Metal-clad laminate and use thereof

Abstract

The application provides a metal-clad laminate and application thereof, and the metal-clad laminate comprises at least one prepreg and a metal foil arranged on at least one side of the prepreg; the prepreg comprises a reinforcing material and a resin composition attached to the reinforcing material; the resin composition comprises a base resin and a maleic anhydride modified polybutadiene; and the side of the metal foil in contact with the prepreg is provided with a silane coupling agent layer, and the silane coupling agent comprises an amino-containing silane coupling agent and / or an epoxy-containing silane coupling agent. The application solves the problem of poor bonding force between a polyphenylene ether resin system and a metal foil, significantly improves the bonding strength between the resin composition and the metal foil, and the metal-clad laminate has excellent heat resistance, dielectric properties and reliability, and has good fluidity and processability, and fully meets the requirements of high-frequency high-speed electronic circuit substrates on low dielectric loss, high copper foil heat resistance, high peel strength and other comprehensive properties.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of copper-clad plate, and particularly relates to a metal-clad laminated plate and application thereof. BACKGROUND

[0002] In recent years, with the development of computers and information communication equipment towards high performance, high functionality and networking, in order to transmit and process high-capacity information at high speed, the operating signal tends to be high frequency, and therefore higher requirements are put forward for the material of the circuit substrate, especially the development of the circuit substrate in electronic equipment using wideband (such as mobile communication devices) is particularly rapid.

[0003] Among the existing materials for printed circuit substrates, the use of epoxy resin is the most widespread, which has good bonding properties, processability and cost advantages. However, the dielectric properties of epoxy resin circuit substrates are poor, generally with high dielectric constant and dielectric loss tangent (dielectric constant greater than 4, dielectric loss tangent about 0.02), insufficient high frequency characteristics, and cannot meet the requirements of signal high frequency. Therefore, the development of resin with excellent dielectric properties, i.e. resin with low dielectric constant and dielectric loss tangent, is a hot issue in recent years.

[0004] Research shows that polyphenyl ether resin has low dielectric constant and low dielectric loss, and is a high-frequency material with good dielectric properties. For example, CN103467967A discloses a thermosetting resin composition, which comprises polyphenyl ether resin containing unsaturated double bonds, epoxy resin, curing agent and initiator, and can also comprise a compound containing both epoxy groups and olefinic bonds, flame retardant and accelerator, etc. The thermosetting resin composition has low dielectric constant and dielectric loss, but the flowability of polyphenyl ether resin is poor, the processing performance is poor, and the molecular structure has symmetry and low polarity, and the bonding force with copper foil is poor. In addition, since polyphenyl ether is applied to the high-speed field and needs to be made into a multi-layer board, high heat resistance is required. If the bonding force with copper foil is poor and the heat resistance is not enough, delamination and board explosion problems are likely to occur, which leads to great hidden dangers in performance reliability.

[0005] Polyolefin resin (hydrocarbon resin) has good dielectric properties and better flowability, which attracts extensive research by technical personnel. For example, CN108659504A discloses a composition of hydrocarbon polymer and a prepreg and a thermosetting copper-clad plate prepared therefrom, the composition is composed of six components of base resin, compatibilizer, modified resin, filler, flame retardant and initiator, the base resin is one or several of ethylene-modified polyphenyl ether or a composite mixture of one or several polydiene; it has good dielectric properties, but poor heat resistance, and is prone to delamination and explosion at high temperature. CN111393724A discloses a resin composition and a prepreg and a circuit material using the same, the resin composition comprises unsaturated polyphenyl ether resin, polyolefin resin, rosin resin and initiator. The resin composition has good adhesion and dielectric properties, but the glass transition temperature of the resin composition is low, the heat resistance is not ideal, and the bonding strength with copper foil is also low.

[0006] Therefore, it is an urgent problem in the art to develop a metal foil-clad plate with excellent dielectric properties, heat resistance and strong bonding force with metal foil. SUMMARY

[0007] In view of the deficiencies of the prior art, the purpose of the present application is to provide a metal foil-clad laminate and its application, by designing the components of the resin composition and compounding with the metal foil containing a silane coupling agent layer, the bonding force between the resin composition and the metal foil is significantly improved, and the metal foil-clad laminate has excellent dielectric properties and heat resistance, thereby effectively solving the reliability problem of high-frequency high-speed multilayer metal foil-clad laminate.

