparing a copolymer, comprising the following steps:

[0181] (1) Under nitrogen protection, 98 parts by weight of phenyltrivinylsilane, 2 parts by weight of 2,4-diphenyl-4-methyl-1-pentene, 0.5 parts by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne (abbreviated as 25B), and 40 parts by weight of toluene were added to a three-necked flask. The mixture was heated to 120°C and stirred for 5 hours. After the reaction was completed, the mixture was cooled to room temperature to obtain crude product 1.

[0182] (2) Under stirring conditions, crude product 1 was slowly poured into anhydrous ethanol, and a white precipitate was formed. After filtration and washing with anhydrous ethanol, white solid 1 was obtained. The obtained white solid 1 was placed in a vacuum drying oven and placed at 50°C to 70°C for 6 to 10 hours to remove the residual solvent. The obtained white solid 2 (i.e. product 2) is copolymer 1, and the content of structural units formed by phenyltrivinylsilane is 98 mol.

[0183] Preparation Example 2

[0184] This preparation example provides a method for preparing a copolymer, which differs from Preparation Example 1 in that: 95 parts by weight of phenyltrivinylsilane and 5 parts by weight of 2,4-diphenyl-4-methyl-1-pentene are added to obtain copolymer 2, and the content of structural units formed by phenyltrivinylsilane is 94 mol.

[0185] Preparation Example 3

[0186] This preparation example provides a method for preparing a copolymer, which differs from Preparation Example 1 in that: 90 parts by weight of phenyltrivinylsilane and 10 parts by weight of 2,4-diphenyl-4-methyl-1-pentene are added to obtain copolymer 3, wherein the content of structural units formed by phenyltrivinylsilane is 92 mol.

[0187] Preparation Example 4

[0188] This preparation example provides a method for preparing a copolymer, which differs from Preparation Example 1 in that: 85 parts by weight of phenyltrivinylsilane and 15 parts by weight of 2,4-diphenyl-4-methyl-1-pentene are added to obtain copolymer 4, and the content of structural units formed by phenyltrivinylsilane is 88 mol.

[0189] Preparation Example 5

[0190] This preparation example provides a method for preparing a copolymer, which differs from Preparation Example 1 in that: 80 parts by weight of phenyltrivinylsilane and 20 parts by weight of 2,4-diphenyl-4-methyl-1-pentene are added to obtain copolymer 5, wherein the content of structural units formed by phenyltrivinylsilane is 84 mol.

[0191] Preparation Example 6

[0192] This preparation example provides a method for preparing a copolymer, which differs from Preparation Example 1 in that: 60 parts by weight of phenyltrivinylsilane and 30 parts by weight of diphenyldivinylsilane are used instead of 98 parts by weight of phenyltrivinylsilane, and 10 parts by weight of 2,4-diphenyl-4-methyl-1-pentene are used instead of 2 parts by weight of 2,4-diphenyl-4-methyl-1-pentene, to obtain copolymer 6, in which the content of the structural units formed by phenyltrivinylsilane and diphenyldivinylsilane is 91 mol.

[0193] Preparation Example 7

[0194] This preparation example provides a method for preparing a copolymer, which differs from Preparation Example 3 in that: diphenyldivinylsilane is used instead of phenyltrivinylsilane to obtain copolymer 7, wherein the content of structural units formed by diphenyldivinylsilane is 90 mol%.

[0195] Preparation Example 8

[0196] This preparation example provides a method for preparing a copolymer, which differs from Preparation Example 3 in that: 2,4-diphenyl-3,4-dimethyl-1-hexene prepared in Preparation Example 1 is used instead of 2,4-diphenyl-4-methyl-1-pentene to obtain copolymer 8, in which the content of structural units formed by phenyltrivinylsilane is 92 mol%.

[0197] Preparation Example 9

[0198] This preparation example provides a method for preparing a copolymer, which differs from Preparation Example 3 in that: 2,4-di(p-methoxy)phenyl-4-methyl-1-pentene prepared in Preparation Example 2 is used instead of 2,4-diphenyl-4-methyl-1-pentene to obtain copolymer 9, in which the content of structural units formed by phenyltrivinylsilane is 93 mol.

[0199] Comparative Preparation Example 1

[0200] This comparative preparation provides a method for preparing a copolymer, which differs from Preparation Example 1 in that: 100 parts by weight of phenyltrivinylsilane are added, and 2,4-diphenyl-4-methyl-1-pentene is not added, to obtain Comparative Self-polymer 1.

[0201] Comparative Preparation Example 2

[0202] This comparative preparation example provides a method for preparing a copolymer, which differs from Preparation Example 1 in that: 100 parts by weight of 2,4-diphenyl-4-methyl-1-pentene are added, and phenyl vinylsilane is not added, to obtain comparative self-polymer 2.

