A resin composition, a resin film including the same, and a printed circuit board

Abstract

The application provides a resin composition, a resin film containing the same and a printed circuit board, the resin composition comprising the following components in parts by mass: 5-95 parts of a benzocyclobutene modified polyphenyl ether resin, 5-95 parts of a component containing a C=C unsaturated bond, 5-300 parts of a modified filler, and 0.1-10 parts of an initiator; the modified filler is an inorganic filler treated on the surface with a double bond group-containing coupling agent. The benzocyclobutene modified polyphenyl ether resin has good reactivity, and when compounded with the component containing the C=C unsaturated bond and the double bond group-containing modified filler, a cured product with high crosslinking density and excellent interface consistency is formed. The cured product of the resin composition has excellent dielectric properties, low dielectric loss tangent Df, good dielectric stability, small change range of △Df (10 GHz) after HAST, high chemical copper bonding force, and can be applied to high-frequency high-speed printed circuit boards prepared by a semi-additive method or an additive method.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor materials technology, specifically relating to a resin composition, a resin film containing the composition, and a printed circuit board. Background Technology

[0002] In recent years, with the development of electronic information technology, the installation of electronic equipment has been developing towards miniaturization, high density, large information capacity, and high frequency, which has put forward higher requirements for the comprehensive performance of printed circuit boards, such as dielectric properties, heat resistance, damp heat resistance, mechanical properties, dimensional stability, water absorption, and chemical resistance.

[0003] As a manufacturing technology for printed circuit boards (PCBs), known manufacturing methods involve stacking insulating and conductive layers alternately on an inner substrate, such as semi-additive and additive methods. In these methods, the insulating layer is typically formed by curing a resin composition. With the miniaturization and high performance of electronic devices, the industry expects PCBs to also feature multi-layer stacking, micro-wiring, and high density. This places demands on the insulating layer to possess excellent heat resistance, damp heat resistance, dimensional stability, and low dielectric loss, as well as high adhesion between the insulating layer and the conductive layer (metal layer).

[0004] Resin compositions used to prepare insulating layers generally include resin and inorganic fillers. To achieve low coefficient of thermal expansion (CTE) and low warpage in the insulating layer, a high-filling inorganic filler content of 30 wt% or more is typically required in the resin composition. On the one hand, high-filling inorganic fillers reduce the moisture and heat resistance of the insulating layer, causing printed circuit boards containing them to perform poorly in HAST (Highly Accelerated Temperature and Humidity Stress Test) tests. On the other hand, appropriate surface treatment agents are usually selected to surface treat the inorganic fillers, thereby improving their moisture resistance and dispersibility, and reducing the arithmetic mean roughness of the insulating layer surface during the wet roughening process, enabling the formation of a conductor layer with sufficient peel strength. However, surface treatment of inorganic fillers can have a significant adverse impact on the dielectric properties and dielectric reliability of the resin composition and the insulating layer.

[0005] For resins used in preparing insulating layers, the industry currently considers thermosetting polyphenylene ether resins, bismaleimide resins, and hydrocarbon resins to be suitable for meeting the basic performance requirements of printed circuit boards. However, with the increasing demands for high frequency, high speed, and high reliability in printed circuit boards, some performance defects of existing resins have attracted industry attention. For example, thermosetting polyphenylene ether resins have relatively high dielectric constants and dielectric losses in cured products; bismaleimide resins are brittle, have short shelf lives, and their dielectric properties have significant room for improvement; and hydrocarbon resins have insufficient heat resistance, a large coefficient of thermal expansion, and dimensional stability that makes it difficult to meet the performance requirements of high-performance electronic devices for printed circuit boards.

[0006] Benzocyclobutene is a thermosetting material with an all-carbon structure, possessing the following performance characteristics: it is heat-curable without generating any small molecules during the curing process; the cured product exhibits excellent heat resistance, a low coefficient of thermal expansion, and high mechanical strength, while also possessing extremely low water absorption and dielectric loss. It holds promise as a next-generation high-performance electronic material for application in high-end microelectronics. Benzocyclobutene is a volatile liquid with a low boiling point of approximately 150°C. To match the high process temperatures of printed circuit boards, it is typically formulated as a resin derivative. However, currently known benzocyclobutene resin derivatives either lack an all-carbon structure, resulting in high dielectric constants and dielectric losses, or the raw materials undergo incomplete reaction, leaving residual polar groups in the system, leading to dielectric property degradation, or they are difficult to prepare and mass-produce.

[0007] In general, existing manufacturing processes easily sacrifice the original dielectric advantages of the benzocyclobutene structure, making it difficult to fully utilize the performance of the benzocyclobutene structure in the insulating layer and printed circuit board. Furthermore, the high filler content of inorganic fillers in the insulating layer can adversely affect the dielectric properties, dielectric stability, reliability, and bonding between the insulating layer and the metal layer. Therefore, developing high-frequency, high-speed resin compositions with excellent dielectric properties, especially maintaining low dielectric loss after HAST, high reliability, and high chemical copper bonding strength, to meet the requirements of semi-addition or addition methods for preparing high-frequency, high-speed printed circuit boards, is an urgent problem to be solved in this field. Summary of the Invention

[0008] To address the shortcomings of existing technologies, the present invention aims to provide a resin composition, a resin film containing the resin composition, and a printed circuit board. The benzocyclobutene-modified polyphenylene ether resin is compounded and reacted with components containing C=C unsaturated bonds and inorganic fillers that have undergone surface treatment with coupling agents containing double bond groups. This increases the crosslinking density of the resin composition and forms a bridging effect between the organic resin components and the inorganic fillers, giving the resin composition excellent dielectric properties and dielectric stability. It maintains low dielectric loss even after HAST and has strong adhesion to the metal layer, fully meeting the requirements for the preparation of high-frequency and high-speed printed circuit boards by semi-addition or addition methods.