[0008] To achieve this purpose, the present application adopts the following technical solutions:

[0009] In a first aspect, the present application provides a metal foil-clad laminate, which comprises at least one prepreg and a metal foil arranged on at least one side of the prepreg; the prepreg comprises a reinforcing material and a resin composition attached to the reinforcing material.

[0010] The resin composition comprises a base resin and a maleic anhydride modified polybutadiene, the base resin comprises a polyphenyl ether resin; the mass of the maleic anhydride modified polybutadiene is 0.5-3 parts based on 100 parts of the mass of the base resin; the side of the metal foil in contact with the prepreg is provided with a silane coupling agent layer, and the silane coupling agent comprises an amino-containing silane coupling agent and / or an epoxy-containing silane coupling agent.

[0011] The metal-clad laminate provided by the present application, wherein the resin composition comprises a combination of a base resin and a maleic anhydride modified polybutadiene, and the side of the metal foil in contact with the prepreg (resin composition) is provided with a silane coupling agent layer containing amino groups and / or epoxy groups, the combination of the two synergistically solves the problem of poor bonding between the polyphenylene ether resin system and the metal foil, significantly improves the bonding strength between the resin composition and the metal foil, and the metal-clad laminate has a high glass transition temperature (T g ), excellent heat resistance and dielectric properties, a low thermal expansion rate, improved reliability, and good flowability and processability, fully meeting the requirements of high-frequency high-speed electronic circuit substrates for low dielectric loss, high copper foil heat resistance, high peel strength, and other comprehensive properties.

[0012] In the resin composition, the mass of the maleic anhydride modified polybutadiene is 0.5-3 parts based on 100 parts of the mass of the base resin (in the present application, the base resin refers to the resin component with an addition amount of more than 5 parts based on 100 parts of the mass of the total base resin, and the mass of the maleic anhydride modified polybutadiene is only 0.5-3 parts, which is not included in the base resin). For example, the mass of the maleic anhydride modified polybutadiene can be 0.6 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, or 2.8 parts, and specific point values between the above point values. Due to the limitation of the length and the consideration of simplicity, the present application does not exhaustively list the specific point values included in the range. The addition of a specific amount of the maleic anhydride modified polybutadiene can improve the bonding strength between the resin composition and the metal foil, and can also reduce the thermal expansion rate of the board and improve the reliability. If the amount of the maleic anhydride modified polybutadiene is too low, the bonding strength between the resin composition and the metal foil cannot be effectively improved, and the thermal expansion rate of the board is large. If the addition amount of the maleic anhydride modified polybutadiene is too high, the dielectric properties and rheological properties of the resin composition will be affected.

[0013] The side of the metal foil in contact with the prepreg is provided with a silane coupling agent layer, the silane coupling agent includes amino-containing silane coupling agent and / or epoxy-containing silane coupling agent. The silane coupling agent content is 0.01-2wt% of the metal foil, for example, it can be 0.03wt%, 0.05wt%, 0.08wt%, 0.1wt%, 0.3wt%, 0.5wt%, 0.8wt%, 1wt%, 1.2wt%, 1.5wt% or 1.8wt%, and specific point values between the above point values, limited to the length and for the sake of simplicity, the present application will not be listed again the specific point values included in the range. The present application has found that the use of amino silane coupling agent and / or epoxy-containing silane coupling agent to treat the metal foil, and the maleic anhydride modified polybutadiene added to the matrix resin, can synergistically improve the bonding force between the resin composition and the metal foil, which is better than the bonding force between the resin composition and the metal foil when other coupling agents such as methacryloxy silane coupling agent are used with maleic anhydride modified polybutadiene. When the silane coupling agent content on the surface of the metal foil is too low, the peel strength PS is low; when the silane coupling agent content on the surface of the metal foil is too high, the coupling agent dispersion effect is poor, which also leads to low PS.

[0014] It should be noted that the metal foil laminated board provided by the present application includes at least one prepreg; for example, the number of prepregs is 1-20, for example, it can be 1, 2, 3, 5, 7, 9, 10, 11, 13, 15, 17 or 19, etc.

[0015] When the metal foil laminated board includes one prepreg, the metal foil is arranged on one side or both sides of the prepreg; when the metal foil laminated board includes at least two prepregs, all the prepregs are laminated to form a laminated board, and the metal foil is arranged on one side or both sides of the laminated board.

[0016] Preferably, the polyphenyl ether resin is a polyphenyl ether resin containing unsaturated groups, and further preferably a polyphenyl ether resin containing unsaturated groups at the end.

