WO2022134230A1 - 一种热固性树脂组合物、使用其的半固化片与覆铜箔层压板 - Google Patents

一种热固性树脂组合物、使用其的半固化片与覆铜箔层压板 Download PDF

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WO2022134230A1
WO2022134230A1 PCT/CN2021/070909 CN2021070909W WO2022134230A1 WO 2022134230 A1 WO2022134230 A1 WO 2022134230A1 CN 2021070909 W CN2021070909 W CN 2021070909W WO 2022134230 A1 WO2022134230 A1 WO 2022134230A1
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weight
parts
tert
resin composition
peroxide
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PCT/CN2021/070909
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English (en)
French (fr)
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关迟记
曾宪平
陈宇航
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广东生益科技股份有限公司
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Publication of WO2022134230A1 publication Critical patent/WO2022134230A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention belongs to the technical field of laminates, and relates to a thermosetting resin composition, a prepreg using the same, and a copper-clad laminate.
  • epoxy resins having excellent adhesive properties are widely used.
  • epoxy resin circuit substrates generally have high dielectric constant and dielectric loss tangent (dielectric constant Dk is greater than 4, dielectric loss tangent Df is about 0.02), and the high-frequency characteristics are insufficient, which cannot meet the requirements of high-frequency signals. . Therefore, it is necessary to develop resins with excellent dielectric properties, that is, resins with low dielectric constant and dielectric loss tangent.
  • thermosetting polyphenylene ether resins bismaleimide resins, vinylbenzyl ether resins, hydrocarbon resins, etc.
  • the hydrocarbon resin polyolefin resin
  • Df dielectric loss tangent
  • PTFE resin parable to PTFE resin
  • good fluidity which has attracted a large number of technical personnel to conduct a lot of in-depth research on it.
  • Df dielectric loss tangent
  • the application of the modified polyphenylene ether resin curable with active groups at the end of the molecular chain or in the side chain in the high-speed circuit substrate is generally to form a resin composition in combination with a cross-linking agent.
  • the crosslinking agent has reactive groups that can react with the modified polyphenylene ether.
  • the commonly used crosslinking agents are polybutadiene, butadiene styrene copolymer, etc.
  • CN 101370866A, CN 102161823, CN 102304264 patents use polybutadiene or butadiene styrene copolymer as the crosslinking agent of modified polyphenylene ether to prepare high-speed circuit substrates. Although the comprehensive properties of the board are excellent, but polybutadiene or butadiene styrene copolymer reduces the peel strength and interlayer adhesion of the board.
  • the sheet has excellent dielectric properties, due to the large molecular weight of styrene-butadiene-styrene triblock copolymer (SBS), SBS is difficult to dissolve, and it is difficult to wet glass fiber cloth, and the resistance to CAF is poor;
  • the content of butadiene added at the 1 and 2 positions in the molecule is relatively low, so that the reaction degree and Tg of the system are low, and the system is still a thermoplastic substrate, which is difficult to meet the lead-free reflow soldering requirements of high-speed transmission and high-layer PCBs. , cannot meet the usage requirements.
  • the purpose of the present invention is to provide a thermosetting resin composition, a prepreg using the same, and a copper-clad laminate.
  • the thermosetting resin composition has low dielectric constant Dk and low dielectric loss Df, excellent heat resistance, interlayer adhesion and peel strength, and excellent CAF resistance, and satisfies the requirements of high-speed circuit substrates for dielectric constant and dielectric loss. , heat resistance, peel strength, interlayer adhesion and CAF and other performance requirements, can be used to prepare high-speed circuit substrates.
  • the present invention provides a thermosetting resin composition
  • a thermosetting resin composition comprising the following components: (A) a styrene-butadiene-styrene triblock copolymer containing 1,2-vinyl units , (B) thermosetting polyphenylene ether resin, (C) silane coupling agent; wherein the number-average molecular weight of the component (A) is less than 20,000, the molecule contains 10-60% by weight of styrene structure, and the molecule The content by weight of butadiene added at the 1 and 2 positions is greater than or equal to 90%.
  • the component (A) styrene-butadiene-styrene triblock copolymer (SBS) containing 1,2-vinyl units can significantly improve the crosslinking density of the resin composition after curing, And effectively improve the interlayer adhesion of the substrate and the peel strength of the copper foil and the substrate, and meet the lead-free reflow soldering requirements of high-speed transmission and high-layer PCB.
  • the number average molecular weight is less than 20000, which can be conducive to solvent dissolution and improve the process It is beneficial to have better compatibility with thermosetting polyphenylene ether. Low molecular weight is beneficial to infiltrating glass fiber cloth, improving CAF resistance, and improving the reliability of multi-layer printed circuit boards.
  • component (A) and component (C) in the present invention can improve the peel strength and interlayer adhesion of the system.
  • the number average molecular weight of component (A) is less than 20000, for example, it can be 18000, 15000, 13000, 10000, 8000, 6000, 4000, 2000, 1000, etc.; preferably, the number average molecular weight of component (A)
  • the molecular weight is 1,000 to 20,000, more preferably 1,000 to 10,000, and still more preferably 1,000 to 6,000.
  • the number-average molecular weight in the present invention refers to the number-average molecular weight measured by gel permeation chromatography.
  • the number average molecular weight of the SBS resin is too large, it is difficult to dissolve, and the compatibility with polyphenylene ether is poor, so it is easy to precipitate.
  • the number average molecular weight of the SBS resin is too large, it is difficult to infiltrate the glass fiber cloth during sizing, and the CAF resistance of the board is poor.
  • the molecule of component (A) contains 10-60% by weight of styrene structure, for example, the weight ratio of styrene can be 10%, 15%, 20%, 25%, 30%, 35% %, 40%, 45%, 50%, 55% or 60%; too high styrene content will result in insufficient butadiene content, resulting in too low crosslinking density of the system, and poor interlayer adhesion and peel strength. If the styrene content is too low, it will lead to poor compatibility with polyphenylene ether and insufficient rigidity.
  • the content of butadiene added at the 1,2 position in the molecule of component (A) is greater than or equal to 90% by weight, which means that the content of butadiene added at the 1,2 position accounts for the proportion of butadiene added in the (A) molecule.
  • the weight ratio of the total diene weight is greater than or equal to 90%, such as 90%, 91%, 92%, 93%, 95%, 96%, 97%, 98% or 99%, etc.
  • thermosetting polyphenylene ether resin is a polyphenylene ether resin having a structure represented by the following formula (1):
  • a and b are independently an integer of 1 to 30 (for example, 1, 3, 5, 8, 10, 15, 20, 25, or 30, etc.), and Z is represented by formula (2) or formula (3)
  • A is an arylene group, a carbonyl group, or an alkylene group having 1 to 10 carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10), m is an integer of 0 to 10 (for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), and R 1 to R 3 are the same or different, and are hydrogen or 10 or less carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10) alkyl;
  • R 4 and R 6 are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8) or benzene group
  • R 5 and R 7 are the same or different, and are halogen atoms, alkyl groups with less than 8 carbon atoms, or phenyl groups;
  • R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are the same or different, and are a hydrogen atom, a halogen atom, or an alkyl group having 8 or less carbon atoms or phenyl, and B is a hydrocarbylene group having 20 or less carbon atoms (for example, 20, 18, 16, 14, 10, 8, 5, 3, etc.),
  • n 0 or 1;
  • R 16 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10).
  • the number-average molecular weight of the thermosetting polyphenylene ether resin is 500-10000 g/mol, such as 500 g/mol, 800 g/mol, 1000 g/mol, 3000 g/mol, 5000 g/mol, 8000 g/mol or 10000 g/mol, Preferably it is 800-8000 g/mol, More preferably, it is 1000-4000 g/mol.
  • the resin component of the thermosetting resin composition of the present invention does not contain polar hydroxyl groups, and does not generate polar groups such as secondary hydroxyl groups during the curing process, which can ensure low water absorption of the circuit substrate and excellent dielectric properties. electrical properties.
  • the amount of the component (B) thermosetting polyphenylene ether resin is 10-90 parts by weight, for example, 15 parts by weight, 25 parts by weight, 35 parts by weight parts, 45 parts by weight, 55 parts by weight, 65 parts by weight, 75 parts by weight, 85 parts by weight, etc.
  • the amount of the styrene-butadiene-styrene triblock copolymer containing 1,2-vinyl unit of component (A) is 10-90 Parts by weight, for example, 15 parts by weight, 25 parts by weight, 35 parts by weight, 45 parts by weight, 55 parts by weight, 65 parts by weight, 75 parts by weight, 85 parts by weight, and the like.
  • the component (C) silane coupling agent is selected from methacrylate-based silane coupling agent, epoxy silane coupling agent, vinyl silane coupling agent, amino silane coupling agent, phenyl silane One or a combination of at least two of a coupling agent, an anilino silane coupling agent or an oligomeric silane coupling agent.
  • the total amount of component (C) silane coupling agent is 0.1 to 5 parts by weight, for example, it can be 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight, etc.
  • silane coupling agent by adding a silane coupling agent, it has a synergistic effect with styrene-butadiene-styrene triblock copolymer (SBS) and polyphenylene ether, which helps to further improve the interlayer adhesion It can improve the peel strength of copper foil and substrate, and prevent the risk of dropped wires and pads during the use of printed circuit boards.
  • SBS styrene-butadiene-styrene triblock copolymer
  • polyphenylene ether polyphenylene ether
  • thermosetting resin composition further includes component (D) a free radical initiator.
  • the amount of the free radical initiator of component (D) is 0.1 to 5 parts by weight, for example, it can be 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight, etc.
  • the free radical initiator is a first initiator, a second initiator or a combination of a first initiator and a second initiator;
  • the 1 min half-life temperature of the first initiator is 50-160°C (for example, it can be is 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C or 160°C, etc.)
  • the 1min half-life temperature of the second initiator is 161-300°C (for example, it can be 162°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C or 300°C, etc.).