[0009] To achieve this objective, the present invention adopts the following technical solution:

[0010] In a first aspect, the present invention provides a resin composition comprising, by weight, the following components:

[0011]

[0012] The modified filler is an inorganic filler that has undergone surface treatment with a coupling agent containing double bond groups.

[0013] In this invention, the benzocyclobutene-modified polyphenylene ether resin contains readily reactive alkenyl groups (benzocyclobutene ring groups undergo thermal ring-opening to form C=C), which can achieve excellent dielectric properties and high crosslinking density through thermosetting, as well as high glass transition temperature and excellent heat resistance. The modified filler is an inorganic filler with a surface-treated coupling agent containing double-bond groups, giving the surface of the inorganic filler double-bond groups. These double-bond groups act as a bridge at the interface between the organic resin system and the inorganic filler, forming chemical bond bridges between the benzocyclobutene-modified polyphenylene ether resin, the component containing C=C unsaturated bonds, and the inorganic filler. The interface consistency after crosslinking and curing is good, resulting in low dielectric loss and excellent dielectric reliability.

[0014] In the resin composition provided by this invention, the benzocyclobutene-modified polyphenylene ether resin, the component containing C=C unsaturated bonds, and the inorganic filler that has undergone surface treatment with a coupling agent containing double bond groups are compounded in specific proportions. After thermal ring-opening, the benzocyclobutene-modified polyphenylene ether resin forms free radicals, which react with the component containing C=C unsaturated bonds and the modified filler containing double bond groups to form a cured product with excellent interfacial consistency. This increases the crosslinking density of the resin composition, giving the resin composition and the resin film containing it a sufficiently low dielectric loss tangent Df, excellent dielectric properties, and excellent dielectric stability. Even after HAST, it can still maintain a low dielectric loss tangent Df, resulting in good reliability. The formed resin film has low roughness after Desmear treatment and high adhesion to the metal layer (chemical copper adhesion), fully meeting the performance requirements of high-frequency and high-speed printed circuit boards prepared by semi-addition or addition methods.

[0015] In the resin composition provided by the present invention, the benzocyclobutene-modified polyphenylene ether resin is 5-95 parts, for example, 10 parts, 15 parts, 20 parts, 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, 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 preferably 10-80 parts.

[0016] The component containing C=C unsaturated bonds is 5-95 parts, for example, it can be 10 parts, 15 parts, 20 parts, 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, but preferably 20-80 parts.

[0017] The modified filler is 5-300 parts, for example, it can be 10 parts, 30 parts, 50 parts, 80 parts, 100 parts, 120 parts, 150 parts, 180 parts, 200 parts, 220 parts, 250 parts or 280 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 preferably 40-300 parts.

[0018] The initiator is 0.1-10 parts, for example, it can be 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or 9 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 preferably 0.2-2 parts.

[0019] The "parts" and "parts by weight" used in this invention are calculated based on solid content and do not include solvents, dispersants, etc.

[0020] Preferably, the benzocyclobutene-modified polyphenylene ether resin is prepared by reacting a bi-hydroxyl-terminated polyphenylene ether of Formula I with a halobenzocyclobutene of Formula II.

[0021]

[0022] In formula I, R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 Each is independently selected from any one of H, F, substituted or unsubstituted C1-C6 (e.g., C1, C2, C3, C4, C5, C6) straight-chain or branched alkyl groups.

[0023] X is selected from

[0024] Any one of them; the dashed line represents the connection site of the group.

[0025] R 31 R32 Each can independently represent unsubstituted, monosubstituted, or polysubstituted. Wherein, when R... 31 When there is no substitution, i.e., the R... 31 For H; when R 31 When representing multiple substitutions (e.g., disubstituted, trisubstituted), multiple (2, 3) R 31 For the same or different groups; R 32 The terms "unsubstituted" and "multi-substituted" have the same meaning, and for the sake of brevity, they will not be elaborated further.

[0026] R 21 R 22 R 23 R 24 R 25 R 26 R 27 R 28 R 31 R 32 Each is independently selected from any one of H, F, substituted or unsubstituted C1-C6 (e.g., C1, C2, C3, C4, C5, C6) straight-chain or branched alkyl groups.

[0027] n1 and n2 are each independently selected from integers greater than 0, such as 1, 2, 3, 4, 5, 6, 8, 10, 12, 15, 18, 20, 22, 25 or 28, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific point values ​​included in the range.

[0028] Preferably, R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 R 21 R 22 R 23 R 24 R 25 R 26 R 27 R 28 R 31 R 32 The substituents described herein are each independently selected from at least one of halogens, for example, at least one of F, Cl, Br or I.

[0029] Preferably, 2≤n1+n2≤30, where n1+n2 can be 3, 5, 8, 10, 12, 15, 18, 20, 22, 25 or 28, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range. More preferably, 2≤n1+n2≤20.

[0030] As a preferred technical solution of the present invention, the bihydroxyl-terminated polyphenylene ether can be a series of resin mixtures with different n1+n2 values. The preferred bihydroxyl-terminated polyphenylene ether of the present invention has a mass percentage of n1+n2 values ​​falling within the range of 2≤n1+n2≤30 ≥90% (e.g., 92%, 95%, 98%, 100%). If the percentage of n1+n2>30 is too high, it will affect the solubility of the modified polyphenylene ether resin and its compatibility with components containing C=C unsaturated bonds.

