Resin composition and prepreg and metal foil-clad laminated board containing same

Abstract

The invention provides a resin composition, and a prepreg and a metal foil-clad laminated board containing the same. The resin composition comprises the following components: a maleimide compound (A) containing an indane structure in a molecule and thermosetting resin (B), the maleimide compound (A) having an indane structure in the molecule has an acid value of 5.0 mgKOH / g or less. According to the present invention, the Df change is small after the cured product of the resin composition is subjected to the extreme environment thermal oxidation treatment, such that the prepared prepreg and the prepared metal foil-coated laminated board have characteristics of excellent dielectric property and extreme environment resistance, and are especially suitable for high-speed packaging.

Description

Technical Field

[0001] This invention belongs to the field of printed circuit board technology, specifically relating to a resin composition and a prepreg containing the same, and a metal foil laminate. Background Technology

[0002] In recent years, information technology has entered a stage of high-speed signaling and high-frequency transmission. To match the ever-increasing data processing volume, electronic devices are operating at increasingly higher frequencies, which places higher demands on the electrical performance of substrates to minimize high-frequency signal loss and latency. With the advent of the 5G era, applications such as high-frequency RF (e.g., PA, WiGig, WiHD / 60GHz), large-size chips, and DDR5 (3.2–6.4Gbps) have placed even higher demands on the performance of packaging substrate materials: they must possess both a low planar thermal expansion coefficient and a lower dielectric loss tangent.

[0003] Bismaleimide (BMI) resin is a traditional encapsulation substrate resin system, characterized by high monomer activity, no molecule release during polymerization, stable finished product performance, and the ability to maintain high physical and mechanical properties over a wide temperature range. CN109825081A discloses a thermosetting resin composition comprising the following components: a combination of bismaleimide resin and benzoxazine resin or a prepolymer of bismaleimide resin and benzoxazine resin, epoxy resin, and reactive ester. The metal-coated laminate prepared by this resin composition exhibits a high glass transition temperature, a low coefficient of thermal expansion, a high temperature modulus, and good heat resistance. However, the cured product of the maleimide resin system is brittle, has a short shelf life, and exhibits poor dielectric loss tangent performance, thus limiting its application in high-frequency, high-speed electronic products. Meanwhile, to ensure the continued use of electronic devices in high-temperature environments, simply reducing the dielectric properties of the printed circuit board is often insufficient; it is also required that the printed circuit board maintain its low dielectric characteristics even under thermal conditions.

[0004] Therefore, it is of great practical significance to develop a resin composition with low dielectric loss and the ability to withstand extreme thermal and oxidative treatments without significant changes in dielectric properties. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a resin composition and a prepreg or metal foil-coated laminate containing the same. The resin composition of the present invention enables the prepared prepreg or metal foil-coated laminate to possess excellent dielectric properties and low ΔD after extreme environmental heat and oxidation treatment. f This adaptability is particularly suitable for high-speed packaging.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] On one hand, the present invention provides a resin composition comprising the following components: a maleimide compound (A) containing an indane structure in its molecule and a thermosetting resin (B);

[0008] The maleimide compound (A) containing an indane structure in its molecule has an acid value of less than 5.0 mg KOH / g.

[0009] In this invention, by using maleimide compounds containing indane structures with an acid value of less than 5.0 mg KOH / g, the cured resin composition can withstand extreme environmental thermo-oxidative treatment, resulting in a ΔD... f The minimal variation results in prepregs and metal foil laminates with excellent dielectric properties and the ability to withstand extreme environments.

[0010] In this invention, the acid value of the maleimide compound (A) containing an indane structure in its molecule can be 4.8 mg KOH / g, 4.5 mg KOH / g, 4 mg KOH / g, 3.8 mg KOH / g, 3.5 mg KOH / g, 3 mg KOH / g, 2.8 mg KOH / g, 2.5 mg KOH / g, 2 mg KOH / g, 1.5 mg KOH / g, 1 mg KOH / g, 0.8 mg KOH / g, 0.5 mg KOH / g, 0.1 mg KOH / g, etc. In this invention, the acid value can be determined according to the method of JIS K-0070:1992.

