A resin composition, a prepreg, a metal-clad laminate, and applications thereof

Abstract

This invention provides a resin composition, a prepreg, a metal foil-coated laminate, and their applications. The resin composition comprises unsaturated polyphenylene ether and an acenaphthene-modified polymer, wherein the mass ratio of the acenaphthene-modified polymer to the unsaturated polyphenylene ether is 1:(0.2-5). The monomers of the acenaphthene-modified polymer include a combination of acenaphthene and polyfunctional vinyl aromatic compounds, and the molar percentage of acenaphthene in the monomers is 10-90%. Through the design of the acenaphthene-modified polymer and its compounding and synergistic effect with the unsaturated polyphenylene ether, the resin composition and the prepreg and metal foil-coated laminate containing it exhibit high glass transition temperatures, excellent performance in heat resistance, dielectric properties, dielectric loss stability, damp heat resistance, and dimensional stability, and good filling performance, greatly improving the internal consistency of the substrate and meeting the performance requirements of high transmission rate substrates.

Description

Technical Field

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

[0002] With the rapid development of electronic technology, information processing in electronic products such as mobile communications, servers, and mainframe computers is constantly evolving towards "high-frequency signal transmission and high-speed digitization." To meet the requirements of high-speed information processing, low-dielectric materials have become the main development direction for high-transmission-rate substrates. The main performance indicators of low-dielectric materials are low dielectric loss and low dielectric constant. Simultaneously, the substrate is also required to have a high glass transition temperature, low thermal expansion coefficient, and good flame retardancy. With the increasing precision of substrate processing and the improvement of circuit board performance, good internal consistency of the substrate material is also required. This consistency includes no resin aggregation after substrate material lamination, good fluidity of the substrate material during the filling process without resin aggregation, and uniform dispersion of fillers.

[0003] To meet the demands of high-speed applications in electronic materials, the industry is researching resin materials with good dielectric properties. For example, CN117106265A discloses a resin composition comprising 5-70% by mass of a vinyl aromatic copolymer and 30-95% by mass of polyphenylene ether. The vinyl aromatic copolymer has a molar ratio of structural units derived from divinyl aromatic compounds of 5-45 mol% and a number average molecular weight of 2000-8000. The polyphenylene ether has a weight average molecular weight of 10000-50000 and a hydroxyl number of 20-900 μmol / g. This resin composition exhibits a low dielectric loss tangent and excellent dielectric properties. CN118019799A discloses a resin composition comprising a polymer A and a compound B in a mass ratio of 1:(0.025-0.7): the structural unit of polymer A includes an aromatic vinyl compound, and the compound B is an organic group with a molecular weight of less than 1000 and containing one carbon-carbon unsaturated bond; the resin composition also includes other thermosetting compounds C selected from at least one of maleimide compounds, polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds, cyanate compounds, epoxy compounds, phenolic compounds, alkenyl-substituted nadicimide compounds, oxetane resins, and benzoxazine compounds, thereby enabling the resin composition to maintain excellent dielectric properties while having good moisture absorption and heat resistance. CN112368311A discloses a resin composition comprising compound A and acenaphthene compound B in a mass ratio of 50:50-95:5, wherein compound A comprises modified polyphenylene ether containing vinyl aryl groups and / or modified olefin polymer containing vinyl aryl groups; the resin composition has low dielectric constant and dielectric loss, good heat resistance, and maintains good dielectric properties even after absorbing water.

[0004] Although the industry has a certain research foundation in low-dielectric materials, existing substrates still struggle to simultaneously meet the performance requirements in multiple aspects, including dielectric properties, heat resistance, damp heat resistance, and dimensional stability. In particular, poor filling properties of the materials lead to significant resin and filler aggregation within the substrate, resulting in poor internal consistency and severely impacting the substrate's processability and performance in subsequent circuit board applications. Therefore, developing a substrate material with excellent dielectric properties, heat resistance, damp heat resistance, dimensional stability, and filling properties is a pressing issue that needs to be addressed in this field. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a resin composition, a prepreg, a metal foil-coated laminate, and their applications. Through the design of acenaphthene-modified polymers and their mutual compounding with unsaturated polyphenylene ether, the resin composition and the prepreg and metal foil-coated laminate containing it exhibit high glass transition temperature, low dielectric loss factor, small coefficient of thermal expansion, and minimal change in dielectric loss factor after wet treatment. These components possess excellent heat resistance, dielectric properties, resistance to damp heat, dielectric loss stability, and filler properties, significantly improving the internal consistency of the substrate and fully meeting the performance requirements of high-transmission-rate substrates.

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

[0007] In a first aspect, the present invention provides a resin composition comprising unsaturated polyphenylene ether and an acenaphthene-modified polymer, wherein the mass ratio of the acenaphthene-modified polymer to the unsaturated polyphenylene ether is 1:(0.2-5); the polymerizing monomer of the acenaphthene-modified polymer comprises a combination of acenaphthene and a polyfunctional vinyl aromatic compound, and the molar percentage of acenaphthene in the polymerizing monomer is 10-90%.