[0031] In this invention, the hydroxyl-terminated polyphenylene ether can be purchased commercially, such as SA90 from Sabic Corporation; SA90 has the structure shown in Formula I, wherein R 11 R 13 R 16 R 18 It is methyl, R 12 R 14 R 15 R 17 Let H be X, and let X be

[0032]

[0033] Hal is selected from any of the halogens, such as F, Cl, Br or I, with Br being more preferred.

[0034] Preferably, the halobenzocyclobutene is (4-Halobenzocyclobutene), further preferably 4-bromobenzocyclobutene

[0035] Preferably, the molar ratio of the dihydroxy-terminated polyphenylene ether to the halobenzocyclobutene is 1:(2.1-2.5), for example, it can be 1:2.2, 1:2.3, 1:2.4 or 1:2.5, etc.

[0036] Preferably, the benzocyclobutene-modified polyphenylene ether resin is prepared by the following method, which includes: reacting the bihydroxyl-terminated polyphenylene ether of Formula I with the halobenzocyclobutene of Formula II in the presence of a catalyst to obtain the benzocyclobutene-modified polyphenylene ether resin.

[0037] Preferably, the catalyst comprises a monovalent copper salt, such as cuprous chloride, cuprous bromide, or cuprous iodide, with cuprous chloride being more preferred.

[0038] Preferably, the reaction is carried out in the presence of an alkaline substance, which preferably includes sodium methoxide.

[0039] Preferably, the reaction temperature is 60-160℃, for example, it can be 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 140℃, 150℃ or 160℃, 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.

[0040] Preferably, the reaction time is 5-30 hours, for example, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 24 hours, 28 hours or 30 hours, 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.

[0041] Preferably, the weight-average molecular weight of the benzocyclobutene-modified polyphenylene ether resin is 1500-20000, for example, it can be 1600, 1800, 2000, 2200, 2500, 3000, 3500, 4000, 5000, 8000, 10000, 12000, 15000 or 18000, 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.

[0042] 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.

[0043] 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, isopropenyl, and maleimide groups.

[0044] Wherein, the (meth)acrylate group is an acrylate group and / or a methacrylate group.

[0045] 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, isopropylene, and maleimide groups.

[0046] 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, vinyl alicyclic polymer, allyl compound, polyfunctional vinyl compound, and maleimide compound.

[0047] Preferably, the unsaturated polyphenylene ether is a polyphenylene ether with C=C unsaturated bonds at the end groups.

[0048] 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.

[0049] In this invention, the polybutadiene, styrene-butadiene copolymer, and styrene-butadiene-styrene triblock copolymer all contain crosslinkable active groups C=C, and can be based on 1,2-vinyl butadiene monomers.

[0050] Preferably, the polybutadiene includes any one or a combination of at least two of unmodified polybutadiene, acrylate-modified polybutadiene, and methacrylate-modified polybutadiene.

[0051] In this invention, the styrene-butadiene copolymer can be a styrene-butadiene random copolymer and / or a styrene-butadiene block copolymer.

[0052] Preferably, the monomers of the polyfunctional vinyl aromatic polymer comprise a combination of divinyl aromatic compounds and monovinyl aromatic compounds.

[0053] 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.

[0054] Preferably, the monovinyl aromatic compound includes styrene, and other monovinyl aromatic compounds besides styrene.

[0055] In this invention, the multifunctional vinyl aromatic polymer can be purchased from the market, such as Nippon Steel's ODV series.

[0056] 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.

[0057] 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.

[0058] Preferably, the maleimide compound includes any one or a combination of at least two of the following: monomaleimide compound, bismaleimide compound, polyfunctional maleimide compound, and maleimide resin.

[0059] As a preferred embodiment of the present invention, the component containing C=C unsaturated bonds includes any one or a combination of at least two of unsaturated polyphenylene ether, polybutadiene, styrene-butadiene copolymer, polyfunctional vinyl aromatic polymer, and allyl compound, and more preferably a combination of at least two (e.g., 2, 3, 4 or 5).

[0060] Preferably, the thermosetting resin composition comprises 0-40 parts by weight of unsaturated polyphenylene ether, for example, 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts or 35 parts, 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.

[0061] Preferably, the thermosetting resin composition comprises 0-40 parts of polybutadiene by weight, for example, 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts or 35 parts, 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.

[0062] Preferably, the thermosetting resin composition comprises 0-30 parts by weight of styrene-butadiene copolymer, for example, 1 part, 5 parts, 10 parts, 15 parts, 20 parts or 25 parts, and 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.

[0063] Preferably, the thermosetting resin composition comprises 0-50 parts by weight of a polyfunctional vinyl aromatic polymer, for example, 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts or 45 parts, 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.

[0064] Preferably, the thermosetting resin composition comprises 0-20 parts by weight of an allyl compound, for example, 1 part, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts or 18 parts, and specific values ​​between the above-mentioned 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.

[0065] As a preferred embodiment of the present invention, the coupling agent containing double bond groups is a silane coupling agent containing double bond groups.

[0066] Preferably, the double bond groups in the coupling agent containing double bond groups include any one or a combination of at least two of vinyl, styrene, acryloyloxy, methacryloyloxy, and polybutadiene groups.

[0067] Preferably, the coupling agent containing double bond groups includes any one or a combination of at least two of the following: vinyl silane coupling agents, styrene silane coupling agents, acryloyloxy silane coupling agents, methacryloxy silane coupling agents, butadiene polymer-modified silane coupling agents, and styrene-butadiene polymer-modified silane coupling agents.