  • the first initiator is selected from tert-butyl peroxyacetate, 2,2-bis(tert-butylperoxy)octane, tert-butylperoxyisopropyl carbonate, 1,1- Bis(tert-butylperoxy)cyclohexanone, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexanone, tert-butylperoxyoctanoate, tert-butylperoxycaprylate Butyl Peroxyisobutyrate, Disuccinic Acid Peroxide, Di-m-Toluoyl Peroxide, Ditoluoyl Peroxide, Diacetyl Peroxide, Cumyl Peroxyoctanoate, Dicaproyl Peroxide, dioctanoyl peroxide, didodecanoyl peroxide, bis(3,5,5-trimethylacetyl peroxide), tert-butyl
  • the second initiator is selected from the group consisting of tert-butyl hydroperoxide, tetramethylbutane peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne, Di-tert-butylperoxide, a,a-bis(tert-butylperoxy-m-cumyl), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane , tert-butyl cumyl peroxide, tert-butyl peroxyallyl bicarbonate, dicumyl peroxide (DCP), tert-butyl peroxybenzoate, di-tert-butyl peroxyiso Phthalate, n-butyl-4,4-bis(tert-butylperoxy)valerate, tert-butylperoxy(3,5,5-trimethylacetate), tert-butylperoxylauryl
  • DCP di
  • thermosetting resin composition further includes component (E) a co-crosslinking agent.
  • the co-crosslinking agent is triallyl cyanurate, triallyl isocyanate, multifunctional acrylate compound, bismaleimide resin, divinylbenzene, styrene - One or a mixture of at least two of butadiene copolymers, polybutadiene and styrene-butadiene-divinylbenzene copolymers, polyfunctional vinylaromatic copolymers. It is preferably one or a mixture of at least two of triallyl cyanurate, triallyl isocyanate, polyfunctional acrylate compound, and polyfunctional vinyl aromatic copolymer.
  • the co-crosslinking agent (E) is added in an amount of 3 to 60 parts by weight, for example, 3 parts by weight, 6 parts by weight, 10 parts by weight, based on the total of components (A)+(B) being 100 parts by weight , 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight or 60 parts by weight.
  • thermosetting resin composition further includes a filler.
  • the filler is used in an amount of 10 to 300 parts by weight, such as 10 parts by weight, 30 parts by weight, 50 parts by weight, 80 parts by weight, 100 parts by weight parts by weight, 150 parts by weight, 200 parts by weight, 250 parts by weight or 300 parts by weight.
  • the filler is an organic filler or an inorganic filler.
  • the inorganic filler is selected from crystalline silica, fused silica, spherical silica, hollow silica, glass powder, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, titanium dioxide, One or a combination of at least two of strontium titanate, barium titanate, alumina, barium sulfate, talc, calcium silicate, calcium carbonate or mica.
  • the organic filler is selected from one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide, polyetherimide, polyphenylene oxide or polyethersulfone powder.
  • thermosetting resin composition further includes a flame retardant.
  • the flame retardant is a bromine-containing flame retardant or a halogen-free flame retardant.
  • thermosetting resin composition of the present invention is determined by the need for flame retardancy, so that the resin cured product has flame retardant properties and meets the requirements of UL 94 V-0.
  • the flame retardant added as needed is not particularly limited, and it is preferable that it does not affect the dielectric properties.
  • the bromine-containing flame retardant is one or at least two of decabromodiphenyl ether, decabromodiphenylethane, ethylenebistetrabromophthalimide or brominated polycarbonate The combination.
  • the optional commercial brominated flame retardants include BT-93, BT-93W, HP-8010 or HP-3010, but are not limited to the above types.
  • the halogen-free flame retardant is one or a combination of at least two of a phosphorus-containing halogen-free flame retardant, a nitrogen-containing halogen-free flame retardant and a silicon-containing halogen-free flame retardant.
  • the halogen-free flame retardant is tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa- 10-Phosphinophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene or 10-phenyl-9,10-dihydro-9-oxa-10-phosphine
  • the optional commercial halogen-free flame retardants are SPB-100, PX-200, PX-202, LR-202, LR-700, OP-930, OP-935, LP-2200, XP-7866, but not Not limited to the above categories.
  • the amount of the flame retardant is determined according to the requirement that the cured product reaches the UL 94 V-0 level, and there is no particular limitation. Considering that the heat resistance, dielectric properties and hygroscopicity of the cured product are not sacrificed, the amount of the flame retardant is 5-80 parts by weight, based on the total of components (A)+(B) being 100 parts by weight, For example, 5 parts by weight, 8 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight or 80 parts by weight, preferably 10-60 parts by weight, more It is preferably 15 to 40 parts by weight.
  • the thermosetting resin composition further comprises additives introduced to solve certain problems, the additives are antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, anti-drip One or a combination of at least two of the additives, antiblocking agents, antistatic agents, flow enhancers, processing aids, substrate adhesives, mold release agents, toughening agents, low shrinkage additives, or stress relief additives.
  • the additives are antioxidants, heat stabilizers, light stabilizers, plasticizers, lubricants, flow modifiers, anti-drip One or a combination of at least two of the additives, antiblocking agents, antistatic agents, flow enhancers, processing aids, substrate adhesives, mold release agents, toughening agents, low shrinkage additives, or stress relief additives.
  • the amount of the additive is not particularly limited, and the amount of the additive is preferably 0.1-10 parts by weight based on the total of components (A) + (B) being 100 parts by weight , such as 0.1 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight or 10 parts by weight, more preferably 0.5 to 8 parts by weight, still more preferably 1 to 5 parts by weight.
  • the present invention provides the above-mentioned preparation method of the thermosetting resin composition, and the preparation method can adopt a known method to compound, stir and mix the styrene-butadiene-styrene triblock Copolymer (SBS), thermosetting polyphenylene ether, silane coupling agent and optional co-crosslinking agent, free radical initiator, powder filler, as well as various flame retardants, various additives, to prepare.
  • SBS styrene-butadiene-styrene triblock Copolymer
  • silane coupling agent silane coupling agent
  • optional co-crosslinking agent free radical initiator
  • powder filler as well as various flame retardants, various additives
  • the present invention provides a resin glue solution obtained by dissolving or dispersing the above-mentioned thermosetting resin composition in a solvent.
  • the solvent in the present invention is not particularly limited, and specific examples include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, and butyl alcohol.
  • Ethers such as base carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc., aromatic hydrocarbons such as toluene, xylene, mesitylene, ethoxy Esters such as ethyl acetate and ethyl acetate, and nitrogen-containing solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.
  • aromatic hydrocarbons such as toluene, xylene, mesitylene, ethoxy Esters such as ethyl acetate and ethyl acetate
  • nitrogen-containing solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.
  • the above-mentioned solvents can be used alone or in combination of two or more, preferably aromatic hydrocarbon solvents such as toluene, xylene, mesitylene and acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isophthalate, etc.
  • aromatic hydrocarbon solvents such as toluene, xylene, mesitylene and acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isophthalate, etc.
  • Ketone fluxes such as butyl ketone and cyclohexanone are used in combination.
  • the amount of the solvent used can be selected by those skilled in the art according to their own experience, so that the obtained resin glue can reach a viscosity suitable for use.
  • an emulsifier may be added.
  • powder fillers and the like can be uniformly dispersed in the glue solution.
  • the present invention provides a prepreg comprising a base material and the above-mentioned thermosetting resin composition adhered to the base material after impregnation and drying.
  • the prepreg of the present invention can also be called a prepreg, which can also be made by impregnating the substrate with the above-mentioned resin glue, and then heating and drying it to remove the organic solvent and partially cure the resin combination in the substrate. material to obtain a prepreg.
  • the substrate can also be referred to as a reinforcing material in the present invention.
  • the substrate is a woven or non-woven fabric made of organic fibers, carbon fibers or inorganic fibers.
  • the organic fibers include aramid fibers, such as Kevlar fibers from DuPont.
  • the components of the woven or non-woven fabrics made from inorganic fibers contain 50 to 99.9% by weight (for example, 50%, 55%, 58%, 60%, 65%, 70%, 75%, 80%, 85%, 88%, 90%, 95% or 99%) of SiO 2 , 0-30% by weight (eg 0%, 5%) , 10%, 15%, 20%, 25% or 30%) of CaO, 0 to 20% by weight (eg 0%, 5%, 10%, 15% or 20%) of Al 2 O 3 , by weight 0-25% (eg 0%, 5%, 10%, 15%, 20% or 25 %) of B2O3, and 0-5% by weight (eg 0%, 0.5%, 1%, 2%) , 3%, 4% or 5%) of MgO, not limited to the above components.
  • SiO 2 0-30% by weight (eg 0%, 5%) , 10%, 15%, 20%, 25% or 30%) of CaO
  • 0 to 20% by weight eg 0%, 5%,
  • the base material is preferably a woven fiber cloth, which can be selected from E-Glass, T-Glass, NE-Glass, L-Glass, L2-Glass, Q-Glass, D-Glass, especially preferred for NE-Glass and/or L-Glass.
  • the thickness of the base material to be used is also not particularly limited.
  • the resin content for impregnating the above-mentioned base material is preferably such that 30 mass % or more of the resin content in semi-curing, for example, 30 mass %, 35 mass %, 40 mass %, 50 mass %, 60 mass %, 70 mass % % or higher. Since the dielectric constant of the base material tends to be higher than that of the resin composition, in order to lower the dielectric constant of the laminates obtained from these prepregs, the content of the resin composition components in the prepreg is preferably higher than the above-mentioned contents.
  • the drying temperature of the above-mentioned prepreg is 80-200°C, such as 80°C, 90°C, 110°C, 120°C, 130°C, 140°C, 150°C, 170°C, 190°C or 200°C, etc.;
  • the drying time is 1 to 30 minutes, such as 1 minute, 5 minutes, 8 minutes, 13 minutes, 17 minutes, 21 minutes, 24 minutes, 28 minutes, or 30 minutes.
  • the present invention provides a laminate comprising at least one prepreg as described above.
  • the present invention provides a metal foil-clad laminate, the metal foil-clad laminate comprising one or at least two superimposed prepregs as described above, and one or two prepregs located on one side or two of the superimposed prepregs. side foil.
  • the metal foil is copper foil.
  • the copper foil is electrolytic copper foil or rolled copper foil, and its surface roughness is less than 5 microns, such as less than 4 microns, less than 3 microns, less than 2 microns, less than 1 microns, less than 0.8 microns, less than 0.5 microns, etc. It can improve and increase the signal loss of laminate materials used in high-frequency and high-speed printed circuit boards.
