Resin composition, resin film containing same and printed circuit board

Abstract

The invention provides a resin composition, a resin film containing the same and a printed circuit board. The resin composition comprises the following components in parts by mass: 5-95 parts of benzocyclobutene modified polyphenyl ether resin, 5-95 parts of a component containing C = C unsaturated bonds, 5-300 parts of a modified filler and 0.1-10 parts of an initiator, the modified filler is an inorganic filler subjected to surface treatment by a double-bond group-containing coupling agent. The benzocyclobutene modified polyphenyl ether resin has good reaction activity, and is compounded with a component containing a C = C unsaturated bond and a modified filler containing a double-bond group to form a condensate with high crosslinking density and excellent interface consistency. The cured product of the resin composition has the advantages of excellent dielectric property, low dielectric loss tangent Df, good dielectric stability, small change amplitude of Df (10GHz) after HAST, and high chemical copper binding force, and can be applied to a high-frequency high-speed printed circuit board prepared by a semi-addition method or an addition method.

Description

Technical Field

[0001] The invention belongs to the technical field of semiconductor materials, and in particular relates to a resin composition, a resin film containing the same, and a printed circuit board. Background Art

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

[0003] As a manufacturing technology for printed circuit boards, it is known to use a stacking (build up) method in which an insulating layer and a conductor layer are alternately overlapped on an inner substrate, such as a semi-additive method and an additive method, wherein the insulating layer is usually formed by curing a resin composition. With the development of miniaturization and high performance of electronic devices, the industry expects printed circuit boards to also have the characteristics of multi-layer stacking, fine wiring and high density, and thus puts forward requirements for the insulating layer to have excellent heat resistance, moisture and heat resistance, dimensional stability and low dielectric loss, and requires the insulating layer to have a high bonding force with the conductor layer (metal layer).

[0004] The resin composition for preparing the insulating layer generally includes a resin and an inorganic filler. In order to make the insulating layer have a low coefficient of thermal expansion (CTE) and low warpage, it is usually necessary to use a highly filled inorganic filler with a mass content of more than 30wt% in the resin composition. On the one hand, the highly filled inorganic filler will reduce the moisture and heat resistance of the insulating layer, so that the printed circuit board containing it will perform poorly in the HAST (Highly Accelerated Temperature and Humidity Stress Test) test. On the other hand, an appropriate surface treatment agent is usually selected to surface treat the inorganic filler, thereby improving the moisture resistance and dispersibility of the inorganic filler, and can also reduce the arithmetic mean roughness of the surface of the insulating layer in the wet roughening process, and can form a conductor layer with sufficient peeling strength; however, the surface treatment of the inorganic filler will have a greater adverse effect on the dielectric properties and dielectric reliability of the resin composition and the insulating layer.

[0005] As for the resins used to prepare the insulating layer, the types that are currently considered in the industry to meet the basic performance requirements of printed circuit boards include thermosetting polyphenylene ether resins, bismaleimide resins, hydrocarbon resins, etc. However, with the development of high frequency, high speed, and high reliability of printed circuit boards, some performance defects of existing resins have attracted attention in the industry, such as the high dielectric constant and dielectric loss of cured thermosetting polyphenylene ether resins; the brittleness of bismaleimide resins is large, the storage period is short, and there is also a large room for improvement in dielectric properties; hydrocarbon resins have insufficient heat resistance, a large thermal expansion coefficient, and dimensional stability that makes it difficult to meet the performance requirements of high-performance electronic equipment for printed circuit boards.

[0006] Benzocyclobutene is a thermosetting material with a full carbon-hydrogen structure. It has the following performance characteristics: it can be thermally cured and the curing process does not produce any small molecules. The cured product has excellent heat resistance, low thermal expansion coefficient, high mechanical strength, and extremely low water absorption and dielectric loss. It is expected to be used as a new generation of high-performance electronic materials in the field of high-end microelectronics. Benzocyclobutene is a volatile liquid with a low boiling point of about 150°C. In order to match the higher process temperature of printed circuit boards, it is usually made into resin derivatives for use. However, the currently known benzocyclobutene resin derivatives are either not full carbon-hydrogen structures, with high dielectric constants and dielectric losses, or the raw materials are not completely reacted and polar groups remain in the system, resulting in attenuation of dielectric properties, or they are difficult to prepare and difficult to mass produce.