[0068] In this invention, the coupling agent containing double bond groups can be purchased commercially. Exemplarily, the vinylsilane-containing coupling agent includes any one or a combination of at least two of ethylenetrimethoxysilane (Shin-Etsu Chemical KBM-1003), ethylenetriethoxysilane (Shin-Etsu Chemical KBE-1003), 7-octenaltrimethoxysilane (Shin-Etsu Chemical KBM-1083), and siloxane (Shin-Etsu Chemical KR-511); the styrylsilane-containing coupling agent includes p-styryltrimethoxysilane (Shin-Etsu Chemical KBM-1403); and the methacryloxysilane-containing coupling agent includes 3-methacryloxypropylmethyldimethoxysilane (KBM-502) and 3-methacryloxypropyltrimethoxysilane (KBM-503). The styrene-butadiene polymer-modified silane coupling agent comprises any one or a combination of at least two of the following: 3-methacryloxypropylmethyldiethoxysilane (KBE-502), 3-methacryloxypropyltriethoxysilane (KBE-503), 8-methacryloxyoctyltrimethoxysilane (KBM-5803), and silane coupling agent X-40-9296; the acryloxysilane-containing coupling agent comprises any one or a combination of at least two of the following: 3-acryloxypropyltrimethoxysilane (KBM-5103), silane coupling agent X-12-1048, silane coupling agent X-12-1050, silane coupling agent KR-513, and silane coupling agent X-40-2430C; the styrene-butadiene polymer-modified silane coupling agent comprises X-12-1281C.

[0069] For example, the acryloyloxysilane coupling agent contains a structure as shown in Formula S1:

[0070]

[0071] In formula S1, R S1 R S2 Each can be methyl or ethyl.

[0072] In formula S1, m and n are each independently selected from integers from 1 to 4, for example, they can be 1, 2, 3 or 4.

[0073] In formula S1, K and L represent the number of repeating units, each independently selected from an integer from 1 to 30, for example, 2, 3, 4, 8, 10, 12, 15, 18, 20, 22, 25 or 28, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific point values ​​included in the range, and 1-10 is further preferred.

[0074] In equation S1, the connection order of each repeating unit is arbitrary.

[0075] Preferably, the number of fluorine atoms in the acryloyloxysilane coupling agent with the structure shown in Formula S1 is 3-30, for example 3, 6, 9, 12, 15, 18, 21, 24, 27 or 30, 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.

[0076] Preferably, the number of acryloyloxy groups in the acryloyloxysilane coupling agent with the structure shown in Formula S1 is 1-10, for example, 2, 3, 4, 5, 6, 7, 8 or 9.

[0077] Preferably, the acryloyloxysilane coupling agent with the structure shown in Formula S1 is a commercially available product, such as Shin-Etsu Chemical X-40-2430C.

[0078] For example, the styrene-butadiene polymer-modified silane coupling agent has a structure as shown in Formula S2:

[0079]

[0080] In formula S2, R S3 R S4 Each is independently selected from any one of C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, etc.) straight-chain or branched alkyl groups, or C6-C10 (e.g., C6, C9, etc.) aryl groups.

[0081] In equation S2, t is an integer from 1 to 3, for example, it can be 1, 2, or 3; when t≥2, multiple (2 or 3) ORs S3 They can be the same or different groups; when t is 1, multiple (2 or 3) R S4 These can be the same or different groups.

[0082] When t is 3, it means that there are 3 -ORs connected to Si. S3 Group, R S4 It does not exist.

[0083] In formula S2, e, f, g, and h represent the number of repeating units, each independently selected from an integer from 1 to 40, for example, 2, 3, 4, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, 35, 35, or 38, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific point values ​​included in the range.

[0084] In Equation S2, the connection order of each repeating unit is arbitrary.

[0085] Preferably, the number average molecular weight of the styrene-butadiene polymer-modified silane coupling agent with the structure shown in Formula S2 is 500-50000, for example, it can be 800, 1000, 3000, 5000, 8000, 10000, 12000, 15000, 18000, 20000, 25000, 30000, 35000, 40000 or 45000, 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, and 1000-20000 is further preferred.

[0086] Preferably, in this invention, based on the description in GB / T 21863-2008, the number-average molecular weight and weight-average molecular weight of the material are tested by gel permeation chromatography (GPC) using polystyrene calibration as the basis.

[0087] Preferably, the styrene-butadiene polymer modified silane coupling agent with the structure shown in Formula S2 is a commercially available product, such as Shin-Etsu Chemical X-12-1281C.

[0088] In this invention, the method of surface treatment of inorganic fillers with coupling agents containing double bond groups to obtain modified fillers can be any surface treatment method known in the prior art.

[0089] For example, the modified filler is prepared by the following method, which includes: placing the inorganic filler in a stirring device, adding a coupling agent containing double bond groups to it under stirring and performing surface treatment to obtain the modified filler.

[0090] Preferably, the surface treatment time is 1-60 min, for example, it can be 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min or 55 min, as well as specific point values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific point values ​​included in the range.

[0091] Preferably, based on the mass of the inorganic filler as 100%, the mass of the coupling agent containing double bond groups is 0.1-5.0%, for example, it can be 0.2%, 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5%, 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.