[0203] Comparative preparation example 3

[0204] This comparative preparation example provides a method for preparing a copolymer, which differs from Comparative Preparation Example 1 in that diphenyldivinylsilane is used instead of phenyltrivinylsilane to obtain comparative self-polymer 3.

[0205] Comparative preparation example 4

[0206] This comparative preparation example provides a method for preparing a copolymer, which differs from Preparation Example 1 in that: 75 parts by weight of phenyltrivinylsilane and 25 parts by weight of 2,4-diphenyl-4-methyl-1-pentene are added to obtain comparative copolymer 4.

[0207] Comparative preparation example 5

[0208] This comparative preparation example provides a method for preparing a copolymer, which differs from preparation example 3 in that methyltrivinylsilane is used instead of phenyltrivinylsilane to obtain comparative copolymer 5.

[0209] Comparative preparation example 6

[0210] This comparative preparation example provides a method for preparing a copolymer, which differs from preparation example 3 in that tetraphenyldivinylsiloxane is used instead of phenyltrivinylsilane to obtain comparative copolymer 6.

[0211] Comparative preparation example 7

[0212] This comparative preparation example provides a method for preparing a copolymer, which differs from preparation example 3 in that vinyltriethoxysilane is used instead of phenyltrivinylsilane to obtain comparative copolymer 7.

[0213] Comparative Preparation Example 8

[0214] This comparative preparation example provides a method for preparing a copolymer, which differs from Preparation Example 3 in that 1,4-naphthoquinone is used instead of 2,4-diphenyl-4-methyl-1-pentene to obtain comparative copolymer 8.

[0215] Comparative preparation example 9

[0216] This comparative preparation example provides a method for preparing a copolymer, which differs from preparation example 3 in that: n-dodecyl mercaptan is used instead of 2,4-diphenyl-4-methyl-1-pentene to obtain comparative copolymer 9.

[0217] Figure 1 The infrared spectra of copolymer 3, phenyltrivinylsilane, and 2,4-diphenyl-4-methyl-1-pentene are shown, where a is the infrared spectrum of 2,4-diphenyl-4-methyl-1-pentene, b is the infrared spectrum of phenyltrivinylsilane, and c is the infrared spectrum of copolymer 3. (1590 cm⁻¹) -1 The peak at 1590 cm⁻¹ is a characteristic infrared absorption peak for the "C=C" double bond. Compared to 2,4-diphenyl-4-methyl-1-pentene and phenyltrivinylsilane, copolymer 3 shows a peak at 1590 cm⁻¹. -1 The characteristic absorption peak at 1428 cm⁻¹ is significantly weakened, indicating that some of the "C=C" double bonds have undergone an addition reaction; in addition, the characteristic absorption peak at 1428 cm⁻¹ is significantly weakened. -1 1110cm -1 The infrared characteristic absorption peak at 1401 cm⁻¹ is for "phenyl-Si". -1 1006cm -1 950cm -1 The infrared characteristic absorption peak of "vinyl-Si" is shown at point 3. Comparing the infrared spectra of phenyltrivinylsilane and copolymer 3, it can be seen that there is no significant difference in the intensity of the "phenyl-Si" characteristic absorption peak between the two. However, the characteristic absorption peak of "vinyl-Si" of copolymer 3 is significantly weaker than that of phenyltrivinylsilane, which also indicates that some vinyl groups in copolymer 3 have undergone addition reactions.

[0218] Figure 2The NMR spectra of copolymer 3, phenyltrivinylsilane, and 2,4-diphenyl-4-methyl-1-pentene (using TSM tetramethylsilane as the standard) are shown below. In the NMR spectrum, a represents phenyltrivinylsilane, b represents 2,4-diphenyl-4-methyl-1-pentene, and c represents copolymer 3. The characteristic peaks of the benzene ring are located at 7.0-7.5 ppm, the characteristic peaks of the C=C junction are located at 4.5-6.5 ppm (5.5-6.5 ppm for phenyltrivinylsilane and copolymer 3, and 4.5-5.5 ppm for 2,4-diphenyl-4-methyl-1-pentene), and the characteristic peaks of -CH3 are located at 1.0-1.5 ppm. It can be observed that the C=C characteristic peak of copolymer 3 at 5.5-6.5 ppm is significantly weaker than that of phenyltrivinylsilane. The "C=C" characteristic peak of 2,4-diphenyl-4-methyl-1-pentene at 4.5-5.5 ppm disappeared after copolymerization. At the same time, the "-CH3" characteristic peak of copolymer 3 appeared at 1.5 ppm, which is solely derived from 2,4-diphenyl-4-methyl-1-pentene. Therefore, it can be concluded that phenyltrivinylsilane and 2,4-diphenyl-4-methyl-1-pentene underwent a copolymerization reaction to generate phenyltrivinylsilane-2,4-diphenyl-4-methyl-1-pentene copolymer 3.

