A resin composition and a prepreg and a metal-clad laminate sheet comprising the same

Abstract

The present application provides a resin composition and a prepreg and a metal-clad laminate comprising the same, the resin composition comprising the following components in parts by weight: 3-60 parts of a sila-arylene resin, 5-95 parts of an olefin polymer and 3-60 parts of a maleimide resin, based on the total of 100 parts of the weight of the sila-arylene resin, the olefin polymer and the maleimide resin. By screening and compounding the polymer components, the compatibility and stability of the resin composition are significantly improved, and a dense three-dimensional network structure can be formed after curing, so that the resin composition and its cured product exhibit good stability, heat resistance, bonding performance, dielectric properties and flame retardancy. The metal-clad laminate comprising the resin composition has high peel strength and heat resistance, low dielectric constant and dielectric loss, low thermal expansion coefficient, and the surface of the plate is flat and uniform, which can fully meet the performance requirements of high-frequency circuit substrates.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of copper-clad plate, and particularly relates to a resin composition, a prepreg containing the same and a metal-clad laminate. BACKGROUND

[0002] In recent years, with the rapid development of electronic information technologies such as communication networks, data centers and cloud computing, and hardware carriers such as application-side mobile phones, base stations and automobiles, the demand for electronic components and electronic materials has also increased, which has led electronic product applications to enter the high-frequency and high-speed transmission field. Therefore, the dielectric properties of related electronic materials have become a major concern. Under the trend of high-frequency and high-speed signal transmission, miniaturization of electronic components and high-density circuit board lines, the demand for low dielectric constant and low dielectric loss of electronic materials is becoming increasingly prominent.

[0003] Printed circuit boards (PCB) are components used for electrical connections in electronic devices and electronic components, and are one of the important parts of the electronic industry. Metal-clad laminates are base laminates for the preparation of PCBs. Therefore, the application performance, processing performance, service life and manufacturing level of PCBs depend largely on the performance of metal-clad laminates.

[0004] Metal-clad laminates generally include a reinforcing material and a resin composition. The most widely used resin composition is currently an epoxy resin system. The cured product of an epoxy resin composition has good heat resistance and insulation, and exhibits good processing properties 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 are generated after curing, which leads to an increase in water absorption, a decrease in dielectric properties and moisture resistance, and difficulty in meeting the use requirements.

[0005] Polyolefin resin (also known as hydrocarbon resin) has good performance in dielectric properties, and can meet the low dielectric requirements of metal-clad laminates. However, the flexibility of the polymer chain segment and the non-polar carbon chain structure of polyolefin resin result in insufficient rigidity and low strength of the cured product, poor heat resistance and poor adhesion, thus causing great difficulties in practical applications. The cured product of maleimide resin has high crosslinking density and thermal stability, and is commonly used in electronic circuit substrates in the fields of packaging and HDI (high-density interconnection). In recent years, products combining maleimide resin and polyolefin resin have appeared on the market, which are used for ultra-low dielectric loss and high heat resistance products.

[0006] CN106243430A discloses a thermosetting resin composition and a prepreg and laminate made using the same, the thermosetting resin composition comprising: 10-100 parts of a hydrocarbon resin, 20-100 parts of a phosphorus-containing maleimide ester and 0.1-8 parts of an initiator. The resin composition uses a maleimide ester having a multi-functional long-chain structure and a rigid imide ring, and cooperates with a flexible hydrocarbon resin to form a thermosetting composition, so that the prepreg and laminate for printed circuits containing the same have good dielectric properties, heat resistance, adhesion, flame retardancy and mechanical properties. However, the maleimide resin is brittle, has poor solubility in weakly polar organic solvents, and has a big problem of compatibility with polyolefin resins, which can easily cause phase separation and even delamination during the glue mixing process, bringing great difficulty to actual processing, and also affecting the apparent uniformity of the prepreg and the substrate.

[0007] In order to improve the compatibility of maleimide resin with other polymers, it is usually necessary to modify it. For example, CN108401433A discloses a resin varnish, a prepreg, a laminate and a printed circuit board, the resin varnish comprising a maleimide compound, an epoxy resin, a copolymer resin of maleic anhydride and an aromatic vinyl compound, and silica treated with an amino silane coupling agent, the maleimide compound used therein containing an acidic substituent and a maleimide group, so as to obtain a thermosetting resin composition material with good performance. However, the maleimide compound used in the resin varnish contains hydroxyl, carboxyl or sulfonic acid group, which generates a secondary alcohol hydroxyl group with large polarity and easy water absorption after curing reaction, thereby adversely affecting the dielectric properties, water absorption and moisture resistance of the cured product.

[0008] Therefore, it is an urgent problem to be solved in the art to develop a resin material with good compatibility and stability, excellent dielectric properties, heat resistance and low thermal expansion, so as to meet the application requirements of metal-clad foil laminates. SUMMARY

[0009] In view of the deficiencies of the prior art, the purpose of the present application is to provide a resin composition and a prepreg and a metal-clad foil laminate containing the same, by compounding a sila-arylene resin, an olefin polymer and a maleimide resin, the stability of the resin composition is significantly improved, and at the same time has excellent heat resistance and dielectric properties, low thermal expansion coefficient, and can fully meet the performance requirements of high-frequency circuit substrates.