  • the copper foil is chemically treated with a silane coupling agent
  • the silane coupling agent used is a methacrylate-based silane coupling agent, an epoxy group
  • silane coupling agents vinyl silane coupling agents, amino silane coupling agents, phenyl silane coupling agents, phenylamino silane coupling agents or oligomeric silane coupling agents The combination.
  • the present invention provides a high-frequency and high-speed circuit substrate, wherein the high-frequency and high-speed circuit substrate includes one or at least two superimposed prepregs as described above.
  • the high-speed circuit substrate of the present invention is prepared by the following method:
  • the overlapping preferably adopts an automatic stacking operation, thereby making the process operation easier.
  • the lamination molding is preferably vacuum lamination molding, which can be achieved by a vacuum laminator.
  • the lamination time is 70-130min, such as 70min, 75min, 80min, 85min, 90min, 95min, 100min, 105min, 110min, 115min, 120min, 125min or 130min, etc.
  • the lamination temperature is 180 ⁇ 220°C , such as 180°C, 185°C, 190°C, 195°C, 200°C, 205°C, 210°C, 215°C or 220°C;
  • the pressure of the lamination is 20-60kg/cm 2 , such as 20kg/cm 2 , 25kg /cm 2 , 30kg/cm 2 , 35kg/cm 2 , 40kg/cm 2 , 45kg/cm 2 , 50kg/cm 2 , 55kg/cm 2 , 58kg/cm 2 or 60kg/cm 2 , etc.
  • the electronic circuit substrate prepared by the method of the present invention has low dielectric constant Dk and low dielectric loss Df, excellent heat resistance, interlayer adhesion and peel strength, and excellent CAF resistance, which satisfies the requirements of the invention.
  • High-speed circuit substrates have the requirements of dielectric constant, dielectric loss, heat resistance, peel strength, interlayer adhesion and CAF and other properties, which are very suitable for high-level multi-layer printed circuit board processing.
  • the copper foil used in order to further improve the application of the material in the field of high frequency and high speed, in the production of the copper clad laminate of the present invention, can be selected from electrolytic copper foil or rolled copper foil, and its surface roughness is less than 5 microns. Improve and increase the signal loss of laminate materials used in high-frequency and high-speed printed circuit boards; at the same time, in order to improve the adhesion of one side of the copper foil prepreg, the copper foil can also be chemically treated with a silane coupling agent.
  • the coupling agent is methacrylate silane coupling agent, epoxy silane coupling agent, vinyl silane coupling agent, amino silane coupling agent, phenyl silane coupling agent, phenylamino silane coupling agent or One of the oligomer silane coupling agents or a combination of at least two of them, the purpose is to provide the bonding force between the copper foil and the substrate, and prevent the dropped wires and pads from occurring during the use of the printed circuit board. risk.
  • the present invention has the following beneficial effects:
  • the styrene-butadiene-styrene triblock copolymer (SBS) containing a large amount of 1,2-vinyl units can be used, which can obviously improve the crosslinking density of the resin composition after curing, and effectively improve the base material.
  • the interlayer adhesion and the peel strength of the copper foil and the substrate meet the lead-free reflow soldering requirements of high-speed transmission and high-layer PCBs; the styrene-butadiene-styrene triblock copolymer (SBS )
  • the number-average molecular weight is less than 20,000, which can be beneficial to solvent dissolution and improve processability.
  • low molecular weight styrene-butadiene-styrene triblock copolymer (SBS) in the resin system is beneficial to the thermosetting polyphenylene ether. Better compatibility and low molecular weight are conducive to infiltrating glass fiber cloth, improving CAF resistance, and improving the reliability of multi-layer printed circuit boards.
  • the molecules of the styrene-butadiene-styrene triblock copolymer (SBS) do not contain polar groups, which can ensure low water absorption and excellent dielectric properties of the circuit substrate.
  • the circuit substrate prepared by the resin composition prepared from styrene-butadiene-styrene triblock copolymer (SBS), polyphenylene ether and co-crosslinking agent has low dielectric constant Dk and low dielectric loss Df, Excellent heat resistance, interlayer adhesion and peel strength, and excellent CAF resistance, meeting the requirements of high-speed circuit substrates for dielectric constant, dielectric loss, heat resistance, peel strength, interlayer adhesion and CAF. It is suitable for use in the field of high-frequency and high-speed printed circuit boards, and is suitable for the processing of multi-layer printed circuit boards.
  • SBS-Atype Styrene-butadiene-styrene triblock copolymer from Japan Caoda, the number average molecular weight (Mn) is 20000, the molecule contains 50% styrene structure by weight, and the 1,2-position addition The content of butadiene is 94% by weight;
  • SBS-Ctype Styrene-butadiene-styrene triblock copolymer of Japan Caoda, the number average molecular weight (Mn) is 5000, the molecule contains 20% by weight of styrene structure, 1, 2-position addition The content of butadiene is 94% by weight;
  • D-1101 Styrene-butadiene-styrene triblock copolymer from Kraton, USA, the number average molecular weight (Mn) is more than 100000, the molecule contains 31% by weight of styrene structure, 1,2-position addition The content of butadiene by weight is less than 60%;
  • SA9000 Sabic's methyl methacrylate-terminated polyphenylene ether resin with a number average molecular weight (Mn) of 2800;
  • OPE-2ST 2200 styrene-terminated polyphenylene ether resin of Mitsubishi Gas, the number average molecular weight (Mn) is 2200;
  • KBM-403 Shin-Etsu Chemical's epoxy silane coupling agent
  • KBM-503 Shin-Etsu Chemical's methacrylate-based silane coupling agent
  • DCP dicumyl peroxide (free radical initiator) from Shanghai Gaoqiao;
  • TAIC triallyl isocyanate from Hunan Fangruida
  • ODV-XET Nippon Steel's multifunctional vinyl aromatic copolymer
  • Ricon 100 Sartomer's styrene-butadiene copolymer (Mn: 4500, 1,2-vinyl content 70%);
  • S0-C2 Spherical silica powder from Admatechs, median particle size D50: 0.5 ⁇ m;
  • Glass cloth L-Glass: 2116 L-Glass from Asahi;
  • HVLP copper foil HS2-M2-VSP H Oz from Taiwan Mitsui Company.
  • Tg Glass transition temperature
  • DMA dynamic thermomechanical analysis
  • Tg Glass transition temperature
  • Dielectric constant Dk and dielectric loss factor Df Tested according to the method of split dielectric column resonator SPDR (Split Post Dielectric Resonator), and the test frequency is 10GHz.
  • Test method for peel strength refers to the tensile force required to peel off each millimeter of copper foil from the copper clad laminate at room temperature.
  • Peel strength (thermal stress) test method refers to the tensile force required to peel off the copper clad laminate per millimeter of copper foil after immersion in tin at 288 ° C for 10 minutes.
  • Interlayer adhesion test method Refers to the tensile force required to peel off each millimeter of copper foil between the bonding sheets of the substrate at room temperature. Pulling force range; .
  • CAF performance test double-sided copper clad laminates are processed out of PCB to form a CAF test model, pre-treated for 5 times of reflow soldering, 85RH%/85°C high temperature and humidity treatment for 96h (no bias), and then placed at 85RH% /85°C constant temperature and humidity box, pass 50V bias test, test 240h.
  • Example 2 Compared with Comparative Examples 1-3, Example 2 used a styrene-butadiene-styrene triblock copolymer (SBS) with small molecules and high 1,2-vinyl unit content, and the peel strength of the substrate and The interlayer adhesion is significantly improved.
  • SBS styrene-butadiene-styrene triblock copolymer
  • the circuit substrate of the present invention has low dielectric constant Dk and low dielectric loss Df, excellent heat resistance, interlayer adhesion and peel strength, and CAF resistance compared with general laminates Excellent, it meets the requirements of high-speed circuit substrates for dielectric constant, dielectric loss, heat resistance, peel strength, interlayer adhesion and CAF, etc., and can be used to prepare high-speed circuit substrates.
  • the present invention is to illustrate the thermosetting resin composition, the prepreg and the copper-clad laminate using the thermosetting resin composition of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on Only the above-mentioned embodiment can be implemented.
  • Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

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Abstract

本发明提供一种热固性树脂组合物、使用其的半固化片与覆铜箔层压板，所述热固性树脂组合物包括如下组分：(A)含有1,2-乙烯基单元的苯乙烯-丁二烯-苯乙烯三嵌段共聚物、(B)热固性聚苯醚树脂、(C)硅烷偶联剂；其中所述的组分(A)的数均分子量小于20000，分子中含有10～60％重量比的苯乙烯结构，且分子中1,2位加成的丁二烯重量比含量大于等于90％。低的介质常数D k及低的介质损耗D f，耐热性能、层间粘合力和剥离强度性能优异，且耐CAF性能优异。

Description

一种热固性树脂组合物、使用其的半固化片与覆铜箔层压板 技术领域
本发明属于层压板技术领域，涉及一种热固性树脂组合物、使用其的半固化片与覆铜箔层压板。
背景技术
近年来，随着计算机和信息通讯设备高性能化、高功能化以及网络化的发展，为了高速传输及处理大容量信息，操作信号趋向于高频化，因而对电路基板的材料提出了要求，尤其是在那些使用宽带的电子设备如移动通信装置上有迅速的发展。
现有的用于印制电路基板的材料中，广泛使用粘接特性优异的环氧树脂。然而，环氧树脂电路基板一般介电常数和介质损耗角正切较高(介电常数Dk大于4，介质损耗角正切Df在0.02左右)，高频特性不充分，不能适应信号高频化的要求。因此必须研制介电特性优异的树脂，即介电常数和介质损耗角正切低的树脂。长期以来本领域的技术人员对介电性能很好的热固性的聚苯醚树脂、双马来酰亚胺树脂、乙烯基苄基醚树脂、碳氢树脂等进行了研究；众所周知，可固化交联的碳氢树脂(聚烯烃树脂)具有较低的介质损耗角正切Df(可以与聚四氟乙烯树脂媲美)、且流动性较好，进而吸引了广大技术人员对其进行了大量的深入研究，但由于其剥离强度和层间粘合力不足，无法满足高多层印制线路板的工艺制作要求，需要与选用特定的树脂配合使用。
分子链末端或侧链带活性基团可固化的改性聚苯醚树脂在高速电路基板中的应用方式一般为与交联剂配合组成树脂组合物。交联剂带有可与改性聚苯醚反应的活性基团。根据文献调研，对于带有C＝C双键的改性聚苯醚，通常采用 的交联剂有聚丁二烯、丁二烯苯乙烯共聚物等。如CN 101370866A、CN 102161823、CN 102304264专利采用聚丁二烯或丁二烯苯乙烯共聚物作为改性聚苯醚的交联剂，制备高速电路基板。虽然板材的介电等综合性能优秀，但聚丁二烯或丁二烯苯乙烯共聚物降低了板材的剥离强度及层间粘合力。
另外根据文献调研，TW201710363A使用含有C＝C双键的改性聚苯醚，交联剂为大分子的苯乙烯-丁二烯-苯乙烯三嵌段共聚物，且其分子中1,2位加成的丁二烯重量比含量较低，制备高速电路基板。虽然板材的具有优良的介电性能，但由于苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)分子量较大，导致SBS难于溶解，且难于浸润玻纤布，耐CAF性能差；分子中1,2位加成的丁二烯重量比含量较低，使体系的反应程度，Tg偏低，体系仍为热塑性基材，难于满足高速传输的高多层PCB的无铅回流焊要求，无法满足使用要求。
发明内容
针对现有技术的不足，本发明的目的在于提供一种热固性树脂组合物、使用其的半固化片与覆铜箔层压板。该热固性树脂组合物具有低的介质常数Dk及低的介质损耗Df，耐热性能、层间粘合力和剥离强度性能优异，且耐CAF性能优异，满足了高速电路基板对介质常数、介质损耗、耐热性能、剥离强度、层间粘合力和CAF等性能的要求，可用于制备高速电路基板。
为达此目的，本发明采用以下技术方案：
一方面，本发明提供一种热固性树脂组合物，所述热固性树脂组合物包括如下组分：(A)含有1,2-乙烯基单元的苯乙烯-丁二烯-苯乙烯三嵌段共聚物、(B)热固性聚苯醚树脂、(C)硅烷偶联剂；其中所述的组分(A)的数均分子量小于20000，分子中含有10～60％重量比的苯乙烯结构，且分子中1,2位加成的丁二烯重量比含量大于等于90％。
在本发明中，所述组分(A)含有1,2-乙烯基单元的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)可明显提高树脂组合物固化后交联密度，并有效改善基材的层间粘合力及铜箔和基材的剥离强度，满足高速传输的高多层PCB的无铅回流焊要求，数均分子量小于20000，可有利于溶剂溶解，改善工艺性，有利于和热固性聚苯醚具有更好的相容性，分子量低有利于浸润玻纤布，提升耐CAF性能，有利于提高多层印制电路板的可靠性。并且其分子不含极性基团，可保证电路基板低吸水率及优异的介电性能。此外在本发明中组分(A)和组分(C)协同作用可以改善体系的剥离强度和层间粘合力。
在本发明中，组分(A)的数均分子量小于20000，例如可以为18000、15000、13000、10000、8000、6000、4000、2000、1000等；优选地，组分(A)的数均分子量为1000～20000，进一步优选为1000～10000，再进一步优选为1000～6000。
如无特殊说明，则本发明中所述数均分子量均是指通过凝胶渗透色谱法测得的数均分子量。
本发明中，若SBS树脂的数均分子量过大，及其难溶解，且与聚苯醚的相容性较差，容易析出。另外，如果SBS树脂的数均分子量过大，在上胶中难以浸润玻纤布，板材的耐CAF性能较差。
在本发明中，组分(A)的分子中含有10～60％重量比的苯乙烯结构，例如含有苯乙烯的重量比可以为10％、15％、20％、25％、30％、35％、40％、45％、50％、55％或60％；苯乙烯含量过高会导致丁二烯含量不足，使体系的交联密度过低，且层间粘合力和剥离强度也较差，无法满足使用要求；如果苯乙烯含量过低，会导致与聚苯醚的相容性变差，且刚性不足。
在本发明中，组分(A)分子中1,2位加成的丁二烯重量比含量大于等于90％， 是指1,2位加成的丁二烯含量占(A)分子中丁二烯总重量的重量比大于等于90％，例如可以为90％、91％、92％、93％、95％、96％、97％、98％或99％等。如果1,2位加成的丁二烯重量比含量低于90％，其反应活性较差(在体系中处于未反应的游离态，形成热塑性的相)，使体系的交联密度过低，且层间粘合力和剥离强度也较差，无法满足使用要求。
优选地，所述组分(B)热固性聚苯醚树脂为具有如下式(1)所示结构的聚苯醚树脂：
Figure PCTCN2021070909-appb-000001
式(1)中，a，b独立地为1～30的整数(例如可以为1、3、5、8、10、15、20、25或30等)，Z为由式(2)或式(3)所定义的结构：
Figure PCTCN2021070909-appb-000002
式(3)中，A为亚芳香基、羰基、或碳原子数为1～10(例如1、2、3、4、5、6、7、8、9或10)的亚烷基，m为0～10的整数(例如0、1、2、3、4、5、6、7、8、9或10)，R 1～R 3相同或不同，为氢或碳原子数10以下(例如1、2、3、4、5、6、7、8、9或10)的烷基；
式(1)中-(-O-Y-)-为由式(4)所定义的结构：
Figure PCTCN2021070909-appb-000003
式(4)中，R 4与R 6相同或不同，为氢原子、卤素原子、碳原子数8以下(例如1、2、3、4、5、6、7、8)的烷基或苯基，R 5与R 7相同或不同，为卤素原子、碳原子数8以下的烷基或苯基；
式(1)中-(-O-X-O-)-为由式(5)所定义的结构：
Figure PCTCN2021070909-appb-000004
式(5)中，R 8、R 9、R 10、R 11、R 12、R 13、R 14及R 15之间相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基，B为碳原子数20以下(例如20、18、16、14、10、8、5、3等)的亚烃基、
Figure PCTCN2021070909-appb-000005
n为0或1；R 16为氢原子或碳原子数为1～10(例如1、2、3、4、5、6、7、8、9或10)的烃基。
优选地，所述热固性聚苯醚树脂的数均分子量为500-10000g/mol，例如500g/mol、800g/mol、1000g/mol、3000g/mol、5000g/mol、8000g/mol或10000g/mol，优选800～8000g/mol，进一步优选1000～4000g/mol。
本发明所述的热固性树脂组合物的树脂成分不含有极性的羟基基团，并且在固化加工过程中不会产生二次羟基等极性基团，可保证电路基板低吸水率以及优异的介电性能。
优选地，以组分(A)+(B)合计为100重量份计，所述组分(B)热固性聚苯醚树脂用量10～90重量份，例如15重量份、25重量份、35重量份、45重量份、55重量份、65重量份、75重量份或85重量份等。以组分(A)+(B)合计为100重量份计，组分(A)含有1,2-乙烯基单元的苯乙烯-丁二烯-苯乙烯三嵌段共聚物的用量10～90重量份，例如15重量份、25重量份、35重量份、45重量份、55重量份、65重量份、75重量份或85重量份等。
优选地，所述组分(C)硅烷偶联剂选自甲基丙烯酸酯基硅烷偶联剂、环氧基硅烷偶联剂、乙烯基硅烷偶联剂、氨基硅烷偶联剂、苯基硅烷偶联剂、苯氨基硅烷偶联剂或低聚物类硅烷偶联剂中的中的一种或至少两种的组合。
优选地，以组分(A)+(B)合计为100重量份计，组分(C)硅烷偶联剂的总用量为0.1～5重量份，例如可以是0.1重量份、0.3重量份、0 5重量份、0 8重量份、1重量份、1.5重量份、2重量份、2.5重量份、3重量份、3.5重量份、4重量份、4.5重量份或5重量份等。
在本发明中，通过添加硅烷偶联剂，使其和苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)及聚苯醚起到协同作用，有助于进一步提高层间粘合力及提高铜箔和基材的剥离强度，防止在印制线路板使用过程中发生掉线、掉焊盘等风险。
优选地，所述热固性树脂组合物还包括组分(D)自由基引发剂。
优选地，以组分(A)+(B)合计为100重量份计，组分(D)自由基引发剂的用量0.1～5重量份，例如可以是0.1重量份、0.3重量份、0 5重量份、0 8重量份、1重量份、1.5重量份、2重量份、2.5重量份、3重量份、3.5重量份、4重量份、4.5重量份或5重量份等。
优选地，所述自由基引发剂为第一引发剂、第二引发剂或第一引发剂与第二引发剂的组合；所述第一引发剂的1min半衰期温度为50-160℃(例如可以是 50℃、60℃、70℃、80℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃或160℃等)，所述第二引发剂的1min半衰期温度为161-300℃(例如可以是162℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃、250℃、260℃、270℃、280℃、290℃或300℃等)。
