WO2017067123A1 - 一种聚苯醚树脂组合物及其在高频电路基板中的应用 - Google Patents

一种聚苯醚树脂组合物及其在高频电路基板中的应用 Download PDF

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WO2017067123A1
WO2017067123A1 PCT/CN2016/075322 CN2016075322W WO2017067123A1 WO 2017067123 A1 WO2017067123 A1 WO 2017067123A1 CN 2016075322 W CN2016075322 W CN 2016075322W WO 2017067123 A1 WO2017067123 A1 WO 2017067123A1
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weight
parts
polyphenylene ether
ether resin
unsaturated double
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PCT/CN2016/075322
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English (en)
French (fr)
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陈广兵
曾宪平
关迟记
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广东生益科技股份有限公司
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Priority to JP2018522836A priority Critical patent/JP6912466B2/ja
Priority to EP16856570.3A priority patent/EP3315555A4/en
Priority to US15/744,446 priority patent/US10745599B2/en
Publication of WO2017067123A1 publication Critical patent/WO2017067123A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09J171/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C08G65/485—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0237—High frequency adaptations
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/012—Flame-retardant; Preventing of inflammation
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0162—Silicon containing polymer, e.g. silicone

Definitions

  • the present invention relates to a polyphenylene ether resin composition, and in particular to a polyphenylene ether resin composition and its use in a high frequency circuit substrate.
  • the relationship between the signal transmission rate and the dielectric constant Dk of the insulating material is such that the lower the dielectric constant Dk of the insulating material, the faster the signal transmission rate. Therefore, in order to achieve high frequency of signal transmission rate, it is necessary to develop a substrate having a low dielectric constant. As the frequency of the signal increases, the loss of the signal in the substrate can no longer be ignored.
  • the relationship between the signal loss and the frequency, the dielectric constant Dk, and the dielectric loss Df is such that the smaller the dielectric constant Dk of the substrate is, the smaller the dielectric loss Df is, and the smaller the signal loss is. Therefore, the development of a high-frequency circuit substrate having a low dielectric constant Dk and a low dielectric loss Df and good heat resistance has become a research and development direction that CCL manufacturers are paying attention to.
  • the polyphenylene ether resin has a large amount of benzene ring structure and no strong polar groups, which gives the polyphenylene ether resin excellent properties, such as high glass transition temperature, good dimensional stability, small linear expansion coefficient, and water absorption. Low rate, especially excellent low dielectric constant, low dielectric loss.
  • polyphenylene ether has disadvantages such as high melting point of the resin, poor processability, and poor solvent resistance.
  • the excellent physical properties, heat resistance, chemical properties and electrical properties of polyphenylene ether have attracted many companies around the world to modify it and achieved certain results.
  • a reactive group such as a vinyl group is introduced at the chain end or side chain of the polyphenylene ether to make it a thermosetting resin.
  • the resin has excellent heat resistance, low dielectric constant and low dielectric loss after heat curing. Comprehensive performance, such as consumption, has become an ideal material for preparing high-frequency circuit substrates.
  • a cross-linking agent of an organosilicon compound containing an unsaturated double bond as a vinyl-reactive group-modified thermosetting polyphenylene ether is used for preparing a high-frequency electronic circuit substrate.
  • CN 102993683 Preparation of a crosslinking agent as a modified polyphenylene ether using an organosilicon compound containing an unsaturated double bond, the prepared high frequency circuit substrate having a high glass transition temperature, a high thermal decomposition temperature, and high interlayer adhesion. Force, low dielectric constant and low dielectric loss.
  • the organosilicon compound structure containing an unsaturated double bond employed in the prior art is a linear or cyclic organosilicon compound.
  • the linear organosilicon compound containing an unsaturated double bond has excellent flexibility, and the prepared high-frequency circuit substrate has a low bending strength.
  • the circuit substrate prepared by using the annular organosilicon compound containing an unsaturated double bond has good comprehensive performance, but due to its small molecular weight, there is a problem of volatilization during the baking process.
  • CN104650574A uses a polyphenylene ether, a polyperfluoroethylene emulsion, a silicone resin and an inorganic filler composition for the preparation of a high frequency electronic circuit substrate.
  • the substrate prepared has the advantages of low dielectric constant, low dielectric loss, good processing performance and the like.
  • the silicone resin used in the prior art is a methylphenyl DQ silicone resin, which does not contain a reactive group and cannot be used as a crosslinking agent for a vinyl-modified thermosetting polyphenylene ether.
  • one of the objects of the present invention is to provide a polyphenylene ether resin composition having a low dielectric constant Dk and a low dielectric loss Df, and having excellent properties.
  • the heat resistance and interlayer adhesion satisfy the requirements of dielectric constant, dielectric loss, heat resistance and interlayer adhesion of a high-frequency circuit substrate, and can be used for preparing a high-frequency circuit substrate.
  • a polyphenylene ether resin composition comprising a vinyl-modified polyphenylene ether resin and a silicone resin having a three-dimensional network structure containing an unsaturated double bond, the three-dimensional network structure containing an unsaturated double bond
  • the silicone resin is a TT silicone resin obtained by hydrolysis-condensation of a trifunctional siloxane unit (T unit) having a three-dimensional network structure containing an unsaturated double bond or a three-dimensional network structure containing an unsaturated double bond. Any one or a mixture of two of TQ silicone resins obtained by hydrolysis-condensation of a trifunctional siloxane unit (T unit) and a tetrafunctional siloxane unit (Q unit).
  • the vinyl modified polyphenylene ether resin is a powdery solid thermosetting resin at room temperature, and has active unsaturated double bonds at both ends thereof, and can be subjected to radical polymerization and solidification in the presence of a curing initiator.
  • a thermosetting resin excellent in heat resistance, dimensional stability, low water absorption, low dielectric constant, and low dielectric loss is obtained.
  • a silicone resin having a three-dimensional network structure containing an unsaturated double bond is used as a crosslinking agent for a vinyl-modified polyphenylene ether, and the polyphenylene ether resin composition has a high crosslinking density after curing, and can provide a high-frequency circuit substrate. Glass transition temperature. Further, the silicone resin having a three-dimensional network structure containing an unsaturated double bond does not contain a polar group, and can ensure low water absorption, low dielectric constant, and low dielectric loss of the high-frequency circuit substrate. The silicone resin having a three-dimensional network structure containing an unsaturated double bond has a high thermal decomposition temperature and can provide excellent heat resistance of a high-frequency circuit substrate. Further, the prepared high-frequency circuit substrate has high interlayer adhesion and bending strength, and the reliability of the substrate can be improved.
  • the vinyl-modified polyphenylene ether resin has excellent properties such as low dielectric constant and low dielectric loss, and a silicone resin having a three-dimensional network structure containing an unsaturated double bond is used as a crosslinking agent for the modified polyphenylene ether resin.
  • the prepared high-frequency circuit substrate has a combination of low dielectric constant, low dielectric loss, low water absorption, high heat resistance, high interlayer adhesion, and high bending strength.
  • the substrate has a higher flexural strength than the linear organosiliconization containing unsaturated double bonds as a crosslinker.
  • a silicone resin having a three-dimensional network structure containing an unsaturated double bond does not have a problem of volatilization when a sizing sheet is used.
  • the vinyl modified polyphenylene ether resin has the following structure:
  • 0 ⁇ x ⁇ 100, 0 ⁇ y ⁇ 100, 2 ⁇ x+y ⁇ 100 0 ⁇ x ⁇ 100, 0 ⁇ y ⁇ 100, 2 ⁇ x+y ⁇ 100.
  • M is selected from:
  • N is selected from any one of -O-, -CO-, -SO-, -SC-, -SO 2 - or -C(CH 3 ) 2 - or a combination of at least two.
  • R 2, R 4, R 6 , R 8, R 11, R 13, R 15 and R 17 are each independently selected from substituted or unsubstituted C1-C8 (e.g. C2, C3, C4, C5, C6 or C7) a straight-chain alkyl group, a substituted or unsubstituted C1-C8 (eg, C2, C3, C4, C5, C6 or C7) branched alkyl group or a substituted or unsubstituted phenyl group or a combination of at least two .
  • R 1 , R 3 , R 5 , R 7 , R 10 , R 12 , R 14 and R 16 are each independently selected from a hydrogen atom, a substituted or unsubstituted C1-C8 (eg C2, C3, C4, C5, C6). Or C7) a linear alkyl group, a substituted or unsubstituted C1-C8 (eg C2, C3, C4, C5, C6 or C7) branched alkyl group or a substituted or unsubstituted phenyl group or at least two Combination of species.
  • R 9 is selected from:
  • A is an arylene group, a carbonyl group or an alkylene group having 1 to 10 (for example, 2, 3, 4, 5, 6, 7, 8, or 9) carbon atoms
  • Z is an integer of 0 to 10, for example, 0. , 9, or 10
  • R 21, R 22 and R 23 are solely carbon atoms or atom selected from hydrogen, 1 to 10 (e.g. 2, 3, An alkyl group of 4, 5, 6, 7, 8, or 9).
  • the vinyl modified polyphenylene ether resin has a number average molecular weight of from 500 to 10,000 g/mol, preferably from 800 to 8000 g/mol, further preferably from 1,000 to 4,000 g/mol.
  • the TT silicone resin obtained by hydrolysis-condensation of a trifunctional siloxane unit (T unit) having a three-dimensional network structure containing an unsaturated double bond has the following structure:
  • 6 ⁇ x1 ⁇ 10 such as 6, 7, 8, 9, or 10;
  • the TQ silicone resin obtained by hydrolytic condensation of a trifunctional siloxane unit (T unit) having a three-dimensional network structure and a tetrafunctional siloxane unit (Q unit) containing an unsaturated double bond has The following structure:
  • 4 ⁇ y1 ⁇ 100 such as 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95
  • 1 ⁇ z1 ⁇ 100 such as 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95
  • 4 ⁇ y1/z1 ⁇ 10 for example 5, 6, 7, 8, 9 or 10;
  • C 2 -C 10 e.g., C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 or C 9
  • the silicone resin having a three-dimensional network structure containing an unsaturated double bond has a weight of 10 to 90 parts by weight, based on 100 parts by weight of the vinyl-modified polyphenylene ether resin, for example, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight Parts, 80 parts by weight or 85 parts by weight, preferably 25 to 90 parts by weight, the preferred parts by weight of the corresponding resin system have a higher glass transition temperature after curing crosslinking.