[0010] To achieve this purpose, the present application adopts the following technical solutions:

[0011] In a first aspect, the present application provides a resin composition comprising, in parts by weight, 3-60 parts of a sila-arylene resin, 5-95 parts of an olefin polymer, and 3-60 parts of a maleimide resin, based on the total of 100 parts of the sila-arylene resin, the olefin polymer, and the maleimide resin.

[0012] The resin composition provided by the present application comprises a combination of a sila-arylene resin, an olefin polymer, and a maleimide resin. The olefin polymer has good curability and dielectric properties, the maleimide resin contains a large number of crosslinking reaction sites and has the characteristics of low dielectric constant, low dielectric loss, and high heat resistance, and the sila-arylene resin not only has excellent dielectric properties and heat resistance, but also has certain flame retardancy, and can significantly improve the overall compatibility and stability of the resin composition. The resin composition and its cured product have excellent stability and heat resistance, low dielectric constant and dielectric loss, low thermal expansion coefficient, and high bonding strength, and can fully meet the performance requirements of the circuit board for the resin composition.

[0013] The sila-arylene resin is 3-60 parts, for example, 4 parts, 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, or 58 parts, etc.

[0014] The olefin polymer is 5-95 parts, for example, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, or 90 parts, etc.

[0015] The maleimide resin is 3-60 parts, for example, 4 parts, 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, or 58 parts, etc.

[0016] Preferably, the sila-arylene resin has a structure as shown in Formula I:

[0017]

[0018] In Formula I, n is an integer selected from 1-50, for example, 1, 2, 3, 4, 5, 8, 10, 15, 18, 20, 21, 25, 27, 30, 35, 38, 40, 43, 45, 48, or 50, etc.

[0019] In formula I, R1, R2are each independently selected from hydrogen, C1-C6 linear or branched alkyl, C3-C6 cycloalkyl.

[0020] The C1-C6 linear or branched alkyl can be C1, C2, C3, C4, C5, C6 linear or branched alkyl, exemplarily including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl or n-hexyl, etc.

[0021] The C3-C6 cycloalkyl can be C3, C4, C5, C6 cycloalkyl, exemplarily including but not limited to cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, etc.

[0022] Ar is selected from The dotted line represents the connecting site of the group.

[0023] M is selected from a single bond, O, S, C1-C5 linear or branched alkylene; the "M is a single bond" means that the two benzene rings are directly connected by a single bond to form a biphenyl structure.

[0024] The C1-C5 linear or branched alkylene can be C1, C2, C3, C4 or C5 linear or branched alkylene, exemplarily including but not limited to methylene, ethylene, 1,2-ethylene or propylene, etc.

[0025] R3, R4are each independently selected from halogen (e.g. fluorine, chlorine, bromine or iodine), C1-C5 (e.g. C1, C2, C3, C4 or C5) linear or branched alkyl.

[0026] m1, m3 are each independently selected from an integer from 0 to 4, e.g. 0, 1, 2, 3 or 4.

[0027] m2 is selected from an integer from 0 to 6, e.g. 0, 1, 2, 3, 4, 5 or 6.

[0028] Preferably, the R1, R2are each independently selected from C1-C3 linear or branched alkyl.

[0029] Preferably, the Ar is

[0030] Preferably, the number average molecular weight of the silaarylene resin is 200-8000, e.g. 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, etc., further preferably 400-4000, and more further preferably 500-3500.

[0031] In the present application, the testing method of molecular weight (number average molecular weight, weight average molecular weight, etc.) is GB / T21863-2008, which is determined by gel permeation chromatography (GPC) based on polystyrene calibration.

[0032] In the present application, the sila-arylene resin can be obtained by the reaction of aryl alkyne compound HC≡C-Ar-C≡CH and silane compound wherein X1, X2 are each independently selected from halogen, preferably chlorine, bromine or iodine.

[0033] Preferably, the polymerized monomer of the olefin-based polymer comprises any one or a combination of at least two of butadiene, isoprene, maleic anhydride- dized diene, divinylbenzene, styrene, dicyclopentadienyl-containing olefin, fluorene- containing olefin, biphenyl-containing olefin, or naphthalene-containing olefin.

[0034] Preferably, the olefin-based polymer is an ungrafted olefin-based polymer and / or a graft-modified olefin-based polymer.

[0035] Preferably, the grafting group of the graft-modified olefin-based polymer comprises any one or a combination of at least two of hydroxyl group, maleic anhydride group, or methacrylate group.

[0036] Preferably, the number average molecular weight of the olefin-based polymer is 1000-500000, such as 2000, 5000, 8000, 10000, 20000, 30000, 50000, 70000, 90000, 100000, 150000, 200000, 250000, 300000, 350000, 400000, or 450000, etc.

[0037] Preferably, the olefin-based polymer comprises a combination of low molecular weight olefin-based polymer and high molecular weight olefin-based polymer; the number average molecular weight of the low molecular weight olefin-based polymer is 1000-10000, and the number average molecular weight of the high molecular weight olefin-based polymer is 100000-500000.

[0038] Preferably, the mass percentage content of the high molecular weight olefin-based polymer in the olefin-based polymer is 1-40%, such as 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, or 38%, etc.