[0219] Figure 3 Table 2 shows the gel permeation chromatogram of the crude product of copolymer 3. The chromatogram shows that the crude product contains polymer molecules with weight average molecular weights of 32,071 and 3,686, which proves that the weight average molecular weight of copolymer 3 of the present invention is significantly larger than that of its raw material monomers. Therefore, copolymer 3 has indeed undergone copolymerization.

[0220] Table 2. Gel permeation chromatography of the crude reaction products.

[0221] name Retention time (min) Mn (Dalton) Mw (Dalton) MP (Dalton) polydispersity area(%) Peak 1 19.550 20,839 32,071 19,944 1.539022 24.75 Peak 2 22.125 2,234 3,686 5,563 1.650171 22.17 Peak 3 29.308 73 79 77 1.080875 53.09

[0222] Copolymer / Comparative Selfpolymer Testing

[0223] Non-volatile component test method

[0224] One gram of the unpurified copolymer of the preparation example, the crude product of the comparative self-polymer of the comparative preparation example, or the unreacted monomer compound was weighed into a tray, containing a theoretical value of a1 grams of solvent, and a theoretical weight of (1-a1) grams of the non-solvent portion. It was baked in an oven at 170°C for 1 hour, cooled, and weighed a2 grams. The non-volatile content was calculated as [a2 / (1-a1)]×100%. The results are shown in Table 3.

[0225] Table 3 shows the test results of the crude products and monomers of the copolymers in the preparation examples and the self-polymers in the comparative preparation examples.

[0226]

[0227] As can be seen, compared with the raw materials phenylvinylsilane and 2,4-diphenyl-4-methyl-1-pentene and the self-polymers of these monomers, the copolymers in the prepared example have significantly increased non-volatile content and greatly reduced volatility.

[0228] This is because phenylvinylsilane and 2,4-diphenyl-4-methyl-1-pentene are low-viscosity liquids at room temperature with low boiling points, and they easily volatilize when directly baked at temperatures above 150°C. At the same time, during the self-polymerization of phenylvinylsilane or 2,4-diphenyl-4-methyl-1-pentene, the monomer conversion rate is low, the self-polymerization reaction is difficult to control, and it is impossible to obtain copolymers with uniform molecular weight, so their non-volatile content is also low. However, through the copolymerization of phenylvinylsilane and 2,4-diphenyl-4-methyl-1-pentene, copolymers with suitable molecular weights and low volatility at high temperatures can be obtained.

[0229] Preparation of Resin Compositions and Articles Thereof in Examples and Comparative Examples

[0230] The specific steps of the preparation method of the resin composition of the present invention are as follows:

[0231] Preparation of varnish (or gelling agent)

[0232] Each embodiment (represented by E, such as E1 to E21) or comparative example (represented by C, such as C1 to C18) is added to a mixing tank according to the amounts in Tables 4 to 8 and stirred. The resulting resin composition is called resin varnish.

[0233] Taking Example E1 as an example, 100 parts by weight of copolymer 1 were added to a stirrer containing an appropriate amount of toluene and an appropriate amount of methyl ethyl ketone and stirred until copolymer 1 was completely dissolved. Then, 50 parts by weight of KPU-6270 were added and stirred evenly. Next, 150 parts by weight of spherical silica SC-2050SMJ were added and stirred until completely dispersed. Then, 0.5 parts by weight of curing accelerator (25B, which was first dissolved into a solution using an appropriate amount of solvent) were added and stirred for 1 hour to obtain the varnish of resin composition E1.

[0234] In Tables 4 to 8, the addition of methyl ethyl ketone (MEK) and toluene is described as "appropriate amount," meaning the amount of solvent used to achieve the ideal solid content of the overall resin composition. For resin compositions using both MEK and toluene, "appropriate amount" means the total amount of these two solvents is sufficient to achieve the ideal solid content of the overall resin composition, for example, 70% by weight, but the present invention is not limited thereto.

[0235] Table 4. Composition (parts by weight) of the resin compositions in the examples.

[0236]

[0237]

[0238] Table 5. Composition (parts by weight) of the resin compositions in the examples.

[0239]

[0240] Table 6. Composition (parts by weight) of the resin compositions in the examples.

