Resin composition, adhesive sheet and metal foil-clad laminate containing the same

Abstract

The present invention provides a resin composition and an adhesive sheet and a metal foil-clad laminate containing the same. The resin composition comprises the following components in parts by weight: 5 to 95 parts of silicon aryl acetylene resin and 5 to 95 parts of multifunctional vinyl aromatic polymer, based on the sum of the parts by weight of silicon aryl acetylene resin and multifunctional vinyl aromatic polymer as 100 parts. The resin composition significantly improves the processability through the compounding of specific polymers, and the cured product has high modulus, excellent dielectric properties and heat resistance, and low thermal expansion ratio, flame retardancy, dimensional stability and good bonding performance. The metal foil-clad laminate plate material containing the resin composition has a smooth and uniform appearance, excellent processability, heat resistance and dimensional stability, high peel strength, low dielectric constant and dielectric loss factor, and can fully meet the requirements of high-frequency circuit substrates in terms of processing and application performance.

Description

Technical Field

[0001] The invention belongs to the technical field of copper-clad laminates, and in particular relates to a resin composition and an adhesive sheet and a metal-clad laminate containing the same. Background Art

[0002] With the rapid development of electronic equipment towards miniaturization, multifunctionality and high performance, electronic materials and electronic components are required to have high precision, high density, high performance, thinness and multilayer performance. Printed Circuit Board (PCB) is one of the important components of the electronics industry and is an indispensable basic material for realizing electrical interconnection in electronic equipment. Metal foil-clad laminate is the base material board for preparing PCB, which has the functions of conducting, insulating and supporting in the whole PCB. The performance, quality, processability, manufacturing cost and long-term reliability of PCB depend to a large extent on the performance level of metal foil-clad laminate.

[0003] Metal foil laminate is a board made by impregnating glass fiber cloth and other reinforcing materials with resin glue, then covering one or both sides with metal foil and hot pressing. The most widely used resin glue is the epoxy resin system. The epoxy resin cured product has good heat resistance and insulation, and has good processability and cost advantages. However, the dielectric constant and dielectric loss of epoxy resin itself are relatively high, and a large amount of secondary hydroxyl groups will be generated after curing, which is easy to absorb water during use. The increase in water absorption rate leads to a decrease in the dielectric properties and moisture and heat resistance of the material, making it difficult to meet the use requirements of high-performance PCBs.

[0004] Polyolefin resin, also known as hydrocarbon resin, has good dielectric properties and can meet the requirements of metal foil-clad laminates in terms of low dielectric constant and low dielectric loss. Therefore, it is increasingly used in laminates. However, olefin polymers are mainly aliphatic carbon chains. Their flexibility and non-polar carbon chain structure cause the cured polyolefin resin to have insufficient rigidity, low strength, and unsatisfactory heat resistance and bonding properties. Therefore, it is difficult to use it alone, and polyolefin resin needs to be used in combination with other polymers.

[0005] CN111825943A discloses a resin composition for carbon-hydrogen copper-clad laminates, comprising the following raw materials by weight: 20-40 parts of polybutadiene, 10-20 parts of a mixture of nitrile-based resin and modified maleimide resin, 25-45 parts of a mixture of ceramic powder and volcanic ash, 15-40 parts of polydiene-styrene-ethylene terpolymer, 8-12 parts of a cross-linking agent, and 4-6 parts of a curing agent; the copper-clad laminate made of the resin composition for carbon-hydrogen copper-clad laminates has the advantages of controllable dielectric constant, low dielectric loss, high peel strength and good heat resistance. However, the compatibility of nitrile-based resin and modified maleimide resin with polyolefin resin is not good, and the problem of stratification or phase separation is prone to occur during the glue mixing process, which brings obstacles to the actual processing process and also affects the apparent uniformity of the plate.

[0006] CN108676209A discloses a hydrocarbon polymer copper-clad laminate composition, which comprises, by weight, 20 to 40 parts by weight of polybutadiene, 15 to 30 parts by weight of styrene-ethylene block copolymer, 15 to 25 parts by weight of polyphenylene ether, 5 to 10 parts by weight of a crosslinking agent, 3 to 5 parts by weight of a curing agent, and 20 to 40 parts by weight of an inorganic filler. The copper-clad laminate made of the composition has a lower dielectric constant and dielectric loss. CN106379006A discloses a high-frequency copper-clad laminate, comprising an insulating layer and a metal foil disposed on one or both sides of the insulating layer, the insulating layer comprising a resin composition and a reinforcing material (glass cloth or glass fiber paper), the resin composition comprising butadiene-styrene resin, polybutadiene resin, a crosslinking agent, and an initiator; the high-frequency copper-clad laminate has the properties of good heat resistance and low dielectric loss, and can meet the performance requirements of high-frequency plates. However, in the polyolefin system represented by the above-mentioned resin composition, the decomposition temperature of the initiator or curing agent is generally ≤150°C, resulting in the cross-linking reaction of olefin polymers such as polybutadiene resin at a relatively low temperature. The resin viscosity is too high, which is not conducive to lamination and bonding, and brings great difficulties to the process of bonding sheets and metal foil-clad laminates.

[0007] Therefore, developing a resin material with excellent processability, dielectric properties, heat resistance and mechanical properties to meet the processing and performance requirements of metal foil-clad laminates is a research focus in this field. Summary of the invention

[0008] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a resin composition and an adhesive sheet and a metal foil-clad laminate containing the same. The processability of the resin composition is significantly improved by compounding the components of a silicon aryl acetylene resin and a multifunctional vinyl aromatic polymer. The cured product thereof has a high modulus, excellent dielectric properties, heat resistance and dimensional stability, and can fully meet the requirements of high-frequency printed circuit boards in terms of processability and application performance.

[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, which comprises the following components in parts by weight: 5 to 95 parts of silicon aryl acetylene resin and 5 to 95 parts of multifunctional vinyl aromatic polymer, based on 100 parts of the sum of the parts by weight of silicon aryl acetylene resin and multifunctional vinyl aromatic polymer; the multifunctional vinyl aromatic polymer is copolymerized by divinyl aromatic compound and other vinyl compounds, and the molar proportion of the divinyl aromatic compound in the repeating units of the copolymer is greater than or equal to 15%.

[0011] The resin composition provided by the present invention comprises a combination of a silicon aryl acetylene resin and a multifunctional vinyl aromatic polymer. The silicon aryl acetylene resin has a very low melt viscosity before the curing reaction and can significantly improve the processability of the multifunctional vinyl aromatic polymer during the curing process. The two are synergistically compounded in a specific ratio so that the resin composition has excellent processability, and the cured product has a high modulus, excellent dielectric properties and heat resistance, and a low thermal expansion ratio, and good flame retardancy, dimensional stability and bonding performance, which fully meets the performance requirements of the printed circuit board for the resin composition.

