A resin composition and use thereof

Abstract

This invention provides a resin composition and its application. The resin composition comprises a combination of an acenaphthene-modified polymer and a component containing C=C unsaturated bonds. The monomers of the acenaphthene-modified polymer include acenaphthene and a polyfunctional vinyl aromatic compound, and the molar percentage of acenaphthene in the monomers is 10-90%. Based on a total mass of 100 parts for the acenaphthene-modified polymer and the component containing C=C unsaturated bonds, the mass of the acenaphthene-modified polymer is 10-80 parts. This invention, through the design of the acenaphthene-modified polymer and its mutual compounding with the component containing C=C unsaturated bonds, enables the resin composition and the prepreg and metal foil laminate containing it to have high glass transition temperatures, excellent heat resistance, dielectric properties, resistance to damp heat, and filler properties, significantly improving the internal consistency of the substrate and fully 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 and its application. Background Technology

[0002] With the rapid development of electronic technology, the information processing of electronic products such as mobile communications, servers, and mainframe computers is constantly moving towards "high-frequency signal transmission and high-speed digitization". Therefore, low-dielectric materials have become the main development direction of high-transmission-rate substrates to meet the requirements of high-speed information processing.

[0003] The main requirements for low dielectric materials include low dielectric loss and low dielectric constant. In addition, the substrate is required to have a high glass transition temperature, low thermal expansion coefficient, and good flammability. At the same time, the substrate material is required to have good internal consistency, which includes no resin agglomeration after the substrate material is pressed, good fluidity of the substrate material during the filling process, no resin agglomeration, and uniform dispersion of fillers.

[0004] To meet the performance requirements of high transmission rate substrates, the industry is committed to researching low dielectric materials. For example, CN118019799A discloses a resin composition comprising polymer A, whose structural unit includes an aromatic vinyl compound; compound B, whose molecular weight is less than 1000 and contains one organic group containing a carbon-carbon unsaturated bond; the mass ratio of polymer A to compound B is 1:(0.025-0.7); and other thermosetting compounds C, such as maleimide compounds, polyphenylene ether compounds containing two or more carbon-carbon unsaturated double bonds, cyanate ester compounds, epoxy compounds, phenolic compounds, alkenyl-substituted nadicimide compounds, oxetane resins, and benzoxazine compounds. This resin composition can maintain excellent dielectric properties while having good moisture absorption and heat resistance. The resin composition disclosed in CN117106265A comprises 5-70% by mass of a vinyl aromatic copolymer and 30-95% by mass of polyphenylene ether, wherein the number-average molecular weight of the vinyl aromatic copolymer is 2000-8000, the molar ratio of structural units derived from divinyl aromatic compounds is 5-45 mol%, and the number of hydroxyl groups of the polyphenylene ether is 20-900 μmol / g, and the weight-average molecular weight is 10000-50000; this resin composition exhibits excellent dielectric properties, especially a low dielectric loss tangent. CN112368311A discloses a resin composition comprising compound (A) and acenaphthene compound (B), wherein compound (A) comprises modified polyphenylene ether containing vinyl aryl groups and / or vinyl aryl modified polyolefins, and the mass ratio of compound (A) to acenaphthene compound (B) is 50:50-95:5; the resin composition has low dielectric constant and dielectric loss, good heat resistance, and maintains good dielectric properties even after absorbing water.

[0005] While current resin compositions and substrates have achieved some success in low dielectric properties, the substrates often fail to meet the requirements of multiple performance aspects, including dielectric properties, heat resistance, damp heat resistance, and thermal expansion. 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 applications. Therefore, developing resin materials that combine excellent dielectric properties, heat resistance, damp heat resistance, and filling properties is a pressing issue that needs to be addressed in this field. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a resin composition and its application. Through the design of acenaphthene-modified polymers and their compounding with components containing C=C unsaturated bonds, the resin composition and its contained prepregs and metal foil laminates exhibit high glass transition temperatures, low dielectric constants and dielectric losses, excellent heat resistance, dielectric properties, resistance to damp heat and filler properties, significantly improved internal consistency of the substrate, and fully meet the performance requirements of high transmission rate substrates.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a resin composition comprising an acenaphthene-modified polymer and a component containing C=C unsaturated bonds; the 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 monomer is 10-90%; based on a total mass of 100 parts of the acenaphthene-modified polymer and the component containing C=C unsaturated bonds, the mass of the acenaphthene-modified polymer is 10-80 parts.