[0039] As a preferred technical solution of the present application, the olefin polymer comprises a combination of a low-molecular-weight olefin polymer and a high-molecular-weight olefin polymer; wherein the low-molecular-weight olefin polymer has high reactivity and good curing efficiency, the high-molecular-weight olefin polymer has large viscosity and better compatibility; the olefin polymers of the two molecular weight ranges are synergistic with each other, so that the resin composition achieves a balance in curing reactivity, curing efficiency, viscosity, flowability, and compatibility, etc.

[0040] Preferably, the maleimide resin comprises at least two maleimide functional groups in the molecular structure.

[0041] In the present application, the maleimide resin is not particularly limited, and a maleimide resin containing two or more (for example, three or four, etc.) maleimide functional groups can achieve the technical effects of the present application. The maleimide resin containing two maleimide functional groups is a bismaleimide resin.

[0042] Preferably, the maleimide resin is a maleimide resin with high solubility in butanone; the greater the solubility of the maleimide resin, the better the compatibility with the olefin polymer; the smaller the solubility, the worse the compatibility, which is prone to turbidity or even stratification.

[0043] Preferably, the solubility of the maleimide resin at room temperature is ≥5g, for example, 6g, 8g, 10g, 12g, 15g, 18g, 20g, 25g, 30g, 35g, or 40g, etc., and is further preferably ≥20g, based on 100g of butanone.

[0044] Preferably, the weight part of the silicofuran resin is 20-50 parts, for example, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts, 45 parts, or 48 parts, etc., based on 100 parts of the sum of the weight parts of the silicofuran resin, the olefin polymer, and the maleimide resin. Too much silicofuran resin will result in too low melt viscosity and too large flow, which is not conducive to the control of the thickness of the board during the lamination process, and will also deteriorate the dielectric constant D k ; too little silicofuran resin will result in reduced heat resistance and deteriorated coefficient of thermal expansion CTE.

[0045] Preferably, the weight parts of the maleimide resin is 10-30 parts, for example 11 parts, 13 parts, 15 parts, 17 parts, 19 parts, 20 parts, 21 parts, 23 parts, 25 parts, 27 parts, or 29 parts, etc., based on 100 parts of the sum of the weight parts of the sila-arylene resin, the olefin-based polymer, and the maleimide resin. Too much maleimide resin can result in poor compatibility with the sila-arylene resin and the olefin-based polymer, and the resin precipitates, resulting in insufficient toughness, reduced heat resistance, and deteriorated adhesion of the cured product. Too little maleimide resin is not conducive to the crosslinking reaction of the cured product at low temperatures, and the resin melt viscosity during lamination is too low, resulting in excessive flow, which is not conducive to the thickness control of the board during lamination, and affects the uniformity of the board.

[0046] Preferably, the resin composition further includes 0.01-10 parts of an initiator by weight, for example the initiator can be 0.03 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 6 parts, 7 parts, 8 parts, or 9 parts, etc.

[0047] Preferably, the initiator includes any one or a combination of at least two of peroxide, azo compound, cumyl, or polycumyl.

[0048] Preferably, the peroxide includes any one or a combination of at least two of dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, t-butyl peroxy isopropyl carbonate, 2,5-dimethyl-2,5-di-t-butylperoxy-3-hexyne, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, p-menthane hydroperoxide, 1,1-bis(t-amylperoxy)cyclohexane, diisopropylbenzene hydroperoxide, benzoyl peroxide, or benzoyl peroxide derivatives.

[0049] Preferably, the azo compound includes azobisisobutyronitrile.

[0050] Preferably, the resin composition further includes 5-60 parts of a crosslinking agent by weight, for example the crosslinking agent can be 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, 45 parts, 50 parts, 55 parts, or 58 parts, etc.

[0051] Preferably, the crosslinking agent is a compound containing at least two unsaturated bonds in the molecular structure.

[0052] Preferably, the crosslinking agent is a compound containing 2 or more (for example 3, 4, etc.) unsaturated double bonds.

[0053] Preferably, the crosslinking agent comprises any one or a combination of at least two of triallyl isocyanurate (TAIC), triallyl isocyanurate, polyisocyanuric acid triallyl ester, triallyl cyanurate, diallyl phthalate, biphenyl containing at least two double bonds, dicyclopentadiene, naphthalene compounds containing at least two double bonds, p,p'-divinyl-1,2-diphenyl ethane, or divinyl benzene.

[0054] Preferably, the resin composition further comprises 10 to 80 parts by weight of a flame retardant, such as 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.

[0055] Preferably, the flame retardant is selected from any one or a combination of at least two of inorganic flame retardants, halogen-based organic flame retardants, phosphorus-based organic flame retardants, nitrogen-based organic flame retardants, or silicon-based organic flame retardants.

[0056] The present application is not particularly limited to the flame retardant, and any flame retardant having a flame retardant effect can be applied to the resin composition. Exemplarily, the flame retardant comprises any one or a combination of at least two of decabromodiphenyl ethane, decabromodiphenyl ethylene, divinyl phenyl phosphonate, diallyl phenyl phosphonate, di(1-butenyl) phenyl phosphonate, phenyl methyl phosphonate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof, bis(2-allylphenoxy) phosphazene, dimethyl phenyl phosphazene, melamine phosphate, melamine pyrophosphate, or polyphosphoric acid melamine.

