A benzocyclobutene resin, a resin composition containing the same, and applications thereof

Abstract

The present invention provides a benzocyclobutene resin, a resin composition containing the same, and their applications. The benzocyclobutene resin contains at least one first structural unit and at least one second structural unit. The first structural unit has a structure shown in Formula I, and the second structural unit has a structure shown in Formula IIA and / or Formula IIB. The benzocyclobutene resin has a fully hydrocarbon structure. Through the design of the polymer structure, it has a sufficiently low dielectric constant Dk and dielectric loss tangent Df, small polarity, low water absorption rate, and has good thermal curing activity, crosslinking efficiency, and crosslinking density. The benzocyclobutene resin has a high glass transition temperature, excellent dielectric properties, heat resistance, and moisture and heat resistance, and at the same time has high modulus and mechanical properties, and excellent processability, and can fully meet the various performance requirements of high-frequency and high-speed PCBs for resin materials.

Description

Technical Field

[0001] The invention belongs to the technical field of communication materials, and in particular relates to a benzocyclobutene resin, a resin composition containing the same and applications thereof. Background Art

[0002] With the development of science and technology and the progress of society, people have put forward higher and higher requirements for communication speed and quality. The 6G technology currently under development will use the terahertz (THz) or submillimeter frequency band, and its transmission capacity will be 100 times higher than that of 5G. With the increase of communication frequency, the requirements for printed circuit boards (PCBs) have also increased, mainly including lower dielectric loss tangent Df, lower dielectric constant Dk, higher reliability, higher heat resistance and lower thermal expansion coefficient CTE. For a long time, the industry has studied thermosetting polyphenylene ether resins, bismaleimide resins, vinyl benzyl ether resins, hydrocarbon resins, etc. with good dielectric properties. The current mass-produced PCBs mainly use composite thermosetting resins containing terminal vinyl polyphenylene ether and triallyl isocyanurate (TAIC). Although it has excellent mechanical properties and heat resistance, due to the polar groups contained in TAIC, Dk and Df cannot meet the requirements of the next generation of communication technology. In order to further improve the dielectric properties, researchers are committed to developing new low-dielectric material systems. Studies have shown that reducing the polarizability of molecules in the material and increasing the porosity are effective means to obtain low dielectric properties. For example, polypropylene and polystyrene have lower Dk and Df; however, the heat resistance of polypropylene and polystyrene is far from meeting the requirements of PCB.

[0003] In recent years, there is a clear trend towards miniaturization and high-density installation methods in electronic equipment such as communications, daily life, and industry. Along with this, printed circuit boards also need to be pressed multiple times to form high-density, high-layer printed circuit boards. The raw material of high-layer printed circuit boards, copper clad laminates, needs to have higher heat resistance, better dimensional stability, and lower thermal expansion coefficients. The above properties are also key indicators for screening resin materials.

[0004] The manufacturing process of integrated circuits requires temperatures above 400°C, and the temperature required in the subsequent processing is even higher. The copper wiring process can be carried out by electroplating or chemical reduction, which can be completed below 250°C, but in order to ensure that the copper deposition is dense and pore-free, annealing treatment is required at 400-450°C. Therefore, the material is required to have excellent heat resistance and a very high glass transition temperature. Although the heat resistance of polyimide and polybenzoxazine can meet the requirements, in order to obtain lower Dk and Df, it is imperative to design and develop new high-heat-resistant resin materials with all-carbon hydrogen structures.

[0005] Dow Chemical Company once launched SiLK resin with a fully hydrocarbon structure, which contains phenylacetylene groups, has an extremely low dielectric constant (Dk is 2.65), and a glass transition temperature as high as 490 °C. However, the synthesis cost of this material is high and its mechanical properties cannot meet the requirements.

[0006] Benzocyclobutene is another type of thermosetting resin with a fully hydrocarbon structure. Due to its excellent heat resistance, mechanical properties, extremely low dielectric loss, extremely low dielectric constant, and relatively low cost, it has gradually become a new generation of high-performance electronic materials and is expected to be applied in the high-end microelectronics field. Benzocyclobutene itself has a relatively low boiling point, about 150 °C, and is a volatile liquid. It is generally prepared as a derivative for use. Benzocyclobutene can react with vinyl at high temperatures to form a cyclohexane structure, or dimerize into a cyclooctane structure at higher temperatures, thereby achieving relatively high heat resistance. The derivatives of benzocyclobutene are also small molecules, generally containing more than two benzocyclobutene functional groups, so that they can further form polymers under high-temperature conditions. There are several benzocyclobutene derivatives initially developed by researchers as follows: (1) Through the Heck coupling reaction of 4-bromobenzocyclobutene and tetramethyldivinyldisiloxane, a siloxane-containing dibenzocyclobutene is obtained; (2) 4-bromobenzocyclobutene and resorcinol are used to prepare a bis-benzocyclobutene derivative containing a phenyl ether and naphthoic acid structure through an etherification reaction catalyzed by copper chloride; (3) 4-bromobenzocyclobutene and phenylboronic acid are used for the Suzuki coupling reaction to prepare a fully hydrocarbon structure derivative; (4) Through the Heck coupling reaction of divinylbenzene and benzocyclobutene, a fully hydrocarbon structure derivative is prepared. However, the above-mentioned benzocyclobutene derivatives all have some defects that cannot be ignored, making it difficult for them to meet the usage requirements of PCBs. For example, (1) and (2) contain siloxane or phenol groups. Since they are not fully hydrocarbon structures, it is difficult to obtain a low dielectric; the phenylboronic acid in (3) has a relatively high cost, and the residual polar boric acid or boric acid end groups will cause a decrease in dielectric properties, thus sacrificing the original dielectric advantage of the benzocyclobutene material; the raw material divinylbenzene in (4) can undergo free radical polymerization at room temperature, easily generating by-products, resulting in difficulties in mass production.