  • the polyphenylene ether resin composition of the present invention further comprises a radical initiator.
  • the free radical initiator acts to initiate a polymerization crosslinked curing resin system. Under heating conditions, the free radical initiator decomposes to generate free radicals, which initiates the reaction cross-linking between the reactive groups in the resin system, and the cross-network structure of the three-dimensional structure of the formal space.
  • the weight of the radical initiator is 1-3, and the sum of the weight of the vinyl-modified polyphenylene ether resin and the silicone resin having a three-dimensional network structure containing an unsaturated double bond is 100 parts by weight. Parts by weight.
  • the weight of the radical initiator is, for example, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2.0 parts by weight, 2.2 parts by weight, 2.4 parts by weight, 2.6 parts by weight, 2.8 parts by weight or 2.9 parts by weight.
  • the radical initiator is selected from the group consisting of organic peroxide initiators, and more preferably from dicumyl peroxide, dibenzoyl peroxide, benzoyl peroxide, t-butyl peroxybenzoate or 4,4- Any one or a mixture of at least two of di(tert-butylperoxy)-n-butyl valerate.
  • the mixture is, for example, a mixture of n-butyl 4,4-di(tert-butylperoxy)pentanoate and t-butyl peroxybenzoate, a mixture of dibenzoyl peroxide and dicumyl peroxide, 4, a mixture of 4-di(tert-butylperoxy)p-butyl valerate and dibenzoyl peroxide, a mixture of tert-butyl peroxybenzoate and dicumyl peroxide, 4,4-di(tert-butyl) A mixture of n-butyl valerate, tert-butyl peroxybenzoate and dibenzoyl peroxide.
  • the radical initiators may be used singly or in combination, and a mixed effect may be used to achieve a better synergistic effect.
  • the polyphenylene ether resin composition of the present invention further comprises a flame retardant.
  • the weight of the flame retardant is from 0 to 40 parts by weight based on 100 parts by weight of the sum of the weight of the vinyl-modified polyphenylene ether resin and the silicone resin having a three-dimensional network structure containing an unsaturated double bond. It is preferably 0 to 40 parts by weight and does not include 0.
  • the parts by weight of the flame retardant are, for example, 1 part by weight, 3 parts by weight, 7 parts by weight, 11 parts by weight, 15 parts by weight, 19 parts by weight, 23 parts by weight, 27 parts by weight, 31 parts by weight, 35 parts by weight, 38 parts by weight. Parts by weight or 39 parts by weight.
  • the weight of the flame retardant is 0 parts by weight, meaning that the resin composition does not contain a flame retardant. The content of the flame retardant is too high, resulting in a decrease in heat resistance and interlayer adhesion.
  • the flame retardant of the present invention is selected from a halogen flame retardant, a phosphorus flame retardant or a nitrogen flame retardant, or a mixture of at least two, preferably a bromine flame retardant or a phosphorus system. Any one or a mixture of at least two of a flame retardant or a nitrogen-based flame retardant.
  • the bromine-based flame retardant is selected from any one or at least two of decabromodiphenyl ether, hexabromobenzene, decabromodiphenylethane or ethylene bis-tetrabromophthalimide. mixture.
  • the mixture is, for example, a mixture of decabromodiphenylethane and hexabromobenzene, a mixture of decabromodiphenyl ether and ethylene bistetrabromophthalimide, decabromodiphenylethane, hexabromobenzene and ten a mixture of brominated diphenyl ethers, ethylene bis-tetrabromophthalate A mixture of imide, decabromodiphenylethane, hexabromobenzene and decabromodiphenyl ether.
  • the phosphorus-based flame retardant is selected from the group consisting of tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa -10-phosphinophen-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene or 10-phenyl-9,10-dihydro-9-oxa-10- One or a mixture of at least two of phosphaphenanthrene-10-oxides.
  • the mixture is, for example, 10-phenyl-9,10-dihydro-9-oxa-10-phosphinophen-10-oxide and 2,6-bis(2,6-dimethylphenyl)phosphinobenzene Mixture, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and tris(2,6-dimethylphenyl) a mixture of phosphines, 10-phenyl-9,10-dihydro-9-oxa-10-phosphinophen-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene And a mixture of 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl) a mixture of phosphine, 10-phenyl-9,10-dihydro
  • the nitrogen-based flame retardant is selected from one or a mixture of at least two of melamine, melamine phosphate, strontium phosphate, cesium carbonate or bismuth sulfamate.
  • the mixture is, for example, a mixture of bismuth sulfamate and cesium carbonate, a mixture of strontium phosphate and melamine phosphate, a mixture of melamine and bismuth sulfamate, a mixture of cesium carbonate, strontium phosphate and melamine, melamine phosphate, bismuth sulfamate.
  • a mixture of melamine and strontium phosphate preferably melamine or/and melamine phosphate.
  • the polyphenylene ether resin composition of the present invention further comprises a powder filler.
  • the powder filler is selected from the group consisting of crystalline silica, amorphous silica, spherical silica, fused silica, titanium dioxide, silicon carbide, glass fiber, alumina, aluminum nitride, boron nitride, Any one or a mixture of at least two of barium titanate or barium titanate.
  • the mixture is, for example, a mixture of crystalline silica and amorphous silica, a mixture of spherical silica and titanium dioxide, a mixture of silicon carbide and glass fibers, a mixture of aluminum oxide and aluminum nitride, boron nitride and titanic acid.
  • the powder filler serves to improve dimensional stability and reduce The coefficient of thermal expansion and the cost of the system are reduced.
  • the shape and particle diameter of the powder filler are not limited in the present invention, and the particle diameter generally used is 0.2 to 10 ⁇ m, for example, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 5 ⁇ m, 8 ⁇ m or 9 ⁇ m, for example, the particle diameter can be selected to be 0.2. - 10 ⁇ m spherical silica.
  • the weight of the powder filler is 0, and the weight of the vinyl-modified polyphenylene ether resin, the silicone resin having a three-dimensional network structure containing an unsaturated double bond, and the flame retardant is 100 parts by weight. ⁇ 150 parts by weight, preferably 0 to 150 parts by weight and excluding 0.
  • the weight of the powder filler is, for example, 5 parts by weight, 15 parts by weight, 25 parts by weight, 35 parts by weight, 45 parts by weight, 55 parts by weight, 75 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, and 120 parts by weight. 130 parts by weight, 140 parts by weight or 145 parts by weight.
  • the weight of the powder filler is 0 parts by weight, meaning that the resin composition does not contain a powder filler.
  • Comprising as used herein means that in addition to the components, it may include other components which impart different characteristics to the polyphenylene ether ester composition.
  • the "include” of the present invention may also be replaced by a closed “for” or “consisting of”.
  • the polyphenylene ether resin composition of the present invention may be added with a thermosetting resin, and specific examples thereof include an epoxy resin, a cyanate resin, a phenol resin, a urethane resin, and a melamine resin, and these may be added.
  • a curing agent or curing agent accelerator for a thermosetting resin include an epoxy resin, a cyanate resin, a phenol resin, a urethane resin, and a melamine resin, and these may be added.
  • a curing agent or curing agent accelerator for a thermosetting resin include an epoxy resin, a cyanate resin, a phenol resin, a urethane resin, and a melamine resin, and these may be added.
  • a curing agent or curing agent accelerator for a thermosetting resin include an epoxy resin, a cyanate resin, a phenol resin, a urethane resin, and a melamine resin, and these may be added.
  • the polyphenylene ether resin composition may further contain various additives, and specific examples thereof include a silane coupling agent, a titanate coupling agent, an antioxidant, a heat stabilizer, an antistatic agent, and ultraviolet absorption. Agents, pigments, colorants and lubricants. These thermosetting resins and various additives may be used singly or in combination of two or more kinds.
  • the vinyl-modified polyphenylene ether resin, a silicone resin having a three-dimensional network structure containing an unsaturated double bond, and the like may be blended, stirred, and mixed by a known method.
  • Free radical initiators, flame retardants, powder fillers, and various thermosetting resins and various additives Add the preparation to prepare.
  • Another object of the present invention is to provide a resin glue obtained by dissolving or dispersing a polyphenylene ether resin composition as described above in a solvent.
  • the solvent in the present invention is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, and butyl.
  • Ethers such as carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and mesitylene; An ester such as ethyl acetate or ethyl acetate; a nitrogen-containing solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more.
  • aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, and acetone, methyl ethyl ketone, methyl ethyl ketone, and methyl group.
  • a ketone flux such as butyl ketone or cyclohexanone is used in combination.
  • the amount of the solvent to be used can be selected by a person skilled in the art according to his own experience, so that the obtained resin glue can reach a viscosity suitable for use.
  • An emulsifier may be added during the process of dissolving or dispersing the resin composition as described above in a solvent. By dispersing by an emulsifier, the powder filler or the like can be uniformly dispersed in the glue.
  • a third object of the present invention is to provide a prepreg obtained by impregnating a reinforcing material such as a glass fiber cloth with a resin glue as described above and drying it.
  • the glass fiber cloth is a reinforcing material, and functions to increase strength, improve dimensional stability, and reduce shrinkage of curing of the thermosetting resin in the composite material.
  • Different types of fiberglass cloth can be used depending on the thickness of the sheet and the like.
  • Exemplary glass fiber cloths are: 7628 fiberglass cloth, 2116 fiberglass cloth.
  • the reinforcing material such as a glass fiber cloth
  • the total weight of the vinyl modified polyphenylene ether resin, the silicone resin having a three-dimensional network structure containing an unsaturated double bond, the flame retardant, and the powder filler is 100 parts by weight.
  • the weight is 50-230 parts by weight, for example 70 parts by weight, 90 parts by weight, 110 parts by weight, 150 Parts by weight, 180 parts by weight, 200 parts by weight, 210 parts by weight or 220 parts by weight.