[0017] Preferably, the number average molecular weight of the polyphenyl ether resin is 500-10000g / mol, for example, it can be 600g / mol, 800g / mol, 1000g / mol, 2000g / mol, 3000g / mol, 4000g / mol, 5000g / mol, 6000g / mol, 7000g / mol, 8000g / mol or 9000g / mol, and specific point values between the above point values, limited to the length and for the sake of simplicity, the present application will not be listed again the specific point values included in the range. The test method of molecular weight (number average molecular weight, weight average molecular weight) in the present application is GB / T 21863-2008, which is determined by gel permeation chromatography based on polystyrene calibration.

[0018] Preferably, the polyphenylene ether resin has a structure as shown in Formula I:

[0019]

[0020] In Formula I, Z is

[0021] A is selected from any one of carbonyl, C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28) arylene, C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) straight chain or branched chain alkylene;

[0022] R5, R6, R7are each independently selected from any one of hydrogen, C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) straight chain or branched chain alkyl;

[0023] n, m are each independently selected from an integer from 0 to 10, e.g., can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; when n is 0, it represents that the benzene ring is connected to the main chain of Formula I through a single bond; when m is 0, it represents that the alkenyl group is connected to the main chain of Formula I through a single bond.

[0024] In Formula I, X is

[0025] R1, R2, R3, R4, R8, R9, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 are each independently selected from any one of hydrogen, halogen, phenyl, C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) straight chain or branched chain alkyl.

[0026] Y is selected from any one of a single bond, C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) straight chain or branched chain alkylene,

[0027] In Formula I, a, b represent the number of repeating units, and are each independently selected from an integer from 1 to 30, e.g., can be 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, or 28, and specific point values between the above-mentioned point values, the specific point values included in the range are not exhaustively listed in the present application due to the limitation of the page and for the sake of simplicity.

[0028] ​The dotted line represents the connecting site of the group.

[0029] Preferably, the Z is selected from any one of The dotted line represents the connecting site of the group.

[0030] Preferably, the R5 is hydrogen or methyl.

[0031] As a preferred technical solution of the present application, the Z is selected from any one of a vinylbenzyl group, a vinylphenyl group, an acrylate group or a methacrylate group.

[0032] As a preferred technical solution of the present application, the polyphenylene ether resin is a terminal unsaturated group-containing polyphenylene ether resin; the unsaturated group is selected from any one of a vinylbenzyl group, a vinylphenyl group, an acrylate group or a methacrylate group.

[0033] Preferably, the matrix resin further comprises a polyolefin resin.

[0034] Preferably, the polyolefin resin comprises any one or a combination of at least two of a styrene-diene copolymer, a styrene-isoprene copolymer, a hydrogenated styrene-diene copolymer, a hydrogenated styrene-isoprene copolymer, a styrene-diene-styrene block copolymer, a hydrogenated styrene-diene-styrene block copolymer or a polybutadiene.

[0035] The polyolefin resin can be non-modified or modified with groups such as acryloyl or maleic anhydride, for example, a maleic anhydride-modified hydrogenated styrene-diene-styrene block copolymer, a maleic anhydride-modified polybutadiene, etc.

[0036] Preferably, the matrix resin comprises 40-80 parts of the polyphenylene ether resin and 20-60 parts of the polyolefin resin, based on 100 parts of the mass of the matrix resin.

[0037] Preferably, the polyphenylene ether resin in the matrix resin is 40-80 parts, for example, can be 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts or 78 parts, and specific point values between the above point values, limited to the length and for the sake of simplicity, the present application will not exhaustively list the specific point values included in the range.

[0038] Preferably, the polyolefin resin in the matrix resin is 20-60 parts, for example, can be 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, and specific point values between the above point values, limited to the length and for the sake of simplicity, the present application will not exhaustively list the specific point values included in the range.

[0039] As a preferred technical solution of the present application, the base resin comprises a combination of polyphenyl ether resin and polyolefin resin, which are compounded together to help improve the system compatibility, dielectric properties, rheological properties and processability of the resin composition, and further improve the bonding strength of the resin composition and the metal foil. If the amount of polyolefin resin is small, it will affect the flowability and processability of the resin composition; if the amount of polyolefin resin is too high, it will cause the bonding force between the resin composition and the metal foil to decrease, which is also not conducive to the formation of a pre-preg with uniform thickness.