[0057] Preferably, the resin composition further comprises 5 to 150 parts by weight of an inorganic filler, such as 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.

[0058] The resin composition of the present application can comprise an optional inorganic filler, and the mass percentage of the inorganic filler in the resin composition can be 1 to 80%, such as 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 78%, etc.

[0059] Preferably, the inorganic filler includes any one or a combination of at least two of silica micropowder, silicon dioxide, aluminum oxide, titanium oxide, mica, silica, 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 (e.g., calcined clay), talc, aluminum borate, or silicon carbide.

[0060] The shape of the inorganic filler is not particularly limited, but is preferably spherical.

[0061] Preferably, the particle size of the inorganic filler is 0.01-30 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 the like, and is further preferably 0.1-15 μm. The particle size is tested using a Malvern 2000 laser particle size analyzer.

[0062] As a preferred technical solution of the present application, the particle size of the inorganic filler is 0.01-30 μm, which can make the resin composition have good flowability, processability, mechanical properties, adhesion properties, and reliability. If the particle size of the inorganic filler is less than 0.01 μm, the flowability of the resin composition will decrease, making the resin composition have poor formability when making prepreg and metal foil laminated board, and being prone to voids. If the particle size of the inorganic filler is greater than 30 μm, the surface area of the inorganic filler will increase, reducing the adhesion area of the metal foil and the resin, and further causing the peel strength of the printed circuit board to decrease, and the insulation reliability between the wiring or the insulation layer to decrease.

[0063] Preferably, the resin composition further includes 0.01-7 parts by weight of a silane coupling agent, such as 0.03 parts, 0.05 parts, 0.08 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, or 6.5 parts, and the like.

[0064] The present application does not have a particular limitation on the type of silane coupling agent, and is preferably a vinyl silane and / or an allyl silane, which is mainly used to promote the dispersion of the inorganic filler or the inorganic flame retardant.

[0065] The preparation method of the resin composition of the present application can be: mixing each component in the resin composition with a solvent uniformly to obtain the resin composition; preferably, the solid can be put in first, then the solvent is added, and after stirring until the solid is completely dissolved, the liquid resin and the curing accelerator are added, and then the stirring is continued until it is uniform.

[0066] The solvent is not particularly limited, and includes any one of an alcohol solvent, an ether solvent, an aromatic hydrocarbon solvent, an ester solvent, a ketone solvent, or a nitrogen-containing solvent, or a combination of at least two thereof. Among them, the alcohol solvent includes any one of methanol, ethanol, or butanol, or a combination of at least two thereof; the ether solvent includes any one of ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, or butyl carbitol, or a combination of at least two thereof; the aromatic hydrocarbon solvent includes any one of benzene, toluene, xylene, or mesitylene, or a combination of at least two thereof; the ester solvent includes any one of ethyl acetate, butyl acetate, methoxyethyl acetate, ethoxyethyl acetate, or butoxyethyl acetate, or a combination of at least two thereof; the ketone solvent includes any one of acetone, butanone, methyl isobutyl ketone, methyl ethyl ketone, or cyclohexanone, or a combination of at least two thereof; and the nitrogen-containing solvent includes any one of N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone, or a combination of at least two thereof.

[0067] Preferably, the solvent includes an aromatic hydrocarbon solvent, and the mass percentage of the aromatic hydrocarbon solvent in the solvent is ≥ 50%, such as 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%, 92%, 95%, or 98%, etc.

[0068] The amount of the solvent can be adjusted according to the actual processing and application requirements.

[0069] The present application also relates to a cured product, which is prepared by curing the resin composition according to the first aspect.

[0070] In another aspect, the present application provides a resin film, which is prepared by coating the resin composition according to the first aspect on a release material, and drying and / or semi-curing.

[0071] The preparation method of the resin film includes: coating the resin composition on a release film, and drying and / or semi-curing to obtain the resin film.

[0072] Preferably, the drying temperature is 180-220°C, such as 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, or 215°C, etc.

[0073] Preferably, the drying is performed at a temperature of 130-180°C, such as 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, or the like.

[0074] In another aspect, the present application provides a prepreg comprising a reinforcing material, and the resin composition as described in the first aspect attached to the reinforcing material.

[0075] Preferably, the reinforcing material comprises any one or a combination of two or more of a quartz cloth, a quartz glass fiber blended cloth, a glass fiber cloth, a glass fiber paper, or a non-woven fabric.

[0076] Preferably, the prepreg is prepared by impregnating a reinforcing material with a resin solution of the resin composition, and drying to obtain the prepreg.

[0077] Preferably, the drying is performed at a temperature of 130-180°C, such as 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, or the like.

[0078] Preferably, the drying is performed for 1-10 minutes, such as 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, or the like.

[0079] The present application also relates to an insulation board comprising at least one prepreg as described above.

[0080] In another aspect, the present application provides a metal-clad laminate comprising at least one prepreg as described above, and a metal foil arranged on one or both sides of the prepreg.

[0081] Preferably, the metal foil is a copper foil, and the metal-clad laminate is a copper-clad laminate.

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

[0083] Preferably, the curing is performed in a hot press.