优选地，所述第一引发剂选自叔丁基过氧化乙酸酯、2,2-双(叔丁基过氧化)辛烷、叔丁基过氧化异丙基碳酸酯、1,1-双(叔丁基过氧基)环己酮、1,1-双(叔丁基过氧基)-3,3,5-三甲基环己酮、叔丁基过氧化辛酸酯、叔丁基过氧化异丁酸酯、二琥珀酸过氧化物、二间甲苯酰过氧化物、二甲苯酰过氧化物、二乙酰过氧化物、异丙苯基过氧化辛酸酯、二葵酰过氧化物、二辛酰过氧化物、双十二烷酰过氧化物、双(3,5,5-三甲基乙酰过氧化物)、叔丁基过氧化新戊酸酯、叔己基过氧化三甲基乙酸酯、叔丁基过氧化新己酸酯、叔己基过氧化新己酸酯、双(3-甲基-3-甲氧基丁基过氧化碳酸氢酯)、叔己基过氧化新葵酸酯、叔丁基过氧化新葵酸酯、异丙苯基过氧化新己酸酯、双甲氧基异丙基过氧化碳酸氢酯、双十四烷基过氧化碳酸氢酯、双烯丙基过氧化碳酸氢酯、异丙苯基过氧化新葵酸酯、二正丙级过氧化碳酸氢酯、双(2-羟乙基己基过氧化碳酸氢酯)、双(2-乙基己基过氧化碳酸氢酯)、二正丁基过氧化碳酸氢酯、二异丁基过氧化碳酸氢酯、二异丁烯过氧化物、二异丙基过氧化碳酸氢酯和乙酰基环己基磺酰基过氧化物中的一种或至少两种的组合；
优选地，所述第二引发剂选自叔丁基过氧化氢、四甲基丁烷过氧化物、2,5-二甲基-2,5-双(叔丁基过氧化)己炔、二叔丁基过氧化物、a,a-双(叔丁基过氧化-间-异丙苯基)、2,5-二甲基-2,5-双(叔丁基过氧化)己烷、叔丁基异丙苯基过氧化物、叔丁基过氧化烯丙基碳酸氢酯、二异丙苯基过氧化物(DCP)、叔丁基过氧化苯甲酸酯、二叔丁过氧化异酞酸酯、正丁基-4,4-双(叔丁基过氧化)戊酸酯、叔丁基过 氧化(3,5,5-三甲基乙酸酯)、叔丁基过氧化月桂酸酯、2,5-二甲-2,5-二(二苯甲酰过氧化)己烷和2,2-双(叔丁基过氧化)丁烷中的一种或至少两种的组合。
优选地，所述热固性树脂组合物还包括组分(E)共交联剂。
优选地，所述共交联剂为三烯丙基三聚氰酸酯、三烯丙基三聚异氰酸酯、多官能团丙烯酸酯化合物、双马马来酰亚胺树脂、二乙烯基苯、苯乙烯-丁二烯共聚物、聚丁二烯和苯乙烯-丁二烯-二乙烯基苯共聚物、多官能乙烯基芳香族共聚物中的一种或至少两种的混合物。优选为三烯丙基三聚氰酸酯、三烯丙基三聚异氰酸酯、多官能团丙烯酸酯化合物、多官能乙烯基芳香族共聚物中的一种或至少两种的混合物。
优选地，以组分(A)+(B)合计为100重量份计，所述共交联剂(E)添加量为3～60重量份，例如3重量份、6重量份、10重量份、15重量份、20重量份、25重量份、30重量份、40重量份、50重量份或60重量份。
优选地，所述热固性树脂组合物还包括填料。
优选地，以组分(A)+(B)合计为100重量份计，所述填料的用量为10～300重量份，例如10重量份、30重量份、50重量份、80重量份、100重量份、150重量份、200重量份、250重量份或300重量份。
优选地，所述填料为有机填料或无机填料。
优选地，所述无机填料选自结晶型二氧化硅、熔融二氧化硅、球形二氧化硅、空心二氧化硅、玻璃粉、氮化铝、氮化硼、碳化硅、氢氧化铝、二氧化钛、钛酸锶、钛酸钡、氧化铝、硫酸钡、滑石粉、硅酸钙、碳酸钙或云母中的一种或至少两种的组合。
优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚、聚醚酰亚胺、聚苯醚或聚醚砜粉末中的一种或至少两种的组合。
优选地，所述热固性树脂组合物还包括阻燃剂。
优选地，所述阻燃剂为含溴阻燃剂或无卤阻燃剂。
在本发明的热固性树脂组合物中包含阻燃剂是由阻燃性的需要而决定的，使树脂固化物具有阻燃特性，符合UL 94 V-0要求。对视需要而添加的阻燃剂并无特别限定，以不影响介电性能为佳。
优选地，所述含溴阻燃剂为十溴二苯醚、十溴二苯乙烷、乙撑双四溴邻苯二甲酰亚胺或溴化聚碳酸酯中的一种或至少两种的组合。可选的商品化的溴系阻燃剂有BT-93、BT-93W、HP-8010或HP-3010，但并不限于以上种类。
优选地，所述无卤阻燃剂为含磷无卤阻燃剂、含氮无卤阻燃剂及含硅无卤阻燃剂中的一种或至少两种的组合。
优选地，所述无卤阻燃剂为三(2,6-二甲基苯基)膦、10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、2,6-二(2,6-二甲基苯基)膦基苯或10-苯基-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基膦氰化合物、磷酸酯或聚磷酸酯中的一种或至少两种的组合。
可选的商品化的无卤阻燃剂有SPB-100、PX-200、PX-202、LR-202、LR-700、OP-930、OP-935、LP-2200、XP-7866，但并不限于以上种类。
在本发明中，所述阻燃剂的用量根据固化产物达到UL 94 V-0级别要求而定，并没有特别的限制。从不牺牲固化产物的耐热性、介电性能、吸湿性方面考虑，以组分(A)+(B)合计为100重量份计，所述阻燃剂的用量为5～80重量份，例如5重量份、8重量份、10重量份、20重量份、30重量份、40重量份、50重量份、60重量份、70重量份或80重量份，优选为10～60重量份，更优选为15～40重量份。当阻燃剂添加量不足时，无法达到很好的阻燃效果；当阻燃剂添加量大于80份时，会带来体系的耐热性下降、吸水率增加的风险，另外体 系的介电性能也会被恶化。
优选地，所述热固性树脂组合物还包含为了解决某些问题而引进的添加剂，所述添加剂为抗氧化剂、热稳定剂、光稳定剂、增塑剂、润滑剂、流动改性剂、防滴剂、防粘连剂、抗静电剂、流动促进剂、加工助剂、基板粘合剂、脱模剂、增韧剂、低收缩添加剂或应力消除添加剂中的一种或至少两种的组合。
在本发明所述的热固性树脂组合物中，所述添加剂的用量无特别限定，以组分(A)+(B)合计为100重量份计，所述添加剂的用量优选为0.1～10重量份，例如0.1重量份、0.5重量份、0.8重量份、1重量份、2重量份、3重量份、4重量份、5重量份、6重量份、7重量份、8重量份、9重量份或10重量份，更优选为0.5～8重量份，进一步优选为1～5重量份。
另一方面，本发明提供了如上所述的热固性树脂组合物的制备方法，所述制备方法可以采用公知的方法来配合、搅拌、混合所述的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)、热固性聚苯醚、硅烷偶联剂以及任选的共交联剂、自由基引发剂、粉末填料，以及各种阻燃剂、各种添加剂，来制备。
另一方面，本发明提供一种树脂胶液，其是将如上所述的热固性树脂组合物溶解或分散在溶剂中得到。
作为本发明中的溶剂，没有特别限定，作为具体例，可以举出甲醇、乙醇、丁醇等醇类，乙基溶纤剂、丁基溶纤剂、乙二醇-甲醚、卡必醇、丁基卡必醇等醚类，丙酮、丁酮、甲基乙基甲酮、甲基异丁基甲酮、环己酮等酮类，甲苯、二甲苯、均三甲苯等芳香族烃类，乙氧基乙基乙酸酯、醋酸乙酯等酯类，N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮等含氮类溶剂。上述溶剂可以单独使用一种，也可以两种或者两种以上混合使用，优选甲苯、二甲苯、均三甲苯等芳香族烃类溶剂与丙酮、丁酮、甲基乙基甲酮、甲基异丁基甲酮、 环己酮等酮类熔剂混合使用。所述溶剂的使用量本领域技术人员可以根据自己的经验来选择，使得到的树脂胶液达到适于使用的粘度即可。
在如上所述的树脂组合物溶解或分散在溶剂的过程中，可以添加乳化剂。通过乳化剂进行分散，可以使粉末填料等在胶液中分散均匀。
另一方面，本发明提供一种半固化片，所述半固化片包括基材及通过含浸干燥后附着于基材上的如上所述热固性树脂组合物。
本发明所述半固化片也可称之为预浸料，其也可以是将如上所述的树脂胶液浸渍基材，而后对其进行加热烘干以除去有机溶剂并部分固化基材内的树脂组合物，便得到半固化片。在本发明中所述基材也可以称之为增强材料。
优选地，所述基材为有机纤维、碳纤维或无机纤维制得的纺织物或无纺织物。
优选地，所述有机纤维包括芳纶纤维，如杜邦公司的Kevlar纤维。
对无机纤维制得纺织物或无纺织物无特别的限定，优选地，所述无机纤维制得纺织物或无纺织物的成分中包含有重量比50～99.9％(例如50％、55％、58％、60％、65％、70％、75％、80％、85％、88％、90％、95％或99％)的SiO 2、重量比0～30％(例如0％、5％、10％、15％、20％、25％或30％)的CaO、重量比0～20％(例如0％、5％、10％、15％或20％)的Al 2O 3、重量比0～25％(例如0％、5％、10％、15％、20％或25％)的B 2O 3、及重量比0～5％(例如0％、0.5％、1％、2％、3％、4％或5％)的MgO，并不局限于以上组分。优选地，所述基材(增强材料)优选为编制纤维布，可选为E-Glass、T-Glass、NE-Glass、L-Glass，L2-Glass，Q-Glass、D-Glass，特别优选为NE-Glass和/或L-Glass。对使用的基材的厚度也没有特别的限定。
用来浸渍上述基材的树脂含量，优选为使得半固化中的树脂含量的30质量％ 或更高，例如30质量％、35质量％、40质量％、50质量％、60质量％、70质量％或更高。由于基材的介电常数往往要高于树脂组合物，为了降低由这些半固化片制得的层压板的介电常数，树脂组合物成分在半固化片中的含量优选于上述含量。
优选地，以上所述的半固化片的干燥温度为80～200℃，例如80℃、90℃、110℃、120℃、130℃、140℃、150℃、170℃、190℃或200℃等；所述干燥时间为1～30min，例如1min、5min、8min、13min、17min、21min、24min、28min或30min等。
另一方面，本发明提供一种层压板，所述层压板包括至少一张如上所述的半固化片。
另一方面，本发明提供一种覆金属箔层压板，所述覆金属箔层压板包括一张或至少两张叠合的如上所述的半固化片，以及位于叠合后的半固化片的一侧或两侧的金属箔。
优选地，所述金属箔为铜箔。优选地，所述铜箔为电解铜箔或压延铜箔，其表面粗糙度小于5微米，例如小于4微米、小于3微米、小于2微米、小于1微米、小于0.8微米、小于0.5微米等。可以改善及提高层压板材料在高频高速印制线路板使用的信号损失。
同时，为了提高铜箔半固化片一面的粘合力，进一步优选地，所述铜箔使用硅烷偶联剂进行化学处理，所用的硅烷偶联剂为甲基丙烯酸酯基硅烷偶联剂、环氧基硅烷偶联剂、乙烯基硅烷偶联剂、氨基硅烷偶联剂、苯基硅烷偶联剂、苯氨基硅烷偶联剂或低聚物类硅烷偶联剂中的中的一种或至少两种的组合。
另一方面，本发明提供一种高频高速电路基板，所述高频高速电路基板包括一张或至少两张叠合的如上所述的半固化片。
具体地，本发明所述高速电路基板是通过以下方法制得的：
重叠至少一张如上所述的半固化片，在重叠半固化片的上下两侧放置铜箔，进行层压成型制备得到。所述重叠优选采用自动堆叠操作，从而使工艺操作更加简便。
所述层压成型优选真空层压成型，真空层压成型可以通过真空层压机实现。所述层压的时间为70～130min，例如70min、75min、80min、85min、90min、95min、100min、105min、110min、115min、120min、125min或130min等；所述层压的温度为180～220℃，例如180℃、185℃、190℃、195℃、200℃、205℃、210℃、215℃或220℃；所述层压的压力为20～60kg/cm 2，例如20kg/cm 2、25kg/cm 2、30kg/cm 2、35kg/cm 2、40kg/cm 2、45kg/cm 2、50kg/cm 2、55kg/cm 2、58kg/cm 2或60kg/cm 2等。
用本发明所述的方法制备出的电子电路基材具有低的介质常数Dk及低的介质损耗Df，耐热性能、层间粘合力和剥离强度性能优异，且耐CAF性能优异，满足了高速电路基板对介质常数、介质损耗、耐热性能、剥离强度、层间粘合力和CAF等性能的要求，非常适合高多层印制电路板加工使用。