[0040] Preferably, the number average molecular weight of the maleic anhydride modified polybutadiene is 2000-10000 g / mol, for example, it can be 3000 g / mol, 4000 g / mol, 5000 g / mol, 6000 g / mol, 7000 g / mol, 8000 g / mol or 9000 g / mol, and specific point values between the above point values. Due to the limitation of the length and for the sake of simplicity, the present application will not exhaustively list the specific point values included in the range.

[0041] Preferably, the mass percentage of maleic anhydride structural units in the maleic anhydride modified polybutadiene is 3-15%, for example, it can be 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13% or 14%, and specific point values between the above point values. Due to the limitation of the length and for the sake of simplicity, the present application will not exhaustively list the specific point values included in the range.

[0042] In the present application, the maleic anhydride modified polybutadiene can be purchased through market channels, for example, it can be Ricon 131MA10 and / or Ricon 131MA20 of Cray Valley Company.

[0043] Preferably, the resin composition further comprises a free radical initiator.

[0044] Preferably, the mass of the free radical initiator is 0.01-5 parts based on 100 parts of the mass of the base resin, for example, it can be 0.05 parts, 0.1 parts, 0.5 parts, 1 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts or 4.5 parts, and specific point values between the above point values. Due to the limitation of the length and for the sake of simplicity, the present application will not exhaustively list the specific point values included in the range.

[0045] Preferably, the half-life temperature of the free radical initiator is ≥ 130℃, for example, it can be 132℃, 135℃, 138℃, 140℃, 142℃ or 145℃, etc.

[0046] Preferably, the radical initiator includes any one or a combination of at least two of an organic peroxide, an azo compound, or a carbon-based radical initiator, further preferably an organic peroxide.

[0047] Preferably, the organic peroxide includes any one or a combination of at least two of dicumyl peroxide, t-butyl peroxybenzoate, 2,5-di(2-ethylhexanoylperoxy)-2,5- dimethylhexane, di(t-butylperoxy isopropyl)benzene, peroxy(2,4-dichlorobenzoyl), 2,5- dimethyl-2,5-bis(t-butylperoxy)hexane, t-butyl peroxy-2-ethylhexyl carbonate, 2,5-dimethyl- 2,5-bis(t-butylperoxy)-3-hexyne, 4,4-di(t-butylperoxy)butyl valerate, 1,1-bis(t-butylperoxy)-3,3,5- trimethylcyclohexane, 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, di-t-butyl peroxide, or t-butylperoxy isopropyl benzene.

[0048] Preferably, the resin composition further includes a filler.

[0049] Preferably, the filler has a mass of 20-100 parts, for example 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, 90 parts, or 95 parts, and specific point values between the aforementioned point values, the specific point values included in the range are not exhaustively listed herein due to the limitation of the page and for the sake of brevity.

[0050] Preferably, the filler includes an inorganic filler and / or an organic filler.

[0051] Preferably, the inorganic filler includes any one or a combination of at least two of crystalline silica, fused silica, spherical silica, angular silica, chemical silica, hollow silica, silica powder, glass powder, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, titanium dioxide, strontium titanate, barium titanate, aluminum oxide, barium sulfate, talc powder, calcium silicate, calcium carbonate, or mica.

[0052] Preferably, the organic filler includes any one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder, polyetherimide powder, polyphenyl ether powder, or polyether sulfone powder.

[0053] Preferably, the resin composition further includes a flame retardant.

[0054] Preferably, the mass of the flame retardant is 0.1-25 parts, for example, 0.5 parts, 1 part, 3 parts, 5 parts, 7 parts, 9 parts, 10 parts, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts, 20 parts, 22 parts, or 24 parts, and specific point values between the above point values, in 100 parts of the mass of the base resin, and the specific point values included in the range are not exhaustively listed in the present application due to the limitation of the length and the consideration of simplicity.

[0055] Preferably, the flame retardant includes any one or a combination of at least two of a halogen-based flame retardant, a phosphorus-based flame retardant, or a nitrogen-based flame retardant.

[0056] As a preferred technical solution of the present application, the resin composition includes the following components in parts by weight: 100 parts of a base resin, 0.5-3 parts of a maleic anhydride modified polybutadiene, and 0.01-5 parts of a free radical initiator; the base resin includes 40-80 parts of a polyphenylene ether resin and 20-60 parts of a polyolefin resin.