[0011] In this invention, the maleimide compound (A) containing an indenmann structure in its molecule has the structure shown in formula (I):

[0012]

[0013] In formula (I), each Rb is independently selected from hydrogen atoms, alkyl groups having 1 to 10 carbon atoms (e.g., 1, 2, 5, 8, or 10), alkoxy groups having 1 to 10 carbon atoms (e.g., 1, 2, 5, 8, or 10), alkylthio groups having 1 to 10 carbon atoms (e.g., 1, 2, 5, 8, or 10), aryl groups having 6 to 10 carbon atoms (e.g., 6, 7, 8, 9, or 10), aryloxy groups having 6 to 10 carbon atoms (e.g., 6, 7, 8, 9, or 10), arylthio groups having 6 to 10 carbon atoms (e.g., 6, 7, 8, 9, or 10), cycloalkyl groups having 3 to 10 carbon atoms (e.g., 3, 4, 5, 6, 8, or 10), halogen atoms, nitro groups, hydroxyl groups, or mercapto groups. r is selected from integers from 0 to 3 (e.g., it can be 0, 1, 2, or 3). When r is 2 to 3, multiple Rb groups can be the same or different from each other.

[0014] Preferably, the maleimide compound (A) containing an indane structure in the molecule is a maleimide with the structure shown in formula (I-1):

[0015]

[0016] In formula (I-1), Ra is independently selected from hydrogen atom, alkyl with 1 to 10 carbon atoms (e.g., 1, 2, 5, 8, or 10), alkoxy with 1 to 10 carbon atoms (e.g., 1, 2, 5, 8, or 10), alkylthio with 1 to 10 carbon atoms (e.g., 1, 2, 5, 8, or 10), aryl with 6 to 10 carbon atoms (e.g., 6, 7, 8, 9, or 10), and aryloxy with 6 to 10 carbon atoms (e.g., 6, 7, 8, 9, or 10). The Rb group is selected from the following groups: arylthioyl group with 6 to 10 carbon atoms (e.g., 6, 7, 8, 9, or 10); cycloalkyl group with 3 to 10 carbon atoms (e.g., 3, 4, 5, 6, 8, or 10); halogen atom; nitro group; hydroxyl group; or mercapto group; Rb is independently selected from hydrogen atom; alkyl group with 1 to 10 carbon atoms (e.g., 1, 2, 5, 8, or 10); alkoxy group with 1 to 10 carbon atoms (e.g., 1, 2, 5 ... The following groups are selected from alkylthio groups (5, 8, or 10), aryl groups (6 to 10 carbon atoms, e.g., 6, 7, 8, 9, or 10), aryloxy groups (6 to 10 carbon atoms, e.g., 6, 7, 8, 9, or 10), arylthio groups (6 to 10 carbon atoms, e.g., 6, 7, 8, 9, or 10), cycloalkyl groups (3 to 10 carbon atoms, e.g., 3, 4, 5, 6, 8, or 10), halogen atoms, nitro groups, hydroxyl groups, or mercapto groups, where q is an integer selected from 0 to 4 (e.g., 0, 1, 2). q is 2 to 4, and multiple Ra can be the same or different from each other. When r is 2 to 3, multiple Rb can be the same or different from each other.

[0017] In this invention, the preparation method of the maleimide compound (A) containing an indane structure in the molecule is not particularly limited. For example, it can be obtained by a maleimination reaction or by commercially available products. The aforementioned maleimination reaction is carried out in an organic solvent such as toluene, where an amine compound of the following formula (I-2) is reacted with maleic anhydride in the presence of a catalyst such as toluenesulfonic acid. More specifically, after the maleimination reaction, unreacted maleic anhydride or other impurities can be removed by washing with water, and the solvent can be removed under reduced pressure to obtain the product. A dehydrating agent can also be used in this reaction. To reduce the amount of unclosed ammonium acid present, a catalyst can be added again, and the mixture can be heated under reflux again to dehydrate and close the remaining ammonium acid, thereby obtaining a maleimide compound (A) containing an indane structure in the molecule with a low acid value.

[0018]

[0019] In Equation (I-2), the constraints on Ra, Rb, q, r, and n are the same as those in Equation (I-1).

[0020] Preferably, the thermosetting resin (B) comprises one or a combination of at least two of epoxy resin, cyanate ester resin, hydrocarbon resin, polyphenylene ether resin, or other maleimide compounds different from (A).