[0007] In general, the existing manufacturing process is very likely to sacrifice the original dielectric advantages of the benzocyclobutene structure, making it difficult to fully exert the performance of the benzocyclobutene structure in the insulating layer and the printed circuit board; moreover, the high-filling inorganic filler in the insulating layer will also have an adverse effect on the dielectric properties, dielectric stability, reliability of the board and the bonding between the insulating layer and the metal layer. Therefore, it is an urgent problem to be solved in this field to develop a high-frequency and high-speed resin composition with excellent dielectric properties, especially low dielectric loss after HAST, good reliability, and high chemical copper bonding to meet the requirements of preparing high-frequency and high-speed printed circuit boards by semi-additive or additive methods. Summary of the invention

[0008] In view of the deficiencies in the prior art, the object of the present invention is to provide a resin composition, a resin film and a printed circuit board containing the same. The benzocyclobutene-modified polyphenylene ether resin is compounded and reacted with a component containing a C=C unsaturated bond and an inorganic filler surface-treated with a coupling agent containing a double bond group, thereby increasing the crosslinking density of the resin composition and forming a bridging effect between the interface of the organic resin component and the inorganic filler, so that the resin composition has excellent dielectric properties and dielectric stability, still maintains low dielectric loss after HAST, and has strong bonding with the metal layer, fully meeting the requirements of preparing high-frequency and high-speed printed circuit boards by a semi-additive method or an additive method.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a resin composition, wherein the resin composition comprises the following components in parts by mass:

[0011]

[0012] The modified filler is an inorganic filler that has been surface-treated with a coupling agent containing a double bond group.

[0013] In the present invention, the molecular structure of the benzocyclobutene-modified polyphenylene ether resin contains an easily reactive alkenyl group (benzocyclobutene ring group is thermally opened to form C=C), and excellent dielectric properties and high crosslinking density can be obtained by thermal curing, and the glass transition temperature is high and the heat resistance is excellent. The modified filler is an inorganic filler surface-treated with a coupling agent containing a double bond group, so that the surface of the inorganic filler has a double bond group, and the double bond group plays a bridging role on the interface between the organic resin system and the inorganic filler, and can form a chemical bond bridge between the interface of the benzocyclobutene-modified polyphenylene ether resin, the component containing the C=C unsaturated bond and the inorganic filler, and the interface consistency after crosslinking and curing is good, and low dielectric loss and excellent dielectric reliability are obtained.

[0014] In the resin composition provided by the present invention, the benzocyclobutene-modified polyphenylene ether resin, the component containing C=C unsaturated bonds and the inorganic filler surface-treated by a coupling agent containing double bond groups are compounded in specific proportions; the benzocyclobutene-modified polyphenylene ether resin forms free radicals after thermal ring opening, and the free radicals react with the component containing C=C unsaturated bonds and the modified filler containing double bond groups to form a cured product with excellent interface consistency, thereby increasing the crosslinking density of the resin composition, so that the resin composition and the resin film containing the resin composition have sufficiently low dielectric loss tangent Df, excellent dielectric properties, and excellent dielectric stability; the low dielectric loss tangent Df can still be maintained after HAST, and the reliability is good; the formed resin film has low roughness after Desmear (drill removal) treatment, and has high bonding strength (chemical copper bonding strength) with the metal layer, thereby fully meeting the performance requirements of preparing high-frequency and high-speed printed circuit boards by a semi-additive method or an additive method.

[0015] In the resin composition provided by the present invention, the benzocyclobutene-modified polyphenylene ether resin 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 points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range, 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 points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range, 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 points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range, 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 parts, 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 points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range, preferably 0.2-2 parts.

[0019] The “parts” and “parts by weight” involved in the present invention are all 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 double-terminated hydroxyl polyphenylene ether of a structure shown in formula I with a halogenated benzocyclobutene of a structure shown in 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, and substituted or unsubstituted C1-C6 (eg, C1, C2, C3, C4, C5, C6) linear or branched alkyl.

[0023] X is selected from

[0024] Any one of the following; the dotted line represents the attachment site of the group.

[0025] R 31 , R 32 Each independently represents unsubstituted, monosubstituted or polysubstituted. 31 When it represents no substitution, that is, the R 31 is H; when R 31 When multiple substitution (e.g., disubstituted or trisubstituted) is represented, multiple (2, 3) R 31 are the same or different groups; R 32 The unsubstituted and polysubstituted have the same meanings and will not be described in detail for the sake of brevity.

[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, and substituted or unsubstituted C1-C6 (eg, C1, C2, C3, C4, C5, C6) linear or branched alkyl.

[0027] n1 and n2 are each independently selected from integers greater than 0, for example, 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 simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said 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 substituted substituents are each independently selected from at least one of halogen, for example, at least one of F, Cl, Br or I.