[0007] Therefore, developing a resin material with excellent dielectric properties, heat resistance, mechanical properties, processability and easy to achieve mass production to meet the application requirements of PCBs is an urgent problem to be solved in this field. Summary of the Invention

[0008] In view of the deficiencies of the prior art, the purpose of the present invention is to provide a benzocyclobutene resin, a resin composition containing the same, and their applications. The benzocyclobutene resin has a fully hydrocarbon structure, and can simultaneously meet the requirements of low dielectric constant, low dielectric loss tangent, excellent thermal stability, moisture and heat resistance, high modulus, and excellent processability. Moreover, the preparation method is simple, easy to mass-produce, and the chemical properties are stable, fully meeting the performance requirements of high-frequency and high-speed PCBs for resin materials.

[0009] To achieve the purpose of this invention, the following technical solutions are adopted:

[0010] In the first aspect, the present invention provides a benzocyclobutene resin, which comprises at least one first structural unit and at least one second structural unit; the first structural unit has the structure shown in Formula I:

[0011]

[0012] In Formula I, R 1 is vinyl, ethyl, and / or phenyl.

[0013] The second structural unit has the structure shown in Formula IIA and / or Formula IIB:

[0014]

[0015] In the benzocyclobutene resin provided by the present invention, the first structural unit is based on polybutadiene (R 1 is vinyl), hydrogenated polybutadiene (R 1 is ethyl), or butadiene-styrene copolymer (R 1 is vinyl and phenyl). The side chain of the second structural unit contains a benzocyclobutene structure and a benzene ring; the benzocyclobutene resin has a fully hydrocarbon structure, low polarity, low dielectric constant Dk and low dielectric loss tangent Df, and low water absorption. At the same time, the polymer chain contains easily reactive alkenyl and benzocyclobutene groups, which have high crosslinking efficiency and crosslinking density in the thermal curing reaction, and can obtain better dielectric properties after thermal curing. The main chain of the benzocyclobutene resin is a flexible carbon chain structure, and the side chain contains a benzene ring, a benzocyclobutene structure and an alkenyl. The specific polymer structure endows it with a high glass transition temperature, low water absorption, excellent dielectric properties, thermal stability and moisture and heat resistance, high modulus and good mechanical properties, and also has excellent processability, which can fully meet the performance requirements of high-frequency and high-speed PCBs for resins.

[0016] Preferably, the benzocyclobutene resin contains the first structural unit A shown in Formula IA, and the molecular structure contains easily reactive vinyl, which has good crosslinking activity and high crosslinking efficiency in the thermal curing reaction;

[0017]

[0018] Preferably, the benzocyclobutene resin comprises a first structural unit B having the structure shown in formula IB;

[0019]

[0020] Optionally, the first structural unit B can be obtained by hydrogenating the first structural unit A. It contains a saturated alkyl structural unit and has a low dielectric loss.

[0021] Preferably, the benzocyclobutene resin comprises a first structural unit C having the structure shown in formula IC, and its side chain contains a phenyl group, which has good compatibility with other resins:

[0022]

[0023] Preferably, the first structural unit of the benzocyclobutene resin may separately contain the first structural unit A (unhydrogenated), or may simultaneously contain the first structural unit A and the first structural unit B structure (partially hydrogenated), or may separately contain the first structural unit B (fully hydrogenated), or may simultaneously contain the first structural unit A and the first structural unit C structure (unhydrogenated), or may simultaneously contain the first structural unit A, the first structural unit B and the first structural unit C structure (partially hydrogenated), or may simultaneously contain the first structural unit B and the first structural unit C structure (fully hydrogenated).

[0024] Preferably, the mass percentage content of the second structural unit in the benzocyclobutene resin is ≥10%, for example, it can be 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is ≥30%, and further preferably 30 - 80%.

[0025] As a preferred technical solution of the present invention, the mass percentage content of the second structural unit in the benzocyclobutene resin is ≥30%. Thus, the benzocyclobutene resin has excellent dielectric properties, heat resistance, modulus and mechanical properties, as well as high thermal curing cross - linking reaction activity and cross - linking density. If the mass percentage content of the second structural unit containing the benzocyclobutene group is too low, the thermal curing reactivity of the benzocyclobutene resin will be reduced, the glass transition temperature and heat resistance will decrease, and the dielectric properties will also be affected; if the molar percentage content of the second structural unit is too high, not only will the synthesis difficulty and production cost of the resin increase, but also the flexibility of the benzocyclobutene resin will be reduced, the fluidity will be poor, and the processing performance will be affected.

[0026] Preferably, the benzocyclobutene resin further comprises a third structural unit having a structure represented by formula IIIA and / or formula IIIB:

[0027]

[0028] The third structural unit represented by formula IIIA and / or formula IIIB is a structural unit formed by 1,4-polymerization of butadiene.

[0029] Preferably, the benzocyclobutene resin further comprises a fourth structural unit which is a polybutadiene structural unit (the first structural unit A, ) and is a structural unit having a cyclic structure formed by polymerization.

[0030] It should be noted that the benzocyclobutene resin of the present invention has a polymer chain segment structure, including at least one (preferably multiple) first structural unit, at least one (preferably multiple) second structural unit, and optionally a third structural unit and optionally a fourth structural unit; the present invention does not limit the connection order of the above structural units, and any connection order / connection method feasible in chemistry is within the scope of the present invention.

[0031] Preferably, the number-average molecular weight of the benzocyclobutene resin is 1,000 - 200,000, for example, it can be 2,000, 5,000, 8,000, 10,000, 12,000, 15,000, 20,000, 50,000, 80,000, 100,000, 120,000, 150,000 or 180,000, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the above range.

[0032] Exemplarily, the preparation method of the benzocyclobutene resin includes: reacting a hydrocarbon resin with a benzocyclobutene monomer to obtain the benzocyclobutene resin; the hydrocarbon resin is polybutadiene or a butadiene-styrene copolymer, which contains a structural unit of 1,2-polymerization of butadiene

[0033] Preferably, the reaction is carried out in the presence of an organic peroxide.