[0012] In the resin composition provided by the present invention, the silicon aryl acetylene resin is 5 to 95 parts, for example, 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts or 92 parts, etc.

[0013] The multifunctional vinyl aromatic polymer is 5 to 95 parts, for example, 8, 10, 15, 20, 25, 30, 35, 40, 42, 45, 48, 50, 52, 55, 58, 60, 62, 65, 68, 70, 72, 75, 78, 80, 82, 85, 88, 90, 92 or 94 parts.

[0014] In the present invention, the silicon arylacetylene resin has a structure as shown in Formula I:

[0015]

[0016] In Formula I, n is selected from an integer of 1 to 50, for example, 1, 2, 3, 4, 5, 8, 10, 15, 18, 21, 25, 27, 30, 35, 38, 40, 43, 45, 48 or 50.

[0017] In formula I, R1 and R2 are each independently selected from hydrogen, C1-C6 straight or branched alkyl, and C3-C6 cycloalkyl.

[0018] The C1-C6 straight or branched alkyl group may be a straight or branched alkyl group of C1, C2, C3, C4, C5 or C6, illustratively including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl or n-hexyl, etc.

[0019] The C3-C6 cycloalkyl group may be a C3, C4, C5 or C6 cycloalkyl group, and illustratively includes but is not limited to: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

[0020] In formula I, Ar is selected from Dashed lines represent the attachment sites of the groups.

[0021] M is selected from a single bond, O, SO2, C1-C5 straight chain or branched alkylene; the "M is a single bond" means that two benzene rings are directly connected by a single bond to form a biphenyl structure.

[0022] The C1-C5 straight or branched alkylene group may be a C1, C2, C3, C4 or C5 straight or branched alkylene group, which may include but is not limited to methylene, ethylene, 1,2-ethylene, propylene or etc., and the dotted lines represent the attachment sites of the groups.

[0023] R3 and R4 are each independently selected from halogen (eg, fluorine, chlorine, bromine or iodine), C1-C5 (eg, C1, C2, C3, C4 or C5) straight chain or branched chain alkyl.

[0024] m1 and m3 are each independently selected from integers of 0 to 4, for example, 0, 1, 2, 3 or 4.

[0025] m2 is selected from an integer of 0 to 6, for example, 0, 1, 2, 3, 4, 5 or 6.

[0026] Preferably, R1 and R2 are each independently selected from C1-C5 (e.g., C1, C2, C3, C4 or C5) straight chain or branched alkyl groups, illustratively including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl or isopentyl, etc.

[0027] Preferably, Ar is

[0028] Preferably, the number average molecular weight of the silicon aryl acetylene resin is 200-8000, for example, 300, 500, 800, 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800, 3000, 3200, 3500, 3800, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500 or 7800, more preferably 400-4000, and even more preferably 500-3500.

[0029] In the present invention, the molecular weight (number average molecular weight, weight average molecular weight, etc.) is measured according to GB / T21863-2008 and is obtained by gel permeation chromatography (GPC) based on polystyrene calibration.

[0030] In the present invention, the silicon aryl acetylene resin can be prepared by combining an aryl acetylene compound HC≡C-Ar-C≡CH and a silane compound. The reaction is carried out in the presence of a Grignard reagent.

[0031] The multifunctional vinyl aromatic polymer is copolymerized by divinyl aromatic compounds and other vinyl compounds, and the molar proportion of divinyl aromatic compounds in the repeating units of the copolymer is greater than or equal to 15%, for example, it can be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90%, etc., with an upper limit of 90%. Exemplarily, the commercially available multifunctional vinyl aromatic polymer can be selected from ODV of Nippon Steel.

[0032] Preferably, the divinyl aromatic compound includes any one or a combination of at least two of divinylbenzene, divinylbiphenyl, divinylnaphthalene, diisopropenylbenzene, diisopropenylnaphthalene and diisopropenylbiphenyl. In the present invention, the above-mentioned divinyl aromatic compounds include all their isomers.

[0033] Wherein, the divinylbenzene includes any one of o-divinylbenzene, m-divinylbenzene or p-divinylbenzene, or a combination of at least two thereof.

[0034] The divinylbiphenyl includes any one of 4,4'-divinylbiphenyl, 4,3'-divinylbiphenyl, 4,2'-divinylbiphenyl, 3,2'-divinylbiphenyl, 3,3'-divinylbiphenyl, 2,2'-divinylbiphenyl or 2,4-divinylbiphenyl, or a combination of at least two thereof.

[0035] The divinylnaphthalene includes any one of 1,3-divinylnaphthalene, 1,4-divinylnaphthalene, 1,5-divinylnaphthalene, 1,8-divinylnaphthalene, 2,3-divinylnaphthalene, 2,6-divinylnaphthalene or 2,7-divinylnaphthalene, or a combination of at least two thereof.

[0036] The diisopropenylbenzene includes any one of 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene or 1,4-diisopropenylbenzene or a combination of at least two thereof.

[0037] The diisopropenylnaphthalene includes any one of 1,3-diisopropenylnaphthalene, 1,4-diisopropenylnaphthalene, 1,5-diisopropenylnaphthalene, 1,8-diisopropenylnaphthalene, 2,3-diisopropenylnaphthalene, 2,6-diisopropenylnaphthalene or 2,7-diisopropenylnaphthalene, or a combination of at least two thereof.

[0038] The diisopropenylbiphenyl includes any one of 4,4'-diisopropenylbiphenyl, 4,3'-diisopropenylbiphenyl, 4,2'-diisopropenylbiphenyl, 3,2'-diisopropenylbiphenyl, 3,3'-diisopropenylbiphenyl, 2,2'-diisopropenylbiphenyl or 2,4-diisopropenylbiphenyl, or a combination of at least two thereof.

[0039] Preferably, the multifunctional vinyl aromatic polymer comprises repeating unit a1 and / or repeating unit a2; the structure of the repeating unit a1 is

[0040] The structure of the repeating unit a2 is

[0041] Here, R5 and R6 are each independently an aromatic hydrocarbon group having 6 to 30 carbon atoms (e.g., 6, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26 or 28).

[0042] Preferably, the molar percentage of repeating units a1 in the multifunctional vinyl aromatic polymer is ≥10%, for example, it can be 12%, 15%, 18%, 20%, 25%, 28%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%, etc., and is further preferably ≥50%.

[0043] Preferably, the other vinyl compound includes but is not limited to any one or a combination of at least two of butadiene, isoprene, dicyclopentadiene, maleated diene, triallyl isocyanurate resin or monovinyl aromatic compound.

