WO2021012619A1 - High-frequency resin composition and use thereof - Google Patents

High-frequency resin composition and use thereof Download PDF

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Publication number
WO2021012619A1
WO2021012619A1 PCT/CN2019/129924 CN2019129924W WO2021012619A1 WO 2021012619 A1 WO2021012619 A1 WO 2021012619A1 CN 2019129924 W CN2019129924 W CN 2019129924W WO 2021012619 A1 WO2021012619 A1 WO 2021012619A1
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Prior art keywords
resin composition
styrene
copolymer
parts
substituted maleimide
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PCT/CN2019/129924
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French (fr)
Chinese (zh)
Inventor
李兵兵
粟俊华
席奎东
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南亚新材料科技股份有限公司
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Priority to JP2021528890A priority Critical patent/JP7170136B2/en
Priority to KR1020217017023A priority patent/KR102523921B1/en
Publication of WO2021012619A1 publication Critical patent/WO2021012619A1/en

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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
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • 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
    • 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
    • C08L53/025—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 modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to the field of high-frequency and high-speed technology, in particular to a high-frequency resin composition and its application.
  • the electrical signal transmission loss is represented by the sum of dielectric loss, conductor loss, and radiation loss.
  • the higher the frequency of the electrical signal the greater the dielectric loss, conductor loss, and radiation loss. Therefore, as an insulator for high-frequency signal transmission, an insulating material with a small dielectric loss tangent can be selected to suppress an increase in dielectric loss.
  • an insulating material for high-frequency signal transmission it is usually made of polytetrafluoroethylene material or hydrocarbon resin material. Due to the difficulty of processing polytetrafluoroethylene materials, hydrocarbon materials are widely used in high frequency.
  • the hydrocarbon resin prepared by block copolymer rubber or unsaturated olefin resin and filler has the disadvantages of low peel strength, poor heat resistance, and low bending strength, and the prepared adhesive sheet may appear due to rubber materials Adhesive problems affect the production, storage and transportation of adhesive sheets. Therefore, it is necessary to develop a high-frequency substrate material with high heat resistance, high peel strength, low dielectric loss, and low expansion coefficient.
  • the purpose of the present invention is to provide a high-frequency resin composition based on hydrocarbon resin in order to overcome the above-mentioned defects in the prior art.
  • a high-frequency resin composition comprising the following components in parts by weight:
  • the N-substituted maleimide copolymer is copolymerized with the following molar parts of monomers: 30-60 parts of styrene monomer, 30-70 parts of N-substituted maleimide, and 1-20 parts of unsaturated acid anhydride Parts;
  • the molecular formula of styrene, N-substituted maleimide, and maleic anhydride copolymer is as follows:
  • the R group is methyl, ethyl, isopropyl, cyclohexyl, phenyl, benzyl, phenylethyl, phenylvinyl, p-hydroxyphenyl , Biphenyl, naphthalene ring group; among them, methyl, phenyl, and phenyl vinyl are preferred.
  • the molecular formulas are as follows:
  • the N-substituted maleimide copolymer used in the present invention is a copolymer of styrene, N-substituted maleimide and maleic anhydride (SMI), which can improve the compatibility between polar and non-polar resins
  • SMI styrene
  • the styrene segment has good compatibility with rubber-like materials, while the maleimide and maleic anhydride segments can have good compatibility with polar resins, and at the same time can improve the interface strength and improve the compatibility with metal foils.
  • N-substituted maleimide copolymer has good heat resistance and excellent thermal stability (no decomposition at 350°C). When mixed with hydrocarbon resins, it can be used as a heat-resistant modifier for hydrocarbon materials to improve The glass transition temperature and heat resistance of the sheet.
  • the content of N-substituted maleimide copolymer is preferably 5-30 parts. If the added N-substituted maleimide copolymer is too small, the improvement of the heat resistance of the material is relatively limited, and the peel strength Lower; if too much N-substituted maleimide copolymer is added, its dielectric properties will increase, and the water absorption will also increase significantly.
  • the molecular weight of the N-substituted maleimide copolymer is not particularly limited. Generally, the number average molecular weight is preferably in the range of 2,000 to 200,000, among which the more preferable range is 5,000 to 50,000, which has rapid and good performance in resin compositions. Solubility, while also ensuring the reliable heat resistance and thermal stability of the material.
  • the block copolymer rubber is a linear triblock copolymer with styrene as the terminal segment and polybutadiene and isoprene as the middle segment. Its number average molecular weight is 5000 to 150,000, and the styrene chain The segment accounts for 10-50% of the total mass of the block copolymer rubber.
  • the thermosetting resin composition contains a block copolymer rubber with a larger molecular weight.
  • the block copolymer is a linear triblock with styrene as the terminal segment and polybutadiene and isoprene as the middle segment. Copolymers, such block copolymers usually do not have a double bond structure and have low reactivity.
  • the block copolymer rubber has the characteristics of low polarity, and can exhibit extremely low dielectric constant and low dielectric loss required for high-frequency and high-speed materials, but often the material has poor heat resistance and peels off from the metal foil. The intensity is low.
  • the block copolymer rubber is one of the main components of the composition, and the ratio of the styrene segment to the butadiene segment is particularly important.
  • the block copolymer rubber is preferably styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene/isoprene-styrene (SBIS) ), hydrogenated styrene-butadiene-styrene (HSBS), hydrogenated styrene-isoprene-styrene (HSIS), hydrogenated styrene-butadiene/isoprene-styrene ( HSBIS).
  • SBS styrene-butadiene-styrene
  • SIS styrene-isoprene-styrene
  • SBIS styrene-butadiene/isoprene-styrene
  • HSIS hydrogenated styrene-butadiene/isoprene
  • the number average molecular weight of the block copolymer rubber is preferably 5,000 to 150,000.
  • the molecular weight of the copolymer is less than 5,000, the material itself is too soft and cannot significantly enhance the resin substrate, and the prepreg is prone to sticking problems;
  • the molecular weight of the copolymer is greater than 150,000, the molecular weight of the block copolymer is too high, the resin has poor solubility in solvents, and the viscosity is too high, which does not have good processing and production conditions, and the prepreg does not have good fluidity during compression. Conducive to the production of substrates and the filling of circuit boards and the patterning features flowing into adjacent layers.
  • the proportion of styrene segments in the total mass of the block copolymer rubber is preferably 10-50%.
  • the proportion of styrene segments is less than 10%, the glass transition temperature of the material is too low; when the styrene segments are greater than 50% , The peel strength of the substrate and the metal foil is low.
  • the mass ratio of the styrene segment to the block copolymer is 10-50%, the material properties such as dielectric properties, glass transition temperature, peel strength, heat resistance, etc. have a good balance.
  • the polymerized monomer of the unsaturated diene rubber includes one or more of unmodified or modified group-containing butadiene or isoprene, and the modified group is selected from epoxy groups , Maleic anhydride, acrylate, hydroxyl or carboxyl group; wherein the number average molecular weight of the diene rubber is 500 to 20,000, and the unsaturated double bond structure accounts for the main chain of the diene rubber 60 to 99% of the quality.
  • the diene rubber is polybutadiene or polyisoprene with a side chain or a double bond structure in the main chain; preferably 1,2-polybutadiene and cis 1,4 polybutadiene, 1,2-polyisoprene, cis-1,4 polyisoprene.
  • the unsaturated diene rubber is selected from polybutadiene resin, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, divinylbenzene- One of butadiene copolymer, divinylbenzene-isoprene copolymer, styrene-butadiene-divinylbenzene copolymer, or styrene-isoprene-divinylbenzene copolymer Or several.
  • the number average molecular weight of the unsaturated diene rubber selected in the present invention is 500-20000, and the more preferred molecular weight is 1000-10000.
  • the molecular weight of the unsaturated polymer resin is less than 500, there is no obvious improvement in reducing the dielectric properties.
  • the molecular weight of the unsaturated polymer resin is greater than 20,000, the glass transition temperature and peel strength of the resin system will become worse;
  • the unsaturated double bond structure in the rubber accounts for 60-99% of the main chain mass of the diene rubber.
  • the content of the unsaturated double bond is too low, there are fewer groups that crosslink with other thermosetting resins, and the peel strength is low.
  • the glass transition temperature is low, and the mechanical strength is poor.
  • the unsaturated diene rubber modification group is selected from one or more of epoxy, maleic anhydride, (meth)acrylate, hydroxyl or carboxyl group; more preferably maleic anhydride, (meth) Acrylate modified unsaturated butadiene polymer.
  • Modified unsaturated diene rubber is beneficial to further improve the peel strength between the resin and the metal foil and the bond strength between the resin interface layers.
  • the modified polyphenylene ether resin is prepared by modifying the terminal groups of the polyphenylene ether resin with vinyl or methacrylate groups, and its number average molecular weight is preferably 500-10,000.
  • Diene rubber with unsaturated double bond structure, matched with modified polyphenylene ether resin, can further reduce the dielectric constant and dielectric loss of the material, and at the same time improve the bonding strength between the resin and the copper foil, and improve the resin interface and the metal layer Reliability between.
  • the number average molecular weight of the modified polyphenylene ether is preferably 500-10,000, more preferably 1,000-5,000.
  • the molecular weight is less than 500, there are too many reactive vinyl groups, it is difficult to obtain lower dielectric properties, and the reaction speed is too fast, and it is difficult to control;
  • the molecular weight is greater than 10,000, the melt viscosity of the polyphenylene ether resin is too high, and it is not easy to control with other resins. Compatibility becomes poor, and the prepared material easily causes poor appearance.
  • the modified polyphenylene ether is vinyl-modified or methacrylate-terminated polyphenylene ether, such as Sabic SA-9000, a modified polyphenylene ether resin terminated with methacrylate; Such as Mitsubishi Chemical OPE-2ST, modified polyphenylene ether resin terminated with phenyl vinyl.
  • the resin composition also contains a small molecule crosslinking agent, which is mainly used to increase the crosslink density of block copolymer rubber, unsaturated diene rubber and N-substituted maleimide copolymer, and increase the density of the crosslink network , Improve the glass transition temperature and heat resistance of the material.
  • a small molecule crosslinking agent which is mainly used to increase the crosslink density of block copolymer rubber, unsaturated diene rubber and N-substituted maleimide copolymer, and increase the density of the crosslink network , Improve the glass transition temperature and heat resistance of the material.
  • the small molecule crosslinking agent is preferably selected from triallyl isocyanurate, triallyl cyanurate, trimethylallyl isocyanurate, trimethylallyl cyanurate, trihydroxyethyl Ethyl isocyanurate, tert-butyl styrene, diallyl isophthalate, diallyl phthalate, trimethylolpropane triacrylate, or pentaerythritol tetraacrylate Or several
  • patent of the present invention also includes flame retardants, fillers and accelerators.
  • the flame retardant used in the present invention is preferably one of bromine-containing flame retardants or phosphorus-containing flame retardants or a mixture of both. Among them, in order to adapt to low-dielectric resin systems, bromine-containing flame retardants or phosphorus-containing flame retardants are preferred. Flame retardants are insoluble in the resin system, and are usually selected from additive bromine-based flame retardants or phosphorus-based flame retardants that are not reactive with polyphenylene ether resins and other resins and do not reduce heat resistance and dielectric properties.
  • the additive bromine-containing flame retardant in the present invention is preferably selected from decabromodiphenyl ether, decabromodiphenylethane, brominated styrene or decabromodiphenyl ether, ethylene bistetrabromophthalimide One or more;
  • the additive phosphorus-containing flame retardant is selected from tris(2,6-dimethylphenyl) phosphorus, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9 -Oxa-10-phosphophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphorylbenzene or 10-phenyl-9,10-dihydro-9-oxa -10-Phosphophenanthrene-10-oxide one or more.
  • the filler used in the present invention is not particularly limited, and can be selected from aluminum nitride, aluminum borate, magnesium oxide, magnesium carbonate, boron nitride, crystalline silica, synthetic silica, hollow silica, spherical silica One or more of fused silica, talc, alumina, barium sulfate, barium titanate, strontium titanate, calcium carbonate or titanium dioxide.
  • an accelerator initiator
  • an accelerator initiator
  • the accelerator used in the present invention is preferably an organic peroxide radical initiator selected from di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxide neodecanoate , Tert-butyl peroxide neodecanoate, tert-butyl peroxide pivalate, tert-butyl peroxy isobutyrate, tert-butyl peroxy-3,5,5-trimethylhexanoate, peroxide Tert-butyl acetate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy-3,5,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane , 2,2-bis(tert-butylperoxy)butane, bis(4-tert-butylcyclohexyl)peroxydicarbonate,
  • the high-frequency resin composition of the present invention can be used to prepare adhesive sheets, metal-clad laminates and printed wiring boards.