[0029] Preferably, 2≤n1+n2≤30, n1+n2 can be 3, 5, 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 no longer exhaustively lists the specific point values ​​included in the range, and it is further preferred that 2≤n1+n2≤20.

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

[0031] In the present invention, the double-terminated hydroxyl polyphenylene ether can be purchased from the market, such as SA90 from Sabic Company; SA90 has a structure shown in Formula I, wherein R 11 , R 13 , R 16 , R 18 is methyl, R 12 , R 14 , R 15 , R 17 is H, X is

[0032]

[0033] Hal is selected from any one of the halogens, for example, F, Cl, Br or I, more preferably Br.

[0034] Preferably, the halogenated benzocyclobutene is (4-halogenated benzocyclobutene), more preferably 4-bromobenzocyclobutene

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

[0036] Preferably, the benzocyclobutene-modified polyphenylene ether resin is prepared by the following method, which comprises: reacting the double-terminated hydroxyl polyphenylene ether of the structure shown in formula I with the halogenated benzocyclobutene of the structure shown in 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, cuprous iodide, and more preferably cuprous chloride.

[0038] Preferably, the reaction is carried out in the presence of a basic substance, and the basic substance preferably comprises sodium methoxide.

[0039] Preferably, the reaction temperature is 60-160°C, for example, it can be 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 140°C, 150°C or 160°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0040] Preferably, the reaction time is 5-30 h, for example, it can be 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 24 h, 28 h or 30 h, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0041] Preferably, the weight average molecular weight of the benzocyclobutene-modified polyphenylene ether resin is 1500-20000, for example, 1600, 1800, 2000, 2200, 2500, 3000, 3500, 4000, 5000, 8000, 10000, 12000, 15000 or 18000, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0042] Preferably, the component containing C=C unsaturated bonds includes a small molecule compound containing C=C unsaturated bonds and / or a resin containing C=C unsaturated bonds.

[0043] Preferably, the group containing a C═C unsaturated bond includes any one of vinyl, vinylphenyl, vinylbenzyl, allyl, (meth)acrylate, isopropenyl, and maleimide, or a combination of at least two of them.

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

[0045] In the present invention, the component containing C=C unsaturated bonds can be a small molecule compound and / or a resin (polymer), illustratively including but not limited to: a small molecule compound and / or a resin (polymer) containing any one or a combination of at least two of vinyl, vinylphenyl, vinylbenzyl, allyl, acrylate, methacrylate, isopropenyl, and maleimide groups.

[0046] Preferably, the component containing C=C unsaturated bonds includes any one of unsaturated polyphenylene ether, polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene triblock copolymer, multifunctional vinyl aromatic polymer, vinyl alicyclic polymer, allyl compound, multifunctional vinyl compound, maleimide compound or a combination of at least two thereof.

[0047] Preferably, the unsaturated polyphenylene ether is a polyphenylene ether having a C=C unsaturated bond at the end group.

[0048] Preferably, the unsaturated polyphenylene ether includes polyphenylene ether whose terminal groups contain any one or at least two of vinylbenzyl, vinylphenyl, acrylate and methacrylate.

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

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

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

[0052] Preferably, the polymerized monomers of the multifunctional vinyl aromatic polymer include a combination of a divinyl aromatic compound and a monovinyl aromatic compound.

[0053] Preferably, the divinyl aromatic compound includes any one of divinylbenzene, divinylbiphenyl, divinylnaphthalene, diisopropenylbenzene, diisopropenylnaphthalene, and diisopropenylbiphenyl, or a combination of at least two thereof; the above-mentioned divinyl aromatic compounds include all their isomers.

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

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

[0056] Preferably, the allyl compound includes any one of triallyl isocyanurate (TAIC), trimethallyl isocyanate (TMAIC), triallyl cyanurate (TAC), triallyl polyisocyanurate, triallyl cyanurate, and diallyl phthalate, or a combination of at least two thereof.

[0057] Preferably, the multifunctional vinyl compound includes any one of divinylbenzene (DVB), 1,2-bis(p-vinylphenyl)ethane (BVPE), and multifunctional (meth)acrylate, or a combination of at least two thereof.

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

[0059] As a preferred technical solution 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, multifunctional vinyl aromatic polymer, and allyl compound, and a combination of at least two (for example, 2, 3, 4 or 5) is further preferred.