[0034] Preferably, the organic peroxide includes any one or a combination of at least two of tert-butyl isopropyl phenyl 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-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane.

[0035] Preferably, the temperature of the reaction is 80 - 130 °C, for example, it can be 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C or 125 °C, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0036] Preferably, the reaction time is 4 - 16 h, for example, it can be 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, 13 h, 14 h or 15 h, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0037] As a preferred technical solution of the present invention, the benzocyclobutene resin is formed by reacting a hydrocarbon resin (polybutadiene or butadiene - styrene copolymer) with a benzocyclobutene monomer (4 - bromobenzocyclobutene - modified styrene). Its chemical properties are stable and it does not require the addition of a polymerization inhibitor for storage; moreover, the preparation process is simple, the yield is high, and the side reactions are few, which is suitable for mass production.

[0038] Preferably, the preparation of the benzocyclobutene resin further includes an optional hydrogenation reaction step. The hydrogenation reaction can be carried out before and / or after the above - mentioned reaction. The hydrogenation reaction can be complete hydrogenation (i.e., all C=C on the main chain and side chains of the benzocyclobutene resin are hydrogenated, preferably after the reaction) or partial hydrogenation (which can be carried out before or after the reaction). The hydrogenation reaction hydrogenates all or part of the C=C double bonds from the hydrocarbon resin (polybutadiene and / or styrene - butadiene copolymer) to form saturated carbon chains; thus, it helps to further optimize the dielectric properties of the benzocyclobutene resin.

[0039] In a second aspect, the present invention provides a resin composition, and the resin in the resin composition includes the benzocyclobutene resin as described in the first aspect.

[0040] It should be noted that the resin composition includes "resin", that is, the organic component, which can be understood as the component forming the continuous phase in subsequent applications; in the description herein, the benzocyclobutene resin, optionally a thermosetting material containing unsaturated groups, and optionally a thermoplastic resin all belong to "resin". The resin composition also includes "non - resin" components, including fillers, flame retardants, processing aids, etc.

[0041] Preferably, the mass percentage content of the benzocyclobutene resin in the resin is 5 - 100%, for example, it can be 8%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0042] Preferably, the resin further comprises a thermosetting material containing unsaturated groups.

[0043] In the present invention, the resin in the resin composition may be used alone as a benzocyclobutene resin or may be used in combination with other thermosetting materials containing unsaturated groups (groups with C=C double bonds), and can be used as a substrate for next-generation communication devices.

[0044] Preferably, the mass percentage content of the thermosetting material containing unsaturated groups in the resin is ≤95%, for example, it can be 0, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range, and further preferably ≤90%.

[0045] Preferably, the unsaturated groups include at least one of vinyl, vinylphenyl, vinylbenzyl, allyl, (meth)acrylate group or isopropenyl.

[0046] In the present invention, the (meth)acrylate group includes acrylate group and / or methacrylate group.

[0047] In the present invention, the thermosetting material containing unsaturated groups can be a resin (polymer) containing unsaturated groups and / or a small molecule compound containing unsaturated groups.

[0048] Preferably, the thermosetting material containing unsaturated groups includes any one or a combination of at least two of polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene triblock copolymer, unsaturated polyphenylene ether resin, maleimide compound, vinyl aromatic polymer, vinyl alicyclic polymer, allyl compound, multifunctional vinyl compound.

[0049] In the present invention, in polybutadiene, styrene-butadiene copolymer, styrene-butadiene-styrene triblock copolymer as thermosetting materials, all contain crosslinkable active group C=C, and it can be 1,2-vinyl based on butadiene monomer

[0050] In the present invention, the styrene-butadiene copolymer can be a styrene-butadiene random copolymer and / or a styrene-butadiene block copolymer.

[0051] Preferably, the unsaturated polyphenylene ether resin includes a polyphenylene ether resin capped with unsaturated groups; the unsaturated groups therein can be any one or several of vinylbenzyl, vinylphenyl, acrylate group, methacrylate group.

[0052] Preferably, the vinyl aromatic polymer includes a polyfunctional vinyl aromatic polymer, and its polymerization monomers include a combination of a divinyl aromatic compound and a monovinyl aromatic compound.

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

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

[0055] In the present invention, the vinyl aromatic polymer can be obtained by market channels, for example, it can be ODV of Nippon Steel & Sumitomo Metal Corporation in Japan.

[0056] Preferably, the allyl compound includes any one or a combination of at least two of triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), poly(triallyl isocyanurate), triallyl cyanurate trimer, diallyl phthalate.

[0057] Preferably, the polyfunctional vinyl compound includes any one or a combination of at least two of trimethacrylic acid, divinylbenzene (DBV), polyfunctional acrylate, 1,2-bis(p-vinylphenyl)ethane (BVPE).

[0058] Preferably, the resin further includes a thermoplastic resin.

[0059] Preferably, the mass percentage content of the thermoplastic resin in the resin ≤ 90%, for example, it can be 0, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 75%, 80% or 85%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0060] Preferably, the thermoplastic resin includes a hydrogenated styrene-butadiene block copolymer (SEBS) and / or a thermoplastic polyphenylene oxide (PPO).

[0061] Preferably, the hydrogenated styrene-butadiene block copolymer includes unmodified SEBS and / or modified SEBS.

[0062] Preferably, the modified SEBS includes any one or a combination of at least two of maleic anhydride grafted SEBS, epoxy modified SEBS, amine modified SEBS, carboxyl modified SEBS.

[0063] Preferably, the resin composition further comprises an initiator. Since the benzocyclobutene groups in the benzocyclobutene resin in the resin composition provided by the present invention can be thermally ring-opened to achieve curing and crosslinking, the initiator is an optional component.