[0241]

[0242]

[0243] Table 7. Composition (parts by weight) of the comparative example resin compositions

[0244]

[0245] Table 8. Composition (parts by weight) of the comparative example resin compositions

[0246]

[0247] Preparation of products

[0248] 1. Prepreg

[0249] The varnishes E1 to E21 prepared in the examples and the varnishes C1 to C18 prepared in the comparative examples were placed in an impregnation tank. Glass fiber cloth (e.g., L-glass fiber cloth of specification 2116) was passed through the impregnation tank to allow the resin composition to adhere to the glass fiber cloth. The mixture was heated at 120°C to 170°C to a semi-cured state (B-Stage) to obtain semi-cured sheet 1 (resin content about 50%).

[0250] 2. Prepreg 2

[0251] The varnishes E1 to E21 prepared in the examples and the varnishes C1 to C18 prepared in the comparative examples were placed in an impregnation tank. Glass fiber cloth (e.g., L-glass fiber cloth with a specification of 1078) was passed through the impregnation tank to allow the resin composition to adhere to the glass fiber cloth. The mixture was heated at 120°C to 170°C to a semi-cured state (B-Stage) to obtain semi-cured sheet 2 (resin content of about 70%).

[0252] 3. Copper foil substrate 1

[0253] Two 18-micrometer (Hoz) thick ultra-low profile copper foils (HVLP3 copper foil) and eight prepregs 1 made from the resin compositions of the various examples and comparative examples (using 2116L glass fiber cloth, each prepreg containing approximately 50% resin) were prepared. The prepregs were stacked in the order of "one of the aforementioned copper foils / eight prepregs 1 / one of the aforementioned copper foils," and pressed under vacuum at 200°C for 130 minutes to form each copper foil substrate 1. The eight stacked prepregs 1 were then cured (C-stage) to form an insulating layer between the two copper foils; the insulating layer contained approximately 50% resin.

[0254] 4. Copper foil substrate 2

[0255] Two 18-micrometer (Hoz) thick ultra-low profile copper foils (HVLP3 copper foil) and two prepreg sheets 1 made from the resin compositions of the various examples and comparative examples (using 2116L glass fiber cloth, each prepreg sheet containing approximately 50% resin) were prepared. The prepreg sheets were stacked in the order of "one of the aforementioned copper foils / two prepreg sheets 1 / one of the aforementioned copper foils," and pressed under vacuum at 200°C for 130 minutes to form each copper foil substrate 2. The two stacked prepreg sheets 1 were cured (C-stage) to form an insulating layer between the two copper foils; the insulating layer contained approximately 50% resin.

[0256] 5. Copper foil substrate 3

[0257] Two 18-micrometer (Hoz) thick ultra-low surface roughness 3 copper foils (HVLP3 copper foil) and two prepreg sheets 2 made from the resin compositions of the various examples and comparative examples (using 1078L glass fiber cloth, each prepreg sheet containing approximately 70% resin) were prepared. The prepreg sheets were stacked in the order of "one of the aforementioned copper foils / two prepreg sheets 2 / one of the aforementioned copper foils," and pressed under vacuum at 200°C for 130 minutes to form each copper foil substrate 3. The two stacked prepreg sheets 2 were cured (C-stage) to form an insulating layer between the two copper foils; the insulating layer contained approximately 70% resin.

[0258] 6. Copper-free substrate 1

[0259] The copper foil substrate 1 (made by pressing eight prepreg sheets 1 together) is etched to remove the copper foil on both sides to obtain a copper-free substrate 1, which is made by pressing eight prepreg sheets 1 together and has a resin content of about 50%.

[0260] 7. Copper-free substrate 2

[0261] The copper foil substrate 2 (made by pressing two prepreg sheets 1 together) is etched to remove the copper foil on both sides to obtain a copper-free substrate 2, which is made by pressing two prepreg sheets 1 together and has a resin content of about 50%.

[0262] 8. Copper-free substrate 3

[0263] The copper foil substrate 3 (made by pressing two prepreg sheets 2 together) is etched to remove the copper foil on both sides to obtain a copper-free substrate 3, which is made by pressing two prepreg sheets 2 together and has a resin content of about 70%.

[0264] Product testing and property analysis

[0265] 1. Glass transition temperature (Tg)

[0266] In the glass transition temperature test, the aforementioned copper-free substrate 1 was selected as the test sample for dynamic mechanical analysis (DMA). The sample was heated at a rate of 2°C per minute, from 35°C to 300°C, and the glass transition temperature (in °C) of each test sample was measured according to the method described in IPC-TM-650 2.4.24.4.

[0267] Similarly, the aforementioned copper-free substrate 1 was selected as the sample for thermomechanical analysis (TMA). The sample was heated at a rate of 10°C per minute, from 35°C to 300°C, and the glass transition temperature (in °C) of each sample was measured according to the method described in IPC-TM-6502.4.24.5.