[0084] Preferably, the temperature of the curing is 100-250°C, such as 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.

[0085] Preferably, the pressure of the curing is 0.5-6 MPa, such as 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.

[0086] Preferably, the time of the curing is 30-150 min, such as 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.

[0087] In another aspect, the present application provides a printed circuit board comprising at least one prepreg as described above or metal-clad laminate as described above.

[0088] Compared with the prior art, the present application has the following advantages:

[0089] The resin composition provided by the present application comprises a combination of sila-arylene resin, olefin polymer and maleimide resin. The compatibility and stability of the resin composition are significantly improved by the synergistic combination of the three components. The resin composition and its cured product can form a dense three-dimensional network structure, and exhibit good stability, heat resistance, bonding performance, dielectric performance and flame retardancy. The metal-clad laminate comprising the resin composition has a glass transition temperature of 190-260°C, a thermal decomposition temperature of 370-420°C, a peel strength of 0.6-0.8 N / mm, a thermal expansion coefficient as low as 1.3-1.7%, a dielectric constant ≤4.1 (10 GHz), a dielectric loss factor ≤0.0043 (10 GHz), a 288°C immersion welding time >10 min, good thermal stress, and a smooth and uniform appearance. The metal-clad laminate has excellent bonding performance, heat resistance, dielectric performance and low thermal expansion coefficient, and can fully meet the performance requirements of high-frequency circuit substrates. DETAILED DESCRIPTION

[0090] The technical solutions of the present application are further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application and should not be regarded as specific limitations on the present application.

[0091] Preparation Example 1

[0092] A silicon aryl alkyne resin, specifically a silicon phenyl alkyne resin, has the following structure:

[0093]

[0094] The preparation method includes the following steps:

[0095] In a reaction kettle filled with nitrogen, 3.5 parts of magnesium powder (chemically pure, Shanghai Reagent Corporation) and 40 parts of tetrahydrofuran (THF) solvent were added, stirred at room temperature, and a mixed solution of 13.5 parts of bromoethane (chemically pure, Shanghai Reagent Corporation) and 40 parts of THF was added dropwise. After the dropwise addition was completed, it was incubated at 50°C for 1h. Then, under ice water cooling conditions, 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, and after the dropwise addition was completed, it was incubated at 65°C for 1h. Again, under ice water cooling conditions, 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, and after the dropwise addition was completed, it was incubated at 40°C and 70°C for 1h, respectively. After the reaction was completed, the THF in the reaction was evaporated, and a mixture of 7.2 parts of glacial acetic acid and 50 parts of toluene solvent was added dropwise under ice water cooling conditions. After sufficient stirring, 140 parts of 2.0% dilute hydrochloric acid aqueous solution was added dropwise, and after sufficient stirring, the upper organic phase was separated. The organic phase was washed with water until neutral, then dried, filtered, and the toluene was evaporated to obtain the silicon aryl alkyne resin.

[0096] The silicon aryl alkyne resin was tested by gel permeation chromatography (GPC, mobile phase THF) to obtain a number average molecular weight of 1200, which is referred to as PSA1200 in the following examples.

[0097] Preparation Example 2

[0098] A silicon aryl alkyne resin, specifically a silicon phenyl alkyne resin, has the same structure as in Preparation Example 1.

[0099] The preparation method includes the following steps:

[0100] In a nitrogen-filled reaction kettle, 3.5 parts of magnesium powder (chemically pure, Shanghai Reagent Corporation) and 40 parts of THF solvent were added, stirred at room temperature and 13.5 parts of bromoethane (chemically pure, Shanghai Reagent Corporation) and 40 parts of THF were added dropwise. After the dropwise addition was completed, it was incubated at 50°C for 1h; then under ice water cooling conditions, 7.5 parts of 1,3-diethynylbenzene (Shandong Jiaozhou Fine Chemical Co., Ltd.) and 40 parts of THF solvent were added dropwise, and after the dropwise addition was completed, it was incubated at 65°C for 1h; cooled again, under ice water cooling conditions, 5.5 parts of dichlorodimethylsilane (chemically pure, Zhejiang Xin'an Chemical Group Co., Ltd., used after distillation) and 40 parts of THF were added dropwise, and after the dropwise addition was completed, it was incubated at 40°C and 70°C for 2h respectively. After the reaction was completed, the THF in the reaction was evaporated, and a mixture of 7.2 parts of glacial acetic acid and 50 parts of toluene solvent was added dropwise under ice water cooling conditions, fully stirred, then 140 parts of 2.0% dilute hydrochloric acid aqueous solution was added dropwise, fully stirred, and then the upper organic phase was separated. The organic phase was washed with water until neutral, then dried, filtered, and toluene was evaporated to obtain the sila-arylene resin.

[0101] The sila-arylene resin was tested by gel chromatography (GPC, mobile phase THF) to obtain a number average molecular weight of 3000, which is referred to as PSA3000 in the following examples.