  • the drying temperature is 80 to 220 ° C, such as 90 ° C, 110 ° C, 150 ° C, 170 ° C, 190 ° C or 200 ° C.
  • the drying time is from 1 to 30 min, such as 5 min, 8 min, 13 min, 17 min, 21 min, 24 min or 28 min.
  • a fourth object of the present invention is to provide a high-frequency circuit substrate which is made of the prepreg as described above.
  • An exemplary method for preparing a high frequency circuit substrate is:
  • At least one prepreg as described above is overlapped, and a copper foil is placed on the upper and lower sides of the overlapping prepreg, and is obtained by lamination molding.
  • the high-frequency circuit substrate having low dielectric constant performance, low dielectric loss, high heat resistance, low water absorption, high interlayer adhesion, and high bending strength can be prepared by the method of the present invention. .
  • the overlap preferably employs an automated stacking operation to make the process operation easier.
  • the laminate molding is preferably vacuum lamination molding, and the vacuum lamination molding can be carried out by a vacuum laminator.
  • the lamination time is from 70 to 120 min, such as 75 min, 80 min, 85 min, 90 min, 95 min, 100 min, 105 min, 110 min or 115 min.
  • the temperature of the lamination is 180 to 220 ° C, such as 185 ° C, 190 ° C, 195 ° C, 200 ° C, 205 ° C, 210 ° C or 215 ° C.
  • the pressure of the lamination is 40 to 60 kg/cm 2 , for example 45 kg/cm 2 , 50 kg/cm 2 , 55 kg/cm 2 or 58 kg/cm 2 .
  • a typical but non-limiting method for preparing a high frequency circuit substrate of the present invention is as follows:
  • each component is weighed: a silicone resin having a three-dimensional network structure containing an unsaturated double bond, calculated by weight of the vinyl-modified polyphenylene ether resin of 100 parts by weight The weight is 10 to 90 parts by weight, and the sum of the weight of the vinyl-modified polyphenylene ether resin and the silicone resin having a three-dimensional network structure containing an unsaturated double bond is 100 parts by weight, the radical initiator The weight is 1 to 3 parts by weight, and the weight of the flame retardant is 0 to 40 parts by weight; the vinyl modified polyphenylene ether resin, including The weight of the silicone resin having a three-dimensional network structure having an unsaturated double bond and the flame retardant is 100 parts by weight, and the weight of the powder filler is 0 to 150 parts by weight;
  • High frequency as used herein means that the frequency is greater than 1 MHz.
  • the present invention has the following beneficial effects:
  • a silicone resin having a three-dimensional network structure containing an unsaturated double bond is used as a crosslinking agent of a vinyl-modified polyphenylene ether resin, and the resin composition has a high crosslinking density after curing, and can provide a high-frequency circuit substrate. High glass transition temperature;
  • the silicone resin having a three-dimensional network structure containing an unsaturated double bond does not contain a polar group, and can ensure low water absorption rate and low dielectric constant and dielectric loss of the high-frequency circuit substrate;
  • the silicone resin having a three-dimensional network structure containing an unsaturated double bond has a high thermal decomposition temperature and can provide excellent heat resistance of a high-frequency circuit substrate;
  • a silicone resin having a three-dimensional network structure containing an unsaturated double bond is used as a crosslinking agent of a vinyl-modified polyphenylene ether resin, and the prepared high-frequency circuit substrate has high interlayer adhesion and high bending strength. Improve the reliability of the substrate.
  • the silicone resin having a three-dimensional network structure containing an unsaturated double bond is not volatile, and there is no problem of volatilization during the baking sheet.
  • High-frequency circuit substrate prepared by silicone resin has high glass transition temperature ( ⁇ 180°C), good heat resistance (thermal decomposition temperature ⁇ 430°C), low water absorption rate (water absorption rate ⁇ 0.08%), interlayer adhesion High ( ⁇ 1N/mm), high bending strength ( ⁇ 450MPa), low dielectric constant (10GHz, ⁇ 3.85), low dielectric loss (10GHz, ⁇ 0.0070), very suitable for the production of circuit boards for high-frequency electronic equipment.
  • Figure 1 Schematic diagram of the high frequency circuit substrate of the present invention.
  • 1 is a schematic view of a high frequency circuit substrate according to the present invention, wherein 2 is a copper foil, and the copper foil is preferably a high peeling reverse copper foil, a low profile copper foil or an ultra low profile copper foil.
  • the number of prepregs is nine. In practical applications, the number of sheets of the prepreg to be used, the type of the glass fiber cloth, and the weight fraction of the glass fiber cloth and the resin composition are determined according to the requirements of the thickness of the high-frequency circuit substrate to be practically applied.
  • the aqueous layer is separated, the oil layer is washed with water to neutrality, and the solvent toluene is removed by distillation and drying to obtain a monotrifunctional vinyl group-containing siloxane unit (T unit) having a three-dimensional network structure containing an unsaturated double bond.
  • the vinyl TQ silicone resin V-2 obtained by hydrolysis-condensation with a tetrafunctional siloxane unit (Q unit) has a molecular weight Mn of 1900.
  • a three-necked flask was charged with a mixture of concentrated hydrochloric acid, deionized water and ethanol, and the mechanical stirrer was turned on, and then rapidly poured into triethyl phenyl silicate and dimethyldiethoxysilane under rapid stirring and heating under reflux. After condensation and hydrolysis for a certain period of time, toluene is added for extraction. After combustion, the reaction solution is poured into a separatory funnel and allowed to stand for stratification.
  • the aqueous layer is separated, the oil layer is washed with water to neutrality, and the solvent toluene is removed by distillation and drying to obtain a difunctional methyl group-containing silicon oxygen unit (D unit) and a trifunctional phenyl group-containing silicon oxygen unit (T unit).
  • D unit difunctional methyl group-containing silicon oxygen unit
  • T unit trifunctional phenyl group-containing silicon oxygen unit
  • the methylphenyl DT silicone resin V-00 obtained by hydrolysis condensation has a molecular weight Mn of 2,000.
  • Table 1 shows the materials used in the examples and comparative examples.
  • styrene-based modified polyphenylene ether resin powder St-PPE-1 100.0 parts by weight of styrene-based modified polyphenylene ether resin powder St-PPE-1, 10.0 parts by weight of a trifunctional vinyl group-containing silicon oxide unit having a three-dimensional network structure containing an unsaturated double bond (T The unit was hydrolyzed and condensed to a vinyl TT silicone resin V-1, and 3.0 parts by weight of a radical initiator dicumyl peroxide (DCP) was dissolved in a toluene solvent and adjusted to a suitable viscosity.
  • DCP radical initiator dicumyl peroxide
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • styrene-based modified polyphenylene ether resin powder St-PPE-1 100.0 parts by weight of styrene-based modified polyphenylene ether resin powder St-PPE-1, 40.0 parts by weight of a trifunctional vinyl group-containing silicon oxide unit having a three-dimensional network structure containing an unsaturated double bond (T The unit was hydrolyzed and condensed to a vinyl TT silicone resin V-1, and 3.0 parts by weight of a radical initiator dicumyl peroxide (DCP) was dissolved in a toluene solvent and adjusted to a suitable viscosity.
  • DCP radical initiator dicumyl peroxide
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • styrene-based modified polyphenylene ether resin powder St-PPE-1 100.0 parts by weight of styrene-based modified polyphenylene ether resin powder St-PPE-1, 90.0 parts by weight of a trifunctional vinyl group-containing silicon oxide unit having a three-dimensional network structure containing an unsaturated double bond (T The unit was hydrolyzed and condensed to a vinyl TT silicone resin V-1, and 3.0 parts by weight of a radical initiator dicumyl peroxide (DCP) was dissolved in a toluene solvent and adjusted to a suitable viscosity.
  • DCP radical initiator dicumyl peroxide
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, and drying in an oven to remove the toluene solvent.
  • Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed circuit substrate.
  • the overall performance of the substrate is shown in Table 3.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed circuit substrate.
  • the overall performance of the substrate is shown in Table 3.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed circuit substrate.
  • the overall performance of the substrate is shown in Table 3.
  • styrene-based modified polyphenylene ether resin powder St-PPE-1 100.0 parts by weight of styrene-based modified polyphenylene ether resin powder St-PPE-1, 40.0 parts by weight of a trifunctional vinyl group-containing silicon oxide unit having a three-dimensional network structure containing an unsaturated double bond (T Unit) Hydrolyzed and condensed vinyl TT silicone resin V-1, 3.0 parts by weight of a radical initiator dicumyl peroxide (DCP), 60.0 parts by weight of silica micropowder 525, 30.0 parts by weight of bromine-containing resistance
  • DCP radical initiator dicumyl peroxide
  • silica micropowder 525 30.0 parts by weight of bromine-containing resistance
  • the fuel agent BT-93W is dissolved and dispersed in a toluene solvent and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed circuit substrate.
  • the overall performance of the substrate is shown in Table 3.
  • Example 7 The vinyl TT silicone resin V-1 obtained by hydrolyzing and condensing a trifunctional vinyl group-containing silicon oxide unit (T unit) having a three-dimensional network structure containing an unsaturated double bond in Example 7 was replaced by linear
  • the silicone resin RH-Vi306 containing an unsaturated double bond was the same as in Example 7.
  • the composition of Example 9, Example 10 and Comparative Example 1 and their performance test results are shown in Table 3.
  • the vinyl TT silicone resin V-1 obtained by hydrolyzing and condensing a trifunctional vinyl group-containing silicon oxide unit (T unit) having a three-dimensional network structure containing an unsaturated double bond in Example 7 was replaced by a ring.
  • the silicone resin WD-V4 containing an unsaturated double bond was the same as in Example 7.
  • the composition of Example 9, Example 10 and Comparative Example 2 and their performance test results are shown in Table 3.
  • the vinyl TT silicone resin V-1 obtained by hydrolyzing and condensing a trifunctional vinyl group-containing silicon oxide unit (T unit) having a three-dimensional network structure containing an unsaturated double bond in Example 7 was replaced with a Phenyl
  • the DT silicone resin V-00 was the same as in Example 7.