[0064] Preferably, based on 100 parts of the sum of the masses of the benzocyclobutene resin and the thermosetting material optionally containing unsaturated groups in the resin, the mass of the initiator is 0.1-3 parts, for example, it can be 0.2 parts, 0.5 parts, 0.8 parts, 1 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts or 2.8 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] 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.

[0066] 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.

[0067] Preferably, the resin composition further comprises a filler.

[0068] Preferably, in the resin composition, based on 100 parts by mass of the resin, the mass of the filler is 5-300 parts, for example, it can be 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 120 parts, 150 parts, 180 parts, 200 parts, 220 parts, 250 parts or 280 parts, as well as specific point values ​​between the above points. 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 5-200 parts are further preferred, and 5-150 parts are further preferred.

[0069] Preferably, the filler is an inorganic filler and / or an organic filler, and an inorganic filler is more preferred.

[0070] Preferably, 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.

[0071] Preferably, the inorganic filler includes any one or a combination of at least two of silica, aluminum hydroxide, alumina, talcum powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica.

[0072] Preferably, the silica may be any one or a combination of at least two of fused silica, crystalline silica, spherical silica, hollow silica.

[0073] Preferably, the organic filler includes any one or a combination of at least two of polyphenylene ether (powder and / or microspheres), polytetrafluoroethylene (powder), polyetheretherketone, polyphenylene sulfide, polyethersulfone (powder).

[0074] Preferably, the median particle size (D 50 ) of the filler is 0.01 - 50 μm, for example, it can be 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is 0.01 - 20 μm, and more preferably 0.01 - 10 μm.

[0075] Exemplarily, the particle size of the filler is measured by an MS3000 Malvern laser particle size analyzer.

[0076] Preferably, the filler includes a surface-treated filler.

[0077] Preferably, the surface treatment agent for the surface treatment includes any one or a combination of at least two of silane coupling agents, organosilicon oligomers, titanate coupling agents.

[0078] Preferably, based on 100 parts by mass of the filler to be treated, the mass of the surface treatment agent is 0.1 - 5 parts, for example, it can be 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts, and specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is 0.5 - 3 parts, and more preferably 0.75 - 2 parts.

[0079] Preferably, the resin composition further includes a flame retardant.

[0080] Preferably, based on 100 parts by mass of the resin in the resin composition, the mass of the flame retardant is 1-50 parts, for example, it can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts or 45 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0081] Preferably, the flame retardant includes any one or a combination of at least two of nitrogen-based flame retardants, halogen-based flame retardants (such as chlorine-containing flame retardants and / or bromine-containing flame retardants), phosphorus-based flame retardants, and metal hydroxide flame retardants.

[0082] Preferably, the resin composition further includes other additives, such as toughening agents and / or viscosity regulators, etc.

[0083] A solvent can also be added to the resin composition. The addition amount of the solvent is selected by those skilled in the art according to experience and process requirements to make the resin composition reach a suitable viscosity for coating, impregnating, processing, etc. of the resin composition. Subsequently, during the drying, semi-curing or full-curing process, the solvent in the resin composition will partially or completely volatilize.

[0084] As the solvent of the present invention, there is no particular limitation. Generally, ketones such as acetone, methyl ethyl ketone, 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 compounds 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, methyl ethyl ketone, and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene are preferred.

[0085] The resin composition provided by the present invention is prepared by the following method. The preparation method includes: mixing and dispersing the components in the resin composition evenly to obtain the resin composition.

[0086] In the third aspect, the present invention provides a resin film, and the material of the resin film includes the resin composition as described in the second aspect.

[0087] Preferably, the resin film is prepared by coating the resin composition on a release material and drying and / or semi-curing.

[0088] Preferably, the drying temperature and the semi-curing temperature are each independently 100-180°C. For example, they can be 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C or 175°C, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0089] Fourthly, the present invention provides a resin-coated copper foil, and the material of the resin-coated copper foil comprises the resin composition as described in the second aspect.

[0090] Preferably, the resin-coated copper foil is prepared by coating the resin composition on a copper foil and then drying and / or semi-curing.

[0091] Preferably, the drying temperature and the semi-curing temperature are each independently 100-180°C. For example, they can be 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C or 175°C, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0092] Fifthly, the present invention provides a prepreg, and the prepreg comprises a reinforcing material and the resin composition as described in the second aspect attached to the reinforcing material.

[0093] Preferably, the resin composition is attached to the reinforcing material after impregnation and drying.

[0094] Preferably, the raw material of the reinforcing material comprises any one or at least two combinations of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fibers; for example, fiberglass cloth, quartz fiberglass blended cloth, non-woven fabric, quartz cloth, fiber paper, wood pulp paper, etc.

[0095] Exemplarily, the preparation method of the prepreg is as follows: the reinforcing material is infiltrated with the resin solution of the resin composition, and then dried to obtain the prepreg.

[0096] Preferably, the drying temperature is 100-180°C. For example, it can be 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C or 175°C, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0097] Preferably, the drying time is 1 - 30 min, for example, it can be 2 min, 5 min, 8 min, 10 min, 15 min, 20 min or 25 min, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0098] In a sixth aspect, the present invention provides a metal foil clad laminate, which includes at least one of the resin film as described in the third aspect, the resin film as described in the fourth aspect, and the prepreg as described in the fifth aspect.

[0099] Preferably, the metal foil in the metal foil clad laminate includes any one or a combination of at least two of copper foil, aluminum foil, nickel foil, and alloy foil, and copper foil is further preferred.

[0100] When the metal foil is copper foil, the metal foil clad laminate is a copper clad laminate.

[0101] Preferably, the number of prepregs in the metal foil clad laminate is 1 - 20, for example, it can be 2, 3, 5, 7, 9, 10, 11, 13, 15, 17 or 19, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0102] Exemplarily, the preparation method of the metal foil clad laminate includes: laminating a metal foil on one side or both sides of a prepreg and curing to obtain the metal foil clad laminate; or, stacking at least two prepregs into a laminate, then laminating a metal foil on one side or both sides of the laminate and curing to obtain the metal foil clad laminate.