[0102] Preparation Example 3

[0103] A sila-arylene resin, specifically a sila-biphenylene acetylene resin, has the following structure:

[0104]

[0105] The preparation method comprises the following steps:

[0106] In a nitrogen-filled reaction kettle, 3.5 parts of magnesium powder (chemically pure, Shanghai Reagent Corporation) and 40 parts of THF solvent were added, stirred at room temperature and 13.5 parts of bromoethane (chemically pure, Shanghai Reagent Corporation) and 40 parts of THF were added dropwise. After the dropwise addition was completed, it was incubated at 50°C for 1h; then under ice water cooling conditions, 12 parts of p-diethynyl biphenyl (Tishai (Shanghai) provided) and 40 parts of THF solvent were added dropwise, and after the dropwise addition was completed, it was incubated at 65°C for 1h; again cooled, under ice water cooling conditions, 5.5 parts of dichlorodimethylsilane (chemically pure, Zhejiang Xin'an Chemical Group Co., Ltd., distilled before use) and 40 parts of THF were added dropwise, and after the dropwise addition was completed, it was incubated at 40°C and 70°C for 2h respectively. After the reaction was completed, the THF in the reaction was evaporated, and a mixture of 7.2 parts of glacial acetic acid and 50 parts of toluene was added dropwise under ice water cooling conditions, and after stirring, 140 parts of 2.0% dilute hydrochloric acid aqueous solution was added dropwise, and after stirring, the upper organic phase was separated. The organic phase was washed with water until neutral, then dried, filtered, and the toluene was evaporated to obtain the sila-arylene resin.

[0107] The sila-arylene resin was tested by gel chromatography (GPC, mobile phase THF), and the number average molecular weight was 3500, which was abbreviated as PSA3500 in the following examples.

[0108] The experimental materials involved in the following examples and comparative examples of the present application include:

[0109] (1) Olefin polymer

[0110] Ricon100, butadiene-styrene copolymer, number average molecular weight M n about 4500, purchased from Kravitz

[0111] B3000, polybutadiene, M n about 3000, purchased from Japan Cabot

[0112] A1535, styrene-butadiene-styrene block copolymer, M n about 200,000, purchased from Cognis;

[0113] A1536, styrene-butadiene-styrene block copolymer, M n about 88,000, purchased from Cognis;

[0114] G1652, hydrogenated styrene-butadiene-styrene block copolymer, M n about 58,000, purchased from Cognis;

[0115] (2) Maleimide resin

[0116] BMI-70, bismaleimide resin, purchased from K.I Chemical Industry Co., Ltd., Japan;

[0117] BMI-50P, poly-maleimide resin, purchased from K.I Chemical Industry Co., Ltd., Japan;

[0118] (3) Crosslinking agent

[0119] TAICROS, triallyl isocyanurate, purchased from Wincat;

[0120] BVPE, p,p'-divinyl-1,2-diphenyl ethane, purchased from Lingchuan Chemical Industry Co., Ltd.;

[0121] DVB, divinyl benzene, purchased from Aldrich;

[0122] (4) Initiator

[0123] Perkadox BC-FF, dicumyl peroxide, purchased from NOF Corporation;

[0124] (5) Inorganic filler

[0125] DQ2028L, spherical silica powder, median particle size D 50 about 3.0 μm, purchased from Jiangsu Lianrui;

[0126] SC2300-svj, spherical silica powder, median particle size D 50 about 0.5 μm, purchased from Japan Yatom;

[0127] (6) Flame retardant

[0128] BT-93w, additive brominated flame retardant, purchased from Albemarle;

[0129] XP7866, additive phosphorus-containing flame retardant, purchased from Albemarle.

[0130] Example 1

[0131] A resin composition includes the following components in parts by weight: 20 parts of sila-arylacetylene resin PSA3000, 40 parts of olefin polymer Ricon100, 5 parts of olefin polymer A1535, 5 parts of olefin polymer A1536, and 30 parts of maleimide resin BMI-70.

[0132] The resin composition is used for the preparation of metal-clad laminate, and the specific method is as follows:

[0133] (1) The resin composition is mixed with 50 parts of toluene and dispersed thoroughly to obtain a glue solution;

[0134] (2) Take the flat and smooth E-type glass fiber cloth of model 2116 to evenly dip the above glue solution, and bake in the air oven at 150°C for 5 min to prepare the prepreg;

[0135] (3) Stack 6 prepregs, cover 35 μm copper foil on the upper and lower surfaces, and press in the vacuum hot press at 3 MPa pressure and 220°C temperature for 90 min to obtain the metal-clad laminate.

[0136] Example 2

[0137] A resin composition includes the following components in parts by weight: 50 parts of sila-arylalkyne resin PSA1200, 25 parts of olefin polymer Ricon100, 5 parts of olefin polymer A1535, 10 parts of olefin polymer G1652, 10 parts of maleimide resin BMI-50P, and 8 parts of inorganic filler DQ2028L.

[0138] The resin composition is used for the preparation of metal-clad laminate, and the specific method is the same as that of Example 1 to obtain the metal-clad laminate.

[0139] Example 3

[0140] A resin composition includes the following components in parts by weight: 20 parts of sila-arylalkyne resin PSA3000, 40 parts of olefin polymer Ricon100, 5 parts of olefin polymer A1535, 5 parts of olefin polymer A1536, 30 parts of maleimide resin BMI-70, 20 parts of crosslinking agent TAICROS, 0.5 parts of initiator Perkadox BC-FF, 90 parts of inorganic filler DQ2028L, and 60 parts of flame retardant BT-93w.