[0268] In this field, a higher glass transition temperature is preferred. A difference in glass transition temperature greater than or equal to 5°C indicates a significant difference in glass transition temperatures between different substrates (presenting significant technical difficulty). For example, an article made from the resin composition disclosed in this invention has a glass transition temperature (DMA-Tg) greater than or equal to 220°C, for example greater than or equal to 221°C, or for example between 221°C and 260°C, measured with reference to the method described in IPC-TM-650 2.4.24.5; and a glass transition temperature (TMA-Tg) greater than or equal to 200°C, for example greater than or equal to 201°C, or for example between 201°C and 230°C, measured with reference to the method described in IPC-TM-650 2.4.24.5.

[0269] 2. Copper foil tensile strength (or peel strength, P / S)

[0270] The aforementioned copper foil substrate 1 was cut into rectangular samples with a width of 24 mm and a length greater than 60 mm. The surface copper foil was then etched, leaving only a strip of copper foil with a width of 3.18 mm and a length greater than 60 mm. Using a universal tensile testing machine, the force required to pull the copper foil away from the substrate surface was measured at room temperature (approximately 25°C) according to the method described in IPC-TM-650 2.4.8, to determine the force (lb / in) required to pull the copper foil away from the substrate surface.

[0271] In this field, higher copper foil tensile strength is preferred. A difference in copper foil tensile strength greater than or equal to 0.1 lb / in is considered significant (indicating significant technical difficulty). For example, articles made from the resin compositions disclosed in this invention have a copper foil tensile strength greater than or equal to 2.00 lb / in, for example, between 2.00 lb / in and 3.00 lb / in, as measured with reference to the method described in IPC-TM-650 2.4.8.

[0272] 3. Ratio of thermal expansion

[0273] In the measurement of thermal expansion ratio (or dimensional change ratio), the aforementioned copper-free substrate 1 was selected as the test sample for thermomechanical analysis (TMA). The sample was heated at a rate of 10°C per minute, from 35°C to 265°C. The Z-axis dimensional change rate of each test sample (temperature range of 50°C-260°C, in %) was measured according to the method described in IPC-TM-650 2.4.24.5. The lower the percentage of dimensional change rate, the better.

[0274] Generally, a high Z-axis thermal expansion coefficient of a substrate indicates a large dimensional change rate. For copper foil substrates, a large dimensional change rate can easily lead to problems such as displacement at circuit connection points (e.g., blind vias or buried vias, but this invention is not limited to these) during the processing of printed circuit boards, reducing yield, or board explosion, reducing reliability. In this field, a lower percentage of thermal expansion coefficient is better, and a difference in thermal expansion coefficient greater than or equal to 0.1% is considered significant. For example, articles made from the resin composition disclosed in this invention have a Z-axis thermal expansion coefficient less than or equal to 1.40%, for example, between 0.70% and 1.40%, as measured with reference to the method described in IPC-TM-650 2.4.24.5.

[0275] 4. X-axis coefficient of thermal expansion (CTE)

[0276] In the measurement of the X-axis thermal expansion coefficient, the copper-free substrate 2 (composed of two prepreg sheets laminated together, with a resin content of approximately 50%) was selected as the test sample for thermomechanical analysis (TMA). The copper-free substrate was cut into samples with a length of 15 mm and a width of 2 mm, and a thickness of 8.4 mils. The samples were heated at a rate of 5°C per minute, from 50°C to 260°C. The X-axis thermal expansion coefficient (in ppm / °C) of each test sample within the temperature range (α1) from 40°C to 125°C was measured according to the method described in IPC-TM-650 2.4.24.5.

[0277] Generally, a lower X-axis coefficient of thermal expansion indicates better dimensional expansion and contraction characteristics. A difference in X-axis coefficient of thermal expansion greater than or equal to 0.1 ppm / ℃ is considered a significant difference (with significant technical difficulty). For example, articles made from the resin composition disclosed in this invention, when measured with reference to the method described in IPC-TM-650 2.4.24.5, have a low X-axis coefficient of thermal expansion, for example, less than or equal to 11.0 ppm / ℃, or for example, between 7.5 ppm / ℃ and 11.0 ppm / ℃.

[0278] 5. Heat resistance after moisture absorption (PCT heat resistance)

[0279] Using the aforementioned copper-free substrate sample 1, and following the method described in IPC-TM-650 2.6.16.1, a pressure cooking test (PCT) was performed for 5 hours (test temperature 121℃, relative humidity 100%). Then, following the method described in IPC-TM-650 2.4.23, the sample was immersed in a solder bath at a constant temperature of 288℃. After immersion for 20 seconds, the sample was removed and observed for any board bursting. For example, interlayer peeling between insulating layers constitutes board bursting. Interlayer peeling will cause bubbling and separation between any layers of the substrate (visible to the naked eye).