[0103] Preferably, the curing is carried out in a press.

[0104] Preferably, the curing temperature is 170 - 280 °C, for example, 180 °C, 190 °C, 200 °C, 210 °C, 220 °C, 230 °C, 240 °C, 250 °C, 260 °C or 270 °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 does not exhaustively list the specific point values included in the range.

[0105] Preferably, the curing pressure is 20 - 60 kg / cm 2 , for example, it can be 25 kg / cm 2 , 30 kg / cm 2 , 35 kg / cm 2 , 40 kg / cm 2 , 45 kg / cm 2 , 50 kg / cm 2 or 55 kg / cm2 , and the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the above range.

[0106] Preferably, the curing time is 60 - 300 min, such as 80 min, 100 min, 120 min, 150 min, 180 min, 200 min, 220 min, 240 min, 260 min or 280 min, and the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the above range.

[0107] Compared with the prior art, the present invention has the following beneficial effects:

[0108] (1) The benzocyclobutene resin provided by the present invention has a fully hydrocarbon structure. Through the design of the polymer structure, it has a sufficiently low dielectric constant Dk and dielectric loss tangent Df, small polarity, low water absorption rate, and has good thermal curing activity, crosslinking efficiency and crosslinking density. The benzocyclobutene resin has a high glass transition temperature, excellent dielectric properties, heat resistance and moisture and heat resistance, and at the same time has high modulus and mechanical properties, and excellent processability, which can fully meet the performance requirements of high-frequency and high-speed PCBs for resin materials.

[0109] (2) The benzocyclobutene resin can be prepared by reacting polybutadiene with a benzocyclobutene monomer with a specific structure. The preparation process is simple, the yield is high, the side reactions are few, and it is suitable for mass production; moreover, the chemical properties of the benzocyclobutene resin are stable and no inhibitor is required for storage.

[0110] (3) Through the design and optimization of the benzocyclobutene resin structure, the resin composition and copper clad laminate containing it have Dk ≤ 3.52, Df ≤ 0.0013 at 10 GHz, the glass transition temperature is 190 - 283 °C, the heat resistance at 300 °C > 60 min, can pass the PCT 6h test, the PCT water absorption rate ≤ 0.09%, and the peel strength is 0.48 - 0.86 N / mm, with excellent dielectric properties, heat resistance and moisture and heat resistance, and high interlayer bonding strength, fully meeting the use requirements of high-performance PCBs in the next-generation communication technology. Description of the Drawings

[0111] Figure 1 It is the infrared spectrum of the benzocyclobutene resin CH - BCBS3 provided in Example 3. Detailed Embodiments

[0112] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0113] In the following specific embodiments of the present invention, the specific information of the hydrocarbon resin and benzocyclobutene monomer used is as follows:

[0114] B1000, polybutadiene, the molar percentage content of the structural unit formed by 1,2-polymerization of butadiene ( the same below) is 85%, Nippon Soda Co., Ltd.;

[0115] B2000, polybutadiene, the molar percentage content of the structural unit formed by 1,2-polymerization is 88%, Nippon Soda Co., Ltd.;

[0116] B3000, polybutadiene, the molar percentage content of the structural unit formed by 1,2-polymerization is 92%, Nippon Soda Co., Ltd.;

[0117] BI3060, partially hydrogenated polybutadiene, the molar percentage content of the structural unit formed by 1,2-polymerization is 60%, Nippon Soda Co., Ltd.;

[0118] Ricon 154, polybutadiene, the molar percentage content of the structural unit formed by 1,2-polymerization is 90%, Sartomer Company, USA;

[0119] Ricon 184, butadiene-styrene copolymer (styrene-butadiene resin), the molar percentage content of the structural unit formed by 1,2-polymerization is 30%, and the molar percentage content of the styrene structural unit is 22%, Sartomer Company, USA;

[0120] Ricon 100, butadiene-styrene copolymer (styrene-butadiene resin), the molar percentage content of the structural unit formed by 1,2-polymerization is 70%, and the molar percentage content of the styrene structural unit is 22%, Sartomer Company, USA;

[0121] Benzocyclobutene monomer, BCBS, the structure is 4-bromobenzocyclobutene modified styrene, purchased from Wuhan Diesai New Materials.

[0122] Example 1

[0123] A benzocyclobutene resin CH-BCBS1, and its preparation method is as follows:

[0124] Weigh 70 g of polybutadiene B1000, 30 g of BCBS, and 80 mL of toluene in a flask, dissolve them into a homogeneous solution, and heat it to the reflux temperature in an argon atmosphere. Dissolve 0.5 g of tert-butyl isopropyl phenyl peroxide BIPB in 20 mL of toluene, then add it dropwise within 35 min, react at the toluene reflux temperature, monitor the reaction by TLC (thin layer chromatography) until the BCBS raw material spot disappears, stop the reaction, and cool to obtain benzocyclobutene resin CH-BCBS1, which can be used without separation.

[0125] Example 2

[0126] A benzocyclobutene resin CH-BCBS2, and its preparation method is as follows:

[0127] Weigh 60 g of polybutadiene B2000, 40 g of BCBS, and 80 mL of toluene in a flask, dissolve them into a homogeneous solution, and heat it to the reflux temperature in an argon atmosphere. Dissolve 0.5 g of BIPB in 20 mL of toluene, then add it dropwise within 30 min, react at the toluene reflux temperature, monitor the reaction by TLC column until the BCBS raw material spot disappears, stop the reaction, and cool to obtain benzocyclobutene resin CH-BCBS2, which can be used without separation.