[0092] As a preferred embodiment of the present invention, with the inorganic filler comprising 100%, the mass of the coupling agent containing double bond groups is 0.1-5.0%, to ensure sufficient surface treatment of the inorganic filler, resulting in a modified filler containing an appropriate amount of double bond groups. This double bond group acts as a bridge between the inorganic filler and the organic resin system, undergoing a cross-linking and curing reaction with the benzocyclobutene-modified polyphenylene ether resin and components containing C=C unsaturated bonds. This results in good interfacial consistency in the cured product, exhibiting excellent dielectric properties and dielectric stability. If the mass of the coupling agent containing double bond groups is too low, the surface treatment of the inorganic filler will be insufficient, failing to form a uniform coating. The bridging effect between the inorganic filler and the organic resin system will be weak, affecting the dielectric properties, reliability, and adhesion to the metal layer of the cured product. If the mass of the coupling agent containing double bond groups is too high, the excess coupling agent will migrate freely, also affecting the adhesion between the cured product and the metal layer. Its copper adhesion to the resin film surface will be low, and the dielectric properties of the resin film will also be reduced.

[0093] In this invention, the inorganic filler includes any one or a combination of at least two of the following: non-metallic oxides, metal oxides, metal hydroxides, metal nitrides, non-metallic nitrides, inorganic hydrates, inorganic salts, metal hydrates, and inorganic phosphorus.

[0094] Preferably, the inorganic filler includes any one or a combination of at least two of the following: silicon dioxide, titanium dioxide, zinc oxide, aluminum hydroxide, aluminum oxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, silicon aluminum carbide, silicon carbide, zirconium oxide, mica, boehmite, calcined talc, talc, silicon nitride, strontium titanate, barium titanate, and calcined kaolin.

[0095] 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.

[0096] Preferably, the median particle size (D) of the inorganic filler is... 50 The value can be 0.01-10μm, for example, it can be 0.05μm, 0.1μm, 0.3μm, 0.5μm, 0.8μm, 1μm, 3μm, 5μm, 8μm or 9μm, 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.

[0097] For example, the particle size of the inorganic filler was obtained using an MS3000 Malvern laser particle size analyzer.

[0098] As a preferred embodiment of the present invention, in the resin composition, the total mass of the benzocyclobutene-modified polyphenylene ether resin and the component containing C=C unsaturated bonds is 100%, and the mass of the modified filler is 30-300%, for example, it can be 50%, 80%, 100%, 120%, 150%, 180%, 200%, 220%, 250% or 280%, 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.

[0099] The resin composition provided by this invention is preferably formulated into a resin film for use as an insulating layer in a printed circuit board (PCB). A conductor layer (metal layer) is preferably formed on this insulating layer using an addition or semi-addition method. The metal is formed on the resin film by chemical plating and / or electrochemical plating. Preferably, a modified filler with a high filler content of 30-300% is used to ensure that the resin film meets the requirements for a low coefficient of thermal expansion (low CTE), low warpage, and excellent dimensional stability as an insulating layer. If the amount of modified filler is too low, the CTE and warpage of the resin film increase, resulting in poor dimensional stability; if the amount of modified filler is too high, the chemical copper adhesion of the resin film decreases.

[0100] Preferably, the initiator is a free radical initiator.

[0101] Preferably, the initiator includes any one or a combination of at least two of organic peroxides, azo initiators, and carbon-based free radical initiators.

[0102] Preferably, the initiator comprises any one or a combination of at least two of the following: tert-butylisopropylphenyl peroxide, dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne, 1,1-bis(tert-butylperoxy)-3,3,5-dimethylcyclohexane, cyclohexane, and polycyclohexane.

[0103] Preferably, the resin composition further includes 1-50 parts by weight of flame retardant, for example, the flame retardant may be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts or 45 parts, and 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.

[0104] Preferably, the flame retardant includes any one or a combination of at least two of halogenated flame retardants, nitrogen-based flame retardants, phosphorus-based flame retardants, and metal hydroxide flame retardants.

[0105] Preferably, the resin composition further includes other additives, such as toughening agents and / or viscosity modifiers.

[0106] 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 coating and other processes. During subsequent drying, semi-curing, or full curing stages, the solvent in the resin composition will partially or completely evaporate.

[0107] 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; alcohols 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.

[0108] 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.

[0109] 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.

[0110] Preferably, the resin film is obtained by coating the resin composition onto a release material and then drying and / or semi-curing it.

[0111] Specifically, the method for preparing the resin film includes: coating the resin liquid of the resin composition onto a release material, drying, removing the release material, and obtaining the resin film.

[0112] Preferably, the release material includes any one of PET release film, polyethylene film, polypropylene film, or polyvinyl chloride film.

[0113] Preferably, the thickness of the release material is 10-150 μm, for example, it can be 20 μm, 30 μm, 50 μm, 80 μm, 100 μm, 110 μm, 120 μm, 130 μm or 140 μm, 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, and 20-60 μm is further preferred.

[0114] Preferably, the drying temperature is 80-120℃, for example, it can be 85℃, 90℃, 95℃, 100℃, 105℃, 110℃ or 115℃, and 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.

[0115] Preferably, the drying time is 1-10 min, for example, it can be 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min or 9 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.

[0116] Preferably, the thickness of the resin film is 10-100μm, for example, it can be 20μm, 30μm, 40μm, 50μm, 60μm, 70μm, 80μm or 90μm, 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.

[0117] 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.

[0118] 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.

[0119] Fourthly, the present invention provides a printed circuit board, the printed circuit board comprising at least one of the resin film as described in the second aspect and the resin-coated copper foil as described in the third aspect.