[0044] Illustratively, the other vinyl compounds can all be copolymerized with the divinyl aromatic compound in the form of monomers to obtain the multifunctional vinyl aromatic polymer; or a portion of the other vinyl compounds can be copolymerized first to form a polymer with a certain molecular weight (for example, to form a styrene-butadiene-styrene block copolymer), which is then copolymerized with the divinyl aromatic compound and the remaining vinyl compound (for example, dicyclopentadiene) to obtain the multifunctional vinyl aromatic polymer; or the other vinyl compounds can be copolymerized first to form a polymer with a certain molecular weight (for example, to form a styrene-butadiene-styrene block copolymer), which is then copolymerized with the divinyl aromatic compound to obtain the multifunctional vinyl aromatic polymer.

[0045] Preferably, the monovinyl aromatic compound includes any one of styrene, fluorene containing one vinyl group, naphthalene containing one vinyl group or biphenyl containing one vinyl group, or a combination of at least two thereof.

[0046] Preferably, the multifunctional vinyl aromatic polymer has a number average molecular weight of 1000 to 500000, for example, 1500, 2000, 2500, 3000, 35000, 4000, 4500, 5000, 6000, 8000, 10000, 20000, 30000, 40000, 50000, 70000, 90000, 100000, 150000, 200000, 250000, 300000, 350000, 400000 or 450000, etc.

[0047] Preferably, the multifunctional vinyl aromatic polymer comprises a combination of a low molecular weight polymer and a high molecular weight polymer; the number average molecular weight of the low molecular weight polymer is 1,000 to 10,000, and the number average molecular weight of the high molecular weight polymer is 100,000 to 500,000.

[0048] Preferably, the mass percentage of the high molecular weight polymer in the multifunctional vinyl aromatic polymer is 1 to 40%, for example, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35% or 38%, etc.

[0049] As a preferred technical solution of the present invention, the multifunctional vinyl aromatic polymer includes a combination of a low molecular weight polymer and a high molecular weight polymer; the polymers in the two molecular weight ranges cooperate with each other to achieve a good balance in the reaction activity, curing efficiency, dielectric properties, viscosity, fluidity and compatibility of the resin composition.

[0050] Silicon aryl acetylene resin tends to crystallize at room temperature, but the viscosity after melting at 120-140°C is very low. Therefore, when the resin composition contains too much silicon aryl acetylene resin, the resin fluidity will be too large and it is not easy to process. Too small a silicon aryl acetylene resin is difficult to form a stable network in the system, and it is difficult to exert its high modulus advantage. Preferably, the mass of the silicon aryl acetylene resin is 20-60 parts, such as 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, 48 ​​parts, 50 parts, 52 parts, 55 parts, 57 parts or 59 parts, etc., based on the sum of the weight parts of the silicon aryl acetylene resin and the multifunctional vinyl aromatic polymer as 100 parts.

[0051] Preferably, the resin composition further comprises 5 to 85 parts of a polyphenylene ether resin containing an unsaturated bond by weight. For example, the polyphenylene ether resin containing an unsaturated bond may be 6, 8, 10, 15, 20, 25, 30, 35, 40, 42, 45, 48, 50, 52, 55, 58, 60, 62, 65, 68, 70, 72, 75, 78, 80 or 82 parts, etc.

[0052] The unsaturated bonds in the polyphenylene ether resin containing unsaturated bonds may be on the end groups or side chains of the polyphenylene ether resin. The main chain structural formula of the polyphenylene ether resin containing unsaturated bonds is m is 8-100. The unsaturated bond-containing polyphenylene ether resin can be prepared by replacing the hydrogen atoms on the end groups or side chains of the low-molecular-weight polyphenylene ether resin with compounds containing unsaturated double bonds. The molecular weight of this type of resin affects its processing technology and the performance of the final cured product. The larger the molecular weight, the greater the viscosity of the resin or solution, the fewer reactive groups, and the worse the compatibility with other components; the smaller the molecular weight, the smaller the viscosity of the resin or solution, the more reactive groups, and the better the compatibility with other components, but too small a molecular weight will cause the dielectric properties and toughness of the cured product to be lost. The unsaturated bond-containing polyphenylene ether can be commercially available materials, for example, SABIC SA9000 (methacryloyl-terminated polyphenylene ether), OPE-2st (polyphenylene ether containing vinyl benzyl at the end) of Mitsubishi Chemical Corporation, etc.

[0053] Preferably, the number average molecular weight of the unsaturated bond-containing polyphenylene ether resin is 1000-7000, for example, 1200, 1500, 1800, 2000, 2200, 2500, 2800, 3000, 3200, 3500, 3800, 4000, 4200, 4500, 4800, 5000, 5500, 6000, 6500 or 6800, and more preferably 1000-4000.

[0054] Preferably, the resin composition further includes 0.01 to 10 parts of initiator by weight, for example, the initiator may be 0.03, 0.05, 0.08, 0.1, 0.3, 0.5, 0.8, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 7, 8 or 9 parts, etc.

[0055] Preferably, the initiator comprises any one of peroxides, azo compounds, dioxanes or polyoxanes, or a combination of at least two thereof.

[0056] Preferably, the peroxide comprises any one or a combination of at least two of diisopropyl peroxide, tert-butyl peroxide, di-tert-butyl peroxide, isopropyl peroxyt-butyl carbonate, 2,5-dimethyl-2,5-di-tert-butylperoxy-3-hexyne, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, p-menthane hydroperoxide, 1,1-bis(tert-amylperoxy)cyclohexane, diisopropyl hydroperoxide, benzoyl peroxide or a benzoyl peroxide derivative.

[0057] Preferably, the azo compound includes azobisisobutyronitrile.

[0058] Preferably, the resin composition further includes 5 to 60 parts of a crosslinking agent by weight, for example, the crosslinking agent may be 6, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, 32, 35, 38, 40, 45, 50, 55 or 58 parts, etc.

[0059] Preferably, the cross-linking agent is a compound having at least two (eg, 2, 3 or 4, etc.) unsaturated bonds in its molecular structure.

[0060] Preferably, the crosslinking agent includes any one or a combination of at least two of triallyl isocyanurate, triallyl polyisocyanurate, triallyl cyanurate, diallyl phthalate, a multifunctional methacrylate compound having two or more methacryloyl groups in the molecule, biphenyl containing at least two double bonds, dicyclopentadiene, a naphthalene compound containing at least two double bonds, p,p'-divinyl-1,2-diphenylethane or divinylbenzene.

[0061] Preferably, the resin composition further includes 10 to 80 parts of flame retardant by weight, for example, the flame retardant may be 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts or 78 parts, etc.

[0062] Preferably, the flame retardant includes any one of a halogen flame retardant, a phosphorus flame retardant or a nitrogen flame retardant, or a combination of at least two thereof.