[0008] In this invention, the acenaphthene-modified polymer is a copolymer of acenaphthene and a polyfunctional vinyl aromatic compound, wherein the molar percentage of acenaphthene is 10-90 mol%. Through the design of the acenaphthene-modified polymer and its compounding and synergistic effect with unsaturated polyphenylene ether containing C=C double bonds, the resin composition and the prepreg and metal foil laminate containing it have high glass transition temperature and low dielectric loss factor, exhibiting excellent performance in heat resistance and dielectric properties. At the same time, it has low water absorption, good resistance to humid heat, small coefficient of thermal expansion, and small change in dielectric loss factor after wet treatment. It also exhibits excellent performance in heat resistance, dielectric properties, dielectric loss stability, humid heat resistance, and dimensional stability. Moreover, it has good filling performance, which greatly improves the internal consistency of the substrate and fully meets the performance requirements of high transmission rate substrates.

[0009] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0010] The acenaphthene-modified polymer of the present invention is a copolymer of acenaphthene and a polyfunctional vinyl aromatic compound. In the polymer monomer, the molar percentage of acenaphthene is 10-90%, for example, it can be 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0011] In this invention, the mass ratio of the acenaphthene-modified polymer to the unsaturated polyphenylene ether is 1:(0.2-5), for example, it can be 1:0.25, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5, 1:2.8, 1:3, 1:3.5, 1:4, 1:4.5, etc., preferably 1:(0.2-2).

[0012] In this invention, the acenaphthene-modified polymer and unsaturated polyphenylene ether are compounded at a mass ratio of 1:(0.2-5) (i.e., 5:1-1:5), which synergistically improves the overall performance of the material. This results in the resin composition, its cured product, prepreg, laminate, and metal foil-coated laminate possessing high glass transition temperature, excellent heat resistance, dielectric properties, dielectric loss stability, dimensional stability, resistance to damp heat, and filler properties. If the amount of acenaphthene-modified polymer is too low, the dielectric loss factor of the resin composition and the sheet containing it will increase, and the dielectric loss factor will rise significantly after wet treatment, leading to an increase in the coefficient of thermal expansion. If the amount of acenaphthene-modified polymer is too high, the filler properties of the resin composition, the prepreg containing it, and the metal foil-coated laminate will severely deteriorate.

[0013] Preferably, the unsaturated polyphenylene ether is a polyphenylene ether with C=C unsaturated bonds at the end groups, and more preferably includes polyphenylene ethers with any one or at least two of vinyl benzyl, vinyl phenyl, acrylate, and methacrylate end groups.

[0014] Preferably, the unsaturated polyphenylene ether comprises any one or a combination of at least two of the following: methacrylate-terminated polyphenylene ether, acrylate-terminated polyphenylene ether, vinyl benzyl-terminated polyphenylene ether, and vinyl phenyl-terminated polyphenylene ether.

[0015] In this invention, the polyfunctional vinyl aromatic compound refers to a compound whose molecular structure contains at least two alkenyl groups and at least one aromatic group, preferably a divinyl aromatic compound.

[0016] Preferably, the polyfunctional vinyl aromatic compound includes any one or a combination of at least two of divinylbenzene, divinylnaphthalene, divinylbiphenyl, and diisopropylbenzene.

[0017] In this invention, the polyfunctional vinyl aromatic compounds listed above include all their isomers.

[0018] Exemplarily, the divinylbenzene includes any one or a combination of at least two of o-divinylbenzene, m-divinylbenzene, and p-divinylbenzene. The divinylnaphthalene includes any one or a combination of at least two of 1,3-divinylnaphthalene, 1,4-divinylnaphthalene, 1,5-divinylnaphthalene, 1,8-divinylnaphthalene, 2,3-divinylnaphthalene, 2,6-divinylnaphthalene, and 2,7-divinylnaphthalene. The divinylbiphenyl includes any one or a combination of at least two of 4,4'-divinylbiphenyl, 4,3'-divinylbiphenyl, 4,2'-divinylbiphenyl, 3,2'-divinylbiphenyl, 3,3'-divinylbiphenyl, 2,2'-divinylbiphenyl, and 2,4-divinylbiphenyl. The diisopropenylbenzene includes any one or a combination of at least two of 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, and 1,4-diisopropenylbenzene.

[0019] Preferably, the polymer monomers of the acenaphthene-modified polymer further include a third monomer, which includes any one or a combination of at least two of monovinyl aromatic compounds, aliphatic olefins, and cyclic olefins.

[0020] Preferably, the monovinyl aromatic compound includes any one or a combination of at least two of styrene, vinylnaphthalene, ethylvinylbenzene, vinyltoluene, fluorene containing one vinyl group, and biphenyl containing one vinyl group.

[0021] Preferably, the aliphatic olefin includes butadiene and / or isoprene.

[0022] Preferably, the cyclic olefin includes any one or a combination of at least two of cyclopentadiene, maleic anhydride diene, norbornene, and dicyclopentadiene.

[0023] Preferably, the molar percentage of the third monomer in the polymeric monomer is ≤50%, for example, it can be 0, 0.1%, 0.5%, 1%, 2%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 48%, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0024] Preferably, the weight-average molecular weight of the acenaphthene-modified polymer is 5,000-300,000, for example, it can be 8,000, 10,000, 20,000, 30,000, 40,000, 50,000, 70,000, 80,000, 100,000, 120,000, 150,000, 180,000, 200,000, 220,000, 250,000, or 280,000, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0025] In this invention, the relevant data on molecular weight (including weight-average molecular weight, number-average molecular weight, etc.) can be obtained by referring to the records in standard GB / T21863-2008, based on polystyrene calibration, and tested by gel permeation chromatography (GPC).