[0009] 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 mutual compounding with components containing C=C unsaturated bonds, the resin composition and the prepreg and metal foil laminate containing it have high glass transition temperature, low dielectric constant 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, and excellent filling performance, greatly improving the internal consistency of the substrate and fully meeting the performance requirements of high transmission rate substrates.

[0010] 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.

[0011] 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.

[0012] In this invention, with a total mass of 100 parts of the acenaphthene-modified polymer and the component containing C=C unsaturated bonds, the mass of the acenaphthene-modified polymer is 10-80 parts, for example, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, or 75 parts, as well as 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.

[0013] The mass of the component containing C=C unsaturated bonds is 20-90 parts, for example, it can be 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts or 85 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.

[0014] The terms "parts" and "parts by weight" used in this invention are calculated based on solid content and do not include solvents, dispersants, etc.

[0015] In this invention, acenaphthene-modified polymer and components containing C=C unsaturated bonds are compounded in a specific mass ratio. The combined effect of these two components endows the resin composition, its cured product, prepreg, laminate, and metal foil-coated laminate with high glass transition temperature, excellent heat resistance, dielectric properties, resistance to damp heat, and filler properties. If the amount of acenaphthene-modified polymer is too low, the dielectric loss of the resin composition and its contained prepreg and metal foil-coated laminate will increase, and the heat resistance will also decrease. If the amount of acenaphthene-modified polymer is too high, the filler properties and resistance to damp heat of the resin composition and its contained prepreg and metal foil-coated laminate will deteriorate across the board.

[0016] 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.

[0017] Preferably, the polyfunctional vinyl aromatic compound includes any one or a combination of at least two of divinylbenzene, divinylnaphthalene, divinylbiphenyl, and diisopropylbenzene.

[0018] In this invention, the polyfunctional vinyl aromatic compounds listed above include all their isomers.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] Preferably, the aliphatic olefin includes butadiene and / or isoprene.

[0023] Preferably, the cyclic olefin includes any one or a combination of at least two of cyclopentadiene, maleic anhydride diene, norbornene, and dicyclopentadiene.

[0024] 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.

[0025] 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.

[0026] 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).

[0027] Preferably, the component containing C=C unsaturated bonds includes small molecule compounds containing C=C unsaturated bonds and / or resins containing C=C unsaturated bonds.

[0028] Preferably, the group containing C=C unsaturated bonds includes any one or a combination of at least two of vinyl, vinylphenyl, vinylbenzyl, allyl, (meth)acrylate, and isopropenyl.

[0029] The (meth)acrylate group includes acrylate group and / or methacrylate group.

[0030] In this invention, the component containing C=C unsaturated bonds can be a small molecule compound and / or resin (polymer), including, but not limited to: a small molecule compound and / or resin (polymer) containing any one or at least two combinations of vinyl, vinylphenyl, vinylbenzyl, allyl, acrylate, methacrylate, and isopropyl groups.

[0031] Preferably, the component containing C=C unsaturated bonds includes any one or a combination of at least two of the following: unsaturated polyphenylene ether, polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene triblock copolymer, polyfunctional vinyl aromatic polymer, polyisoprene, styrene-isoprene copolymer, allyl compound, and polyfunctional vinyl compound.

[0032] Preferably, the unsaturated polyphenylene ether is a polyphenylene ether with C=C unsaturated bonds at the end groups.

[0033] Preferably, the unsaturated polyphenylene ether comprises polyphenylene ether with end groups containing any one or at least two of vinyl benzyl, vinyl phenyl, acrylate, and methacrylate groups.

[0034] 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 ).

[0035] 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.

[0036] Preferably, the monomers of the polyfunctional vinyl aromatic polymer comprise a combination of divinyl aromatic compounds and monovinyl aromatic compounds.

[0037] 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.

[0038] 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, vinylnaphthalene, fluorene containing one vinyl group, and biphenyl containing one vinyl group; the monovinyl aromatic compounds listed above include all their isomers.