[0021] Preferably, the polyphenylene ether resin is a polyphenylene ether with unsaturated groups at the ends.

[0022] Preferably, the unsaturated group includes any one or a combination of at least two of vinylbenzyl, vinylphenyl, or acrylate groups.

[0023] In this invention, the structural formula of the vinylbenzyl group is as follows: The dashed lines represent the bonding sites of the functional groups.

[0024] The structural formula of the acrylate group is as follows: The dashed line represents the linking site of the group; R3 is selected from hydrogen, C1 to C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C12, C14, C16, C18 or C19, etc.) straight-chain or branched alkyl groups, and is more preferably hydrogen, C1 to C10 straight-chain or branched alkyl groups.

[0025] The acrylate group is further preferably an acrylate group or a methacrylate group.

[0026] As a preferred embodiment of the present invention, the polyphenylene ether containing unsaturated bonds in component (B) is a polyphenylene ether with vinyl benzyl groups at the ends, which further helps to improve the dielectric properties and heat resistance of the resin composition. The polyphenylene ether with vinyl benzyl groups at the ends can be commercially available products, including but not limited to: Mitsubishi Gas Chemical Co., Ltd.'s OPE-2st 1200 (number average molecular weight M... n (1200) and / or OPE-2st 2200 (number average molecular weight M) n The number-average molecular weight (NMR) can be determined by GB / T 21863-2008, based on polystyrene calibration, by gel permeation chromatography (GPC).

[0027] In the resin composition of the present invention, the content of component (A) is 20 to 90 parts by weight, for example, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 70 parts, 75 parts, 78 parts, 80 parts, 85 parts, or 88 parts, etc.; the content of component (B) is 10 to 70 parts, for example, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, or 70 parts, etc.

[0028] The "parts" and "parts by weight" used in this invention are calculated based on solid content and do not include solvents, dispersants, etc.

[0029] In this invention, if the content of maleimide compound (A) containing an indane structure in the resin composition is less than 20 parts by weight, then after heat-oxidation treatment, for ΔD... f The improvement effect of the change is worse; if the content exceeds 90 parts by weight, the dielectric properties of the resin composition will deteriorate.

[0030] In this invention, if the content of thermosetting resin (B) in the resin composition is less than 10 parts by weight, the dielectric properties are poor and cannot meet the requirements for high-speed signal transmission; if the content exceeds 70 parts by weight, the heat resistance and mechanical properties are poor and it is difficult to meet the requirements for low warpage in encapsulation.

[0031] Preferably, the resin composition further includes one or a combination of at least two of the following: a polyolefin resin (C), a curing accelerator (D), and an inorganic filler (E).

[0032] As a preferred embodiment of the present invention, the polyolefin resin helps to improve the dielectric properties of the resin composition. However, if the content of polyolefin resin is too high, the adhesion between the resin composition and the metal foil decreases, and at the same time, the melt flowability of the resin composition decreases, which is not conducive to preparing a resin composition with uniform thickness.

[0033] Preferably, the polyolefin resin comprises a styrene-based copolymer. A styrene-based copolymer is, for example, a copolymer comprising olefin structural units and styrene structural units. The olefin structural units are derived from olefin monomers, such as structural units derived from butadiene or isoprene; the styrene structural units are derived from styrene monomers, such as structural units derived from styrene or structural units derived from styrene with substituents. In addition to containing structural units derived from olefins and styrene, the styrene-based copolymer may also contain structural units other than olefin and styrene structural units, such as structural units derived from epoxy groups, amino groups, or maleic anhydride.

[0034] Styrene-based copolymers can be random copolymers or block copolymers. If a styrene-based copolymer is a random copolymer, it is a copolymer in which multiple olefin structural units and multiple styrene structural units are arranged randomly. If a styrene-based copolymer is a block copolymer, it is a copolymer in which one or more olefin blocks and one or more styrene blocks are arranged. The olefin blocks consist of multiple olefin structural units, and the styrene blocks consist of multiple styrene structural units.

[0035] The olefin-derived structural units of the polyolefin resin can be hydrogenated or partially hydrogenated. For dielectric properties, it is preferable that the olefin-derived structural units of the polyolefin resin are hydrogenated.