[0026] Preferably, the resin composition further includes an allyl compound.

[0027] Preferably, the allyl compound includes any one or a combination of at least two of the following: 1,3,5-triallyl cyanurate, trimethylallyl isocyanurate, triallyl isocyanurate, 1,2,4-triallyl benzoic acid, and compounds with the structure shown in Formula I.

[0028]

[0029] Among them, X1, X2, and X3 are each independently selected from any one of C2-C15 alkenyl or C8-C21 alkenylphenyl.

[0030] In this invention, the C2-C15 alkenyl group can be a straight-chain or branched alkenyl group of C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, or C19, etc., containing at least one C=C, and exemplary including but not limited to: vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, butadienyl, pentadienyl, etc.

[0031] The C8-C21 alkenylphenyl group can be an alkenylphenyl group of C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, or C20, etc. It is a monovalent group obtained by attaching an alkenyl group to a phenyl group. Specific examples of alkenyl groups include, but are not limited to: vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, butadienyl, pentadienyl, etc.

[0032] Preferably, X1, X2, and X3 are each independently selected from any one of C2-C6 alkenyl, vinylphenyl, and allylphenyl.

[0033] Preferably, based on 100 parts by total mass of organic resin components in the resin composition, the mass of the allyl compound is ≤30 parts, for example, it can be 0, 1, 2, 5, 8, 10, 12, 15, 18, 20, 22, 25 or 28 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but 5-30 parts is further preferred.

[0034] In this invention, the "total mass of organic resin components" in the resin composition represents the total mass of the acenaphthene-modified polymer, unsaturated polyphenylene ether, optionally allyl compound (if any), optionally other components containing C=C unsaturated bonds (if any), and optionally thermoplastic polymer (if any); it should be noted that the mass of the organic initiator is not included in the total mass of the organic resin components. The same descriptions used below have the same meaning.

[0035] As a preferred embodiment of the present invention, the resin composition further includes an allyl compound, which, when compounded with unsaturated polyphenylene ether and acenaphthene-modified polymers, can further reduce the coefficient of thermal expansion of the resin composition and the sheet, and improve dimensional stability. Simultaneously, by designing the amount of the allyl compound, the resin composition and the sheet can achieve excellent comprehensive performance in terms of dimensional stability, resistance to damp heat, dielectric properties, dielectric loss stability, and filling properties. However, if the amount of the allyl compound is excessive, the dielectric properties and dielectric loss stability of the material will decrease.

[0036] Preferably, the resin composition further includes other components containing C=C unsaturated bonds.

[0037] The other components containing C=C unsaturated bonds refer to components that contain C=C unsaturated bonds other than unsaturated polyphenylene ethers and allyl compounds, including small molecule compounds and / or resins (polymers), exemplary including but not limited to: small molecule compounds and / or resins (polymers) containing any one or at least two combinations of vinyl, vinylphenyl, vinylbenzyl, allyl, acrylate, methacrylate, and isopropyl groups.

[0038] Preferably, the other components containing C=C unsaturated bonds include any one or a combination of at least two of the following: benzocyclobutene compounds, polybutadiene, styrene-butadiene copolymers, styrene-butadiene-styrene triblock copolymers, polyfunctional vinyl aromatic polymers, polyisoprene, styrene-isoprene copolymers, and polyfunctional vinyl compounds.

[0039] Preferably, the benzocyclobutene compounds include polymers containing benzocyclobutene groups.

[0040] In this invention, the polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene triblock copolymer, polyisoprene, and styrene-isoprene copolymer all contain crosslinkable active groups C=C, and can be 1,2-vinyl groups based on butadiene monomers. Based on the alkenyl side chain of isoprene monomer ( and / or ).

[0041] In this invention, the styrene-butadiene copolymer can be a styrene-butadiene random copolymer and / or a styrene-butadiene block copolymer. The styrene-isoprene copolymer can be a styrene-isoprene random copolymer and / or a styrene-isoprene block copolymer.

[0042] Preferably, the monomers of the polyfunctional vinyl aromatic polymer comprise a combination of divinyl aromatic compounds and monovinyl aromatic compounds.

[0043] Preferably, the divinyl aromatic compound includes any one or a combination of at least two of divinylbenzene, divinylbiphenyl, divinylnaphthalene, diisopropenylbenzene, diisopropenylnaphthalene, and diisopropenylbiphenyl; the divinyl aromatic compounds listed above include all their isomers.

[0044] Preferably, the monovinyl aromatic compound includes styrene, and also includes other monovinyl aromatic compounds besides styrene, including, but not limited to, any one or a combination of at least two of ethylvinylbenzene, methylvinylbenzene, and vinylnaphthalene; the monovinyl aromatic compounds listed above include all their isomers.

[0045] In this invention, the multifunctional vinyl aromatic polymer can be purchased from the market, for example, it can be Nippon Steel's ODV.