[0128] Example 3

[0129] A benzocyclobutene resin CH-BCBS3, and its preparation method is as follows:

[0130] Weigh 50 g of polybutadiene B3000, 50 g of BCBS, and 80 mL of toluene in a flask, dissolve them into a homogeneous solution, and heat it to the reflux temperature in an argon atmosphere. Dissolve 0.5 g of BIPB in 20 mL of toluene, then add it dropwise within 40 min, react at the toluene reflux temperature, monitor the reaction by TLC column until the BCBS raw material spot disappears, stop the reaction, and cool to obtain benzocyclobutene resin CH-BCBS3, which can be used without separation.

[0131] Example 4

[0132] A benzocyclobutene resin CH-BCBS4, and its preparation method is as follows:

[0133] Weigh 90 g of partially hydrogenated polybutadiene BI3060, 10 g of BCBS, and 80 mL of toluene in a flask, dissolve them into a homogeneous solution, and heat it to the reflux temperature in an argon atmosphere. Dissolve 0.5 g of BIPB in 20 mL of toluene, then add it dropwise within 35 min, react at the toluene reflux temperature, monitor the reaction by TLC column until the BCBS raw material spot disappears, stop the reaction, and cool to obtain benzocyclobutene resin CH-BCBS4, which can be used without separation.

[0134] Example 5

[0135] A benzocyclobutene resin CH-BCBS5, and its preparation method is as follows:

[0136] Weigh 30 g of polybutadiene Ricon 154, 70 g of BCBS, and 80 mL of toluene in a flask, dissolve them into a homogeneous solution, and heat to the reflux temperature in an argon atmosphere. Dissolve 0.5 g of BIPB in 20 mL of toluene and then add it dropwise within 35 min. React at the toluene reflux temperature, monitor the reaction by TLC chromatographic column until the BCBS raw material spot disappears, stop the reaction, and cool to obtain the benzocyclobutene resin CH-BCBS5, which can be used without separation.

[0137] Example 6

[0138] A benzocyclobutene resin CH-BCBS6, and its preparation method is as follows:

[0139] Weigh 40 g of styrene-butadiene resin Ricon 184, 60 g of BCBS, and 80 mL of toluene in a flask, dissolve them into a homogeneous solution, and heat to the reflux temperature in an argon atmosphere. Dissolve 0.5 g of BIPB in 20 mL of toluene and then add it dropwise within 35 min. React at the toluene reflux temperature, monitor the reaction by TLC chromatographic column until the BCBS raw material spot disappears, stop the reaction, and cool to obtain the benzocyclobutene resin CH-BCBS6, which can be used without separation.

[0140] Example 7

[0141] A benzocyclobutene resin CH-BCBS7, and its preparation method is as follows:

[0142] Weigh 20 g of styrene-butadiene resin Ricon 100, 80 g of BCBS, and 80 mL of toluene in a flask, dissolve them into a homogeneous solution, and heat to the reflux temperature in an argon atmosphere. Dissolve 0.5 g of BIPB in 20 mL of toluene and then add it dropwise within 35 min. React at the toluene reflux temperature, monitor the reaction by TLC chromatographic column until the BCBS raw material spot disappears, stop the reaction, and cool to obtain the benzocyclobutene resin CH-BCBS7, which can be used without separation.

[0143] Structure characterization of the benzocyclobutene resin:

[0144] Use a Fourier transform infrared spectrometer (FTIR, IS10 FT-IR, Thermo Fisher) to perform structure characterization on the aforementioned benzocyclobutene resin. Among them, the infrared spectrum of the benzocyclobutene resin CH-BCBS3 provided in Example 3 is as Figure 1 shown. It can be seen from Figure 1 that at 1473 cm -1The characteristic absorption attributed to the benzocyclobutene four-membered ring indicates the presence of a benzocyclobutene structure in the CH-BCBS3 resin. The disappearance of the raw materials shown by the TLC chromatographic column indicates that benzocyclobutene has been incorporated into polybutadiene. At 1495 cm -1 The absorption of non-aromatic cyclic structures appears, indicating that there are double bonds forming rings in polybutadiene; however, the absorption of terminal double bonds at 905 cm -1 and 995 cm -1 is still very strong, indicating that the polybutadiene structure is partially polymerized.

[0145] The specific information of the benzocyclobutene resins provided in Examples 1-7 is summarized in Table 1; among them, the second structural unit (%) represents its mass percentage in the benzocyclobutene resin, which is calculated from the feed amount of BCBS and the mass of the hydrocarbon resin (since thin layer chromatography was used for detection during the preparation process to ensure complete reaction of BCBS, BCBS is completely converted into the second structural unit.

[0146] Table 1

[0147]

[0148] Comparative Preparation Example 1

[0149] The benzocyclobutene resin CH-BCB-D1 was synthesized by the method in Example 1 of the prior art CN107501459A, which is copolymerized from 4-vinylbiphenyl and 4-vinylbenzocyclobutene.

[0150] In the following specific embodiments of the present invention, the materials involved are as follows:

[0151] (1) Benzocyclobutene resin

[0152] The benzocyclobutene resins CH-BCB1 to CH-BCB7 provided in Examples 1-7;

[0153] CH-BCB-D1 provided by Comparative Preparation Example 1.

[0154] (2) Thermosetting materials containing unsaturated groups

[0155] Unsaturated polyphenylene ether resin (PPO), MX9000, SABIC Corporation, USA;

[0156] Polybutadiene, B3000, Nippon Soda Co., Ltd., Japan;

[0157] Styrene-butadiene resin, Ricon 100, Sartomer Company, USA;

[0158] Bismaleimide, BMI-70, Daiwa Kasei Kogyo Co., Ltd.;

[0159] Multifunctional vinyl aromatic polymer, ODV-XET, Nippon Steel Chemical Co., Ltd.;

[0160] 1,2-bis(p-vinylphenyl)ethane (BVPE), Shandong Xingshun;

[0161] Triallyl isocyanurate (TAIC), Hunan Fangruida.