[0036] The polyolefin resin can be a commercially available product, and exemplary examples include, but are not limited to, any one or a combination of at least two of the following: Ricon 153 (butadiene copolymer, Cray Valley), Ricon 100 (butadiene-styrene copolymer, Cray Valley), Ricon 181 (butadiene-styrene copolymer, Cray Valley), Tuftec H1051 (hydrogenated styrene-butadiene copolymer with a styrene content of 42% by mass, Asahi Kasei Chemicals Co., Ltd.), or Tuftec M1913 (hydrogenated styrene-butadiene copolymer with maleic anhydride structural units, with a styrene content of 30% by mass, Asahi Kasei Chemicals Co., Ltd.).

[0037] Preferably, the resin composition contains 5 to 30 parts by weight of polyolefin resin (C), for example, 6, 8, 10, 12, 15, 18, 20, 22, 25, or 28 parts.

[0038] Preferably, the curing accelerator includes any one or a combination of at least two of the following: acidic curing accelerators, organophosphorus curing accelerators, imidazole curing accelerators, pyridine curing accelerators, amine curing accelerators, peroxides, or organometallic salts.

[0039] Exemplary examples include acidic curing accelerators such as p-toluenesulfonic acid; organophosphorus curing accelerators such as triphenylphosphine; imidazole curing accelerators such as imidazole or imidazole derivatives (e.g., 2-ethyl-4-methylimidazolium); pyridine curing accelerators such as pyridine or pyridine derivatives (e.g., 4-dimethylaminopyridine); amine curing accelerators such as secondary amine compounds, tertiary amine compounds, or quaternary ammonium salts; peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyn-3, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, or α,α'-bis(tert-butylperoxy)dicumyl peroxide; and organometallic salts such as zinc naphthenate, cobalt naphthenate, tin octoate, or cobalt octoate. The curing accelerators can be used alone or in combination of at least two.

[0040] Preferably, the resin composition contains 0.01 to 5 parts by weight of curing accelerator (D), for example, 0.03 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 4.8 parts, etc.

[0041] Preferably, the present invention does not particularly limit the type of inorganic filler, and exemplary components include: silicon dioxide, aluminum hydroxide, magnesium hydroxide, boehmite, molybdenum oxide, zinc oxide, zinc molybdate, zinc borate, zinc stannate, titanium dioxide, strontium titanate, barium titanate, barium sulfate, clay, kaolin, talc, mica, boron nitride, aluminum nitride, silicon carbide, alumina, composite silica powder, glass powder, short glass fibers, or hollow glass, or a combination of at least two of these. To improve the heat resistance, damp heat resistance, and dimensional stability of the resin composition, it is preferred to use any one or a combination of at least two of the following: silicon dioxide, aluminum hydroxide, magnesium hydroxide, boehmite, boron nitride, aluminum nitride, silicon carbide, alumina, composite silica powder, glass powder, short glass fibers, or hollow glass. The silicon dioxide can be crystalline silicon dioxide, fused silicon dioxide, amorphous silicon dioxide, spherical silicon dioxide, or hollow silicon dioxide, and is more preferably spherical silicon dioxide.

[0042] The average particle size (D) of inorganic fillers 50 There are no specific limitations, but from the perspective of dispersibility, the average particle size (D) 50 The preferred particle size distribution is 0.01-20 micrometers, such as 0.02 micrometers, 0.05 micrometers, 0.1 micrometers, 0.2 micrometers, 0.8 micrometers, 1.5 micrometers, 2.1 micrometers, 2.6 micrometers, 3.5 micrometers, 4.5 micrometers, 5.2 micrometers, 5.5 micrometers, 6 micrometers, 6.5 micrometers, 7 micrometers, 7.5 micrometers, 8 micrometers, 8.5 micrometers, 9 micrometers, 9.5 micrometers, 12 micrometers, 13.5 micrometers, 15 micrometers, 17.5 micrometers, 18 micrometers, and 19.5 micrometers, and more preferably 0.1-10 micrometers. Different types of inorganic fillers with different particle size distributions or different average particle sizes can be used alone or in combination as needed.