[0046] Preferably, the polyfunctional vinyl compound includes any one or a combination of at least two of divinylbenzene (DVB), 1,2-bis(p-vinylphenyl)ethane (BVPE), and polyfunctional (meth)acrylates.

[0047] Preferably, based on a total mass of 100 parts of organic resin components in the resin composition, the mass of other components containing C=C unsaturated bonds is ≤50 parts, for example, 0, 5, 8, 10, 15, 20, 25, 30, 35, 40, or 45 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0048] Preferably, the resin composition further includes a thermoplastic polymer.

[0049] Preferably, the thermoplastic polymer includes any one or a combination of at least two of styrene-based polymers, hydrogenated styrene-based polymers, polyolefin resins, acrylonitrile-butadiene copolymers, and acrylonitrile-butadiene-styrene copolymers, more preferably hydrogenated styrene-based polymers.

[0050] Preferably, the styrene-based polymer is a copolymer comprising olefin structural units and styrene-based structural units. The olefin structural units are derived from olefin monomers, such as structural units derived from butadiene or isoprene; the styrene-based 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 olefin and styrene-based structural units, the styrene-based polymer may also contain structural units other than olefin and styrene-based structural units, such as structural units containing epoxy groups, amino groups, or maleic anhydride groups.

[0051] It should be noted that the styrene-based polymer can be a random copolymer and / or a block copolymer.

[0052] Preferably, the hydrogenated styrene polymer is obtained by partially or completely hydrogenating the olefin structural units in the aforementioned styrene polymers, and includes, but is not limited to, any one or a combination of at least two of the following: hydrogenated styrene-butadiene copolymer, hydrogenated styrene-butadiene-styrene triblock copolymer (SEBS), and hydrogenated styrene-isoprene copolymer.

[0053] Preferably, based on a total mass of 100 parts of organic resin components in the resin composition, the mass of the thermoplastic polymer is ≤30 parts, for example, it can be 0, 1, 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, or 28 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0054] Preferably, the resin composition further includes an initiator.

[0055] Preferably, the initiator includes any one or a combination of at least two of carbon-based initiators and peroxide radical initiators.

[0056] Preferably, the carbon-based initiator includes any one or a combination of at least two of 2,3-dimethyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-bis(4-methylphenyl)butane, 2,3-dimethyl-2,3-bis(4-isopropylphenyl)butane, and 3,4-dimethyl-3,4-diphenylhexane.

[0057] Preferably, the peroxide radical initiator includes any one or a combination of at least two of the following: dicumyl peroxide, 1,3-bis(tert-butylperoxide-isopropyl)benzene, 1,4-bis(tert-butylperoxide-isopropyl)benzene, 2,5-di-tert-butylperoxide-2,5-dimethylhexane, 2,5-di-tert-butylperoxide-2,5-dimethylhexyne-3, di-tert-butylperoxide, and tert-butylperoxide-isopropylbenzene.

[0058] Preferably, based on 100 parts by total mass of organic resin components in the resin composition, the mass of the initiator is 0.1-5 parts, for example, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts, or 4.8 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0059] Preferably, the resin composition further includes fillers and / or flame retardants.

[0060] Preferably, the filler comprises any one or a combination of at least two of the following: silica, hollow glass microspheres, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, and mica; more preferably, spherical silica.

[0061] Preferably, the silicon dioxide can be any one or a combination of at least two of molten silicon dioxide, crystalline silicon dioxide, spherical silicon dioxide, and hollow silicon dioxide, and more preferably spherical silicon dioxide.

[0062] This invention does not impose a particular limitation on the particle size of the filler; preferably, the median particle size (D) of the filler is... 50The value can be 0.01-50μm, for example, 0.05μm, 0.1μm, 0.5μm, 1μm, 5μm, 10μm, 15μm, 20μm, 25μm, 30μm, 35μm, 40μm, 45μm, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific values ​​included in the range, but 0.01-20μm is further preferred.

[0063] For example, the particle size of the filler was obtained using an MS3000 Malvern laser particle size analyzer.

[0064] Preferably, based on a total mass of 100 parts of the resin composition, the mass of the filler is ≤70 parts, for example, it can be 0, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 or 65 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but 20-70 parts is further preferred.

[0065] Preferably, the flame retardant includes a phosphorus-containing flame retardant and / or a bromine-containing flame retardant.

[0066] Preferably, the phosphorus-containing flame retardant includes any one or a combination of at least two of DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) flame retardants, phosphorus oxides, and organic phosphonates.

[0067] Preferably, the DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) flame retardant includes any one or a combination of at least two of bisDOPO and bisDOPO derivative structures. The phosphorus oxide flame retardant includes, but is not limited to, one or a combination of at least two of diphenylphosphine oxide and its derivatives.

[0068] Preferably, the brominated flame retardant includes any one or a combination of at least two of the following: decabromodiphenyl ethane, 1,2-bis(tetrabromophthalimide) (ethane ethylene bis(tetrabromoimide)), and brominated polystyrene.

[0069] Preferably, based on 100 parts of total organic resin components in the resin composition, the flame retardant has a mass of ≤30 parts, for example, 0, 1, 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, or 28 parts, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but 5-30 parts is further preferred.