[0280] For example, articles made from the resin composition disclosed in this invention, after undergoing a heat resistance test for 5 hours of moisture absorption according to the methods described in IPC-TM-650 2.6.16.1 and IPC-TM-650 2.4.23, do not exhibit plate bursting. A result of no plate bursting is recorded as "pass" to indicate a pass, while a result of plate bursting is recorded as "fail" to indicate a fail.

[0281] 6. Dielectric constant (Dk) and dielectric loss (Df)

[0282] The aforementioned copper-free substrate 3 was selected as the sample to be tested. A microwave electrochemical analyzer (purchased from AET Corporation, Japan) was used to measure each sample at a frequency of 10 GHz, following the method described in JIS C2565.

[0283] In this field, a lower dielectric constant or lower dielectric loss indicates better dielectric properties of the sample under test. At a measurement frequency of 10 GHz, with a Dk value less than or equal to 3.50 and a Df value less than or equal to 0.004, a difference in Dk values ​​greater than or equal to 0.05 indicates a significant difference in dielectric constant between different substrates (presenting significant technical difficulty), while a difference in Dk values ​​less than 0.05 indicates no significant difference in dielectric constant between substrates. Similarly, a difference in Df values ​​less than 0.00005 indicates no significant difference in dielectric loss between substrates, while a difference in Df values ​​greater than or equal to 0.00005 indicates a significant difference in dielectric loss between different substrates (presenting significant technical difficulty). For example, an article made from the resin composition disclosed in this invention has a dielectric constant less than or equal to 3.40, for example, between 3.20 and 3.40, measured at a frequency of 10 GHz by the method described in JIS C2565; and a dielectric loss less than or equal to 0.00300, for example, between 0.00240 and 0.00300.

[0284] Following the above method, the characteristic test results of the embodiments and comparative examples are shown in Tables 9 to 13 below:

[0285] Table 9. Test results of the properties of the resin compositions in the examples.

[0286] Feature testing unit E1 E2 E3 E4 E5 E6 E7 DMA-Tg ℃ 249 238 253 242 247 243 239 TMA-Tg ℃ 220 212 223 211 215 213 210 P / S lb / in 2.0 2.0 2.2 2.4 2.4 2.4 2.4 Z-axis thermal expansion coefficient ％ 0.80 0.95 0.75 1.00 1.40 1.20 1.15 X-CTE ppm / ℃ 9.7 10.2 9.5 9.0 11.0 9.0 9.5 PCT (5hr) none pass pass pass pass pass pass pass Dk none 3.40 3.40 3.38 3.38 3.35 3.36 3.39 Df none 0.00290 0.00288 0.00285 0.00262 0.00260 0.00261 0.00263

[0287] Table 10. Test results of the properties of the resin compositions in the examples.

[0288] Feature testing unit E8 E9 E10 E11 E12 E13 E14 DMA-Tg ℃ 234 225 221 235 248 230 260 TMA-Tg ℃ 210 204 201 210 215 210 230 P / S lb / in 2.5 2.6 2.7 2.4 2.6 2.6 2.4 Z-axis thermal expansion coefficient ％ 1.40 1.10 1.10 1.05 1.05 1.05 0.70 X-CTE ppm / ℃ 11.0 9.2 9.5 9.0 9.0 9.5 7.5 PCT (5hr) none pass pass pass pass pass pass pass Dk none 3.40 3.38 3.38 3.38 3.38 3.20 3.40 Df none 0.00264 0.00258 0.00254 0.00264 0.00280 0.00240 0.00300

[0289] Table 11. Test results of the properties of the resin compositions in the examples.

[0290] Feature testing unit E15 E16 E17 E18 E19 E20 E21 DMA-Tg ℃ 245 237 250 238 237 236 240 TMA-Tg ℃ 215 210 220 210 213 210 224 P / S lb / in 2.4 2.6 2.4 2.5 2.4 2.4 3.0 Z-axis thermal expansion coefficient ％ 0.85 1.08 0.80 0.85 1.00 1.00 0.98 X-CTE ppm / ℃ 8.3 9.2 8.2 8.3 9.2 9.0 9.0 PCT (5hr) none pass pass pass pass pass pass pass Dk none 3.40 3.28 3.35 3.40 3.40 3.33 3.40 Df none 0.00290 0.00240 0.00270 0.00275 0.00257 0.00280 0.00288

[0291] Table 12. Test results of the properties of the comparative resin compositions.

[0292]

[0293]

[0294] Table 13. Test results of the properties of the comparative resin compositions.