  • the composition of Example 9, Example 10 and Comparative Example 3 and their performance test results are shown in Table 3.
  • Comparing Comparative Example 1 with Example 9 and Example 10 it is understood that a silicone resin having a three-dimensional network structure containing an unsaturated double bond is used as a crosslinking as compared with the linear unsaturated compound-containing organosilicon compound RH-Vi306.
  • the high speed circuit substrate obtained by the bonding agent has a higher bending strength.
  • the cross-linking agent does not have the problem of volatilization during the sizing process.
  • the high-speed circuit substrate prepared by using the resin as a crosslinking agent has high glass transition temperature, high thermal decomposition temperature, low water absorption, high interlayer adhesion, high bending strength, low dielectric constant and low
  • the dielectric loss is such that the silicone resin having a three-dimensional network structure containing an unsaturated double bond is an excellent cross-linking agent and can be used for preparation of a high-speed circuit substrate.
  • the resin paste was impregnated with 120.0 parts by weight of 7628 glass fiber cloth, controlled by a pinch shaft, and dried in an oven to remove the solvent to obtain a 7628 prepreg.
  • Four 7628 prepregs were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated for 90 min in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed circuit substrate.
  • the silicone resin having a three-dimensional network structure containing an unsaturated double bond is a TT silicone resin obtained by hydrolytic condensation of a trifunctional siloxane unit (T unit) having a three-dimensional network structure containing an unsaturated double bond.
  • T unit trifunctional siloxane unit
  • a methacrylate-modified polyphenylene ether resin 100.0 parts by weight of a methacrylate-modified polyphenylene ether resin, 40.0 parts by weight of a trifunctional vinyl group-containing silicon oxide unit (T unit) having a three-dimensional network structure containing an unsaturated double bond a vinyl TT silicone resin, 1.5 parts by weight of a free radical initiator dibenzoyl peroxide (BPO), 125.0 parts by weight of aluminum nitride, 25.0 parts by weight of decabromodiphenyl ether, dissolved and dispersed In a toluene solvent, and adjusted to a suitable viscosity.
  • BPO free radical initiator dibenzoyl peroxide
  • the emulsifier is used for emulsification, and the powder filling and the flame retardant are uniformly dispersed in the mixed liquid to obtain a resin glue.
  • the resin paste was impregnated with 500.0 parts by weight of 2116 glass fiber cloth, controlled by a pinch shaft to be suitable for a single weight, and dried in an oven to remove the toluene solvent to obtain a 2116 prepreg.
  • Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-speed circuit substrate.
  • the molecular weight of the methacrylate-modified polyphenylene ether resin is 8000 g/mol
  • the silicone resin having a three-dimensional network structure containing an unsaturated double bond contains an unsaturated double bond
  • the TT silicone resin obtained by hydrolytic condensation of a trifunctional siloxane unit (T unit) having a three-dimensional network structure is a compound represented by the following formula:
  • a styrene-based modified polyphenylene ether resin 100.0 parts by weight of a styrene-based modified polyphenylene ether resin, 50.0 parts by weight of a trifunctional vinyl group-containing silicon oxide unit (T unit) having a three-dimensional network structure containing an unsaturated double bond Vinyl TT silicone resin, 1.0 part by weight of a free radical initiator dibenzoyl peroxide (BPO), 100.0 parts by weight of alumina, 30.0 parts by weight of decabromodiphenyl ether, dissolved in toluene solvent, And adjust to the appropriate viscosity.
  • BPO free radical initiator dibenzoyl peroxide
  • alumina 100.0 parts by weight of alumina
  • decabromodiphenyl ether 100.0 parts by weight of alumina
  • decabromodiphenyl ether 100.0 parts by weight of alumina
  • decabromodiphenyl ether 100.0 parts by weight of alumina
  • the resin paste was impregnated with 230.0 parts by weight of 2116 glass fiber cloth, controlled by a clamp shaft to suit a single weight, and baked in an oven to remove the toluene solvent to obtain a 2116 prepreg.
  • Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated and cured for 120 min in a press, a curing pressure of 40 kg/cm 2 , and a curing temperature of 180 ° C to obtain a high-speed circuit substrate.
  • the structural formula of the styrene-based modified polyphenylene ether resin is:
  • the molecular weight of the styrene-based modified polyphenylene ether resin is 1000 g/mol.
  • the silicone resin having a three-dimensional network structure containing an unsaturated double bond is a TT-silicone obtained by hydrolysis-condensation of a trifunctional siloxane unit (T unit) having a three-dimensional network structure containing an unsaturated double bond.
  • T unit trifunctional siloxane unit
  • the resin is a compound represented by the following formula:
  • a styrene-based modified polyphenylene ether resin 100.0 parts by weight of a styrene-based modified polyphenylene ether resin, 50.0 parts by weight of a trifunctional vinyl group-containing silicon oxide unit (T unit) having a three-dimensional network structure containing an unsaturated double bond, and a tetrafunctional group a vinyl TQ silicone resin obtained by hydrolysis-condensation of a silicon oxide unit (Q unit), 1.5 parts by weight of a radical initiator dibenzoyl peroxide (BPO), 125.0 parts by weight of boron nitride, and 25.0 parts by weight of ten
  • BPO radical initiator dibenzoyl peroxide
  • BPO radical initiator dibenzoyl peroxide
  • boron nitride 25.0 parts by weight of ten
  • the bromodiphenyl ether is mixed, dissolved in a toluene solvent, and adjusted to a suitable viscosity.
  • the emulsifier is used for emulsification, and the powder filler and the emulsifier are uniformly dispersed in the mixed solution to obtain a resin glue.
  • the resin was impregnated with 450.0 parts by weight of 2116 glass fiber cloth, controlled by a pinch shaft to suit a single weight, and baked in an oven to remove the toluene solvent to obtain a 2116 prepreg.
  • Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 70 min in a press, a curing pressure of 60 kg/cm 2 , and a curing temperature of 220 ° C to obtain a high-speed circuit substrate.
  • the structural formula of the styrene-based modified polyphenylene ether resin is:
  • TQ silicone resin obtained by hydrolysis-condensation of a trifunctional siloxane unit (T unit) having a three-dimensional network structure and a tetrafunctional siloxane unit (Q unit) containing an unsaturated double bond is represented by the following formula Chemicalization Compound:
  • Table 4 shows the performance test results of the high-speed circuit substrate of Example 13-16.

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Abstract

本发明涉及一种聚苯醚树脂组合物及其在高频电路基板中的应用。所述聚苯醚树脂组合物包括乙烯基改性聚苯醚树脂和含有不饱和双键的具有三维网状结构的有机硅树脂。本发明所述高频电路基板具有高的玻璃化转变温度，高的热分解温度，高的层间粘合力，低介电常数及低介质损耗正切，非常适合作为高速电子设备的电路基板。

Description

一种聚苯醚树脂组合物及其在高频电路基板中的应用 技术领域
本发明涉及一种聚苯醚树脂组合物，具体地，本发明涉及一种聚苯醚树脂组合物及其在高频电路基板中的应用。
背景技术
近年来，随着电子信息技术的发展，电子设备安装的小型化、高密度化，信息的大容量化、高频化，对电路基板的耐热性、吸水性、耐化学性、机械性能、尺寸稳定性、介质常数、介质损耗等综合性能提出了更高的要求。
就介质常数性能而言，在高频电路中，信号的传输速率与绝缘材料介质常数Dk的关系为：绝缘材料介质常数Dk越低，信号传输速率越快。因此要实现信号传输速率的高频化，必须开发低介质常数的基板。随着信号频率的高频化，基板中信号的损耗不能再忽略不计。信号损耗与频率、介质常数Dk、介质损耗Df的关系为：基板介质常数Dk越小、介质损耗Df越小，信号损失就越小。因此开发具有低的介质常数Dk及低的介质损耗Df，且耐热性能良好的高频电路基板，成为CCL厂家共同关注的研发方向。
聚苯醚树脂分子结构中含有大量的苯环结构，且无强极性基团，赋予了聚苯醚树脂优异的性能，如玻璃化转变温度高、尺寸稳定性好、线性膨胀系数小、吸水率低，尤其是出色的低介电常数、低介电损耗。但聚苯醚作为热塑性的树脂，存在树脂熔点高，加工性能欠佳，耐溶剂性能差等缺点。聚苯醚出色的物理性能、耐热性能、化学性能及电性能等吸引着世界各大公司等对其进行改性，并取得了一定的成果。如在聚苯醚分子链端或侧链引入活性基团(如乙烯基)，使之成为热固性树脂。该树脂热固化后具有优异的耐热、低介质常数和低介质损 耗等综合性能，成为制备高频电路基板的理想材料。
采用含有不饱和双键的有机硅化合物作为乙烯基活性基团改性的热固性聚苯醚的交联剂，用于制备高频电子电路基材。
CN 102993683采用含有不饱和双键的有机硅化合物制备作为改性聚苯醚的交联剂，所制备的高频电路基板具有高的玻璃化转变温度，高的热分解温度，高的层间粘合力，低介电常数及低介质损耗。但是该已有技术所采用的含有不饱和双键的有机硅化合物结构为线性或者环形的有机硅化合物。采用线性的含有不饱和双键的有机硅化合物具有很好的柔性，其所制备的高频电路基板弯曲强度偏低。采用环形的含有不饱和双键的有机硅化合物所制备的电路基材综合性能良好，但由于其分子量偏小，存在上胶烘片过程中挥发的问题。
CN104650574A采用聚苯醚、聚全氟乙烯乳液、有机硅树脂及无机填料组合物，用于高频电子电路基材的制备。其所制备的基材具有低的介质常数、低的介质损耗、良好的加工性能等优点。但是，该已有技术采用的有机硅树脂为甲基苯基DQ有机硅树脂，不含活性基团，不能作为乙烯基改性的热固性聚苯醚的交联剂。
发明内容
针对现有技术中存在的问题，本发明的目的之一在于提供一种聚苯醚树脂组合物，该聚苯醚树脂组合物具有低的介质常数Dk及低的介质损耗Df，以及具有优异的耐热性能和层间粘合力，满足了高频电路基板对介质常数、介质损耗、耐热性能以及层间粘合力等性能的要求，可用于制备高频电路基板。
为了达到上述目的，本发明采用了如下技术方案：
一种聚苯醚树脂组合物，包括乙烯基改性聚苯醚树脂和含有不饱和双键的具有三维网状结构的有机硅树脂，所述含有不饱和双键的具有三维网状结构的 有机硅树脂为含有不饱和双键的具有三维网状结构的由三官能度硅氧烷单元(T单元)水解缩合而成的TT有机硅树脂或含有不饱和双键的具有三维网状结构的三官能度硅氧烷单元(T单元)和四官能度硅氧烷单元(Q单元)水解缩合而成的TQ有机硅树脂的任意一种或两种的混合物。
所述乙烯基改性聚苯醚树脂，在室温状态下为粉末状的固体热固性树脂，其两端带有活性的不饱和双键，在固化引发剂存在条件下，可进行自由基聚合固化，得到耐热性、尺寸稳定性、低吸水率、低介质常数和低介质损耗等综合性能均十分优异的热固性树脂。
采用含有不饱和双键的具有三维网状结构的有机硅树脂作为乙烯基改性聚苯醚的交联剂，聚苯醚树脂组合物固化后交联密度大，可提供高频电路基板的高玻璃化转变温度。而且，含有不饱和双键的具有三维网状结构的有机硅树脂不含极性基团，可保证高频电路基板低的吸水率、低的介质常数及低的介质损耗。含有不饱和双键的具有三维网状结构的有机硅树脂热分解温度高，可提供高频电路基板优异的耐热性能。另外，所制备得到的高频电路基板层间粘合力与弯曲强度高，可提高基板的可靠性。
乙烯基改性聚苯醚树脂具有优异的低介电常数及低介质损耗等性能，采用含有不饱和双键的具有三维网状结构的有机硅树脂作为改性聚苯醚树脂的交联剂，所制备的高频电路基板具有低的介质常数、低的介质损耗、低的吸水性、高的耐热性、高的层间粘合力和高的弯曲强度等综合性能。与线性的含有不饱和双键的有机硅化合作为交联剂相比，基板具有更高的弯曲强度。与环形的含有不饱和双键的有机硅化合物作为交联剂相比，含有不饱和双键的具有三维网状结构的有机硅树脂不存在上胶烘片时挥发的问题。
优选地，所述乙烯基改性聚苯醚树脂具有如下结构：
Figure PCTCN2016075322-appb-000001
其中，0≤x≤100，0≤y≤100，2≤x+y≤100。示例性的有15≤x+y≤30，25≤x+y≤40，30≤x+y≤55，60≤x+y≤85，80≤x+y≤98，10≤x+y≤20，35≤x+y≤45，65≤x+y≤75，85≤x+y≤95等。
M选自：
Figure PCTCN2016075322-appb-000002
N选自-O-、-CO-、-SO-、-SC-、-SO2-或-C(CH3)2-中的任意一种或者至少两种的组合。
R2、R4、R6、R8、R11、R13、R15和R17均独立地选自取代或未取代的C1-C8(例如C2、C3、C4、C5、C6或C7)直链烷基、取代或未取代的C1-C8(例如C2、C3、C4、C5、C6或C7)支链烷基或取代或未取代的苯基中的任意一种或者至少两种的组合。
R1、R3、R5、R7、R10、R12、R14和R16均独立地选自氢原子、取代或未取代的C1-C8(例如C2、C3、C4、C5、C6或C7)直链烷基、取代或未取代的C1-C8(例如C2、C3、C4、C5、C6或C7)支链烷基或取代或未取代的苯基中的任意 一种或者至少两种的组合。
R9选自：
Figure PCTCN2016075322-appb-000003
其中，A为亚芳香基、羰基或碳原子数为1～10(例如2、3、4、5、6、7、8或9)的亚烷基，Z为0～10的整数，例如0、1、2、3、4、5、6、7、8、9或10，R21、R22和R23均独自地选自氢原子或碳原子数为1～10(例如2、3、4、5、6、7、8或9)的烷基。
优选地，所述乙烯基改性聚苯醚树脂的数均分子量为500-10000g/mol，优选800～8000g/mol，进一步优选1000～4000g/mol。
优选地，所述含有不饱和双键的具有三维网状结构的由三官能度硅氧烷单元(T单元)水解缩合而成的TT有机硅树脂具有如下结构：
(R24SiO3/2)x1
其中，6≤x1≤10，例如6、7、8、9或10；
R24选自取代或未取代的C2-C10(例如C2、C3、C4、C5、C6、C7、C8或C9)含C＝C的基团；
优选地，所述含有不饱和双键的具有三维网状结构的三官能度硅氧烷单元(T单元)和四官能度硅氧烷单元(Q单元)水解缩合而成的TQ有机硅树脂具有如下结构：
(R25SiO3/2)y1(SiO4/2)z1
其中，4≤y1≤100，例如5、10、15、20、25、30、35、40、45、50、55、60、65、70、75、80、85、90或95，1≤z1≤100，例如5、10、15、20、25、30、35、40、45、50、55、60、65、70、75、80、85、90或95，且4≤y1/z1≤10，例如5、6、7、8、9或10；