[0141] The resin composition is used for the preparation of metal-clad laminate, and the specific method is as follows:

[0142] (1) Mix the resin composition, 50 parts of butanone and 100 parts of toluene, and then add the inorganic filler and the flame retardant, and obtain the glue solution after high-speed shearing emulsification;

[0143] (2) Take the flat and smooth E-type glass fiber cloth of model 2116 to evenly dip the above glue solution, and bake in the air oven at 150°C for 5 min to prepare the prepreg;

[0144] (3) Stack 6 prepregs, cover 35 μm copper foil on the upper and lower surfaces, and press in the vacuum hot press at 3 MPa pressure and 220°C temperature for 90 min to obtain the metal-clad laminate.

[0145] Examples 4-11, Comparative Examples 1-3

[0146] A resin composition, components and contents thereof are shown in Table 1 and Table 2; the amount of each component in Table 1 and Table 2 is in "parts".

[0147] Table 1

[0148]

[0149] Table 2

[0150]

[0151] The above resin composition was made into metal-clad laminates according to the method in Example 3, and its performance was tested, and the testing method was as follows:

[0152] (1) Glass transition temperature Tg g : using dynamic mechanical analyzer (DMA), according to the DMA test method specified in standard IPC-TM-650 2.4.24;

[0153] (2) Thermal decomposition temperature Td d : tested using thermal gravimetric analysis TGA, according to the method specified in standard IPC-TM-650 2.4.24.6;

[0154] (3) Peel strength PS: the pulling force required to peel off the copper foil per millimeter of copper-clad laminate at room temperature, according to the "as-received" experimental conditions specified in standard IPC-TM-650 2.4.8, test the peel strength of the metal cover layer;

[0155] (4) Dielectric constant D k and dielectric loss factor D f : 10GHz using resonant cavity method (SPDR) method, according to the method specified in standard IPC-TM-650 2.5.5.5;

[0156] (5) Coefficient of thermal expansion CTE: tested using static thermal analyzer TMA, according to the method specified in standard IPC-TM-650 2.4.24; both CTE and 50-260℃ thermal expansion ratio are values measured in the length direction of the laminate sample;

[0157] (6) Thermal stress: immerse the 5cm x 5cm copper-clad laminate in tin at 288℃, observe the delamination or blistering time, less than 10min is recorded as fail;

[0158] (7) Sample plate appearance: after etching the copper foil, visually inspect the flatness of the plate, whether there are gullies, poor flow glue, etc., and test the thickness uniformity of the plate.

[0159] The test results are shown in Table 3:

[0160] Table 3

[0161]

[0162]

[0163] According to the performance test data of Table 3, compared with Comparative Examples 1, 2 and 3, the resin composition provided by the present application has a glass transition temperature of 190-260℃, a thermal decomposition temperature of 370-420℃, a peel strength of 0.6-0.8 N / mm, a thermal expansion coefficient as low as 1.3-1.7%, a dielectric constant ≤4.1 (10 GHz), a dielectric loss factor ≤0.0043 (10 GHz), a 288℃ immersion soldering time >10 min, good thermal stress, and a smooth and uniform appearance of the board, and has excellent adhesive properties, heat resistance, dielectric properties and low thermal expansion coefficient, which can fully meet the performance requirements of high-frequency circuit boards.

[0164] Comparative Example 1 and Example 3 are compared, and the silicon aryl alkyne resin is missing, T g and T d is relatively low, and the heat stress resistance is insufficient; Comparative Example 2 and Example 11 are compared, and the olefin polymer is missing, T g and T d is higher, but the dielectric properties are significantly degraded, the overall board is brittle, and the adhesive properties are insufficient; Comparative Example 3 and Example 11 are compared, and the maleimide resin is missing, the early reaction is slower, the resin flows excessively, the board thickness is uneven, and the adhesive properties are insufficient, and the PS is too low.

[0165] The applicant declares that the resin composition of the present application and the prepreg and metal-clad laminate comprising the same are illustrated by the above examples, but the present application is not limited to the above examples, i.e. it does not mean that the present application must rely on the above examples to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific methods, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. A resin composition, characterized by comprising: The resin composition comprises the following components in parts by weight: 12 to 60 parts of the sila-arylene resin, 5 to 95 parts of the olefin-based polymer, and 6 to 60 parts of the maleimide resin, based on the total of 100 parts of the sum of the weight parts of the sila-arylene resin, the olefin-based polymer, and the maleimide resin. The olefin-based polymer comprises a combination of a low-molecular-weight olefin-based polymer and a high-molecular-weight olefin-based polymer; the low-molecular-weight olefin-based polymer has a number average molecular weight of 1000 to 10000, and the high-molecular-weight olefin-based polymer has a number average molecular weight of 100000 to 500000.

2. The resin composition according to claim 1, characterized by The sila-arylene resin has a structure as shown in Formula I: n is an integer selected from 1 to 50; R1 and R2 are each independently selected from hydrogen, C1 to C6 linear or branched alkyl, and C3 to C6 cycloalkyl; Ar is selected from Dotted lines represent the point of attachment of the group; M is selected from a single bond, O, S, and C1 to C5 linear or branched alkylene; R3 and R4 are each independently selected from halogen and C1 to C5 linear or branched alkyl; m1 and m3 are each independently an integer selected from 0 to 4; m2 is an integer selected from 0 to 6.