[0120] Compared with the prior art, the present invention has the following beneficial effects:

[0121] (1) In the resin composition provided by the present invention, the benzocyclobutene-modified polyphenylene ether resin has good reactivity. It is compounded with components containing C=C unsaturated bonds and modified fillers containing double bond groups. The double bond groups in the modified fillers act as bridges between the organic resin components and the inorganic fillers. It is fully cured with the benzocyclobutene-modified polyphenylene ether resin and components containing C=C unsaturated bonds to form a cured product with high crosslinking density and excellent interface consistency. The cured resin composition has excellent dielectric properties, with a low dielectric loss tangent Df, and good dielectric stability. The change in ΔDf (10GHz) after HAST is small.

[0122] (2) The resin film prepared by the resin composition of the present invention has a low dielectric loss tangent Df, Df≤0.00221; the change range of ΔDf (10GHz) after HAST is small, the change range of Df after HAST (ΔDf)≤0.00014; and the chemical copper bonding force after Desmear treatment is ≥0.42N / cm, which can be used as an insulating layer and fully meets the performance requirements of high frequency and high speed printed circuit boards prepared by semi-addition or addition methods. Detailed Implementation

[0123] 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.

[0124] Preparation Example 1

[0125] A benzocyclobutene-modified polyphenylene ether resin PPO-BCB1 is prepared by the following method:

[0126] (1) Dissolve 1 mol of dihydroxyl-terminated polyphenylene ether (SA90, purchased from Sabic) in toluene, then add sodium methoxide (0.1 mol), 2.2 mol of 4-bromobenzocyclobutene, and 0.1 mol of cuprous chloride. React at 110 °C for 10 h. After cooling, filter the reactants and rotary evaporate to obtain a solid. Recrystallize the solid with 5 times its weight of anhydrous ethanol and dry under vacuum at 50 °C for 24 h to obtain purified benzocyclobutene-modified polyphenylene ether resin PPO-BCB1. Its weight-average molecular weight is 2100, and its structure is as follows.

[0127]

[0128] Preparation Example 2

[0129] A modified filler, comprising silica (spherical silica powder, D) surface-treated with p-styrenetrimethoxysilane (Shin-Etsu Chemical KBM-1403). 50 The particle size is 0.63 μm, SO-Cl (Admatechs Corporation, Japan). The specific preparation method is as follows:

[0130] By mass, 100 parts of spherical silica powder were placed in a mixer. Under stirring conditions, 2 parts of vaporized KBM-1403 were injected into the mixer. The mixture was stirred for 10 minutes to obtain the modified filler, denoted as F1.

[0131] Preparation Example 3

[0132] A modified filler, comprising silica (spherical silica powder, D) surface-treated with 3-methacryloyloxypropyltriethoxysilane (Shin-Etsu Chemical KBE-503).50 The particle size is 0.5 μm, SO-C2 (Admatechs Corporation, Japan). The specific preparation method is as follows:

[0133] By mass, 100 parts of spherical silica powder were placed in a mixer. Under stirring conditions, 2 parts of vaporized KBE-503 were injected into the mixer. The mixture was stirred for 10 minutes to obtain the modified filler, denoted as F2.

[0134] Preparation Example 4

[0135] A modified filler, comprising silica (spherical silica powder, D) surface-treated with butadiene-styrene copolymer modified silane coupling agent (Shin-Etsu Chemical X-12-1281C). 50 The particle size is 0.5 μm, SO-C2 (Admatechs Corporation, Japan). The specific preparation method is as follows:

[0136] By mass, 100 parts of spherical silica powder were placed in a mixer. Under stirring conditions, 0.1 parts of vaporized X-12-1281C were injected into the mixer. The mixture was stirred for 10 minutes to obtain the modified filler, denoted as F3.

[0137] Preparation Example 5

[0138] A modified filler, comprising silica (spherical silica powder, D) surface-treated with vinyl silane coupling agent (Shin-Etsu Chemical KBE-1003). 50 The particle size is 0.5 μm, SO-C2 (Admatechs Corporation, Japan). The specific preparation method is as follows:

[0139] By mass, 100 parts of spherical silica powder were placed in a mixer. Under stirring conditions, 5 parts of vaporized KBE-1003 were injected into the mixer. The mixture was stirred for 10 minutes to obtain the modified filler, denoted as F4.

[0140] Comparative Preparation Example 1

[0141] A modified filler, comprising silica (spherical silica powder, D) surface-treated with the aminosilane coupling agent N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical KBM-573). 50 The particle size is 0.5 μm, SO-C2 (Admatechs Corporation, Japan). The specific preparation method is as follows:

[0142] By mass, 100 parts of spherical silica powder were placed in a mixer. Under stirring conditions, 2 parts of vaporized KBM-573 were injected into the mixer. The mixture was stirred for 10 minutes to obtain the modified filler, denoted as F5.

[0143] In the following specific embodiments of the present invention, the materials involved are as follows:

[0144] 1. Benzocyclobutene-modified polyphenylene ether resin

[0145] The benzocyclobutene-modified polyphenylene ether resin PPO-BCB1 provided in Preparation Example 1.

[0146] 2. Benzocyclobutene derivatives

[0147] CYCLOTENE 3022, purchased from Dow Chemical Company, has the following structure:

[0148]

[0149] 3. Components containing C=C unsaturated bonds

[0150] 3.1 The group containing a C=C unsaturated bond is a (meth)acrylate group.

[0151] MX9000, acrylate-terminated PPO (polyphenylene oxide), SABIC Corporation, USA;

[0152] Ricacryl 3500, methacrylate-modified polybutadiene, Krevili;

[0153] 3.2 Groups containing C=C unsaturated bonds are vinyl groups (CH resins)

[0154] B3000, polybutadiene, Nippon Soda Corporation;

[0155] Ricon 100, styrene-butadiene resin, Sartomer Corporation, USA;

[0156] 3.3 The group containing a C=C unsaturated bond is vinylphenyl.