[0060] Preferably, the thermosetting resin composition comprises 0-40 parts by mass of unsaturated polyphenylene ether, for example, 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts or 35 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0061] Preferably, the thermosetting resin composition includes 0-40 parts of polybutadiene by mass, for example, it can be 1 part, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts or 35 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0062] Preferably, the thermosetting resin composition includes 0-30 parts of styrene-butadiene copolymer in parts by mass, for example, it can be 1 part, 5 parts, 10 parts, 15 parts, 20 parts or 25 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0063] Preferably, the thermosetting resin composition comprises 0-50 parts by mass of a multifunctional 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, as well as specific values ​​between the above points. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific points included in the range.

[0064] Preferably, the thermosetting resin composition includes 0-20 parts of allyl compounds by mass, for example, 1 part, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts or 18 parts, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0065] As a preferred technical solution of the present invention, the coupling agent containing a double bond group is a silane coupling agent containing a double bond group.

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

[0067] Preferably, the double bond group-containing coupling agent includes any one of a vinyl-containing silane coupling agent, a styrene-containing silane coupling agent, an acryloxy-containing silane coupling agent, a methacryloxy-containing silane coupling agent, a butadiene polymer-modified silane coupling agent, and a styrene-butadiene polymer-modified silane coupling agent, or a combination of at least two thereof.

[0068] In the present invention, the double bond group-containing coupling agent can be purchased from the market. For example, the vinyl-containing silane coupling agent includes any one of ethylene trimethoxysilane (Shin-Etsu Chemical KBM-1003), ethylene triethoxysilane (Shin-Etsu Chemical KBE-1003), 7-octenal trimethoxysilane (Shin-Etsu Chemical KBM-1083), and siloxane (Shin-Etsu Chemical KR-511) or a combination of at least two thereof; the styrene-containing silane coupling agent includes p-styrene trimethoxysilane (Shin-Etsu Chemical KBM-1403); the methacryloxy-containing silane coupling agent includes 3-methacryloxypropyl methyl dimethoxysilane (KBM-502), 3-methacryloxypropyl trimethoxysilane (KBM-503 ), 3-methacryloxypropylmethyldiethoxysilane (KBE-502), 3-methacryloxypropyltriethoxysilane (KBE-503), 8-methacryloxyoctyltrimethoxysilane (KBM-5803), silane coupling agent X-40-9296, any one or a combination of at least two; the acryloxy-containing silane coupling agent includes 3-acryloxypropyltrimethoxysilane (KBM-5103), silane coupling agent X-12-1048, silane coupling agent X-12-1050, silane coupling agent KR-513, silane coupling agent X-40-2430C, any one or a combination of at least two; the styrene-butadiene polymer modified silane coupling agent includes X-12-1281C.

[0069] Exemplarily, the acryloxy-containing silane coupling agent contains a structure as shown in Formula S1:

[0070]

[0071] In formula S1, R S1 , R S2 Each is independently methyl or ethyl.

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

[0073] In formula S1, K and L represent the number of repeating units, and are independently selected from integers of 1-30, 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 no longer exhaustively enumerates the specific point values ​​included in the range, and 1-10 is further preferred.

[0074] In formula S1, the linking order of each repeating unit is arbitrary.

[0075] Preferably, the number of fluorine atoms in the acryloxy silane coupling agent of the structure shown in Formula S1 is 3-30, for example 3, 6, 9, 12, 15, 18, 21, 24, 27 or 30, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

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

[0077] Preferably, the acryloxy-containing silane coupling agent having the structure shown in Formula S1 is a commercially available product, such as X-40-2430C produced by Shin-Etsu Chemical.

[0078] Exemplarily, 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 (eg, C2, C3, C4, C5, C6, C7, C8, etc.) straight chain or branched chain alkyl, C6-C10 (eg, C6, C9, etc.) aryl.

[0081] In formula S2, t is an integer from 1 to 3, for example, 1, 2 or 3; when t ≥ 2, multiple (2 or 3) OR S3 are the same or different groups; when t is 1, multiple (2 or 3) R S4 are the same or different groups.

[0082] When t is 3, it means there are 3 -OR connected to Si. S3 Group, R S4 Does not exist.

[0083] In formula S2, e, f, g, and h represent the number of repeating units, and are independently selected from integers of 1-40, 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 simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0084] In formula S2, the linking order of each repeating unit is arbitrary.

[0085] Preferably, the number average molecular weight of the styrene-butadiene polymer modified silane coupling agent of 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 point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and 1000-20000 is further preferred.

[0086] Preferably, in the present invention, according to 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) method based on polystyrene calibration.