[0070] Preferably, the resin composition further includes other additives that those skilled in the art are motivated to add, such as any one or a combination of at least two of toughening agents, viscosity modifiers, and coupling agents.

[0071] Solvents may also be added to the above-mentioned resin composition. The amount of solvent added is selected by those skilled in the art based on experience and process requirements, so that the resin composition reaches a suitable viscosity for use, facilitating impregnation, coating, etc. During subsequent drying, semi-curing, or complete curing stages, the solvent in the resin composition will partially or completely evaporate.

[0072] The solvent used in this invention is not particularly limited, and generally can be ketones such as acetone, butanone, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol, or butanol; ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, or butyl carbitol; and nitrogen-containing solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone. The solvent can be used alone or in mixtures of two or more. Preferably, ketones such as acetone, butanone, and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene are used.

[0073] The resin composition provided by the present invention is prepared by the following method, the preparation method comprising: mixing and dispersing the components in the resin composition evenly to obtain the resin composition.

[0074] In a second aspect, the present invention provides a resin film, the material of which comprises the resin composition as described in the first aspect.

[0075] Preferably, the resin film is obtained by coating the resin composition onto a release material and then drying and / or semi-curing it.

[0076] Thirdly, the present invention provides a resin-coated copper foil, the resin-coated copper foil comprising a copper foil layer and a resin layer, wherein the material of the resin layer comprises the resin composition as described in the first aspect.

[0077] Preferably, the resin-coated copper foil is obtained by coating the resin composition onto a copper foil and then drying and / or semi-curing it.

[0078] Fourthly, the present invention provides a prepreg comprising a reinforcing material and a resin composition as described in the first aspect attached to the reinforcing material.

[0079] Preferably, the resin composition is attached to the reinforcing material after impregnation and drying.

[0080] Preferably, the raw materials of the reinforcing material include any one or at least two combinations of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fibers; for example, glass fiber cloth, quartz glass fiber blended cloth, non-woven fabric, quartz cloth, fiber paper, wood pulp paper, etc.

[0081] For example, the method for preparing the prepreg is as follows: impregnate the reinforcing material with the resin solution of the resin composition, and then dry it to obtain the prepreg.

[0082] Preferably, the drying temperature is 100-180℃, for example, it can be 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃ or 175℃, as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0083] Preferably, the drying time is 1-30 min, for example, it can be 2 min, 5 min, 8 min, 10 min, 15 min, 20 min or 25 min, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0084] On the other hand, the present invention provides a laminate comprising at least one prepreg as described in the fourth aspect.

[0085] Fifthly, the present invention provides a metal foil laminate, the metal foil laminate comprising at least one of the following: a resin film as described in the second aspect, a resin-coated copper foil as described in the third aspect, and a prepreg as described in the fourth aspect.

[0086] Preferably, the metal foil in the metal foil-coated laminate includes any one or a combination of at least two of copper foil, aluminum foil, nickel foil, and alloy foil, with copper foil being more preferred.

[0087] Preferably, the metal foil is copper foil, and the metal foil laminate is copper clad laminate.

[0088] Preferably, the number of prepreg sheets in the metal foil laminate is 1-20, for example, 2, 3, 5, 7, 9, 10, 11, 13, 15, 17 or 19, and the specific point values ​​between the above point values ​​are not exhaustively listed in this invention due to space limitations and for the sake of brevity.

[0089] For example, the method for preparing the metal foil laminate includes: pressing a metal foil onto one or both sides of a prepreg, curing it, and obtaining the metal foil laminate; or, stacking at least two prepregs into a laminate, then pressing a metal foil onto one or both sides of the laminate, curing it, and obtaining the metal foil laminate.

[0090] Preferably, the curing is carried out in a press.

[0091] Preferably, the curing temperature is 170-280℃, such as 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃ or 270℃, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but 200-220℃ is further preferred.

[0092] Preferably, the curing pressure is 10-60 MPa, for example, it can be 15 MPa, 20 MPa, 25 MPa, 30 MPa, 35 MPa, 40 MPa, 45 MPa, 50 MPa or 55 MPa, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, and 20-50 MPa is further preferred.

[0093] Preferably, the curing time is 60-300 min, such as 80 min, 100 min, 120 min, 150 min, 180 min, 200 min, 220 min, 240 min, 260 min or 280 min, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, and 90-120 min is further preferred.

[0094] In a sixth aspect, the present invention provides a printed circuit board, the printed circuit board comprising at least one of the following: a resin film as described in the second aspect, a resin-coated copper foil as described in the third aspect, a prepreg as described in the fourth aspect, and a metal foil laminate as described in the fifth aspect.

[0095] Compared with the prior art, the present invention has the following beneficial effects:

[0096] (1) In the resin composition provided by the present invention, through the design of acenaphthene-modified polymer and its compounding and synergistic effect with unsaturated polyphenylene ether, the resin composition and the prepreg and metal foil laminate containing it have high glass transition temperature, low dielectric loss factor, low water absorption, good resistance to damp heat, small coefficient of thermal expansion, and small change in dielectric loss factor after wet treatment. It has excellent performance in terms of heat resistance, dielectric properties, dielectric loss stability, resistance to damp heat and dimensional stability. Moreover, it has good filling performance, which greatly improves the consistency inside the substrate and can meet the performance requirements of high transmission rate substrates.