[0162] (3) Thermoplastic resin

[0163] Hydrogenated styrene-butadiene block copolymer (SEBS), SEBS-MA, grade KIC19-023, Shanghai Kaiteng.

[0164] (4) Initiator

[0165] tert-Butyl isopropyl phenyl peroxide, BIPB, Hunan Fangruida.

[0166] (5) Filler

[0167] Silica, HM102YJ, Jiangsu Huimai.

[0168] (6) Flame retardant

[0169] SYTELX 8010, Albemarle Corporation, USA.

[0170] Application Example 1

[0171] A resin composition comprising the following components in parts by mass: 100 parts of benzocyclobutene resin CH-BCBS1.

[0172] A prepreg and a copper clad laminate comprising the resin composition are prepared as follows:

[0173] (1) Mix the resin composition with toluene according to the formulation amount to prepare a sizing solution with a solid content of 65%; impregnate 1035L of fiberglass cloth with the sizing solution, control the appropriate thickness, and then bake in an oven at 130 °C for 4 min to obtain a prepreg;

[0174] (2) Stack 10 prepregs, stack 18 μHVLP copper foils on both the upper and lower sides thereof, and cure at a temperature of 210 °C and a pressure of 30 kg / cm 2 for 120 min to obtain the copper clad laminate.

[0175] The performance of the copper clad laminate is tested as follows:

[0176] (1) Glass transition temperature Tg: Tested with a dynamic mechanical analyzer (DMA) Rheometric RSAIII;

[0177] (2) Dielectric constant Dk and dissipation factor Df: Measured using the split post dielectric resonator (SPDR) method with a Dielectric Analyzer HP Agilent E4991A at a frequency of 10 GHz;

[0178] (3) Peel strength PS: Tested in accordance with the IPC-TM-650 2.4.8C standard, the peel strength after thermal stress between the copper foil and the circuit carrier board;

[0179] (4) Damp heat resistance: PCT / 6h. Samples with a size of 100 mm × 100 mm are made from the board after etching the copper foil, three pieces. The board samples are steamed in a pressure cooker at 105 °C and 103.4 KPa for 360 min, and then tested by immersing in a 288 °C tin furnace to measure the delamination and explosion time. If it is less than 300 s, record the specific time; stop the test after reaching 5 min and record the time as > 300 s. ○ indicates that the sample did not delaminate or explode within 300 s and the damp heat resistance passed; × represents that the sample delaminated or exploded within 300 s and the damp heat resistance test did not pass;

[0180] (5) Heat resistance T300: Tested in accordance with the IPC-TM-650 2.4.24.1 standard to measure the heat resistance of the material;

[0181] (6) PCT water absorption (%) / 6h: Samples with a size of 100 mm × 100 mm are made from the board after etching the copper foil, three pieces. The board samples are steamed in a pressure cooker at 105 °C and 103.4 KPa for 360 min, and then the mass before and after PCT is measured. The change in mass after PCT / mass before PCT × 100% is the PCT water absorption;

[0182] The test results are shown in Table 2.

[0183] Application Examples 2 - 13, Comparative Examples 1 - 2

[0184] A resin composition, a prepreg containing the same, and a copper clad laminate, which are different from those in Application Example 1 in that the formulation of the resin composition is different, as specifically shown in Tables 2, 3, and 4; wherein, the dosage unit of each component is "parts", and "--" represents that the component is not added; the preparation methods and performance test methods of the prepreg and the copper clad laminate are the same as those in Application Example 1.

[0185] Table 2

[0186]

[0187]

[0188] Table 3

[0189]

[0190]

[0191]

[0192] Table 4

[0193]

[0194]

[0195] Combined with the foregoing performance test data, it can be seen that through the design and optimization of the benzocyclobutene resin structure, the resin composition and copper clad laminate containing it of the present invention have excellent dielectric properties, heat resistance and moisture and heat resistance, and at the same time have high modulus and mechanical properties, high peel strength, excellent processability, and can fully meet the performance requirements of high-frequency and high-speed PCBs for resin materials; specifically, the glass transition temperature Tg of the copper clad laminate is 190-283 °C, Dk at 10 GHz is 2.91-3.52, Df is 0.0005-0.0013, it can pass the PCT 6h test, the PCT water absorption rate is 0.05-0.09%, the heat resistance at 300 °C > 60 min, and the peel strength is 0.48-0.86 N / mm; moreover, the benzocyclobutene resin alone as the resin component of the resin composition makes the Dk of the copper clad laminate at 10 GHz 2.91-3.10 and Df 0.0005-0.0009, having outstanding dielectric property advantages.

[0196] The resin composition of Comparative Example 1 does not contain the benzocyclobutene resin defined in the present invention. Due to the high content of benzene ring structure in its structure, the dielectric property is poor. In Comparative Example 2, benzocyclobutene monomer is blended with polybutadiene. Since benzocyclobutene is not grafted into the polybutadiene resin, compared with Application Example 10, under the same process conditions, the bleeding is too large, resulting in skidding and unable to press out a normal board.

[0197] The applicant declares that the present invention uses the above embodiments to illustrate the benzocyclobutene resin, resin composition containing it and its application of the present invention, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvement to the present invention, equivalent substitution of the raw materials selected by 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 benzocyclobutene resin, characterized in that, the benzocyclobutene resin comprises at least one first structural unit and at least one second structural unit; the first structural unit has a structure as shown in Formula I: Formula I; R 1 is vinyl, ethyl and / or phenyl; the second structural unit has a structure as shown in Formula IIA and / or as shown in Formula IIB: Formula IIA; Formula IIB; the mass percentage content of the second structural unit in the benzocyclobutene resin is ≥ 30%.

2. The benzocyclobutene resin according to claim 1, characterized in that, the mass percentage content of the second structural unit in the benzocyclobutene resin is 30 - 80%.