[0043] Preferably, the resin composition contains 5 to 250 parts by weight of inorganic filler (E), for example, 8, 10, 20, 30, 50, 70, 90, 100, 110, 130, 150, 170, 190, 200, 210, or 230 parts. The inorganic filler helps improve the heat resistance, damp heat resistance, and mechanical properties of the resin composition, and reduces the coefficient of thermal expansion. Excessive use of inorganic filler can lead to an increase in the dielectric loss tangent of the resin composition, which is detrimental to signal transmission.

[0044] Preferably, the resin composition further comprises 0.01 to 10 parts by weight of coupling agent (F), for example, the coupling agent may be 0.03 parts, 0.05 parts, 0.1 parts, 0.3 parts, 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 parts, and more preferably 0.1 to 6 parts of coupling agent; the coupling agent helps to improve the compatibility between inorganic filler and resin composition.

[0045] Preferably, the coupling agent comprises a silane coupling agent.

[0046] The present invention does not particularly limit the type of silane coupling agent, but can exemplarily be any one or a combination of at least two of the following: epoxy silane coupling agent, amino silane coupling agent, vinyl silane coupling agent, styryl silane coupling agent, isobutylene silane coupling agent, propylene silane coupling agent, urea silane coupling agent, mercapto silane coupling agent, chloropropyl silane coupling agent, sulfur-based silane coupling agent, or isocyanate-based silane coupling agent.

[0047] Preferably, the resin composition further includes a flame retardant (G). There is no particular limitation on the flame retardant, which may be selected from halogenated or non-halogenated flame retardants that are soluble or insoluble in organic solvents. Exemplarily, the non-halogenated flame retardant includes inorganic phosphorus flame retardants, organophosphorus flame retardants, metal hydrates, etc.

[0048] From the perspectives of environmental protection and excellent dielectric properties, flame retardants are preferably organophosphorus flame retardants. For example, the organophosphorus flame retardants include aromatic phosphates, monosubstituted phosphonate diesters, disubstituted hypophosphite esters, metal salts of disubstituted hypophosphite acids, organic nitrogen- and phosphorus-containing compounds, cyclic organophosphorus compounds, etc.

[0049] For example, the aromatic phosphate esters include triphenyl phosphate, tricresyl phosphate, tri(xyl) phosphate, toluene diphenyl phosphate, toluene di-2,6-xylene phosphate, resorcinol bis(diphenyl phosphate), 1,3-phenylene bis(di(2,6-dimethylphenyl) phosphate), 4,4'-biphenyl bis(di(2,6-dimethylphenyl) phosphate), bisphenol A-bis(di(2,6-dimethylphenyl) phosphate), bisphenol A-bis(diphenyl phosphate), 1,3-phenylene bis(diphenyl phosphate), etc.; the monosubstituted phosphonic acid diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl) phenylphosphonate, etc.; the disubstituted hypophosphonates include Diphenylphosphine ester, methyl diphenylphosphine ester, etc.; the metal salts of the disubstituted phosphine acids include metal salts of dialkylphosphine acids, metal salts of diallylphosphine acids, metal salts of divinylphosphine acids, metal salts of diarylphosphine acids, metal salts of diarylphosphine acids, etc.; the organic nitrogen-phosphorus compounds include phosphazene compounds, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, etc.; the cyclic organophosphorus compounds include 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.

[0050] Flame retardants can be used alone or in combination of at least two.

[0051] On the other hand, the present invention provides a resin adhesive obtained by dissolving or dispersing the resin composition described above in a solvent.

[0052] In this invention, the amount of solvent is not limited, as long as the components in the resin composition can be dissolved and dispersed and do not separate during mixing.

[0053] In this invention, the type of solvent is not particularly limited, including any one or a combination of at least two of alcohol solvents, ether solvents, aromatic hydrocarbon solvents, ester solvents, ketone solvents or nitrogen-containing solvents, preferably any one or a combination of at least two of acetone, butanone, methyl ethyl ketone, cyclohexanone, toluene or xylene.

[0054] On the other hand, the present invention provides a prepreg comprising a substrate and a resin composition as described above, which is attached to the substrate by impregnation and drying.

[0055] The present invention does not have any particular limitation on the substrate. Preferably, the substrate includes any one of glass fiber cloth, organic fiber cloth or glass fiber paper.