  • the high-frequency resin composition of the present invention is coated on reinforcing fibers to form a prepreg;
  • the reinforcing fibers may be a reinforced textile formed by weaving organic fibers or inorganic fibers, preferably glass fiber woven fiber cloth, including E-glass, T-glass, NE-glass, L-glass and Q-glass.
  • the metal-clad laminate is made by hot pressing the above-mentioned bonding sheet to laminate one or at least two metal foils;
  • the metal foil is preferably copper foil, more preferably electrolytic copper foil, and its surface roughness Rz is preferably Less than 5um, for example, RTF copper foil, VLP copper foil, HVLP copper foil, HVLP2 copper foil, which can further improve the signal loss of high-frequency and high-speed circuit boards.
  • the printed circuit board includes at least one of the above-mentioned adhesive sheet or the above-mentioned metal-clad laminate.
  • the resin composition of the present invention has good mechanical strength and toughness, good glass transition temperature, peel strength and low dielectric properties, and is therefore suitable for the processing of preparing high multilayer printed circuit boards.
  • N-substituted maleimide copolymers are used in the resin composition as rubber heat-resistant modifiers and compatibilizers, and the triblock copolymer contains N-substituted maleimides Structure and maleic anhydride structure.
  • N-substituted maleimide copolymer is used in the resin base material of block copolymer rubber containing vinyl and unsaturated diene rubber.
  • Maleimide is used The structure improves the heat resistance of the vinyl segment and enhances the heat resistance of the resin substrate.
  • the maleic anhydride structure also improves the polarity of the vinyl segment.
  • the present invention has the following advantages:
  • N-substituted maleimide copolymers improves the heat resistance of the resin substrate, improves the compatibility with inorganic materials and flame retardants, and improves the high resin substrate and metal foil
  • the resin composition of the present invention as an insulator, it has good dielectric and mechanical properties
  • Modified polyphenylene ether resin is added to the resin substrate to further improve the heat resistance of the high-frequency resin composition and the peeling strength of the copper foil.
  • a high-frequency resin composition comprising the following components in parts by weight: 15-40 parts of block copolymer rubber, 25-50 parts of modified polyphenylene ether resin, 10-50 parts of unsaturated diene rubber, N -Substitute 5-30 parts of maleimide copolymer, 10-50 parts of small molecule crosslinking agent, flame retardant, filler and accelerator.
  • the N-substituted maleimide copolymer is copolymerized with the following molar parts of monomers: 30-60 parts of styrene monomer, 30-70 parts of N-substituted maleimide, and 1-20 parts of unsaturated acid anhydride Parts;
  • the molecular formula of styrene, N-substituted maleimide, and maleic anhydride copolymer is as follows:
  • the R group is methyl, ethyl, isopropyl, cyclohexyl, phenyl, benzyl, phenylethyl, phenylvinyl, p-hydroxyphenyl , Biphenyl, naphthalene ring group; among them, methyl, phenyl, and phenyl vinyl are preferred.
  • the molecular formulas are as follows:
  • the high-frequency resin composition contains a block copolymer rubber with a larger molecular weight.
  • the block copolymer is a linear tri-block copolymer with styrene as the terminal segment and polybutadiene and isoprene as the middle segment.
  • the segment copolymer has a number average molecular weight of 5,000 to 150,000, and the styrene segment accounts for 10 to 50% of the total mass of the block copolymer rubber.
  • Such block copolymers usually do not have a double bond structure and have low reactivity.
  • the block copolymer rubber is preferably styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene/isoprene -Styrene (SBIS), hydrogenated styrene-butadiene-styrene (HSBS), hydrogenated styrene-isoprene-styrene (HSIS), hydrogenated styrene-butadiene/isoprene En-styrene (HSBIS).
  • SBS styrene-butadiene-styrene
  • SIS styrene-isoprene-styrene
  • SI styrene-butadiene/isoprene -Styrene
  • HSIS hydrogenated styrene-butadiene-styrene
  • the polymerized monomer of unsaturated diene rubber in the resin composition includes one or more of unmodified or modified group-containing butadiene or isoprene.
  • the diene rubber contains side chains or Polybutadiene and polyisoprene with double bond structure in the main chain; preferably 1,2-polybutadiene, cis 1,4 polybutadiene, 1,2-polyisoprene, cis 1,4 polyisoprene.
  • the unsaturated diene rubber modification group is selected from one or more of epoxy, maleic anhydride, (meth)acrylate, hydroxyl or carboxyl group; more preferably maleic anhydride, (meth) Acrylate modified unsaturated butadiene polymer.
  • Modified unsaturated diene rubber is beneficial to further improve the peel strength between the resin and the metal foil and the bond strength between the resin interface layers.
  • unsaturated diene rubbers examples include polybutadiene resin, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, divinylbenzene-butadiene copolymer One or more of styrene, divinylbenzene-isoprene copolymer, styrene-butadiene-divinylbenzene copolymer or styrene-isoprene-divinylbenzene copolymer.
  • the modified polyphenylene ether resin is prepared by modifying the terminal groups of the polyphenylene ether resin with vinyl or methyl methacrylate groups, and its molecular weight can be selected to be 500-10,000.
  • small-molecule crosslinking agents are triallyl isocyanurate, triallyl cyanurate, trimethylallyl isocyanurate, trimethylallyl cyanurate, three Among the hydroxyethyl isocyanurate, tert-butyl styrene, diallyl isophthalate, diallyl phthalate, trimethylolpropane triacrylate or pentaerythritol tetraacrylate
  • triallyl isocyanurate triallyl cyanurate
  • trimethylallyl isocyanurate trimethylallyl cyanurate
  • patent of this embodiment also includes flame retardants, fillers and accelerators.
  • the flame retardant used in this embodiment is preferably a bromine-containing flame retardant or a phosphorus-containing flame retardant or a mixture of both.
  • the bromine-containing flame retardant or the phosphorus-containing flame retardant is preferable
  • Phosphorus flame retardants are insoluble in the resin system, and are usually selected from added bromine flame retardants or phosphorus flame retardants that are not reactive with polyphenylene ether resins and other resins and do not reduce heat resistance and dielectric properties .
  • the additive bromine-containing flame retardant is preferably selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or decabromodiphenyl ether, ethylene bis tetrabromophthalimide
  • the additive phosphorus-containing flame retardant is selected from tris(2,6-dimethylphenyl) phosphorus, 10-(2,5-dihydroxyphenyl)-9,10-dihydro- 9-oxa-10-phosphophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphorylbenzene or 10-phenyl-9,10-dihydro-9-oxy One or more of hetero-10-phosphorophenanthrene-10-oxide.
  • the filler used in this embodiment is not particularly limited, and can be selected from aluminum nitride, aluminum borate, magnesium oxide, magnesium carbonate, boron nitride, crystalline silica, synthetic silica, hollow silica, and spherical dioxide.
  • aluminum nitride aluminum borate
  • magnesium oxide magnesium carbonate
  • boron nitride crystalline silica
  • synthetic silica synthetic silica
  • hollow silica and spherical dioxide.
  • an accelerator initiator
  • an accelerator initiator
  • the accelerator used in this embodiment is preferably an organic peroxide radical initiator, selected from the group consisting of di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumene neodecanoate peroxide Ester, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-butylperoxyisobutyrate, tert-butylperoxy-3,5,5-trimethylhexanoate, peroxy Tert-butyl oxyacetate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy-3,5,5-trimethylcyclohexane, 1,1-di-tert-butylcyclohexane Alkyl, 2,2-bis(tert-butylperoxy)butane, bis(4-tert-butylcyclohexyl)peroxydi
  • the high-frequency resin composition of the present invention can be used to prepare adhesive sheets, metal-clad laminates and printed wiring boards.
  • the high-frequency resin composition is coated on the reinforcing fiber to form a prepreg;
  • the reinforcing fiber may be a reinforced textile formed by weaving organic fibers or inorganic fibers, preferably fiber cloth woven with glass fibers, Including E-glass, T-glass, NE-glass, L-glass and Q-glass.
  • the metal-clad laminate is made by hot pressing the above-mentioned bonding sheet to laminate one or at least two metal foils;
  • the metal foil is preferably copper foil, more preferably electrolytic copper foil, and its surface roughness Rz is preferably Less than 5um, for example, RTF copper foil, VLP copper foil, HVLP copper foil, HVLP2 copper foil, which can further improve the signal loss of high-frequency and high-speed circuit boards.
  • the printed circuit board includes at least one of the above-mentioned adhesive sheet or the above-mentioned metal-clad laminate.
  • the resin composition of this embodiment has good mechanical strength and toughness, good glass transition temperature, peel strength and low dielectric properties, and is therefore suitable for the processing of preparing high multilayer printed circuit boards.
  • the preparation method of the high-frequency resin composition in this implementation includes the following steps:
  • the block copolymer rubber, the unsaturated diene rubber and the N-substituted maleimide are copolymerized and dissolved in a solvent, a crosslinking agent is added, and a high frequency resin composition is obtained after dispersion treatment.
  • step (2) is to copolymerize the block copolymer rubber, unsaturated diene rubber and N-substituted maleimide in the solvent Add flame retardant, inorganic filler and accelerator, stir evenly, and obtain a low dielectric resin composition after dispersion treatment.
  • test method Perform performance test on the prepared copper clad laminate, the test method is:
  • Glass transition temperature (Tg) Use a DMA instrument to test and measure it in accordance with the DMA test method specified in IPC-TM-650 2.4.24.4.
  • CTE Coefficient of Thermal Expansion
  • Copper foil peel strength Use Shimadzu tensile machine to test and measure according to the test method specified in IPC-TM-650 2.4.8.
  • Dielectric constant (Dk) and dielectric loss factor (Df) The dielectric constant and dielectric loss factor test methods are determined in accordance with the test methods specified in IPC-TM-650 2.5.5.9.
  • PCT Pressure cooker cooking experiment
  • T288 Use TMA instrument to test and measure according to the test method specified in IPC-TM-650 2.4.24.1.
  • Flame retardancy According to the material flammability method specified by UL-94, it is tested and classified.
  • Resin fluidity The resin fluidity was measured by Shimadzu capillary rheometer. 2g resin powder pressed ingot extruded the resin from the small hole at a certain pressure, and evaluated based on the resin flow out of the rheometer. The longer the outflow stroke, the better the resin fluidity.
  • Heat resistance refers to the properties of a substance that can maintain its excellent physical and mechanical properties under heated conditions.
  • Resin system compatibility Take the cross-section of the substrate and observe the micro-uniformity of the cured resin under SEM. If resin agglomeration occurs, it means that the resin is incompatible.
  • a high-frequency resin composition comprising the following components in parts by weight: modified polyphenylene ether resin, block copolymer rubber, unsaturated diene rubber, N-substituted maleimide copolymer, and small molecule Crosslinking agent, flame retardant, filler and accelerator, the source and selection of each component in this embodiment are shown in Table 1, and the content of each component is shown in Table 2.
  • a high-frequency resin composition comprising the following components in parts by weight: modified polyphenylene ether resin, block copolymer rubber, unsaturated diene rubber, N-substituted maleimide copolymer, and small molecule Crosslinking agent, flame retardant, filler and accelerator, the content of each component is shown in Table 2.
  • the filler used is a high-Dk filler (Dk>10), which results in a higher dielectric loss.
  • a high-frequency resin composition comprising the following components in parts by weight: modified polyphenylene ether resin, block copolymer rubber, unsaturated diene rubber, N-substituted maleimide copolymer, and small molecule Crosslinking agent, flame retardant, filler and accelerator, the content of each component is shown in Table 2.
  • the modified polyphenylene ether resin is prepared by modifying the end groups of the polyphenylene ether resin with vinyl;
  • the block copolymer rubber is made of styrene as the end segment and polybutadiene and isoprene as the middle chain
  • the number average molecular weight of the block copolymer rubber is 5000, and the styrene segment content is 10%;
  • the unsaturated diene rubber is styrene-isoprene copolymer and diethylene Benzene-isoprene copolymer, in which 1,4-cis double bond structure accounts for 60%, and its number average molecular weight is 1000;
  • the monomers of the N-substituted maleimide copolymer are styrene, N- Phenyl maleimide, unsaturated acid anhydride, wherein the mole part of styrene is 30 parts, the mole part of unsaturated acid anhydride is 1 part, the mole
  • a high frequency resin composition comprising the following components in parts by weight: block copolymer rubber, unsaturated diene rubber, N-substituted maleimide copolymer, small molecule crosslinking agent, flame retardant , Fillers and accelerators, the content of each component is shown in Table 2.