[0039] In this invention, the multifunctional vinyl aromatic polymer can be purchased from the market, for example, it can be Nippon Steel's ODV.

[0040] Preferably, the allyl compound comprises any one or a combination of at least two of the following: triallyl isocyanurate (TAIC), trimethylallyl isocyanurate (TMAIC), triallyl cyanurate (TAC), polyisocyanurate, triallyl cyanurate, and diallyl phthalate.

[0041] 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.

[0042] Preferably, the resin composition further includes a thermoplastic polymer.

[0043] 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.

[0044] 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.

[0045] It should be noted that the styrene-based polymer can be a random copolymer and / or a block copolymer.

[0046] 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.

[0047] 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.

[0048] In this invention, the "total mass of organic resin components" in the resin composition represents the total mass of the acenaphthene-modified polymer, the component containing C=C unsaturated bonds, and optionally the 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.

[0049] Preferably, the resin composition further includes an initiator.

[0050] Preferably, the initiator includes any one or a combination of at least two of carbon-based initiators and peroxide radical initiators.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] Preferably, the resin composition further includes fillers and / or flame retardants.

[0055] 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.

[0056] 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.

[0057] 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... 50 The 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.

[0058] For example, the particle size of the filler was obtained using an MS3000 Malvern laser particle size analyzer.

[0059] 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.

[0060] Preferably, the flame retardant includes a phosphorus-containing flame retardant and / or a bromine-containing flame retardant.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] 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.

[0069] In a second aspect, the present invention provides a resin film, the material of which includes the resin composition as described in the first aspect;

[0070] Preferably, the resin film is obtained by coating the resin composition onto a release material and then drying and / or semi-curing it.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] Preferably, the resin composition is attached to the reinforcing material after impregnation and drying.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] On the other hand, the present invention provides a laminate comprising at least one prepreg as described in the fourth aspect.

[0080] 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.

[0081] 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.

[0082] Preferably, the metal foil is copper foil, and the metal foil laminate is copper clad laminate.

[0083] 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.

[0084] 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.

[0085] Preferably, the curing is carried out in a press.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] Compared with the prior art, the present invention has the following beneficial effects:

[0091] (1) In the resin composition provided by the present invention, through the design of acenaphthene-modified polymer and its mutual compounding with components containing C=C unsaturated bonds, the resin composition and the prepreg and metal foil laminate containing it have high glass transition temperature, low dielectric constant and low dielectric loss factor, and have excellent performance in terms of heat resistance and dielectric properties. At the same time, it has low water absorption, good resistance to damp heat and excellent filling performance, which greatly improves the consistency inside the substrate and fully meets the performance requirements of high transmission rate substrate.

[0092] (2) Through the design and optimization of the resin composition, the present invention enables the copper clad laminate to have excellent comprehensive performance with Dk≤3.5, Df≤0.0023, glass transition temperature Tg>180℃, water absorption rate≤0.06% at 10GHz, excellent resistance to damp heat and filling performance. Detailed Implementation

[0093] 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.

[0094] 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.

[0095] In one specific embodiment, the copolymerization reaction is carried out in the presence of an initiator.

[0096] 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.

[0097] Preparation Example 1

[0098] 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:

[0099] 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.

[0100] Preparation Example 2

[0101] 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:

[0102] 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).

[0103] Preparation Example 3

[0104] 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:

[0105] 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).

[0106] 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.

[0107] In the following examples, materials for which no preparation method is provided are commercially available chemicals, as detailed in the table below:

[0108]

[0109]

[0110] Examples 1-8, Comparative Examples 1-5

[0111] 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.

[0112] A prepreg and a copper-clad laminate comprising the resin composition are prepared by the following method:

[0113] (1) Mix each component of the resin composition with toluene according to the formula amount and disperse them evenly to prepare a glue solution with a solid content of 65%; impregnate 2116NE glass fiber cloth with the glue solution, and then heat it at 130°C for 5 minutes to form a semi-cured state (B-Stage) to obtain a semi-cured sheet;

[0114] (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 at a temperature of 210°C and a pressure of 30 MPa to obtain the copper-clad laminate.