[0295]

[0296] Based on the test results in Tables 9 to 13, the following phenomena can be observed.

[0297] The copolymers of phenylvinylsilane and alkenyl compounds retain some double bonds, exhibiting strong crosslinking reactivity. When added to resin compositions, they can further participate in the crosslinking reaction, thereby simultaneously improving the glass transition temperature, thermal expansion coefficient, and dielectric loss characteristics of the products.

[0298] The E1-E3 samples prepared by the examples confirm that the products prepared by the present invention using copolymers of phenyl vinyl silane and alkenyl compounds with styrene-terminated phenolic resins with different R-group structures can achieve multiple or all of the following functions: high glass transition temperature, high copper foil tensile strength, low Z-axis thermal expansion coefficient, low X-axis thermal expansion coefficient, excellent PCT heat resistance, low dielectric constant, and low dielectric loss characteristics.

[0299] By comparing E4-E10 prepared in the comparative examples with C1-C4 prepared in the comparative examples, it can be confirmed that by using 80-98 parts by weight of a copolymer of phenylvinylsilane and 2-20 parts by weight of an alkenyl compound, compared with copolymers or self-polymers with amounts outside the above range, the product prepared by the present invention can simultaneously achieve at least one of the following technical effects: increasing glass transition temperature, increasing copper foil tensile strength, reducing Z-axis thermal expansion coefficient, reducing X-axis thermal expansion coefficient, passing PCT test, and reducing dielectric loss characteristics.

[0300] By comparing E4 and E9-E12 prepared in the comparative examples with C5-C9 prepared in the comparative examples, it can be confirmed that by using copolymers of phenylvinylsilane and alkenyl compounds, the products prepared by the present invention can simultaneously achieve at least one of the following technical effects: increasing glass transition temperature, increasing copper foil tensile strength, reducing Z-axis thermal expansion coefficient, reducing X-axis thermal expansion coefficient, reducing dielectric constant, and reducing dielectric loss characteristics, compared to compounds with monomer types outside the above range.

[0301] By comparing E1, E4, E13-E16 prepared in the comparative examples with C10-C12 prepared in the comparative examples, it can be confirmed that the present invention uses 100 parts by weight of a copolymer of phenyl vinyl silane and an alkenyl compound and 20-100 parts by weight of styrene-terminated phenolic resin, or further combines it with 5-30 parts by weight of polyolefin resin. Compared with the use of styrene-terminated phenolic resin or polyolefin outside the above range, the product prepared by the present invention can simultaneously achieve at least one of the technical effects of increasing glass transition temperature, reducing Z-axis thermal expansion coefficient, reducing X-axis thermal expansion coefficient, passing PCT test, reducing dielectric constant, and reducing dielectric loss characteristics.

[0302] By comparing E4 prepared in the examples with C14-C15 and C17 prepared in the comparative examples; E10 prepared in the examples with C13 and C15-C16 prepared in the comparative examples; and E9 prepared in the examples with C18 prepared in the comparative examples, it can be confirmed that by using a copolymer of phenylvinylsilane and an alkenyl compound, compared with adding phenylvinylsilane alone, adding an alkenyl compound alone, or adding phenylvinylsilane and an alkenyl compound that have not undergone copolymerization, the product prepared by the present invention can simultaneously achieve at least one of the following technical effects: increasing glass transition temperature, increasing copper foil tensile strength, reducing Z-axis thermal expansion coefficient, reducing X-axis thermal expansion coefficient, passing PCT test, and reducing dielectric loss characteristics.

[0303] By comparing E1-E21 prepared in the comparative examples with C1-C18 prepared in the comparative examples, it can be confirmed that the present invention, by using 80-98 parts by weight of a copolymer of phenyl vinyl silane and 2-20 parts by weight of an alkenyl compound and 20-100 parts by weight of styrene-terminated phenolic resin, or further combining it with 5-30 parts by weight of a polyolefin, enables the substrate to simultaneously achieve a glass transition temperature (TMA-Tg) greater than or equal to 201°C, a Z-axis thermal expansion coefficient less than or equal to 1.40%, an X-axis thermal expansion coefficient less than or equal to 11.0 ppm / °C, and a dielectric loss less than or equal to 0.00300. Conversely, the comparative examples C1-C18, which did not use the technical solution of the present invention, could not achieve the aforementioned technical effects.