  • the modified polyphenylene ether resin is prepared by modifying the end groups of the polyphenylene ether resin with vinyl;
  • the block copolymer rubber is made of styrene as the end segment and polybutadiene and isoprene as the middle chain Segment linear triblock copolymer, the number average molecular weight of the block copolymer rubber is 15000, and the styrene segment content is 50%;
  • the unsaturated diene rubber is styrene-isoprene copolymer and diethylene Benzene-isoprene copolymer, in which the 1,4-cis double bond structure accounts for 95%, and its number average molecular weight is 10,000;
  • the monomers of the N-substituted maleimide copolymer are styrene, N- Phenyl maleimide, unsaturated acid anhydride, wherein the mole part of styrene is 60 parts, the mole part of unsaturated acid
  • Comparative Example 1 is a resin composition whose raw material composition includes modified polyphenylene ether resin, unsaturated diene rubber, N-substituted maleimide copolymer, small molecule crosslinking agent, flame retardant, and filler And accelerators, the specific content and selection of each component are shown in Table 2.
  • Comparative Example 1 The main difference between Comparative Example 1 and Examples is that there is no block copolymer rubber added in the Comparative Example. From the test data in Table 1, it can be seen that the glass transition temperature of the resin composition in Comparative Example 1 is 185°C, which is far It is much lower than the glass transition temperature of the resin composition in any embodiment of the present invention. In addition, its copper foil peel strength is low, indicating poor mechanical properties, and the layering time at 288°C is short, indicating its thermal stability Poor sex. Therefore, adding a block copolymer rubber to the resin substrate is beneficial to improve the heat resistance and peel strength of the resin composition.
  • Comparative Example 2 is a resin composition
  • the raw material composition includes modified polyphenylene ether resin, block copolymer rubber, unsaturated diene rubber, BDM maleimide, small molecule crosslinking agent, flame retardant Agents, fillers and accelerators, the specific content and selection of each component are shown in Table 2.
  • Comparative Example 2 The main difference between Comparative Example 2 and the Examples is that BDM maleimide is used instead of N-substituted maleimide copolymer. It can be seen from the test data in Table 1 that the resin composition in Comparative Example 2 The glass transition temperature is 205°C, which is lower than the glass transition temperature of the resin composition in any embodiment of the present invention, and its dielectric loss is high, energy consumption is large, resin fluidity is poor, and heat resistance is poor , Indicating that the addition of N-substituted maleimide copolymer can reduce the heat resistance and peel strength of the resin composition.
  • Comparative Example 3 is a resin composition
  • the raw material composition includes modified polyphenylene ether resin, block copolymer rubber, unsaturated diene rubber, styrene, maleic anhydride copolymer, small molecule crosslinking agent, resistance Burning agent, filler and accelerator, the specific content and selection of each component are shown in Table 2.
  • Comparative Example 3 The main difference between Comparative Example 3 and the Examples is that styrene and maleic anhydride copolymers are used instead of N-substituted maleimide copolymers. From the test data in Table 1, it can be seen that the resin combination in Comparative Example 3 In addition, the resin composition has very low peel strength and very short delamination time at 288°C. Therefore, the addition of N-substituted maleimide copolymer is very important. The synergy between the imine structure and the maleic anhydride structure and the resin substrate is beneficial to improve the mechanical properties and dielectric properties of the resin composition.

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Abstract

The present invention relates to a high-frequency resin composition and use thereof. The high-frequency resin composition comprises 25-50 parts of a modified polyphenylene ether resin, 15-40 parts of a block copolymer rubber, 10-50 parts of an unsaturated diene-based rubber, 5-30 parts of an N-substituted maleimide copolymer, 10-30 parts of a small molecule cross-linking agent, a flame retardant, a filler and an accelerator. Compared with the prior art, the present invention introduces an N-substituted maleimide copolymer into a rubber system, so that the glass transition temperature and peeling strength of a material can be significantly improved, and achieves advantages such as small dielectric loss and good heat resistance at the same time.

Description

一种高频树脂组合物及其应用High-frequency resin composition and its application 技术领域Technical field
本发明涉及高频高速技术领域，尤其是涉及一种高频树脂组合物及其应用。The invention relates to the field of high-frequency and high-speed technology, in particular to a high-frequency resin composition and its application.
背景技术Background technique
随着5G时代的到来，终端应用和网络速度的不断提高，设备间的数据传输速率已从几百Mbps提升到20Gbps，目前PCB的产业技术不管软板与硬板都是往高频、高速以及高密度构装的方法发展，对应产品轻、薄、可携带、多功能化的发展趋势，对于材料以及制备方法的需求会越来越严苛，在高频高速和小型化需求下，高频传输及低损耗材料将全面替代传输线，其中最重要的材料特性需求就是超低介电性能、高耐热性、良好的阻燃性。With the advent of the 5G era, terminal applications and network speeds continue to increase, and the data transmission rate between devices has increased from several hundred Mbps to 20Gbps. The current PCB industry technology, regardless of soft board and hard board, is going to high frequency, high speed and The development of high-density packaging methods corresponds to the development trend of light, thin, portable, and multi-functional products. The requirements for materials and preparation methods will become more and more stringent. Under the requirements of high frequency, high speed and miniaturization, high frequency Transmission and low-loss materials will fully replace transmission lines. The most important material characteristics are ultra-low dielectric properties, high heat resistance, and good flame retardancy.
在高频信号传输的电路中，电信号传输损失通过介电损耗、导体损失与辐射损失之和表示。电信号频率越高，则介电损耗、导体损失、辐射损失越大。由此，作为高频信号传输的绝缘体，可以通过选择介质损耗角正切小的绝缘材料，以抑制介电损耗的增大。In high-frequency signal transmission circuits, the electrical signal transmission loss is represented by the sum of dielectric loss, conductor loss, and radiation loss. The higher the frequency of the electrical signal, the greater the dielectric loss, conductor loss, and radiation loss. Therefore, as an insulator for high-frequency signal transmission, an insulating material with a small dielectric loss tangent can be selected to suppress an increase in dielectric loss.
目前，作为高频信号传输的绝缘材料通常通过聚四氟乙烯材料或碳氢树脂材料制备，由于聚四氟乙烯材料加工困难，碳氢材料在高频方面得到广泛应用。通过嵌段共聚物橡胶或不饱和化的烯烃树脂以及填料制备的碳氢树脂，存在剥离强度低、耐热性不佳、弯曲强度小的缺点，而且制备的粘结片由于橡胶材料而可能出现粘粘问题，影响粘结片的生产、保存及运输。因此，需要开发出一种高耐热性、高剥离强度、低介电损耗、低膨胀系数的高频基板材料。At present, as an insulating material for high-frequency signal transmission, it is usually made of polytetrafluoroethylene material or hydrocarbon resin material. Due to the difficulty of processing polytetrafluoroethylene materials, hydrocarbon materials are widely used in high frequency. The hydrocarbon resin prepared by block copolymer rubber or unsaturated olefin resin and filler has the disadvantages of low peel strength, poor heat resistance, and low bending strength, and the prepared adhesive sheet may appear due to rubber materials Adhesive problems affect the production, storage and transportation of adhesive sheets. Therefore, it is necessary to develop a high-frequency substrate material with high heat resistance, high peel strength, low dielectric loss, and low expansion coefficient.
发明内容Summary of the invention
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种以碳氢树脂为主的高频树脂组合物。The purpose of the present invention is to provide a high-frequency resin composition based on hydrocarbon resin in order to overcome the above-mentioned defects in the prior art.
本发明的目的可以通过以下技术方案来实现：The purpose of the present invention can be achieved through the following technical solutions:
一种高频树脂组合物，包括以下重量份含量的组分：A high-frequency resin composition comprising the following components in parts by weight:
Figure PCTCN2019129924-appb-000001
Figure PCTCN2019129924-appb-000001
Figure PCTCN2019129924-appb-000002
Figure PCTCN2019129924-appb-000002
〈N-取代马来酰亚胺共聚物〉〈N-substituted maleimide copolymer〉
N-取代马来酰亚胺共聚物由以下摩尔份含量的单体共聚而成：苯乙烯单体30-60份，N-取代马来酰亚胺30-70份，不饱和酸酐1-20份；苯乙烯、N-取代马来酰亚胺、马来酸酐共聚物的分子式如下：The N-substituted maleimide copolymer is copolymerized with the following molar parts of monomers: 30-60 parts of styrene monomer, 30-70 parts of N-substituted maleimide, and 1-20 parts of unsaturated acid anhydride Parts; The molecular formula of styrene, N-substituted maleimide, and maleic anhydride copolymer is as follows:
Figure PCTCN2019129924-appb-000003
Figure PCTCN2019129924-appb-000003
式中，x、y、z分别为苯乙烯单体、N-取代马来酰亚胺、不饱和酸酐的摩尔比，x:y:z＝0.3～0.6:0.3～0.7:0.01～0.2。In the formula, x, y, and z are the molar ratios of styrene monomer, N-substituted maleimide, and unsaturated acid anhydride, respectively, and x:y:z=0.3~0.6:0.3~0.7:0.01~0.2.
上述N-取代马来酰亚胺共聚物分子式中R基团为甲基、乙基、异丙基、环己基、苯基、苄基、苯基乙基、苯基乙烯基、对羟基苯基、联苯基、萘环基；其中优选甲基、苯基、苯基乙烯基，分子式分别如下所示：In the above N-substituted maleimide copolymer molecular formula, the R group is methyl, ethyl, isopropyl, cyclohexyl, phenyl, benzyl, phenylethyl, phenylvinyl, p-hydroxyphenyl , Biphenyl, naphthalene ring group; among them, methyl, phenyl, and phenyl vinyl are preferred. The molecular formulas are as follows:
a)N-甲基马来酰亚胺共聚物：a) N-methyl maleimide copolymer:
Figure PCTCN2019129924-appb-000004
Figure PCTCN2019129924-appb-000004
b)N-苯基马来酰亚胺共聚物：b) N-phenylmaleimide copolymer:
Figure PCTCN2019129924-appb-000005
Figure PCTCN2019129924-appb-000005
c)N-苯基乙烯基马来酰亚胺共聚物：c) N-phenylvinyl maleimide copolymer:
Figure PCTCN2019129924-appb-000006
Figure PCTCN2019129924-appb-000006
本发明采用的N-取代马来酰亚胺共聚物为苯乙烯、N-取代马来酰亚胺、马来酸酐的共聚物(SMI)，能够提升极性与非极性树脂间的相容性，苯乙烯链段与橡胶类材料由良好相容性，而马来酰亚胺和马来酸酐链段能够与极性树脂有良好的相容性，同时能够提升界面强度，提高与金属箔的剥离强度以及与玻纤束的结合力。N-取代马来酰亚胺共聚物具有良好的耐热性，优秀的热稳定性(350℃不分解)，与碳氢树脂混合使用时，用作碳氢材料的耐热改性剂，提高板材的玻璃化转变温度和耐热性。The N-substituted maleimide copolymer used in the present invention is a copolymer of styrene, N-substituted maleimide and maleic anhydride (SMI), which can improve the compatibility between polar and non-polar resins The styrene segment has good compatibility with rubber-like materials, while the maleimide and maleic anhydride segments can have good compatibility with polar resins, and at the same time can improve the interface strength and improve the compatibility with metal foils. The peel strength and the bonding force with the glass fiber bundle. N-substituted maleimide copolymer has good heat resistance and excellent thermal stability (no decomposition at 350°C). When mixed with hydrocarbon resins, it can be used as a heat-resistant modifier for hydrocarbon materials to improve The glass transition temperature and heat resistance of the sheet.
其中，N-取代马来酰亚胺共聚物的含量优选为5-30份，如果添加的N-取代马来酰亚胺共聚物过少，对材料的耐热性改善比较有限，并且剥离强度较低；如果添加的N-取代马来酰亚胺共聚物过多，则其介电性能有所上升，吸水率也会明显增加。Among them, the content of N-substituted maleimide copolymer is preferably 5-30 parts. If the added N-substituted maleimide copolymer is too small, the improvement of the heat resistance of the material is relatively limited, and the peel strength Lower; if too much N-substituted maleimide copolymer is added, its dielectric properties will increase, and the water absorption will also increase significantly.
N-取代马来酰亚胺共聚物的分子量没有特别的限制，通常数均分子量可优选的范围为2000-200000，其中，更优选的范围为5000-50000，在树脂组合物中具有快速良好的溶解性，同时也能保证材料可靠的耐热性和热稳定性。The molecular weight of the N-substituted maleimide copolymer is not particularly limited. Generally, the number average molecular weight is preferably in the range of 2,000 to 200,000, among which the more preferable range is 5,000 to 50,000, which has rapid and good performance in resin compositions. Solubility, while also ensuring the reliable heat resistance and thermal stability of the material.