此外，为了进一步提高材料在高频高速领域的应用，在本发明的覆铜箔层压板生产中，使用的铜箔，可以选择电解铜箔或压延铜箔，其表面粗糙度小于5微米，可以改善及提高层压板材料在高频高速印制线路板使用的信号损失；同时，为了提高铜箔半固化片一面的粘合力，所述铜箔还可以使用硅烷偶联剂进行化学处理，所用的硅烷偶联剂为为甲基丙烯酸酯基硅烷偶联剂、环氧基硅烷偶联剂、乙烯基硅烷偶联剂、氨基硅烷偶联剂、苯基硅烷偶联剂、苯氨基硅烷偶联剂或低聚物类硅烷偶联剂中的中的一种或至少两种的组合，目的是提供铜箔和基材的结合力，防止在印制线路板使用过程中发生掉线、掉焊盘等风险。
相对于现有技术，本发明具有以下有益效果：
采用本发明使用了含有大量1,2-乙烯基单元的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)，可明显提高树脂组合物固化后交联密度，并有效改善基材的层间粘合力及铜箔和基材的剥离强度，满足高速传输的高多层PCB的无铅回流焊要求；所述的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)数均分子量小于20000，可有利于溶剂溶解，改善工艺性，另外低分子量的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)在树脂体系中有利于和热固性聚苯醚具有更好的相容性，分子量低有利于浸润玻纤布，提升耐CAF性能，有利于提高多层印制电路板的可靠性。此外，所述的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)的分子不含极性基团，可保证电路基板低吸水率及优异的介电性能，总之，采用所述的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)、聚苯醚和共交联剂制备的树脂组合物制备的电路基板的具有低的介质常数Dk及低的介质损耗Df，耐热性能、层间粘合力和剥离强度性能优异，且耐CAF性能优异，满足了高速电路基板对介质常数、介质损耗、耐热性能、剥离强度、层间粘合力和CAF等性能的要求，适合高频高速印制线路板领域使用，并适合于多层印制线路板加工。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
本发明实施例和比较例中所选取的原料如下：
(A)组分：
SBS-Atype：日本曹达的苯乙烯-丁二烯-苯乙烯三嵌段共聚物，数均分子量(Mn)为20000，分子中含有50％重量比的苯乙烯结构，1,2位加成的丁二烯重量比含量94％；
SBS-Ctype：日本曹达的苯乙烯-丁二烯-苯乙烯三嵌段共聚物，数均分子量(Mn)为5000，分子中含有20％重量比的苯乙烯结构，1,2位加成的丁二烯重量比含量94％；
D-1101：美国科腾的苯乙烯-丁二烯-苯乙烯三嵌段共聚物，数均分子量(Mn)大于100000，分子中含有31％重量比的苯乙烯结构，1,2位加成的丁二烯重量比含量小于60％；
(B)聚苯醚：
SA9000：Sabic的甲基丙烯酸甲酯封端聚苯醚树脂，数均分子量(Mn)为2800；
OPE-2ST 2200：三菱瓦斯的苯乙烯封端聚苯醚树脂，数均分子量(Mn)为2200；
(C)硅烷偶联剂：
KBM-403：信越化学的环氧基硅烷偶联剂；
KBM-503：信越化学的甲基丙烯酸酯基硅烷偶联剂；
(D)自由基引发剂：
DCP：上海高桥的过氧化二异丙苯(自由基引发剂)；
(E)共交联剂
TAIC：湖南方锐达的三烯丙基三聚异氰酸酯；
ODV-XET：日铁公司的多官能乙烯基芳香族共聚物；
Ricon 100：Sartomer公司的苯乙烯-丁二烯共聚物(Mn:4500，1,2-乙烯基含量70％)；
填料：S0-C2：Admatechs的球形硅微粉，中位粒径D50:0.5μm；
阻燃剂：Saytex 8010：Albemarle的含溴阻燃剂十溴二苯乙烷；
玻璃布：L-Glass：Asahi公司的2116 L-Glass；
铜箔：HVLP铜箔：台湾三井公司的HS2-M2-VSP H Oz。
实施例1
将70.0重量份的甲基丙烯酸甲酯封端聚苯醚树脂SA9000，30.0重量份的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS-Atype)，2.0重量份的自由基引发剂DCP，1.0重量份的甲基丙烯酸酯基硅烷偶联剂KBM-503，25重量份的溴阻燃剂Saytex8010，80重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用Low Dk-玻纤布(Asahi，型号2116L)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以HOZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm 2，固化温度为210℃，制得两种厚度规格(12*2116-1.52mm厚板用于外发加工CAF图形测试)的高速电路基板。测试所制成的铜箔基板的物性，其结果详见表2。
实施例2
将70.0重量份的甲基丙烯酸甲酯封端聚苯醚树脂SA9000，30.0重量份的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS-Ctype)，2.0重量份的自由基引发剂DCP，1.0重量份的甲基丙烯酸酯基硅烷偶联剂KBM-503，25重量份的溴阻燃剂Saytex 8010，80重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用Low Dk-玻纤布(Asahi，型号2116L)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以HOZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm 2，固化温度为210℃，制得两种厚度规格(12*2116-1.52mm厚板用于外发加工CAF图形测试)的高速电路基板。测试所 制成的铜箔基板的物性，其结果详见表2。
实施例3
将70.0重量份的三菱瓦斯的苯乙烯封端聚苯醚树脂OPE-2ST 2200，30.0重量份的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS-Ctype)，2.0重量份的自由基引发剂DCP，1.0重量份的甲基丙烯酸酯基硅烷偶联剂KBM-503，25重量份的溴阻燃剂Saytex 8010，80重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用Low Dk-玻纤布(Asahi，型号2116L)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以HOZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm 2，固化温度为210℃，制得两种厚度规格(12*2116-1.52mm厚板用于外发加工CAF图形测试)的高速电路基板。测试所制成的铜箔基板的物性，其结果详见表2。
实施例4
将85.0重量份的甲基丙烯酸甲酯封端聚苯醚树脂SA9000，15.0重量份的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS-Ctype)，15.0重量份的三烯丙基三聚异氰酸酯TAIC，2.0重量份的自由基引发剂DCP，1.0重量份的甲基丙烯酸酯基硅烷偶联剂KBM-503，25重量份的溴阻燃剂Saytex 8010，80重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用Low Dk-玻纤布(Asahi，型号2116L)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以HOZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm 2，固化温度为210℃，制得两种厚度规格(12*2116-1.52mm厚板用于外发加工CAF图形测试)的高速电路基板。测试所制成的铜箔基板的物性， 其结果详见表2。
实施例5
将85.0重量份的甲基丙烯酸甲酯封端聚苯醚树脂SA9000，15.0重量份的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS-Ctype)，15.0重量份的苯乙烯-丁二烯共聚物Ricon 100，2.0重量份的自由基引发剂DCP，1.0重量份的甲基丙烯酸酯基硅烷偶联剂KBM-503，25重量份的溴阻燃剂Saytex 8010，80重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用Low Dk-玻纤布(Asahi，型号2116L)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以HOZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm 2，固化温度为210℃，制得两种厚度规格(12*2116-1.52mm厚板用于外发加工CAF图形测试)的高速电路基板。测试所制成的铜箔基板的物性，其结果详见表2。
实施例6
将85.0重量份的甲基丙烯酸甲酯封端聚苯醚树脂SA9000，15.0重量份的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS-Ctype)，15.0重量份的日铁公司的多官能乙烯基芳香族共聚物ODV-XET，2.0重量份的自由基引发剂DCP，1.0重量份的甲基丙烯酸酯基硅烷偶联剂KBM-503，25重量份的溴阻燃剂Saytex 8010，80重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用Low Dk-玻纤布(Asahi，型号2116L)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以HOZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm 2，固化温度为210℃，制得两种厚度规格 (12*2116-1.52mm厚板用于外发加工CAF图形测试)的高速电路基板。测试所制成的铜箔基板的物性，其结果详见表2。
实施例7
将40.0重量份的甲基丙烯酸甲酯封端聚苯醚树脂SA9000，60.0重量份的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS-Ctype)，30.0重量份的日铁公司的多官能乙烯基芳香族共聚物ODV-XET，4.0重量份的自由基引发剂DCP，3.0重量份的信越化学的环氧基硅烷偶联剂KBM-403，40.0重量份的溴阻燃剂Saytex 8010，110重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用Low Dk-玻纤布(Asahi，型号2116L)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以HOZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm 2，固化温度为210℃，制得两种厚度规格(12*2116-1.52mm厚板用于外发加工CAF图形测试)的高速电路基板。测试所制成的铜箔基板的物性，其结果详见表2。