R25选自取代或未取代的C2-C10(例如C2、C3、C4、C5、C6、C7、C8或C9)含C＝C的基团。
在本发明中，优选地，以乙烯基改性聚苯醚树脂的重量为100重量份计，含有不饱和双键的具有三维网状结构的有机硅树脂的重量为10～90重量份，例如15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份或85重量份，优选25-90重量份，所优选的重量份对应的树脂体系固化交联后具有更高的玻璃化转变温度。
优选地，本发明所述聚苯醚树脂组合物还包括自由基引发剂。所述自由基引发剂起引发聚合交联固化树脂体系的作用。在加热条件下，自由基引发剂发生分解产生自由基，引发树脂体系中活性基团之间反应交联，形式空间三维结构的交联网状结构。
优选地，以乙烯基改性聚苯醚树脂和含有不饱和双键的具有三维网状结构的有机硅树脂的重量之和为100重量份计，所述自由基引发剂的重量为1～3重量份。所述自由基引发剂的重量例如1.2重量份、1.4重量份、1.6重量份、1.8重量份、2.0重量份、2.2重量份、2.4重量份、2.6重量份、2.8重量份或2.9重量份。选择本发明所述的自由基引发剂的含量，可以在固化过程中得到适当的反应速度，在制造预浸料或者高频电路基板的固化反应中，可以得到良好的固化性。
所述自由基引发剂选自有机过氧化物引发剂，进一步优选自过氧化二异丙苯、过氧化二苯甲酰、过氧化苯甲酰、过氧化苯甲酸叔丁酯或4，4-二(叔丁基过氧化)戊酸正丁酯中的任意一种或者至少两种的混合物。所述混合物例如4，4-二(叔丁基过氧化)戊酸正丁酯和过氧化苯甲酸叔丁酯的混合物，过氧化二苯甲酰和过氧化二异丙苯的混合物，4，4-二(叔丁基过氧化)戊酸正丁酯和过氧化二苯甲酰的混合物，过氧化苯甲酸叔丁酯和过氧化二异丙苯的混合物，4，4-二(叔丁基过氧化)戊酸正丁酯、过氧化苯甲酸叔丁酯和过氧化二苯甲酰的混合物。所述自由基引发剂可以单独使用，也可以混合使用，混合使用可以达到更好的协同效果。
优选地，本发明所述聚苯醚树脂组合物还包括阻燃剂。
优选地，以乙烯基改性聚苯醚树脂和含有不饱和双键的具有三维网状结构的有机硅树脂的重量之和为100重量份计，阻燃剂的重量为0～40重量份，优选为0～40重量份且不包括0。所述阻燃剂的重量份例如1重量份、3重量份、7重量份、11重量份、15重量份、19重量份、23重量份、27重量份、31重量份、35重量份、38重量份或39重量份。所述阻燃剂的重量为0重量份，意指，所述树脂组合物中不含有阻燃剂。阻燃剂的含量太高，会导致耐热性和层间粘合力的降低。
优选地，本发明所述阻燃剂选自卤系阻燃剂、磷系阻燃剂或氮系阻燃剂中的任意一种或者至少两种的混合物，优选溴系阻燃剂、磷系阻燃剂或氮系阻燃剂中的任意一种或者至少两种的混合物。
优选地，所述溴系阻燃剂选自十溴二苯醚、六溴苯、十溴二苯乙烷或乙撑双四溴邻苯二甲酰亚胺中的任意一种或者至少两种的混合物。所述混合物例如十溴二苯乙烷和六溴苯的混合物，十溴二苯醚和乙撑双四溴邻苯二甲酰亚胺的混合物，十溴二苯乙烷、六溴苯和十溴二苯醚的混合物，乙撑双四溴邻苯二甲 酰亚胺、十溴二苯乙烷、六溴苯和十溴二苯醚的混合物。
优选地，所述磷系阻燃剂选自三(2，6-二甲基苯基)膦、10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、2，6-二(2，6-二甲基苯基)膦基苯或10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物中的一种或者至少两种的混合物。所述混合物例如10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物和2，6-二(2，6-二甲基苯基)膦基苯的混合物，10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-膦菲-10-氧化物和三(2，6-二甲基苯基)膦的混合物，10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、2，6-二(2，6-二甲基苯基)膦基苯和10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-膦菲-10-氧化物的混合物，三(2，6-二甲基苯基)膦、10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物和2，6-二(2，6-二甲基苯基)膦基苯的混合物。
优选地，所述氮系阻燃剂选自三聚氰胺、三聚氰胺磷酸盐、磷酸胍、碳酸胍或氨基磺酸胍中的一种或者至少两种的混合物。所述混合物例如氨基磺酸胍和碳酸胍的混合物，磷酸胍和三聚氰胺磷酸盐的混合物，三聚氰胺和氨基磺酸胍的混合物，碳酸胍、磷酸胍和三聚氰胺的混合物，三聚氰胺磷酸盐、氨基磺酸胍、三聚氰胺和磷酸胍的混合物，优选三聚氰胺或/和三聚氰胺磷酸盐。
优选地，本发明所述聚苯醚树脂组合物还包括粉末填料。优选地，所述粉末填料选自结晶型二氧化硅、无定形二氧化硅、球形二氧化硅、熔融二氧化硅、二氧化钛、碳化硅、玻璃纤维、氧化铝、氮化铝、氮化硼、钛酸钡或钛酸锶中的任意一种或至少两种的混合物。所述混合物例如结晶型二氧化硅和无定形二氧化硅的混合物，球形二氧化硅和二氧化钛的混合物，碳化硅和玻璃纤维的混合物，氧化铝和氮化铝的混合物，氮化硼和钛酸钡的混合物，钛酸锶和碳化硅的混合物，球形二氧化硅、结晶型二氧化硅和无定形二氧化硅的混合物。
在本发明所述聚苯醚树脂组合物中，粉末填料起着提高尺寸稳定性、降低 热膨胀系数和降低体系成本等作用。所述粉末填料的形状和粒径本发明对此不作限定，通常使用的粒径为0.2-10μm，例如0.5μm、1μm、2μm、3μm、5μm、8μm或9μm，例如，可选择粒径为0.2-10μm的球形二氧化硅。
优选地，以乙烯基改性聚苯醚树脂、含有不饱和双键的具有三维网状结构的有机硅树脂和阻燃剂的重量之和为100重量份计，所述粉末填料的重量为0～150重量份，优选0～150重量份且不包括0。
所述粉末填料的重量例如5重量份、15重量份、25重量份、35重量份、45重量份、55重量份、75重量份、90重量份、100重量份、110重量份、120重量份、130重量份、140重量份或145重量份。所述粉末填料的重量为0重量份，意指，所述树脂组合物中不含有粉末填料。
本发明所述的“包括”，意指其除所述组分外，还可以包括其他组分，这些其他组分赋予所述树聚苯醚脂组合物不同的特性。除此之外，本发明所述的“包括”，还可以替换为封闭式的“为”或“由……组成”。
例如，本发明所述聚苯醚树脂组合物可以添加配合的热固性树脂，作为具体例，可以举出环氧树脂、氰酸酯树脂、酚醛树脂、聚氨酯树脂和蜜胺树脂等，也可以添加这些热固性树脂的固化剂或者固化剂促进剂。
另外，所述聚苯醚树脂组合物还可以含有各种添加剂，作为具体例，可以举出硅烷偶联剂、钛酸酯偶联剂、抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂和润滑剂等。这些热固性树脂以及各种添加剂可以单独使用，也可以两种或者两种以上混合使用。
作为本发明树脂组合物之一的制备方法，可以通过公知的方法配合、搅拌、混合所述的乙烯基改性聚苯醚树脂、含有不饱和双键的具有三维网状结构的有机硅树脂、自由基引发剂、阻燃剂、粉末填料，以及各种热固性树脂和各种添 加剂，来制备。
本发明的目的之二在于提供一种树脂胶液，其是将如上所述的聚苯醚树脂组合物溶解或分散在溶剂中得到。
作为本发明中的溶剂，没有特别限定，作为具体例，可以举出甲醇、乙醇、丁醇等醇类，乙基溶纤剂、丁基溶纤剂、乙二醇-甲醚、卡必醇、丁基卡必醇等醚类，丙酮、丁酮、甲基乙基甲酮、甲基异丁基甲酮、环己酮等酮类，甲苯、二甲苯、均三甲苯等芳香族烃类，乙氧基乙基乙酸酯、醋酸乙酯等酯类，N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、N-甲基-2-吡咯烷酮等含氮类溶剂。上述溶剂可以单独使用一种，也可以两种或者两种以上混合使用，优选甲苯、二甲苯、均三甲苯等芳香族烃类溶剂与丙酮、丁酮、甲基乙基甲酮、甲基异丁基甲酮、环己酮等酮类熔剂混合使用。所述溶剂的使用量本领域技术人员可以根据自己的经验来选择，使得到的树脂胶液达到适于使用的粘度即可。
在如上所述的树脂组合物溶解或分散在溶剂的过程中，可以添加乳化剂。通过乳化剂进行分散，可以使粉末填料等在胶液中分散均匀。
本发明的目的之三在于提供一种预浸料，其是将玻璃纤维布等增强材料浸润如上所述的树脂胶液后，干燥得到。
在本发明中，玻璃纤维布为增强材料，在复合材料中起着提高强度、提高尺寸稳定性、降低热固性树脂固化的收缩等作用。根据板材厚度等要求不同，可选用不同类型的玻璃纤维布。示例性的玻璃纤维布如：7628玻纤布、2116玻纤布。
优选地，以乙烯基改性聚苯醚树脂、含有不饱和双键的具有三维网状结构的有机硅树脂、阻燃剂和粉末填料的总重量为100重量份计，玻璃纤维布等增强材料的重量为50-230重量份，例如70重量份、90重量份、110重量份、150 重量份、180重量份、200重量份、210重量份或220重量份。
所述干燥温度为80～220℃，例如90℃、110℃、150℃、170℃、190℃或200℃。所述干燥时间为1～30min，例如5min、8min、13min、17min、21min、24min或28min。
本发明的目的之四在于提供一种高频电路基板，所述高频电路基板由如上所述的预浸料制成。
示例性的一种高频电路基板的制备方法，所述方法为：
重叠至少一张如上所述的预浸料，在重叠预浸料的上下两侧放置铜箔，进行层压成型制备得到。采用本发明所述的方法可以制备得到具有低的介质常数性能、低的介质损耗、高的耐热性能、低的吸水率、高的层间粘结力、高的弯曲强度的高频电路基板。
所述重叠优选采用自动堆叠操作，使工艺操作更加简便。
所述层压成型优选真空层压成型，真空层压成型可以通过真空层压机实现。所述层压的时间为70～120min，例如75min、80min、85min、90min、95min、100min、105min、110min或115min。所述层压的温度为180～220℃，例如185℃、190℃、195℃、200℃、205℃、210℃或215℃。所述层压的压力为40～60kg/cm2，例如45kg/cm2、50kg/cm2、55kg/cm2或58kg/cm2。
本发明典型但非限制性的高频电路基板的制备方法如下：
(1)按上述所述树脂组合物配方，称取各组分：以乙烯基改性聚苯醚树脂的重量为100重量份计算，含有不饱和双键的具有三维网状结构的有机硅树脂的重量为10～90重量份，以乙烯基改性聚苯醚树脂和含有不饱和双键的具有三维网状结构的有机硅树脂的重量之和为100重量份计，所述自由基引发剂的重量为1～3重量份，阻燃剂的重量为0～40重量份；以乙烯基改性聚苯醚树脂、含 有不饱和双键的具有三维网状结构的有机硅树脂和阻燃剂的重量之和为100重量份计，所述粉末填料的重量为0～150重量份；
(2)将乙烯基改性聚苯醚树脂、含有不饱和双键的具有三维网状结构的有机硅树脂、自由基引发剂、粉料填料和阻燃剂混合，并加入适量溶剂，搅拌分散均匀，使粉料填料与阻燃剂均匀分散在树脂胶液中。用制备的胶液浸润玻璃纤维布等增强材料，烘干，除去溶剂，得到预浸料；
(3)重叠至少一张的预浸料，在预浸料的两侧放置铜箔，在真空层压机中层压固化，从而得到高频电路基板。
本发明所述“高频”意指频率大于1MHz。
与已有技术相比，本发明具有如下有益效果：
(1)采用含有不饱和双键的具有三维网状结构的有机硅树脂作为乙烯基改性聚苯醚树脂的交联剂，树脂组合物固化后交联密度大，可提供高频电路基板的高玻璃化转变温度；
(2)含有不饱和双键的具有三维网状结构的有机硅树脂不含极性基团，可保证高频电路基板低的吸水率及低的介质常数和介质损耗；
(3)含有不饱和双键的具有三维网状结构的有机硅树脂热分解温度高，可提供高频电路基板优异的耐热性能；
(4)采用含有不饱和双键的具有三维网状结构的有机硅树脂作为乙烯基改性聚苯醚树脂的交联剂，所制备的高频电路基板层间粘合力高、弯曲强度高，提高了基板的可靠性。