[0057] As another preferred technical solution of the present application, the resin composition includes the following components in parts by weight: 100 parts of a base resin, 0.5-3 parts of a maleic anhydride modified polybutadiene, 0.01-5 parts of a free radical initiator, 20-200 parts of a filler, and 0.1-20 parts of a flame retardant; the base resin includes 40-80 parts of a polyphenylene ether resin and 20-60 parts of a polyolefin resin.

[0058] In consideration of the need for preparation and processing, a solvent is further included in the resin composition, and the amount of the solvent is not limited as long as the glue viscosity of the resin composition meets the processing requirements.

[0059] The type of the solvent is not particularly limited, and includes any one or a combination of at least two of an alcohol solvent, an ether solvent, an aromatic hydrocarbon solvent, an ester solvent, a ketone solvent, or a nitrogen-containing solvent; and exemplarily includes, but is not limited to, methanol, ethanol, butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol, butyl carbitol, acetone, butanone, methyl ethyl ketone, cyclohexanone, toluene, xylene, ethyl acetate, ethoxyethyl acetate, N,N-dimethylformamide, or N,N-dimethylacetamide; the above solvents can be used alone or in combination of two or more.

[0060] Preferably, the solvent includes any one or a combination of at least two of acetone, butanone, methyl ethyl ketone, cyclohexanone, toluene, or xylene.

[0061] Preferably, the reinforcing material includes any one of an organic fiber cloth, an inorganic fiber woven cloth, or a non-woven cloth.

[0062] Preferably, the reinforcing material comprises any one of glass fiber cloth, quartz cloth, quartz glass blended cloth, glass fiber paper, non-woven fabric or organic fiber cloth; exemplary ones include, but are not limited to, E-glass fiber cloth, D-glass fiber cloth, S-glass fiber cloth, T-glass fiber cloth, NE-glass fiber cloth or quartz cloth.

[0063] Preferably, the organic fiber cloth comprises aramid cloth.

[0064] Preferably, the thickness of the reinforcing material is 0.01-0.2 mm, for example, 0.03 mm, 0.05 mm, 0.08 mm, 0.1 mm, 0.11 mm, 0.13 mm, 0.15 mm, 0.17 mm or 0.19 mm, and specific point values between the above point values; for the sake of brevity and simplicity, the present application does not list all the specific point values included in the range.

[0065] Preferably, the reinforcing material is subjected to a fibrillation treatment and / or a silane coupling agent treatment.

[0066] Preferably, the silane coupling agent comprises any one or a combination of at least two of an epoxy silane coupling agent, an amino silane coupling agent or a vinyl silane coupling agent.

[0067] Preferably, the method for preparing the silane coupling agent layer on the metal foil comprises uniformly coating an aqueous solution of a silane coupling agent on the metal foil, and drying to obtain the silane coupling agent layer.

[0068] Preferably, the metal foil comprises any one of a copper foil, a nickel foil, an aluminum foil or a SUS foil, and further preferably a copper foil.

[0069] In the present application, the side of the metal foil in contact with the prepreg is provided with a silane coupling agent layer, and the side of the metal foil away from the prepreg is not particularly limited, and can be provided with or not provided with a silane coupling agent layer.

[0070] In the present application, the copper foil comprises any one of a common copper foil, a roughness copper foil or a low-profile copper foil, and in the high-speed field, a HVLP copper foil is preferred; the thickness of the copper foil is not particularly limited.

[0071] Exemplarily, the present application provides a method for preparing a metal foil-clad laminate, which comprises: pressing a metal foil on one side or both sides of a prepreg, and curing to obtain the metal foil-clad laminate; or, stacking at least two prepregs into a laminate, pressing a metal foil on one side or both sides of the laminate, and curing to obtain the metal foil-clad laminate; the side of the metal foil in contact with the prepreg is provided with a silane coupling agent layer.

[0072] Preferably, the temperature of the curing is 200-250℃, such as 205℃, 210℃, 212℃, 215℃, 218℃, 220℃, 223℃, 225℃, 228℃, 230℃, 235℃, 240℃ or 245℃, and the like, further preferably 210-230℃.

[0073] Preferably, the pressure of the curing is 10-60kg / cm 2 , such as 15kg / cm 2 , 20kg / cm 2 , 25kg / cm 2 , 30kg / cm 2 , 35kg / cm 2 , 40kg / cm 2 , 45kg / cm 2 , 50kg / cm 2 or 55kg / cm 2 , and the like.

[0074] Preferably, the time of the curing is 30-180min, such as 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min or 175min, and the like.

[0075] Preferably, the prepreg is prepared by a method comprising: infiltrating a resin solution of the resin composition into a reinforcing material, and then drying to obtain the prepreg.