〈嵌段共聚物橡胶〉〈Block copolymer rubber〉
所述嵌段共聚物橡胶是以苯乙烯为末端段，以聚丁二烯、异戊二烯为中间链段的线性三嵌段共聚物，其数均分子量在5000～150000，并且苯乙烯链段占所述嵌段共聚物橡胶总质量的10～50％。The block copolymer rubber is a linear triblock copolymer with styrene as the terminal segment and polybutadiene and isoprene as the middle segment. Its number average molecular weight is 5000 to 150,000, and the styrene chain The segment accounts for 10-50% of the total mass of the block copolymer rubber.
热固性树脂组合物中含有较大分子量的嵌段共聚物橡胶，所述的嵌段共聚物是以苯乙烯为末端段，以聚丁二烯、异戊二烯为中间链段的线性三嵌段共聚物，这种嵌段共聚物通常不具有双键结构，具有较低反应性。所述嵌段共聚物 橡胶具有低极性特征，可以表现出高频高速材料所需的极低的介电常数和低介电损耗，但往往材料的耐热性不佳，与金属箔的剥离强度较低。使用这种低极性材料与少量的极性材料如聚苯醚、氰酸酯、马来酰亚胺等树脂组合，可以取得良好的性能平衡性。因此所述的嵌段共聚物橡胶作为组合物的主要成分之一，其苯乙烯链段与丁二烯链段的比例选择尤为重要。The thermosetting resin composition contains a block copolymer rubber with a larger molecular weight. The block copolymer is a linear triblock with styrene as the terminal segment and polybutadiene and isoprene as the middle segment. Copolymers, such block copolymers usually do not have a double bond structure and have low reactivity. The block copolymer rubber has the characteristics of low polarity, and can exhibit extremely low dielectric constant and low dielectric loss required for high-frequency and high-speed materials, but often the material has poor heat resistance and peels off from the metal foil. The intensity is low. Using this low-polarity material in combination with a small amount of polar materials such as polyphenylene ether, cyanate ester, maleimide and other resins, a good performance balance can be achieved. Therefore, the block copolymer rubber is one of the main components of the composition, and the ratio of the styrene segment to the butadiene segment is particularly important.
上述嵌段共聚物橡胶优选苯乙烯-丁二烯-苯乙烯(SBS)，苯乙烯-异戊二烯-苯乙烯(SIS)，苯乙烯-丁二烯/异戊二烯-苯乙烯(SBIS)，氢化的苯乙烯-丁二烯-苯乙烯(HSBS)，氢化的苯乙烯-异戊二烯-苯乙烯(HSIS)，氢化的苯乙烯-丁二烯/异戊二烯-苯乙烯(HSBIS)。The block copolymer rubber is preferably styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene/isoprene-styrene (SBIS) ), hydrogenated styrene-butadiene-styrene (HSBS), hydrogenated styrene-isoprene-styrene (HSIS), hydrogenated styrene-butadiene/isoprene-styrene ( HSBIS).
所述的嵌段共聚物橡胶其数均分子量优选5000-150000，当共聚物分子量小于5000时，材料本身过于柔软，不能对树脂基材起到明显的增强作用，而且半固化片容易发生粘粘问题；当共聚物分子量大于150000，嵌段共聚物分子量过高，树脂在溶剂中溶解性不佳，且粘度过高，不具有良好的加工生产条件，而且半固化片在压合时没有良好的流动性，不利于基板的生产和线路板的填充和流入相邻层的图案化特征。The number average molecular weight of the block copolymer rubber is preferably 5,000 to 150,000. When the molecular weight of the copolymer is less than 5,000, the material itself is too soft and cannot significantly enhance the resin substrate, and the prepreg is prone to sticking problems; When the molecular weight of the copolymer is greater than 150,000, the molecular weight of the block copolymer is too high, the resin has poor solubility in solvents, and the viscosity is too high, which does not have good processing and production conditions, and the prepreg does not have good fluidity during compression. Conducive to the production of substrates and the filling of circuit boards and the patterning features flowing into adjacent layers.
苯乙烯链段占所述嵌段共聚物橡胶总质量的比例优选为10～50％，苯乙烯链段比例小于10％时，材料的玻璃化转变温度过低；当苯乙烯链段大于50％，基材与金属箔剥离强度较低。苯乙烯链段占嵌段共聚物质量比例为10-50％时，材料各项性能如介电性能、玻璃化转变温度、剥离强度、耐热性等具有较好的均衡性。The proportion of styrene segments in the total mass of the block copolymer rubber is preferably 10-50%. When the proportion of styrene segments is less than 10%, the glass transition temperature of the material is too low; when the styrene segments are greater than 50% , The peel strength of the substrate and the metal foil is low. When the mass ratio of the styrene segment to the block copolymer is 10-50%, the material properties such as dielectric properties, glass transition temperature, peel strength, heat resistance, etc. have a good balance.
〈不饱和二烯系橡胶〉〈Unsaturated Diene Rubber〉
所述不饱和二烯系橡胶的聚合单体包括未改性或含改性基团的丁二烯或异戊二烯中的一种或几种，所述改性基团选自环氧基、马来酸酐、丙烯酸酯、羟基或羧基中的一种或几种；其中，所述二烯系橡胶的数均分子量为500～20000，不饱和双键结构占所述二烯系橡胶主链质量的60～99％。The polymerized monomer of the unsaturated diene rubber includes one or more of unmodified or modified group-containing butadiene or isoprene, and the modified group is selected from epoxy groups , Maleic anhydride, acrylate, hydroxyl or carboxyl group; wherein the number average molecular weight of the diene rubber is 500 to 20,000, and the unsaturated double bond structure accounts for the main chain of the diene rubber 60 to 99% of the quality.
具体地，二烯系橡胶为含有侧链或主链含有双键结构的聚丁二烯、聚异戊二烯；优选1,2-聚丁二烯、顺式1,4聚丁二烯，1,2-聚异戊二烯、顺式1,4聚异戊二烯。Specifically, the diene rubber is polybutadiene or polyisoprene with a side chain or a double bond structure in the main chain; preferably 1,2-polybutadiene and cis 1,4 polybutadiene, 1,2-polyisoprene, cis-1,4 polyisoprene.
更具体地，所述不饱和二烯系橡胶选自聚丁二烯树脂、聚异戊二烯、苯乙烯-丁二烯共聚物、苯乙烯-异戊二烯共聚物、二乙烯基苯-丁二烯共聚物、二乙 烯基苯-异戊二烯共聚物、苯乙烯-丁二烯-二乙烯基苯共聚物或苯乙烯-异戊二烯-二乙烯基苯共聚物中的一种或几种。More specifically, the unsaturated diene rubber is selected from polybutadiene resin, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, divinylbenzene- One of butadiene copolymer, divinylbenzene-isoprene copolymer, styrene-butadiene-divinylbenzene copolymer, or styrene-isoprene-divinylbenzene copolymer Or several.
本发明所选的不饱和二烯橡胶的数均分子量为500-20000，进一步优选的分子量为1000-10000。当不饱和高分子树脂的分子量小于500时，对降低介电性能无明显改善，当不饱和高分子树脂的分子量大于20000时，树脂体系的玻璃化转变温度和剥离强度会变差；二烯系橡胶中不饱和双键结构占所述二烯系橡胶主链质量的60～99％，不饱和双键含量过低时，与其他热固性树脂发生交联反应的基团较少，剥离强度低，玻璃化转变温度较低，且力学强度不佳。The number average molecular weight of the unsaturated diene rubber selected in the present invention is 500-20000, and the more preferred molecular weight is 1000-10000. When the molecular weight of the unsaturated polymer resin is less than 500, there is no obvious improvement in reducing the dielectric properties. When the molecular weight of the unsaturated polymer resin is greater than 20,000, the glass transition temperature and peel strength of the resin system will become worse; The unsaturated double bond structure in the rubber accounts for 60-99% of the main chain mass of the diene rubber. When the content of the unsaturated double bond is too low, there are fewer groups that crosslink with other thermosetting resins, and the peel strength is low. The glass transition temperature is low, and the mechanical strength is poor.
其中，不饱和二烯系橡胶改性基团选自环氧基、马来酸酐、(甲基)丙烯酸酯、羟基或羧基中的一种或几种；进一步优选马来酸酐、(甲基)丙烯酸酯改性的不饱和丁二烯类聚合物。改性不饱和二烯系橡胶有利于进一步提高树脂与金属箔的剥离强度、树脂界面层间的粘结强度。Among them, the unsaturated diene rubber modification group is selected from one or more of epoxy, maleic anhydride, (meth)acrylate, hydroxyl or carboxyl group; more preferably maleic anhydride, (meth) Acrylate modified unsaturated butadiene polymer. Modified unsaturated diene rubber is beneficial to further improve the peel strength between the resin and the metal foil and the bond strength between the resin interface layers.
〈改性聚苯醚树脂〉〈Modified polyphenylene ether resin〉
所述改性聚苯醚树脂为将聚苯醚树脂的末端基团采用乙烯基或甲基丙烯酸酯基改性制备得到，其数均分子量优选500-10000。The modified polyphenylene ether resin is prepared by modifying the terminal groups of the polyphenylene ether resin with vinyl or methacrylate groups, and its number average molecular weight is preferably 500-10,000.
具有不饱和双键结构的二烯系橡胶，与改性聚苯醚树脂搭配，可以进一步降低材料介电常数和介电损耗，同时提高树脂与铜箔的粘结强度，提升树脂界面与金属层间的可靠性。Diene rubber with unsaturated double bond structure, matched with modified polyphenylene ether resin, can further reduce the dielectric constant and dielectric loss of the material, and at the same time improve the bonding strength between the resin and the copper foil, and improve the resin interface and the metal layer Reliability between.
改性聚苯醚数均分子量优选500-10000，进一步优选为1000-5000为佳。当分子量小于500时，反应性乙烯基过多，不易获得较低介电性能，而且反应速度过快，不易控制；当分子量大于10000时，聚苯醚树脂熔融粘度过高，且与其他树脂的相容性变差，制备的材料容易引起外观不良。The number average molecular weight of the modified polyphenylene ether is preferably 500-10,000, more preferably 1,000-5,000. When the molecular weight is less than 500, there are too many reactive vinyl groups, it is difficult to obtain lower dielectric properties, and the reaction speed is too fast, and it is difficult to control; when the molecular weight is greater than 10,000, the melt viscosity of the polyphenylene ether resin is too high, and it is not easy to control with other resins. Compatibility becomes poor, and the prepared material easily causes poor appearance.
所述的改性聚苯醚为乙烯基改性或甲基丙烯酸酯末端封端的聚苯醚，可以举例如Sabic SA-9000，以甲基丙烯酸酯封端的改性聚苯醚树脂；还可以举例如三菱化学OPE-2ST，以苯基乙烯基封端的改性聚苯醚树脂。The modified polyphenylene ether is vinyl-modified or methacrylate-terminated polyphenylene ether, such as Sabic SA-9000, a modified polyphenylene ether resin terminated with methacrylate; Such as Mitsubishi Chemical OPE-2ST, modified polyphenylene ether resin terminated with phenyl vinyl.
〈小分子交联剂〉〈Small molecule crosslinking agent〉
树脂组合物中还含有小分子交联剂，主要用于提高嵌段共聚物橡胶、不饱和二烯系橡胶和N-取代马来酰亚胺共聚物的交联密度，增加交联网络致密性，提高材料玻璃化转变温度和耐热性。The resin composition also contains a small molecule crosslinking agent, which is mainly used to increase the crosslink density of block copolymer rubber, unsaturated diene rubber and N-substituted maleimide copolymer, and increase the density of the crosslink network , Improve the glass transition temperature and heat resistance of the material.
小分子交联剂优选自三烯丙基异氰脲酸酯、三烯丙基氰脲酸酯、三甲代烯 丙基异氰脲酸酯、三甲代烯丙基氰脲酸酯、三羟乙基异氰尿酸酯、叔丁基苯乙烯、间苯二甲酸二烯丙基酯、邻苯二甲酸二烯丙基酯、三羟甲基丙烷三丙烯酸酯或季戊四醇四丙烯酸酯中的一种或几种；The small molecule crosslinking agent is preferably selected from triallyl isocyanurate, triallyl cyanurate, trimethylallyl isocyanurate, trimethylallyl cyanurate, trihydroxyethyl Ethyl isocyanurate, tert-butyl styrene, diallyl isophthalate, diallyl phthalate, trimethylolpropane triacrylate, or pentaerythritol tetraacrylate Or several
此外，本发明专利还包括阻燃剂、填料和促进剂。In addition, the patent of the present invention also includes flame retardants, fillers and accelerators.