[0097] (2) Through the design and optimization of the resin composition, the present invention enables the copper clad laminate to achieve Df≤0.0019 at 10GHz, glass transition temperature Tg of 203-235℃, ΔDf≤0.0004 after wet treatment, Y / CTE≤18ppm / ℃, water absorption rate≤0.08%, and pass the 288℃ immersion soldering test. It also achieves excellent comprehensive performance in terms of heat resistance, damp heat resistance, dimensional stability, dielectric properties, dielectric loss stability and filling performance. Detailed Implementation

[0098] 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 in any way.

[0099] In one specific embodiment, the acenaphthene-modified polymer can be prepared by copolymerization of acenaphthene, a polyfunctional vinyl aromatic compound, and optionally a third monomer.

[0100] In one specific embodiment, the copolymerization reaction is carried out in the presence of an initiator.

[0101] The preparation method of the acenaphthene-modified polymer is illustrated below with specific preparation examples, but the preparation method of the acenaphthene-modified polymer is not limited to these examples. Except for acenaphthene, all raw materials in the preparation examples are derived from Aladdin reagents.

[0102] Preparation Example 1

[0103] Acenaphthene-modified polymer A1 is a copolymer of acenaphthene and divinylbenzene, with acenaphthene comprising 60% of the total molar amount of acenaphthene and divinylbenzene (100% total molar amount). The specific preparation method is as follows:

[0104] 1.5 mol of acenaphthene, 200 mL of toluene, and 1 mol of divinylbenzene (a mixture of m- and p-divinylbenzene) were added to a 1 L reactor and stirred until homogeneous. Then, 0.015 mol of benzoyl peroxide (dissolved in 100 mL of toluene) was added at 80 °C with stirring. After reacting for 4 hours, the mixture was washed with methanol precipitation and dried to obtain acenaphthene-modified polymer A1. The Mw obtained by gel permeation chromatography (GPC) was 62500.

[0105] Preparation Example 2

[0106] Acenaphthene-modified polymer A2 is a copolymer of acenaphthene and divinylbiphenyl, with acenaphthene comprising 33.3% molar amount based on the total molar amount of acenaphthene and divinylbiphenyl being 100%. The preparation method is as follows:

[0107] 1 mol of acenaphthene, 200 mL of toluene, and 2 mol of divinylbiphenyl (4,4'-divinyl-1,1'-biphenyl) were added to a 1 L reactor and stirred until dissolved. Then, 0.02 mol of benzoyl peroxide (dissolved in 100 mL of toluene) was added at 80 °C with stirring. After reacting for 4 hours, the mixture was washed with methanol precipitation and dried to obtain acenaphthene-modified polymer A2. The Mw of the polymer was 85600 as determined by gel permeation chromatography (GPC).

[0108] Preparation Example 3

[0109] Acenaphthene-modified polymer A3 is a copolymer of acenaphthene, divinylbiphenyl, and ethylvinylbenzene, with acenaphthene comprising 24.2% of the total molar amount of the three (100%). The preparation method is as follows:

[0110] 0.8 mol of acenaphthene, 200 mL of toluene, 2 mol of divinylbiphenyl (4,4'-divinyl-1,1'-biphenyl) and 0.5 mol of ethylvinylbenzene (a mixture of 1-ethyl-4-vinylbenzene and 1-ethyl-3-vinylbenzene) were added to a 1 L reactor and stirred until homogeneous. Then, 0.02 mol of benzoyl peroxide (dissolved in 100 mL of toluene) was added at 80 °C with stirring. After reacting for 3 hours, the mixture was washed with methanol precipitation and dried to obtain acenaphthene-modified polymer A3, with a Mw of 26700 as determined by gel permeation chromatography (GPC).

[0111] The resin composition and its application described in this invention will be described in detail below with reference to several embodiments, but the resin composition and its application are not limited to these embodiments.

[0112] In the following examples, materials for which no preparation method is provided are commercially available chemicals, as detailed in the table below:

[0113]

[0114] Examples 1-9, Comparative Examples 1-4

[0115] A resin composition, the types and amounts of each component are shown in Table 1 and Table 2. The unit of amount of each component is "parts" (parts by mass), and "--" indicates that the component was not added.

[0116] A prepreg and a copper-clad laminate comprising the resin composition are prepared by the following method:

[0117] (1) Mix each component of the resin composition with toluene according to the formula amount and disperse it evenly to prepare a glue solution with a solid content of 65%; immerse 1035L2 glass fiber cloth in the glue solution to make the resin composition adhere to the glass fiber cloth, and then heat it at 130°C for 5 minutes to form a semi-cured state (B-Stage) to obtain a semi-cured sheet.

[0118] (2) Stack 8 prepreg sheets together, and stack 0.5 ounces of HVLP4 copper foil on the top and bottom sides. Press and cure for 120 minutes under vacuum conditions, temperature of 210°C and pressure of 30MPa to obtain the copper-clad laminate.

[0119] The copper-clad laminate was subjected to performance testing, and the specific method is as follows:

[0120] (1) Glass transition temperature Tg (DMA): The glass transition temperature Tg was tested using a dynamic mechanical tester (DMA) with a vibration frequency of 1 Hz. The temperature corresponding to the maximum tanδ peak when the temperature was increased from room temperature to 350℃ at a heating rate of 5℃ / min was set as Tg.