[0157] ODV-XET, a vinyl aromatic polymer, Nippon Steel Chemical Industry Co., Ltd.

[0158] OPE-2ST, a PPO with a terminal vinyl phenyl group, Mitsubishi Chemical Corporation.

[0159] 3.4 The group containing a C=C unsaturated bond is allyl.

[0160] Trimethylallyl isocyanate (TMAIC), Hunan Fangruida.

[0161] 4. Initiator

[0162] tert-Butylisopropylphenyl peroxide, BIPB.

[0163] 5. Packing material

[0164] The modified fillers F1 to F4 provided in Examples 2-5 were prepared;

[0165] Compare with the modified filler F5 provided in Preparation Example 1.

[0166] 6. Flame retardants

[0167] SYTELX 8010, Albemarle, USA.

[0168] Example 1

[0169] A resin composition comprising, by weight, the following components: 20 parts of benzocyclobutene-modified polyphenylene ether resin PPO-BCB1, 30 parts of unsaturated polyphenylene ether MX9000, 30 parts of vinyl aromatic polymer ODV-XET, 20 parts of styrene-butadiene resin Ricon 100, 0.35 parts of initiator BIPB, and 200 parts of modified filler F1.

[0170] A resin film comprising the resin composition and a printed circuit board (multilayer printed circuit board) are prepared by the following method:

[0171] (1) Mix each component of the resin composition with toluene according to the above formula to prepare a resin solution with a solid content of 65%; coat the resin solution onto the release film, dry it, and bake it in an oven at 120°C for 5 minutes to obtain a resin film with a semi-cured resin layer and a thickness of 40μm.

[0172] (2) The resin film obtained in step (1) and the browned PCB board are pressed and cured. The curing temperature is 100℃, the pressure is 0.5MPa, and the time is 1min. The release film is removed and the surface is treated. Copper plating is performed to form a multilayer printed circuit board with lines.

[0173] The following performance tests were performed on the resin film and printed circuit board provided in Example 1:

[0174] (1) HAST test

[0175] The Highly Accelerated Temperature and Humidity Stress Test (HAST) was conducted according to JESD22-A110 at a temperature of 130°C and a humidity of 85%RH for 100 hours.

[0176] (2) Dielectric loss tangent Df

[0177] Referring to IPC-TM-650 2.5.5.15, the dielectric loss tangent Df of the cured resin film at 10 GHz was determined using the Split PostDielectric Resonator (SPDR) method.

[0178] (3) Dielectric loss tangent Df after HAST

[0179] The above-mentioned sample with tested Df was processed by HAST, and the dielectric loss tangent Df of the resin film at 10 GHz was determined by SPDR method.

[0180] △Df: Dielectric loss tangent Df after HAST - Dielectric loss tangent Df before HAST.

[0181] (4) Chemical Copper Bonding Strength PS

[0182] The roughened resin film was subjected to the following copper plating, electroplating and post-curing treatment: soaking in chemical copper solution (MVTP1, ATOTECH) for 20 min — electroplating copper to a thickness of 25 μm — curing in an oven at 200℃ for 60 min, and testing the chemical copper adhesion of the resin film using a copper foil peel strength tester.

[0183] The test results are shown in Table 1.

[0184] Examples 2-4, Comparative Examples 1-3

[0185] A resin composition and a resin film and a multilayer printed circuit board comprising the resin composition are disclosed. The difference between this and Example 1 is that the formulation of the resin composition is different, as shown in Table 1. The amount of each component is in parts. The preparation method and performance testing method of the resin film and the multilayer printed circuit board are the same as those in Example 1.

[0186] Table 1

[0187]

[0188]

[0189] Based on the aforementioned performance test data, it can be seen that the resin composition and the resin film containing it prepared by the present invention, which is compounded in specific proportions with benzocyclobutene-modified polyphenylene ether resin, components containing C=C unsaturated bonds, and inorganic fillers that have undergone surface treatment with coupling agents containing double bond groups, exhibit excellent dielectric properties. Even after HAST, it can still maintain a low dielectric loss tangent Df, demonstrating good reliability. After Desmear treatment, the resulting resin film has high adhesion to the metal layer (chemical copper adhesion), with Df of 0.00196-0.00221, ΔDf of 0.00010-0.00014, and chemical copper adhesion of 0.42-0.51 N / cm, fully meeting the performance requirements for the preparation of high-frequency and high-speed printed circuit boards by semi-addition or addition methods.

[0190] In Comparative Example 1, an inorganic filler surface-treated with an aminosilane coupling agent was used. This inorganic filler lacked double bond groups and could not act as a bridge at the interface between the unsaturated organic resin system and the inorganic filler. The resulting resin composition had a low crosslinking density at the filler-resin interface, making it difficult to maintain low dielectric loss after HAST, with ΔDf reaching as high as 0.00081. In Comparative Example 2, other benzocyclobutene derivatives were used to replace the benzocyclobutene-modified polyphenylene ether resin. The resulting thermosetting resin composition had poor dielectric properties, with a dielectric loss tangent as high as 0.00227. In Comparative Example 3, a physical mixture of dihydroxyl-terminated polyphenylene ether and 4-bromobenzocyclobutene was directly used, along with the same other components as in Example 1. Since the benzocyclobutene was not grafted onto the dihydroxyl-terminated polyphenylene ether, the 4-bromobenzocyclobutene essentially volatilized during the pre-curing process, resulting in poor dielectric properties in Comparative Example 3, with Df reaching as high as 0.00311.