〈阻燃剂〉〈Flame retardant〉
本发明使用的阻燃剂优选自含溴阻燃剂或含磷阻燃剂中的一种或二者的混合物，其中，为了适应低介电树脂体系，优选的含溴阻燃剂或含磷阻燃剂均不溶于树脂体系中，通常选自与聚苯醚树脂及其他树脂没有反应性且不会降低耐热性和介电特性的添加型溴系阻燃剂或磷系阻燃剂。The flame retardant used in the present invention is preferably one of bromine-containing flame retardants or phosphorus-containing flame retardants or a mixture of both. Among them, in order to adapt to low-dielectric resin systems, bromine-containing flame retardants or phosphorus-containing flame retardants are preferred. Flame retardants are insoluble in the resin system, and are usually selected from additive bromine-based flame retardants or phosphorus-based flame retardants that are not reactive with polyphenylene ether resins and other resins and do not reduce heat resistance and dielectric properties.
本发明中添加型含溴阻燃剂优选自十溴二苯醚、十溴二苯乙烷、溴化苯乙烯或十溴二苯醚、乙撑双四溴邻苯二甲酰亚胺中的一种或几种；添加型含磷阻燃剂选自三(2,6-二甲基苯基)磷、10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-磷菲-10-氧化物、2,6-二(2,6-二甲基苯基)磷基苯或10-苯基-9,10-二氢-9-氧杂-10-磷菲-10-氧化物中的一种或几种。The additive bromine-containing flame retardant in the present invention is preferably selected from decabromodiphenyl ether, decabromodiphenylethane, brominated styrene or decabromodiphenyl ether, ethylene bistetrabromophthalimide One or more; the additive phosphorus-containing flame retardant is selected from tris(2,6-dimethylphenyl) phosphorus, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9 -Oxa-10-phosphophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphorylbenzene or 10-phenyl-9,10-dihydro-9-oxa -10-Phosphophenanthrene-10-oxide one or more.
〈填料〉<filler>
本发明中所使用的填料没有特别限定，可以选自氮化铝、硼酸铝、氧化镁、碳酸镁、氮化硼、结晶二氧化硅、合成二氧化硅、中空二氧化硅、球形二氧化硅、熔融二氧化硅、滑石粉、氧化铝、硫酸钡、钛酸钡、钛酸锶、碳酸钙或二氧化钛中的一种或多种。The filler used in the present invention is not particularly limited, and can be selected from aluminum nitride, aluminum borate, magnesium oxide, magnesium carbonate, boron nitride, crystalline silica, synthetic silica, hollow silica, spherical silica One or more of fused silica, talc, alumina, barium sulfate, barium titanate, strontium titanate, calcium carbonate or titanium dioxide.
〈促进剂〉〈Accelerator〉
为了促进树脂组合物的进行反应，增强交联密度，提高玻璃化转变温度和耐热性，可使用促进剂(引发剂)来进一步加速反应。In order to promote the reaction of the resin composition, increase the crosslink density, increase the glass transition temperature and heat resistance, an accelerator (initiator) can be used to further accelerate the reaction.
本发明所使用的促进剂优选为有机过氧化物自由基引发剂，选自二叔丁基过氧化物、过氧化二月桂酰、过氧化二苯甲酰、过氧化新癸酸异丙苯酯、过氧化新癸酸叔丁酯、过氧化特戊酸叔丁酯、叔丁基过氧化异丁酸酯、叔丁基过氧化-3,5,5-三甲基己酸酯、过氧化乙酸叔丁酯、过氧化苯甲酸叔丁酯、1,1-二叔丁基过氧化-3，5,5-三甲基环己烷、1,1-二叔丁基过氧化环己烷、2,2-二(叔丁基过氧化)丁烷、双(4-叔丁基环己基)过氧化二碳酸酯、过氧化二碳酸酯十六酯、过氧化二碳酸酯十四酯、二特戊己过氧化物、二异丙苯过氧化物、双(叔丁基过氧化异丙基)苯、2,5-二甲基-2,5-二叔丁基过氧化己烷、2,5-二甲基-2,5-二叔丁基过 氧化己炔、二异丙苯过氧化氢、异丙苯过氧化氢、特戊基过氧化氢、叔丁基过氧化氢、叔丁基过氧化异丙苯、二异丙苯过氧化氢、过氧化碳酸酯-2-乙基己酸叔丁酯、叔丁基过氧化碳酸-2-乙基己酯、4,4-二(叔丁基过氧化)戊酸正丁酯、过氧化甲乙酮或过氧化环己烷中的一种或几种。The accelerator used in the present invention is preferably an organic peroxide radical initiator selected from di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxide neodecanoate , Tert-butyl peroxide neodecanoate, tert-butyl peroxide pivalate, tert-butyl peroxy isobutyrate, tert-butyl peroxy-3,5,5-trimethylhexanoate, peroxide Tert-butyl acetate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy-3,5,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane , 2,2-bis(tert-butylperoxy)butane, bis(4-tert-butylcyclohexyl)peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, two special Pentylene peroxide, dicumyl peroxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2, 5-Dimethyl-2,5-di-tert-butyl hexyne peroxide, dicumyl hydroperoxide, cumene hydroperoxide, tert-pentyl hydroperoxide, tert-butyl hydroperoxide, tert-butyl Cumene peroxide, dicumyl hydroperoxide, tert-butyl peroxycarbonate-2-ethylhexanoate, tert-butylperoxycarbonate-2-ethylhexyl, 4,4-bis( One or more of n-butyl valerate, methyl ethyl ketone peroxide or cyclohexane peroxide.
本发明的高频树脂组合物可用用于制备粘结片、覆金属箔层压板以及印刷线路板。The high-frequency resin composition of the present invention can be used to prepare adhesive sheets, metal-clad laminates and printed wiring boards.
制备粘结片：本发明中高频树脂组合物涂敷在增强纤维上形成半固化片；所述的增强纤维可以是有机纤维或无机纤维通过编织形成的增强纺织物，优选玻璃纤维编织的纤维布，包括E-glass，T-glass，NE-glass，L-glass和Q-glass。Preparation of bonding sheet: The high-frequency resin composition of the present invention is coated on reinforcing fibers to form a prepreg; the reinforcing fibers may be a reinforced textile formed by weaving organic fibers or inorganic fibers, preferably glass fiber woven fiber cloth, including E-glass, T-glass, NE-glass, L-glass and Q-glass.
制备覆金属箔层压板：该覆金属箔层压板采用上述粘结片叠合一面或者至少两面金属箔热压制成；金属箔优选铜箔，进一步优选为电解铜箔，其表面粗糙度Rz优选小于5um，可举例RTF铜箔、VLP铜箔、HVLP铜箔、HVLP2铜箔，可以进一步改善高频高速线路板的信号损失问题。Preparation of metal-clad laminate: The metal-clad laminate is made by hot pressing the above-mentioned bonding sheet to laminate one or at least two metal foils; the metal foil is preferably copper foil, more preferably electrolytic copper foil, and its surface roughness Rz is preferably Less than 5um, for example, RTF copper foil, VLP copper foil, HVLP copper foil, HVLP2 copper foil, which can further improve the signal loss of high-frequency and high-speed circuit boards.
制备印刷线路板：印刷线路板至少包含一张上述粘结片或者上述覆金属箔层压板。本发明的树脂组合物具有良好的力学强度及韧性，良好的玻璃化转变温度、剥离强度和低介电性能，因此，适合制备高多层印刷线路板的加工。Preparation of a printed circuit board: the printed circuit board includes at least one of the above-mentioned adhesive sheet or the above-mentioned metal-clad laminate. The resin composition of the present invention has good mechanical strength and toughness, good glass transition temperature, peel strength and low dielectric properties, and is therefore suitable for the processing of preparing high multilayer printed circuit boards.
本发明中，树脂组合物中使用了N-取代马来酰亚胺类共聚物作为橡胶的耐热改性剂和相容剂，该三嵌段共聚物中含有N-取代马来酰亚胺结构和马来酸酐结构，将了N-取代马来酰亚胺类共聚物用于含有乙烯基的嵌段共聚物橡胶和不饱和二烯系橡胶的树脂基材中，利用马来酰亚胺结构提高了乙烯基链段的耐热性，增强了树脂基材的耐热性能，另外马来酸酐结构还提高了乙烯基链段的极性。In the present invention, N-substituted maleimide copolymers are used in the resin composition as rubber heat-resistant modifiers and compatibilizers, and the triblock copolymer contains N-substituted maleimides Structure and maleic anhydride structure. N-substituted maleimide copolymer is used in the resin base material of block copolymer rubber containing vinyl and unsaturated diene rubber. Maleimide is used The structure improves the heat resistance of the vinyl segment and enhances the heat resistance of the resin substrate. In addition, the maleic anhydride structure also improves the polarity of the vinyl segment.
与现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
(1)采用N-取代马来酰亚胺类共聚物，提高了树脂基材的耐热性、提高了与无机材料和阻燃剂的相容性，并且提高了高树脂基材与金属箔的界面剥离强度，以本发明的树脂组合物作为绝缘体，具有良好的介电性能和机械性能；(1) The use of N-substituted maleimide copolymers improves the heat resistance of the resin substrate, improves the compatibility with inorganic materials and flame retardants, and improves the high resin substrate and metal foil With the resin composition of the present invention as an insulator, it has good dielectric and mechanical properties;
(2)优化了树脂基材中的不饱和二烯系橡胶的选择，采用高含量不饱和双键结构的液体聚丁二烯，进一步提高了树脂组合物的电绝缘性、剥离强度和玻璃化转变温度；(2) Optimize the selection of unsaturated diene rubber in the resin base material, and use liquid polybutadiene with a high content of unsaturated double bond structure to further improve the electrical insulation, peel strength and vitrification of the resin composition Transition temperature
(3)树脂基材中添加了改性聚苯醚树脂，进一步提高了高频树脂组合物 的耐热性以及铜箔剥离强度。(3) Modified polyphenylene ether resin is added to the resin substrate to further improve the heat resistance of the high-frequency resin composition and the peeling strength of the copper foil.
具体实施方式Detailed ways
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below in conjunction with specific embodiments. The following examples will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be pointed out that, for those of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present invention. These all belong to the protection scope of the present invention.
一种高频树脂组合物，包括以下重量份含量的组分：嵌段共聚物橡胶15-40份，改性聚苯醚树脂25-50份，不饱和二烯系橡胶10-50份，N-取代马来酰亚胺共聚物5-30份，小分子交联剂10-50份、阻燃剂、填料和促进剂。A high-frequency resin composition comprising the following components in parts by weight: 15-40 parts of block copolymer rubber, 25-50 parts of modified polyphenylene ether resin, 10-50 parts of unsaturated diene rubber, N -Substitute 5-30 parts of maleimide copolymer, 10-50 parts of small molecule crosslinking agent, flame retardant, filler and accelerator.
〈N-取代马来酰亚胺共聚物〉〈N-substituted maleimide copolymer〉
N-取代马来酰亚胺共聚物由以下摩尔份含量的单体共聚而成：苯乙烯单体30-60份，N-取代马来酰亚胺30-70份，不饱和酸酐1-20份；苯乙烯、N-取代马来酰亚胺、马来酸酐共聚物的分子式如下：The N-substituted maleimide copolymer is copolymerized with the following molar parts of monomers: 30-60 parts of styrene monomer, 30-70 parts of N-substituted maleimide, and 1-20 parts of unsaturated acid anhydride Parts; The molecular formula of styrene, N-substituted maleimide, and maleic anhydride copolymer is as follows:
Figure PCTCN2019129924-appb-000007
Figure PCTCN2019129924-appb-000007
式中，x、y、z分别为苯乙烯单体、N-取代马来酰亚胺、不饱和酸酐的摩尔比，x:y:z＝0.3～0.6:0.3～0.7:0.01～0.2。In the formula, x, y, and z are the molar ratios of styrene monomer, N-substituted maleimide, and unsaturated acid anhydride, respectively, and x:y:z=0.3~0.6:0.3~0.7:0.01~0.2.