[0056] The fiberglass cloth includes Q-fiberglass cloth, E-fiberglass cloth, D-fiberglass cloth, L-fiberglass cloth, M-fiberglass cloth, S-fiberglass cloth, T-fiberglass cloth, or NE-fiberglass cloth, etc.

[0057] The organic fiber cloth includes polyimide fiber cloth, polyamide fiber cloth, polyester fiber cloth, polyphenylene ether fiber cloth, or liquid crystal polymer fiber cloth, etc.

[0058] For example, the prepreg is prepared by impregnating a substrate with the resin solution of the resin composition and then drying it to obtain the prepreg.

[0059] Preferably, the solvent in the resin solution is not particularly limited, but more preferably any one or a combination of at least two of acetone, butanone, methyl ethyl ketone, cyclohexanone, toluene or xylene.

[0060] Preferably, the drying temperature is 100-180℃, such as 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃ or 175℃.

[0061] Preferably, the drying time is 1 to 10 minutes, such as 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, or 9 minutes.

[0062] On the other hand, the present invention provides a metal foil laminate, the metal foil laminate comprising at least one prepreg as described above, and metal foil disposed on one or both sides of the prepreg.

[0063] The metal foil may be copper foil, aluminum foil, nickel foil, or alloy foil; preferably, the metal foil is copper foil.

[0064] Preferably, the prepreg in the metal foil laminate consists of 1 to 20 sheets, for example, 1, 3, 5, 7, 9, 10, 11, 13, 15, 17, or 19 sheets.

[0065] For example, the method for preparing the metal-clad laminate is as follows: pressing metal foil onto one or both sides of a prepreg and curing to obtain the metal-clad laminate; or, stacking at least two prepregs and then pressing metal foil onto one or both sides of the stacked prepregs and curing to obtain the metal-clad laminate.

[0066] Preferably, the curing is carried out in a press.

[0067] Preferably, the curing temperature is 200-250℃, such as 205℃, 210℃, 212℃, 215℃, 218℃, 220℃, 223℃, 225℃, 228℃, 230℃, 235℃, 240℃ or 245℃.

[0068] Preferably, the curing pressure is 10–60 kg / cm². 2 For example, 15kg / cm 2 20kg / cm 2 25kg / cm 2 30kg / cm 2 35kg / cm 2 40kg / cm 2 45kg / cm 2 50kg / cm 2 Or 55kg / cm 2 wait.

[0069] Preferably, the curing time is 30 to 180 minutes, such as 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, 120 minutes, 130 minutes, 140 minutes, 150 minutes, 160 minutes, 170 minutes, or 175 minutes.

[0070] On the other hand, the present invention provides a printed circuit board comprising at least one prepreg as described above or a metal foil laminate as described above.

[0071] Compared with the prior art, the present invention has the following beneficial effects:

[0072] This invention utilizes maleimide compounds containing indane structures with an acid value below 5.0 mg KOH / g, enabling the cured resin composition to withstand extreme environmental thermo-oxidative treatments with a ΔD value lower than that of the original. fThe minimal variation results in prepregs and metal foil laminates with excellent dielectric properties and the ability to withstand extreme environments, making them particularly suitable for high-speed packaging. Detailed Implementation

[0073] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention.

[0074] The experimental materials involved in the embodiments and comparative examples of this invention include:

[0075] 1) Component (A):

[0076] BMI A1, a maleimide compound containing an indane structure, NE-X-series-1, provided by DIC Corporation, with an acid value of 1.3 mg KOH / g;

[0077] BMI A2, a maleimide compound containing an indane structure, NE-X-series-2, provided by DIC Corporation, with an acid value of 2.5 mg KOH / g;

[0078] BMI A3, a maleimide compound containing an indane structure, NE-X-series-3, supplied by DIC Corporation, with an acid value of 4.1 mg KOH / g;

[0079] BMI C1, a maleimide compound containing an indane structure, was prepared according to Synthesis Example 2 of CN113727970A, and its acid value was measured to be 6.7 mg KOH / g;

[0080] 2) Component (B): Thermosetting resin

[0081] OPE-2st 2200, a polyphenylene ether with vinyl benzyl groups at the end, Mitsubishi Gas Chemical Co., Ltd.