[0115] The copper-clad laminate was subjected to performance testing, and the specific method is as follows:

[0116] (1) Glass transition temperature Tg (DMA): The glass transition temperature Tg was tested using a dynamic mechanical tester (DMA); the vibration frequency was 1 Hz, and 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.

[0117] (2) Dielectric constant Dk and dielectric loss factor Df: After etching the copper foil, it was placed in a drying oven at 23°C and 50% humidity for 48 hours, and then Dk and Df were tested at 10GHz using the SPDR method.

[0118] (3) Water absorption rate: Tested according to the method of IPC-TM-650 2.6.2.1.

[0119] (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".

[0120] (5) 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 2 atmospheres of pressure and 100% humidity 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 288℃ tin bath, but no white spots or delamination occurred after 10 seconds in the 260℃ tin bath and repeated 10 times, the evaluation was "good". If white spots or delamination appeared in the 260℃ tin bath, the evaluation was "poor".

[0121] The performance test data are shown in Tables 1 and 2.

[0122] Table 1

[0123]

[0124]

[0125] Table 2

[0126]

[0127]

[0128] According to the effect data in Table 1, the present invention, through the design of acenaphthene-modified polymer and its mutual compounding with components containing C=C unsaturated bonds, enables the resin composition and the prepreg and metal foil laminate containing it to have high glass transition temperatures, excellent heat resistance, dielectric properties, resistance to damp heat and filling properties, resulting in copper-clad laminates with Dk of 3.4-3.5, Df of 0.0019-0.0023, glass transition temperature Tg of 185-221℃, and water absorption rate of 0.05-0.06% at 10GHz. It can pass the 288℃ immersion soldering test and has excellent comprehensive performance.

[0129] Comparing the data in Tables 1 and 2, it can be seen that in Comparative Example 1, replacing the acenaphthene-modified polymer of the present invention with an equal mass of acenaphthene resulted in significant resin aggregation in the resin composition and substrate during the filling test, and the resistance to damp heat also deteriorated. Comparative Examples 2 and 3 show that if the acenaphthene-modified polymer is not used in combination with components containing C=C unsaturated bonds, or if the amount of acenaphthene-modified polymer is excessive, its resistance to damp heat tends to deteriorate significantly, and the filling performance also worsens. In Comparative Example 4, the amount of acenaphthene-modified polymer was too low, leading to a deterioration in the glass transition temperature and filling performance; in Comparative Example 5, replacing the acenaphthene-modified polymer of the present invention with a copolymer of polyfunctional vinyl aromatic compounds and monovinyl aromatic compounds resulted in a deterioration in the glass transition temperature and a worsening of the filling performance.

[0130] The applicant declares that the above embodiments illustrate the resin composition and its application, but 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 product of the present invention, addition of auxiliary components, and 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 comprises an acenaphthene-modified polymer and a component containing C=C unsaturated bonds; The polymer monomers of the acenaphthene-modified polymer include a combination of acenaphthene and polyfunctional vinyl aromatic compounds, and the molar percentage of acenaphthene in the polymer monomers is 10-90%. With a total mass of 100 parts for the acenaphthene-modified polymer and the component containing C=C unsaturated bonds, the mass of the acenaphthene-modified polymer is 10-80 parts.

2. The resin composition according to claim 1, characterized by 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 polymeric monomer is ≤50%.

3. The resin composition according to claim 1 or 2, characterized by 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 to 3, characterized by The components containing C=C unsaturated bonds include small molecule compounds containing C=C unsaturated bonds and / or resins containing C=C unsaturated bonds; Preferably, the group containing C=C unsaturated bonds includes any one or a combination of at least two of vinyl, vinylphenyl, vinylbenzyl, allyl, (meth)acrylate, and isopropenyl groups; Preferably, the component containing C=C unsaturated bonds includes any one or a combination of at least two of the following: unsaturated polyphenylene ether, polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene triblock copolymer, polyfunctional vinyl aromatic polymer, polyisoprene, styrene-isoprene copolymer, allyl compound, and polyfunctional vinyl compound.

5. The resin composition according to any one of claims 1 to 4, characterized in that, The resin composition also includes 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 by, 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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