[0063] The present invention is not particularly limited to the flame retardant, and the flame retardant with flame retardant effect can be applied to the resin composition. Exemplarily, the flame retardant includes decabromodiphenylethane, decabromodiphenylethylene, divinyl phenylphosphonate, diallyl phenylphosphonate, di(1-butenyl)phenylphosphonate, phenyl diphenylphosphonate, methyl diphenylphosphonate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and its derivatives, bis(2-allylphenoxy)phosphazene, dimethylphenolphosphazene, melamine phosphate, melamine pyrophosphate or polyphosphate melamine. Any one or a combination of at least two.

[0064] Preferably, the resin composition further comprises 5 to 120 parts of inorganic filler by weight, for example, the inorganic filler may be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts or 145 parts, etc.

[0065] Preferably, the inorganic filler includes any one of silicon dioxide, silicon powder, aluminum oxide, titanium dioxide, mica, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate or silicon carbide, or a combination of at least two thereof.

[0066] The shape of the inorganic filler is not particularly limited, and may be spherical, angular, sheet-shaped, or hollow, and is preferably spherical.

[0067] Preferably, the particle size of the inorganic filler is 0.01 to 30 μm, such as 0.02 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.5 μm, 0.5 μm, 0.8 μm, 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 18 μm, 20 μm, 22 μm, 25 μm or 28 μm, and more preferably 0.1 to 15 μm. The particle size is measured by Malvern 2000 laser particle size analyzer.

[0068] As a preferred technical solution of the present invention, the particle size of the inorganic filler is 0.01 to 30 μm, which can make the resin composition have good fluidity, processing formability, mechanical properties, bonding properties and reliability. If the particle size of the inorganic filler is less than 0.01 μm, the fluidity of the resin composition will decrease, making its formability worse when making bonding sheets and metal foil-clad laminates, and easily generating voids; if the particle size of the inorganic filler is greater than 30 μm, the surface area of ​​the inorganic filler becomes larger, which reduces the bonding area between the metal foil and the resin, thereby causing the peel strength of the printed circuit board to decrease, and the insulation reliability of the wiring room or the insulation layer to decrease.

[0069] Preferably, the resin composition further comprises 0.01 to 7 parts of a silane coupling agent by weight, for example, the silane coupling agent may be 0.03, 0.05, 0.08, 0.1, 0.3, 0.5, 0.8, 1, 1.2, 1.5, 1.8, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6 or 6.5 parts, etc.

[0070] The present invention does not particularly limit the type of silane coupling agent, but vinyl silane and / or allyl silane are preferred, and are mainly used to promote the dispersion of inorganic fillers and / or inorganic flame retardants.

[0071] Illustratively, the preparation method of the resin composition may be: uniformly mixing the components in the resin composition with a solvent to obtain the resin composition; preferably, the solid may be put in first, and then the solvent is added, and stirred until the solid is completely dissolved, and then the liquid resin and curing accelerator are added, and the stirring is continued until uniform.

[0072] The solvent is not particularly limited, and includes any one or a combination of at least two of alcohol solvents, ether solvents, aromatic hydrocarbon solvents, ester solvents, ketone solvents or nitrogen-containing solvents. Among them, the alcohol solvent includes any one or a combination of at least two of methanol, ethanol or butanol; the ether solvent includes any one or a combination of at least two of ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol or butyl carbitol; the aromatic hydrocarbon solvent includes any one or a combination of at least two of benzene, toluene, xylene or mesitylene; the ester solvent includes any one or a combination of at least two of ethyl acetate, butyl acetate, methoxyethyl acetate, ethoxyethyl acetate or butoxyethyl acetate; the ketone solvent includes any one or a combination of at least two of acetone, butanone, methyl isobutyl ketone, methyl ethyl ketone or cyclohexanone; the nitrogen-containing solvent includes any one or a combination of at least two of N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone.

[0073] Preferably, the solvent comprises an aromatic hydrocarbon solvent, and the mass percentage of the aromatic hydrocarbon solvent in the solvent is ≥50%, for example, 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%, 92%, 95%, 98% or 100%, etc.

[0074] The amount of the solvent used can be adjusted according to actual processing and application requirements.

[0075] The present invention also relates to a cured product, which is prepared by curing the resin composition as described in the first aspect.

[0076] On the other hand, the present invention provides a resin film, the raw material of which includes the resin composition as described in the first aspect; the resin film is obtained by coating the resin composition as described in the first aspect on a release material and then drying and / or semi-curing.

[0077] Illustratively, the method for preparing the resin film is: coating the resin composition as described in the first aspect on a release material (eg, a release film), and drying and / or semi-curing to obtain the resin film.

[0078] Preferably, the drying temperature is 180-220°C, for example, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C or 215°C.

[0079] Preferably, the drying time is 3 to 120 min, for example, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 105 min, 110 min or 115 min, etc.

[0080] In another aspect, the present invention provides an adhesive sheet, comprising a reinforcing material, and the resin composition according to the first aspect attached to the reinforcing material.

[0081] Preferably, the reinforcing material includes any one of quartz cloth, quartz glass fiber blended cloth, glass fiber cloth, glass fiber paper or non-woven fabric.

[0082] Illustratively, the bonding sheet is prepared by: using the resin composition of the resin glue to infiltrate the reinforcing material, and then drying to obtain the bonding sheet.

[0083] Preferably, the solvent in the resin glue solution is not particularly limited, and further preferably has the same selection range as above.

[0084] Preferably, the drying temperature is 130-180°C, for example, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C or 175°C.

[0085] Preferably, the drying time is 1 to 10 min, for example, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min or 9 min.

[0086] The present invention also relates to an insulating board, comprising at least one bonding sheet as described above.

[0087] In another aspect, the present invention provides a metal foil-clad laminate, comprising at least one bonding sheet as described above, and metal foil disposed on one side or both sides of the bonding sheet.

[0088] Preferably, the metal foil is copper foil, and the metal foil-clad laminate is a copper-clad laminate.

[0089] Exemplarily, the preparation method of the metal-clad laminate is: laminating metal foil on one side or both sides of an adhesive sheet and curing to obtain the metal-clad laminate; or, bonding at least two adhesive sheets to form an insulating board, and then laminating metal foil on one side or both sides of the insulating board and curing to obtain the metal-clad laminate.

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

[0091] Preferably, the curing temperature is 100-250°C, for example, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C or 245°C, etc.

[0092] Preferably, the curing pressure is 0.5-6 MPa, for example, 0.8 MPa, 1 MPa, 1.2 MPa, 1.5 MPa, 1.8 MPa, 2 MPa, 2.2 MPa, 2.5 MPa, 2.8 MPa, 3 MPa, 3.2 MPa, 3.5 MPa, 3.8 MPa, 4 MPa, 4.2 MPa, 4.5 MPa, 4.8 MPa, 5 MPa, 5.2 MPa, 5.5 MPa or 5.8 MPa, etc.