上述N-取代马来酰亚胺共聚物分子式中R基团为甲基、乙基、异丙基、环己基、苯基、苄基、苯基乙基、苯基乙烯基、对羟基苯基、联苯基、萘环基；其中优选甲基、苯基、苯基乙烯基，分子式分别如下所示：In the above N-substituted maleimide copolymer molecular formula, the R group is methyl, ethyl, isopropyl, cyclohexyl, phenyl, benzyl, phenylethyl, phenylvinyl, p-hydroxyphenyl , Biphenyl, naphthalene ring group; among them, methyl, phenyl, and phenyl vinyl are preferred. The molecular formulas are as follows:
a)N-甲基马来酰亚胺共聚物：a) N-methyl maleimide copolymer:
Figure PCTCN2019129924-appb-000008
Figure PCTCN2019129924-appb-000008
b)N-苯基马来酰亚胺共聚物：b) N-phenylmaleimide copolymer:
Figure PCTCN2019129924-appb-000009
Figure PCTCN2019129924-appb-000009
c)N-苯基乙烯基马来酰亚胺共聚物：c) N-phenylvinyl maleimide copolymer:
Figure PCTCN2019129924-appb-000010
Figure PCTCN2019129924-appb-000010
〈嵌段共聚物橡胶〉〈Block copolymer rubber〉
高频树脂组合物中含有较大分子量的嵌段共聚物橡胶，所述的嵌段共聚物是以苯乙烯为末端段，以聚丁二烯、异戊二烯为中间链段的线性三嵌段共聚物，其数均分子量在5000～150000，并且苯乙烯链段占所述嵌段共聚物橡胶总质量的10～50％。这种嵌段共聚物通常不具有双键结构，具有较低反应性。本发明的实施例中嵌段共聚物橡胶优选苯乙烯-丁二烯-苯乙烯(SBS)，苯乙烯-异戊二烯-苯乙烯(SIS)，苯乙烯-丁二烯/异戊二烯-苯乙烯(SBIS)，氢化的苯乙烯-丁二烯-苯乙烯(HSBS)，氢化的苯乙烯-异戊二烯-苯乙烯(HSIS)，氢化的苯乙烯-丁二烯/异戊二烯-苯乙烯(HSBIS)。The high-frequency resin composition contains a block copolymer rubber with a larger molecular weight. The block copolymer is a linear tri-block copolymer with styrene as the terminal segment and polybutadiene and isoprene as the middle segment. The segment copolymer has a number average molecular weight of 5,000 to 150,000, and the styrene segment accounts for 10 to 50% of the total mass of the block copolymer rubber. Such block copolymers usually do not have a double bond structure and have low reactivity. In the embodiment of the present invention, the block copolymer rubber is preferably styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene/isoprene -Styrene (SBIS), hydrogenated styrene-butadiene-styrene (HSBS), hydrogenated styrene-isoprene-styrene (HSIS), hydrogenated styrene-butadiene/isoprene En-styrene (HSBIS).
〈不饱和二烯系橡胶〉〈Unsaturated Diene Rubber〉
树脂组合物中不饱和二烯系橡胶的聚合单体包括未改性或含改性基团的丁二烯或异戊二烯中的一种或几种，二烯系橡胶为含有侧链或主链含有双键结构的聚丁二烯、聚异戊二烯；优选1,2-聚丁二烯、顺式1,4聚丁二烯，1,2-聚异戊二烯、顺式1,4聚异戊二烯。The polymerized monomer of unsaturated diene rubber in the resin composition includes one or more of unmodified or modified group-containing butadiene or isoprene. The diene rubber contains side chains or Polybutadiene and polyisoprene with double bond structure in the main chain; preferably 1,2-polybutadiene, cis 1,4 polybutadiene, 1,2-polyisoprene, cis 1,4 polyisoprene.
其中，不饱和二烯系橡胶改性基团选自环氧基、马来酸酐、(甲基)丙烯酸酯、羟基或羧基中的一种或几种；进一步优选马来酸酐、(甲基)丙烯酸酯改性的 不饱和丁二烯类聚合物。改性不饱和二烯系橡胶有利于进一步提高树脂与金属箔的剥离强度、树脂界面层间的粘结强度。Among them, the unsaturated diene rubber modification group is selected from one or more of epoxy, maleic anhydride, (meth)acrylate, hydroxyl or carboxyl group; more preferably maleic anhydride, (meth) Acrylate modified unsaturated butadiene polymer. Modified unsaturated diene rubber is beneficial to further improve the peel strength between the resin and the metal foil and the bond strength between the resin interface layers.
不饱和二烯系橡胶的选择举例为聚丁二烯树脂、聚异戊二烯、苯乙烯-丁二烯共聚物、苯乙烯-异戊二烯共聚物、二乙烯基苯-丁二烯共聚物、二乙烯基苯-异戊二烯共聚物、苯乙烯-丁二烯-二乙烯基苯共聚物或苯乙烯-异戊二烯-二乙烯基苯共聚物中的一种或几种。Examples of the selection of unsaturated diene rubbers are polybutadiene resin, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, divinylbenzene-butadiene copolymer One or more of styrene, divinylbenzene-isoprene copolymer, styrene-butadiene-divinylbenzene copolymer or styrene-isoprene-divinylbenzene copolymer.
〈改性聚苯醚树脂〉〈Modified polyphenylene ether resin〉
改性聚苯醚树脂为将聚苯醚树脂的末端基团采用乙烯基或甲基丙烯酸甲酯基改性制备得到，其分子量可以选择为500～10000。The modified polyphenylene ether resin is prepared by modifying the terminal groups of the polyphenylene ether resin with vinyl or methyl methacrylate groups, and its molecular weight can be selected to be 500-10,000.
〈小分子交联剂〉〈Small molecule crosslinking agent〉
小分子交联剂的选择举例为三烯丙基异氰脲酸酯、三烯丙基氰脲酸酯、三甲代烯丙基异氰脲酸酯、三甲代烯丙基氰脲酸酯、三羟乙基异氰尿酸酯、叔丁基苯乙烯、间苯二甲酸二烯丙基酯、邻苯二甲酸二烯丙基酯、三羟甲基丙烷三丙烯酸酯或季戊四醇四丙烯酸酯中的一种或几种；Examples of small-molecule crosslinking agents are triallyl isocyanurate, triallyl cyanurate, trimethylallyl isocyanurate, trimethylallyl cyanurate, three Among the hydroxyethyl isocyanurate, tert-butyl styrene, diallyl isophthalate, diallyl phthalate, trimethylolpropane triacrylate or pentaerythritol tetraacrylate One or more
此外，本实施例专利还包括阻燃剂、填料和促进剂。In addition, the patent of this embodiment also includes flame retardants, fillers and accelerators.
〈阻燃剂〉〈Flame retardant〉
本实施例使用的阻燃剂优选自含溴阻燃剂或含磷阻燃剂中的一种或二者的混合物，其中，为了适应低介电树脂体系，优选的含溴阻燃剂或含磷阻燃剂均不溶于树脂体系中，通常选自与聚苯醚树脂及其他树脂没有反应性且不会降低耐热性和介电特性的添加型溴系阻燃剂或磷系阻燃剂。The flame retardant used in this embodiment is preferably a bromine-containing flame retardant or a phosphorus-containing flame retardant or a mixture of both. Among them, in order to adapt to the low dielectric resin system, the bromine-containing flame retardant or the phosphorus-containing flame retardant is preferable Phosphorus flame retardants are insoluble in the resin system, and are usually selected from added bromine flame retardants or phosphorus flame retardants that are not reactive with polyphenylene ether resins and other resins and do not reduce heat resistance and dielectric properties .
本实施例中添加型含溴阻燃剂优选自十溴二苯醚、十溴二苯乙烷、溴化苯乙烯或十溴二苯醚、乙撑双四溴邻苯二甲酰亚胺中的一种或几种；添加型含磷阻燃剂选自三(2,6-二甲基苯基)磷、10-(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-磷菲-10-氧化物、2,6-二(2,6-二甲基苯基)磷基苯或10-苯基-9,10-二氢-9-氧杂-10-磷菲-10-氧化物中的一种或几种。In this embodiment, the additive bromine-containing flame retardant is preferably selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or decabromodiphenyl ether, ethylene bis tetrabromophthalimide One or more of; the additive phosphorus-containing flame retardant is selected from tris(2,6-dimethylphenyl) phosphorus, 10-(2,5-dihydroxyphenyl)-9,10-dihydro- 9-oxa-10-phosphophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphorylbenzene or 10-phenyl-9,10-dihydro-9-oxy One or more of hetero-10-phosphorophenanthrene-10-oxide.
〈填料〉<filler>
本实施例中所使用的填料没有特别限定，可以选自氮化铝、硼酸铝、氧化镁、碳酸镁、氮化硼、结晶二氧化硅、合成二氧化硅、中空二氧化硅、球形二氧化硅、熔融二氧化硅、滑石粉、氧化铝、硫酸钡、钛酸钡、钛酸锶、碳酸钙或二氧化钛中的一种或多种。The filler used in this embodiment is not particularly limited, and can be selected from aluminum nitride, aluminum borate, magnesium oxide, magnesium carbonate, boron nitride, crystalline silica, synthetic silica, hollow silica, and spherical dioxide. One or more of silicon, fused silica, talc, alumina, barium sulfate, barium titanate, strontium titanate, calcium carbonate, or titanium dioxide.
〈促进剂〉〈Accelerator〉
为了促进树脂组合物的进行反应，增强交联密度，提高玻璃化转变温度和耐热性，可使用促进剂(引发剂)来进一步加速反应。In order to promote the reaction of the resin composition, increase the crosslink density, increase the glass transition temperature and heat resistance, an accelerator (initiator) can be used to further accelerate the reaction.
本实施例所使用的促进剂优选为有机过氧化物自由基引发剂，选自二叔丁基过氧化物、过氧化二月桂酰、过氧化二苯甲酰、过氧化新癸酸异丙苯酯、过氧化新癸酸叔丁酯、过氧化特戊酸叔丁酯、叔丁基过氧化异丁酸酯、叔丁基过氧化-3,5,5-三甲基己酸酯、过氧化乙酸叔丁酯、过氧化苯甲酸叔丁酯、1,1-二叔丁基过氧化-3，5,5-三甲基环己烷、1,1-二叔丁基过氧化环己烷、2,2-二(叔丁基过氧化)丁烷、双(4-叔丁基环己基)过氧化二碳酸酯、过氧化二碳酸酯十六酯、过氧化二碳酸酯十四酯、二特戊己过氧化物、二异丙苯过氧化物、双(叔丁基过氧化异丙基)苯、2,5-二甲基-2,5-二叔丁基过氧化己烷、2,5-二甲基-2,5-二叔丁基过氧化己炔、二异丙苯过氧化氢、异丙苯过氧化氢、特戊基过氧化氢、叔丁基过氧化氢、叔丁基过氧化异丙苯、二异丙苯过氧化氢、过氧化碳酸酯-2-乙基己酸叔丁酯、叔丁基过氧化碳酸-2-乙基己酯、4,4-二(叔丁基过氧化)戊酸正丁酯、过氧化甲乙酮或过氧化环己烷中的一种或几种。The accelerator used in this embodiment is preferably an organic peroxide radical initiator, selected from the group consisting of di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumene neodecanoate peroxide Ester, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-butylperoxyisobutyrate, tert-butylperoxy-3,5,5-trimethylhexanoate, peroxy Tert-butyl oxyacetate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy-3,5,5-trimethylcyclohexane, 1,1-di-tert-butylcyclohexane Alkyl, 2,2-bis(tert-butylperoxy)butane, bis(4-tert-butylcyclohexyl)peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, two Tertpentyl peroxide, dicumyl peroxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2 ,5-Dimethyl-2,5-di-tert-butyl hexyne peroxide, dicumyl hydroperoxide, cumene hydroperoxide, tert-pentyl hydroperoxide, tert-butyl hydroperoxide, tert Butyl cumene peroxide, dicumyl hydroperoxide, tert-butyl peroxycarbonate-2-ethylhexanoate, tert-butylperoxycarbonate-2-ethylhexyl, 4,4-di (Tert-butyl peroxy) one or more of n-butyl valerate, methyl ethyl ketone peroxide or cyclohexane peroxide.
本发明的高频树脂组合物可用用于制备粘结片、覆金属箔层压板以及印刷线路板。The high-frequency resin composition of the present invention can be used to prepare adhesive sheets, metal-clad laminates and printed wiring boards.
制备粘结片：本实施例中高频树脂组合物涂敷在增强纤维上形成半固化片；所述的增强纤维可以是有机纤维或无机纤维通过编织形成的增强纺织物，优选玻璃纤维编织的纤维布，包括E-glass，T-glass，NE-glass，L-glass和Q-glass。制备覆金属箔层压板：该覆金属箔层压板采用上述粘结片叠合一面或者至少两面金属箔热压制成；金属箔优选铜箔，进一步优选为电解铜箔，其表面粗糙度Rz优选小于5um，可举例RTF铜箔、VLP铜箔、HVLP铜箔、HVLP2铜箔，可以进一步改善高频高速线路板的信号损失问题。Preparation of bonding sheet: In this embodiment, the high-frequency resin composition is coated on the reinforcing fiber to form a prepreg; the reinforcing fiber may be a reinforced textile formed by weaving organic fibers or inorganic fibers, preferably fiber cloth woven with glass fibers, Including E-glass, T-glass, NE-glass, L-glass and Q-glass. Preparation of a metal-clad laminate: the metal-clad laminate is made by hot pressing the above-mentioned bonding sheet to laminate one or at least two metal foils; the metal foil is preferably copper foil, more preferably electrolytic copper foil, and its surface roughness Rz is preferably Less than 5um, for example, RTF copper foil, VLP copper foil, HVLP copper foil, HVLP2 copper foil, which can further improve the signal loss of high-frequency and high-speed circuit boards.