[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 the present invention, the method of surface treating the inorganic filler with a coupling agent containing a double bond group to obtain a modified filler can be any surface treatment method known in the prior art.

[0089] Illustratively, the modified filler is prepared by the following method, which includes: placing an inorganic filler in a stirring device, adding a coupling agent containing a double bond group thereto 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 point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists 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 a double bond group 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%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0092] As a preferred technical solution of the present invention, based on 100% of the inorganic filler, the mass of the coupling agent containing double bond groups is 0.1-5.0%, so that the inorganic filler is fully surface treated, so that the modified filler obtained contains an appropriate amount of double bond groups, plays a bridging role between the inorganic filler and the organic resin system, and crosslinks and cures with the benzocyclobutene modified polyphenylene ether resin and the component containing C=C unsaturated bonds, so that the interface consistency of the cured product is good, and it has 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 is insufficient, and a uniform coating cannot be formed, and the bridging effect between the inorganic filler and the organic resin system is weak, which affects the dielectric properties, reliability and bonding strength of the cured product with the metal layer. If the mass of the coupling agent containing double bond groups is too high, the excess coupling agent containing double bond groups will migrate freely, and will also affect the bonding strength of the cured product with the metal layer. Its copper bonding strength as the surface of the resin film is low, and the dielectric properties of the resin film will be reduced at the same time.

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

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

[0095] The silica may be any one of fused silica, crystalline silica, spherical silica, hollow silica, or a combination of at least two thereof.

[0096] Preferably, the median particle size (D 50 ) is 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 point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the said range.

[0097] For example, the particle size of the inorganic filler is measured using a MS3000 Malvern laser particle size analyzer.

[0098] As a preferred technical solution of the present invention, in the resin composition, based on the total mass of the benzocyclobutene-modified polyphenylene ether resin and the component containing C=C unsaturated bonds as 100%, 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%, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0099] The resin composition provided by the present invention is preferably made into a resin film and used as an insulating layer of a printed circuit board (PCB board). The conductor layer (metal layer) is preferably formed on the insulating layer by an addition method or a semi-additive method, and the metal is formed on the resin film by chemical plating and / or electrochemical plating. Preferably, a 30-300% high-filled modified filler is used to make the resin film meet the requirements of low thermal expansion coefficient (low CTE), low warpage and excellent dimensional stability as an insulating layer. If the amount of the modified filler is too low, the CTE and warpage of the resin film will increase, and the dimensional stability will be poor; if the amount of the modified filler is too high, the chemical copper bonding force of the resin film will be reduced.

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

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

[0102] Preferably, the initiator includes any one of tert-butyl isopropylphenyl peroxide, dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne, 1,1-di(tert-butylperoxy)-3,3,5-dimethylcyclohexane, dicumyl, and polydicumyl, or a combination of at least two thereof.

[0103] Preferably, the resin composition further includes 1-50 parts of flame retardant by mass, 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, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

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

[0105] Preferably, the resin composition further comprises other additives, such as a toughening agent and / or a viscosity regulator.

[0106] A solvent may also be added to the above resin composition, and the amount of the solvent added is selected by a person skilled in the art based on experience and process requirements, so that the resin composition reaches a viscosity suitable for use, so as to facilitate coating of the resin composition, etc. The solvent in the resin composition will partially or completely evaporate during subsequent drying, semi-curing or complete curing.

[0107] The solvent of the present invention is not particularly limited, and generally, 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 can be selected; the solvent can be used alone or in combination of two or more. Ketones such as acetone, butanone, and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene are preferred.

[0108] The resin composition provided by the present invention is prepared by the following method, which comprises: mixing and uniformly dispersing the components in the resin composition to obtain the resin composition.

[0109] In a second aspect, the present invention provides a resin film, wherein the material of the resin film includes the resin composition as described in the first aspect.

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

[0111] Specifically, the method for preparing the resin film comprises: coating the resin glue of the resin composition on a release material, drying, and removing the release material to obtain the resin film.

[0112] Preferably, the release material includes any one of a PET release film, a polyethylene film, a polypropylene film or a 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 point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range, and 20-60 μm is further preferred.

[0114] Preferably, the drying temperature is 80-120°C, for example, it can be 85°C, 90°C, 95°C, 100°C, 105°C, 110°C or 115°C, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point 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 point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0116] Preferably, the thickness of the resin film is 10-100 μm, for example, it can be 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm or 90 μm, as well as specific point values ​​between the above point values. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0117] In a third aspect, the present invention provides a resin-coated copper foil, wherein 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 the first aspect.