[0093] Preferably, the curing time is 30 to 150 min, for example, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min or 145 min, etc.

[0094] In another aspect, the present invention provides a printed circuit board, comprising at least one bonding sheet as described above or at least one metal foil-clad laminate as described above.

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

[0096] The resin composition provided by the present invention comprises a combination of a silicon aryl acetylene resin and a multifunctional vinyl aromatic polymer. The resin composition has excellent processability through compounding of specific polymers, and the cured product has high modulus, excellent dielectric properties and heat resistance, low thermal expansion ratio, good flame retardancy, dimensional stability and bonding performance. By further optimizing and compounding the components in the resin composition, the metal foil-clad laminate containing the resin composition has a glass transition temperature of 210-270°C, a thermal decomposition temperature of 400-460°C, a peel strength of 0.7-0.9N / mm, a dielectric constant of ≤3.9 (10GHz), a dielectric loss factor of ≤0.0045 (10GHz), a thermal expansion ratio as low as 1.2-2.2%, a flame retardancy of V-0 level, a flat and uniform surface of the plate, a thermal stress (288°C tinning)>10min, excellent processability, adhesion, heat resistance, dielectric properties and dimensional stability, and can fully meet the requirements of high-frequency circuit substrates in terms of processing and application performance. DETAILED DESCRIPTION

[0097] 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.

[0098] Preparation Example 1

[0099] A silicon aryl acetylene resin, specifically a silicon phenylacetylene resin, has the following structural formula:

[0100]

[0101] The preparation method comprises the following steps:

[0102] 3.5 parts of magnesium powder (chemically pure, Shanghai Sinopharm Chemical Reagent Co., Ltd.) and 40 parts of tetrahydrofuran (THF) solvent were added to a reactor filled with nitrogen, and a mixed solution of 13.5 parts of ethyl bromide (chemically pure, Shanghai Sinopharm Chemical Reagent Co., Ltd.) and 40 parts of THF was added dropwise at room temperature with stirring. After the addition was completed, the mixture was kept at 50°C for 1 hour; then, a mixture of 7.5 parts of 1,3-diethynylbenzene (Shandong Jiaozhou Fine Chemical Co., Ltd.) and 40 parts of THF solvent was added dropwise under ice-water cooling conditions. After the addition was completed, the mixture was kept at 65°C for 1 hour; the mixture was cooled again, and a mixture of 5.5 parts of dichlorodimethylsilane (chemically pure, Zhejiang Xin'an Chemical Group Co., Ltd., used after distillation) and 40 parts of THF was added dropwise under ice-water cooling conditions. After the addition was completed, the mixture was kept at 40°C and 70°C for 1 hour, respectively. After the reaction is completed, THF in the reactant is evaporated, and a mixture of 7.2 parts of glacial acetic acid and 50 parts of toluene solvent is added dropwise under ice-water cooling conditions, and then 140 parts of 2.0% dilute hydrochloric acid aqueous solution are added dropwise after sufficient stirring, and the upper organic phase is separated after sufficient stirring. The organic phase is fully washed with water until neutral, then dried, filtered, and toluene is evaporated to obtain the silicon aryl acetylene resin.

[0103] The silicon arylacetylene resin was tested by gel chromatography (GPC, mobile phase is THF), and the number average molecular weight was 1200, which is referred to as PSA1200 in the following examples.

[0104] Preparation Example 2

[0105] A silicon aryl acetylene resin, specifically a silicon phenylacetylene resin, whose structural formula is the same as that in Preparation Example 1.

[0106] The preparation method comprises the following steps:

[0107] 3.5 parts of magnesium powder (chemically pure, Shanghai Sinopharm Chemical Reagent Co., Ltd.) and 40 parts of THF solvent were added to a reactor filled with nitrogen, and a mixed solution of 13.5 parts of ethyl bromide (chemically pure, Shanghai Sinopharm Chemical Reagent Co., Ltd.) and 40 parts of THF was added dropwise at room temperature with stirring. After the addition was completed, the mixture was kept at 50°C for 1 hour; then, a mixture of 7.5 parts of 1,3-diethynylbenzene (Shandong Jiaozhou Fine Chemical Co., Ltd.) and 40 parts of THF solvent was added dropwise under ice-water cooling conditions. After the addition was completed, the mixture was kept at 65°C for 1 hour; the mixture was cooled again, and a mixture of 5.5 parts of dichlorodimethylsilane (chemically pure, Zhejiang Xin'an Chemical Group Co., Ltd., used after distillation) and 40 parts of THF was added dropwise under ice-water cooling conditions. After the addition was completed, the mixture was kept at 40°C and 70°C for 2 hours respectively. After the reaction is completed, THF in the reactant is evaporated, and a mixture of 7.2 parts of glacial acetic acid and 50 parts of toluene is added dropwise under ice-water cooling conditions, and then 140 parts of 2.0% dilute hydrochloric acid aqueous solution are added dropwise after sufficient stirring, and the upper organic phase is separated after sufficient stirring. The organic phase is fully washed with water until neutral, then dried, filtered, and toluene is evaporated to obtain the silicon aryl acetylene resin.

[0108] The silicon arylacetylene resin was tested by gel chromatography (GPC, mobile phase is THF), and the number average molecular weight was 3000, which is referred to as PSA3000 in the following examples.

[0109] Preparation Example 3

[0110] A silicon aryl acetylene resin, specifically a silicon biphenyl acetylene resin, has the following structural formula:

[0111]

[0112] The preparation method comprises the following steps:

[0113] 3.5 parts of magnesium powder (chemically pure, Shanghai Sinopharm Chemical Reagent Co., Ltd.) and 40 parts of THF solvent were added to a reactor filled with nitrogen, and a mixed solution of 13.5 parts of ethyl bromide (chemically pure, Shanghai Sinopharm Chemical Reagent Co., Ltd.) and 40 parts of THF was added dropwise at room temperature with stirring. After the addition was completed, the mixture was kept warm at 50°C for 1 hour; then, a mixture of 12 parts of p-diethynylbiphenyl (reagent, provided by TCI (Shanghai)) and 40 parts of THF solvent was added dropwise under ice-water cooling conditions. After the addition was completed, the mixture was kept warm at 65°C for 1 hour; the mixture was cooled again, and a mixture of 5.5 parts of dichlorodimethylsilane (chemically pure, Zhejiang Xin'an Chemical Group Co., Ltd., used after distillation) and 40 parts of THF was added dropwise under ice-water cooling conditions. After the addition was completed, the mixture was kept warm at 40°C and 70°C for 2 hours respectively. After the reaction is completed, THF in the reactant is evaporated, and a mixture of 7.2 parts of glacial acetic acid and 50 parts of toluene is added dropwise under ice-water cooling conditions, and then 140 parts of 2.0% dilute hydrochloric acid aqueous solution are added dropwise after sufficient stirring, and the upper organic phase is separated after sufficient stirring. The organic phase is fully washed with water until neutral, then dried, filtered, and toluene is evaporated to obtain the silicon aryl acetylene resin.