比较例1
将70.0重量份的甲基丙烯酸甲酯封端聚苯醚树脂SA9000，30.0重量份的三烯丙基三聚异氰酸酯TAIC，2.0重量份的自由基引发剂DCP，1.0重量份的甲基丙烯酸酯基硅烷偶联剂KBM-503，25重量份的溴阻燃剂Saytex 8010，80重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用Low Dk-玻纤布(Asahi，型号2116L)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以HOZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm 2，固化温度为210℃，制得两种厚度规格(12*2116-1.52mm 厚板用于外发加工CAF图形测试)的高速电路基板。测试所制成的铜箔基板的物性，其结果详见表3。
比较例2
将70.0重量份的甲基丙烯酸甲酯封端聚苯醚树脂SA9000，30.0重量份的苯乙烯-丁二烯共聚物Ricon 100，2.0重量份的自由基引发剂DCP，1.0重量份的甲基丙烯酸酯基硅烷偶联剂KBM-503，25重量份的溴阻燃剂Saytex 8010，80重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用Low Dk-玻纤布(Asahi，型号2116L)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以HOZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm 2，固化温度为210℃，制得两种厚度规格(12*2116-1.52mm厚板用于外发加工CAF图形测试)的高速电路基板。测试所制成的铜箔基板的物性，其结果详见表3。
比较例3
将70.0重量份的甲基丙烯酸甲酯封端聚苯醚树脂SA9000，30.0重量份日铁公司的多官能乙烯基芳香族共聚物ODV-XET，2.0重量份的自由基引发剂DCP，1.0重量份的甲基丙烯酸酯基硅烷偶联剂KBM-503，25重量份的溴阻燃剂Saytex 8010，80重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用Low Dk-玻纤布(Asahi，型号2116L)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以HOZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm 2，固化温度为210℃，制得两种厚度规格(12*2116-1.52mm厚板用于外发加工CAF图形测试)的高速电路基板。测 试所制成的铜箔基板的物性，其结果详见表3。
比较例4
将70.0重量份的甲基丙烯酸甲酯封端聚苯醚树脂SA9000，30.0重量份的大分子的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(D-1101)，2.0重量份的自由基引发剂DCP，1.0重量份的甲基丙烯酸酯基硅烷偶联剂KBM-503，25重量份的溴阻燃剂Saytex 8010，80重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用Low Dk-玻纤布(Asahi，型号2116L)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以HOZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm 2，固化温度为210℃，制得两种厚度规格(12*2116-1.52mm厚板用于外发加工CAF图形测试)的高速电路基板。测试所制成的铜箔基板的物性，其结果详见表3。
比较例5
将70.0重量份的三菱瓦斯的苯乙烯封端聚苯醚树脂OPE-2ST 2200，30.0重量份的大分子的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(D-1101)，15.0重量份的苯乙烯-丁二烯共聚物Ricon 100，2.0重量份的自由基引发剂DCP，1.0重量份的甲基丙烯酸酯基硅烷偶联剂KBM-503，25重量份的溴阻燃剂Saytex 8010，80重量份的硅微粉S0-C2，溶解于甲苯溶剂中，并调节至适合粘度。用Low Dk-玻纤布(Asahi，型号2116L)浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116的半固化片。将6张2116半固化片和12张2116半固化片分别重叠，上下两面配以HOZ厚度的铜箔，在压机中真空层压固化120min，固化压力为50kg/cm 2，固化温度为210℃，制得两种厚度规格(12*2116-1.52mm厚板用于外发加工CAF图形测试)的高速电路基板。测试所 制成的铜箔基板的物性，其结果详见表1、表2。
表1
Figure PCTCN2021070909-appb-000006
表2
Figure PCTCN2021070909-appb-000007
以上特性的测试方法如下：
1)玻璃化转变温度(Tg)：根据动态热机械分析法(DMA)，按照IPC-TM-650 2.4.24.4所规定的DMA方法进行测定层压板的Tg。
2)玻璃化转变温度(Tg)：根据动态热机械分析法(DSC)，按照IPC-TM-650 2.4.25D所规定的DSC方法进行测定层压板的Tg。
3)介电常数Dk和介电损耗因子Df：根据分离介质柱谐振腔SPDR(Split Post Dielectric Resonator)方法测试，测试频率为10GHz。
4)剥离强度(A态)测试方法：指在室温下将每毫米铜箔剥离覆铜板所需的拉力。
5)剥离强度(热应力)测试方法：指在在288℃浸锡10min后，将每毫米铜箔剥离覆铜板所需的拉力。
6)层间粘合力测试方法：指在室温下将每毫米铜箔剥离基材的粘结片间所需的拉力，随着测试进行拉力值在不停波动，记录最低值和最高值的拉力范围；。
7)CAF性能测试：双面覆铜板外发PCB加工，形成CAF测试模型，进行回流焊5次前处理，进行85RH％/85℃高温高湿处理96h(无偏压)，再放在85RH％/85℃的恒温恒湿箱，通50V偏压测试，测试240h。
物性分析：
从表2和表3的物性数据可知，实施例1-7中，采用小分子和高1,2-乙烯基单元含量的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)和热固性聚苯醚固化后，基材具有低的介质常数D k及低的介质损耗D f，耐热性能、层间粘合力和剥离强度性能优异，且耐CAF性能优异；而比较例4和比较例5中，使用大分子和低1,2-乙烯基单元含量的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(D-1101)后，基材的交联密度明显较低，Tg明显大幅度降低(主要呈现热塑性)，耐热性能明显恶化，且由于大分子的苯乙烯-丁二烯-苯乙烯三嵌段共聚物对玻纤的浸润性较差，耐CAF明显不足。
实施例2相对于比较例1-3，使用了小分子和高1,2-乙烯基单元含量的苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)，基材的剥离强度和层间粘合力得到明显的改善。
如上所述，与一般的层压板相比，本发明的电路基板具有有低的介质常数Dk及低的介质损耗Df，耐热性能、层间粘合力和剥离强度性能优异，且耐CAF 性能优异，满足了高速电路基板对介质常数、介质损耗、耐热性能、剥离强度、层间粘合力和CAF等性能的要求，可用于制备高速电路基板。
申请人声明，本发明通过上述实施例来说明本发明的热固性树脂组合物、使用其的半固化片与覆铜箔层压板，但本发明并不局限于上述实施例，即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种热固性树脂组合物，其特征在于，所述热固性树脂组合物包括如下组分：(A)含有1,2-乙烯基单元的苯乙烯-丁二烯-苯乙烯三嵌段共聚物、(B)热固性聚苯醚树脂、(C)硅烷偶联剂；其中所述的组分(A)的数均分子量小于等于20000，分子中含有10～60％重量比的苯乙烯结构，且分子中1,2位加成的丁二烯重量比含量大于等于90％。
  2. 根据权利要求1所述的热固性树脂组合物，其特征在于，所述组分(A)的数均分子量为1000～20000，进一步优选为1000～10000，再进一步优选为1000～6000。
  3. 根据权利要求1或2所述的热固性树脂组合物，其特征在于，所述组分(B)热固性聚苯醚树脂为具有如下式(1)所示结构的聚苯醚树脂：
    Figure PCTCN2021070909-appb-100001
    式(1)中，a，b独立地为1～30的整数，Z为由式(2)或式(3)所定义的结构：
    Figure PCTCN2021070909-appb-100002
    式(3)中，A为亚芳香基、羰基、或碳原子数为1～10的亚烷基，m为0～10的整数，R 1～R 3相同或不同，为氢或碳原子数10以下的烷基；
    式(1)中-(-O-Y-)-为由式(4)所定义的结构：
    Figure PCTCN2021070909-appb-100003
    式(4)中，R 4与R 6相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基，R5与R7相同或不同，为卤素原子、碳原子数8以下的烷基或苯基；
    式(1)中-(-O-X-O-)-为由式(5)所定义的结构：
    Figure PCTCN2021070909-appb-100004
    式(5)中，R 8、R 9、R 10、R 11、R 12、R 13、R 14及R 15之间相同或不同，为氢原子、卤素原子、碳原子数8以下的烷基或苯基，B为碳原子数20以下的亚烃基、
    Figure PCTCN2021070909-appb-100005
    n为0或1；R 16为氢原子或碳原子数为1～10的烃基；
    优选地，所述热固性聚苯醚树脂的数均分子量为500-10000g/mol，优选800～8000g/mol，进一步优选1000～4000g/mol；
    优选地，以组分(A)+(B)合计为100重量份计，所述组分(B)热固性聚苯醚树脂为10～90重量份；组分(A)含有1,2-乙烯基单元的苯乙烯-丁二烯-苯乙烯三嵌段共聚物为10～90重量份。
  4. 根据权利要求1-3中任一项所述的热固性树脂组合物，其特征在于，所述组分(C)硅烷偶联剂选自甲基丙烯酸酯基硅烷偶联剂、环氧基硅烷偶联剂、 乙烯基硅烷偶联剂、氨基硅烷偶联剂、苯基硅烷偶联剂、苯氨基硅烷偶联剂或低聚物类硅烷偶联剂中的中的一种或至少两种的组合；
    优选地，以组分(A)+(B)合计为100重量份计，组分(C)硅烷偶联剂的总用量为0.1～5重量份；
    优选地，所述热固性树脂组合物还包括组分(D)自由基引发剂；
    优选地，以成分(A)+(B)合计为100重量份计，组分(D)自由基引发剂的用量0.1～5重量份；