(5)含有不饱和双键的具有三维网状结构的有机硅树脂不挥发，不存在上胶烘片过程中挥发的问题。
总之，采用乙烯基改性聚苯醚树脂和含有不饱和双键的具有三维网状结构 的有机硅树脂制备的高频电路基板玻璃化转变温度高(≥180℃)、耐热性好(热分解温度≥430℃)、吸水率低(吸水率≤0.08％)、层间粘合力高(≥1N/mm)、弯曲强度高(≥450MPa)、介质常数低(10GHz，≤3.85)、介质损耗低(10GHz，≤0.0070)，非常适合制备高频电子设备的电路基板。
附图说明
下面结合附图并通过具体实施方式来进一步说明本发明的技术方案。
图1：本发明所述高频电路基板的示意图。
本发明说明书附图中标记如下所示：
1-预浸料；2-铜箔。
具体实施方式
为更好地说明本发明，便于理解本发明的技术方案，本发明的典型但非限制性的实施例如下：
如本发明说明书附图1所示为本发明的高频电路基板示意图，其中2为铜箔，铜箔优选高剥离反转铜箔、低轮廓铜箔或超低轮廓铜箔。该图中，预浸料张数为9张。在实际应用中，采用的预浸料的张数、玻璃纤维布的种类、玻璃纤维布与树脂组合物的重量分数比需根据实际应用的高频电路基板的厚度等要求来决定。
制备例1
在三口烧瓶中加入浓盐酸、去离子水及乙醇的混合液，开启机械搅拌机，然后于快速搅拌和加热回流条件下快速滴入乙烯基硅酸三乙酯水解缩合，水解一定时间后，加入甲苯萃取，然后将反应液倒入分液漏斗，静置分层。将水层分去，油层用水洗至中性，蒸馏、干燥除去溶剂甲苯后得到含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧烷单元(T单元)水解缩合而成的 乙烯基TT有机硅树脂V-1，分子量Mn为2000。
制备例2
在三口烧瓶中加入浓盐酸、去离子水及乙醇的混合液，开启机械搅拌机，然后于快速搅拌和加热回流条件下快速滴入乙烯基硅酸三乙酯、正硅酸乙酯水解缩合，水解一定时间后，加入甲苯萃取，然后将反应液倒入分液漏斗，静置分层。将水层分去，油层用水洗至中性，蒸馏、干燥除去溶剂甲苯后得到含有不饱和双键的具有三维网状结构的由单三官能度含乙烯基的硅氧烷单元(T单元)与四官能度的硅氧烷单元(Q单元)水解缩合而成的乙烯基TQ有机硅树脂V-2，分子量Mn为1900。
制备例3
在三口烧瓶中加入浓盐酸、去离子水及乙醇的混合液，开启机械搅拌机，然后于快速搅拌和加热回流条件下快速滴入苯基硅酸三乙酯、二甲基二乙氧基硅烷水解缩合，水解一定时间后，加入甲苯萃取，燃后将反应液倒入分液漏斗，静置分层。将水层分去，油层用水洗至中性，蒸馏、干燥除去溶剂甲苯后得到由二官能度含甲基的硅氧单元(D单元)与三官能度含苯基的硅氧单元(T单元)水解缩合而成的甲基苯基DT有机硅树脂V-00，分子量Mn为2000。
为更好地说明本发明，便于理解本发明的技术方案，本发明的典型但非限制性的实施例如下：
表1所示为实施例及比较例所用原料。
表1实施例及比较例所用原料
制造厂商 产品名称或牌号 材料描述
Sabic SA9000 甲基丙烯酸酯基改性聚苯醚树脂
三菱化学公司 St-PPE-1 乙烯基苄基醚改性聚苯醚树脂
润禾化工 RH-Vi306 线性含不饱和双键的有机硅化合物
武大有机硅 WD-V4 环形含不饱和双键的有机硅化合物
自制 V-00 甲基苯基DT有机硅树脂
自制 V-1 乙烯基TT有机硅树脂
自制 V-2 乙烯基TQ有机硅树脂
上海高桥 DCP 过氧化二异丙苯
东莞芯威化工 BPO 过氧化二苯甲酰
Sibelco 525 熔融二氧化硅
美国雅宝 XP-7866 磷系阻燃剂
美国雅宝 XP-7866 磷系阻燃剂
上海宏和 2116 玻璃纤维布
实施例1
将100.0重量份的甲基丙烯酸酯基改性聚苯醚树脂粉末SA9000，10.0重量份的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基苯基TT有机硅树脂V-1，3.0重量份的自由基引发剂过氧化二异丙苯(DCP)，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高速电路基板。基材综合性能如表2所示。
实施例2
将100.0重量份的甲基丙烯酸酯基改性聚苯醚树脂粉末SA9000，25.0重量份的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基苯基TT有机硅树脂V-1，3.0重量份的自由基引发剂过氧化二异丙苯(DCP)，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高速电路基板。基材综合性能如表2所示。
实施例3
将100.0重量份的甲基丙烯酸酯基改性聚苯醚树脂粉末SA9000，30.0重量份的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基苯基TT有机硅树脂V-1，3.0重量份的自由基引发剂过氧化二异丙苯(DCP)，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高速电路基板。基材综合性能如表2所示。
实施例4
将100.0重量份的甲基丙烯酸酯基改性聚苯醚树脂粉末SA9000，40.0重量份的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基TT有机硅树脂V-1，3.0重量份的自由基引发剂过氧化二异丙苯(DCP)，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得 2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高速电路基板。基材综合性能如表2所示。
实施例5
将100.0重量份的甲基丙烯酸酯基改性聚苯醚树脂粉末SA9000，90.0重量份的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基TT有机硅树脂V-1，3.0重量份的自由基引发剂过氧化二异丙苯(DCP)，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高速电路基板。基材综合性能如表2所示。
实施例6
将100.0重量份的苯乙烯基改性聚苯醚树脂粉末St-PPE-1，10.0重量份的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基TT有机硅树脂V-1，3.0重量份的自由基引发剂过氧化二异丙苯(DCP)，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高速电路基板。基材综合性能如表2所示。
实施例7
将100.0重量份的苯乙烯基改性聚苯醚树脂粉末St-PPE-1，40.0重量份的含 有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基TT有机硅树脂V-1，3.0重量份的自由基引发剂过氧化二异丙苯(DCP)，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高速电路基板。基材综合性能如表2所示。
实施例8
将100.0重量份的苯乙烯基改性聚苯醚树脂粉末St-PPE-1，90.0重量份的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基TT有机硅树脂V-1，3.0重量份的自由基引发剂过氧化二异丙苯(DCP)，溶解于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高速电路基板。基材综合性能如表2所示。
实施例9
将100.0重量份的甲基丙烯酸酯基改性聚苯醚树脂粉末SA9000，40.0重量份的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基TT有机硅树脂V-1，3.0重量份的自由基引发剂过氧化二异丙苯(DCP)，60.0重量份的硅微粉525，30.0重量份的含溴阻燃剂BT-93W，溶解分散于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预 浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高速电路基板。基材综合性能如表3所示。
实施例10
将100.0重量份的甲基丙烯酸酯基改性聚苯醚树脂粉末SA9000，40.0重量份的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)与四官能的硅氧单元(Q单元)水解缩合而成的乙烯基TQ有机硅树脂V-2，3.0重量份的自由基引发剂过氧化二异丙苯(DCP)，60.0重量份的硅微粉525，30.0重量份的含溴阻燃剂BT-93W，溶解分散于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高速电路基板。基材综合性能如表3所示。
实施例11
将100.0重量份的甲基丙烯酸酯基改性聚苯醚树脂粉末SA9000，40.0重量份的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基TT有机硅树脂V-1，3.0重量份的自由基引发剂过氧化二苯甲酰(BPO)，60.0重量份的硅微粉525，30.0重量份的含溴阻燃剂BT-93W，溶解分散于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高速电路基板。基材综合性能如表3所示。
实施例12
将100.0重量份的苯乙烯基改性聚苯醚树脂粉末St-PPE-1，40.0重量份的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基TT有机硅树脂V-1，3.0重量份的自由基引发剂过氧化二异丙苯(DCP)，60.0重量份的硅微粉525，30.0重量份的含溴阻燃剂BT-93W，溶解分散于甲苯溶剂中，并调节至适合粘度。用2116玻纤布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高速电路基板。基材综合性能如表3所示。
比较例1
将实施例7中的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基TT有机硅树脂V-1换为线性含不饱和双键的有机硅树脂RH-Vi306，其余与实施例7相同。如表3所示为实施例9、实施例10与对比例1的组成及其性能测试结果。
比较例2
将实施例7中的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基TT有机硅树脂V-1换为环型含不饱和双键的有机硅树脂WD-V4，其余与实施例7相同。如表3所示为实施例9、实施例10与对比例2的组成及其性能测试结果。
比较例3
将实施例7中的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基TT有机硅树脂V-1换为甲基苯基 DT有机硅树脂V-00，其余与实施例7相同。如表3所示为实施例9、实施例10与对比例3的组成及其性能测试结果。
表2
Figure PCTCN2016075322-appb-000004
表3
Figure PCTCN2016075322-appb-000005
Figure PCTCN2016075322-appb-000006
从比较例1与实施例9、实施例10对比可知，与线性含不饱和双键的有机硅化合物RH-Vi306相比，采用含有不饱和双键的具有三维网状结构的有机硅树脂作为交联剂，得到的高速电路基板具有更高的弯曲强度。从比较例2和与实施例9、实施例10对比可知，与环型含不饱和双键的有机硅化合物WD-V4相比，含有不饱和双键的具有三维网状结构的有机硅树脂作为交联剂在上胶烘片过程中不存在挥发的问题。采用含有不饱和双键的具有三维网状结构的有机硅 树脂作为交联剂所制备的高速电路基材具有高的玻璃化转变温度、高的热分解温度、低的吸水率、高的层间粘合力、高的弯曲强度、低的介质常数及低的介质损耗，因此含有不饱和双键的具有三维网状结构的有机硅树脂是一种综合性能优异的交联剂，可用于高速电路基板的制备。