[0114] The silicon aryl acetylene resin was tested by gel chromatography (GPC, mobile phase is THF), and the number average molecular weight was 3500, which is referred to as PSA3500 in the following examples.

[0115] Preparation Example 4

[0116] A multifunctional vinyl aromatic polymer, the preparation method is as follows:

[0117] 65 parts of p-divinylbenzene (DVB) and 5 parts of A1536 (styrene-butadiene-styrene block copolymer, number average molecular weight M n 88,000, purchased from Kraton) were mixed evenly in toluene solvent, and then 0.14 parts of initiator diisopropyl peroxide (DCP) were added, the temperature was raised to 100° C. and stirred for reaction for 6 hours, and then cooled to room temperature to obtain the multifunctional vinyl aromatic polymer, which is referred to as B-1 in the following examples.

[0118] Preparation Example 5

[0119] A multifunctional vinyl aromatic polymer, the preparation method is as follows:

[0120] 30 parts of p-divinylbenzene (DVB), 5 parts of A1535 (styrene-butadiene-styrene block copolymer, M n 200,000, purchased from Kraton) and 5 parts of dicyclopentadiene were evenly mixed in toluene, and then 0.08 parts of initiator DCP were added, the temperature was raised to 120° C. and stirred for reaction for 6 hours, and the mixture was cooled to room temperature to obtain the multifunctional vinyl aromatic polymer, which is referred to as B-2 in the following examples.

[0121] Preparation Example 6

[0122] A multifunctional vinyl aromatic polymer, the preparation method is as follows:

[0123] 42 parts of p-divinylbenzene (DVB), 5 parts of A1536 (styrene-butadiene-styrene block copolymer, M n 88,000, purchased from Kraton) and 3 parts of dicyclopentadiene were mixed in toluene, and then 0.1 parts of initiator DCP were added, the temperature was raised to 120° C. and stirred for reaction for 7 hours, and the reaction was cooled to room temperature to obtain the multifunctional vinyl aromatic polymer, which is referred to as B-3 in the following examples.

[0124] The experimental materials involved in the following embodiments and comparative examples of the present invention include:

[0125] (1) Silicon aryl acetylene resin

[0126] PSA1200, Preparation Example 1

[0127] PSA3000, Preparation Example 2

[0128] PSA3500, Preparation Example 3

[0129] (2) Multifunctional vinyl aromatic polymers

[0130] B-1, Preparation Example 4

[0131] B-2, Preparation Example 5

[0132] B-3, Preparation Example 6

[0133] B-4, RICON257, butadiene-styrene-divinylbenzene branched terpolymer, purchased from Cray Valley;

[0134] B-5, ODV-XET, multifunctional vinyl aromatic polymer, M n 2400, purchased from Nippon Steel

[0135] Polyolefin resin: A1536, styrene-butadiene-styrene block copolymer, number average molecular weight M n 88,000, purchased from Kraton

[0136] (3) Polyphenylene ether resin containing unsaturated bonds

[0137] SA9000, purchased from SABIC

[0138] OPE-2st, purchased from Mitsubishi Chemical

[0139] (4) Cross-linking agent

[0140] TAICROS, triallyl isocyanurate, purchased from Evonik

[0141] 4,4'-divinylbiphenyl was purchased from Linchuan Chemical;

[0142] BVPE, p,p'-divinyl-1,2-diphenylethane, was purchased from Linchuan Chemical;

[0143] (5) Initiator

[0144] Perkadox BC-FF, dicumyl peroxide, purchased from Nouryon

[0145] (6) Inorganic fillers

[0146] DQ1028L, spherical silica powder, median particle size D 50 About 3.0μm, purchased from Jiangsu Lianrui

[0147] (7) Flame retardant

[0148] BT-93w, additive brominated flame retardant, purchased from Albemarle

[0149] XP7866, additive phosphorus-containing flame retardant, purchased from Albemarle

[0150] Example 1

[0151] This embodiment provides a resin composition, which includes the following components in parts by weight: 30 parts of silanol resin PSA3000 and 70 parts of multifunctional vinyl aromatic polymer B-1.

[0152] This embodiment also provides a metal foil-clad laminate, and the specific preparation method is as follows:

[0153] (1) The resin composition provided in this embodiment is mixed with 50 parts of toluene and dispersed evenly to obtain a resin glue solution;

[0154] (2) taking a smooth and clean E-type glass fiber cloth of model 2116 and evenly impregnating it with the resin glue obtained in step (1), and baking it in a blast oven at 150° C. for 5 minutes to obtain a bonding sheet;

[0155] (3) Stacking 6 adhesive sheets obtained in step (2), covering the upper and lower surfaces with 35 μm copper foil, and pressing in a vacuum hot press at a pressure of 3 MPa and a temperature of 220° C. for 90 minutes to obtain the metal foil-clad laminate.

[0156] Example 2

[0157] This embodiment provides a resin composition, which includes the following components in parts by weight: 60 parts of silicon aryl acetylene resin PSA1200, 40 parts of multifunctional vinyl aromatic polymer B-2, 0.1 parts of initiator Perkadox BC-FF, and 110 parts of inorganic filler DQ1028L.

[0158] This embodiment also provides a metal foil-clad laminate, and the specific preparation method is as follows:

[0159] (1) The resin composition provided in this embodiment is mixed with 50 parts of toluene and dispersed evenly to obtain a resin glue solution;

[0160] (2) taking a smooth and clean E-type glass fiber cloth of model 2116 and evenly impregnating it with the resin glue obtained in step (1), and baking it in a blast oven at 150° C. for 5 minutes to obtain a bonding sheet;

[0161] (3) Stacking 6 adhesive sheets obtained in step (2), covering the upper and lower surfaces with 35 μm copper foil, and pressing in a vacuum hot press at a pressure of 3 MPa and a temperature of 220° C. for 90 minutes to obtain the metal foil-clad laminate.

[0162] Example 3

[0163] The present embodiment provides a resin composition, which includes the following components in parts by weight: 50 parts of silicon aryl acetylene resin PSA3000, 50 parts of multifunctional vinyl aromatic polymer B-3, 80 parts of unsaturated bond-containing polyphenylene ether resin SA9000, 20 parts of cross-linking agent BVPE, 0.4 parts of initiator Perkadox BC-FF, 110 parts of inorganic filler DQ1028L, and 50 parts of flame retardant BT-93w.