[0118] Preferably, the resin-coated copper foil is obtained by coating the resin composition on a copper foil and then drying and / or semi-curing the resin composition.

[0119] In a fourth aspect, the present invention provides a 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, and is compounded with a component containing a C=C unsaturated bond and a modified filler containing a double bond group. The double bond group in the modified filler plays a bridging role between the interface of the organic resin component and the inorganic filler, and the benzocyclobutene-modified polyphenylene ether resin and the component containing a C=C unsaturated bond are fully cured to form a cured product with high crosslinking density and excellent interface consistency. The cured product of the resin composition has excellent dielectric properties, low dielectric loss tangent Df, good dielectric stability, and a small change in ΔDf (10GHz) after HAST.

[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 △Df (10GHz) after HAST is small, the change range of Df after HAST (△Df)≤0.00014, and the chemical copper bonding force after Desmear treatment is ≥0.42N / cm. It can be used as an insulating layer and fully meets the performance requirements of preparing high-frequency and high-speed printed circuit boards by semi-additive method or additive method. DETAILED DESCRIPTION

[0123] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0124] Preparation Example 1

[0125] A benzocyclobutene-modified polyphenylene ether resin PPO-BCB1, the preparation method is as follows:

[0126] (1) Dissolve dihydroxy-terminated polyphenylene ether (SA90, purchased from Sabic) (1 mol) in toluene, add sodium methoxide (0.1 mol), 4-bromobenzocyclobutene (2.2 mol), and cuprous chloride (0.1 mol) again, and react at 110°C for 10 h. After cooling, the reactant is filtered and then rotary evaporated to obtain a solid, which is recrystallized with 5 times the weight of anhydrous ethanol and vacuum dried at 50°C for 24 h to obtain a purified benzocyclobutene-modified polyphenylene ether resin PPO-BCB1, whose weight average molecular weight is measured to be 2100 and whose structure is as follows.

[0127]

[0128] Preparation Example 2

[0129] A modified filler, which is silicon dioxide (spherical silicon powder, D 50 0.63 μm, SO-C1, Japan Admatechs Co., Ltd.), the specific preparation method is as follows:

[0130] 100 parts by mass of spherical silicon powder were placed in a mixer, and 2 parts of vaporized KBM-1403 were sprayed into the mixer under stirring. The mixture was reacted for 10 minutes under stirring to obtain a modified filler, which was recorded as F1.

[0131] Preparation Example 3

[0132] A modified filler, which is silicon dioxide (spherical silicon powder, D50 0.5 μm, SO-C2, Japan Admatechs Co., Ltd.), the specific preparation method is as follows:

[0133] 100 parts by mass of spherical silicon powder were placed in a mixer, into which 2 parts of vaporized KBE-503 were sprayed under stirring, and the mixture was reacted for 10 minutes under stirring to obtain a modified filler, which was recorded as F2.

[0134] Preparation Example 4

[0135] A modified filler, which is silicon dioxide (spherical silicon powder, D 50 0.5 μm, SO-C2, Japan Admatechs Co., Ltd.), the specific preparation method is as follows:

[0136] 100 parts by mass of spherical silicon powder were placed in a mixer, into which 0.1 parts of vaporized X-12-1281C were sprayed under stirring, and the mixture was reacted for 10 minutes under stirring to obtain a modified filler, which was recorded as F3.

[0137] Preparation Example 5

[0138] A modified filler, which is silicon dioxide (spherical silicon powder, D 50 0.5 μm, SO-C2, Japan Admatechs Co., Ltd.), the specific preparation method is as follows:

[0139] 100 parts by mass of spherical silicon powder were placed in a mixer, into which 5 parts of vaporized KBE-1003 were sprayed under stirring, and the mixture was reacted for 10 minutes under stirring to obtain a modified filler, which was recorded as F4.

[0140] Comparative Preparation Example 1

[0141] A modified filler, which is silicon dioxide (spherical silicon powder, D 50 0.5 μm, SO-C2, Japan Admatechs Co., Ltd.), the specific preparation method is as follows:

[0142] 100 parts by mass of spherical silicon powder were placed in a mixer, into which 2 parts of vaporized KBM-573 were sprayed under stirring, and the mixture was reacted for 10 minutes under stirring to obtain a modified filler, which was recorded as F5.

[0143] In the following specific implementation 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 The Dow Chemical Company, has the following structure:

[0148]

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

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

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

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

[0153] 3.2 The group containing C=C unsaturated bond is vinyl (CH resin)

[0154] B3000, polybutadiene, Nippon Soda Co., Ltd.;

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

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

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

[0158] OPE-2ST, PPO containing terminal vinylphenyl groups, Mitsubishi Chemical Corporation.