    优选地，所述自由基引发剂为第一引发剂、第二引发剂或第一引发剂与第二引发剂的组合；所述第一引发剂的1min半衰期温度为50-160℃，所述第二引发剂的1min半衰期温度为161-300℃；
    优选地，所述第一引发剂选自叔丁基过氧化乙酸酯、2,2-双(叔丁基过氧化)辛烷、叔丁基过氧化异丙基碳酸酯、1,1-双(叔丁基过氧基)环己酮、1,1-双(叔丁基过氧基)-3,3,5-三甲基环己酮、叔丁基过氧化辛酸酯、叔丁基过氧化异丁酸酯、二琥珀酸过氧化物、二间甲苯酰过氧化物、二甲苯酰过氧化物、二乙酰过氧化物、异丙苯基过氧化辛酸酯、二葵酰过氧化物、二辛酰过氧化物、双十二烷酰过氧化物、双(3,5,5-三甲基乙酰过氧化物)、叔丁基过氧化新戊酸酯、叔己基过氧化三甲基乙酸酯、叔丁基过氧化新己酸酯、叔己基过氧化新己酸酯、双(3-甲基-3-甲氧基丁基过氧化碳酸氢酯)、叔己基过氧化新葵酸酯、叔丁基过氧化新葵酸酯、异丙苯基过氧化新己酸酯、双甲氧基异丙基过氧化碳酸氢酯、双十四烷基过氧化碳酸氢酯、双烯丙基过氧化碳酸氢酯、异丙苯基过氧化新葵酸酯、二正丙级过氧化碳酸氢酯、双(2-羟乙基己基过氧化碳酸氢酯)、双(2-乙基己基过氧化碳酸氢酯)、二正丁基过氧化碳酸氢酯、二异丁基过氧化碳酸氢酯、二异丁烯过氧化物、二异丙基过氧化碳酸氢酯和乙酰基环己基磺酰基过氧化物中的一种 或至少两种的组合；
    优选地，所述第二引发剂选自叔丁基过氧化氢、四甲基丁烷过氧化物、2,5-二甲基-2,5-双(叔丁基过氧化)己炔、二叔丁基过氧化物、a,a-双(叔丁基过氧化-间-异丙苯基)、2,5-二甲基-2,5-双(叔丁基过氧化)己烷、叔丁基异丙苯基过氧化物、叔丁基过氧化烯丙基碳酸氢酯、二异丙苯基过氧化物(DCP)、叔丁基过氧化苯甲酸酯、二叔丁过氧化异酞酸酯、正丁基-4,4-双(叔丁基过氧化)戊酸酯、叔丁基过氧化(3,5,5-三甲基乙酸酯)、叔丁基过氧化月桂酸酯、2,5-二甲-2,5-二(二苯甲酰过氧化)己烷和2,2-双(叔丁基过氧化)丁烷中的一种或至少两种的组合。
  5. 根据权利要求1-4中任一项所述的热固性树脂组合物，其特征在于，所述热固性树脂组合物还包括组分(E)共交联剂；
    优选地，所述共交联剂为三烯丙基三聚氰酸酯、三烯丙基三聚异氰酸酯、多官能团丙烯酸酯化合物、双马马来酰亚胺树脂、二乙烯基苯、苯乙烯-丁二烯共聚物、聚丁二烯和苯乙烯-丁二烯-二乙烯基苯共聚物、多官能乙烯基芳香族共聚物中的一种或至少两种的混合物。优选为三烯丙基三聚氰酸酯、三烯丙基三聚异氰酸酯、多官能团丙烯酸酯化合物、多官能乙烯基芳香族共聚物中的一种或至少两种的混合物；
    优选地，以成分(A)+(B)合计为100重量份计，所述共交联剂(E)添加量为3～60重量份；
    优选地，所述热固性树脂组合物还包括填料；
    优选地，以成分(A)+(B)合计为100重量份计，所述填料的用量为10～300重量份；
    优选地，所述填料为有机填料或无机填料；
    优选地，所述无机填料选自结晶型二氧化硅、熔融二氧化硅、球形二氧化 硅、空心二氧化硅、玻璃粉、氮化铝、氮化硼、碳化硅、氢氧化铝、二氧化钛、钛酸锶、钛酸钡、氧化铝、硫酸钡、滑石粉、硅酸钙、碳酸钙或云母中的一种或至少两种的组合；
    优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚、聚醚酰亚胺、聚苯醚或聚醚砜粉末中的一种或至少两种的组合；
    优选地，所述热固性树脂组合物还包括阻燃剂；
    优选地，所述阻燃剂为含溴阻燃剂或无卤阻燃剂；
    优选地，所述含溴阻燃剂为十溴二苯醚、十溴二苯乙烷、乙撑双四溴邻苯二甲酰亚胺或溴化聚碳酸酯中的一种或至少两种的组合；
    优选地，所述无卤阻燃剂为三(2,6-二甲基苯基)膦、10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、2,6-二(2,6-二甲基苯基)膦基苯或10-苯基-9,10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基膦氰化合物、磷酸酯或聚磷酸酯中的一种或至少两种的组合；
    优选地，以成分(A)+(B)为100重量份计，所述阻燃剂的用量为5～80重量份；
    优选地，所述热固性树脂组合物还包括添加剂，所述添加剂为抗氧化剂、热稳定剂、光稳定剂、增塑剂、润滑剂、流动改性剂、防滴剂、防粘连剂、抗静电剂、流动促进剂、加工助剂、基板粘合剂、脱模剂、增韧剂、低收缩添加剂或应力消除添加剂中的任意一种或至少两种的组合；
    优选地，以成分(A)+(B)为100重量份计，所述添加剂的用量优选为0.1～10重量份。
  6. 一种树脂胶液，其特征在于，其是将如权利要求1-5中任一项所述的热固性树脂组合物溶解或分散在溶剂中得到。
  7. 一种半固化片，其特征在于，所述半固化片包括基材及通过含浸干燥后附着于基材上的如权利要求1-5中任一项所述热固性树脂组合物；
    优选地，所述基材为有机纤维、碳纤维或无机纤维制得的纺织物或无纺织物；
    优选地，所述无机纤维制得纺织物或无纺织物的成分中包含有重量比50～99.9％的SiO 2、重量比0～30％的CaO、重量比0～20％的Al 2O 3、重量比0～25％的B 2O 3、及重量比0～5％的MgO。
  8. 一种层压板，其特征在于，所述层压板包括至少一张如权利要求7所述的半固化片。
  9. 一种覆金属箔层压板，其特征在于，所述覆金属箔层压板包括一张或至少两张叠合的如权利要求7所述的半固化片，以及位于叠合后的半固化片的一侧或两侧的金属箔。
  10. 一种高频高速电路基板，其特征在于，所述高频高速电路基板包括一张或至少两张叠合的如权利要求7所述的半固化片。
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WO2023042780A1 (ja) * 2021-09-14 2023-03-23 日油株式会社 熱硬化性組成物、樹脂フィルム、プリプレグ、金属張積層板、及びプリント配線板
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CN114106267B (zh) * 2021-11-30 2024-05-28 南亚新材料科技股份有限公司 含苯乙烯化合物的热固性树脂组合物及其制备方法和应用
CN114316567B (zh) * 2021-12-31 2024-01-16 广东盈骅新材料科技有限公司 树脂组合物以及半固化片、应用
CN114573975B (zh) * 2022-01-25 2023-08-04 南亚新材料科技股份有限公司 一种含填料粒子簇的覆金属箔层压板及其制备方法
TWI822113B (zh) * 2022-06-15 2023-11-11 南亞塑膠工業股份有限公司 低介電樹脂組成物
TWI830462B (zh) * 2022-10-27 2024-01-21 南亞塑膠工業股份有限公司 樹脂組成物

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102807658A (zh) * 2012-08-09 2012-12-05 广东生益科技股份有限公司 聚苯醚树脂组合物及使用其制作的半固化片与覆铜箔层压板
JP2018095815A (ja) * 2016-12-16 2018-06-21 パナソニックＩｐマネジメント株式会社 熱硬化性樹脂組成物、並びに、それを用いた樹脂ワニス、プリプレグ、樹脂付金属箔、樹脂フィルム、金属張積層板及びプリント配線板
CN111253702A (zh) * 2020-03-30 2020-06-09 广东生益科技股份有限公司 一种树脂组合物及使用其的预浸料和电路材料
CN111253888A (zh) * 2020-03-30 2020-06-09 广东生益科技股份有限公司 一种电路材料及包含其的电路板
CN111372372A (zh) * 2020-03-30 2020-07-03 广东生益科技股份有限公司 一种电路材料及包含其的电路板
CN111393724A (zh) * 2020-03-30 2020-07-10 广东生益科技股份有限公司 一种树脂组合物及使用其的预浸料和电路材料

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2628759B1 (en) * 2010-10-13 2021-06-30 Asahi Kasei Kabushiki Kaisha Polyphenylene ether as well as resin composition and molding thereof
CN104725857B (zh) * 2015-03-05 2017-11-03 广东生益科技股份有限公司 一种树脂组合物以及使用它的预浸料和层压板
TWI560234B (en) * 2015-09-07 2016-12-01 Zhen Ding Technology Co Ltd Thermoplastic resin composition, method for making the same, adhesive sheet, and printed circuit board

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102807658A (zh) * 2012-08-09 2012-12-05 广东生益科技股份有限公司 聚苯醚树脂组合物及使用其制作的半固化片与覆铜箔层压板
JP2018095815A (ja) * 2016-12-16 2018-06-21 パナソニックＩｐマネジメント株式会社 熱硬化性樹脂組成物、並びに、それを用いた樹脂ワニス、プリプレグ、樹脂付金属箔、樹脂フィルム、金属張積層板及びプリント配線板
CN111253702A (zh) * 2020-03-30 2020-06-09 广东生益科技股份有限公司 一种树脂组合物及使用其的预浸料和电路材料
CN111253888A (zh) * 2020-03-30 2020-06-09 广东生益科技股份有限公司 一种电路材料及包含其的电路板
CN111372372A (zh) * 2020-03-30 2020-07-03 广东生益科技股份有限公司 一种电路材料及包含其的电路板
CN111393724A (zh) * 2020-03-30 2020-07-10 广东生益科技股份有限公司 一种树脂组合物及使用其的预浸料和电路材料

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117384457A (zh) * 2023-10-16 2024-01-12 江苏耀鸿电子有限公司 一种无卤阻燃碳氢树脂覆铜板及其制备方法
CN117384457B (zh) * 2023-10-16 2024-03-19 江苏耀鸿电子有限公司 一种无卤阻燃碳氢树脂覆铜板及其制备方法
CN117416107A (zh) * 2023-10-23 2024-01-19 江苏耀鸿电子有限公司 一种低膨胀高阻燃ppo树脂覆铜板及其加工工艺
CN117416107B (zh) * 2023-10-23 2024-03-19 江苏耀鸿电子有限公司 一种低膨胀高阻燃ppo树脂覆铜板及其加工工艺

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