[0082] BA-3000S, cyanate ester resin, Lonza Corporation;

[0083] BVPE, 1,2-bis(p-vinylphenyl)ethane, Jiangsu Linchuan Chemical Co., Ltd.

[0084] 3) Component (C): Polyolefin resin

[0085] Tuftec H1051, hydrogenated styrene-butadiene copolymer, Asahi Kasei Chemicals Co., Ltd.;

[0086] 4) Component (D): Curing accelerator

[0087] Triginox 311, 3,3,5,7,7-pentamethyl-1,2,4-trioxane, AkzoNobel, Inc., USA;

[0088] 2E4MI, 2-ethyl-4-methylimidazole, Shikoku Chemical Co., Ltd., Japan;

[0089] 5) Component (E): Inorganic filler

[0090] SC2300-SVJ, spherical silica surface-treated with vinyl silane coupling agent, median particle size D 50 0.5μm, Admatechs Co., Ltd., Japan;

[0091] 6) Component (F): Coupling agent

[0092] KBM-573, N-phenyl-3-aminopropyltrimethoxysilane, Shin-Etsu Corporation, Japan.

[0093] Example 1

[0094] This embodiment provides a resin composition comprising, by weight, the following components: (A) 60 parts BMI A1, (B) 40 parts polyphenylene ether OPE-2st 2200 containing unsaturated bonds, 1 part curing accelerator Triginox 311, 2 parts coupling agent KBM-573, and 150 parts inorganic filler SC2300-SVJ.

[0095] This embodiment also provides a metal foil-coated laminate, the specific preparation method of which is as follows:

[0096] (1) Mix the resin composition provided in this embodiment, toluene and methyl ethyl ketone, dissolve and disperse them evenly to obtain a resin solution with a solid content of 60%;

[0097] (2) Impregnate the glass fiber cloth (Low Dk3313 manufactured by Hubel, Taiwan, China) with the resin solution obtained in step (1), and heat and dry it in a forced-air oven at 130°C for 4 minutes to transform the resin composition in the varnish state into a semi-cured resin composition to obtain a prepreg with a thickness controlled at 0.10 mm.

[0098] (3) Stack the two prepregs obtained in step (2) together, and press an electrolytic copper foil with a thickness of 12 μm onto the top and bottom sides of the stack. 220℃, 45 kg / cm 2 After curing for 2 hours, a copper-clad laminate with a core board thickness of 0.20 mm is obtained.

[0099] After etching the copper foil of the above copper-clad laminate, a laminate with a thickness of 0.20 mm is obtained.

[0100] Examples 2-5, Comparative Example 1

[0101] A resin composition, the components of which and their contents are shown in Table 1; the unit of measurement for each component in Table 1 is "parts".

[0102] Table 1

[0103]

[0104]

[0105] The above resin composition was used to prepare a metal foil-coated laminate according to the method in Example 1. The performance of the laminate was tested as follows:

[0106] (1) Dielectric loss tangent (D f A laminate measuring 100 mm in length, 100 mm in width, and 0.20 mm in thickness was used as a sample. After ultrasonic cleaning to remove surface impurities in deionized water, the sample was dried in a 105°C oven for 1 hour and then cooled to room temperature in a desiccator. The dielectric loss tangent (Di) at a frequency of 10 GHz was measured using a cavity resonator. f );

[0107] Dielectric loss tangent (D) after thermo-oxidative treatment f ): Take the loss tangent of the above-mentioned test medium (D) f The sample was baked at 130℃ for 168 hours (thermal-oxidative treatment condition 1), and the dielectric loss tangent (D) at a frequency of 10 GHz was measured using a cavity resonator. f );

[0108] Dielectric loss tangent (Df) after heat and oxidation treatment: Take the sample with the above-mentioned dielectric loss tangent (Df) test, bake at 150℃ for 720 hours (heat and oxidation treatment condition 2), and then use a cavity resonator device to measure the dielectric loss tangent (Df) at a frequency of 10GHz.

[0109] △D f : Dielectric loss tangent after thermo-oxidative treatment (D) f - Dielectric loss tangent before thermo-oxidative treatment (D) f ).