[0121] (2) Dielectric loss factor Df: After etching the copper foil, the substrate after etching the copper foil was baked in an oven at 105℃ for 2 hours using the SPDR method. After being taken out of the oven and cooled to room temperature, Df was tested at a frequency of 10GHz.

[0122] (3) ΔDf after wet treatment: Using the SPDR method, the substrate after etching copper foil was baked in an oven at 105℃ for 22 hours, then removed from the oven and cooled to room temperature. Df was then measured at 10GHz and recorded as Df1. Next, the substrate was placed in a constant temperature and humidity chamber at 23℃ and 50% humidity for 100 hours. After wiping off the surface moisture with test paper, Df was measured at 10GHz and recorded as Df2. ΔDf = Df2 - Df1. ΔDf ≤ 0.0002 is recorded as "Excellent", 0.0004 ≥ ΔDf > 0.0002 is recorded as "Good", 0.0006 ≥ ΔDf > 0.004 is recorded as "Medium", and ΔDf > 0.0006 is recorded as "Poor".

[0123] (4) Filling property: Press the prepared semi-cured sheet with a 0.20mm insulating plate with a 5×5mm square hole, and then use a scanning electron microscope (SEM) to observe the aggregation of resin in the hole. If there is no aggregation, it is marked as "OK".

[0124] (5) Coefficient of thermal expansion Y / CTE: The plate was made into an 8mm×8mm plate and placed in a thermomechanical analyzer (TMA). The temperature was increased to 260℃ at 5℃ / min. The CTE in the 50-150℃ range was tested and calculated.

[0125] (6) Water absorption rate: Tested according to the method of IPC-TM-650 2.6.2.1;

[0126] (7) Resistance to damp heat: After etching away the copper foil from the fabricated copper-clad laminate, a copper-free substrate of size 100×100mm was formed. The substrate was treated in an environment with 100% humidity at 2 atmospheres for 4 hours. Then, the substrate was immersed in a tin bath at 288℃ for 10 seconds, and this was repeated 10 times. The substrate was then observed for white spots or delamination. If no white spots or delamination occurred, the evaluation was "excellent". If white spots or delamination appeared in the tin bath at 288℃, but no white spots or delamination occurred after 10 seconds in the tin bath at 260℃ and repeated 10 times, the evaluation was "good". If white spots or delamination appeared in the tin bath at 260℃, the evaluation was "poor".

[0127] The performance test data are shown in Tables 1 and 2.

[0128] Table 1

[0129]

[0130]

[0131] Table 2

[0132]

[0133]

[0134] According to the effect data in Tables 1 and 2, the present invention, through the design of acenaphthene-modified polymer and its mutual compounding with unsaturated polyphenylene ether, enables the resin composition and the prepreg and metal foil laminate containing it to have high glass transition temperatures, excellent heat resistance, dielectric properties, dielectric loss stability, damp heat resistance, dimensional stability and filling performance. The copper clad laminate has a Df of 0.0013-0.0019 at 10GHz, a glass transition temperature Tg of 203-235℃, a water absorption rate of ≤0.08%, a ΔDf of ≤0.0004 after wet treatment, and a Y / CTE of 13-18ppm / ℃. It can pass the 288℃ immersion soldering test and has excellent comprehensive performance.

[0135] Furthermore, as can be seen from the examples in Tables 1 and 2, the introduction of the allyl compound TAIC into the resin composition can further optimize Y / CTE; however, if the amount of TAIC is too high (e.g., in Example 9), Df and ΔDf after wet treatment will deteriorate.

[0136] Comparing the examples and comparative examples in Table 1, it can be seen that in Comparative Example 1, the mass ratio of acenaphthene-modified polymer to unsaturated polyphenylene ether was >5:1, leading to deterioration of the filling performance and significant resin aggregation during the filling test. In Comparative Example 2, the mass ratio of acenaphthene-modified polymer to unsaturated polyphenylene ether was <1:5, resulting in an increase in Df, and a significant deterioration in ΔDf after wet treatment. In Comparative Example 3, the use of acenaphthene monomer instead of acenaphthene-modified polymer led to an increase in Df, a significant deterioration in ΔDf, and a deterioration in Y / CTE. In Comparative Example 4, the use of a copolymer of polyfunctional vinyl aromatic compounds and monovinyl aromatic compounds to replace the acenaphthene-modified polymer of the present invention led to an increase in Df, a significant deterioration in Y / CTE, and a significant deterioration in filling performance.

[0137] The applicant declares that the above embodiments illustrate the resin composition, prepreg, metal foil laminate, and their applications, but the present invention is not limited to the above embodiments, i.e., 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 product, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection and disclosure scope of the present invention.

Claims

1. A resin composition, characterized in that, The resin composition comprises unsaturated polyphenylene ether and acenaphthene-modified polymer, wherein the mass ratio of acenaphthene-modified polymer to unsaturated polyphenylene ether is 1:(0.2-5); The monomers of the acenaphthene-modified polymer include a combination of acenaphthene and polyfunctional vinyl aromatic compounds, and the molar percentage of acenaphthene in the monomers is 10-90%.