[0076] Preferably, the temperature of the drying is 100-180℃, such as 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃ or 175℃, and the like.

[0077] Preferably, the time of the drying is 1-10min, such as 2min, 3min, 4min, 5min, 6min, 7min, 8min or 9min, and the like.

[0078] In the second aspect, the present application provides a printed wiring board, which comprises at least one metal-clad laminate as described in the first aspect.

[0079] Compared with the prior art, the present application has the following beneficial effects:

[0080] The metal-clad laminate provided by the present application solves the problem of poor bonding between the polyphenyl ether resin system and the metal foil by designing the components of the resin composition and matching the metal foil containing a silane coupling agent layer, significantly improves the bonding strength between the resin composition and the metal foil, and in the HOZ copper foil metal-clad laminate, the peel strength of the A state is > 0.70 N / mm, the peel strength after thermal stress treatment is > 0.65 N / mm, and the metal-clad laminate has a high glass transition temperature, T g > 190℃, has excellent heat resistance, dielectric properties and reliability, and has good flowability and processability, fully meeting the requirements of high-frequency high-speed electronic circuit substrates for low dielectric loss, high copper foil heat resistance, high peel strength and other comprehensive properties. DETAILED DESCRIPTION

[0081] The technical solutions of the present application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations of the present application.

[0082] The materials designed in the following examples and comparative examples of the present application include:

[0083] (1) Polyphenyl ether resin

[0084] SA9000, thermosetting polyphenyl ether containing a methyl methacrylate group at the end, Sabic Company;

[0085] OPE-2ST, thermosetting polyphenyl ether containing a vinyl benzyl group at the end, Mitsubishi Chemical;

[0086] (2) Polyolefin resin

[0087] Ricon 100, styrene-butadiene copolymer, Cray Valley Company;

[0088] D1118, styrene-butadiene-styrene copolymer, Kraton Company;

[0089] (3) Maleic anhydride modified polybutadiene

[0090] Ricon 131MA10, Cray Valley Company;

[0091] Ricon 131MA20, Cray Valley Company;

[0092] B3000, polybutadiene (unmodified, as a comparative example), Japan Zeon;

[0093] (4) Free radical initiator

[0094] DCP, dicumyl peroxide, Shanghai Gaqiao;

[0095] (5) Silane coupling agent

[0096] KBM-403, epoxy silane coupling agent, Shin-Etsu Chemical;

[0097] KBM-602, amino silane coupling agent, Shin-Etsu Chemical;

[0098] KBM-503, methacryloxy silane coupling agent, Shin-Etsu Chemical;

[0099] (6) Filler

[0100] SC6500-SVC, fused silica micropowder, average particle size 2.5 μm, Adematacs Company;

[0101] (7) Flame retardant

[0102] DE-295, phosphorus-based flame retardant, Jiangsu Yak;

[0103] (8) Reinforcing material

[0104] Glass fiber cloth 2116, Taiwan, China;

[0105] (9) Metal foil

[0106] BFNN, HOZ copper foil, Luxembourg (RZ≤1.5 μm);

[0107] BFNN, 10OZ copper foil, Luxembourg (RZ≤1.5 μm).

[0108] Example 1

[0109] A metal-clad laminate, comprising 6 prepregs and copper foils arranged on both sides of the laminate; the prepregs comprise reinforcing material (glass fiber cloth, 2116) and a resin composition attached to the reinforcing material.

[0110] The resin composition comprises the following components by weight: 60 parts of polyphenylene ether resin SA9000, 40 parts of polyolefin resin Ricon 100, 1.0 parts of maleic anhydride modified polybutadiene Ricon 131MA10, 2.0 parts of free radical initiator DCP, 50 parts of filler SC6500-SVC, 3.0 parts of flame retardant DE-295.

[0111] The surface of the copper foil is provided with a silane coupling agent layer containing epoxy groups, and the arrangement method is as follows: the silane coupling agent KBM-403 is dispersed in an aqueous solution and coated on the HOZ copper foil, and dried to obtain a silane coupling agent layer; the content of the silane coupling agent containing epoxy groups is 0.5 wt% of the metal foil.