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

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

[0161] 4. Initiator

[0162] Tert-butylisopropylphenyl peroxide, BIPB.

[0163] 5. Filler

[0164] Modified fillers F1 to F4 provided in Preparation Examples 2-5;

[0165] The modified filler F5 provided in Comparative Preparation Example 1.

[0166] 6. Flame retardant

[0167] SYTELX 8010, Albemarle, USA.

[0168] Example 1

[0169] A resin composition comprises the following components by mass: 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 and a printed circuit board (build-up printed circuit board) comprising the resin composition, the preparation method of which is as follows:

[0171] (1) Mixing the components of the resin composition with toluene according to the above formula to prepare a resin glue solution with a solid content of 65%; coating the resin glue solution on a release film, drying it, and baking it in an oven at 120° C. for 5 minutes to obtain a resin film with a semi-cured resin layer having a thickness of 40 μm;

[0172] (2) The resin film obtained in step (1) and the browned PCB board are pressed and cured at a curing temperature of 100° C., a pressure of 0.5 MPa, and a time of 1 min. The release film is removed and the surface is treated and copper electroplated to form a laminated printed circuit board with circuits.

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

[0174] (1) HAST test

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

[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 measured using the Split Post Dielectric Resonator (SPDR) method.

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

[0179] Take the above-mentioned sample with tested Df, and after HAST treatment, use SPDR method to measure the dielectric loss tangent Df of the resin film at 10GHz;

[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 deposition, electroplating and post-curing treatments: soaked in chemical copper solution (MVTP1, ATOTECH) for 20 min—electroplated copper with a thickness of 25 μm—cured in an oven at 200°C for 60 min, and the chemical copper bonding strength of the resin film was tested 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, a resin film and a laminated printed circuit board comprising the same, which differ from Example 1 in that the formula of the resin composition is different, as shown in Table 1; wherein the dosage unit of each component is "part"; the preparation method and performance testing method of the resin film and the laminated printed circuit board are the same as those in Example 1.

[0186] Table 1

[0187]

[0188]

[0189] Combined with the above performance test data, it can be seen that the present invention compounds the benzocyclobutene-modified polyphenylene ether resin, the component containing the C=C unsaturated bond and the inorganic filler surface-treated with the double bond group coupling agent in specific parts, and the obtained resin composition and the resin film containing the same have excellent dielectric properties, can still maintain a low dielectric loss tangent Df after HAST, and have good reliability. The formed resin film has a high bonding strength (chemical copper bonding strength) with the metal layer after Desmear (drill removal) treatment, Df is 0.00196-0.00221, △Df is 0.00010-0.00014, and the chemical copper bonding strength is 0.42-0.51N / cm, which fully meets the performance requirements of preparing high-frequency and high-speed printed circuit boards by semi-additive method or addition method.

[0190] In Comparative Example 1, an inorganic filler surface treated with an aminosilane coupling agent is used. The inorganic filler surface has no double bond groups and cannot play a bridging role at the interface between the unsaturated organic resin system and the inorganic filler. The filler and the resin interface crosslinking density in the obtained resin composition is low, and it is difficult to maintain low dielectric loss after HAST. The △Df after HAST is as high as 0.00081. In Comparative Example 2, other benzocyclobutene derivatives are used to replace the benzocyclobutene modified polyphenylene ether resin, and the obtained thermosetting resin composition has poor dielectric properties, and the dielectric loss tangent is as high as 0.00227. In Comparative Example 3, directly using double-terminal hydroxyl polyphenylene ether and 4-bromobenzocyclobutene physical mixing, and then adding the same other components as in Example 1, since benzocyclobutene is not grafted into the double-terminal hydroxyl polyphenylene ether, 4-bromobenzocyclobutene is basically volatilized during the heating precuring process, which leads to the deterioration of the dielectric properties of Comparative Example 3, and Df is as high as 0.00311.

[0191] The applicant declares that the present invention uses the above embodiments to illustrate the resin composition, the resin film and the printed circuit board containing the same, 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 improvement of the present invention, equivalent replacement of the raw materials of the product 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 mass: The modified filler is an inorganic filler that has been surface-treated with a coupling agent containing a double bond group.