从比较例3与实施例9、实施例10对比可知，由于甲基苯基DT有机硅树脂不含有活性的乙烯基基团，不能固化含有乙烯基改性的热固性聚苯醚，所制备的板材玻璃化转变温度、耐浸焊性能、层间粘合力、弯曲强度等综合性能差，不能满足终端对高速电子电路基材综合性能的要求。
实施例13
将100.0重量份的甲基丙烯酸酯基改性聚苯醚树脂，40.0重量份的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基TT有机硅树脂，3.0重量份的自由基引发剂4，4-二(叔丁基过氧化)戊酸正丁酯，50.0重量份的碳化硅，40.0重量份的阻燃剂三(2，6-二甲基苯基)膦，溶解于甲苯和丁酮的混合溶剂中，并调节至适合粘度，制得树脂胶液。用120.0重量份的7628玻璃纤维布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去溶剂，制得7628预浸料。将4张7628预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高速电路基板。
所述甲基丙烯酸酯基改性聚苯醚的结构式为：
Figure PCTCN2016075322-appb-000007
其中，15＜x＜50，15＜y＜50，15＜x+y＜100；甲基丙烯酸酯基改性聚苯醚的分 子量为8000g/mol。
所述含有不饱和双键的具有三维网状结构的有机硅树脂为含有不饱和双键的具有三维网状结构的由三官能度硅氧单元(T单元)水解缩合而成的TT有机硅树脂是由如下通式代表的化合物：
(R24SiO3/2)x1
其中，x1＝6；
R24选自取代或未取代的C2-C10含C＝C的基团。
实施例14
将100.0重量份的甲基丙烯酸酯基改性聚苯醚树脂，40.0重量份的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基TT有机硅树脂，1.5重量份的自由基引发剂过氧化二苯甲酰(BPO)，125.0重量份的氮化铝，25.0重量份的十溴二苯醚混合，溶解分散于甲苯溶剂中，并调节至适合粘度。采用乳化剂进行乳化，使粉末填和阻燃剂等均匀分散在混合液中，制得树脂胶液。用500.0重量份的2116玻璃纤维布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中干燥，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化90min，固化压力50kg/cm2，固化温度200℃，制得高速电路基板。
所述甲基丙烯酸酯基改性聚苯醚的结构式为：
Figure PCTCN2016075322-appb-000008
50＜x＜100，甲基丙烯酸酯基改性聚苯醚树脂的分子量为8000g/mol；
所述含有不饱和双键的具有三维网状结构的有机硅树脂为含有不饱和双键 的具有三维网状结构的由三官能度硅氧单元(T单元)水解缩合而成的TT有机硅树脂是由如下通式代表的化合物：
(R24SiO3/2)x1
其中，x1＝8；
R24选自取代或未取代的C2-C10含C＝C的基团。
实施例15
将100.0重量份的苯乙烯基改性聚苯醚树脂，50.0重量份的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)水解缩合而成的乙烯基TT有机硅树脂，1.0重量份的自由基引发剂过氧化二苯甲酰(BPO)，100.0重量份的氧化铝，30.0重量份的十溴二苯醚混合，溶解于甲苯溶剂中，并调节至适合粘度。采用乳化剂进行乳化，使粉末填料和阻燃剂均匀分散在混合液中，制得树脂胶液。用230.0重量份的2116玻璃纤维布浸润树脂胶液，过夹轴控制适合单重，并在烘箱中烘片，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化120min，固化压力40kg/cm2，固化温度180℃，制得高速电路基板。
所述苯乙烯基改性聚苯醚树脂的结构式为：
Figure PCTCN2016075322-appb-000009
5＜y＜15，苯乙烯基改性聚苯醚树脂的分子量为1000g/mol。
所述含有不饱和双键的具有三维网状结构的有机硅树脂为含有不饱和双键的具有三维网状结构的由三官能度硅氧单元(T单元)水解缩合而成的TT有机硅 树脂是由如下通式代表的化合物：
(R24SiO3/2)x1
其中，x1＝10；
R24选自取代或未取代的C2-C10含C＝C的基团。
实施例16
将100.0重量份的苯乙烯基改性聚苯醚树脂，50.0重量份的含有不饱和双键的具有三维网状结构的由三官能度含乙烯基的硅氧单元(T单元)和四官能的硅氧单元(Q单元)水解缩合而成的乙烯基TQ有机硅树脂，1.5重量份的自由基引发剂过氧化二苯甲酰(BPO)，125.0重量份的氮化硼，25.0重量份的十溴二苯醚混合，溶解于甲苯溶剂中，并调节至适合粘度。采用乳化剂进行乳化，使粉末填料和乳化剂均匀分散在混合液中，制得树脂胶液。用450.0重量份的2116玻璃纤维布浸润树脂，过夹轴控制适合单重，并在烘箱中烘片，除去甲苯溶剂，制得2116预浸料。将4张2116预浸料重叠，上下两面配以1OZ厚度的铜箔，在压机中真空层压固化70min，固化压力60kg/cm2，固化温度220℃，制得高速电路基板。
所述苯乙烯基改性聚苯醚树脂的结构式为：
Figure PCTCN2016075322-appb-000010
50＜x＜60，25＜y＜45，75＜x+y＜100，苯乙烯基改性聚苯醚的分子量为9500g/mol。
所述含有不饱和双键的具有三维网状结构的三官能度硅氧单元(T单元)和四官能度硅氧单元(Q单元)水解缩合而成的TQ有机硅树脂是由如下通式代表的化 合物：
(R25SiO3/2)y1(SiO4/2)z1
其中，y1＝10，z1＝2，且y1/z1＝5；
R25选自取代或未取代的C2-C10含C＝C的基团。
表4所示为实施例13-16高速电路基板性能测试结果。
表4
Figure PCTCN2016075322-appb-000011
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范 围和公开范围之内。

Claims (10)

  1. 一种聚苯醚树脂组合物，包括乙烯基改性聚苯醚树脂和含有不饱和双键的具有三维网状结构的有机硅树脂，所述含有不饱和双键的具有三维网状结构的有机硅树脂为含有不饱和双键的具有三维网状结构的由三官能度硅氧烷单元(T单元)水解缩合而成的TT有机硅树脂或含有不饱和双键的具有三维网状结构的三官能度硅氧烷单元(T单元)和四官能度硅氧烷单元(Q单元)水解缩合而成的TQ有机硅树脂的任意一种或两种的混合物。
  2. 如权利要求1所述的聚苯醚树脂组合物，其特征在于，所述乙烯基改性聚苯醚树脂具有如下结构：
    Figure PCTCN2016075322-appb-100001
    其中，0≤x≤100，0≤y≤100，2≤x+y≤100；
    M选自：
    Figure PCTCN2016075322-appb-100002
    N选自-O-、-CO-、-SO-、-SC-、-SO2-或-C(CH3)2-中的任意一种或者至少两种的组合；
    R2、R4、R6、R8、R11、R13、R15和R17均独立地选自取代或未取代的C1-C8 直链烷基、取代或未取代的C1-C8支链烷基或取代或未取代的苯基中的任意一种或者至少两种的组合；
    R1、R3、R5、R7、R10、R12、R14和R16均独立地选自氢原子、取代或未取代的C1-C8直链烷基、取代或未取代的C1-C8支链烷基或取代或未取代的苯基中的任意一种或者至少两种的组合；
    R9选自：
    Figure PCTCN2016075322-appb-100003
    其中，A为亚芳香基、羰基或碳原子数为1～10的亚烷基，Z为0～10的整数，R21、R22和R23均独自地选自氢原子或碳原子数为1～10的烷基；
    优选地，所述乙烯基改性聚苯醚树脂的数均分子量为500-10000g/mol，优选800～8000g/mol，进一步优选1000～4000g/mol。
  3. 如权利要求1或2所述的聚苯醚树脂组合物，其特征在于，所述含有不饱和双键的具有三维网状结构的由三官能度硅氧烷单元(T单元)水解缩合而成的TT有机硅树脂具有如下结构：
    (R24SiO3/2)x1
    其中，6≤x1≤10；
    R24选自取代或未取代的C2-C10含C＝C的基团；
    优选地，所述含有不饱和双键的具有三维网状结构的三官能度硅氧烷单元(T单元)和四官能度硅氧烷单元(Q单元)水解缩合而成的TQ有机硅树脂具有如 下结构：
    (R258iO3/2)y1(SiO4/2)z1
    其中，4≤y1≤100，1≤z1≤100，且4≤y1/z1≤10；
    R25选自取代或未取代的C2-C10含C＝C的基团。
  4. 如权利要求1-3之一所述的聚苯醚树脂组合物，其特征在于，以乙烯基改性聚苯醚树脂的重量为100重量份计，含有不饱和双键的具有三维网状结构的有机硅树脂的重量为10～90重量份，优选25-90重量份。
  5. 如权利要求1-4之一所述的聚苯醚树脂组合物，其特征在于，所述聚苯醚树脂组合物还包括自由基引发剂；
    优选地，以乙烯基改性聚苯醚树脂和含有不饱和双键的具有三维网状结构的有机硅树脂的重量之和为100重量份计，所述自由基引发剂的重量为1～3重量份；
    优选地，所述自由基引发剂选自有机过氧化物引发剂，进一步优选自过氧化二异丙苯、过氧化二苯甲酰、过氧化苯甲酰、过氧化苯甲酸叔丁酯或4，4-二(叔丁基过氧化)戊酸正丁酯中的任意一种或者至少两种的混合物。
  6. 如权利要求1-5之一所述的聚苯醚树脂组合物，其特征在于，所述聚苯醚树脂组合物还包括阻燃剂；
    优选地，以乙烯基改性聚苯醚树脂和含有不饱和双键的具有三维网状结构的有机硅树脂的重量之和为100重量份计，阻燃剂的重量为0～40重量份，优选为0～40重量份且不包括0；
    优选地，所述阻燃剂选自卤系阻燃剂、磷系阻燃剂或氮系阻燃剂中的任意一种或者至少两种的混合物，优选溴系阻燃剂、磷系阻燃剂或氮系阻燃剂中的任意一种或者至少两种的混合物；
    优选地，所述溴系阻燃剂选自十溴二苯醚、六溴苯、十溴二苯乙烷或乙撑双四溴邻苯二甲酰亚胺中的任意一种或者至少两种的混合物；
    优选地，所述磷系阻燃剂选自三(2，6-二甲基苯基)膦、10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、2，6-二(2，6-二甲基苯基)膦基苯或10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物中的任意一种或者至少两种的混合物；
    优选地，所述氮系阻燃剂选自三聚氰胺、三聚氰胺磷酸盐、磷酸胍、碳酸胍或氨基磺酸胍中的任意一种或者至少两种的混合物；
    优选地，所述聚苯醚树脂组合物还包括粉末填料；
    优选地，所述粉末填料选自结晶型二氧化硅、无定形二氧化硅、球形二氧化硅、熔融二氧化硅、二氧化钛、碳化硅、玻璃纤维、氧化铝、氮化铝、氮化硼、钛酸钡或钛酸锶中的任意一种或至少两种的混合物；
    优选地，以乙烯基改性聚苯醚树脂、含有不饱和双键的具有三维网状结构的有机硅树脂和阻燃剂的重量之和为100重量份计，所述粉末填料的重量为0～150重量份，优选0～150重量份且不包括0。
  7. 一种树脂胶液，其是将如权利要求1-6之一所述的聚苯醚树脂组合物溶解或分散在溶剂中得到。
  8. 一种预浸料，其是将增强材料浸润如权利要求7所述的树脂胶液后，干燥得到。
  9. 如权利要求8所述的预浸料，其特征在于，以乙烯基改性聚苯醚树脂、含有不饱和双键的具有三维网状结构的有机硅树脂、阻燃剂和粉末填料的种粮直和为100重量份计，增强材料的重量为50～230重量份。
  10. 一种高频电路基板，所述高频电路基板由至少一张如权利要求8或9所述的预浸料制成。
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