[0112] The method for preparing the metal-clad laminate includes the following steps:

[0113] (1) The resin composition is mixed with methyl ethyl ketone (MEK) according to the formulation amount to prepare a resin glue with a solid content of 65%; after the glass fiber cloth is impregnated with the resin glue, it is dried at 150°C for 3 min to obtain a prepreg;

[0114] (2) Six prepregs are stacked, and copper foils with silane coupling agent layers on the upper and lower sides are arranged on the upper and lower sides of the prepregs, and then placed in a press at a temperature of 200°C and a pressure of 25 kg / cm 2 and cured for 2 h to obtain the metal-clad laminate.

[0115] The preparation methods of Examples 2-4 and Comparative Examples 1-6 are the same as those of Example 1, and the addition amounts of the components are shown in Tables 1 and 2.

[0116] The metal-clad laminates provided by Examples 1-4 and Comparative Examples 1-6 are tested for the following properties:

[0117] (1) Dielectric constant Dk and dielectric loss factor Df: tested according to the Split Post Dielectric Resonator (SPDR) method, and the test frequency is 10 GHz.

[0118] (2) Peel strength (A state): tested according to the method in IPC-TM-650 2.4.8, and the test instrument is a copper foil peel tester.

[0119] (3) Peel strength (thermal stress): after the metal-clad laminate to be tested is immersed in tin at 288°C for 20 min, the tensile force required to peel the copper foil per millimeter of the metal-clad laminate is tested according to the method in IPC-TM-650 2.4.8.

[0120] (4) Glass transition temperature Tg: tested by dynamic mechanical thermal analysis (DMA) according to the standard method in IPC-TM-650 2.4.24.4. g

[0121] (5) Flowability PP (RF): tested in a press according to the method in IPC-TM-650 2.3.17.

[0122] The addition amounts of the components and the test results are shown in Tables 1 and 2:

[0123] Table 1

[0124]

[0125] ​

[0126] Table 2

[0127]

[0128]

[0129] Note: The non-dimensional amount of addition in Table 1 and Table 2 refers to "parts by mass", and the amount of addition of silane coupling agent refers to the percentage by weight of the metal foil. The copper foil of HOZ is used in Examples 1-4 and Comparative Examples 1-6, and the roughness of the copper foil is low (RZ≤1.5 μm), and the copper is thin, so the peel strength of the system is much lower than that of thick copper. The copper foil of 10Z is used in Example 5, and the peel strength of the prepared plate is as high as 1.4 N / mm.

[0130] According to the performance data in Table 1, in the metal-clad laminate provided by the application, by introducing maleic anhydride modified polybutadiene into the resin composition and compounding with the metal foil containing a layer of silane coupling agent of a specific type, the bonding strength of the resin composition and the metal foil is significantly improved, the peel strength in A state is 0.73-0.79 N / mm (copper foil of HOZ, RZ≤1.5 μm), and the peel strength after 20 min hot stress treatment at 288℃ is as high as 0.66-0.74 N / mm (copper foil of HOZ, RZ≤1.5 μm), and the metal-clad laminate has high T g , and good processability.

[0131] As can be seen from the comparison between Comparative Example 1 and Comparative Example 1, if the copper foil is treated with a silane coupling agent other than an amino-containing silane coupling agent and an epoxy-containing silane coupling agent, the peel strength of the resin composition and the copper foil is low. As can be seen from Comparative Examples 2-3, without the addition of maleic anhydride modified polybutadiene, the peel strength of the copper foil treated with a silane coupling agent alone is low. As can be seen from the comparison between Example 1 and Comparative Example 4, when polybutadiene is used to replace maleic anhydride modified polybutadiene, the coupling agent on the surface of the copper foil lacks the synergistic effect of maleic anhydride, resulting in poor peel strength. As can be seen from the comparison between Example 1 and Comparative Example 5, when maleic anhydride modified polybutadiene is added to the resin composition, and the copper foil is not treated with a coupling agent, the bonding strength of the resin composition and the copper foil is very low. As compared with Example 1, Comparative Example 6 has a large amount of maleic anhydride modified polybutadiene added, although the peel strength is improved, the flowability of the plate is significantly reduced, and the processability is poor.

[0132] The applicant states that the metal-clad laminate and the use thereof of the present application are illustrated by the above-mentioned embodiments, but the present application is not limited to the above-mentioned embodiments, i.e. it does not mean that the present application must rely on the above-mentioned embodiments 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 modes, etc. fall within the protection scope and disclosure scope of the present application.