[0191] The applicant declares that the present invention is illustrated by the above embodiments to describe the resin composition, the resin film containing the resin, and the printed circuit board of the present invention. However, the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the products of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A resin composition, characterized in that, The resin composition comprises the following components in parts by weight: 5-95 parts of benzocyclobutene-modified polyphenylene ether resin 5-95 parts of components containing C=C unsaturated bonds 5-300 parts of modified filler Initiator 0.1-10 parts; The modified filler is an inorganic filler that has undergone surface treatment with a coupling agent containing double bond groups; The benzocyclobutene-modified polyphenylene ether resin is prepared by reacting a bi-hydroxyl-terminated polyphenylene ether of Formula I with a halogenated benzocyclobutene of Formula II. ； Among them, R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 Each is independently selected from any one of H, F, substituted or unsubstituted C1-C6 straight-chain or branched alkyl groups; X is selected from , , , , , , , or Any one of them; the dashed line represents the connection site of the group; R 31 R 32 Each can independently represent unsubstituted, monosubstituted, or polysubstituted. R 21 R 22 R 23 R 24 R 25 R 26 R 27 R 28 R 31 R 32 Each is independently selected from any one of H, F, substituted or unsubstituted C1-C6 straight-chain or branched alkyl groups; n1 and n2 are each independently selected from integers greater than 0; ； Hal is selected from any of the halogens.

2. The resin composition according to claim 1, characterized in that, 2≤n1+n2≤30.

3. The resin composition according to claim 1, characterized in that, The molar ratio of the dihydroxyl-terminated polyphenylene ether to the halobenzocyclobutene is 1:(2.1-2.5).

4. The resin composition according to claim 1, characterized in that, The weight-average molecular weight of the benzocyclobutene-modified polyphenylene ether resin is 1500-20000.

5. The resin composition according to claim 1, characterized in that, The components containing C=C unsaturated bonds include small molecule compounds containing C=C unsaturated bonds and / or resins containing C=C unsaturated bonds.

6. The resin composition according to claim 5, characterized in that, The group containing C=C unsaturated bonds includes any one or a combination of at least two of vinyl, vinylphenyl, vinylbenzyl, allyl, (meth)acrylate, isopropenyl, and maleimide.

7. The resin composition according to claim 1, characterized in that, The components containing C=C unsaturated bonds include 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, vinyl alicyclic polymer, allyl compound, polyfunctional vinyl compound, and maleimide compound.

8. The resin composition according to claim 7, characterized in that, The unsaturated polyphenylene ether is a polyphenylene ether with C=C unsaturated bonds at the end groups.

9. The resin composition according to claim 7, characterized in that, The allyl compound includes any one or a combination of at least two of the following: triallyl isocyanurate, trimethylallyl isocyanurate, triallyl cyanurate, polyisocyanurate, triallyl cyanurate, and diallyl phthalate.

10. The resin composition according to claim 7, characterized in that, The polyfunctional vinyl compound includes any one or a combination of at least two of divinylbenzene, 1,2-bis(p-vinylphenyl)ethane, and polyfunctional (meth)acrylates.

11. The resin composition according to claim 1, characterized in that, The double bond groups in the coupling agent containing double bond groups include any one or a combination of at least two of vinyl, styrene, acryloyloxy, methacryloyloxy, and polybutadiene groups.

12. The resin composition according to claim 1, characterized in that, The coupling agent containing double bond groups includes any one or a combination of at least two of the following: vinyl silane coupling agents, styrene silane coupling agents, acryloyloxy silane coupling agents, methacryloxy silane coupling agents, butadiene polymer-modified silane coupling agents, and styrene-butadiene polymer-modified silane coupling agents.

13. The resin composition according to claim 1, characterized in that, Based on the inorganic filler mass being 100%, the mass of the coupling agent containing double bond groups is 0.1-5.0%.

14. The resin composition according to claim 1, characterized in that, The inorganic filler includes any one or a combination of at least two of the following: silicon dioxide, titanium dioxide, zinc oxide, aluminum hydroxide, aluminum oxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, silicon aluminum carbide, silicon carbide, zirconium oxide, mica, boehmite, calcined talc, talc, silicon nitride, strontium titanate, barium titanate, and calcined kaolin.

15. The resin composition according to claim 1, characterized in that, The median particle size of the inorganic filler is 0.01-10 μm.

16. The resin composition according to claim 1, characterized in that, The initiator includes any one or a combination of at least two of the following: organic peroxides, azo initiators, and carbon-based free radical initiators.

17. The resin composition according to claim 16, characterized in that, The initiator includes any one or a combination of at least two of the following: tert-butylisopropylphenyl peroxide, dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne, 1,1-bis(tert-butylperoxy)-3,3,5-dimethylcyclohexane, cyclohexane, and polycyclohexane.

18. The resin composition according to claim 1, characterized in that, The resin composition further includes 1-50 parts by weight of flame retardant.

19. The resin composition according to claim 18, characterized in that, The flame retardant includes any one or a combination of at least two of the following: halogenated flame retardants, nitrogen-based flame retardants, phosphorus-based flame retardants, and metal hydroxide flame retardants.

20. A resin film, characterized in that, The resin film is made of the resin composition as described in any one of claims 1-19.

21. The resin film according to claim 20, characterized in that, The resin film is obtained by coating the resin composition onto a release material and then drying and / or semi-curing it.

22. The resin film according to claim 21, characterized in that, The thickness of the resin film is 10-100 μm.

23. 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 1-19.

24. A printed circuit board, characterized in that, The printed circuit board includes at least one of the resin film as described in any one of claims 20-22 and the resin-coated copper foil as described in claim 23.

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