2. The resin composition according to claim 1, characterized in that, The unsaturated polyphenylene ether is a polyphenylene ether with C=C unsaturated bonds at the end groups, preferably including polyphenylene ethers with any one or at least two of vinyl benzyl, vinyl phenyl, acrylate, and methacrylate end groups.

3. The resin composition according to claim 1 or 2, characterized in that, The multifunctional vinyl aromatic compounds include any one or a combination of at least two of divinylbenzene, divinylnaphthalene, divinylbiphenyl, and diisopropylbenzene; Preferably, the polymer monomers of the acenaphthene-modified polymer further include a third monomer, which includes any one or a combination of at least two of monovinyl aromatic compounds, aliphatic olefins, and cyclic olefins. Preferably, the molar percentage of the third monomer in the polymerized monomer is ≤50%; Preferably, the weight-average molecular weight of the acenaphthene-modified polymer is 5,000-300,000.

4. The resin composition according to any one of claims 1-3, characterized in that, The resin composition also includes an allyl compound; Preferably, the allyl compound comprises any one or a combination of at least two of the following: 1,3,5-triallyl cyanurate, trimethylallyl isocyanurate, triallyl isocyanurate, 1,2,4-triallyl benzoic acid, and compounds with the structure shown in Formula I. Among them, X1, X2, and X3 are each independently selected from any one of C2-C15 alkenyl and C8-C21 alkenylphenyl; Preferably, based on 100 parts by total mass of organic resin components in the resin composition, the mass of the allyl compound is ≤30 parts, more preferably 5-30 parts.

5. The resin composition according to any one of claims 1-3, characterized in that, The resin composition also includes other components containing C=C unsaturated bonds; Preferably, the other components containing C=C unsaturated bonds include any one or a combination of at least two of the following: benzocyclobutene compounds, polybutadiene, styrene-butadiene copolymers, styrene-butadiene-styrene triblock copolymers, polyfunctional vinyl aromatic polymers, polyisoprene, styrene-isoprene copolymers, and polyfunctional vinyl compounds. Preferably, based on a total mass of 100 parts of organic resin components in the resin composition, the mass of the other components containing C=C unsaturated bonds is ≤50 parts; Preferably, the resin composition further comprises a thermoplastic polymer; Preferably, the thermoplastic polymer includes any one or a combination of at least two of the following: styrene-based polymers, hydrogenated styrene-based polymers, polyolefin resins, acrylonitrile-butadiene copolymers, and acrylonitrile-butadiene-styrene copolymers. Preferably, based on a total mass of 100 parts of organic resin components in the resin composition, the mass of the thermoplastic polymer is ≤30 parts; Preferably, the resin composition further includes an initiator; Preferably, the initiator includes any one or a combination of at least two of carbon-based initiators and peroxide radical initiators; Preferably, the carbon-based initiator includes any one or a combination of at least two of 2,3-dimethyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-bis(4-methylphenyl)butane, 2,3-dimethyl-2,3-bis(4-isopropylphenyl)butane, and 3,4-dimethyl-3,4-diphenylhexane; Preferably, the peroxide radical initiator includes any one or a combination of at least two of the following: dicumyl peroxide, 1,3-bis(tert-butylperoxide), 1,4-bis(tert-butylperoxide), 2,5-di-tert-butylperoxide-2,5-dimethylhexane, 2,5-di-tert-butylperoxide-2,5-dimethylhexyn-3, di-tert-butylperoxide, and tert-butylperoxide. Preferably, the initiator is 0.1-5 parts by mass, based on 100 parts by total mass of organic resin components in the resin composition; Preferably, the resin composition further includes fillers and / or flame retardants; Preferably, the filler comprises any one or a combination of at least two of the following: silica, hollow glass microspheres, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, and mica; more preferably, spherical silica. Preferably, based on 100 parts by weight of the total resin composition, the mass of the filler is ≤70 parts, more preferably 20-70 parts; Preferably, the flame retardant includes a phosphorus-containing flame retardant and / or a bromine-containing flame retardant; Preferably, based on 100 parts by weight of the total organic resin components in the resin composition, the flame retardant has a mass of ≤30 parts, more preferably 5-30 parts.

6. A resin film, characterized in that, The resin film is made of the resin composition as described in any one of claims 1-5; Preferably, the resin film is obtained by coating the resin composition onto a release material and then drying and / or semi-curing it.

7. A resin-coated copper foil, characterized in that, The resin-coated copper foil comprises a copper foil layer and a resin layer, wherein the material of the resin layer comprises the resin composition as described in any one of claims 1-5.

8. A semi-cured sheet, characterized in that, The prepreg comprises a reinforcing material and a resin composition as described in any one of claims 1-5 attached to the reinforcing material; Preferably, the resin composition is attached to the reinforcing material after impregnation and drying.

9. A metal foil-coated laminate, characterized in that, The metal-clad foil includes at least one of the resin film as described in claim 6, the resin-coated copper foil as described in claim 7, and the prepreg as described in claim 8.

10. A printed circuit board, characterized in that, The printed circuit board includes at least one of the following: the resin film as described in claim 6, the resin-coated copper foil as described in claim 7, the prepreg as described in claim 8, and the metal foil-coated laminate as described in claim 9.

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