[0164] This embodiment also provides a metal foil-clad laminate, and the specific preparation method is as follows:

[0165] (1) The polymer and initiator in the resin composition provided in this embodiment, 50 parts of butanone and 100 parts of toluene are mixed and fully dispersed, and then an inorganic filler and a flame retardant are added, and a resin glue is obtained after high-speed shear emulsification;

[0166] (2) taking a smooth and clean E-type glass fiber cloth of model 2116 and evenly impregnating it with the resin glue obtained in step (1), and baking it in a blast oven at 150° C. for 5 minutes to obtain a bonding sheet;

[0167] (3) Stacking 6 adhesive sheets obtained in step (2), covering the upper and lower surfaces with 35 μm copper foil, and pressing in a vacuum hot press at a pressure of 3 MPa and a temperature of 220° C. for 90 minutes to obtain the metal foil-clad laminate.

[0168] Examples 4 to 9, Comparative Examples 1 to 3

[0169] A resin composition, the components and contents of which are shown in Table 1; the dosage units of each component in Table 1 are all "parts".

[0170] Table 1

[0171]

[0172]

[0173] The above resin composition was made into a metal foil-clad laminate according to the method in Example 3, and its performance was tested. The test method is as follows:

[0174] (1) Glass transition temperature T g :Use dynamic mechanical analyzer (DMA) to measure according to the DMA test method specified in standard IPC-TM-6502.4.24;

[0175] (2) Thermal decomposition temperature T d :Use thermal gravimetric analysis TGA, and test according to the method specified in standard IPC-TM-650 2.4.24.6;

[0176] (3) Peel strength PS: The tensile force required to peel off the metal foil laminate (copper clad laminate) per millimeter of copper foil at room temperature. The peel strength of the metal cover layer is tested according to the "received state" experimental conditions specified in standard IPC-TM-650 2.4.8;

[0177] (4) Dielectric constant D k and dielectric loss factor D f :10GHz using the resonant cavity method (SPDR) method, according to the method specified in standard IPC-TM-650 2.5.5.5;

[0178] (5) Flame retardancy: tested according to the UL94 "50W (20mm) vertical burning test: V-0, V-1 and V-2" test method, V-0 is recognized as flame retardant;

[0179] (6) Thermal expansion ratio CTE: The test is conducted using a static thermal analyzer TMA according to the method specified in standard IPC-TM-6502.4.24; the thermal expansion ratio at 50-260°C is the value measured in the length direction of the laminate sample;

[0180] (7) Thermal stress: 5 cm × 5 cm copper-clad laminate was immersed in tin at 288 ° C and the delamination or blistering time was observed. If it was less than 10 min, it was recorded as a fail.

[0181] (8) Sample board appearance: visually inspect the board flatness, whether there are grooves, poor glue flow, etc., and test the uniformity of board thickness;

[0182] (9) Processability: If the copper clad laminate can be directly processed into shape according to the conventional copper clad laminate lamination procedure (1.5-2℃ / min heating rate, 90℃ pressurization, 200℃ insulation for 90min), it is considered easy to process; if the procedure needs to be adjusted, it is considered difficult to process; if it is still difficult to process after multiple procedure adjustments, it is considered extremely difficult to process.

[0183] The test results are shown in Table 2:

[0184] Table 2

[0185]

[0186] According to the performance test data in Table 2, compared with Comparative Example 1 not containing silicon aromatic acetylene resin and Comparative Example 2 not containing multifunctional vinyl aromatic polymer, the resin composition provided in the embodiment of the present invention has a glass transition temperature of 210-270°C, a thermal decomposition temperature of 400-460°C, a peel strength of 0.7-0.9N / mm, a thermal expansion ratio as low as 1.2-2.2%, a dielectric constant of ≤3.90 (10GHz), a dielectric loss factor of ≤0.0045 (10GHz), a flame retardancy of V-0 level, a flat and uniform surface of the board, and a thermal stress (288°C tinning time)>10min. It has excellent processability, adhesion, heat resistance, dielectric properties and dimensional stability, and can fully meet the requirements of high-frequency circuit substrates in processability and application performance.

[0187] Furthermore, the present invention can optimize and improve the performance of the metal foil-clad laminate by adjusting the components and dosage of the silicon aryl acetylene resin and the multifunctional vinyl aromatic polymer. According to the test results of Example 4, when the dosage of the multifunctional vinyl aromatic monomer (divinylbenzene) in the multifunctional vinyl aromatic polymer is too low, the curing crosslinking density of the system is low, and the T g The content of silicon aryl acetylene resin in Example 7 is very high, and the T g The T of the plate sample is obviously higher, but due to the high fluidity of the silicon aryl acetylene resin, it is difficult to process the plate, which easily leads to uneven thickness of the plate. g The T of the plate is significantly lower than that of the polyfunctional vinyl aromatic polymer. In addition, due to the large amount of polyfunctional vinyl aromatic monomer (divinylbenzene) used in the polyfunctional vinyl aromatic polymer, the resin curing speed is fast, the flow rate is low during the plate processing, the flow is poor, and it is difficult to process. The aromatic group in the silyl aryl acetylene resin used in Example 9 is biphenyl, and the T of the plate is gIt is slightly higher than Example 5 and has better performance in CTE.

[0188] Comparative Example 1 did not add silicon aryl acetylene, and compared with Example 5, the heat resistance and CTE were worse; Comparative Example 2 did not add multifunctional vinyl aromatic polymer, and compared with Example 2, the peel strength, dielectric properties, appearance and processability were worse; in Comparative Example 3, ordinary butadiene-styrene-butadiene block polymer was used to replace the multifunctional vinyl aromatic polymer, and its curing reaction was more difficult and it was not easy to completely crosslink. The board sample T g The thermal resistance and processability of the substrate are too low and the substrate is prone to delamination and blistering during thermal stress testing. It cannot meet the requirements for high-frequency circuit substrates in terms of heat resistance and processability.

[0189] The applicant declares that the present invention uses the above embodiments to illustrate a resin composition of the present invention and an adhesive sheet and a metal foil-clad laminate comprising 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 various 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 weight: 25 to 65 parts of silicon aryl acetylene resin and 35 to 75 parts of multifunctional vinyl aromatic polymer, based on 100 parts of the sum of the parts by weight of silicon aryl acetylene resin and multifunctional vinyl aromatic polymer; the multifunctional vinyl aromatic polymer is copolymerized by divinyl aromatic compound and other vinyl compounds, and the molar proportion of the divinyl aromatic compound in the repeating units of the copolymer is greater than or equal to 30%.