Claims

1. A resin composition, characterized by comprising: The resin composition comprises, by weight parts: 100 parts of a copolymer of phenyl vinylsilane and an alkenyl compound, and 20 to 100 parts of styrene-terminated phenolic resin; The copolymer of phenylvinylsilane and alkenyl compound comprises structural units formed by phenylvinylsilane and alkenyl compound; the raw materials of the copolymer include phenylvinylsilane and alkenyl compound, based on a total weight of 100 parts by weight of phenylvinylsilane and alkenyl compound, wherein phenylvinylsilane is 80 to 98 parts by weight and alkenyl compound is 2 to 20 parts by weight. The phenylvinylsilane has the structure shown in formula (1) and / or formula (2), the alkenyl compound has the structure shown in formula (3), and the styrene-terminated phenolic resin has the structure shown in formula (4). Wherein, Ra, Rb, Rc, and Rd are each independently H or a monovalent alkyl or alkoxy group having 1 to 10 carbon atoms, m and n are each independently integers from 0 to 5, and Re, Rf, Rg, and Rh are each independently H or a monovalent alkyl group having 1 to 4 carbon atoms. Furthermore, R is at least one of methylene, dicyclopentadienyl, substituted or unsubstituted aryl groups, and n1 is an integer from 1 to 10.

2. The resin composition according to claim 1, characterized by The copolymer of phenylvinylsilane and alkenyl compound has a weight-average molecular weight of 2,000 to 50,000.

3. The resin composition according to claim 1, characterized in that, The preparation method of the copolymer of phenylvinylsilane and alkenyl compound includes: 80 to 98 parts by weight of phenylvinylsilane are reacted with 2 to 20 parts by weight of an alkenyl compound at 80 to 150°C for 2 to 10 hours.

4. The resin composition according to claim 3, characterized by The preparation method of the copolymer further includes adding an initiator, a catalyst, or a combination thereof.

5. The resin composition according to claim 1, characterized by The copolymer of phenyl vinylsilane and alkenyl compound contains structural unit A and structural unit B. Structural unit A is at least one of the structures shown in formula (5), formula (6), formula (7), formula (8), and formula (9). The number of structures shown in formula (5), formula (6), formula (7), formula (8), and formula (9) in the copolymer are J1, J2, J3, K1, and K2, respectively. The structural unit B is the structure shown in formula (10), and the number of structures shown in formula (10) in the copolymer is L1; Where * represents the bonding position, J1, J2, J3, K1, and K2 are each independently 0 or positive integers, but not all of them are 0 at the same time, and L1 is a positive integer; and 10≤J1+J2+J3+L1≤268, or 8≤K1+K2+L1≤212, or 8≤J1+J2+J3+K1+K2+L1≤268.

6. The resin composition according to claim 1, characterized by The chemical structure of the alkenyl compound is shown in at least one of formulas (11), (12), and (13):

7. The resin composition according to claim 1, characterized in that, The resin composition further includes 5 to 30 parts by weight of polyolefin resin.

8. The resin composition according to claim 1, characterized by The resin composition further includes at least one of the following: vinyl polyphenylene ether resin, maleimide resin, maleimide triazine resin, small molecule vinyl resin, small molecule vinyl resin prepolymer, styrene maleic anhydride resin, epoxy resin, phenolic resin, benzoxazine resin, cyanate ester resin, polyester resin, polyamide resin, and polyimide resin.

9. The resin composition according to claim 1, characterized by The resin composition further includes at least one of the following: amine curing agent, flame retardant, inorganic filler, curing accelerator, polymerization inhibitor, dye, solvent, toughening agent, and silane coupling agent.

10. An article of manufacture characterized by, The article is made of the resin composition according to any one of claims 1 to 9, and the article includes a prepreg, a resin film, a laminate, a printed circuit board, or a cured insulator.

11. The article of claim 10, characterized in that, The glass transition temperature of the product, measured according to IPC-TM-650 2.4.24.4, is greater than or equal to 220°C.

12. The article of claim 10, wherein, The glass transition temperature of the product, measured according to the method described in IPC-TM-650 2.4.24.5, is greater than or equal to 200°C.

13. The article of claim 10, wherein, The copper foil tensile strength of the product, measured according to IPC-TM-650 2.4.8, is greater than or equal to 2.00 lb / in.

14. The article of claim 10, wherein, The Z-axis thermal expansion coefficient of the product, measured according to IPC-TM-650 2.4.24.5, is less than or equal to 1.40%.

15. The article of claim 10, wherein, The X-axis coefficient of thermal expansion of the product, measured according to IPC-TM-650 2.4.24.5, is less than or equal to 11.0 ppm / ℃.

16. The article of claim 10, wherein The dielectric constant of the product, measured at a frequency of 10 GHz according to the JIS C2565 method, is less than or equal to 3.

40.

17. The article of claim 10, wherein The dielectric loss of the product, measured at a frequency of 10 GHz according to the JIS C2565 method, is less than or equal to 0.00300.

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