Claims

1. A metal foil-coated laminate, characterized in that, The metal foil laminate includes at least one prepreg and a metal foil disposed on at least one side of the prepreg; The prepreg includes a reinforcing material and a resin composition attached to the reinforcing material; The resin composition comprises a matrix resin and maleic anhydride-modified polybutadiene, wherein the matrix resin comprises 40-80 parts of polyphenylene ether resin and 20-60 parts of polyolefin resin; and the maleic anhydride-modified polybutadiene comprises 0.5-3 parts by mass of 100 parts of the matrix resin. A silane coupling agent layer is provided on the side of the metal foil that is in contact with the prepreg, wherein the silane coupling agent is an amino-containing silane coupling agent and / or an epoxy-containing silane coupling agent.

2. The metal foil-coated laminate according to claim 1, characterized in that, The polyphenylene ether resin is a polyphenylene ether resin containing unsaturated groups.

3. The metal foil-coated laminate according to claim 1, characterized in that, The number average molecular weight of the polyphenylene ether resin is 500-10000 g / mol.

4. The metal foil-coated laminate according to claim 1, characterized in that, The silane coupling agent content is 0.01-2 wt% of the metal foil.

5. The metal foil-coated laminate according to claim 1, characterized in that, The polyphenylene ether resin has the structure shown in Formula I: ； Where Z is or ; A is selected from any one of carbonyl, C6-C30 arylene, C1-C10 straight-chain or branched alkylene groups; R5, R6, and R7 are each independently selected from hydrogen, C1-C10 straight-chain or branched alkyl groups; n and m are each independently selected from integers between 0 and 10; X is ; R1, R2, R3, R4, R8, R9, R 10 R 11 R 12 R 13 R 14 R 15 Each is independently selected from any one of hydrogen, halogen, phenyl, C1-C10 straight-chain or branched alkyl groups; Y is selected from single bonds, C1-C10 straight-chain or branched alkylene groups, , , , or Any one of them; a and b are each independently selected from integers between 1 and 30; The dashed lines represent the bonding sites of the functional groups.

6. The metal foil-coated laminate according to claim 1, characterized in that, The polyolefin resin includes any one or a combination of at least two of the following: styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, or polybutadiene.

7. The metal foil-coated laminate according to claim 1, characterized in that, The maleic anhydride-modified polybutadiene has a number-average molecular weight of 2000-10000 g / mol.

8. The metal foil-coated laminate according to claim 1, characterized in that, The maleic anhydride-modified polybutadiene contains 3-15% maleic anhydride structural units by mass.

9. The metal foil-coated laminate according to claim 1, characterized in that, The resin composition also includes a free radical initiator.

10. The metal foil-coated laminate according to claim 9, characterized in that, The free radical initiator is 0.01-5 parts by mass of 100 parts of the matrix resin.

11. The metal foil-coated laminate according to claim 9, characterized in that, The free radical initiator includes any one or a combination of at least two of organic peroxides, azo compounds, or carbon-based free radical initiators.

12. The metal foil-coated laminate according to claim 11, characterized in that, The free radical initiator is an organic peroxide.

13. The metal foil-coated laminate according to claim 1, characterized in that, The resin composition also includes fillers.

14. The metal foil-coated laminate according to claim 13, characterized in that, The filler is 20-100 parts by weight of 100 parts of the matrix resin.

15. The metal foil-coated laminate according to claim 13, characterized in that, The packing material includes inorganic packing material and / or organic packing material.

16. The metal foil-coated laminate according to claim 1, characterized in that, The resin composition also includes a flame retardant.

17. The metal foil-coated laminate according to claim 16, characterized in that, The flame retardant is 0.1-25 parts by mass of 100 parts of the matrix resin.

18. The metal foil-coated laminate according to claim 1, characterized in that, The reinforcing material includes any one of glass fiber cloth, quartz cloth, quartz glass blended cloth, glass fiber paper, non-woven cloth or organic fiber cloth.

19. The metal foil-coated laminate according to claim 1, characterized in that, The thickness of the reinforcing material is 0.01-0.2 mm.

20. The metal foil-coated laminate according to claim 1, characterized in that, The method for preparing the silane coupling agent layer on the metal foil includes: coating an aqueous solution of silane coupling agent onto the metal foil and drying it to obtain the silane coupling agent layer.

21. The metal foil-coated laminate according to claim 1, characterized in that, The metal foil includes any one of copper foil, nickel foil, aluminum foil, or SUS foil.

22. The metal foil-coated laminate according to claim 21, characterized in that, The metal foil is copper foil.

23. A printed circuit board, characterized in that, The printed circuit board includes at least one metal foil laminate as described in any one of claims 1-22.

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