2. The resin composition according to claim 1, characterized in that The silicon arylacetylene resin has a structure as shown in Formula I: Wherein, n is selected from an integer of 1 to 50; R1 and R2 are each independently selected from hydrogen, C1-C6 straight or branched alkyl, C3-C6 cycloalkyl; Ar is selected from Dashed lines represent the attachment sites of the groups; M is selected from a single bond, O, SO2, C1-C5 straight or branched chain alkylene; R3 and R4 are each independently selected from halogen, C1-C5 straight chain or branched alkyl; m1 and m3 are each independently selected from integers of 0 to 4; m2 is selected from integers of 0-6.

3. The resin composition according to claim 2, characterized in that The R1 and R2 are each independently selected from C1-C5 straight chain or branched chain alkyl groups.

4. The resin composition according to claim 2, characterized in that The Ar is 5. The resin composition according to claim 2, characterized in that The number average molecular weight of the silicon aryl acetylene resin is 200-8000.

6. The resin composition according to claim 1, characterized in that The number average molecular weight of the silicon arylacetylene resin is 400-4000.

7. The resin composition according to claim 1, characterized in that The number average molecular weight of the silicon aryl acetylene resin is 500-3500.

8. The resin composition according to claim 1, characterized in that The multifunctional vinyl aromatic polymer comprises repeating unit a1 and / or repeating unit a2; The structure of the repeating unit a1 is The structure of the repeating unit a2 is Here, R5 and R6 are each independently an aromatic hydrocarbon group having 6 to 30 carbon atoms.

9. The resin composition according to claim 8, characterized in that The molar percentage of the repeating unit a1 in the multifunctional vinyl aromatic polymer is ≥10%.

10. The resin composition according to claim 9, characterized in that The molar percentage of the repeating unit a1 in the multifunctional vinyl aromatic polymer is ≥50%.

11. The resin composition according to claim 1, characterized in that The other vinyl compound includes any one or a combination of at least two of butadiene, isoprene, dicyclopentadiene, maleated diene, triallyl isocyanurate resin or monovinyl aromatic compound.

12. The resin composition according to claim 11, characterized in that The monovinyl aromatic compound includes any one of styrene, fluorene containing one vinyl group, naphthalene containing one vinyl group, or biphenyl containing one vinyl group, or a combination of at least two thereof.

13. The resin composition according to claim 1, characterized in that The number average molecular weight of the multifunctional vinyl aromatic polymer is 1,000 to 500,000.

14. The resin composition according to claim 1, characterized in that The multifunctional vinyl aromatic polymer comprises a combination of a low molecular weight polymer and a high molecular weight polymer; the number average molecular weight of the low molecular weight polymer is 1,000 to 10,000, and the number average molecular weight of the high molecular weight polymer is 100,000 to 500,000.

15. The resin composition according to claim 14, characterized in that The mass percentage of the high molecular weight polymer in the multifunctional vinyl aromatic polymer is 1 to 40%.

16. The resin composition according to claim 1, characterized in that The resin composition further comprises 5 to 85 parts by weight of a polyphenylene ether resin containing an unsaturated bond.

17. The resin composition according to claim 16, characterized in that The number average molecular weight of the unsaturated bond-containing polyphenylene ether resin is 1000-7000.

18. The resin composition according to claim 16, characterized in that The number average molecular weight of the unsaturated bond-containing polyphenylene ether resin is 1000-4000.

19. The resin composition according to claim 1, characterized in that The resin composition further comprises 0.01 to 10 parts by weight of an initiator.

20. The resin composition according to claim 19, characterized in that The initiator includes any one of peroxides, azo compounds, dioxins or polyoxins, or a combination of at least two of them.

21. The resin composition according to claim 20, characterized in that The peroxide includes any one or a combination of at least two of diisopropylbenzene peroxide, tert-butyl cumene peroxide, di-tert-butyl peroxide, isopropyl peroxy tert-butyl carbonate, 2,5-dimethyl-2,5-di-tert-butylperoxy-3-hexyne, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, p-menthane hydroperoxide, 1,1-bis(tert-amylperoxy)cyclohexane, diisopropyl hydroperoxide, benzoyl peroxide or a benzoyl peroxide derivative.

22. The resin composition according to claim 1, characterized in that The resin composition further comprises 5 to 60 parts by weight of a crosslinking agent.

23. The resin composition according to claim 22, characterized in that The cross-linking agent is a compound containing at least two unsaturated bonds in its molecular structure.

24. The resin composition according to claim 22, characterized in that The crosslinking agent includes any one or a combination of at least two of triallyl isocyanurate, triallyl polyisocyanurate, triallyl cyanurate, diallyl phthalate, a multifunctional methacrylate compound having two or more methacryloyl groups in the molecule, biphenyl containing at least two double bonds, dicyclopentadiene, a naphthalene compound containing at least two double bonds, p,p'-divinyl-1,2-diphenylethane or divinylbenzene.

25. The resin composition according to claim 1, characterized in that The resin composition further comprises 10 to 80 parts by weight of a flame retardant.

26. The resin composition according to claim 25, characterized in that The flame retardant includes any one of a halogen flame retardant, a phosphorus flame retardant or a nitrogen flame retardant, or a combination of at least two thereof.

27. The resin composition according to claim 1, characterized in that The resin composition further comprises 5 to 120 parts by weight of inorganic filler.

28. The resin composition according to claim 27, characterized in that The inorganic filler includes any one of silicon dioxide, silicon powder, aluminum oxide, titanium dioxide, mica, beryllium oxide, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate or silicon carbide, or a combination of at least two thereof.

29. The resin composition according to claim 27, characterized in that The particle size of the inorganic filler is 0.01 to 30 μm.

30. The resin composition according to claim 27, characterized in that The particle size of the inorganic filler is 0.1 to 15 μm.

31. The resin composition according to claim 1, characterized in that The resin composition further comprises 0.01 to 7 parts by weight of a silane coupling agent.

32. A resin film, characterized in that: The resin film is obtained by coating the resin composition according to any one of claims 1 to 31 on a release material and then drying and / or semi-curing the film.

33. A bonding sheet, characterized in that: The bonding sheet comprises a reinforcing material, and the resin composition according to any one of claims 1 to 31 attached to the reinforcing material.

34. The bonding sheet according to claim 33, characterized in that: The reinforcing material includes any one of quartz cloth, quartz glass blended cloth, glass fiber cloth, glass fiber paper or non-woven fabric.

35. A metal foil-clad laminate, characterized in that: The metal foil-clad laminate comprises at least one bonding sheet as claimed in claim 33 and a metal foil disposed on one side or both sides of the bonding sheet.

36. The metal-clad laminate according to claim 35, characterized in that: The metal foil is copper foil.

37. A printed circuit board, characterized in that: The printed circuit board includes at least one bonding sheet according to claim 34 or the metal-clad laminate according to claim 35 .

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