3. The resin composition according to claim 2, characterized by R1 and R2 are each independently selected from C1 to C3 linear or branched alkyl.

4. The resin composition according to claim 2, characterized by The Ar is 5. The resin composition according to claim 1, characterized by The sila-arylene resin has a number average molecular weight of 200 to 8000.

6. The resin composition according to claim 5, characterized by The sila-arylene resin has a number average molecular weight of 400 to 4000.

7. The resin composition according to claim 6, characterized by The sila-arylene resin has a number average molecular weight of 500 to 3500.

8. The resin composition according to claim 1, characterized by The polymerized monomers of the olefin-based polymer include any one or a combination of at least two of butadiene, isoprene, maleated diene, divinylbenzene, styrene, dicyclopentadienyl-containing olefin, fluorenyl-containing olefin, biphenyl-containing olefin, or naphthyl-containing olefin.

9. The resin composition according to claim 1, characterized by The olefin-based polymer is an ungrafted olefin-based polymer and / or a graft-modified olefin-based polymer.

10. The resin composition according to claim 9, characterized by The grafting group of the graft-modified olefin-based polymer includes any one or a combination of at least two of a hydroxyl group, a maleic anhydride group, or a methacrylate group.

11. The resin composition according to claim 1, characterized by The mass percentage content of the high-molecular-weight olefin-based polymer in the olefin-based polymer is 1 to 40%.

12. The resin composition according to claim 1, characterized by The maleimide resin comprises at least two maleimide functional groups in the molecular structure thereof.

13. The resin composition according to claim 1, characterized by The weight parts of the sila-arylene resin are 20 to 50 parts, based on the total of 100 parts of the sum of the weight parts of the sila-arylene resin, the olefin-based polymer, and the maleimide resin.

14. The resin composition according to claim 1, characterized by The weight parts of the maleimide resin are 10 to 30 parts, based on the total of 100 parts of the sum of the weight parts of the sila-arylene resin, the olefin-based polymer, and the maleimide resin.

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

16. The resin composition according to claim 15, characterized by The initiator includes any one or a combination of at least two of a peroxide, an azo compound, cumyl, or polycumyl.

17. The resin composition according to claim 16, characterized by The peroxide includes any one or a combination of at least two of dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, t-butyl peroxy isopropyl carbonate, 2,5-dimethyl-2,5-di-t-butylperoxy-3-hexyne, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, p-menthane hydroperoxide, 1,1-bis(t-amylperoxy)cyclohexane, diisopropylbenzene hydroperoxide, benzoyl peroxide, or a benzoyl peroxide derivative.

18. The resin composition according to claim 16, characterized by The azo-based compound includes azobisisobutyronitrile.

19. The resin composition according to claim 1, characterized by The resin composition further includes 5 to 60 parts by weight of a crosslinking agent.

20. The resin composition according to claim 19, characterized by The crosslinking agent is a compound having at least two unsaturated bonds in a molecular structure.

21. The resin composition according to claim 19, characterized by The crosslinking agent includes any one of triallylisocyanurate, polytriallylisocyanurate, triallyl cyanurate, diallyl phthalate, biphenyl having at least two double bonds, dicyclopentadiene, naphthalene-based compound having at least two double bonds, p,p'-divinyl-1,2-diphenyl ethane, or divinylbenzene, or a combination of at least two thereof.

22. The resin composition according to claim 1, characterized by The resin composition further includes 10 to 80 parts by weight of a flame retardant.

23. The resin composition according to claim 22, characterized by The flame retardant is selected from any one of inorganic flame retardant, halogen-based organic flame retardant, phosphorus-based organic flame retardant, nitrogen-based organic flame retardant, or silicon-based organic flame retardant, or a combination of at least two thereof.

24. The resin composition according to claim 1, characterized by The resin composition further includes 5 to 150 parts by weight of an inorganic filler.

25. The resin composition according to claim 24, characterized by The inorganic filler has a particle size of 0.01 to 30 μm.

26. The resin composition according to claim 25, characterized by The inorganic filler has a particle size of 0.1 to 15 μm.

27. The resin composition according to claim 1, characterized by The resin composition further includes 0.01 to 7 parts by weight of a silane coupling agent.

28. A resin film, characterized by, The resin film is prepared by coating the resin composition according to any one of claims 1 to 27 on a release material, and drying and / or semi-curing.

29. A prepreg, characterized by, The prepreg includes a reinforcing material, and the resin composition according to any one of claims 1 to 27 attached to the reinforcing material.

30. The prepreg according to claim 29, wherein, The reinforcing material includes any one of quartz cloth, quartz glass mixed cloth, glass cloth, glass paper, or non-woven fabric, or a combination of at least two thereof.

31. A metal-clad laminate characterized by comprising: The metal-clad laminate includes at least one prepreg according to claim 29 or 30, and a metal foil disposed on one side or both sides of the prepreg.

32. The metal-clad laminate of Claim 31, wherein The metal foil is a copper foil.

33. A printed circuit board, characterized by The printed circuit board includes at least one prepreg according to claim 29 or 30, or a metal-clad laminate according to claim 31 or 32.

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