3. The benzocyclobutene resin according to claim 1, characterized in that, the benzocyclobutene resin further comprises a third structural unit, and the third structural unit has a structure as shown in Formula IIIA and / or Formula IIIB: Formula IIIA; Formula IIIB.

4. The benzocyclobutene resin according to claim 1, characterized in that, the benzocyclobutene resin further comprises a fourth structural unit, and the fourth structural unit is a structural unit with a cyclic structure formed by polymerizing polybutadiene structural units.

5. The benzocyclobutene resin according to claim 1, characterized in that, the number-average molecular weight of the benzocyclobutene resin is 1000 - 200000.

6. A resin composition, characterized in that, the resin in the resin composition includes the benzocyclobutene resin according to any one of claims 1 - 5.

7. The resin composition according to claim 6, characterized in that, the mass percentage content of the benzocyclobutene resin in the resin is 5 - 100%.

8. The resin composition according to claim 6, characterized in that, the resin further includes a thermosetting material containing an unsaturated group.

9. The resin composition according to claim 8, characterized in that, the mass percentage content of the thermosetting material containing an unsaturated group in the resin is ≤ 95%.

10. The resin composition according to claim 9, characterized in that, the mass percentage content of the thermosetting material containing an unsaturated group in the resin is ≤ 90%.

11. The resin composition according to claim 8, characterized in that, the unsaturated group includes at least one of vinyl, vinylphenyl, vinylbenzyl, allyl, (meth)acrylate group or isopropenyl.

12. The resin composition according to claim 8, characterized in that, the thermosetting material containing an unsaturated group includes any one or a combination of at least two of polybutadiene, styrene-butadiene copolymer, unsaturated polyphenylene ether resin, maleimide compound, vinyl aromatic polymer, vinyl alicyclic polymer, allyl compound, multifunctional vinyl compound.

13. The resin composition according to claim 6, characterized in that, the resin further includes a thermoplastic resin.

14. The resin composition according to claim 13, characterized in that, the mass percentage content of the thermoplastic resin in the resin is ≤ 90%.

15. The resin composition according to claim 13, characterized in that, the thermoplastic resin includes a hydrogenated styrene-butadiene block copolymer and / or a thermoplastic polyphenylene ether.

16. The resin composition according to claim 6, wherein, the resin composition further comprises an initiator.

17. The resin composition according to claim 16, wherein, based on the sum of the masses of benzocyclobutene resin and optionally a thermosetting material containing an unsaturated group in the resin being 100 parts, the mass of the initiator is 0.1 - 3 parts.

18. The resin composition according to claim 16, wherein, the initiator comprises any one or a combination of at least two of organic peroxides, azo initiators, and carbon - based free - radical initiators.

19. The resin composition according to claim 16, wherein, the initiator comprises any one or a combination of at least two of tert - butyl isopropyl phenyl peroxide, dicumyl peroxide, benzoyl peroxide, 2,5 - dimethyl - 2,5 - bis(tert - butylperoxy)hexane, 2,5 - dimethyl - 2,5 - bis(tert - butylperoxy)hexyne, di - alpha - cumyl peroxide, and poly - di - alpha - cumyl peroxide.

20. The resin composition according to claim 6, wherein, the resin composition further comprises a filler.

21. The resin composition according to claim 20, wherein, based on the mass of the resin being 100 parts, the mass of the filler is 5 - 300 parts in the resin composition.

22. The resin composition according to claim 21, wherein, based on the mass of the resin being 100 parts, the mass of the filler is 5 - 200 parts in the resin composition.

23. The resin composition according to claim 20, wherein, the filler is an inorganic filler and / or an organic filler.

24. The resin composition according to claim 23, wherein, the filler is an inorganic filler.

25. The resin composition according to claim 23, wherein, the inorganic filler comprises any one or a combination of at least two of silica, aluminum hydroxide, alumina, talc powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, and mica.

26. The resin composition according to claim 23, wherein, the organic filler comprises any one or a combination of at least two of polyphenylene ether, polytetrafluoroethylene, polyetheretherketone, polyphenylene sulfide, and polyethersulfone.

27. The resin composition according to claim 20, wherein, the median particle size of the filler is 0.01 - 50 μm.

28. The resin composition according to claim 27, wherein, the median particle size of the filler is 0.01 - 20 μm.

29. The resin composition according to claim 20, wherein, the filler comprises a surface - treated filler.

30. The resin composition according to claim 29, wherein, the surface treatment agent for the surface treatment comprises any one or a combination of at least two of silane coupling agents, organosilicon oligomers, and titanate coupling agents.

31. The resin composition according to claim 30, wherein, Based on 100 parts by mass of the filler to be processed, the mass of the surface treatment agent is 0.1 - 5 parts.

32. The resin composition according to claim 6, wherein, the resin composition further comprises a flame retardant.

33. The resin composition according to claim 32, wherein, based on 100 parts by mass of the resin in the resin composition, the mass of the flame retardant is 1 - 50 parts.

34. A resin film, wherein, the material of the resin film comprises the resin composition according to any one of claims 6 - 33.

35. The resin film according to claim 34, wherein, the resin film is obtained by coating the resin composition on a release material and drying and / or semi-curing.

36. A resin-coated copper foil, wherein, the material of the resin-coated copper foil comprises the resin composition according to any one of claims 6 - 33.

37. The resin-coated copper foil according to claim 36, wherein, the resin-coated copper foil is obtained by coating the resin composition on a copper foil and drying and / or semi-curing.

38. A prepreg, wherein, the prepreg comprises a reinforcing material and the resin composition according to any one of claims 6 - 33 attached to the reinforcing material.

39. The prepreg according to claim 38, wherein, the resin composition is attached to the reinforcing material after impregnation and drying.

40. A metal foil-clad laminate, wherein, the metal foil-clad laminate comprises at least one of the resin film according to claim 34 or 35, the resin-coated copper foil according to claim 36 or 37, and the prepreg according to claim 38 or 39.

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