2. The resin composition according to claim 1, characterized in that The benzocyclobutene-modified polyphenylene ether resin is prepared by reacting a double-terminated hydroxyl polyphenylene ether having a structure shown in formula I with a halogenated benzocyclobutene having a structure shown in 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 or branched alkyl; X is selected from Any one of the following; the dotted line represents the attachment site of the group; R 31 , R 32 Each independently represents 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 or branched alkyl; n1 and n2 are each independently selected from an integer greater than 0; Hal is selected from any one of the halogens; Preferably, 2≤n1+n2≤30; Preferably, the molar ratio of the double-terminated hydroxyl polyphenylene ether to the halogenated benzocyclobutene is 1:(2.1-2.5); Preferably, the weight average molecular weight of the benzocyclobutene-modified polyphenylene ether resin is 1500-20000.

3. The resin composition according to claim 1 or 2, characterized in that The component containing C=C unsaturated bonds includes small molecule compounds containing C=C unsaturated bonds and / or resins containing C=C unsaturated bonds; Preferably, the group containing a C=C unsaturated bond includes any one of vinyl, vinylphenyl, vinylbenzyl, allyl, (meth)acrylate, isopropenyl, and maleimide, or a combination of at least two thereof; Preferably, 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, styrene-butadiene-styrene triblock copolymer, multifunctional vinyl aromatic polymer, vinyl alicyclic polymer, allyl compound, multifunctional vinyl compound, maleimide compound; Preferably, the unsaturated polyphenylene ether is a polyphenylene ether having a terminal group containing a C=C unsaturated bond; Preferably, the allyl compound includes any one of triallyl isocyanurate, trimethallyl isocyanate, triallyl cyanurate, triallyl polyisocyanurate, triallyl cyanurate, and diallyl phthalate, or a combination of at least two thereof; Preferably, the multifunctional vinyl compound includes any one of divinylbenzene, 1,2-bis(p-vinylphenyl)ethane, and multifunctional (meth)acrylate, or a combination of at least two thereof.

4. The resin composition according to any one of claims 1 to 3, characterized in that The double bond group in the double bond group-containing coupling agent includes any one of vinyl, styrene, acryloxy, methacryloxy, and polybutadiene groups, or a combination of at least two thereof; Preferably, the double bond group-containing coupling agent includes any one of a vinyl-containing silane coupling agent, a styrene-containing silane coupling agent, an acryloxy-containing silane coupling agent, a methacryloxy-containing silane coupling agent, a butadiene polymer-modified silane coupling agent, and a styrene-butadiene polymer-modified silane coupling agent, or a combination of at least two thereof; Preferably, based on the mass of the inorganic filler being 100%, the mass of the coupling agent containing a double bond group is 0.1-5.0%; Preferably, the inorganic filler includes any one of silicon dioxide, titanium dioxide, zinc oxide, aluminum hydroxide, aluminum oxide, magnesium oxide, magnesium hydroxide, calcium carbonate, aluminum nitride, boron nitride, aluminum silicon carbide, silicon carbide, zirconium oxide, mica, boehmite, calcined talc, talc, silicon nitride, strontium titanate, barium titanate, and calcined kaolin, or a combination of at least two thereof; Preferably, the median particle size of the inorganic filler is 0.01-10 μm.

5. The resin composition according to any one of claims 1 to 4, characterized in that The initiator includes any one of an organic peroxide, an azo initiator, and a carbon-based free radical initiator, or a combination of at least two thereof; Preferably, the initiator includes any one of tert-butyl isopropylphenyl peroxide, dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne, 1,1-di(tert-butylperoxy)-3,3,5-dimethylcyclohexane, dicumyl, and polydicumyl, or a combination of at least two thereof.

6. The resin composition according to any one of claims 1 to 5, characterized in that The resin composition further comprises 1-50 parts by mass of a flame retardant; Preferably, the flame retardant includes any one of a halogen flame retardant, a nitrogen flame retardant, a phosphorus flame retardant, and a metal hydroxide flame retardant, or a combination of at least two thereof.

7. A resin film, characterized in that: The material of the resin film includes the resin composition according to any one of claims 1 to 6.

8. The resin film according to claim 7, characterized in that The resin film is obtained by coating the resin composition on a release material and then drying and / or semi-curing the resin film; Preferably, the resin film has a thickness of 10-100 μm.

9. A resin-coated copper foil, characterized in that: The resin-coated copper foil comprises a copper foil layer and a resin layer, and the material of the resin layer comprises the resin composition according to any one of claims 1 to 6.

10. A printed circuit board, characterized in that: The printed circuit board includes at least one of the resin film according to claim 7 or 8 and the resin-coated copper foil according to claim 9.

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