[0110] The performance test results of the laminates in Examples 2-5 and Comparative Example 1 are shown in Table 2:

[0111] Table 2

[0112]

[0113]

[0114] In Table 2 above, regarding △D fThe change in value is denoted as follows: ≤0.001 is denoted as “A”, greater than 0.001 and less than 0.002 is denoted as “B”, greater than 0.002 and less than 0.003 is denoted as “C”, and greater than 0.003 is denoted as “D”.

[0115] According to the performance test data in Table 2, the resin compositions prepared in Examples 1-5 of this application by selecting maleimide compounds (A) containing indane structures with an acid value below 5.0 mg KOH / g and thermosetting resins (B) exhibit good performance even after being subjected to extreme thermal and oxygen treatment. f The changes were small; among them, after baking at 130℃ for 168 hours (thermal-oxygen treatment condition 1), △D f The change in ΔD is ≤0.001; after baking at 150℃ for 720 hours (thermal-oxygen treatment condition 2), ΔD f The change is at most greater than 0.001 and less than 0.002, demonstrating excellent dielectric properties and the ability to withstand extreme environments.

[0116] Compared to Example 1, the maleimide compound containing the indane structure in Comparative Example 1 had a higher acid value, and after baking at 130°C for 168 hours (thermal-oxidative treatment condition 1), ΔD f The change was greater than 0.002 and less than 0.003; after baking at 150℃ for 720 hours (thermal-oxygen treatment condition 2), ΔD f The change is greater than 0.003, making it difficult to maintain its low dielectric properties under harsh thermal environments.

[0117] The applicant declares that the present invention is illustrated by the above embodiments to demonstrate the resin composition and prepreg containing the same, and the metal foil laminate thereof. However, the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the products of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A resin composition, characterized by comprising: The resin composition includes the following components: a maleimide compound (A) having an indane structure in the molecule and a thermosetting resin (B); The maleimide compound (A) having an indane structure in the molecule has an acid value of 5.0 mgKOH / g or less.

2. The resin composition according to claim 1, characterized by The maleimide compound (A) having an indane structure in the molecule has a structure including the following formula (I): In formula (I), Rb is independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group, r is an integer selected from 0 to 3, and in the case where r is 2 to 3, a plurality of Rb can be the same or different from each other.

3. The resin composition according to claim 1 or 2, characterized by The maleimide compound (A) having an indane structure in the molecule is a maleimide having the following formula (I-1): In formula (I-1), Ra is independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group, Rb is independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group, or a mercapto group, q is an integer selected from 0 to 4, r is an integer selected from 0 to 3, and n is 0.95 to 10, and in the case where q is 2 to 4, a plurality of Ra can be the same or different from each other, and in the case where r is 2 to 3, a plurality of Rb can be the same or different from each other.

4. The resin composition according to any one of claims 1 to 3, characterized by The thermosetting resin (B) includes one or a combination of at least two of an epoxy resin, a cyanate ester resin, a hydrocarbon resin, a polyphenylene ether resin, or another maleimide compound different from (A); Preferably, the polyphenylene ether resin is a polyphenylene ether having an unsaturated group at a terminal end. Preferably, the unsaturated group includes any one or a combination of at least two of a vinylbenzyl group, a vinylphenyl group, or an acrylate group.

5. The resin composition according to any one of claims 1 to 4, characterized in that, The resin composition includes the following components: a maleimide compound (A) having an indane structure in the molecule and a thermosetting resin (B); 6. The resin composition according to any one of claims 1 to 5, characterized in that, Preferably, the resin composition includes the polyphenylene ether resin (C) in an amount of 5 to 30 parts by weight. Preferably, the resin composition includes the curing accelerator (D) in an amount of 0.01 to 5 parts by weight. ​ Preferably, the resin composition contains inorganic filler (E) in an amount of 5 to 250 parts by weight.

7. A resin glue solution, characterized by, The resin sizing solution is obtained by dissolving or dispersing the resin composition according to any one of claims 1 to 6 in a solvent.

8. A prepreg, characterized by, The prepreg comprises a substrate and the resin composition according to any one of claims 1 to 6 attached to the substrate by impregnation and drying.

9. A metal-clad laminate sheet comprising at least one prepreg according to claim 8 and a metal foil provided on one or both sides of the prepreg.

10. A printed circuit board comprising at least one prepreg according to claim 8 or a metal-clad laminate sheet according to claim 9.

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