制备印刷线路板：印刷线路板至少包含一张上述粘结片或者上述覆金属箔层压板。本实施例的树脂组合物具有良好的力学强度及韧性，良好的玻璃化转变温度、剥离强度和低介电性能，因此，适合制备高多层印刷线路板的加工。Preparation of a printed circuit board: the printed circuit board includes at least one of the above-mentioned adhesive sheet or the above-mentioned metal-clad laminate. The resin composition of this embodiment has good mechanical strength and toughness, good glass transition temperature, peel strength and low dielectric properties, and is therefore suitable for the processing of preparing high multilayer printed circuit boards.
本实施中的高频树脂组合物的制备方法，包括以下步骤：The preparation method of the high-frequency resin composition in this implementation includes the following steps:
(1)按配方进行备料；(1) Prepare materials according to the formula;
(2)将嵌段共聚物橡胶、不饱和二烯系橡胶和N-取代马来酰亚胺共聚溶于溶 剂中，加入交联剂，分散处理后得到高频树脂组合物。(2) The block copolymer rubber, the unsaturated diene rubber and the N-substituted maleimide are copolymerized and dissolved in a solvent, a crosslinking agent is added, and a high frequency resin composition is obtained after dispersion treatment.
进一步的，如果组合物配方中含有阻燃剂、无机填料和促进剂，步骤(2)为将嵌段共聚物橡胶、不饱和二烯系橡胶和N-取代马来酰亚胺共聚溶于溶剂中，加入阻燃剂、无机填料和促进剂，搅拌均匀，分散处理后得到低介电树脂组合物。Further, if the composition formula contains flame retardants, inorganic fillers and accelerators, step (2) is to copolymerize the block copolymer rubber, unsaturated diene rubber and N-substituted maleimide in the solvent Add flame retardant, inorganic filler and accelerator, stir evenly, and obtain a low dielectric resin composition after dispersion treatment.
对制备得到的覆铜板进行性能测试，测试方法为：Perform performance test on the prepared copper clad laminate, the test method is:
玻璃化转变温度(Tg)：使用DMA仪器测试，按照IPC-TM-650 2.4.24.4所规定的DMA测试方法进行测定。Glass transition temperature (Tg): Use a DMA instrument to test and measure it in accordance with the DMA test method specified in IPC-TM-650 2.4.24.4.
Z轴热膨胀系数(CTE):使用TMA仪器测试，按照IPC-TM-650 2.4.24所规定的TMA测试方法测定。Coefficient of Thermal Expansion (CTE) of Z-axis: Use TMA instrument to test and measure according to the TMA test method specified in IPC-TM-650 2.4.24.
铜箔剥离强度(PS)：使用岛津拉力机测试，按照IPC-TM-650 2.4.8所规定的测试方法测定。Copper foil peel strength (PS): Use Shimadzu tensile machine to test and measure according to the test method specified in IPC-TM-650 2.4.8.
介电常数(Dk)和介电损耗因子(Df)：介电常数和介电损耗因子测试方法按照IPC-TM-650 2.5.5.9所规定的测试方法测定。Dielectric constant (Dk) and dielectric loss factor (Df): The dielectric constant and dielectric loss factor test methods are determined in accordance with the test methods specified in IPC-TM-650 2.5.5.9.
高压锅蒸煮实验(PCT)：层压板在120℃进行高温蒸煮实验，按照IPC-TM-650 2.6.16所规定的测试方法测定。Pressure cooker cooking experiment (PCT): The laminate is subjected to a high-temperature cooking experiment at 120°C, and measured according to the test method specified in IPC-TM-650 2.6.16.
288℃分层时间(T288):使用TMA仪器测试，按照IPC-TM-650 2.4.24.1所规定的测试方法测定。288°C delamination time (T288): Use TMA instrument to test and measure according to the test method specified in IPC-TM-650 2.4.24.1.
阻燃性：按照UL-94所规定的材料燃烧性方法进行测试分级。Flame retardancy: According to the material flammability method specified by UL-94, it is tested and classified.
吸水率：按照IPC-TM-650 2.6.2.1所规定的层压板吸水率测试方法进行测定。Water absorption: Measured in accordance with the water absorption test method of laminates specified in IPC-TM-650 2.6.2.1.
树脂流动性：通过岛津毛细管流变仪对树脂流动性进行测定，2g树脂粉压锭以一定压力将树脂从小孔中挤出，根据树脂在流变仪中流出的行程进行评估。流出行程越长，树脂流动性越好。Resin fluidity: The resin fluidity was measured by Shimadzu capillary rheometer. 2g resin powder pressed ingot extruded the resin from the small hole at a certain pressure, and evaluated based on the resin flow out of the rheometer. The longer the outflow stroke, the better the resin fluidity.
耐热性：指物质在受热的条件下仍能保持其优良的物理机械性能的性质。Heat resistance: refers to the properties of a substance that can maintain its excellent physical and mechanical properties under heated conditions.
树脂体系相容性：取基材横截面在SEM下观察固化树脂的微观均匀性，如果出现树脂团聚现象，即为树脂不相容。Resin system compatibility: Take the cross-section of the substrate and observe the micro-uniformity of the cured resin under SEM. If resin agglomeration occurs, it means that the resin is incompatible.
以下为本发明的具体实施情况。The following is the specific implementation of the present invention.
一种高频树脂组合物，包括以下重量份含量的组分：改性聚苯醚树脂、嵌段共聚物橡胶、不饱和二烯系橡胶、N-取代马来酰亚胺共聚物、小分子交联剂、阻燃剂、填料和促进剂，本实施例中各组分的来源和选择如表1所示，各组分的 含量如表2所示。A high-frequency resin composition comprising the following components in parts by weight: modified polyphenylene ether resin, block copolymer rubber, unsaturated diene rubber, N-substituted maleimide copolymer, and small molecule Crosslinking agent, flame retardant, filler and accelerator, the source and selection of each component in this embodiment are shown in Table 1, and the content of each component is shown in Table 2.
表1实施例1～13和对比例1～3中原料组分的来源Table 1 Sources of raw material components in Examples 1-13 and Comparative Examples 1-3
Figure PCTCN2019129924-appb-000011
Figure PCTCN2019129924-appb-000011
表2实施例1～13和对比例1～3的组分配比数据Table 2 Group distribution ratio data of Examples 1-13 and Comparative Examples 1-3
Figure PCTCN2019129924-appb-000012
Figure PCTCN2019129924-appb-000012
表2实施例1～13和对比例1～3的组分配比数据(续表)Table 2 Group distribution ratio data of Examples 1-13 and Comparative Examples 1-3 (continued table)
Figure PCTCN2019129924-appb-000013
Figure PCTCN2019129924-appb-000013
Figure PCTCN2019129924-appb-000014
Figure PCTCN2019129924-appb-000014
表3实施例1～13和对比例1～3的组分配比数据(续表)Table 3 Group distribution ratio data of Examples 1-13 and Comparative Examples 1-3 (continued table)
Figure PCTCN2019129924-appb-000015
Figure PCTCN2019129924-appb-000015
Figure PCTCN2019129924-appb-000016
Figure PCTCN2019129924-appb-000016
表4实施例1～13和对比例1～3的组分配比数据(续表)Table 4 Group distribution ratio data of Examples 1-13 and Comparative Examples 1-3 (continued table)
Figure PCTCN2019129924-appb-000017
Figure PCTCN2019129924-appb-000017
Figure PCTCN2019129924-appb-000018
Figure PCTCN2019129924-appb-000018
实施例11Example 11
一种高频树脂组合物，包括以下重量份含量的组分：改性聚苯醚树脂、嵌段共聚物橡胶、不饱和二烯系橡胶、N-取代马来酰亚胺共聚物，小分子交联剂、阻燃剂、填料和促进剂，其中，各组分的含量如表2所示。A high-frequency resin composition comprising the following components in parts by weight: modified polyphenylene ether resin, block copolymer rubber, unsaturated diene rubber, N-substituted maleimide copolymer, and small molecule Crosslinking agent, flame retardant, filler and accelerator, the content of each component is shown in Table 2.
其中，采用的填料为高Dk填料(Dk>10)，导致其介电损耗较高。Among them, the filler used is a high-Dk filler (Dk>10), which results in a higher dielectric loss.
实施例12Example 12
一种高频树脂组合物，包括以下重量份含量的组分：改性聚苯醚树脂、嵌段共聚物橡胶，不饱和二烯系橡胶，N-取代马来酰亚胺共聚物，小分子交联剂、阻燃剂、填料和促进剂，其中，各组分的含量如表2所示。A high-frequency resin composition comprising the following components in parts by weight: modified polyphenylene ether resin, block copolymer rubber, unsaturated diene rubber, N-substituted maleimide copolymer, and small molecule Crosslinking agent, flame retardant, filler and accelerator, the content of each component is shown in Table 2.
改性聚苯醚树脂为将聚苯醚树脂的末端基团采用乙烯基改性制备得到；嵌段共聚物橡胶为以苯乙烯为末端段，以聚丁二烯、异戊二烯为中间链段的线性三嵌段共聚物，嵌段共聚物橡胶的数均分子量在5000，并且苯乙烯链段含量为10％；不饱和二烯系橡胶为苯乙烯-异戊二烯共聚物和二乙烯基苯-异戊二烯共聚物，其中1,4-顺式双键结构占60％，其数均分子量为1000；N-取代马来酰亚胺共聚物的单体为苯乙烯、N-苯基马来酰亚胺、不饱和酸酐，其中苯乙烯的摩尔份数为30份，不饱和酸酐的摩尔份数为1份，N-取代马来酰亚胺的摩尔份数为30 份、小分子交联剂采用三烯丙基异氰脲酸酯、三烯丙基氰脲酸酯、三甲代烯丙基异氰脲酸酯、三甲代烯丙基氰脲酸酯、三羟乙基异氰尿酸酯的混合物，阻燃剂为含溴阻燃剂，填料采用球形硅微粉，为低Dk材料，促进剂为过氧化物类的促进剂。The modified polyphenylene ether resin is prepared by modifying the end groups of the polyphenylene ether resin with vinyl; the block copolymer rubber is made of styrene as the end segment and polybutadiene and isoprene as the middle chain The number average molecular weight of the block copolymer rubber is 5000, and the styrene segment content is 10%; the unsaturated diene rubber is styrene-isoprene copolymer and diethylene Benzene-isoprene copolymer, in which 1,4-cis double bond structure accounts for 60%, and its number average molecular weight is 1000; the monomers of the N-substituted maleimide copolymer are styrene, N- Phenyl maleimide, unsaturated acid anhydride, wherein the mole part of styrene is 30 parts, the mole part of unsaturated acid anhydride is 1 part, the mole part of N-substituted maleimide is 30 parts, Small molecule crosslinking agent uses triallyl isocyanurate, triallyl cyanurate, trimethylallyl isocyanurate, trimethylallyl cyanurate, trihydroxyethyl A mixture of isocyanurates, the flame retardant is a bromine-containing flame retardant, the filler is made of spherical silica powder, which is a low-Dk material, and the accelerator is a peroxide accelerator.
实施例13Example 13
一种高频树脂组合物，包括以下重量份含量的组分：嵌段共聚物橡胶，不饱和二烯系橡胶，N-取代马来酰亚胺共聚物，小分子交联剂、阻燃剂、填料和促进剂，其中，各组分的含量如表2所示。A high frequency resin composition comprising the following components in parts by weight: block copolymer rubber, unsaturated diene rubber, N-substituted maleimide copolymer, small molecule crosslinking agent, flame retardant , Fillers and accelerators, the content of each component is shown in Table 2.
改性聚苯醚树脂为将聚苯醚树脂的末端基团采用乙烯基改性制备得到；嵌段共聚物橡胶为以苯乙烯为末端段，以聚丁二烯、异戊二烯为中间链段的线性三嵌段共聚物，嵌段共聚物橡胶的数均分子量在15000，并且苯乙烯链段含量为50％；不饱和二烯系橡胶为苯乙烯-异戊二烯共聚物和二乙烯基苯-异戊二烯共聚物，其中1,4-顺式双键结构占95％，其数均分子量为10000；N-取代马来酰亚胺共聚物的单体为苯乙烯、N-苯基马来酰亚胺、不饱和酸酐，其中苯乙烯的摩尔份数为60份，不饱和酸酐的摩尔份数为20份，N-取代马来酰亚胺的摩尔份数为70份、小分子交联剂采用叔丁基苯乙烯、间苯二甲酸二烯丙基酯、邻苯二甲酸二烯丙基酯、三羟甲基丙烷三丙烯酸酯或季戊四醇四丙烯酸酯的混合物，阻燃剂为含溴阻燃剂，填料采用球形硅微粉，为低Dk材料，促进剂为过氧化物类的促进剂。The modified polyphenylene ether resin is prepared by modifying the end groups of the polyphenylene ether resin with vinyl; the block copolymer rubber is made of styrene as the end segment and polybutadiene and isoprene as the middle chain Segment linear triblock copolymer, the number average molecular weight of the block copolymer rubber is 15000, and the styrene segment content is 50%; the unsaturated diene rubber is styrene-isoprene copolymer and diethylene Benzene-isoprene copolymer, in which the 1,4-cis double bond structure accounts for 95%, and its number average molecular weight is 10,000; the monomers of the N-substituted maleimide copolymer are styrene, N- Phenyl maleimide, unsaturated acid anhydride, wherein the mole part of styrene is 60 parts, the mole part of unsaturated acid anhydride is 20 parts, the mole part of N-substituted maleimide is 70 parts, The small molecule crosslinking agent is a mixture of tert-butyl styrene, diallyl isophthalate, diallyl phthalate, trimethylolpropane triacrylate or pentaerythritol tetraacrylate, flame retardant The agent is a bromine-containing flame retardant, the filler is spherical silica powder, which is a low-Dk material, and the accelerator is a peroxide accelerator.
对比例1Comparative example 1
对比例1为一种树脂组合物，其原料组成包括改性聚苯醚树脂、不饱和二烯系橡胶，N-取代马来酰亚胺共聚物，小分子交联剂、阻燃剂、填料和促进剂，具体各组分的含量和选择如表2所示。Comparative Example 1 is a resin composition whose raw material composition includes modified polyphenylene ether resin, unsaturated diene rubber, N-substituted maleimide copolymer, small molecule crosslinking agent, flame retardant, and filler And accelerators, the specific content and selection of each component are shown in Table 2.
对比例1与实施例的主要区别在于，对比例中没有添加嵌段共聚物橡胶，从表1的检测数据中可以看出，对比例1中的树脂组合物的玻璃转变温度为185℃，远远低于本发明中任一实施例中的树脂组合物的玻璃转变温度，另外，其铜箔剥离强度较低，表明其机械性能不佳，288℃下分层时间较短，表明其热稳定性较差。因此，树脂基材中加入嵌段共聚物橡胶，有利于提高树脂组合物的耐热性和剥离强度。The main difference between Comparative Example 1 and Examples is that there is no block copolymer rubber added in the Comparative Example. From the test data in Table 1, it can be seen that the glass transition temperature of the resin composition in Comparative Example 1 is 185°C, which is far It is much lower than the glass transition temperature of the resin composition in any embodiment of the present invention. In addition, its copper foil peel strength is low, indicating poor mechanical properties, and the layering time at 288°C is short, indicating its thermal stability Poor sex. Therefore, adding a block copolymer rubber to the resin substrate is beneficial to improve the heat resistance and peel strength of the resin composition.
对比例2Comparative example 2
对比例2为一种树脂组合物，其原料组成包括改性聚苯醚树脂、嵌段共聚物橡胶、不饱和二烯系橡胶、BDM型马来酰亚胺、小分子交联剂、阻燃剂、填料和促进剂，具体各组分的含量和选择如表2所示。Comparative Example 2 is a resin composition, the raw material composition includes modified polyphenylene ether resin, block copolymer rubber, unsaturated diene rubber, BDM maleimide, small molecule crosslinking agent, flame retardant Agents, fillers and accelerators, the specific content and selection of each component are shown in Table 2.
对比例2与实施例的主要区别在于，用BDM型马来酰亚胺代替N-取代马来酰亚胺共聚物，从表1的检测数据中可以看出，对比例2中的树脂组合物的玻璃转变温度为205℃，低于本发明中任一实施例中的树脂组合物的玻璃转变温度，而且其介电损耗较高，能耗大，树脂流动性较差，耐热性不佳，表明添加N-取代马来酰亚胺共聚物可以降低树脂组合物的耐热性和剥离强度。The main difference between Comparative Example 2 and the Examples is that BDM maleimide is used instead of N-substituted maleimide copolymer. It can be seen from the test data in Table 1 that the resin composition in Comparative Example 2 The glass transition temperature is 205°C, which is lower than the glass transition temperature of the resin composition in any embodiment of the present invention, and its dielectric loss is high, energy consumption is large, resin fluidity is poor, and heat resistance is poor , Indicating that the addition of N-substituted maleimide copolymer can reduce the heat resistance and peel strength of the resin composition.
对比例3Comparative example 3
对比例3为一种树脂组合物，其原料组成包括改性聚苯醚树脂、嵌段共聚物橡胶、不饱和二烯系橡胶、苯乙烯、马来酸酐共聚物、小分子交联剂、阻燃剂、填料和促进剂，具体各组分的含量和选择如表2所示。Comparative Example 3 is a resin composition, the raw material composition includes modified polyphenylene ether resin, block copolymer rubber, unsaturated diene rubber, styrene, maleic anhydride copolymer, small molecule crosslinking agent, resistance Burning agent, filler and accelerator, the specific content and selection of each component are shown in Table 2.
对比例3与实施例的主要区别在于，用苯乙烯、马来酸酐共聚物代替N-取代马来酰亚胺共聚物，从表1的检测数据中可以看出，对比例3中的树脂组合物相容性较差，另外，该树脂组合物的剥离强度极低，288℃下分层时间很短，因此，N-取代马来酰亚胺共聚物的添加十分重要，其中的马来酰亚胺结构和马来酸酐结构与树脂基材之间的协同作用有利于改善树脂组合物的机械性能以及介电性能。The main difference between Comparative Example 3 and the Examples is that styrene and maleic anhydride copolymers are used instead of N-substituted maleimide copolymers. From the test data in Table 1, it can be seen that the resin combination in Comparative Example 3 In addition, the resin composition has very low peel strength and very short delamination time at 288°C. Therefore, the addition of N-substituted maleimide copolymer is very important. The synergy between the imine structure and the maleic anhydride structure and the resin substrate is beneficial to improve the mechanical properties and dielectric properties of the resin composition.
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various deformations or modifications within the scope of the claims, which does not affect the essence of the present invention.

Claims (10)

  1. 一种高频树脂组合物，其特征在于，包括以下重量份含量的组分：A high-frequency resin composition, characterized in that it comprises the following components in parts by weight:
    Figure PCTCN2019129924-appb-100001
    Figure PCTCN2019129924-appb-100001
  2. 根据权利要求1所述的一种高频树脂组合物，其特征在于，所述N-取代马来酰亚胺共聚物由以下摩尔份含量的单体共聚而成：N-取代马来酰亚胺30-70份、乙烯基单体30-60份，不饱和酸酐1-10份。The high-frequency resin composition of claim 1, wherein the N-substituted maleimide copolymer is copolymerized with the following molar parts of monomers: N-substituted maleimide 30-70 parts of amine, 30-60 parts of vinyl monomer, 1-10 parts of unsaturated acid anhydride.
  3. 根据权利要求2所述的一种高频树脂组合物，其特征在于，所述N-取代马来酰亚胺共聚物的分子通式为：The high-frequency resin composition of claim 2, wherein the general molecular formula of the N-substituted maleimide copolymer is:
    Figure PCTCN2019129924-appb-100002
    Figure PCTCN2019129924-appb-100002
    式中，x、y、z分别为苯乙烯单体、N-取代马来酰亚胺、不饱和酸酐的摩尔比，x:y:z＝0.3～0.6:0.3～0.7:0.01～0.2。In the formula, x, y, and z are the molar ratios of styrene monomer, N-substituted maleimide, and unsaturated acid anhydride, respectively, and x:y:z=0.3~0.6:0.3~0.7:0.01~0.2.
  4. 根据权利要求3所述的一种高频树脂组合物，其特征在于，所述R基团为甲基、乙基、异丙基、环己基、苯基、苄基、苯基乙基、苯基乙烯基、对羟基苯基、联苯基、萘环基。The high-frequency resin composition according to claim 3, wherein the R group is methyl, ethyl, isopropyl, cyclohexyl, phenyl, benzyl, phenylethyl, benzene Base vinyl group, p-hydroxyphenyl group, biphenyl group, naphthalene ring group.
  5. 根据权利要求1所述的一种高频树脂组合物，其特征在于，所述嵌段共聚物橡胶是以苯乙烯为末端段，以聚丁二烯、异戊二烯为中间链段的线性三嵌段共聚物，其数均分子量在5000～150000，并且苯乙烯链段占所述嵌段共聚物橡胶总质量的10～50％。The high-frequency resin composition according to claim 1, wherein the block copolymer rubber is linear with styrene as the terminal segment and polybutadiene and isoprene as the middle segment. The triblock copolymer has a number average molecular weight of 5000-150000, and the styrene segment accounts for 10-50% of the total mass of the block copolymer rubber.
  6. 根据权利要求1所述的一种高频树脂组合物，其特征在于，所述不饱和二烯系橡胶的聚合单体包括未改性或含改性基团的丁二烯或异戊二烯中的一种或几种，所述改性基团选自环氧基、马来酸酐、丙烯酸酯、羟基或羧基中 的一种或几种；其中，所述二烯系橡胶的数均分子量为500～20000，不饱和双键结构占所述二烯系橡胶主链质量的60～99％。The high-frequency resin composition according to claim 1, wherein the polymerized monomer of the unsaturated diene rubber comprises unmodified or modified group-containing butadiene or isoprene One or more of the modified groups are selected from epoxy, maleic anhydride, acrylate, hydroxyl, or carboxyl; wherein the number average molecular weight of the diene rubber It is 500 to 20000, and the unsaturated double bond structure accounts for 60 to 99% of the mass of the main chain of the diene rubber.
  7. 根据权利要求6所述的一种高频树脂组合物，其特征在于，所述不饱和二烯系橡胶选自聚丁二烯树脂、聚异戊二烯、苯乙烯-丁二烯共聚物、苯乙烯-异戊二烯共聚物、二乙烯基苯-丁二烯共聚物、二乙烯基苯-异戊二烯共聚物、苯乙烯-丁二烯-二乙烯基苯共聚物或苯乙烯-异戊二烯-二乙烯基苯共聚物中的一种或几种。The high-frequency resin composition according to claim 6, wherein the unsaturated diene rubber is selected from polybutadiene resin, polyisoprene, styrene-butadiene copolymer, Styrene-isoprene copolymer, divinylbenzene-butadiene copolymer, divinylbenzene-isoprene copolymer, styrene-butadiene-divinylbenzene copolymer or styrene- One or more of isoprene-divinylbenzene copolymers.
  8. 根据权利要求1所述的一种高频树脂组合物，其特征在于，所述改性聚苯醚树脂为将聚苯醚树脂的末端基团采用乙烯基或甲基丙烯酸酯基改性制备得到，其数均分子量为500～10000。The high-frequency resin composition according to claim 1, wherein the modified polyphenylene ether resin is prepared by modifying the terminal groups of the polyphenylene ether resin with vinyl or methacrylate groups , And its number average molecular weight is 500 to 10,000.
  9. 根据权利要求1所述的一种高频树脂组合物，其特征在于，所述小分子交联剂选自三烯丙基异氰脲酸酯、三烯丙基氰脲酸酯、三甲代烯丙基异氰脲酸酯、三甲代烯丙基氰脲酸酯、三羟乙基异氰尿酸酯、叔丁基苯乙烯、间苯二甲酸二烯丙基酯、邻苯二甲酸二烯丙基酯、三羟甲基丙烷三丙烯酸酯或季戊四醇四丙烯酸酯中的一种或几种。The high-frequency resin composition according to claim 1, wherein the small molecule crosslinking agent is selected from triallyl isocyanurate, triallyl cyanurate, trimethyene Propyl isocyanurate, trimethylallyl cyanurate, trihydroxyethyl isocyanurate, tert-butyl styrene, diallyl isophthalate, diene phthalate One or more of propyl ester, trimethylolpropane triacrylate or pentaerythritol tetraacrylate.
  10. 根据权利要求1所述的一种高频树脂组合物，其特征在于，还包括阻燃剂、填料和促进剂。A high frequency resin composition according to claim 1, characterized in that it further comprises flame retardants, fillers and accelerators.
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